- Selective aldehyde reductions in neutral water catalysed by encapsulation in a supramolecular cage
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The enhancement of reactivity inside supramolecular coordination cages has many analogies to the mode of action of enzymes, and continues to inspire the design of new catalysts for a range of reactions. However, despite being a near-ubiquitous class of reactions in organic chemistry, enhancement of the reduction of carbonyls to their corresponding alcohols remains very much underexplored in supramolecular coordination cages. Herein, we show that encapsulation of small aromatic aldehydes inside a supramolecular coordination cage allows the reduction of these aldehydes with the mild reducing agent sodium cyanoborohydride to proceed with high selectivity (ketones and esters are not reduced) and in good yields. In the absence of the cage, low pH conditions are essential for any appreciable conversion of the aldehydes to the alcohols. In contrast, the specific microenvironment inside the cage allows this reaction to proceed in bulk solution that is pH-neutral, or even basic. We propose that the cage acts to stabilise the protonated oxocarbenium ion reaction intermediates (enhancing aldehyde reactivity) whilst simultaneously favouring the encapsulation and reduction of smaller aldehydes (which fit more easily inside the cage). Such dual action (enhancement of reactivity and size-selectivity) is reminiscent of the mode of operation of natural enzymes and highlights the tremendous promise of cage architectures as selective catalysts.
- Paul, Avishek,Shipman, Michael A.,Onabule, Dolapo Y.,Sproules, Stephen,Symes, Mark D.
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- Selective hydrogenation of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) under atmospheric hydrogen pressure over carbon supported PdAu bimetallic catalyst
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Hydrogenation of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) was examined by PdxAuy/C catalysts prepared with various Pd/Au molar ratio (x/y) in the presence of hydrochloric acid (HCl) under an atmospheric hydrogen pressure. Bimetallic PdxAuy/C catalysts had a significant activity for a selective hydrogenation of HMF toward DMF comparing to monometallic Pd/C and Au/C catalysts. To clarify the novelty of PdxAuy/C catalysts, characterizations by using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectra (XAFS), a transmission electron microscopy (TEM) and other analytical techniques were studied. XPS and X-ray absorption near-edge structure (XANES) analyses indicated that there was the charge transfer phenomenon from Pd to Au atoms in PdxAuy/C. Existence of PdAu alloy structures in PdxAuy/C was expected by XRD, TEM and extended X-ray absorption fine structure (EXAFS) analyses. Accordingly, we concluded that PdAu alloys supported carbon exhibited a good catalytic performance for a selective hydrogenation of HMF to DMF using an atmospheric hydrogen pressure.
- Nishimura, Shun,Ikeda, Naoya,Ebitani, Kohki
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- Investigation of the Hydrogenation of 5-Methylfurfural by Noble Metal Nanoparticles in a Microcapillary Reactor
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On-column reaction gas chromatography (ocRGC) was successfully utilized as high-throughput platform for monitoring of the conversion and selectivity of hydrogenation of 5-methylfurfural catalyzed by polymer-stabilized Ru and Pd nanoparticles. We were able to elucidate the effect of various reaction conditions, mainly together with the catalyst loading on the conversion rate and the selectivity of the reaction. Our strategy yields significant improvements in reaction analysis times and cost effectiveness in comparison to standard methods. We are able to demonstrate that ocRGC approach provides valuable information about the reaction system that gives scientists a tool to design suitable catalytic systems for enhanced sustainable chemistry in the future. Capillary catalysis: A high-throughput study of the hydrogenation of 5-methylfurfural catalyzed by polymer-stabilized noble metal nanoparticles employing on-column reaction gas chromatography (ocRGC) as high-throughput platform to monitor several reaction pathways and intermediates is presented. The ocRGC approach is shown to provide valuable information about the reaction system that gives scientists a tool to design sustainable catalytic systems.
- Gmeiner, Julia,Seibicke, Max,Behrens, Silke,Spliethoff, Bernd,Trapp, Oliver
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- Palladium catalyzed hydrogenation of biomass derived halogenated furfurals
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The formation of valuable products and especially fuel candidates from lignocellulosic biomass is highly desirable. Lignocellulose derived halogenated furfurals formation was reported as highly efficient in comparison to the current existing methods of lignocellulose transformation. However, halogenated furfurals are platform chemicals and not end use chemicals, certainly not for fuels. Therefore, transformation methods of halogenated furfurals into fuels, fuels additives, or other valuable compounds are desirable. In this work we present the hydrogenation of halogenated furfurals over carbon supported palladium catalysts. Palladium catalysts showed better performance in the formation of 5-methyl furfural (MF) from halogenated furfurals compared to other catalysts. The reaction products were identified using GC-MS, FT-IR and NMR, and they were quantified using GC analysis. Catalysts were characterized with SEM, BET and pH meter. The role of catalysts properties and reaction parameters in MF preparation, and their effect on MF yields and selectivity were examined. In addition, the catalysts recovery and reuse in subsequent cycles was examined together with the recovery of hydrochloric acid or hydrobromic acid, formed as by products in halogenated furfurals hydrogenation.
- Meller, Elad,Sasson, Yoel,Aizenshtat, Zeev
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p. 103149 - 103159
(2016)
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- Untangling the active sites in the exposed crystal facet of zirconium oxide for selective hydrogenation of bioaldehydes
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The present study reports the influence of the crystal phase, facets, and active sites of zirconium oxide (ZrO2) on the conversion of bio-aldehydes to their corresponding alcohols in isopropanol under mild reaction conditions. Various ZrO2-based catalysts, having different compositions of monoclinic and tetragonal crystal phases, are successfully prepared in the presence of a base via a solvothermal process. From the detailed characterization through XRD, TEM, CO2-TPD, XPS, AES, BET and poisoning studies, M-ZrO2-U-N, synthesized using zirconium oxynitrate and urea as a precursor and precipitant, respectively, in water, possesses a 100% monoclinic crystal phase with a maximum amount of exposed (-111) facets and surface oxygen concentration along with the highest number of basic sites. The catalytic study on the transformation of furfural (FFA) into furfuryl alcohol (FOH) reveals that M-ZrO2-U-N exhibits the best efficiency with a nearly quantitative yield of FOH. On the other hand, T-ZrO2-U-N, synthesized using zirconium oxynitrate and urea as a precursor and precipitant, respectively, in methanol, is found to have a 94.4% tetragonal phase and a 2.2-fold lower number of basic sites in comparison with M-ZrO2-U-N. The catalytic result with T-ZrO2-U-N displays the lowest activity in terms of the FOH yield (8.1%). According to the comparative and systematic catalytic studies with the various ZrO2 catalysts having different amounts of tetragonal and monoclinic phases, the ZrO2 catalyst having a more monoclinic phase with more exposed (-111) facets, basic sites, surface oxygen species and surface area is found to be crucial for the FFA conversion to FOH with high selectivity. M-ZrO2-U-N is found to be stable and recyclable and also shows excellent activity towards the transformation of other bio-aldehydes and ketones into their corresponding alcohols. This journal is
- Devi, Mayanglambam Manolata,Kansal, Sushil Kumar,Kumar, Sahil,Saravanamurugan, Shunmugavel
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- Highly efficient catalytic transfer hydrogenation of biomass-derived furfural to furfuryl alcohol using UiO-66 without metal catalysts
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In this paper, the as-prepared metal-organic frameworks material UiO-66 and other Zr-MOFs were directly used as catalytic transfer hydrogenation (CTH) catalysts to catalyze furfural (FF) to furfuryl alcohol (FAL) with 2-propanol (IPA) acted as both solvent and hydrogen donor. The results showed that the as-prepared UiO-66 had satisfactory catalytic activity and selectivity in yielding FAL (97 %) from the CTH of FF at 140 °C within 5 h. Moreover, the as-prepared UiO-66 exhibited relatively stable catalytic activity over five cycles and easy regeneration. Interestingly, UiO-66 was also applicable for the CTH of the other aldehydes such as 5-hydroxymethyfurfural, 5-methylfurfural, 4-methoxybenzaldehyde, and n-hexanal to the corresponding alcohols, affording high product yields up to 98 %. This work provides a green, simple and sustainable process for the catalytic production of FAL from biomass-based furfural, which has certain significance for the sustainable utilization of biomass.
