- Vapor phase hydrodeoxygenation of furfural to 2-methylfuran on molybdenum carbide catalysts
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Vapor phase hydrodeoxygenation (HDO) of furfural over Mo2C catalysts at low temperatures (423 K) and ambient pressure showed high/low selectivity to CO bond/C-C bond cleavage, resulting in selectivity to 2-methylfuran (2MF) and furan of ~50-60% and 2 for deoxygenation, instead of unwanted sequential hydrogenation, was evidenced by the low selectivity to 2-methyltetrahydrofuran. The apparent activation energy and H2 order for 2MF production rates were both found to be invariant with furfural conversion caused by catalyst deactivation, suggesting that (1) the measured reaction kinetics are not influenced by the products of furfural HDO and (2) the loss of active sites, presumably by formation of carbonaceous species observed by TEM analysis, is the reason for the observed catalyst deactivation. The observed half order dependence of 2MF production rates on H2 pressure at different furfural pressures (~0.12-0.96 kPa) and the 0-0.3 order dependence in furfural pressure support the idea of two distinct sites required for vapor phase furfural HDO reactions on Mo2C catalysts. The invariance of 2MF production rates normalized by the number of catalytic centers assessed via ex situ CO chemisorption suggests that metal-like sites on Mo2C catalysts are involved in selective HDO reactions.
- Lee, Wen-Sheng,Wang, Zhenshu,Zheng, Weiqing,Vlachos, Dionisios G.,Bhan, Aditya
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- Ruthenium on phosphorous-modified alumina as an effective and stable catalyst for catalytic transfer hydrogenation of furfural
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Supported ruthenium was used in the liquid phase catalytic transfer hydrogenation of furfural. To improve the stability of Ru against leaching, phosphorous was introduced on a Ru/Al2O3 based catalyst upon impregnation with ammonium hypophosphite followed by either reduction or calcination to study the effect of phosphorous on the physico-chemical properties of the active phase. Characterization using X-ray diffraction, solid state 31P nuclear magnetic resonance spectroscopy, X-ray absorption spectroscopy, temperature programmed reduction with H2, infrared spectroscopy of pyridine adsorption from the liquid phase and transmission electron microscopy indicated that phosphorous induces a high dispersion of Ru, promotes Ru reducibility and is responsible for the formation of acid species of Br?nsted character. As a result, the phosphorous-based catalyst obtained after reduction was more active for catalytic transfer hydrogenation of furfural and more stable against Ru leaching under these conditions than a benchmark Ru catalyst supported on activated carbon.
- Campisi, Sebastiano,Ferri, Davide,Fovanna, Thibault,Kambolis, Anastasios,Kr?cher, Oliver,Nachtegaal, Maarten,Peng, Gael,Rentsch, Daniel,Villa, Alberto
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- Highly dispersed Cu nanoparticles as an efficient catalyst for the synthesis of the biofuel 2-methylfuran
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Cu/SiO2 catalysts were synthesized by different methods, which greatly influenced their texture and the catalytic performance. The AE-Cu/SiO2 catalyst was prepared via the ammonia evaporation method and showed a 95.5% yield for 2-methylfuran (a promising fuel additive) because of the cooperative effects of surface Cu0, Cu+ species and acid sites, which respectively stemmed from the reduction of highly dispersed CuO species, copper species that fiercely interacted with the support SiO2, and the special structure. The ammonia evaporation method favored the formation of a copper phyllosilicate phase with a lamellar structure, which could provide a large number of Cu nanoparticles and acid sites and further improve the activity and selectivity. Crucially, the stability of the AE-Cu/SiO2 catalyst (>210 h) was also significantly improved due to the enhanced copper-silicon interactions, which could immobilize copper particles and resist the fast transmigration (aggregation and loss) of copper particles in the thermal treatment process. In contrast, the CP-Cu/SiO2 catalyst was synthesized via the conventional precipitation method and presented poor activity and stability toward 2-methylfuran because of large copper particles, severe aggregation and a loss of copper species during reaction. Compared with the conventional CP-Cu/SiO2 catalyst, the use of the AE-Cu/SiO2 catalyst in the synthesis of the biofuel 2-methylfuran could not only improve the yield of the desired product, but also decrease by at least 20 °C the reaction temperature which is propitious for prolonging the lifetime of the Cu/SiO2 catalyst.
- Dong, Fang,Ding, Guoqiang,Zheng, Hongyan,Xiang, Xiaoming,Chen, Linfeng,Zhu, Yulei,Li, Yongwang
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- Cyclodextrins as growth controlling agents for enhancing the catalytic activity of PVP-stabilized Ru(0) nanoparticles
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Cyclodextrins act as growth controllers in the synthesis of PVP-stabilized Ru(0) nanoparticles, leading to enhancement of the catalytic activity in the hydrogenation of furfural.
- Herbois, Rudy,Noel, Sebastien,Leger, Bastien,Bai, Lei,Roucoux, Alain,Monflier, Eric,Ponchel, Anne
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- Fe/FeOx embedded in LDH catalyzing C-C bond forming reactions of furfural with alcohols in the absence of a homogeneous base
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Fe/FeOx embedded in LDH was prepared by reducing the pre-synthesized [Fe(C2O4)3]3? anions intercalated LDH and used as a multi-functional catalyst for synthesis of C7-C9 compound via transfer hydrogenation between furfural (C5) and short-chain alcohols (C2-C4) and a subsequent aldol reaction of furfural with intermediate short-chain aldehydes in the absence of a homogeneous base with furfuryl alcohol as a byproduct. Screening reaction conditions, evaluation and improvement of the cyclic catalytic performance, and determination of catalytically active components were performed, and the results demonstrated that both high conversion and high selectivity to the C[sbnd]C bond forming product can be obtained under a non-oxidizing atmosphere of Ar or H2/Ar mixed gas, a reaction temperature of 140 °C and a reaction time of 4 h; the catalyst was easily deactivated during the cycle experiments, however, its catalytic stability can be effectively improved by depositing Ni with weak reducibility on the surface of Fe nanoparticles at the cost of reducing partial catalytic activity. Fe/FeOx together with LDH as a whole proved to be effective in catalyzing the transfer hydrogenation reaction and the support LDH imparted basic catalytic function to the composite realizing the aldol reaction in the absence of a homogeneous base.
- Wang, Lijun,Zhong, Yang,Zhou, Bo
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- Properties of copper chromite catalysts in hydrogenation reactions
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A pretreatment involving a 4-h reduction under H2 at 573 K, compared to either 473 or 673 K, gave the highest specific activity for furfural and crotonaldehyde hydrogenation over an unpromoted copper chromite catalyst. Both H2 and CO chemisorption declined monotonically with increasing reduction temperature, but turnover frequencies also showed a maximum after a pretreatment at 573 K. DRIFTS identified a band, associated with CO adsorbed on Cu+1 sites, which reached a maximum intensity after a 573 K pretreatment, while XRD patterns also provided evidence for a CuCrO2 phase and showed a continuous increase in Cu0 as temperature increased. Selectivity to furfuryl alcohol ranged from 35-80% and reaction orders on furfural and H2 were near unity. In contrast, crotonaldehyde hydrogenation gave primarily butyraldehyde with only around 3% crotyl alcohol and a near zero-order dependence on crotonaldehyde, although the H2 dependence was still near first order. IR spectra under reaction conditions revealed adsorbed crotonaldehyde, provided evidence for an unsaturated alkoxide intermediate and detected no butyraldehyde on the surface. A simple Langmuir-Hinshelwood sequence nicely explained both reactions, it was consistent with the DRIFTS results obtained during crotonaldehyde hydrogenation, and the resultant rate expression gave meaningful entropies and enthalpies of adsorption for H2 and crotonaldehyde.
- Rao,Dandekar,Baker,Vannice
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- Efficient catalytic transfer hydrogenation of biomass-based furfural to furfuryl alcohol with recycable Hf-phenylphosphonate nanohybrids
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An acid-base bifunctional nanohybrid phenylphosphonic acid (PhP) - hafnium (1:1.5) was synthesized through assembly of PhP with HfCl4 for catalytic transfer hydrogenation of furfural (FUR) to furfuryl alcohol (FFA) using 2-propanol as both reaction solvent and hydrogen donor source. An FFA yield of 97.6 % with formation rate of 9760 μmol g?1 h?1 at 99.2 % FUR conversion was obtained with the reaction system at 120 °C for 2 h reaction time. Activation energy (Ea) was estimated to be 60.8 kJ/mol with respect to FUR concentration, which is comparable with or even lower than Ea values attained over metal catalysts. The pronounced catalytic activity of PhP-Hf (1:1.5) is attributed to its moderate acidity and relatively strong basicity. The PhP-Hf (1:1.5) catalyst was demonstrated to maintain its activity for five consecutive reuse cycles.
- Li, Hu,Li, Yan,Fang, Zhen,Smith, Richard L.
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- Transfer hydrogenation of furfural catalyzed by multi-centers collaborative Ni-based catalyst and kinetic research
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We propose a simple preparation route that converting biomass-derived furfural (FUR) to furfuryl alcohol (FOL) over a series of Ni-Mg-Al catalysts (NMA-n) with different molar ratios. Yield of FOL can reach 96.8 % over NMA-2 catalyst under the mild reacti
- Kong, Deyu,Liu, Junhua,Mao, Weizhong,Miao, Shiwen,Wang, Fang,Yin, Bingqian
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- A gas-phase coupling process for simultaneous production of γ-butyrolactone and furfuryl alcohol without external hydrogen over bifunctional base-metal heterogeneous catalysts
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A solvent-free gas-phase coupling process through hydrogen transfer without external hydrogen supply over novel bifunctional base-metal heterogeneous catalysts was developed for the simultaneous production of γ-butyrolactone and furfuryl alcohol with high yields of 95.0% from biomass-derived compounds. Such a practical, unparallely efficient and environmentally benign process makes it promising in terms of both green sustainable chemistry and industrial perspective.
- Hu, Qi,Fan, Guoli,Yang, Lan,Cao, Xinzhong,Zhang, Peng,Wang, Baoyi,Li, Feng
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- A new synthesis of 2,3-dihydrofurans: Cycloisomerization of alkynyl alcohols to endocyclic enol ethers
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Molybdenum pentacarbonyl-trimethylamine promotes the cyclization of 1-alkyn-4-ols to the isomeric 2,3-dihydrofurans.
- McDonald,Connolly,Gleason,Towne,Treiber
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- Cr-free Co-Cu/SBA-15 catalysts for hydrogenation of biomass-derived α-, β-unsaturated aldehyde to alcohol
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Cr-free bi-metallic SBA-15-supported Co-Cu catalysts were examined in the conversion of biomass-derived α-, β-unsaturated aldehyde (furfural) to value-added chemical furfuryl alcohol (FOL). Co-Cu/SBA-15 catalysts with a fixed Cu loading of 10 wt% and varying Co loadings (2.5, 5, and 10 wt%) were prepared by the impregnation method. The catalysts were characterized by X-ray diffraction, N2 sorption, H2 temperature-programmed reduction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, high-resolution transmission electron microscopy, CO chemisorption, and inductively coupled plasma mass spectrometry. The influence of different reaction parameters such as temperature, pressure, catalyst dosage, and furfural concentration on the catalyst performance was evaluated. Relative to catalysts supported on amorphous silica, the current SBA-15-supported Co-Cu catalysts displayed higher performance, attaining a furfural conversion of 99% and furfuryl alcohol selectivity of 80%. The catalytic reactions were conducted in a 100-mL autoclave at 170 °C and 2 MPa H2 pressure for 4 h.
- Srivastava, Sanjay,Mohanty, Pravakar,Parikh, Jigisha K.,Dalai, Ajay K.,Amritphale,Khare, Anup K.
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- Pd(II) and Pt(II) catalysed selective synthesis of furfuryl alcohol: Solvent effects and insights into the mechanism
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Selective conversion of furfural to furfural alcohol, a bio-based commodity chemical with applications in the agriculture, metal casting and polymer industries is presented. Pd(II) and Pt(II) complexes were synthesized and characterized using multi-nuclear magnetic resonance spectroscopy, infrared spectroscopy, high resolution electrospray ionisation mass spectrometry as well as elemental analysis. These complexes were found to serve as excellent pre-catalysts for furfural alcohol synthesis with excellent conversion and selectivity (>99%), more so under solvent-free conditions via transfer hydrogenation method. Catalysts C1 and C5 also showed enhanced activity and selectivity as pre-catalysts for the hydrogenation of furfural using formic acid as a hydrogen carrier. The platinum catalyst C5 was recycled twice (with consistent activity and selectivity), and proved to function as a molecular catalyst as evidenced by mercury poisoning experiments. In situ NMR studies were performed using C5 culminated in the proposition of plausible reaction mechanism, and a likely catalytically active species has been identified with the aid of 1H and 31P{1H} NMR.
- Makhubela, Banothile C. E.,Matsinha, Leah C.,Moyo, Pamela S.
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- Highly Selective Reduction of Bio-Based Furfural to Furfuryl Alcohol Catalyzed by Supported KF with Polymethylhydrosiloxane (PMHS)
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Hydrogenation of bio-based furfural (FUR) to furfuryl alcohol (FFA) is tremendously expanding the application of biomass in many industries such as resins, biofuels, and pharmaceuticals. However, mass manufacture of FFA from FUR is restrained by strict requirements of reaction conditions and expensive catalysts. In this work, an economical and benign catalytic system, containing an easily prepared and reusable catalyst 5 wt.% KF/ZrO2 and a low-cost hydrogen source polymethylhydrosiloxane (PMHS), was developed to be efficient for the hydrogenation of FUR to high-value FFA under mild conditions. The catalyst reactivity was found to be remarkably influenced by the support acid-base properties and KF loading doge. In the presence of 5 wt.% KF/ZrO2, a high FFA yield of 97% and FUR conversion of 99% could be obtained at 25°C in just 0.5 h, which was superior to those attained with other tested catalysts. The KF/ZrO2 catalyst could be recycled at least five times, with the FFA yield slightly decreasing from 97% to 71%. The spare decrease in FFA yield is possibly attributed to the catalyst pore blocking, as clarified by SEM, BET, XPS, and ICP-MS measurements of the fresh and reused catalysts.
