- Isolated Single-Atomic Ru Catalyst Bound on a Layered Double Hydroxide for Hydrogenation of CO2 to Formic Acid
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In order to achieve an economical CO2-mediated hydrogen energy cycle, the development of heterogeneous catalysts for CO2 hydrogenation to formic acid is an urgent and challenging task. In this study, a stable and well-defined single-site Ru catalyst on the surface of a layered double hydroxide (LDH) in a basic medium is proven to be efficient for selective hydrogenation of CO2 to formic acid under mild reaction conditions (2.0 MPa, 100°C). The electron-donating ability of triads of basic hydroxyl ligands with a particular location is crucial for an active electron-rich Ru center. There is a strong correlation between catalytic activity and adjustable CO2 adsorption capacity in the vicinity of the Ru center. Such electronic metal-support interactions and a CO2 concentration effect result in a significant positive influence on the catalytic activity. (Chemical Equation Presented).
- Mori, Kohsuke,Taga, Tomohisa,Yamashita, Hiromi
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- Toward solar-driven photocatalytic CO2 reduction using water as an electron donor
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Developing a system for the production of organic chemicals via CO2 reduction is an important area of research that has the potential to address global warming and fossil fuel consumption. In addition, CO2 reduction promotes carbon source recycling. Solar energy is the largest exploitable resource among renewable energy resources, providing more energy to Earth per hour than the total energy consumed by humans in 1 year. This report describes the advantages and disadvantages of the available CO2 reduction and H2O oxidation photocatalysts and the conjugation of photocatalytic CO2 reduction with H2O oxidation for the creation of an artificial photosynthesis system. In this system, CO2 photoreduction and H2O photooxidation proceeded simultaneously within one system under sunlight irradiation using a hybrid of semiconductors and molecular metal-complex catalysts.
- Sato, Shunsuke,Arai, Takeo,Morikawa, Takeshi
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- A photocatalyst-enzyme coupled artificial photosynthesis system for solar energy in production of formic acid from CO2
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The photocatalyst-enzyme coupled system for artificial photosynthesis process is one of the most promising methods of solar energy conversion for the synthesis of organic chemicals or fuel. Here we report the synthesis of a novel graphene-based visible light active photocatalyst which covalently bonded the chromophore, such as multianthraquinone substituted porphyrin with the chemically converted graphene as a photocatalyst of the artificial photosynthesis system for an efficient photosynthetic production of formic acid from CO2. The results not only show a benchmark example of the graphene-based material used as a photocatalyst in general artificial photosynthesis but also the benchmark example of the selective production system of solar chemicals/solar fuel directly from CO2.
- Yadav, Rajesh K.,Baeg, Jin-Ook,Oh, Gyu Hwan,Park, No-Joong,Kong, Ki-Jeong,Kim, Jinheung,Hwang, Dong Won,Biswas, Soumya K.
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- Surface Engineering of a Supported PdAg Catalyst for Hydrogenation of CO2 to Formic Acid: Elucidating the Active Pd Atoms in Alloy Nanoparticles
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The hydrogenation of carbon dioxide (CO2) to formic acid (FA; HCOOH), a renewable hydrogen storage material, is a promising means of realizing an economical CO2-mediated hydrogen energy cycle. The development of reliable heterogeneous catalysts is an urgent yet challenging task associated with such systems, although precise catalytic site design protocols are still lacking. In the present study, we demonstrate that PdAg alloy nanoparticles (NPs) supported on TiO2 promote the efficient selective hydrogenation of CO2 to give FA even under mild reaction conditions (2.0 MPa, 100 °C). Specimens made using surface engineering with atomic precision reveal a strong correlation between increased catalytic activity and decreased electron density of active Pd atoms resulting from a synergistic effect of alloying with Ag atoms. The isolated and electronically promoted surface-exposed Pd atoms in Pd@Ag alloy NPs exhibit a maximum turnover number of 14 839 based on the quantity of surface Pd atoms, which represents a more than 10-fold increase compared to the activity of monometallic Pd/TiO2. Kinetic and density functional theory (DFT) calculations show that the attack on the C atom in HCO3- by a dissociated H atom over an active Pd site is the rate-determining step during this reaction, and this step is boosted by PdAg alloy NPs having a low Pd/Ag ratio.