- Guo, Tianmeng,Li, Danni,Qi, Xinhua,Qiu, Mo,Xi, Ran
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- Cu1-Cu0 bicomponent CuNPs@ZIF-8 for highly selective hydrogenation of biomass derived 5-hydroxymethylfurfural
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99% yield of 2,5-dihydroxymethylfuran (DHMF) was achieved from biomass derived 5-hydroxymethylfurfural (HMF) with novel CuNPs@ZIF-8 using a relatively low hydrogen pressure and short reaction time. The activation energy of transformation of HMF to DHMF is only 39 kJ mol-1 and the TOF value reached is 21 h-1. The coexistence of Cu1 and Cu0 in Cu species is demonstrated to contribute to the high activity for the hydrogenation of HMF to DHMF.
- Feng, Yunchao,Yan, Guihua,Wang, Ting,Jia, Wenlong,Zeng, Xianhai,Sperry, Jonathan,Sun, Yong,Tang, Xing,Lei, Tingzhou,Lin, Lu
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- Catalytic conversion of starch into valuable furan derivatives using supported metal nanoparticles on mesoporous aluminosilicate materials
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Catalytically active supported metal nanoparticles on aluminosilicates including Cu and Pd-based systems were investigated in the microwave-assisted conversion to a range of valuable furanic compounds via tandem formic acid-promoted dehydration and subsequent selective hydrogenation processes. Results show that interesting selectivities to reduced products including 5-methylfurfural and 5-methylfurfuryl alcohol as well as hydroxymethylfurfural and furfural could be obtained in various proportions depending on the type of catalyst and the investigated reaction conditions. The investigation of reaction parameters including time of reaction, type of catalyst, quantity of catalyst and formic acid content indicated that reaction conditions can in principle be fine-tuned to maximise selectivity towards individual products. The Royal Society of Chemistry.
- Yepez, Alfonso,Garcia, Angel,Climent,Romero, Antonio A.,Luque, Rafael
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- Catalytic in-situ hydrogenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran over Cu-based catalysts with methanol as a hydrogen donor
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A series of Cu-based catalysts with different supports were synthesized and studied for the in situ hydrogenation of 5-hydroxymethylfurfural (5-HMF) to dimethylfuran (DMF) using methanol as an economical hydrogen donor. The structures and properties of the four catalysts (Cu/Al2O3, Cu/ZnO, Cu/ZrO2, and Cu/CeO2) were characterized using X-ray diffraction (XRD), temperature-programmed reduction (H2-TPR), and temperature-programmed desorption of ammonia (NH3-TPD). The experimental results showed that the use of different supports for the Cu-based catalysts significantly influenced their activity for both H2 production from methanol and hydrogenation of 5-HMF. The catalyst Cu/Al2O3 showed the best catalytic activity, which can be attributed to the highest activity for the in situ H2 production from methanol, smallest Cu crystallite size, and strongest acidity. The effects of the substrate concentration, catalyst loading, and reaction temperature and time on the in situ hydrogenation of 5-HMF were systematically investigated to determine the optimum reaction conditions.
- Zhang, Zihao,Wang, Changxue,Gou, Xin,Chen, Hao,Chen, Kequan,Lu, Xiuyang,Ouyang, Pingkai,Fu, Jie
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- Multifunctional NiCoTi?Catalyst Derived from Layered Double Hydroxides for Selective Hydrogenation of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran
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Multifunctional NiCoTi metal oxide catalysts (denoted herein as NiCoTi-x, where x is the molar ratio Ni + Co:Ti) were successfully prepared by thermal treatment of NiCoTi layered double hydroxide (LDH) precursors. The NiCoTi-x catalysts were then applied to the hydrogenation of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF). The Ni:Co:Ti molar ratio in the catalysts was found to strongly influence both catalyst activity and product selectivity. A NiCoTi-8 catalyst, containing Ni, Co and Ti in a 4:4:1 molar ratio (i.e. Ni + Co/Ti = 8), displayed outstanding performance for HMF hydrogenation at 200?°C and 1.5?MPa, evidenced by a 90.7% HMF conversion and 95.8% selectivity to DMF. Graphic Abstract: A ternary metal oxide catalyst derived from a layered double hydroxide was proposed for the efficient and selective hydrogenation of 5-hydroxymethylfurfural to 2,5-methylfuran.[Figure not available: see fulltext.]
- Ma, Ning,Song, Yong,Han, Feng,Waterhouse, Geoffrey I. N.,Li, Yan,Ai, Shiyun
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- Addressing the Metabolic Stability of Antituberculars through Machine Learning
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We present the first prospective application of our mouse liver microsomal (MLM) stability Bayesian model. CD117, an antitubercular thienopyrimidine tool compound that suffers from metabolic instability (MLM t1/2 1/2 values greater than or equal to 60 min. It is noteworthy that whole-cell efficacy and lack of relative mammalian cell cytotoxicity could not be predicted simultaneously. These results support the utility of our new MLM stability model in chemical tool and drug discovery optimization efforts.
- Stratton, Thomas P.,Perryman, Alexander L.,Vilchèze, Catherine,Russo, Riccardo,Li, Shao-Gang,Patel, Jimmy S.,Singleton, Eric,Ekins, Sean,Connell, Nancy,Jacobs, William R.,Freundlich, Joel S.
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- Ruthenium on carbonaceous materials for the selective hydrogenation of HMF
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We report the use of Ru catalysts supported in the activated carbon (AC) and carbon nanofibers (CNFs) for the selective production of liquid fuel dimethylfuran (DMF) and fuel additives alkoxymethyl furfurals (AMF). Parameters such as the reaction temperature and hydrogen pressure were firstly investigated in order to optimise the synthesis of the desired products. Simply by using a different support, the selectivity of the reaction drastically changed. DMF was produced with AC as support, while a high amount of AMF was produced when CNFs were employed. Moreover, the reusability of the catalysts was tested and deactivation phenomena were identified and properly addressed. Further studies need to be performed in order to optimise the stability of the catalysts.
- Cattaneo, Stefano,Naslhajian, Hadi,Somodi, Ferenc,Evangelisti, Claudio,Villa, Alberto,Prati, Laura
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- Metal Catalyst and Hydrogen Gas-Free Selective Reduction of Biomass-Derived Substituted Furfuraldehyde to Alkyl Furan as a Key Biofuel Additive
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A metal catalyst and a hydrogen gas-free approach has been developed for selective reduction of aldehyde to an alkyl group of different substituted furan compounds. In this process, hydrazine hydrate under basic conditions at reflux temperature selectively participated in the reduction of the aldehyde moiety to the corresponding alkyl group of highly reactive furan compounds in a selective manner. The developed protocol was applied for selective and scalable reduction of 5-hydroxymethylfurfural (5-HMF) up to 250 g to 5-methylfurfuryl alcohol (MFA) in a 70% yield. Under the same process, furfuraldehyde was also tested in a 250 g reaction for 2-methylfuran (MF) synthesis in a highly selective manner and the product was distilled out from a single-pot reaction with gas chromatography (GC) purity ≥90%. The scope of the process was further extended for different substituted furfuraldehydes successfully. In addition, the protocol is found to be efficient for scalable production and easy separation of the product.
- Chauhan, Arvind Singh,Kumar, Ajay,Das, Pralay
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- Reductive Amination, Hydrogenation and Hydrodeoxygenation of 5-Hydroxymethylfurfural using Silica-supported Cobalt- Nanoparticles
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Efficient and selective conversion of renewable feedstocks to essential chemicals and fuels applying green and sustainable catalytic processes is of central importance and attracts scientific interest. Among different biomass-based feedstocks, 5-hydroxymethylfurfural (HMF) represents valuable platform compound widely used for the synthesis of valuable chemicals, fuels, and polymers. Here we report cobalt nanoparticles catalyzed reductive amination, hydrogenation and hydrodeoxygenation of HMF to produce furan based primary, secondary and tertiary amines including N-methylamines as well as 2,5-bis(hydroxymethyl)furan, (5-methylfuran-2-yl)methanol and selected N-, O-, and S-containing heterocycles. Key to success for this HMF valorization is the use of reusable silica supported cobalt-based nanoparticles, which have been prepared by the immobilization and pyrolysis of Co-terephthalic acid-piperazine MOF template on silica.