- Yu, Zhaozhuo,Wu, Weibo,Li, Hu,Yang, Song
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- Optimization and Kinetic Studies on Hydrogenation of Furfural to Furfuryl Alcohol over SBA-15 Supported Bimetallic Copper-Cobalt Catalyst
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In present work, hydrogenation of furfural to furfuryl alcohol (FA) is studied over Co-Cu/SBA-15 as FA has wide range of industrial applications such as in the resin production, acid proof bricks, fibre glass, fibre concrete etc. The effects of different operating parameters such as temperature, pressure, catalyst amount, and furfural to 2-propanol molar ratio on the conversion of furfural to FA were determined and parameters were optimized by implementing Taguchi method as statistical tool. At the optimized conditions, the yield of FA was 96.7 %. The yield of FA was influenced by the parameters such as temperature and pressure significantly, as obtained by analysis of variance. Kinetic study revealed that the reaction followed pseudo-first order pathway with an activation energy of 9.2 kcal mol-1. (Figure Presented).
- Srivastava, Sanjay,Solanki, Naveen,Mohanty, Pravakar,Shah, Krunal A.,Parikh, Jigisha K.,Dalai, Ajay K.
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- Gas-phase hydrogenation of furfural over Cu/CeO2 catalysts
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Cu-CeO2-x catalysts, with a Cu/Ce molar ratio between 0.2 and 6.0, have been synthesized by coprecipitation, calcination and subsequent reduction. These samples have been characterized by X-ray diffraction, H2 temperature-programmed reduction, N2O titration, N2 adsorption-desorption at ?196 °C and X-ray photoelectronic spectroscopy, among other techniques. They exhibit small average particle sizes, high dispersion of copper species, porosity and high metal surface. Their catalytic behavior was evaluated in the gas-phase hydrogenation of furfural (FUR), evidencing high activity and stability due to the strong interaction Cu-CeO2. The highest conversion was attained for catalysts with higher copper content, which display higher metal surface, with a value of 83% after 5 h of time-on-stream (TOS) for the Cu-CeO2-6 catalyst, at 190 °C, by using a H2:FUR molar ratio of 11.5 and a WHSV of 1.5 h?1. In all cases, only furfuryl alcohol (FOL) and 2-methylfuran (MF) were obtained as reaction products, being majority MF for shorter TOS and FOL for longer, which can be explained by the deactivation of the highly hydrogenating sites by carbonaceous deposits and the oxidation of the active phase by water generated in the dehydration process to obtain MF.
- Jiménez-Gómez, Carmen P.,Cecilia, Juan A.,Márquez-Rodríguez, Imanol,Moreno-Tost, Ramón,Santamaría-González, José,Mérida-Robles, Josefa,Maireles-Torres, Pedro
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- Enhancement of aggregation-induced emission by introducing multiple o-carborane substitutions into triphenylamine
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The enhancement of aggregation-induced emission (AIE) is presented on the basis of the strategy for improving solid-state luminescence by employing multiple o-carborane substituents. We synthesized the modified triphenylamines with various numbers of o-carborane units and compared their optical properties. From the optical measurements, the emission bands from the twisted intramolecular charge transfer (TICT) state were obtained from the modified triphenylamines. It was notable that emission efficiencies of the multi-substituted triphenylamines including two or three o-carborane units were enhanced 6- to 8-fold compared to those of the mono-substituted triphenylamine. According to mechanistic studies, it was proposed that the single o-carborane substitution can load the AIE property via the TICT mechanism. It was revealed that the additional o-carborane units contribute to improving solid-state emission by suppressing aggregation-caused quenching (ACQ). Subsequently, intense AIEs were obtained. This paper presents a new role of the o-carborane substituent in the enhancement of AIEs.
- Nishino, Kenta,Uemura, Kyoya,Gon, Masayuki,Tanaka, Kazuo,Chujo, Yoshiki
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- Doping Pd/SiO2 with Na+: Changing the reductive etherification of CO to furan ring hydrogenation of furfural in ethanol
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The production of biofuels and chemicals by hydrogenation of furfural has attracted much attention recently. Herein the effect of Na+ doping on the catalytic performance of Pd/SiO2 in hydrogenation and reductive-etherification of furfural in ethanol was systematically studied. Two Pd/SiO2 catalysts with and without the modification by Na+ were prepared by impregnation and calcination. Their catalytic properties were compared for the hydrogenation of furfural and furfural diethyl acetal under mild conditions. The silanol groups on Pd/SiO2 catalysed the acetalization of furfural and alcohol and the resulted acetal underwent hydrogenolysis on Pd nanoparticles (NPs) with an average particle size of 8 nm, leading to a moderate yield (~58%) of furfuryl ethyl ether. Doping Na+ on Pd/SiO2 led to the diminishing of silanol groups as well as strong interaction between Na+ and Pd NPs. No acetalization occurred on Na+ modified Pd/SiO2 due to the exchange of H+ of Si-OH with Na+, thus the reductive etherification of CO group in furfural was completely inhibited. Meanwhile the hydrogenation of furan-ring over Na+ coordinated Pd NPs could proceed with very high selectivity (>90%) forming tetrahydrofurfural in high yield. Kinetics study on the hydrogenation of furfural diethyl acetal over Pd/SiO2 and Na+ doped Pd/SiO2 suggested that the Na+ greatly impeded the hydrogenolysis of C-O-C bond of acetal, while the hydrogenation of the furan ring took place selectively.
- Long, Yinshuang,Wang, Yun,Wu, Haihong,Xue, Teng,Wu, Peng,Guan, Yejun
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- One-pot cascade conversion of xylose to furfuryl alcohol over a bifunctional Cu/SBA-15-SO3H catalyst
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The conversion of hemicellulose-derived xylose to furfuryl alcohol is a practical procedure for producing value-added chemicals from biomass. In this study, a bifunctional Cu/SBA-15-SO3H catalyst was employed for the one-pot catalytic conversion of xylose to furfuryl alcohol with a yield of up to 62.6% at the optimized conditions of 140 °C, 4 MPa, and for 6 h in a biphasic water/n-butanol solvent. A high reaction temperature resulted in further hydrogenation to 2-methyl furan, while a high hydrogen pressure led to a side hydrogenation reaction to xylitol. The biphasic solvent allowed xylose solvation as well as furfuryl product extraction. The acidic –SO3H sites and Cu sites co-existed, maintained a balance, and cooperatively catalyzed the cascade conversion. Excessive acidic sites and large pores could promote the xylose conversion, although a low furfuryl alcohol yield was obtained. This catalytic system could be potentially applied to the one-pot synthesis of furfuryl alcohol from hemicellulose-derived xylose.
- Deng, Tianyu,Xu, Guangyue,Fu, Yao
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- Bifunctional Lewis and Br?nsted acidic zeolites permit the continuous production of bio-renewable furanic ethers
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The catalytic valorisation of bio-renewable feedstock often relies upon multi-stage processing of highly-functionalised substrates, resulting in selectivity and processs engineering challenges. Herein, we demonstrate that a bifunctional zeolitic material, containing both Lewis and Br?nsted acid sites in a single catalytic material, permits the continuous production of bio-renewable furanic ethers, such as (butoxy)methyl furan, which possess potential as fuel additives. In contrast to mono-functional catalysts and physical mixtures thereof, the bifunctional Sn- and Al-containing BEA zeolite results in uniquely-high levels of activity, selectivity and stability. Optimal results were obtained over a bifunctional catalyst containing 2 wt% Sn and 0.5 wt% Al, prepared by modified solid state incorporation, which was highly selective (>75%) to the desired ether for over 100 h on stream, and for over 3000 substrate turnovers.
- Padovan,Al-Nayili,Hammond
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- Highly efficient nitrogen-doped hierarchically porous carbon supported Ni nanoparticles for the selective hydrogenation of furfural to furfuryl alcohol
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Nickel nanoparticles supported on nitrogen doped hierarchically porous carbon (Ni/CN) are found to be highly efficient and reusable catalysts for the selective hydrogenation of biomass-derived furfural to furfuryl alcohol (FA). Various characterization methods were used to study the structural and morphological features of the catalysts. Furfural conversion of 96% and 95% FA selectivity was obtained using a 5 wt% Ni/CN catalyst. This catalyst showed excellent recyclability without any loss in activity and FA selectivity when it was reused four times. The higher catalytic performance is attributed to the nitrogen incorporated hierarchical porous 3D carbon network.
- Kotbagi, Trupti V.,Gurav, Hanmant R.,Nagpure, Atul S.,Chilukuri, Satyanarayana V.,Bakker, Martin G.
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- Biocatalytic transformation of furfural into furfuryl alcohol using resting cells of Bacillus cereus
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The bioconversion of furfural to furfuryl alcohol is an attractive route in biomass valorization that could replace traditional contaminant methods. The use of whole cells has been explored for this purpose. Bacillus cereus without previous treatment with furanic compounds was used to selectively obtain furfuryl alcohol. Growing and resting cells were employed. Using growing cells of B. cereus, lower yields to alcohol were obtained because of furfural toxicity. However, employing resting cells it was possible to reach higher yields to furfuryl alcohol. Optimal operative conditions were studied: different concentrations of furfural, glucose and molybdenum, pH, and temperature. Thus, glucose (100 mM) and molybdenum (0.1 mM) were added to maintain cell biomass obtaining a yield to furfuryl alcohol close to 80% at 30 °C, pH 7.2 from 30 mM of furfural.
- Rodríguez M, Alejandra,Rache, Leidy Y.,Brijaldo, María H.,Romanelli, Gustavo P.,Luque, Rafael,Martinez, José J.
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- tert-Butanol intervention enables chemoselective conversion of xylose to furfuryl alcohol over heteropolyacids
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Both the solvent and catalyst play important roles in the chemoselective transformation of biomass-related compounds to fine chemicals and fuels. We report herein an innovative catalytic strategy for the direct valorization of xylose without external H2producing high yield of furfuryl alcohol (FA), which is a versatile platform molecule. The solventtert-butanol served not only as a precursor of the hydrogen honor, but also as a shield to facilitate xylose dehydration and inhibit the polymerization and decomposition reactions of FA. Commercial H4SiW12O40was found to work as a multifunctional catalyst during the cascade conversion and had good reusability. The underlying catalytic mechanism revealed that the Br?nsted and Lewis acid sites co-existed cooperatively to catalyze the xylose dehydration step and the active metal site of W atom adsorbed the hydrogen proton for the transfer hydrogenation of furfural to FA. After the incorporation of the formic acid as a supplemental hydrogen source, an unprecedented FA yield of 90% could be accomplished in a batch reactor under mild conditions. The kinetic behavior describing the conversion of xylose to FA was investigated to monitor the process. The estimated activation energies for xylose dehydration, furfural hydrogenation, and FA decomposition were 85.1, 78.8, and 101.1 kJ mol?1, respectively. This study opens a new avenue for the selective production of FA from hemicellulose-derived pentose in a green and straightforward manner.
- He, Liang,Li, Hui,Peng, Lincai,Wang, Juan,Wang, Mengmeng,Zhang, Junhua
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- Efficient and Selective Ni/Al2O3–C Catalyst Derived from Metal–Organic Frameworks for the Hydrogenation of Furfural to Furfuryl Alcohol
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Abstract: Currently, precious metal catalysts or toxic copper-chromium catalysts are widely used in the catalytic hydrogenation of furfural. In this study, the selective hydrogenation of furfural to furfuryl alcohol was performed over alumina-carbon matrix embedded Ni nanoparticles catalyst. The Ni-loaded metal organic framework precursors were synthesized by reverse microemulsion method (water in oil), then the Ni/Al2O3–C catalysts were obtained by pyrolysis under a nitrogen atmosphere. Various characterizations including XRD, XPS, SEM, TEM, TPR, TPD and TG were carried out to reveal the microstructure and chemical composition of the prepared samples. The results showed that the hexagonal platelet structure and the smaller nickel nanoparticle size(~ 8?nm) benefits from the alumina–carbon matrix support, which helped the uniform dispersion and prevented it from accumulation at high temperatures. In addition, the catalyst performance was greatly affected by the calcination conditions and metal loading. At optimized operating conditions, 98.7% conversion of furfural and 92% yield of furfuryl alcohol could be achieved over Ni0.15/Al2O3–C catalyst in the liquid phase hydrogenation reaction with a good reusability. Graphical Abstract: [Figure not available: see fulltext.].
- Hu, Feng,Wang, Yuan,Xu, Siquan,Zhang, Zongqi,Chen, Yuan,Fan, Jingdeng,Yuan, Hui,Gao, Lijing,Xiao, Guomin
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- Insights into influence of nanoparticle size and metal-support interactions of Cu/ZnO catalysts on activity for furfural hydrogenation
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Cu/ZnO catalysts primarily derived from aurichalcite with Cu/Zn = 0.4-1.1 (mol/mol) were prepared via "decreased pH" coprecipitation method and introduced in hydrogenation of furfural to furfuryl alcohol. The "precursor effect" was clearly confirmed and the catalyst with a Cu/Zn = 0.8 provided the best conversion and TOF. Catalysts were characterized via XRD, FT-IR, N2O titration, TEM, H2-TPR, XPS and AES. The size of Cu nanoparticles and Cu-ZnO interactions were systematically investigated and were found to remarkably influence catalytic activity of the catalysts. Consequently, the best catalytic performance for the catalyst with Cu/Zn = 0.8 was due to the suitable Cu particle size (8 nm) and strong metal-support interactions (SMSI), acting as the Cu-ZnO synergy.