- Mori, Kohsuke,Sano, Taiki,Kobayashi, Hisayoshi,Yamashita, Hiromi
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- Silicone wastes as reducing agents for carbon dioxide transformation: Fluoride-catalyzed formic acid synthesis from CO2, H2O, and disilanes
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Disilanes were found to be reactive reducing agents for the transformation of carbon dioxide to formic acid in the presence of H2O. The reaction is catalyzed by fluoride salts such as tetrabutylammonium fluoride. Isotopic experiments revealed that the proposed reaction pathway includes Si-Si bond cleavage to afford hydrosilane followed by the hydrosilylation of CO2, and, finally, the hydrolysis of silyl formate.
- Motokura, Ken,Naijo, Masaki,Yamaguchi, Sho,Miyaji, Akimitsu,Baba, Toshihide
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- Highly efficient, selective, and durable photocatalytic system for CO2 reduction to formic acid
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We discovered an extremely suitable sacrificial electron donor, 1,3-dimethyl-2-(o-hydroxyphenyl)-2,3-dihydro-1H-benzo[d]imidazole, for the selective photocatalytic reduction of CO2 to formic acid using a Ru(ii)-Ru(ii) supramolecular photocatalyst. The efficiency, durability, and rate of photocatalysis are significantly increased (Pdbl;HCOOH = 0.46, TONHCOOH = 2766, TOFHCOOH = 44.9 min-1) in comparison with those using 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole or 1-benzyl-1,4-dihydronicotinamide.
- Tamaki, Yusuke,Koike, Kazuhide,Ishitani, Osamu
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- Gold(III)-induced oxidation of glycinet
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NMR investigations of isotopically-labelled glycine show that AuIII induces deamination and subsequent decarboxylation of the amino acid with formation of glyoxylic acid, NH4+, formic acid, CO2 and metallic gold.
- Zou, Juan,Guo, Zijian,Parkinson, John A.,Yu, Chen,Sadler, Peter J.
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- Photochemical Reduction of Carbon Dioxide to Formic Acid using Ruthenium(II)-Based Catalysts and Visible Light
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A photocatalytic system that consists of an Ir-based photosensitizer and a RuII bipyridine catalyst was developed for the selective reduction of CO2 to formic acid using triethanolamine as the electron donor. Catalyst turnover numbers up to 526 and a selectivity of 80 % towards formic acid were observed if the photocatalytic reaction was performed with [Ir(ppy)2(bpy)]PF6 (ppy=2-(pyridine-2-yl)benzene-1-ide, bpy=2,2′-bipyridine) as the photosensitizer and [Ru(bpy)2(Cl)(CO)]PF6 as the catalyst under visible-light irradiation (λ=400-700 nm). Interestingly, this photocatalytic system showed activity for the photoreduction of Na2CO3 to formic acid as well. The investigation of different ruthenium(II) catalysts revealed the positive influence of carbonyl ligands coordinated to the metal center. The enhancement of the catalytic activity is explained by a more favorable electron transfer from the photosensitizer to the catalyst, which is supported by the redox potentials of the complexes.