- Alenad, Asma M.,Alshammari, Ahmad S.,Chandrashekhar, Vishwas G.,Jagadeesh, Rajenahally V.,Kreyenschulte, Carsten,Natte, Kishore
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- METAL CATALYST AND HYDROGEN GAS FREE APPROACHES FOR SELECTIVE REDUCTION OF ALDEHYDE TO METHYL GROUP OF DIFFERENT SUBSTITUTED FURANS
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The present invention relates to 5-methyl substituted furan compounds of general formula (I) and process for the preparation thereof: OR1R2 R3CH3(I) Particularly, the present invention relates to a metal catalyst and hydrogen gas free, atom-economy, highly selective and low-cost process for the preparation of methyl substituted furan compounds from different aldehyde substituted furan compounds.
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Page/Page column 15-16
(2021/08/27)
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- Formic acid enabled selectivity boosting in transfer hydrogenation of 5-hydroxymethylfurfural to 2,5-furandimethanol on highly dispersed Co-Nxsites
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Catalytic transfer hydrogenation (CTH) reaction is considered as a potential route for upgrading bio-based carbonyl compounds to their corresponding alcohols. Herein, ordered mesoporous N-doped carbon confined Co-Nx(Co-NC) was adopted as a catalyst for converting cellulose-derived 5-hydroxymethylfurfural (HMF) to 2,5-furandimethanol (FDM) using formic acid (FA) as a hydrogen donor. Different catalysts and preparation methods were screened, by varying cobalt phases and template removal procedures. It is found that highly dispersed N-confined Co species (Co-Nx) other than naked Co NPs acted as catalytic species for the CTH of HMF with FA, which gave 86% yield of FDM at 100% HMF conversion. Kinetic experiments revealed that, compared with molecular hydrogen, Co-NC could effectively accelerate HMF hydrogenation and suppress as-formed FDM hydrogenolysis in the presence of FA, which is ascribed to its superior activity toward hydrogen transfer from FA and fast desorption toward FDM. Mechanism studies indicated that C-H dissociation of FA could be the rate-determining step in the CTH reaction, and the hydrogenation of HMF could proceed through an intermolecular hydride transfer route. This work shows that the bifunctional nature of the catalyst is critical in the efficient CTH of biomass-derived carbonyl compounds and provides insights toward the rational design of such catalysts.
- Xu, Ling,Nie, Renfeng,Chen, Xujie,Li, Yanchen,Jiang, Yuxi,Lu, Xiuyang
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p. 1451 - 1457
(2021/03/14)
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- From Furan-Yne Systems to para -Benzoquinone Derivatives: Gold-Catalyzed Cyclization and Oxidation, and Further Reduction by Sodium Dithionate
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A series of furan-yne systems were transformed into the corresponding para -benzoquinone derivatives by gold(ΙΙΙ) catalyst. The two-step procedure consisted of a phenol synthesis and subsequent oxidation with iodobenzene diacetate. The reactions can be carried out in a one-pot procedure with the same precatalyst. The para -benzoquinone could simply be converted into the corresponding hydroquinones by reduction with sodium dithionate. This protocol features high efficiency, mild conditions, and wide substrate scopes.
- Ahmadi, Saman,Ghanbari, Mohammad
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p. 775 - 784
(2020/10/13)
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- Manganese=Catalyzed Achmatowicz Rearrangement Using Green Oxidant H2O2
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Oxidation reactions have been extensively studied in the context of the transformations of biomass=derived furans. However, in contrast to the vast literature on utilizing the stoichiometric oxidants, such as m=CPBA and NBS, catalytic methods for the oxidative furan=recyclizations remain scarcely investigated. Given this, we report a means of manganese=catalyzed oxidations of furan with low loading, achieving the Achmatowicz rearrangement in the presence of hydrogen peroxide as an environmentally benign oxidant under mild conditions with wide functional group compatibility.
- Gao, Ziwei,Gou, Jing,Hao, Zhe,Hou, Jing,Li, Chaoqun,Li, Gaoqiang,Xing, Qingzhao,Yu, Binxun
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p. 9563 - 9586
(2021/07/20)
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- Efficient single-atom Ni for catalytic transfer hydrogenation of furfural to furfuryl alcohol
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The employment of single-atom catalysts in the catalytic transfer hydrogenation (CTH) of furfural (FF) to furfuryl alcohol (FAL) has never been effectively explored. Herein, a catalyst of Ni single-atoms supported on nitrogen doped carbon (Ni-SAs/NC) is synthesized and first ever utilized in the CTH of FF to FAL. Atomically dispersed Ni-N4 sites change the electron density at the metal center and exhibit specific adsorption and desorption to FF and FAL, promoting an outstanding catalytic performance with a turnover frequency (TOF) of 832 h-1 and selectivity as high as 97.1% at 130 °C for 2 h. Such performance is 9-fold higher than that of supported Ni nanocatalysts. The Ni-SAs/NC catalyst also exhibits superior stability for the CTH of FF and excellent catalytic activity for other α,β-unsaturated aldehydes. This work provides a new strategy of producing green chemical compounds using catalytic biomass conversion and suggests the future application of long-lasting single-atom catalysts for emerging sustainable technologies.
- Fan, Yafei,Zhuang, Changfu,Li, Shangjing,Wang, Ying,Zou, Xiaoqin,Liu, Xiaoteng,Huang, Weimin,Zhu, Guangshan
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p. 1110 - 1118
(2021/01/25)
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- Air-Stable and Reusable Cobalt Phosphide Nanoalloy Catalyst for Selective Hydrogenation of Furfural Derivatives
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While metal phosphides have begun to attract attention as electrocatalysts, they remain underutilized in the field of liquid-phase molecular transformations. Herein, we describe a supported cobalt phosphide nanoalloy (nano-Co2P) that functions as a highly efficient, reusable heterogeneous catalyst for the selective hydrogenation of furfural derivatives. The carbonyl moieties of several furfural derivatives were selectively hydrogenated to produce the desired products in high yields. In contrast to conventional nonprecious metal catalysts, nano-Co2P uniquely exhibited air stability, which enabled easy and safe handling and precluded the need for H2 pretreatment. Infrared and density functional theory studies revealed that the highly efficient hydrogenation is due to the favorable activation of the carbonyl moiety of furfural derivatives through the backdonation to its π? orbital from the Co d-electrons.
- Ishikawa, Hiroya,Sheng, Min,Nakata, Ayako,Nakajima, Kiyotaka,Yamazoe, Seiji,Yamasaki, Jun,Yamaguchi, Sho,Mizugaki, Tomoo,Mitsudome, Takato
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p. 750 - 757
(2021/02/05)
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- Ni2P Nanoalloy as an Air-Stable and Versatile Hydrogenation Catalyst in Water: P-Alloying Strategy for Designing Smart Catalysts
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Non-noble metal-based hydrogenation catalysts have limited practical applications because they exhibit low activity, require harsh reaction conditions, and are unstable in air. To overcome these limitations, herein we propose the alloying of non-noble metal nanoparticles with phosphorus as a promising strategy for developing smart catalysts that exhibit both excellent activity and air stability. We synthesized a novel nickel phosphide nanoalloy (nano-Ni2P) with coordinatively unsaturated Ni active sites. Unlike conventional air-unstable non-noble metal catalysts, nano-Ni2P retained its metallic nature in air, and exhibited a high activity for the hydrogenation of various substrates with polar functional groups, such as aldehydes, ketones, nitriles, and nitroarenes to the desired products in excellent yields in water. Furthermore, the used nano-Ni2P catalyst was easy to handle in air and could be reused without pretreatment, providing a simple and clean catalyst system for general hydrogenation reactions.