- Yang, Xiaohai,Chen, Hongmei,Meng, Qingwei,Zheng, Hongyan,Zhu, Yulei,Li, Yong Wang
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- A Comprehensive Study on the Reductive Amination of 5-Hydroxymethylfurfural into 2,5-Bisaminomethylfuran over Raney Ni Through DFT Calculations
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Reductive amination of furfuryl alcohol, furfural and 5-hydroxymethylfurfural (5-HMF) were carried out on various metal catalysts. Over Raney Ni catalyst, we obtained the highest furfurylamine yields of 81.8 % and 94.0 % from furfuryl alcohol in absence and presence of H2, respectively. While furfural was used as the substrate, 100 % yield of furfurylamine could be achieved over Raney Ni under rather moderate conditions. Although 5-HMF was completely converted over all catalysts used, the highest yield of 2,5-bisaminomethylfuran (60.7 %) was obtained over Raney Ni at 160 °C in 12 h. The DFT calculations on the adsorption behavior of NH3 and H2 on different metal surfaces showed that the difference of the adsorption energy between NH3 and H2 on Ni is lower than those of other metals, indicating that less metal active sites on Ni surface is occupied by NH3, which leaves more active sites for dehydrogenation/hydrogenation reactions and in the end promotes the reductive amination reactions.
- Zhou, Kuo,Liu, Haiyan,Shu, Huimin,Xiao, Shuwen,Guo, Dechao,Liu, Yingxin,Wei, Zuojun,Li, Xiaonian
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- Activity of continuous flow synthesized Pd-based nanocatalysts in the flow hydroconversion of furfural
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A number of synthesized supported Pd nanomaterials on aluminosilicate supports were investigated in the continuous flow hydroconversion of furfural to a range of furanic derivatives as compared to a commercial Pd/C catalyst. Excellent furfural conversions (>60%) and varying selectivities to products at mild temperatures (90 °C) could be obtained for most catalytic systems, with interesting selectivities to furfuryl alcohol (FOL), 2-methylfuran (MF) and tetrahydrofurfuryl alcohol (THFOL) depending on type of Pd catalyst. A significant deactivation with time on stream was observed for continuous flow synthesized nanomaterials with respect to commercial 5%Pd/C.
- Garcia-Olmo, Antonio J.,Yepez, Alfonso,Balu, Alina M.,Prinsen, Pepijn,Garcia, Araceli,Maziere, Audrey,Len, Christophe,Luque, Rafael
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- Iron-Promotion of Silica-Supported Copper Catalysts for Furfural Hydrodeoxygenation
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The catalytic hydrodeoxygenation of furfural is an important reaction for the production of biofuels because its product, 2-methylfuran, has excellent fuel properties: it can be added easily to the existing gasoline pool and it is renewable and, therefore, carbon neutral. The reaction network of hydrodeoxygenation is a two-step reaction from furfural to furfuryl alcohol and then to 2-methylfuran. Silica-supported Cu is a mild hydrogenation catalyst that is selective for the hydrogenation of the carbonyl group of furfural to furfuryl alcohol. We have found that Fe-containing Cu-based catalysts show much higher reactivity and very high selectivity towards 2-methylfuran (85 %+). It is of interest to understand the structural and chemical effects of the Fe promotion (0.15 % w/w) over the Cu catalyst (1 % Cu w/w) and characterize the species responsible for the high hydrogenation performance. Our investigations indicate that after the catalyst is pretreated in hydrogen, Cu is reduced fully, whereas Fe is only reduced partially (a mixture of FeIII and FeII is observed). In situ diffuse reflectance infrared Fourier transform spectroscopy suggests that FeII species are present on the catalyst surface, as indicated by the adsorption of NO.
- Sheng, Huibo,Lobo, Raul F.
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- Carbon-embedded Ni nanocatalysts derived from MOFs by a sacrificial template method for efficient hydrogenation of furfural to tetrahydrofurfuryl alcohol
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We report a fast and simple method for the synthesis of Ni-based metal-organic-frameworks (Ni-MOFs). Due to the existence of nickel ions and an organic ligand, the MOFs are employed as a sacrificial template for the facile preparation of carbon-embedded Ni (Ni/C) catalysts by a direct thermal decomposition method. The obtained Ni/C catalysts exhibit excellent catalytic activity for selectively transforming furfural (FAL) to tetrahydrofurfuryl alcohol (THFOL) due to the Ni nanoparticles (NPs) embedded uniformly in the ligand-derived carbon. The exemplified results illustrate that the catalytic performance of the Ni/C catalyst is greatly affected by the calcination conditions (temperature and time), composition of the Ni-MOF precursor and the catalysis conditions. The conversion of FAL and selectivity of THFOL both reached 100% under the conditions of 120 °C, 1 MPa H2 pressure and 120 min of hydrogenation over the Ni/C-500 catalyst, derived from the pyrolysis of Ni-MOFs (Ni:BTC mole ratio of 1.0) at 500 °C for 120 min, which exhibits an average nanoparticle size of ~14 nm and uniform dispersion, and the highest BET surface area (~92 m2 g-1) among all investigated Ni/C catalysts. This facilely prepared heterogeneous catalyst would be very promising for the replacement of noble metal catalysts for the efficient catalytic conversion of biomass-derived feedstocks into value-added chemicals.
- Su, Yanping,Chen, Chun,Zhu, Xiaoguang,Zhang, Yong,Gong, Wanbing,Zhang, Haimin,Zhao, Huijun,Wang, Guozhong
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- Hydrogenation in supercritical conditions catalyzed by palladium supported on modified activated carbon
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Biomass is expected to be a substitute for traditional fossil fuels because it is renewable and environmentally friendly. Bio-oil, as an important utilization of biomass, has a complex composition. Accordingly, it remains a great challenge for oxygenated compounds in bio-oil to be upgraded, especially for furfural. In this research, a highly active catalyst with 1 wt% palladium supported on activated carbon (Pd/AC) was prepared by impregnating Pd species on modified activated carbon, which was applied to furfural catalytic hydrogenation in super critical carbon dioxide (scCO2). The conversion rate (79%) was higher than that obtained in toluene as solvent (60%). A selectivity of furfuralcohol and tetrahydrofurfuryl alcohol of up to 100% was achieved in scCO2 conditions with no byproducts obtained. In contrast, the total selectivity was only 60% using ethanol as solvent. Meanwhile, the reaction conditions in the scCO2 including hydrogen pressure and catalyst amount have been investigated. The Pd/AC catalysts were characterized by XRD, SEM, IR and BET techniques. A green solvent, and high activity and selectivity present real advantages of this method over other methods.
- Liu, Lu-Jie,Guo, Hong-Mei,Xue, Bo,Lou, Hui,Chen, Min
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- Tandem dehydration-transfer hydrogenation reactions of xylose to furfuryl alcohol over zeolite catalysts
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Dehydration and transfer hydrogenation tandem reactions of xylose to furfuryl alcohol in water/isopropanol were performed on MFI, FAU and BEA zeolites. An unprecedented selectivity of 75% was accomplished on zeolite beta, evidencing the crucial role of th
- Paulino, Priscilla N.,Perez, Rafael F.,Figueiredo, Natália G.,Fraga, Marco A.
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- Effect of promoter on selective hydrogenation of furfural over Cu-Cr/TiO2 catalyst
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Cu-based TiO2-supported catalysts were prepared to study their performance in the selective gas-phase hydrogenation of furfural (FF). The catalytic performance was assessed over 4 hr of run length under atmospheric pressure at the H2-to-hydrocarbon ration of 10.6 and 453 K. The effect of Cr as a promoter was also assessed. An extremely poor performance was observed for the non-promoted catalyst due to the lack of Cu species on the surface of the catalyst. When Cr was applied as a promoter, the dispersion of the Cu species was improved, and, as a result, the Cu-Cr/TiO2 catalyst showed high FF conversion and high furfuryl alcohol yield.
- Ghashghaee, Mohammad,Shirvani, Samira,Farzaneh, Vahid
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- Pd-Ru/TiO2 catalyst - An active and selective catalyst for furfural hydrogenation
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The selective hydrogenation of furfural at ambient temperature has been investigated using a Pd/TiO2 catalyst. The effect of the solvent was studied and high activity and selectivity to 2-methylfuran and furfuryl alcohol was observed using octane as solvent but a number of byproducts were observed. The addition of Ru to the PdTiO2 catalyst decreased the catalytic activity but improved the selectivity towards 2-methylfuran and furfuryl alcohol with decreased byproduct formation. Variation of the Ru/Pd ratio has shown an interesting effect on the selectivity. The addition of a small amount of Ru (1 wt%) shifted the selectivity towards furfuryl alcohol and 2-methylrofuran. Further increasing the Ru ratio decreased the catalytic activity and also showed a very poor selectivity to 2-methylfuran.
- Aldosari, Obaid F.,Iqbal, Sarwat,Miedziak, Peter J.,Brett, Gemma L.,Jones, Daniel R.,Liu, Xi,Edwards, Jennifer K.,Morgan, David J.,Knight, David K.,Hutchings, Graham J.
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- Catalytic hydrogenation of furfural to furfuryl alcohol over chromium-free catalyst: Enhanced selectivity in the presence of solvent
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Copper chromite (Cr2CuO4) catalyst is commercially being used for hydrogenation of furfural (FAL) to furfuryl alcohol (FA). However, due to the negative environmental impact of chromium, the use of a chromium-free catalyst has become a logical choice. In order to develop Cr-free catalysts, several Cu-Zn-X-Y [X and Y = additives] based trimetallic and tetrametallic catalysts were synthesized and tested for selective hydrogenation of furfural to furfuryl alcohol in different solvents. The characterization of catalysts using XRD, N2 sorption, H2-TPR, and HRTEM reveals the synergetic effect between CuO and ZnO interface. Interestingly, the strong influence of solvents was observed on the catalytic activity and selectivity. The positive influence of the solvent on enhancing selectivity was associated with the hydrogen bond donation (HBD) and hydrogen bond acceptance (HBA) capability. Water, a green solvent, has been found the most effective solvent. The high hydrogen bond donor capability of water was responsible for the strong positive effect. The effect of parameters, such as H2 pressure, catalyst loading, furfural concentration, temperature, and reaction time, was studied on catalyst performance. Excellent selectivity for furfuryl alcohol ≥ 99% was obtained at mild operating conditions of temperature of 100 °C and H2 pressure of 1 MPa. The kinetic study revealed that the furfural conversion profile was well fitted by the first-order kinetic model. The best CZAl catalyst showed reproducible activity up to 5 cycles.
- Singh, Gurmeet,Singh, Lovjeet,Gahtori, Jyoti,Gupta, Rishi Kumar,Samanta, Chanchal,Bal, Rajaram,Bordoloi, Ankur
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- Role of alkali earth metals over Pd/Al2O3 for decarbonylation of 5-hydroxymethylfurfural
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A series of Pd/Al2O3 catalysts with different alkali earth metals (Mg, Ca, Sr, Ba) and varying Sr loadings (1.8, 3.5, 5.3, 7 and 8.8 wt%) were investigated for 5-hydroxymethylfurfural (HMF) decarbonylation. The alkali earth metal and content were demonstrated to have profound influences on the metal dispersion, electron density of the metal, acid-base properties of the catalyst, and catalytic performance. The Pd3Sr/Al2O3 catalyst exhibited the highest initial activity and furfuryl alcohol selectivity, achieving a yield of 92%. The key to high decarbonylation selectivity is the suppression of hydrogenolysis and etherification side reactions through the attenuation of the acidity of catalysts. Successful catalytic activity not only lies in the increased metallic surface area, but is also affected by the adsorption properties of the carbonyl group and the poisoning CO produced. The catalytic activity is linearly correlated to the surface metallic area at low modifier loading over PdM/Al2O3 catalysts. But along with further increased metallic surface area over PdXSr/Al2O3, HMF conversion initially increased, reaching a plateau over Pd3Sr/Al2O3 and then decreased with increasing Sr loading. A synergistic effect between the Sr species and metallic Pd was proposed, which promoted the migration of carbonyl adsorption from the support to the surface Pd through the electron donation of Sr species to Al2O3 and metallic Pd.
- Meng, Qingwei,Qiu, Chengwu,Ding, Guoqiang,Cui, Jinglei,Zhu, Yulei,Li, Yongwang
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- Highly Selective Transfer Hydrogenation of Carbonyl Compounds Using La2O3
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In the present study, we used rare earth oxides for the catalytic transfer hydrogenation of carbonyl compounds. Pretreated La2O3 showed better catalytic performance than various rare earth oxides for the reduction of carbonyl compounds. Reaction conditions, precursors, and donor hydrogen sources were also investigated to optimize the hydrogen transfer to furfural in 2-propanol. La2O3 provided a conversion of different carbonyl compounds and selectivity to the corresponding alcohols up to 100% and 99%, respectively. We also investigated a plausible mechanism using in situ IR and found that furfural was adsorbed on the catalyst surface in a different adsorption mode. Meanwhile, La(OH)3, a hydroxide derivative of La2O3 formed during the reaction, was also catalytically active.
- Natsir, Taufik Abdillah,Hara, Takayoshi,Ichikuni, Nobuyuki,Shimazu, Shogo
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- Solvents as Phase-transfer Catalysts in Reactions initiated by Solid Bases
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For reactions initiated by solid bases (e.g. potassium hydroxide, sodium hydroxide, potassium carbonate), solvents (e.g. water, ButOH, polyethylene glycol, MeCN, Me2SO) may act as solid-liquid phase transfer catalysts (e.g. for C-H, N-H or O-H alkylation by alkyl halides, or epoxidation by sulfonium or sulfoxonium salts).
- Bentley, T. William,Jones, Ray V. H.,Larder, Annette H.,Lock, Stephen J.