- Fujita, Shu,Yamaguchi, Sho,Yamasaki, Jun,Nakajima, Kiyotaka,Yamazoe, Seiji,Mizugaki, Tomoo,Mitsudome, Takato
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supporting information
p. 4439 - 4446
(2021/02/09)
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- Highly Efficient Ir-CoOX Hybrid Nanostructures for the Selective Hydrogenation of Furfural to Furfuryl Alcohol
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Decoration of noble metals with transition-metal oxides has been intensively studied for heterogeneous catalysis. However, controllable syntheses of metal-metal oxide heterostructures are difficult, and elucidation of such interfaces is still challenging. In this work, supported IrCo alloy nanoparticles are transformed into supported Ir-CoOx close-contact nanostructures by in situ calcination and following selective reduction. Relative to Ir/Al2O3, Ir-CoOx/Al2O3 shows greatly enhanced activities for the hydrogenation of furfural derivatives to the corresponding furfuryl alcohol derivatives with more than 99% selectivity and demonstrates significantly improved activities and selectivity for hydrogenations of α,β-unsaturated aldehydes to α,β-unsaturated alcohols. The modification of Ir surfaces with CoOx prevents Ir nanoparticles from growing, achieving high thermal and catalytic stabilities. Theoretic calculation suggests that the better catalytic performance of Ir-CoOx/Al2O3 is ascribed to the Ir-CoOx interaction, which promotes the absorption of furfural as well as desorption of furfuryl alcohol, resulting in enhanced catalytic activities.
- Yu, Hongbo,Zhao, Jihao,Wu, Chunzheng,Yan, Bo,Zhao, Shuangliang,Yin, Hongfeng,Zhou, Shenghu
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p. 1894 - 1901
(2021/02/27)
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- Modulation of Ru and Cu nanoparticle contents over CuAlPO-5 for synergistic enhancement in the selective reduction and oxidation of biomass-derived furan based alcohols and carbonyls
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Furfural (FAL) and 5-hydroxymethylfurfural (HMF) are important and sustainable platform chemicals. They are produced from lignocellulose biomass and attract significant attention as precursors for producing value-added chemicals and fuels. The selective conversion of these chemicals requires precise modulation of reaction parameters, solvent, and catalyst. In this study, FAL is selectively reduced to furfuryl alcohol (FOL), and HMF is selectively oxidized to 2,5-diformylfuran (DFF) over a Cu and Ru decorated copper aluminophosphate (CuAlPO-5) catalyst. A high FAL conversion (99.5%) and FOL selectivity (99.6%) are obtained in water under mild reaction conditions of 353 K and 1 MPa H2pressure. On the other hand, 94.0% HMF conversion and 99.9% DFF selectivity are obtained at 1 atm O2flow at 413 K. Both these processes are efficiently conducted over Cu and Ru nanoparticles supported CuAlPO-5 at optimized Cu and Ru contents and under different reaction conditions. The calculated activation energies for these processes are 21.5 kJ mol?1(for FAL hydrogenation) and 34.5 kJ mol?1(for HMF oxidation). The temperature-programmed reduction/oxidation (TPR/TPO) and adsorption results suggest the synergy between Cu and Ru, resulting in higher catalytic activity. Systematic and precise modulation of active metal contents and minimizing the Ru content in the Cu-Ru bimetallic catalyst system would be desirable from the industrial and academic perspective, especially for achieving oxidation/reduction capabilities in biomass conversion using a single catalyst.
- Bal, Rajaram,Kumar, Abhinav,Srivastava, Rajendra
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p. 4133 - 4148
(2021/06/30)
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- Gold(I)-Catalyzed Reactivity of Furan-ynes with N-Oxides: Synthesis of Substituted Dihydropyridinones and Pyranones
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The reactivity of "furan-ynes"in combination with pyridine and quinoline N-oxides in the presence of a Au(I) catalyst, has been studied, enabling the synthesis of three different heterocyclic scaffolds. Selective access to two out of the three possible products, a dihydropyridinone and a furan enone, has been achieved through the fine-tuning of the reaction conditions. The reactions proceed smoothly at room temperature and open-air, and were further extended to a broad substrate scope, thus affording functionalized dihydropyridinones and pyranones.
- Maranzana, Andrea,Marra, Francesco,Nejrotti, Stefano,Prandi, Cristina,Priola, Emanuele
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supporting information
p. 8295 - 8307
(2021/07/02)
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- Ni-Al/CoOx-catalyzed hydrodeoxygenation of 5-hydroxymethylfurfural into 2,5-dimethylfuran at low temperatures without external hydrogen
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Catalytic hydrodeoxygenation of 5-hydroxymethylfurfural into 2,5-dimethylfuran has received great interest in recent years. In this work, a ternary Ni-Al/CoOx-1 catalyst was fabricated, which provided 96% yield of DMF from in situ hydrodeoxygenation of HMF under mild reaction conditions. XRD, TEM and TPR revealed that the addition of Al to the Ni-Co bimetallic system could make the structure more stable and improve the dispersion of Ni and Co species. XPS, CO-DRIFTS and EPR verified that an enhanced electron transfer from Co species to Ni occurred on Ni-Al/CoOx-1. Reaction mechanism studies unraveled that the Al addition results in promoting in situ H2 production from 2-propanol and accelerating the aldehyde group hydrogenation to a hydroxymethyl group and the subsequent hydrogenolysis into a methyl group, due to the formation of a charge separated metal-couple-site (Niδ-Coδ+) and stronger Lewis acid sites in Ni-Al/CoOx-1. In addition, this ternary Ni-Al/CoOx-1 catalyst exhibits superior recyclability without significant loss of activity for 7 cycles.
- An, Yadan,Bai, Guoyi,Bian, Gang,Li, Tianming,Niu, Libo,Xia, Zhanghui
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p. 7763 - 7772
(2021/10/12)
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- The thermal stability and safety of 2, 5-dimethylfuran (DMF) oxidation
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DMF is renewable energy obtained from glucose, its thermal stability and safety need to be investigated. Accelerated rate calorimeter (ARC) is widely used to evaluate the risk of hazardous materials. In this paper, the thermal stability and safety of DMF oxidation were investigated using an ARC. DMF does not react even when the temperature reaches 452 K under nitrogen atmosphere. In oxygen atmosphere, the onset temperature (T0) of DMF oxidation is 323.49 K, and the activation energy (Ea) is 172.35 kJ/mol. The peroxide concentration of oxidation process was determined by iodometry, and the oxidation products were analyzed by gas chromatography - mass spectrometry. The pressure and exothermic behavior of ARC are related to the reaction mechanism. A simple three steps mechanism of DMF oxidation was described: fist DME reacts with oxygen to form peroxide; second is the main oxidation stage, oxidation products are complex; the third step is thermal decomposition.
- Huang, Pinxian,Kubota, Shiro,Liu, Pin,Liu, Xiongmin,Saburi, Tei,Wada, Yuji
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- Direct Visualization of Substitutional Li Doping in Supported Pt Nanoparticles and Their Ultra-selective Catalytic Hydrogenation Performance
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It has only recently been established that doping light elements (lithium, boron, and carbon) into supported transition metals can fill interstitial sites, which can be observed by the expanded unit cell. As an example, interstitial lithium (intLi) can block H filling octahedral interstices of palladium metal lattice, which improves partial hydrogenation of alkynes to alkenes under hydrogen. In contrast, herein, we report intLi is not found in the case of Pt/C. Instead, we observe for the first time a direct ‘substitution’ of Pt with substitutional lithium (subLi) in alternating atomic columns using scanning transmission electron microscopy-annular dark field (STEM-ADF). This ordered substitutional doping results in a contraction of the unit cell as shown by high-quality synchrotron X-ray diffraction (SXRD). The electron donation of d-band of Pt without higher orbital hybridizations by subLi offers an alternative way for ultra-selectivity in catalytic hydrogenation of carbonyl compounds by suppressing the facile CO bond breakage that would form alcohols.