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- Controllable chemoselective hydrogenation of furfural by PdAg/C bimetallic catalysts under ambient operating conditions: An interesting Ag switch
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Hydrogenation of furfural to value-added chemical products is largely hindered by its multiple reaction pathways and complicated product distribution. Thus, to selectively achieve the desired products, catalysts with precise catalytic properties are highly required. Herein, a series of PdAg bimetallic nanoparticles (NPs) of similar size and tunable composition supported on activated carbon (Pd4Ag1/C, Pd2Ag1/C, Pd1Ag1/C and Pd2Ag3/C) were synthesized in a controlled manner and applied in the selective hydrogenation of furfural. Interestingly, an obvious composition-dependent catalytic performance was observed: upon incrementally increasing the proportion of Ag in PdAg NPs, the hydrogenation selectivity can transform from tetrahydrofurfuryl alcohol (sel. 94% for Pd4Ag1/C) to furfuryl alcohol (sel. 95% for Pd1Ag1/C) with nearly complete conversion (99%) of furfural. DFT calculations revealed that the adsorption free energy of in situ generated furfuryl alcohol on Pd(111) surface is inversely proportional correlated with the Ag content in PdAg bimetallic NPs, which accounts for the alteration of chemoselectivity. Importantly, the present study is the first demonstration of composition-induced selectivity reversal for the hydrogenation of furfural under ambient conditions (25 °C, 0.1 MPa H2).
- Wu, Zhi-Lei,Wang, Jian,Wang, Shuo,Zhang, Ya-Xin,Bai, Guo-Yi,Ricardez-Sandoval, Luis,Wang, Gui-Chang,Zhao, Bin
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- Furfuryl alcohol from furfural hydrogenation over copper supported on SBA-15 silica catalysts
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Vapor phase furfural hydrogenation has been investigated over Cu supported on SBA-15 silica catalysts. These SBA-Cu catalysts, with variable Cu loadings (8, 15 and 20 wt%), have been prepared by impregnation and characterized by N2 sorption, XRD, XPS, N2O decomposition and TEM techniques. Compared with copper chromite, SBA-Cu catalysts showed a better catalytic performance, reaching a furfural conversion of 54 mol% and a selectivity to furfuryl alcohol of 95 mol%, after 5 h of time-on-stream at 170 °C, with the 15 wt% Cu catalyst. The studies of the used catalysts by CNH analysis and thermo-programmed oxidation (TPO) evidenced a lower amount of carbonaceous deposits on this used SBA-15Cu catalyst. Moreover, the study of the copper dispersion by XPS, before and after the catalytic test, revealed that this intermediate copper loading gives rise to the most stable copper particles. The evaluation of the effect of different reaction parameters, such as reaction temperature (170-270 °C), catalyst loadings and furfural concentration and H2 flow, on the catalytic performance has demonstrated that higher conversion are attained at low reaction temperature, and, as expected, by using high catalyst weight and low furfural feed.
- Vargas-Hernández,Rubio-Caballero,Santamaría-González,Moreno-Tost,Mérida-Robles,Pérez-Cruz,Jiménez-López,Hernández-Huesca,Maireles-Torres
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- A self-cleaving DNA nucleoside
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An allyl-modified nucleoside has been shown to self-alkylate and depurinate on treatment with iodine and heat; placement in DNA strands yields site-directed cleavage of the DNA.
- Gupta, Vineet,Kool, Eric T.
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- The electrocatalytic hydrogenation of furanic compounds in a continuous electrocatalytic membrane reactor
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The electrocatalytic hydrogenation of biomass derived oxygenates in a continuous electrocatalytic membrane reactor presents a promising method of fuel and chemical production that minimizes usage of solvents and has the potential to be powered using renewable electricity. In this paper we demonstrate the use of a continuous-flow electrocatalytic membrane reactor for the reduction of aqueous solutions of furfural into furfuryl alcohol (FA), tetrahydrofurfuryl alcohol (THFA), 2-methylfuran (MF) and 2-methyltetrahydrofuran (MTHF). Protons needed for hydrogenation were obtained from the electrolysis of water at the anode of the reactor. Pd was identified as the most active monometallic catalyst of 5 different catalysts tested for the hydrogenation of aqueous furfural with hydrogen gas in a high-throughput reactor. Thus Pd/C was tested as a cathode catalyst for the electrocatalytic hydrogenation of furfural. At a power input of 0.1W, Pd/C was 4.4 times more active (per active metal site) as a cathode catalyst in the electrocatalytic hydrogenation of furfural than Pt/C. The main products for the electrocatalytic hydrogenation of furfural were FA (54-100% selectivity) and THFA (0-26% selectivity). MF and MTHF were also detected in selectivities of 8%. Varying the reactor temperature between 30 °C and 70 °C had a minimal effect on reaction rate for furfural conversion. Using hydrogen gas at the anode, in place of water electrolysis, produced slightly higher rates of product formation at a lower power input. Sparging hydrogen gas on the cathode had no effect on reaction rate or selectivity, and was used to examine the addition of recycling loops to the continuous electrocatalytic membrane reactor.
- Green, Sara K.,Lee, Jechan,Kim, Hyung Ju,Tompsett, Geoffrey A.,Kim, Won Bae,Huber, George W.
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- Highly selective hydrogenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran at low temperature over a Co-N-C/NiAl-MMO catalyst
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Currently there is tremendous interest in the discovery of catalysts which can selectively hydrogenate biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF). Herein, a highly selective catalyst for this transformation was developed, by adsorption of a cobalt porphyrin (CoTAPP) onto a nickel-aluminium layered double hydroxide (NiAl-LDH) support, followed by a pyrolysis step at 500 °C under a N2 atmosphere. The obtained catalyst (denoted here as Co-N-C/NiAl-MMO), comprising cobalt species (Co0 and CoOx) and N-doped carbon on a NiAl mixed metal oxide support, showed outstanding initial selectivity (99.9%) for the hydrogenation of HMF to DMF at 170 °C in tetrahydrofuran (THF). This is one of the highest selectivities reported to date for this reaction, with the reaction temperature being very mild. After 3 cycles of catalytic tests, with catalyst regeneration by heating at 300 °C in N2 between tests, the HMF conversion efficiency and DMF selectivity of Co-N-C/NiAl-MMO had both decreased by >70% compared to the initial values. This deactivation resulted from the loss of surface basic sites needed for H2 activation, as well as a change in the Co speciation on the catalyst surface (i.e. Co0 oxidation to CoOx). Results guide the development of improved catalysts for the selective conversion of HMF to DMF. This journal is
- Ai, Shiyun,Han, Feng,Li, Yan,Ma, Ning,Song, Yong,Waterhouse, Geoffrey I. N.
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- A selective oxidative valorization of biomass-derived furfural and ethanol with the supported gold catalysts
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The oxidative upgrading of renewable furfural (FUR) and ethanol is an important way to produce high-quality liquid fuel and value-added furanic derivatives. In this work, a series of supported Au catalysts were prepared using the colloid-immobilization technique, and further employed for catalytic oxidative condensation of FUR with ethanol in the presence of molecular oxygen. It is found that, with Au@CaO as the catalyst, 85.9% conversion of FUR and 81.8% selectivity of the product furan-2-acrolein were achieved in the absence of any homogeneous basic additive. The effects of different reactions such as reaction time, temperature and catalyst amount were explored in detail. Also, the influences of calcination temperature and amount of protective agent during the preparation of catalyst were investigated. According to the characterization results of catalyst, it is concluded that the synergistic effect of metallic Au and basic site of CaO support plays a significant role on the selective oxidative condensation. At last, a possible reaction mechanism is proposed based on the catalytic principle and experimental results.
- Gao, Yiqi,Tong, Xinli,Zhang, Haigang
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- Selective electrochemical hydrogenation of furfural to 2-methylfuran over a single atom Cu catalyst under mild pH conditions
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Furfural is regarded as one of the most promising bio-based feedstocks in the bio-refinery industry. Selective hydrogenation of the carbonyl bond in furfural plays a vital role in its conversion to downstream products. Electrochemical hydrogenation (ECH) method provides a green and sustainable way for this reaction. Yet, it still suffers from harsh pH conditions and low selectivity for highly reduced products, such as 2-methylfuran. In this study, high faradaic efficiencies of over 90% for furfuryl alcohol and 60% for 2-methylfuran were obtained in a near-neutral environment (pH = 5) at ?0.75 V and ?0.90 Vvs. the reversible hydrogen electrode, respectively. The key to this success is the integration of single atom copper active sites and the oxophilic phosphorus dopants in a single catalyst. Single atom Cu sites are found to be the active centers for this reaction and decreasing the size of Cu sites to a single atom enhances the efficiencies of the ECH reactions by suppressing the competing hydrogen evolution reaction. Phosphorus doping facilitates furfural hydrogenation to 2-methylfuranviaa sequential two-step reduction process. This study opens up possibilities for the selective electrochemical hydrogenation of furfural to 2-methylfuran under mild conditions.
- Chaffee, Alan L.,Chen, Yu,Gu, Qinfen,Guo, Si-Xuan,Johannessen, Bernt,Luan, Peng,Mollah, Mamun,Turner, David R.,Yuan, Ziliang,Zhang, Jie,Zhang, Xiaolong,Zhou, Peng
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- Selective Production of 2-Methylfuran by Gas-Phase Hydrogenation of Furfural on Copper Incorporated by Complexation in Mesoporous Silica Catalysts
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Copper species have been incorporated in mesoporous silica (MS) through complexation with the amine groups of dodecylamine, which was used as a structure-directing agent in the synthesis. A series of Cu/SiO2 catalysts (xCu-MS) with copper loadings (x) from 2.5 to 20 wt % was synthesized and evaluated in the gas-phase hydrogenation of furfural (FUR). The most suitable catalytic performance in terms of 2-methylfuran yield was obtained with an intermediate copper content (10 wt %). This 10Cu-MS catalyst exhibits a 2-methylfuran yield higher than 95 mol % after 5 h time-on-stream (TOS) at a reaction temperature of 210 °C with a H2/FUR molar ratio of 11.5 and a weight hourly space velocity (WHSV) of 1.5 h?1. After 14 h TOS, this catalyst still showed a yield of 80 mol %. In all cases, carbonaceous deposits on the external surface were the cause of the catalyst deactivation, although sintering of the copper particles was observed for higher copper loadings. This intermediate copper loading (10 wt %) offered a suitable balance between resistance to sintering and tendency to form carbonaceous deposits.
- Jiménez-Gómez, Carmen Pilar,Cecilia, Juan A.,Moreno-Tost, Ramón,Maireles-Torres, Pedro
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- One-Pot Deoxygenation of Fructose to Furfuryl Alcohol by Sequential Dehydration and Decarbonylation
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Fructose was deoxygenated to furfuryl alcohol (FFA) by tandem dehydration and decarbonylation in one pot over the AlCl3·6 H2O/Pd(OAc)2 catalyst combination to give a high FFA yield of 40.6 %. AlCl3·6 H2O behaves as an effective Lewis acid to catalyze the dehydration of fructose to 5-hydroxymethylfurfural (HMF), and subsequently, Pd(OAc)2 catalyzes the removal of a CO moiety from HMF to produce FFA selectively. The hydroxyl group on the HMF intermediate was stabilized by poly(1-vinyl-2-pyrrolidinone) through an intermolecular hydrogen bond, which accelerated the dehydration of fructose and inhibited the hydrogenation of HMF by formic acid. The decarbonylation of HMF was promoted and the unwanted decomposition of fructose was inhibited through the use of 4 ? molecular sieves. This research highlights a "one-pot" catalytic system to transform renewable carbohydrates into fine chemicals by tandem dehydration and decarbonylation reactions without the separation or purification of HMF.
- Dai, Jinhang,Fu, Xing,Zhu, Liangfang,Tang, Jinqiang,Guo, Xiawei,Hu, Changwei
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- Solvent Tunes the Selectivity of Hydrogenation Reaction over α-MoC Catalyst
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Selective activation of chemical bonds in multifunctional oxygenates on solid catalysts is a crucial challenge for sustainable biomass upgrading. Molybdenum carbides and nitrides preferentially activate C=O and C-OH bonds over C=C and C-C bonds in liquid-phase hydrogenation of bioderived furfural, leading to highly selective formations of furfuryl alcohol (FA) and its subsequent hydrogenolysis product (2-methyl furan (2-MF)). We demonstrate that pure-phase α-MoC is more active than β-Mo2C and γ-Mo2N for catalyzing furfural hydrogenation, and the hydrogenation selectivity on these catalysts can be conveniently manipulated by alcohol solvents without significant changes in reaction rates (e.g., > 90% yields of FA in methanol solvent and of 2-MF in 2-butanol solvent at 423 K). Combined experimental and theoretical assessments of these solvent effects unveil that it is the hydrogen donating ability of the solvents that governs the hydrogenation rate of the reactants, while strong dissociative adsorption of the alcohol solvent on Mo-based catalysts results in surface decoration which controls the reaction selectivity via enforcing steric hindrance on the formation of relevant transient states. Such solvent-induced surface modification of Mo-based catalysts provides a compelling strategy for highly selective hydrodeoxygenation processes of biomass feedstocks.
- Deng, Yuchen,Gao, Rui,Lin, Lili,Liu, Tong,Wen, Xiao-Dong,Wang, Shuai,Ma, Ding
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- Selective conversion of furfural into value-added chemical commodity in successive fixed-bed reactors
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Successive hydrogenation of furfural in two fixed-bed reactors connected in tandem with Cu/SiO2 and Ni/SiO2 as the catalysts was achieved under atmospheric pressure. Various targeting products including furfuryl alcohol (yield: 98.8%), 2-methylfuran (yield: 95.1%), 2-methyltetrahydrofuran (yield: 96.2%) and tetrahydrofurfuryl alcohol (yield: 78.2%) could be obtained by variation of the reactor configurations.
- Liu, Qianhe,Liu, Qing,Hu, Xun
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- Low-temperature catalytic hydrogenation of bio-based furfural and relevant aldehydes using cesium carbonate and hydrosiloxane
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Selective hydrogenation of unsaturated compounds is mainly carried out by using high-pressure hydrogen in the presence of a precious or transition metal catalyst. Here, we describe a benign approach to efficiently catalyze the hydrogenation of furfural (FUR) to furfuryl alcohol (FFA) over commercially available cesium carbonate using nontoxic and cheap polymethylhydrosiloxane (PMHS) as hydrogen source. Good to excellent FFA yields (≥90%) could be obtained at 25-80 °C by appropriate control of the catalyst dosage, reaction time, and the hydride amount. FUR-to-FFA hydrogenation was clarified to follow a pseudo-first order kinetics with low apparent activation energy of 20.6 kJ mol-1. Mechanistic insights manifested that PMHS was redistributed to H3SiMe, which acted as the active silane for the hydrogenation reactions. Importantly, this catalytic system was able to selectively reduce a wide range of aromatic aldehydes to the corresponding alcohols in good yields of 81-99% at 25-80 °C in 2-6 h.
- Long, Jingxuan,Zhao, Wenfeng,Xu, Yufei,Wu, Weibo,Fang, Chengjiang,Li, Hu,Yang, Song
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- Novel preparation method of bimetallic Ni-In alloy catalysts supported on amorphous alumina for the highly selective hydrogenation of furfural
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A novel preparation method for bimetallic nickel-indium alloy catalysts supported on amorphous alumina (Ni-In(x)/AA; x = Ni/In molar ratio) catalysts has been developed and evaluated for the highly selective hydrogenation of biomass-derived furfural. Ni-In(x)/AA catalysts were obtained via the hydrothermal treatment of Raney nickel supported on aluminium hydroxide (R-Ni/AlOH) and an InCl2·H2O solution in an ethanol/H2O mixture at 423 K for 2 h, followed by reduction with H2 at 573–873 K for 1.5 h. The formation of Ni-In alloy phases such as Ni3In2, Ni3In, Ni2In, and NiIn in Ni-In(2.0)/AA was clearly observed after reduction with H2 at 873 K for 1.5 h. Ni-In(2.0)/AA contained a Ni2In alloy as the major phase, which exhibited the best catalytic performance for the selective hydrogenation of furfural into furfuryl alcohol and was stable for at least five consecutive reaction runs.
- Rodiansono,Astuti, Maria Dewi,Mujiyanti, Dwi Rasy,Santoso, Uripto Trisno,Shimazu, Shogo
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- Manganese-Catalyzed Hydrogenation of Sclareolide to Ambradiol
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The hydrogenation of (+)-Sclareolide to (?)-ambradiol catalyzed by a manganese pincer complex is reported. The hydrogenation reaction is performed with an air- and moisture-stable manganese catalyst and proceeds under relatively mild reaction conditions at low manganese and base loadings. A range of other esters could be successfully hydrogenated leading to the corresponding alcohols in good to quantitative yields using this easy-to-make catalyst. A scale-up experiment was performed leading to 99.3 % of the isolated yield of (?)-Ambradiol.
- Zubar, Viktoriia,Lichtenberger, Niels,Schelwies, Mathias,Oeser, Thomas,Hashmi, A. Stephen K.,Schaub, Thomas
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- Highly effective and chemoselective hydrodeoxygenation of aromatic alcohols
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Effective hydrodeoxygenation (HDO) of aromatic alcohols is very attractive in both conventional organic synthesis and upgrading of biomass-derived molecules, but the selectivity of this reaction is usually low because of the competitive hydrogenation of the unsaturated aromatic ring and the hydroxyl group. The high activity of noble metal-based catalysts often leads to undesired side reactions (e.g., saturation of the aromatic ring) and excessive hydrogen consumption. Non-noble metal-based catalysts suffer from unsatisfied activity and selectivity and often require harsh reaction conditions. Herein, for the first time, we report chemoselective HDO of various aromatic alcohols with excellent selectivity, using porous carbon-nitrogen hybrid material-supported Co catalysts. The C-OH bonds were selectively cleaved while leaving the aromatic moiety intact, and in most cases the yields of targeted compounds reached above 99% and the catalyst could be readily recycled. Nitrogen doping on the carbon skeleton of the catalyst support (C-N matrix) significantly improved the yield of the targeted product. The presence of large pores and a high surface area also improved the catalyst efficiency. This work opens the way for efficient and selective HDO reactions of aromatic alcohols using non-noble metal catalysts.
- Han, Buxing,He, Mingyuan,Mei, Xuelei,Wu, Haihong,Wu, Wei,Xu, Caiyun,Zhai, Jianxin,Zhang, Kaili,Zhang, Zhanrong,Zheng, Bingxiao
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p. 1629 - 1635
(2022/02/21)
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- Platinum thiolate complexes supported by PBP and POCOP pincer ligands as efficient catalysts for the hydrosilylation of carbonyl compounds
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Diphosphino-boryl-based PBP pincer platinum thiolate complexes, [Pt(SR){B(NCH2PtBu2)2-1,2-C6H4}] (R = H, 1a; Ph, 1b), and benzene-based bisphosphinite POCOP pincer platinum thiolate complexes, [Pt(SR)(tBu2PO)2-1,3-C6H3] (R = H, 2a; Ph, 2b), were prepared
- Chang, Jiarui,Chen, Xuenian,Xue, Man-Man,Zhang, Jie
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supporting information
p. 2304 - 2312
(2022/02/21)
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- High-Temperature Synthesis of Carbon-Supported Bimetallic Nanocluster Catalysts by Enlarging the Interparticle Distance
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Supported bimetallic nanoparticle catalysts with small size have attracted wide research attention in catalysis but are difficult to synthesize because high-temperature annealing required for alloying inevitably accelerates metal sintering and leads to larger particles. Here, we report a simple and scalable critical interparticle distance method for the synthesis of a family of bimetallic nanocluster catalysts with an average particle size of only 1.5 nm by using large-surface-area carbon black supports at high temperatures, which consist of 12 diverse combinations of 3 noble metals (Pt, Ru, and Rh) and 4 other metals (Cr, Fe, Zr, and Sn). In this strategy, high-temperature treatments ensure the formation of alloyed bimetallic nanoparticles and enlargement of the interparticle distance on high-surface-area supports significantly suppresses metal sintering. The prepared ultrafine Pt2Sn and RuSn nanocluster catalysts exhibited enhanced performance in catalyzing the synthesis of aromatic secondary amines and the selective hydrogenation of furfural, respectively.
- Zuo, Lu-Jie,Xu, Shi-Long,Wang, Ao,Yin, Peng,Zhao, Shuai,Liang, Hai-Wei
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supporting information
p. 2719 - 2723
(2022/02/16)
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- Solvent effect on the rate and direction of furfural transformations during hydrogenation over the Pd/C catalyst
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The rate and directions of transformations during the liquid-phase hydrogenation of furfural with molecular hydrogen in the presence of the 5%Pd/C catalyst (at 423 K, 3 MPa) depend substantially on the chemical nature of the solvent. The main products of
- Belskaya, O. B.,Likholobov, V. A.,Mironenko, R. M.
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- PNO ligand containing planar chiral ferrocene and application thereof
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The invention discloses a PNO ligand containing planar chiral ferrocene and application thereof. The PNO ligand containing planar chiral ferrocene is a planar chiral ferrocene-containing and phenol-containing PNO ligand as shown in a general formula (I) or (II) which is described in the specification, or a planar chiral ferrocene-containing and aryl-phosphoric-acid-containingPNO ligand containing as shown in a general formula (III) or (IV) which is described in the specification, or a planar chiral ferrocene-containing and carbon-chiral-phenol-containingPNO ligand as shown in a general formula (V) or (VI) which is described in the specification. The invention provides tridentate PNO ligands and processes for their complexation with transition metal salts or transition metal complexes; the introduction of salicylaldehyde and derivatives thereof, which are simple and easy to obtain, enables the ligands to have a bifunctionalization effect, and -OH in a formed catalyst has stronger acidity and is beneficial to combination with N/O in polar double bonds. Therefore, due to the bifunctionalization effect of the catalyst, the interaction between the catalyst and a substrate can be greatly improved, so a reaction can obtain higher catalytic activity and stereoselectivity.
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Paragraph 0114-0118
(2021/06/21)
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- Me3SI-promoted chemoselective deacetylation: a general and mild protocol
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A Me3SI-mediated simple and efficient protocol for the chemoselective deprotection of acetyl groups has been developedviaemploying KMnO4as an additive. This chemoselective deacetylation is amenable to a wide range of substrates, tolerating diverse and sensitive functional groups in carbohydrates, amino acids, natural products, heterocycles, and general scaffolds. The protocol is attractive because it uses an environmentally benign reagent system to perform quantitative and clean transformations under ambient conditions.
- Gurawa, Aakanksha,Kashyap, Sudhir,Kumar, Manoj
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p. 19310 - 19315
(2021/06/03)
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- A Bifunctional Copper Catalyst Enables Ester Reduction with H2: Expanding the Reactivity Space of Nucleophilic Copper Hydrides
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Employing a bifunctional catalyst based on a copper(I)/NHC complex and a guanidine organocatalyst, catalytic ester reductions to alcohols with H2 as terminal reducing agent are facilitated. The approach taken here enables the simultaneous activation of esters through hydrogen bonding and formation of nucleophilic copper(I) hydrides from H2, resulting in a catalytic hydride transfer to esters. The reduction step is further facilitated by a proton shuttle mediated by the guanidinium subunit. This bifunctional approach to ester reductions for the first time shifts the reactivity of generally considered "soft"copper(I) hydrides to previously unreactive "hard"ester electrophiles and paves the way for a replacement of stoichiometric reducing agents by a catalyst and H2.
- Kaicharla, Trinadh,Ngoc, Trung Tran,Teichert, Johannes F.,Tzaras, Dimitrios-Ioannis,Zimmermann, Birte M.
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supporting information
p. 16865 - 16873
(2021/10/20)
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- A mild and selective Cu(II) salts-catalyzed reduction of nitro, azo, azoxy, N-aryl hydroxylamine, nitroso, acid halide, ester, and azide compounds using hydrogen surrogacy of sodium borohydride
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The first mild, in situ, single-pot, high-yielding well-screened copper (II) salt-based catalyst system utilizing the hydrogen surrogacy of sodium borohydride for selective hydrogenation of a broad range of nitro substrates into the corresponding amine under habitancy of water or methanol like green solvents have been described. Moreover, this catalytic system can also activate various functional groups for hydride reduction within prompted time, with low catalyst-loading, without any requirement of high pressure or molecular hydrogen supply. Notably, this system explores a great potential to substitute expensive traditional hydrogenation methodologies and thus offers a greener and simple hydrogenative strategy in the field of organic synthesis.
- Kalola, Anirudhdha G.,Prasad, Pratibha,Mokariya, Jaydeep A.,Patel, Manish P.
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supporting information
p. 3565 - 3589
(2021/10/12)
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- Valorization of furfural using ruthenium (II) complexes containing phosphorus-nitrogen ligands under homogeneous transfer hydrogen condition
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In this paper, we report the catalytic activity of a series of ruthenium (II) complexes containing phosphorus-nitrogen bidentated (P-N) ligands in the hydrogenation of furfural via hydrogen transfer reaction using two hydrogen donor sources: 2-propanol in basic medium and formic acid under mild conditions. The results showed that all the ruthenium complexes studied are catalytically active in the hydrogenation of furfural by hydrogen transfer reaction; they showed 100% conversion with both hydrogen sources. However, selectivities towards the formation of furfuryl alcohol were better when formic acid was used. It was also found that the reaction studied in a basic medium competes with the Cannizzaro reaction, obtaining furfuryl alcohol and furoic acid in a 70/30 ratio; on the other hand, using formic acid as the hydrogen source yields furfuryl alcohol with 100% selectivity. Although formic acid can be used as a hydrogen source successfully. The optimal substrate/acid ratio was found to be 1:1, as a higher concentration of formic acid can cause catalyst decomposition. The yielded products, furfuryl alcohol and furoic acid, obtained from renewable sources, have multiple applications in the organic chemical industry, replacing or complementing similar fossil-derived products.
- Aguirre, Pedro,Aranda, Braulio,López, Vicente,Moya, Sergio A.,Parra-Melipán, Sebastián,Valdebenito, Gonzalo
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- Method for preparing 2,5 - furandicarboxylic acid from furfural
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The method comprises 2,5 - steps of selective hydrogenation of furfural into furfuryl alcohol, first steps of furfuryl alcohol hydroxymethylation to second furan dimethanol, 2,5 - step of third furan dimethanol oxidation and 2,5 - 2,5 - furandicarboxylic acid. The biomass platform derived compound furfural has the advantages that the biomass platform derived compound furfural is a raw material and is wide in source. The process for hydroxymethylation of furfuryl alcohol is simple, and accords with the idea of sustainable development of green.
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Paragraph 0008; 0023-0026; 0033-0037; 0043-0047
(2021/10/30)
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- Efficient hydrogenation of furfural to fufuryl alcohol over hierarchical MOF immobilized metal catalysts
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Transformation of furfural, a typical biomass-derived robust platform molecule, into value-added chemical furfuryl alcohol has drawn intense attention. The conventional supported catalysts which are restricted in the microporous regime suffered from high mass diffusion resistances and limited catalytic activity. We herein demonstrate the synthesis of a series of transition-metal catalysts by using hierarchical porous H-UiO-66 as the support for highly efficient conversion of furfural to furfuryl alcohol. The unique nanoarchitecture endows the catalyst with low mass diffusion resistance, high accessibility of metal active sites and high durability in the liquid phase reaction. A nearly quantitate yield of furfuryl alcohol was achieved over the Pd/H-UiO-66 catalyst at 60 °C, 0.5 MPa H2 in the aqueous medium within 3 h.