- Chen, Tianyi,Foo, Christopher,Zheng, Jianwei J. W.,Fang, Huihuang,Nellist, Peter,Tsang, Shik Chi Edman
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supporting information
p. 12041 - 12046
(2021/07/14)
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- Formic Acid-Assisted Selective Hydrogenolysis of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran over Bifunctional Pd Nanoparticles Supported on N-Doped Mesoporous Carbon
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Biomass-derived 5-hydroxymethylfurfural (HMF) is regarded as one of the most promising platform chemicals to produce 2,5-dimethylfuran (DMF) as a potential liquid transportation fuel. Pd nanoparticles supported on N-containing and N-free mesoporous carbon materials were prepared, characterized, and applied in the hydrogenolysis of HMF to DMF under mild reaction conditions. Quantitative conversion of HMF to DMF was achieved in the presence of formic acid (FA) and H2 over Pd/NMC within 2 h. The reaction mechanism, especially the multiple roles of FA, was explored through a detailed comparative study by varying hydrogen source, additive, and substrate as well as by applying in situ ATR-IR spectroscopy. The major role of FA is to shift the dominant reaction pathway from the hydrogenation of the aldehyde group to the hydrogenolysis of the hydroxymethyl group via the protonation by FA at the C-OH group, lowering the activation barrier of the C?O bond cleavage and thus significantly enhancing the reaction rate. XPS results and DFT calculations revealed that Pd2+ species interacting with pyridine-like N atoms significantly enhance the selective hydrogenolysis of the C?OH bond in the presence of FA due to their high ability for the activation of FA and the stabilization of H?.
- Hu, Bin,Warczinski, Lisa,Li, Xiaoyu,Lu, Mohong,Bitzer, Johannes,Heidelmann, Markus,Eckhard, Till,Fu, Qi,Schulwitz, Jonas,Merko, Mariia,Li, Mingshi,Kleist, Wolfgang,H?ttig, Christof,Muhler, Martin,Peng, Baoxiang
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supporting information
p. 6807 - 6815
(2021/02/01)
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- Magnetic gold-cobalt composite catalyst as well as preparation method and application thereof
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The invention provides a magnetic gold-cobalt composite catalyst and a preparation method and application thereof, and belongs to the technical field of catalysts. The magnetic cobalt-cobalt composite catalyst comprises a magnetic cobalt oxide carrier and a gold-cobalt alloy loaded on the surface of the magnetic cobalt oxide carrier. The chemical composition of the magnetic cobalt oxide carrier is CoO. x , 1 _AOMARKENCODTX0AOA x _AOMARKENCODELTA AOA 1.5. In the catalyst provided by the invention, a metal synergistic effect is generated between gold and cobalt in the gold-cobalt alloy. CoOx A large number of surface defects are found in the invention, and a large number of reaction active sites are provided. The catalytic activity of the catalyst for 5 -hydroxymethylfurfural hydrogenation preparation 2, 5 -dimethylfuran is improved, the conversion rate 5 - hydroxymethylfurfural is high, 2,5 -dimethylfuran is high in yield and selectivity.
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Paragraph 0094-0098; 0101-0106
(2021/08/25)
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- Tandem catalyzing the hydrodeoxygenation of 5-hydroxymethylfurfural over a Ni3Fe intermetallic supported Pt single-atom site catalyst
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Single-atom site catalysts (SACs) have been used in multitudinous reactions delivering ultrahigh atom utilization and enhanced performance, but it is challenging for one single atom site to catalyze an intricate tandem reaction needing different reactive sites. Herein, we report a robust SAC with dual reactive sites of isolated Pt single atoms and the Ni3Fe intermetallic support (Pt1/Ni3Fe IMC) for tandem catalyzing the hydrodeoxygenation of 5-hydroxymethylfurfural (5-HMF). It delivers a high catalytic performance with 99.0% 5-HMF conversion in 30 min and a 2, 5-dimethylfuran (DMF) yield of 98.1% in 90 min at a low reaction temperature of 160 °C, as well as good recyclability. These results place Pt1/Ni3Fe IMC among the most active catalysts for the 5-HMF hydrodeoxygenation reaction reported to date. Rational control experiments and first-principles calculations confirm that Pt1/Ni3Fe IMC can readily facilitate the hydrodeoxygenation reaction by a tandem mechanism, where the single Pt site accounts for C-O group hydrogenation and the Ni3Fe interface promotes the C-OH bond cleavage. This interfacial tandem catalysis over the Pt single-atom site and Ni3Fe IMC support may develop new opportunities for the rational structural design of SACs applied in other heterogeneous tandem reactions.
- Meng, Ge,Ji, Kaiyue,Zhang, Wei,Kang, Yiran,Wang, Yu,Zhang, Ping,Wang, Yang-Gang,Li, Jun,Cui, Tingting,Sun, Xiaohui,Tan, Tianwei,Wang, Dingsheng,Li, Yadong
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p. 4139 - 4146
(2021/04/02)
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- Efficient and selective catalytic hydrogenation of furanic aldehydes using well defined Ru and Ir pincer complexes
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We report the homogeneous catalytic hydrogenation of biomass derived furanic aldehydes to furfuryl alcohols using low loadings of PNP metal complexes under mild conditions. Our strategy represents an efficient and selective approach to the direct hydrogenation of furan derivatives to promising platform chemicals. This journal is
- Koranchalil, Sakhitha,Nielsen, Martin,Padilla, Rosa
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supporting information
p. 6767 - 6772
(2020/11/10)
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- Catalytic Transfer Hydrogenation of Furfural to Furfuryl Alcohol under Mild Conditions over Zr-MOFs: Exploring the Role of Metal Node Coordination and Modification
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The catalytic transfer hydrogenation (CTH) reaction is considered as a potential route for upgrading bio-based carbonyls to their corresponding alcohols. Herein, a series of Zr-based metal-organic frameworks (Zr-MOFs) containing various types of metal node to ligand coordinations were synthesized and tested for CTH of furfural (FUR) to furfuryl alcohol (FOL). It was found that metal node coordination plays a more important role than porosity in Zr-MOFs. MOF-808 (synthesized using a scaled-up approach to achieve a higher batch yield), with the lowest metal node to ligand coordination (coordination number 6), was found to be the most active catalyst among the various tested Zr-MOFs. Furthermore, M-MOF-808, modified by simple methanol activation (M), outperformed the pristine MOF-808 in CTH of FUR to FOL even at 30 °C in the presence of 2-propanol (IPA) as the hydrogen source. The simple modification of the metal node in the Zr-MOF changed the acid-base properties of the MOF-808 surface through the development of coordinatively unsaturated sites (CUS), hydroxyl and methoxy groups in the framework of the Zr-MOF, which probably help to facilitate the adsorption of FUR and IPA onto the metal node surfaces of the catalyst. To evaluate the versatility of methanol activation in CTH, further substrates, including other types of biomass and representative carbonyl compounds over M-MOF-808, were tested. To demonstrate heterogeneous catalysis, the catalyst was recycled for five consecutive cycles, with little loss after the first cycle, and was fully characterized to observe any changes in its structure. Mechanistic insights were provided by isotopically labeled 2-propanol-d8 experiments, indicating FUR reduction through transfer hydrogenation. Finally, the reaction mechanism for CTH of FUR to FOL was proposed in detail using density functional theory (DFT) calculations over metal node modified model systems of a 6-connected Zr-MOF.
- Cha, Ga-Young,Chang, Jong-San,Hong, Do-Young,Hwang, Young Kyu,Jung, Jaehoon,Kwak, Jaesung,Kwon, Young-Uk,Lee, Minhui,Oh, Kyung-Ryul,Valekar, Anil H.,Yoon, Ji Woong
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p. 3720 - 3732
(2020/04/15)
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- Diethylsilane as a Powerful Reagent in Au Nanoparticle-Catalyzed Reductive Transformations
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Diethylsilane (Et2SiH2), a simple and readily available dihydrosilane, that exhibits superior reactivity, as compared to monohydrosilanes, in a series of reductive transformations catalyzed by recyclable and reusable Au nanoparticles (1 mol-%) supported on TiO2. It reduces aldehydes or ketones almost instantaneously at ambient conditions. It can be used in a one pot rapid reductive amination procedure, in which premixing of aldehyde and amine is required prior to the addition of the reducing agent and the catalyst, even in a protic solvent. An unprecedented method for the synthesis of N-arylisoindolines is also shown in the reductive amination between o-phthalaldehyde and anilines. In this transformation, it is proposed that the intermediate N,2-diphenylisoindolin-1-imines are reduced stepwise to the isoindolines. Finally, Et2SiH2 readily reduces amides into amines in excellent yields and shorter reaction times relative to previously known analogous nano Au(0)-catalyzed protocols.
- Louka, Anastasia,Kidonakis, Marios,Saridakis, Iakovos,Zantioti-Chatzouda, Elisavet-Maria,Stratakis, Manolis
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p. 3508 - 3514
(2020/06/02)
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- Chemoenzymatic Synthesis of 5-Hydroxymethylfurfural (HMF)-Derived Plasticizers by Coupling HMF Reduction with Enzymatic Esterification
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Biobased plasticizers, as substitutes for phthalates, have been synthesized from 5-hydroxymethylfurfural (HMF) and carboxylic acids (or esters) through a chemoenzymatic cascade process that involves as its first step the reduction of 5-hydroxymethylfurfural into 2,5-bis(hydroxymethyl)furan (BHMF), followed by the esterification of BHMF with carboxylic acids (or esters) by using a supported lipase (Novozym 435). The reduction of HMF into BHMF is performed by using monodisperse metallic Co nanoparticles with a thin carbon shell (Co@C) with high activity and selectivity. After optimization of reaction conditions (temperature, hydrogen pressure, and solvent), it is possible to achieve 97 % conversion of HMF with 99 % selectivity to BHMF after 2 h reaction time. The reduction of HMF and esterification of BHMF using carboxylic acids or vinyl esters as acyl donors by lipase are optimized separately in batch and in fixed-bed continuous reactors. The coupling of two flow reactors (for reduction and subsequent esterification) working under optimized reaction conditions affords the diesters of BHMF in roughly 90 % yield with no loss of activity during 60 h of operation.
- Arias, Karen S.,Carceller, Jose M.,Climent, Maria J.,Corma, Avelino,Iborra, Sara
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p. 1864 - 1875
(2020/03/11)
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- Manganese catalyzed transfer hydrogenation of biomass-derived aldehydes: Insights to the catalytic performance and mechanism
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Manganese catalyzed transfer hydrogenation (CTH) of aldehydes is an attractive method for the synthesis of alcohols. Here, we report a novel and efficient MnO?C-N catalyst for the CTH of biomass-derived 5-hydroxymethylfurfural and other aldehydes to alcohols in high yields. Catalytic experimental studies showed that the MnO and nitrogen-doping are responsible for the high selectivity and high conversion, respectively. Isotopic labelling experiments demonstrated that the CTH of aldehydes to alcohols over MnO?C-N is via a route by direct hydrogen transfer. Kinetic studies revealed that the N-doping can improve the reaction rate and reduce the activation energy of the aldehydes conversion. DFT calculations also indicated that both pyridine N and pyrrolic N doping can reduce the energy barrier for acetone desorption by the interaction between N and hydroxyl-H of alcohol. Furthermore, MnO?C-N showed good recyclability for at least five reaction cycles. We anticipate that these results can drive progress in the manganese catalyzed transfer hydrogenation reaction.
- Chen, Binglin,Feng, Yunchao,Lin, Lu,Long, Sishi,Sperry, Jonathan,Sun, Yong,Tang, Xing,Xu, Wanjie,Yan, Guihua,Zeng, Xianhai
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p. 157 - 165
(2020/06/27)
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- Ammonia borane enabled upgrading of biomass derivatives at room temperature
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Simplifying biomass conversion to valuable products with high efficiency is pivotal for the sustainable development of society. Herein, an efficient catalyst-free system using ammonia borane (AB) as the hydrogen donor is described, which enables controllable reaction selectivity towards four value-added products in excellent yield (82-100%) under very mild conditions. In particular, the system is uniquely efficient to produce γ-valerolactone (GVL) at room temperature. Combined in situ NMR and computational studies elucidate the hydrogen transfer mechanism of AB in methanol, the novel pathway of GVL formation from levulinate in water, and a competitive mechanism between reduction and reductive amination in the same system. Moreover, carbohydrates are converted directly into GVL in good yield, using a one-pot, two-step strategy. Products of a rather broad scope are prepared within a short reaction time of 30 min by using this catalyst-free strategy in methanol at room temperature. This journal is
- Meier, Sebastian,Riisager, Anders,Yang, Song,Zhao, Wenfeng
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supporting information
p. 5972 - 5977
(2020/11/03)
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- Efficient Cu catalyst for 5-hydroxymethylfurfural hydrogenolysis by forming Cu-O-Si bonds
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Selective hydrogenolysis of C-O bonds of biomass derived precursors has been identified as a promising and essential way to produce fuel additives. Supported transition metals were explored to give efficient reactivity commonly based on a bifunctionality strategy. Here, we report that covalent bonding between SiO2 and Cu features a homologous bifunctional catalyst with metallic Cu and Lewis acidic Cu cations. The catalyst gave superior reactivity for the conversion of 5-hydroxymethylfurfural into 2,5-dimethylfuran. Lewis acidic cations had more predominant roles than metallic sites for C-O hydrogenolysis by stretching and dissociating C-O bonds, whereas they remained inactive for CC bonds. The results rationalize the valence-state-sensitive catalysis for chemistry involving C-O cleavage. The covalent metal-O-Si bonding provides an alternative for developing efficient catalysts since silicates with such a feature are versatile in nature.
- Fang, Zhen,Kong, Xiao,Li, Luping,Peng, Bo,Zhu, Yifeng,Zhu, Yulei
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p. 7323 - 7330
(2020/11/25)
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- Flow hydrogenation of 5-acetoxymethylfurfural over Cu-based catalysts
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5-Acetoxymethylfurfural (AMF) is a promising starting material for synthesis of the valuable furan derivatives. The catalytic properties of Cu-based catalysts obtained from layered double hydroxides were studied in flow hydrogenation of AMF to 5-(acetoxymethyl)-2-furanmethanol (AMFM) in the present work. The resulting product can be easily converted to 2,5-bis(hydroxymethyl)furan which has significant potential in the production of polymers and pharmaceuticals. It was found that hydrogenation of AMF gives AMFM with selectivity of 98 percent at the full conversion of the substrate under mild reaction conditions (90°C and 10 bar). The influence of the solvent nature, Cu/Al ratio and calcination temperature on the catalyst performance was investigated.
- Bukhtiyarova, Galina A.,Bukhtiyarova, Marina V.,Bulavchenko, Olga A.,Nuzhdin, Alexey L.
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- Self-tuned properties of CuZnO catalysts for hydroxymethylfurfural hydrodeoxygenation towards dimethylfuran production
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5-Hydroxymethylfurfural (HMF) is a very valuable platform molecule obtained from biomass. It can be catalytically transformed to many industrially relevant products of both oxidation and reduction reactions. In this work, we showed that robust CuZnO can be an efficient, self-tuned catalyst for 2,5-dimethylfuran (DMF) (biofuel additive) synthesis. We showed that CuZnO catalysts can be further activated in the reaction environment and this process depends strongly on the initial catalyst properties and therefore on the catalyst preparation method. Smaller copper particles are more active but more prone to carbon deposit formation. Based on activity tests and extensive characterization, we have concluded that both Cun+ and Cu0 sites are necessary for high HMF conversion. While these two sites favor high conversion and high 2,5-bishydroxymethylfuran (BHMF) yield, the in situ formation of Lewis acid sites is proposed to be necessary for achieving a high DMF yield.
- Brzezińska, Magdalena,Keller, Nicolas,Ruppert, Agnieszka M.