- Fang, Ruiqi,Chen, Liyu,Shen, Zirong,Li, Yingwei
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p. 217 - 223
(2020/03/24)
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- A Water/Toluene Biphasic Medium Improves Yields and Deuterium Incorporation into Alcohols in the Transfer Hydrogenation of Aldehydes
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Deuterium labeling is an interesting process that leads to compounds of use in different fields. We describe the transfer hydrogenation of aldehydes and the selective C1 deuteration of the obtained alcohols in D2O, as the only deuterium source. Different aromatic, alkylic and α,β-unsaturated aldehydes were reduced in the presence of [RuCl(p-cymene)(dmbpy)]BF4, (dmbpy=4,4′-dimethyl-2,2′-bipyridine) as the pre-catalyst and HCO2Na/HCO2H as the hydrogen source. Moreover, furfural and glucose, were selectively reduced to the valuable alcohols, furfuryl alcohol and sorbitol. The processes were carried out in neat water or in a biphasic water/toluene system. The biphasic system allowed easy recycling, higher yields, and higher selective D incorporation (using D2O/toluene). The deuteration took place due to an efficient effective M–H/D+ exchange from D2O that allows the inversion of polarity of D+ (umpolung). DFT calculations that explain the catalytic behavior in water are also included.
- Ruiz-Casta?eda, Margarita,Santos, Lucía,Manzano, Blanca R.,Espino, Gustavo,Jalón, Félix A.
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p. 1358 - 1372
(2021/03/16)
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- Efficient and chemoselective hydrogenation of aldehydes catalyzed by well-defined PN3-pincer manganese(ii) catalyst precursors: An application in furfural conversion
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Well-defined and air-stable PN3-pincer manganese(ii) complexes were synthesized and used for the hydrogenation of aldehydes into alcohols under mild conditions using MeOH as a solvent. This protocol is applicable for a wide range of aldehydes containing various functional groups. Importantly, α,β-unsaturated aldehydes, including ynals, are hydrogenated with the CC double bond/CC triple bond intact. Our methodology was demonstrated for the conversion of biomass derived feedstocks such as furfural and 5-formylfurfural to furfuryl alcohol and 5-(hydroxymethyl)furfuryl alcohol respectively.
- Gholap, Sandeep Suryabhan,Dakhil, Abdullah Al,Chakraborty, Priyanka,Li, Huaifeng,Dutta, Indranil,Das, Pradip K.,Huang, Kuo-Wei
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supporting information
p. 11815 - 11818
(2021/11/30)
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- Iron-catalyzed chemoselective hydride transfer reactions
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A Diaminocyclopentadienone iron tricarbonyl complex has been applied in chemoselective hydrogen transfer reductions. This bifunctional iron complex demonstrated a broad applicability in mild conditions in various reactions, such as reduction of aldehydes over ketones, reductive alkylation of various functionalized amines with functionalized aldehydes and reduction of α,β-unsaturated ketones into the corresponding saturated ketones. A broad range of functionalized substrates has been isolated in excellent yields with this practical procedure.
- Coufourier, Sébastien,Ndiaye, Daouda,Gaillard, Quentin Gaignard,Bettoni, Léo,Joly, Nicolas,Mbaye, Mbaye Diagne,Poater, Albert,Gaillard, Sylvain,Renaud, Jean-Luc
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supporting information
(2021/06/07)
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- Heterogeneous Hydrogenation of Quinoline Derivatives Effected by a Granular Cobalt Catalyst
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We communicate a convenient method for the pressure hydrogenation of quinolines in aqueous solution by using a particulate cobalt-based catalyst that is prepared in situ from simple Co(OAc)2 4H2O through reduction with abundant zinc powder. This catalytic protocol permits a brisk and atom-efficient access to a variety of 1,2,3,4-tetrahydroquinolines thereby relying solely on easy-to-handle reagents that are all readily obtained from commercial sources. Both the reaction setup assembly and the autoclave charging procedure are conducted on the bench outside an inert-gas-operated containment system, thus rendering the overall synthesis time-saving and operationally very simple.
- Timelthaler, Daniel,Topf, Christoph
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p. 629 - 642
(2021/11/22)
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- Transfer hydrogenation of furfural to furfuryl alcohol over modified Zr-based catalysts using primary alcohols as H-donors
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Catalytic transfer hydrogenation is gaining increasing attention as a promising alternative to conventional hydrogenation with H2. In present work, a series of modified Zr-based catalysts were synthesized and tested for furfural catalytic transfer hydrogenation into furfuryl alcohol (FA). The results indicated that more than 13 % of furfural conversion and furfuryl alcohol yield could be achieved with modified zirconium hydroxide (mZrH) at 140 °C when compared with zirconium hydroxide (ZrH) using ethanol as H-donor and solvent in continuous flow regime, and the activity could be further enhanced by increasing the reaction temperature or Ru loading on the catalyst. The best result of 92 % furfural conversion with ~99 % FA selectivity was obtained at 150 °C with 6% Ru/mZrH as catalyst, and the productivity of FA is 5.5 mmol g?1 h?1 which is 2 times higher than that reported with ZrH in batch. Moreover, long-term stability study of the catalysts indicated that 6% Ru/mZrH not only performs a better activity, but also a better stability than 6% Ru/ZrH. Characterizations of the catalysts by BET, XRD, EA, IR, SEM-EDS, XPS and CO2 adsorption indicated that zirconium hydroxide (ZrH) was successfully modified with hydroxylamine, leading to significantly change of its morphology and basic sites. And the deactivation of the catalysts was due to both the leaching of Ru and the deposition of side-products on its surface.
- Wang, Yantao,Zhao, Deyang,Liang, Rui,Triantafyllidis, Konstantinos S.,Yang, Weiran,Len, Christophe
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- Direct use of the solid waste from oxytetracycline fermentation broth to construct Hf-containing catalysts for Meerwein-Ponndorf-Verley reactions
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The oxytetracycline fermentation broth residue (OFR) is an abundant solid waste in the fermentation industry, which is hazardous but tricky to treat. The resource utilization of the waste OFR is still challenging. In this study, a novel route of using OFR was proposed that OFR was used as the organic ligands to construct a new hafnium based catalyst (Hf-OFR) for Meerwein-Ponndorf-Verley (MPV) reactions of biomass-derived platforms. The acidic groups in OFR were used to coordinate with Hf4+, and the carbon skeleton structures in OFR were used to form the spatial network structures of the Hf-OFR catalyst. The results showed that the synthesized Hf-OFR catalyst could catalyze the MPV reduction of various carbonyl compounds under relatively mild reaction conditions, with high conversions and yields. Besides, the Hf-OFR catalyst could be recycled at least 5 times with excellent stability in activity and structures. The prepared Hf-OFR catalyst possesses the advantages of high efficiency, a simple preparation process, and low cost in ligands. The proposed strategy of constructing catalysts using OFR may provide new routes for both valuable utilization of the OFR solid waste in the fermentation industry and the construction of efficient catalysts for biomass conversion.
- Chen, Yuxin,Yao, Xuefeng,Wang, Xiaolu,Zhang, Xuefeng,Zhou, Huacong,He, Runxia,Liu, Quansheng
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p. 13970 - 13979
(2021/04/22)
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- A Resol-Assisted Cationic Coordinative Co-assembly Approach to Mesoporous ABO3 Perovskite Oxides with Rich Oxygen Vacancy for Enhanced Hydrogenation of Furfural to Furfuryl Alcohol
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It is a challenge to obtain ABO3 perovskite oxides with favorable crystal phase and well-defined porous structure via existing approaches. Here, we design an effective and versatile strategy to construct mesoporous ABO3 perovskite oxides with functionalized nanocrystal frameworks and abundant oxygen vacancy sites via a resol-assisted cationic coordinative co-assembly approach. The as-prepared oxygen vacancy-rich mesoporous LaMnO3 as heterogeneous catalyst exhibits remarkable catalytic activity and stability for hydrogenation of furfural to furfuryl alcohol, including over 99 % conversion and 96 % selectivity. Combined with density functional theory calculation, the catalytic mechanism is elucidated, revealing that porous LaMnO3 nanocrystal framework is conducive to expose oxygen deficiency sites, which can facilitate the interaction between catalyst surface and catalytic substrate, leading to lower barrier in hydrogenation process.
- Zheng, Yuenan,Zhang, Rui,Zhang, Ling,Gu, Qinfen,Qiao, Zhen-An
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supporting information
p. 4774 - 4781
(2021/01/15)
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- KB3H8: An environment-friendly reagent for the selective reduction of aldehydes and ketones to alcohols
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Selective reduction of aldehydes and ketones to their corresponding alcohols with KB3H8, an air- and moisture-stable, nontoxic, and easy-to-handle reagent, in water and THF has been explored under an air atmosphere for the first time. Control experiments illustrated the good selectivity of KB3H8 over NaBH4 for the reduction of 4-acetylbenzaldehyde and aromatic keto esters. This journal is
- Li, Xinying,Mi, Tongge,Guo, Wenjing,Ruan, Zhongrui,Guo, Yu,Ma, Yan-Na,Chen, Xuenian
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supporting information
p. 12776 - 12779
(2021/12/10)
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- Thermally Sensitive Protecting Groups for Cysteine, and Manufacture and Use Thereof
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In a preferred embodiment, there is provided a protecting group for protecting the thiol side chain of a cysteine residue, the protecting group comprising a Diels-Alder cycloadduct of a furan and a maleimide, and optionally, a linker interposed between the thiol side chain and the Diels-Alder cycloadduct.
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Paragraph 0153
(2021/02/12)
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- Comparative account of catalytic activity of Ru- and Ni-based nanocomposites towards reductive amination of biomass derived molecules
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This work includes an effective comparison of metallic ruthenium and nickel nanoparticles loaded on montmorillonite clay (MMT) for reductive amination reaction of biomass-derived molecules. It comprises an eco-friendly reaction using water as a solvent, utilizing molecular hydrogen and liquor ammonia (25% aq. solution) for the synthesis of primary amines from bio-derived aldehydes within 3–10 h of reaction time. Various parameters such as temperature, hydrogen pressure, substrate/ammonia concentration ratio, and reaction time were optimized while comparing the selectivity of primary amines for both catalysts. The applicability scope of these catalysts was explored with a library of aryl and heterocyclic aldehydes. The reductive amination of crude furfural extracted from biomass feedstock (rice husk) and pure xylose sugar was tested, showing yields in the range of 11–36%, to show the wider industrial scope of both nanocomposites. Gram scale conversion was also carried out to showcase the bulk scalability of the Ru/MMT catalyst.
- Bhanage, Bhalchandra M.,Gokhale, Tejas A.,Raut, Amol B.
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- Self-regulated catalysis for the selective synthesis of primary amines from carbonyl compounds
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Most current processes for the general synthesis of primary amines by reductive amination are performed with enormously excessive amounts of hazardous ammonia. It remains unclear how catalysts should be designed to regulate amination reaction dynamics at a low ammonia-to-substrate ratio for the quantitative synthesis of primary amines from the corresponding carbonyl compounds. Herein we show a facile control of the reaction selectivity in the layered boron nitride supported ruthenium catalyzed reductive amination reaction. Specifically, locating ruthenium to the edge surface of layered boron nitride leads to an increased hydrogenation activity owing to the enhanced interfacial electronic effects between ruthenium and the edge surface of boron nitride. This enables self-accelerated reductive amination reactions which quantitatively synthesize structurally diverse primary amines by reductive amination of carbonyl compounds with twofold ammonia. This journal is
- Fan, Xiaomeng,Gao, Jin,Gao, Mingxia,Jia, Xiuquan,Ma, Jiping,Xu, Jie
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supporting information
p. 7115 - 7121
(2021/09/28)
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- Selective tandem hydrogenation and rearrangement of furfural to cyclopentanone over CuNi bimetallic catalyst in water
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Tandem catalysis for the hydrogenation rearrangement of furfural (FA) provides an attractive solution for manufacturing cyclopentanone (CPO) from renewable biomass resources. The CuNi/Al-MCM-41 catalyst was synthesized and afforded excellent catalytic performance with 99.0% conversion and 97.7% selectivity to CPO in a near-neutral solution under 2.0 MPa H2 at 160 °C for 5 h, much higher than those on other molecular sieve supports including MCM-41, SBA-15, HY, and ZSM-5. A small amount of Al highly dispersed in MCM-41 plays an anchoring role and ensures the formation of highly dispersed CuNi bimetallic nanoparticles (NPs). The remarkably improved catalytic performance may be attributed to the bimetallic synergistic and charge transfer effects. In addition, the initial FA concentration and the aqueous system pH required precise control to minimize polymerization and achieve high selectivity of CPO. Fourier transform infrared spectroscopy and mass spectra results indicated that polymerization was sensitive to pH values. Under acidic conditions, FA and intermediate furfuryl alcohol polymerize, while the intermediate 4-hydroxy-2-cyclopentenone mainly polymerizes under alkaline conditions, blocking the cascade of multiple reactions. Therefore, near-neutral conditions are most suitable for minimizing the impact of polymerization. This study provides a useful solution for the current universal problems of polymerization side reactions and low carbon balance for biomass conversion.
- Gao, Jin,Liu, Xin,Luo, Yang,Ma, Hong,Sun, Yuxia,Xu, Jie,Zhang, Meiyun,Zhang, Shujing
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p. 2216 - 2224
(2021/09/20)
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- One-pot self-assembly synthesis of Ni-doped ordered mesoporous carbon for quantitative hydrogenation of furfural to furfuryl alcohol
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Ni-Doped ordered mesoporous carbon (Ni@OMC) was prepared by a one-pot solvent evaporation-induced self-assembly (EISA) process with sustainable biomass-derived gallic acid as the carbon precursor, F127 as the soft template and Ni2+as the cross-linker and catalytically active ingredient. Ni particles withca.7.8 nm diameter were uniformly dispersed in the carbon skeleton of the synthesized OMC due to the confinement effects of Ni particles in the carbon skeleton of OMC by coordination between gallic acid molecules and metal Ni2+ions in the EISA process. The as-synthesized Ni@OMC sample showed excellent catalytic performance for the hydrogenation of biomass-derived furfural into furfuryl alcohol (FFA), and a FFA yield as high as 98% could be achieved at 180 °C in 4 h reaction time in 1-propanol solvent in the presence of 3 MPa H2pressure. The prepared Ni@OMC exhibited good stability and recyclability. This work provides a green and simple one-pot strategy for the synthesis of metal-doped OMCs without using harmful phenolic and formaldehyde compounds, which should have many applications in fields such as catalysis, drug delivery and energy storage.