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p. 658 - 670
(2020/02/27)
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- Hydroconversion of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran and 2,5-Dimethyltetrahydrofuran over Non-promoted Ni/SBA-15
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The selective hydroconversion of 5-hydroxymethylfurfural (HMF) to biofuels is currently highly sought-for. While the literature has demonstrated that this reaction is possible on promoted Ni catalysts, we show here that a monometallic, non-promoted Ni/SBA-15 catalyst, prepared by incipient wetness impregnation, can convert HMF to 2,5-dimethylfuran (DMF) and to 2,5-dimethyltetrahydrofuran (DMTHF) at 180 °C, in a consecutive way. Through a control over reaction time, high yields to DMF (71 %, at conversion of 93 %) or DMTHF (97 %, at conversion of 100 %) can be achieved. Kinetic modelling suggests a preferential route to DMF via 5-methylfurfural (MFFR) as intermediate, though the route via 2,5-bis(hydroxylmethyl)furan (BHMF) is also present. The favored route in the experimental conditions involves the hydrogenolysis of the hydroxyl group of HMF as first step, followed by the hydrogenation of the aldehyde function, to methylfurfuryl alcohol (MFOL). It is suggested a higher reaction rate of hydrogenation or hydrogenolysis of the side group is linked to the presence of a methyl group in the molecule. No hydrogenation of the furan ring is detected on the intermediates.
- Chen, Shuo,Ciotonea, Carmen,De Oliveira Vigier, Karine,Jér?me, Fran?ois,Wojcieszak, Robert,Dumeignil, Franck,Marceau, Eric,Royer, Sebastien
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p. 2050 - 2059
(2020/03/04)
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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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p. 4010 - 4018
(2020/08/28)
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- Application of ferro-nickel hydrotalcite catalyst in preparation of benzyl alcohol
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The invention discloses application of a ferro-nickel hydrotalcite catalyst in preparation of benzyl alcohol, and belongs to the technical field of synthesis of benzyl alcohol. In the application, thebenzyl alcohol is prepared by catalyzing benzaldehyde via a catalytic transfer hydrogenation reaction under the own pressure condition in a hydrothermal reaction kettle by taking alcohol compounds asa solvent and a hydrogen donor and taking Ni-Fe(2/1)LDH, Ni-Fe(3/1)LDH or Ni-Fe(4/1)LDH as a catalyst, the reaction temperature is 110-160 DEG C, and the reaction time is 6-11 hours. A method for preparing the benzyl alcohol is simple in process and convenient in operation and is safe and environmentally friendly. The ferro-nickel hydrotalcite catalyst is prepared from common non-noble metals, islow in cost and is easy to obtain; the ferro-nickel hydrotalcite catalyst can be also used for reducing other compounds containing C=O bonds and is beneficial for commercial application.
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Paragraph 0093; 0094; 0096
(2019/05/08)
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- Catalyst-free synthesis of biodiesel precursors from biomass-based furfuryl alcohols in the presence of H2O and air
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Production of biodiesel from biomass resources usually requires elongation of carbon numbers from typical C5 and C6 platform molecules through C-C coupling reactions, which were catalyzed by acid, base or metal catalysts traditionally. Herein, a catalyst-free method was developed to produce bis(furan-2-yl)methane derivatives (BFMs) from furfuryl alcohol derivatives (FAs) in the presence of H2O and air without any other additional catalysts. An 81% yield of bis(5-methylfuran-2-yl)methane (BMFM) can be obtained from 5-methylfurfuryl alcohol (5-MFA) and a 59% total yield of C11 biodiesel was obtained from 5-methylfurfural (5-MF). In addition, a H2O and air mediated free radical decarboxylation mechanism was proposed based on the detailed mechanistic studies. This strategy offers a green, low-cost and environmentally friendly approach to synthesize biodiesel precursors from biomass based platform molecules.
- Qin, Shengxiang,Li, Teng,Zhang, Man,Liu, Hongyu,Yang, Xin,Rong, Nianxin,Jiang, Jun,Wang, Yalin,Zhang, Hua,Yang, Weiran
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supporting information
p. 6326 - 6334
(2019/12/03)
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- Surfactant-assisted synthesis of mesoporous hafnium- imidazoledicarboxylic acid hybrids for highly efficient hydrogen transfer of biomass-derived carboxides
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Catalytic transfer hydrogenations of biomass-derived carbonyl compounds to produce corresponding alcohols are important pathway for biomass transformation. Herein, a facile route was developed to synthesize the surfactant-assisted heterogeneous acid-base bifunctional 4,5-imidazoledicarboxylic acid-hafnium hybrid catalyst (Hf-H3IDC-T) by hydrothermal self-assembly method. The as-prepared Hf-H3IDC-T was characterized by SEM and TEM, FT-IR spectra, N2 adsorption-desorption, X-ray diffraction patterns (XRD), X-ray photoelectron spectroscopy (XPS), Thermogravimetry analysis (TG), NH3/CO2-TPD, NMR, GC[sbnd]MS, ICP-OES and elemental analysis. Hf-H3IDC-T hybrid had mesoporous structure and acid-base couple sites. A quantitative yield (99.2%) of furfuryl alcohol (FFA) was obtained from furfural (FUR) over Hf-H3IDC-T using 2-propanol as the hydrogen source under mild conditions. It's found that the amino groups on the imidazole ring is beneficial to enhance the base sites of catalyst. Meanwhile, the addition of hexadecyl trimethyl ammonium bromide (CTAB) as template agents can improve the specific surface area of the catalyst. Dynamic analysis showed that the apparent activation energy of FUR reduction was as low as 50.89 kJ / mol. The as-prepared catalyst has good stability and can be recycled. Finally, the catalyst also has a good catalytic effect on the hydrogenation reaction of aldehydes and ketones of biomass-derived compounds.
- Dai, Fanglin,Zhou, Shenghui,Qin, Xingzhen,Liu, Detao,Qi, Haisong
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- Porous Zr–Thiophenedicarboxylate Hybrid for Catalytic Transfer Hydrogenation of Bio-Based Furfural to Furfuryl Alcohol
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Furfural (FAL) is one of the most important biomass-derived platform compounds. The catalytic transformation of FAL was investigated with three porous Zr–thiophenedicarboxylate hybrids for the production of furfuryl alcohol (FOL). Three Zr-based catalysts, including DUT-67(Zr), DUT-68(Zr) and DUT-69(Zr) were synthesized through a facile assembly of 2,5-thiophenedicarboxylate acid with ZrCl4 using the acetic acid as a modulator under hydrothermal conditions. These catalysts were also characterized using FT-IR, XRD, SEM, TEM, N2 adsorption–desorption, XPS and TG. The specific surface area of the DUT-69(Zr) is smaller than that of the DUT-68(Zr) and slightly larger than that of the DUT-67(Zr), but it has a relatively large pore volume and pore diameter. Although all three catalysts showed excellent catalytic activity towards the catalytic transfer hydrogenation of FAL into FOL, the DUT-69(Zr) material has slightly higher catalytic activity than the other two catalysts. Besides, considering the cost of catalyst preparation, the DUT-69(Zr) material was used as the optimal catalyst and studied in detail. A high FOL yield of 92.2% at 95.9% FAL conversion was achieved at 120?°C for 4?h over DUT-69(Zr). Meanwhile, the DUT-69(Zr) could be reused more than six times with a minor decrease in catalytic activity. Finally, a plausible mechanism for catalytic transfer hydrogenation of carbonyl compounds to produce corresponding alcohols was presented based on the results of the experiments and previous reports. Graphical Abstract: [Figure not available: see fulltext.].
- Wang, Tao,Hu, Aiyun,Xu, Guangzhi,Liu, Chen,Wang, Haijun,Xia, Yongmei
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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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p. 3063 - 3071
(2019/02/10)
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- Catalytic transfer hydrogenation of furfural into furfuryl alcohol over Ni–Fe-layered double hydroxide catalysts
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Layered double hydroxides (LDHs) and their derivatives have been reported to be widely used as heterogeneous catalysts in various reactions. Herein, Ni-Fe LDHs with the controlled Ni/Fe molar ratios (2:1, 3:1, 4:1) were synthesized via an easy hydrothermal method, which were used to catalyze the selective reduction of biomass-derived furfural into furfuryl alcohol using 2-propanol as a H-donor under autogenous pressure and characterized using FT-IR, XRD, TGA, BET, SEM, NH3-TPD, and CO2-TPD. It was found that the LDH with a Ni/Fe molar ratio of 3:1 demonstrated the best catalytic activity among the LDHs with different Ni/Fe molar ratios, which showed 97.0% conversion of furfural and 90.2% yield of furfuryl alcohol at 140°C for 5 hr. This was attributable to the synergistic effect of acidic sites and basic sites of the catalyst.
- Wang, Tao,Hu, Aiyun,Wang, Haijun,Xia, Yongmei
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p. 1610 - 1618
(2019/04/08)
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- Hierarchically constructed NiO with improved performance for catalytic transfer hydrogenation of biomass-derived aldehydes
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A 3D nano-/micrometer-scaled NiO material with urchin-like structure was prepared via a facile, green synthesis route, and served as a highly efficient and durable catalyst for catalytic transfer hydrogenation (CTH) of bio-based furfural (FF) to furfuryl alcohol (FAOL) using 2-propanol as H-donor and solvent. The as-prepared NiO possessed a good active-site accessibility owing to a high surface area and large amount of acid-base sites, resulting in high FF conversion of 97.3% with 94.2% FAOL yield at 120 °C and 3 h of reaction, which was a superior catalytic performance compared to commercial NiO nanoparticles. Besides, the excellent catalytic performance of the sea urchin-like NiO was validated for gram-scale FAOL synthesis, and recyclability test confirmed the catalyst to be reusable for multiple reaction runs without significant activity loss after intermediary calcination in air. Notably, the introduced catalytic system was also applicable to CTH of alternative bio-derived aldehydes.
- He, Jian,Nielsen, Monia Runge,Hansen, Thomas Willum,Yang, Song,Riisager, Anders
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p. 1289 - 1300
(2019/03/11)
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- Towards Improved Biorefinery Technologies: 5-Methylfurfural as a Versatile C6 Platform for Biofuels Development
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Low chemical stability and high oxygen content limit utilization of the bio-based platform chemical 5-(hydroxymethyl)furfural (HMF) in biofuels development. In this work, Lewis-acid-catalyzed conversion of renewable 6-deoxy sugars leading to formation of more stable 5-methylfurfural (MF) is carried out with high selectivity. Besides its higher stability, MF is a deoxygenated analogue of HMF with increased C/O ratio. A highly selective synthesis of the innovative liquid biofuel 2,5-dimethylfuran starting from MF under mild conditions is described. The superior synthetic utility of MF against HMF in benzoin and aldol condensation reactions leading to long-chain alkane precursors is demonstrated.
- Galkin, Konstantin I.,Ananikov, Valentine P.
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p. 185 - 189
(2018/12/05)
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- Tsuji-Wacker-Type Oxidation beyond Methyl Ketones: Reacting Unprotected Carbohydrate-Based Terminal Olefins through the "uemura System" to Hemiketals and α,β-Unsaturated Diketones
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Aerobic Pd(AcO)2/pyridine-catalyzed oxidation of unprotected carbohydrate-based terminal alkenes was studied. In accordance with previous reports, the initial reaction step gave methyl ketones. However, our substrates partially gave subsequent α,β-water elimination and alcohol oxidation to α,β-unsaturated 2,5-diketones. Upon increasing the pressure of O2, the reaction was shifted toward formation of α,β-epoxy-2-ketones. The reactions were stereoselective and gave up to quantitative conversions. However, isolated yields were substantially lower because of the complexity of the product mixtures.
- Runeberg, Patrik A.,Eklund, Patrik C.
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supporting information
p. 8145 - 8148
(2019/10/11)
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- A non-noble bimetallic alloy in the highly selective electrochemical synthesis of the biofuel 2,5-dimethylfuran from 5-hydroxymethylfurfural
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The conversion of HMF to DMF has received great attention due to its potential as a gasoline alternative. Electrosynthesis is a powerful green tool due to its significant advantages and provides an efficient and environmentally friendly route. In this work, the process uses water as the hydrogen source in the electro-catalytic reduction of 5-hydromethylfurfural (HMF) for the synthesis of 2,5-dimethyl-furan (DMF). The performance of a non-noble CuNi bimetallic electrode was investigated in the electro-catalytic hydrogenation of HMF. The electrodes prepared were characterized using XRD, SEM, XPS, and BET techniques. 88.0% faradaic efficiency of DMF and 91.1% conversion selectivity of DMF were achieved. The CuNi bimetallic electrode also displayed a good stability during the reduction of HMF to DMF.
- Zhang, Yan-Ru,Wang, Bing-Xin,Qin, Lei,Li, Qiang,Fan, Yong-Ming
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supporting information
p. 1108 - 1113
(2019/03/11)
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- Solvent-free mechanochemical oxidation and reduction of biomass-derived 5-hydroxymethyl furfural
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The simultaneous synthesis of 5-hydroxymethyl-2-furoic acid and 2,5-hydroxymethylfuran from biomass-derived 5-hydroxymethyl furan was developed using a solvent-free mechanochemical approach. The results obtained for the Cannizzaro disproportionation reaction show quantitative conversions of the starting materials with reaction times of only 5 min. Employing solvent-free conditions allows for a more sustainable synthetic approach that is reflected in an Efactor 7 times smaller than that in previous reports. Additionally, initial results of the use of a sacrificial reagent, with the same solvent-free mechanochemical approach, for the selective reduction and oxidation of HMF are presented.
- Chacón-Huete,Messina,Chen,Cuccia,Ottenwaelder,Forgione
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p. 5261 - 5265
(2018/12/05)
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- Catalytic Transfer Hydrogenation of Furfural to Furfuryl Alcohol with Recyclable Al–Zr@Fe Mixed Oxides
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A series of magnetic, acid/base bifunctional Al–Zr@Fe3O4 catalysts were successfully prepared by a facile coprecipitation method and utilized in the catalytic transfer hydrogenation (CTH) of furfural to furfuryl alcohol with 2-propanol as hydrogen source. The physicochemical properties and morphologies of the as-prepared catalysts were characterized by various techniques, including XRD analysis, N2 physisorption, vibrating sample magnetometry, thermal gravimetry analysis, X-ray fluorescence spectroscopy, NH3/CO2 temperature-programmed desorption, SEM, and TEM. The Al7Zr3@Fe3O4(1/1) catalyst with a Al3+/Zr4+/Fe3O4 molar ratio of 21:9:3 was found to exhibit a high furfuryl alcohol yield of 90.5 % in the CTH from furfural at 180 °C after 4 h with a comparatively low activation energy of 45.3 kJ mol?1, as calculated from the Arrhenius equation. Moreover, leaching and recyclability tests confirmed Al7Zr3@Fe3O4(1/1) to function as a heterogeneous catalyst that could be reused for at least five consecutive reaction runs without significant loss of catalytic activity after simple recovery by an external magnet. Notably, the catalyst proved also efficient for hydrogenation of other biomass-derived furanic aldehydes.
- He, Jian,Li, Hu,Riisager, Anders,Yang, Song
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p. 430 - 438
(2018/02/06)
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- Magnetic nickel ferrite nanoparticles as highly durable catalysts for catalytic transfer hydrogenation of bio-based aldehydes
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Magnetic nickel ferrite (NiFe2O4) nanoparticles were exploited as stable and easily separable heterogeneous catalysts for catalytic transfer hydrogenation (CTH) of furfural to furfuryl alcohol with 2-propanol as both the hydrogen source and the solvent providing 94% product yield at 180 °C after 6 h of reaction. The magnetic properties of the catalysts provided facile recovery using an external magnet after reaction allowing it to be reused in five reaction cycles without loss of catalytic performance. Importantly, the NiFe2O4 nanoparticles were also applicable to CTH of other alkenyl/allyl/aromatic aldehydes affording over 94% selectivity towards the targeted alcohol products, thus being attractive as highly universal catalysts for CTH of aldehydes.
- He, Jian,Yang, Song,Riisager, Anders
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p. 790 - 797
(2018/02/14)
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