- Tang, Yiwei,Qiu, Mo,Yang, Jirui,Shen, Feng,Wang, Xiaoqi,Qi, Xinhua
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p. 1861 - 1870
(2021/03/09)
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- Furfural hydrodeoxygenation (HDO) over silica-supported metal phosphides – The influence of metal–phosphorus stoichiometry on catalytic properties
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The gas-phase hydrodeoxygenation (HDO) of furfural, a model compound for bio-based conversion, was investigated over transition metal phosphide catalysts. The HDO activity decreases in the order Ni2P ≈ MoP > Co2P ≈ WP ? Cu3P > Fe2P. Nickel phosphide phases (e.g., Ni2P, Ni12P5, Ni3P) are the most promising catalysts in the furfural HDO. Their selectivity to the gasoline additives 2-methylfuran and tetrahydro-2-methylfuran can be adjusted by varying the P/Ni ratio. The effect of P on catalyst properties as well as on the reaction mechanism of furfural HDO were investigated in depth for the first time. An increase of the P stoichiometry weakens the furan-ring/catalyst interaction, which contributes to a lower ring-opening and ring-hydrogenation activity. On the other hand, an increasing P content does lead to a stronger carbonyl/catalyst interaction, i.e., to a stronger η2(C, O) adsorption configuration, which weakens the C1[sbnd]O1 bond (Scheme 1) in the carbonyl group and enhances the carbonyl conversion. Phosphorus species can also act as Br?nsted acid sites promoting C1[sbnd]O1 (Scheme 1) hydrogenolysis of furfuryl alcohol, hence contributing to higher production of 2-methylfuran.
- Lan, Xuefang,Pestman, Robert,Hensen, Emiel J.M.,Weber, Thomas
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p. 181 - 193
(2021/02/27)
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- Aqueous phase hydrogenation of furfural to tetrahydrofurfuryl alcohol over Pd/UiO-66
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A Pd/UiO-66 catalyst was synthesized with well-dispersed Pd nanoparticles. The obtained catalyst was tested in the hydrogenation of furfural to tetrahydrofurfuryl alcohol in various solvents, Water was found to be the most suitable solvent. Pd/UiO-66 exhibited much higher activity than Pd/SiO2 and Pd/γ-Al2O3, completely converting furfural to tetrahydrofurfuryl alcohol with 100% selectivity under mild conditions. The hydrogenation of C[dbnd]O moiety in tetrahydrofurfural was rate-determining step. Static adsorption measurement indicated that the adsorption of furfural on UiO-66 was significantly stronger than that on SiO2 or γ-Al2O3, suggesting that the adsorption play an important role in the gas-liquid-solid furfural hydrogenation reaction.
- Kogan, Victor M.,Liu, Ying-Ya,Sun, Zhichao,Wang, Anjie,Wang, Chunhua,Wang, Yao,Yu, Zhiquan
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- Selective hydrogenation of furfural to furfuryl alcohol over Pd/TiH2 catalyst
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In this work, the selective hydrogenation of furfural to furfuryl alcohol has been studied over Pd/TiH2 catalysts. The catalytic performances of several catalysts with different Pd loading (0.2–3% in weight) were discussed, among which a higher selectivity to furfuryl alcohol was obtained over 0.5Pd/TiH2 and it gave rise to a 73% furfural alcohol selectivity at complete conversion at 60 °C. The physicochemical properties of catalysts were well characterized by TEM, XRD, XPS, Raman, TPR and TPD, as well as in-situ DRIFT for the adsorption of the reactant. The size and the electronic state of Pd particles, and the surface defects of catalysts presented significant influence on the catalytic performance. The furfural is preferentially adsorbed with its C=O bond on the boundary of Pd particle and TiH2 support, leading to the high selectivity to furfuryl alcohol.
- Wang, Zhuangqing,Wang, Xinchao,Zhang, Chao,Arai, Masahiko,Zhou, Leilei,Zhao, Fengyu
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- Interfacial effect of Pd supported on mesoporous oxide for catalytic furfural hydrogenation
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Highly dispersed Pd is loaded onto different types of mesoporous oxide supports to investigate the synergetic metal-support effect in catalytic furfural (FAL) hydrogenation. Ordered mesoporous Co3O4, MnO2, NiO, CeO2, and Fe2O3 are prepared by the nanocasting and the supported Pd on mesoporous oxide catalysts are obtained by the chemical reduction method. It is revealed that mesoporous oxides play an important role on Pd dispersion as well as the redox behavior of Pd, which determines the final FAL conversion. Among the catalysts used, Pd/Co3O4 shows the highest conversion in FAL hydrogenation and distinct product selectivity toward 2-methylfuran (MF). While FAL is converted via two distinct pathways to produce either furfuryl alcohol (FA) via aldehyde hydrogenation or MF via hydrogenolysis, MF as a secondary product is derived from FA via the hydrogenolysis of C–O over the Pd/Co3O4 catalyst. It is revealed that FAL is hydrogenated to FA preferentially on the Pd surface; then the secondary hydrogenolysis to MF from FA is further promoted at the interface between Pd and Co3O4. We confirm that the reaction pathway over Pd/Co3O4 is totally different from other catalysts such as Pd/MnO2, which produces FA dominantly. The characteristics of the mesoporous oxides influence the Pd-oxide interfaces, which determine the activity and selectivity in FAL hydrogenation.
- Lee, Hojeong,Nguyen-Huy, Chinh,Jeong Jang, Eun,Lee, Jihyeon,Yang, Euiseob,Lee, Man Sig,Kwak, Ja Hun,An, Kwangjin
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p. 291 - 300
(2020/03/05)
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- Highly selective reduction of biomass-derived furfural by tailoring the microenvironment of Rh@BEA catalysts
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Furfural is a renewable lignocellulose-derived platform molecule, which can be transformed into biofuels and value-added chemicals (e.g., furfuryl alcohol and 2-methylfuran over metal-supported catalysts). Despite a number of approaches proposed for designing hydrogenation catalysts, highly selective furfural hydrogenation towards furfuryl alcohol (FA) or 2-methylfuran (2-MF) is still challenging. Here, we report on selective transformation of furfural either to FA or 2-MF achieved over zeolite BEA-supported Rh catalysts by optimizing Si/Al ratio and charge-balancing cations of the support. Among studied H- and Na-exchanged aluminosilicate BEA zeolite supports (Si/Al = 12.5; 25; 68; 150), Rh@Na-BEA catalysts lacking Br?nsted and strong Lewis acidity showed enhanced selectivity towards FA (75 – 94% depending on the Si/Al ratio) at 74 – 84% conversion of furfural. In turn, selective formation of 2-MF (98% selectivity at 87% conversion) was observed over Al-rich Rh@H-BEA catalyst (Si/Al=12.5) with the highest concentration of Br?nsted acid sites. Weaker adsorption of FA on Na- vs. H-form of Rh@BEA-12.5 catalyst was verified by FTIR spectroscopy and is assumed a key factor governing selective hydrogenation of furfural to FA over Rh@Na-BEA catalysts.
- ?ejka, Ji?í,Kub?, Martin,Li, Ang,Shamzhy, Mariya,Zhang, Yuyan
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- Conversion of furfural to 2-methylfuran over CuNi catalysts supported on biobased carbon foams
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In this study, carbon foams prepared from the by-products of the Finnish forest industry, such as tannic acid and pine bark extracts, were examined as supports for 5/5% Cu/Ni catalysts in the hydrotreatment of furfural to 2-methylfuran (MF). Experiments were conducted in a batch reactor at 503 K and 40 bar H2. Prior to metal impregnation, the carbon foam from tannic acid was activated with steam (S1), and the carbon foam from pine bark extracts was activated with ZnCl2 (S2) and washed with acids (HNO3 or H2SO4). For comparison, a spruce-based activated carbon (AC) catalyst and two commercial AC catalysts as references were investigated. Compressive strength of the foam S2 was 30 times greater than that of S1. The highest MF selectivity of the foam-supported catalysts was 48 % (S2, washed with HNO3) at a conversion of 91 %. According to the results, carbon foams prepared from pine bark extracts can be applied as catalyst supports.
- Varila, Toni,M?kel?, Eveliina,Kupila, Riikka,Romar, Henrik,Hu, Tao,Karinen, Reetta,Puurunen, Riikka L.,Lassi, Ulla
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- Pd-Catalysed Decarbonylation Free Approach to Carbonylative Esterification of 5-HMF to Its Aryl Esters Synthesis Using Aryl Halides and Oxalic Acid as C1 Source
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A decarbonylation free, polystyrene-supported, Pd (Pd@PS)-catalysed carbonylative esterification of the hydroxy group of 5-hydroxymethyl furfural (5-HMF) to its corresponding aryl esters has been developed. The use of Pd@PS, oxalic acid as CO source, and aryl halides was first explored for the aryl ester of 5-HMF synthesis. Here, we investigated the vital role of a polystyrene support to avoid the commonly known decarbonylation of 5-HMF. The reaction exhibits vast substrate scope with comparably good yield and catalyst recyclability.
- Singh Chauhan, Arvind,Kumar, Ajay,Kumar Sharma, Ajay,Das, Pralay
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p. 12971 - 12975
(2021/08/06)
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- Electrocatalytic hydrogenation of furfural using non-noble-metal electrocatalysts in alkaline medium
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The production of bio-oil from agricultural waste is a promising route to improve the agricultural value chain. Herein, furfural (FF), a model bio-oil compound, was subjected to electrocatalytic hydrogenation (ECH) in an alkaline medium to produce economically important furfuryl alcohol (FA) and hydrofuroin (HF). The selectivity of ECH products (FA and HF) on Cu, Pt, and Ni-foam electro-catalysts showed that their generation was dependent upon the availability of Hads, which in turn varied with the choice of electrocatalyst and applied potential. Cu-NPNi/NF was obtained through dealloying Cu from a co-electrodeposited Ni-Cu electrode on a Ni-foam substrate, followed by re-electrodeposition of Cu. A porous, high-surface-area bimetallic Ni-Cu catalyst (Cu-NPNi/NF) on Ni-foam yielded high rates of FA and HF generation from furfural, e.g. 118.7 ± 8 and 176.3 ± 3.4 μmol h-1 cm-2 at -1.45 V vs. Ag/AgCl/sat KCl after 1 h of electrolysis in an alkaline electrolyte. 100% conversion of furfural was observed after 2 h of electrolysis with the same catalyst. The high rate of FA and HF formation was ascribed to enhanced adsorbed FF because of the formation of Cu-nanoplates and bimetallic Ni-Cu. We have provided a rational, high-throughput design for preparing highly active nanoporous electrodes for producing industrially relevant chemicals (furfuryl alcohol and hydrofuroin).
- Basu, Suddhasatwa,Bhattacharyya, Kaustava,Dixit, Ram Ji,Ramani, Vijay K.
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p. 4201 - 4212
(2021/06/18)
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- Catalytic Transfer Hydrogenation of Furfural over CuNi@C Catalyst Prepared from Cu–Ni Metal-Organic Frameworks
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Abstract: Cu/Ni-based metal-organic frameworks (CuNi@BTC) were prepared with benzene-1,3,5-tricarboxylate (H3BTC) as the organic ligand via the solvothermal method, and were then calcinated under N2 atmosphere to form C-coated CuNi catalysts (CuNi@C). TEM showed that carbon material on the surface of CuNi@C was a graphene-like structure. Then transfer hydrogenation of furfural catalyzed by CuNi@C was tested with alcohols as the hydrogen donor to optimize the Cu : Ni ratio, metal : organic ligand ratio, solvothermal synthesis, and calcination conditions. It was found that strong synergistic effect between Cu and Ni in the CuNi@C significantly enhanced the furfural transfer hydrogenation activity and raised the furfural selectivity. The reaction conditions of furfural transfer hydrogenation such as catalyst dosage, hydrogen donor, reaction temperature, and reaction time were studied. The catalytic mechanism for CTH of FF over CuNi@C catalyst was discussed.
- Feng Li,Jiang, Shanshan,Wang, Yue,Huang, Jin,Li, Cuiqin
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- Ru Nanoparticles on a Sulfonated Carbon Layer Coated SBA-15 for Catalytic Hydrogenation of Furfural into 1, 4-pentanediol
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Furfural (FFR) is one of the most important biomass-derived chemicals. Its large-scale availability calls for the exploration of new transformation methods for further valorization. Herein, we demonstrate that Ru nanoparticles (Ru NPs)-supported on a sulfonated carbon layer coated SBA-15 can be employed as an efficient bi-functional catalyst for one step conversion of FFR into 1,4-pentanediol (1,4-PeDO). The optimum bi-functional catalyst can afford the full the conversion of FFR and 86% selectivity to 1,4-PeDO. The catalysts have been characterized thoroughly by using a complementary combination of powder X-ray diffraction, N2 adsorption–desorption, scanning/transmission electron microscopy, Fourier transform infrared spectroscopy, elemental analysis, and X-ray photoelectron spectroscopy. The characterization revealed that acidic groups (–SO3H) have been introduced on the surface of the carbon layer coated SBA-15 support after sulfonation with 98% H2SO4 and the surface acidity can be tuned facilely by the sulfonating time. Meantime, Ru(0) sites was highly dispersed via an impregnation and sequential reduction and directly adjacent to the surface –SO3H group. There existed an electronic interaction between Ru(0) sites and sulfonic groups, in which the electronic transfer from sulfonic sites to Ru(0) sites occurred. Br?nsted acid sites (–SO3H) have a significant influence on the FFR conversion and the selectivity to 1,4-PeDO. The ordered mesoporous structure, the appropriate density of acid sites and the electron-rich Ru(0) sites accounted for the the excellent performance of the catalyst for an efficient production of 1,4-PeDO from FFR. Graphic Abstract: [Figure not available: see fulltext.].
- Cui, Kai,Qian, Wei,Shao, Zhengjiang,Zhao, Xiuge,Gong, Honghui,Wei, Xinjia,Wang, Jiajia,Chen, Manyu,Cao, Xiaoming,Hou, Zhenshan
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p. 2513 - 2526
(2021/02/05)
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- Catalytic hydrogenation of furfural to tetrahydrofurfuryl alcohol using competitive nickel catalysts supported on mesoporous clays
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Nickel catalysts supported on mesoporous clays with different acid properties, such as montmorillonite MK-10, Al-pillared montmorillonite, mesoporous Na-saponite and mesoporous H-saponite, were prepared, characterized and tested for the hydrogenation of furfural to tetrahydrofurfuryl alcohol (THFA). Clays were also modified introducing basicity through magnesium oxide in different amounts. Catalysts with higher acidity or low amounts of metallic centres favoured deactivation and/or selectivity to the non-desired products. Interestingly, the addition of MgO both neutralized the acidity of the montmorillonite supports and improved the hydrogenation of the furanic ring, resulting in higher selectivity to THFA. The best catalyst was the one prepared with montmorillonite MK-10 covered by 30 wt% of magnesium oxide and with 8.8 % of the Ni metal phase achieving total conversion and total selectivity to THFA. The activity of this catalyst was maintained after several reuses.
- Sunyol,English Owen,González,Salagre,Cesteros
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- A Cationic Ru(II) Complex Intercalated into Zirconium Phosphate Layers Catalyzes Selective Hydrogenation via Heterolytic Hydrogen Activation
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Catalytic hydrogenations constitute economic and clean transformations to produce pharmaceutical and a multitude of fine chemicals in chemical industry. Herein, we report a cationic Ru(II) complex intercalated into zirconium phosphate (ZrP) layers that enables the efficient catalytic conversion of furfural and other biomass-derived carbonyl compounds into the corresponding alcohols through selective hydrogenation of C=O group. The ZrP layers acted not only as a support for the Ru-complex, but also as the new ligands to tune the Ru(II) center via forming Ru?O bond. The resulting catalysts exhibit excellent catalytic performance and can be easily recycled for six times without significant loss of activity and selectivity. The Ru(II) complex-intercalated catalysts have been characterized by XRD, SEM, HRTEM, HAADF-STEM, XPS, FT-IR, DR-UV/Vis, EXAFS and XANES. Especially, it is observed that the appropriate interlayer spacing between ZrP layers is favorable to stabilize the Ru(II) complex. Notably, on the basis of the further characterization and density functional theory (DFT) calculation, it is identified that the interaction of cationic Ru(II) complex and P?OH group within ZrP layers leads to the high catalytic performance in selective hydrogenation, and the newly formed Ru?O?P species plays a crucial role in the heterolytic hydrogen activation and selective hydrogenation of biomass-derived compounds containing a carbonyl group.
- Chen, Manyu,Xia, Jie,Li, Huan,Zhao, Xiuge,Peng, Qingpo,Wang, Jiajia,Gong, Honghui,Dai, Sheng,An, Pengfei,Wang, Haifeng,Hou, Zhenshan
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p. 3801 - 3814
(2021/08/03)
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- Bimetallic RuNi nanoparticles as catalysts for upgrading biomass: Metal dilution and solvent effects on selectivity shifts
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RuNi nanoparticles (NP) were prepared by decomposition of [Ru(η4-C8H12)(η6-C8H10)] and [Ni(η4-C8H12)2] by H2 in the presence of polyvinylpyrrolidone (PVP) at 85 °C using several Ru/Ni ratios. The nanoparticles display a segregated structure in which Ni is on the surface, as ascertained by wide angle X-ray scattering (WAXS). The catalytic activity in the selective hydrogenation of furfural of these RuNi NP was correlated with the Ru content. High selectivity towards the partially hydrogenated product 2-(hydroxymethyl)furan (HF) was found when carrying out the reaction in tetrahydrofuran (THF). A different scenario was found when using a protic polar solvent, 1-propanol. Catalysts displaying Ru on the surface were able to hydrogenate the heteroaromatic ring, while those with Ni on the surface were highly selective towards the partially hydrogenated product. In addition, Ru surfaces were prone to catalyse the acetalization reaction in the presence of the alcoholic solvent, while the addition of Ni supressed this reactivity. Density functional theory (DFT) calculations performed on hydrogenated Ru nanoparticles (Ru55H70) show differences in the adsorption energies of several reagents, products, reaction intermediates, and solvents onto the Ru NP surface, which are in line with the experimental catalytic results. This journal is
- Axet, M. Rosa,Cardona-Farreny, Miquel,Del Rosal, Iker,Dinoi, Chiara,Esvan, Jerome,Lecante, Pierre,Philippot, Karine,Poteau, Romuald
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supporting information
p. 8480 - 8500
(2021/11/17)
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- Investigating hydrogenation and decarbonylation in vapor-phase furfural hydrotreating over Ni/SiO2 catalysts: Propylene production
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Furfural can be mass-produced from lignocellulose biomass and can be a platform chemical for producing valuable chemicals. In this study, we examine Ni/SiO2 catalysts for the conversion of furfural under a hydrogen atmosphere. The reactivity an
- Chen, Szu-Hua,Tseng, Ya-Chun,Yang, Sheng-Chiang,Lin, Shawn D.
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- Silver-Catalyzed Hydroboration of C-X (X = C, O, N) Multiple Bonds
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AgSbF6 was developed as an effective catalyst for the hydroboration of various unsaturated functionalities (nitriles, alkenes, and aldehydes). This atom-economic chemoselective protocol works effectively under low catalyst loading, base- A nd solvent-free moderate conditions. Importantly, this process shows excellent functional group tolerance and compatibility with structurally and electronically diverse substrates (>50 examples). Mechanistic investigations revealed that the reaction proceeds via a radical pathway. Further, the obtained N,N-diborylamines were showcased to be useful precursors for amide synthesis.
- Pandey, Vipin K.,Tiwari, Chandra Shekhar,Rit, Arnab
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supporting information
p. 1681 - 1686
(2021/03/03)
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- Hydrogenative ring-rearrangement of furfural to cyclopentanone over pd/uio-66-no2 with tunable missing-linker defects
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Upgrading furfural (FAL) to cyclopentanone (CPO) is of great importance for the synthesis of high-value chemicals and biomass utilization. The hydrogenative ring-rearrangement of FAL is catalyzed by metal-acid bifunctional catalysts. The Lewis acidity is a key factor in promoting the rearrangement of furan rings and achieving a high selectivity to CPO. In this work, highly dispersed Pd nanoparticles were successfully encapsulated into the cavities of a Zr based MOF, UiO-66-NO2, by impregnation using a double-solvent method (DSM) followed by H2 reduction. The obtained Pd/UiO-66-NO2 catalyst showed a significantly better catalytic performance in the aforementioned reaction than the Pd/UiO-66 catalyst due to the higher Lewis acidity of the support. Moreover, by using a thermal treatment. The Lewis acidity can be further increased through the creating of missing-linker defects. The resulting defective Pd/UiO-66-NO2 exhibited the highest CPO selectivity and FAL conversion of 96.6% and 98.9%, respectively. In addition, the catalyst was able to maintain a high activity and stability after four consecutive runs. The current study not only provides an efficient catalytic reaction system for the hydrogenative ring-rearrangement of furfural to cyclopentanone but also emphasizes the importance of defect sites.
- Leus, Karen,Liu, Ying-Ya,Shi, Chuan,Sun, Zhichao,Van Der Voort, Pascal,Wang, Anjie,Wang, Chunhua,Wang, Yao,Yang, Yuhao,Yu, Zhiquan
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- Selective aqueous-phase hydrogenation of furfural to cyclopentanol over Ni-based catalysts prepared from Ni-MOF composite
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Metal-organic frameworks (MOFs) as an emerging class of porous materials exhibit some unique advantages, including controllable composition, a large surface area, high porosity, and so on. In this work, the spherical NiMo bimetal catalysts supported on porous carbon matrix were prepared using a simple wet impregnation method and studied for selective hydrogenation of furfural (FFA). Three different catalysts were investigated including Ni/C-Mo-BTC, Ni/C-Mo-DHTA and Ni/C-Mo-PTA. Of the catalysts studied the Ni/C-Mo-BTC catalyst could achieve the highest selectivity of CPL (up to 90%) under moderate reaction conditions (140 °C, 2 MPa, 2 h) in aqueous medium. In addition, other Ni-based catalysts (Ni/C-Fe, Ni/C-Zn, Ni/C-Cu, Ni/C-Ce) were also investigated to achieve yields of 20–70% under the same reaction conditions. The influence of temperature, H2 pressure, time and solvent were investigated for the best performing catalyst. Based on the optimal reaction condition, various of furfural derivatives could also be effectively transferred to produce corresponding products. The detailed physicochemical characterization was carried out by means of XRD, SEM, TEM, XPS, NH3-TPD and Raman analysis. In the end, the optimal Ni/C-Mo0.4 catalyst could be recycled magnetically and efficiently applied in the next run for five consecutive recycling tests in the FFA hydrogenation to CPL. The results suggested Ni/C-Mo0.4 catalyst occurred to increasingly favor the formation of Ni-Mo alloys and suggested a metallic active site in FFA hydrogenation with the addition of element Mo. Mechanism study indicated that water was a key factor contributing to the formation of different desired products, which was responsible for the arrangement of furan compound.
- Chen, Changzhou,Jiang, Jianchun,Li, Jing,Ren, Jurong,Wu, Dichao,Xia, Haihong,Zhou, Minghao
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- Nitrogen-Doped Carbon Composites with Ordered Macropores and Hollow Walls
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Metal-organic frameworks provide versatile templates for the fabrication of various metal/carbon materials, but most of the derived composites possess only microspores, limiting the accessibility of embedded active sites. Herein, we report the construction of cobalt/nitrogen-doped carbon composites with a three-dimensional (3D) ordered macroporous and hollow-wall structure (H-3DOM-Co/NC) using a single-crystal ordered macropore (SOM)-ZIF-8@ZIF-67 as precursor. During the pyrolysis, the interconnected macroporous structure of SOM-ZIF-8@ZIF-67 is mostly preserved, whereas the pore wall achieves a solid-to-hollow transformation with Co nanoparticles formed in the hollow walls. The 3D-ordered macroporous carbon skeleton may effectively promote long-range mass transfer and the hollow wall can facilitate local accessibility of active sites. This unique structure can greatly boost its catalytic activity in the selective hydrogenation of biomass-derived furfural to cyclopentanol, much superior to its counterparts without this well-designed hierarchically porous structure.
- Chen, Jianmin,Chen, Liyu,Fang, Ruiqi,Li, Yingwei,Qin, Ze,Wang, Yajing,Yang, Xianfeng,Yao, Wen
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supporting information
p. 23729 - 23734
(2021/10/04)
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- Highly efficient catalytic transfer hydrogenation of furfural over defect-rich amphoteric ZrO2with abundant surface acid-base sites
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Currently, the catalytic transformation and utilization of biomass-derived compounds are of great importance to the alleviation of environmental problems and sustainable development. Among them, furfural alcohol derived from biomass resources has been found to be one of the most prospective biomass platforms for high-value chemicals and biofuels. Herein, high-surface-area ZrO2 with abundant oxygen defects and surface acid-base sites was synthesized and used as a heterogeneous catalyst for the catalytic transfer hydrogenation of furfural into furfural alcohol using alcohol as a hydrogen donor. The as-synthesized ZrO2 exhibited excellent catalytic performance with 98.2% FA conversion and 97.1% FOL selectivity, even comparable with that of a homogeneous Lewis acid catalyst. A series of characterization studies and experimental results revealed that acid sites on the surface of ZrO2 could adsorb and activate the CO bond in furfural and base sites could facilitate the formation of alkoxide species. The synergistic effect of surface acid-base sites affords a harmonious environment for the reaction, which is crucial for catalytic transfer hydrogenation of furfural with high efficiency. Furthermore, the as-prepared ZrO2 catalyst also exhibited a potential application for the efficient catalytic transfer hydrogenation of a series of biomass-derived carbonyl compounds. This journal is
- Zhu, Zekun,Yang, Lingling,Ke, Changxuan,Fan, Guoli,Yang, Lan,Li, Feng
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p. 2616 - 2626
(2021/03/03)
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- Efficient Solvent-Free Hydrosilylation of Aldehydes and Ketones Catalyzed by Fe2(CO)9/C6H4-o-(NCH2PPh2)2BH
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An efficient solvent-free catalyst system for hydrosilylation of aldehydes and ketones was developed based on iron pre-catalyst Fe2(CO)9/C6H4-o-(NCH2PPh2)2BH. The reactions were tolerant of many functional groups and the corresponding alcohols were isolated in good to excellent yields following basic hydrolysis of the reaction products. The reaction is likely catalyzed by an in situ generated pincer ligated iron hydride complex. Graphic Abstract: [Figure not available: see fulltext.]
- Fang, Fei,Chang, Jiarui,Zhang, Jie,Chen, Xuenian
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p. 3509 - 3515
(2021/03/16)
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- Development of bimetallic Ni-Cu/SiO2 catalysts for liquid phase selective hydrogenation of furfural to furfuryl alcohol
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Bimetallic Ni-Cu/SiO2 catalysts with different Cu loading (2–5 wt%) were developed for liquid phase selective hydrogenation of furfural to furfuryl alcohol. Among these, bimetallic 2%Ni-X%Cu/SiO2 (X = 2, 5) catalysts exhibited better
- Weerachawanasak, Patcharaporn,Krawmanee, Pacharaporn,Inkamhaeng, Weerachat,Cadete Santos Aires, Francisco J.,Sooknoi, Tawan,Panpranot, Joongjai
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