- Rosas-Hernández, Alonso,Junge, Henrik,Beller, Matthias
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- Visible-Light Photocatalytic Reduction of CO2 to Formic Acid with a Ru Catalyst Supported by N,N″-Bis(diphenylphosphino)-2,6-diaminopyridine Ligands
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Visible-light photocatalytic CO2 reduction is carried out by using a RuII complex supported by N,N′-bis(diphenylphosphino)-2,6-diaminopyridine (“PNP”) ligands, an unprecedented molecular architecture for this reaction that breaks the
- Hameed, Yasmeen,Rao, Gyandshwar Kumar,Ovens, Jeffrey S.,Gabidullin, Bulat,Richeson, Darrin
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- Matrix Infrared Spectra and Photolysis and Pyrolysis of Isotopic Secondary Ozonides of Ethylene
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The secondary ozonide of ethylene (SOZ) has been prepared in six isotopic modifications by reacting ozone and ethylene in CF3Cl near -150 deg C.The SOZ vibrations are characterized by 18O, 13C, and D isotopic shifts from matrix infrared spectra.Photolysis and pyrolysis of the SOZ is proposed to proceed via excited hydroxymethyl formate (HMF*).Under the conditions of pyrolysis, this activated species decomposes completely to formic acid and formaldehyde, but matrix photolysis of SOZ leads to quenching of HMF* and trapping of the ground-state molecule.An open chain trans and a hydrogen-bonded cis conformer of HMF are observed; photoexcitation decomposes the former to formic anhydride (FAN) and the latter to a specific formaldehyde-formic acid dimer (F/A).The dimer F/A is also observed following pyrolysis of SOZ and codeposition of formic acid and formaldehyde.The origin of CO2 produced on SOZ pyrolysis and of CO2, CO, and H2O produced on SOZ photolysis is discussed.A brief comparison of results from ethylene-ozone gas-phase studies with matrix photolysis of SOZ suggests that ground- or excited-state SOZ may play an important role in the gas-phase ethylene-ozone reaction, even though it is rarely detected.
- Hawkins, Michael,Kohlmiller, Christopher K.,Andrews, Lester
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- Semiconductive Amine-Functionalized Co(II)-MOF for Visible-Light-Driven Hydrogen Evolution and CO2 Reduction
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A Co-MOF, [Co3(HL)2·4DMF·4H2O] was simply synthesized through a one-pot solvothermal method. With the semiconductor nature, its band gap was determined to be 2.95 eV by the Kubelka-Munk method. It is the first trinuclear Co-MOF employed for photocatalytic hydrogen evolution and CO2 reduction with cobalt-oxygen clusters as catalytic nodes. Hydrogen evolution experiments indicated the activity was related to the photosensitizer, TEOA, solvents, and size of catalyst. After optimization, the best activity of H2 production was 1102 μmol/(g h) when catalyst was ground and then soaked in photosensitizer solution before photoreaction. To display the integrated design of Co-MOF, we used no additional photosensitizer and cocatalyst in the CO2 reduction system. When -NH2 was used for light absorption and a Co-O cluster was used as catalyst, Co-MOF exhibited an activity of 456.0 μmol/(g h). The photocatalytic mechanisms for hydrogen evolution and CO2 reduction were also proposed.
- Liao, Wei-Ming,Zhang, Jian-Hua,Wang, Zheng,Lu, Yu-Lin,Yin, Shao-Yun,Wang, Hai-Ping,Fan, Ya-Nan,Pan, Mei,Su, Cheng-Yong
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- Transition-Metal-Modified Vanadoborate Clusters as Stable and Efficient Photocatalysts for CO2Reduction
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Photocatalytic carbon dioxide reduction (CO2RR) is considered to be a promising sustainable and clean approach to solve environmental issues. Polyoxometalates (POMs), with advantages in fast, reversible, and stepwise multiple-electron transfer without changing their structures, have been promising catalysts in various redox reactions. However, their performance is often restricted by poor thermal or chemical stability. In this work, two transition-metal-modified vanadoborate clusters, [Co(en)2]6[V12B18O54(OH)6]·17H2O (V12B18-Co) and [Ni(en)2]6[V12B18O54(OH)6]·17H2O (V12B18-Ni), are reported for photocatalytic CO2 reduction. V12B18-Co and V12B18-Ni can preserve their structures to 200 and 250 °C, respectively, and remain stable in polar organic solvents and a wide range of pH solutions. Under visible-light irradiation, CO2 can be converted into syngas and HCOO- with V12B18-Co or V12B18-Ni as catalysts. The total amount of gaseous products and liquid products for V12B18-Co is up to 9.5 and 0.168 mmol g-1 h-1. Comparing with V12B18-Co, the yield of CO for V12B18-Ni declines by 1.8-fold, while that of HCOO- increases by 35%. The AQY of V12B18-Co and V12B18-Ni is 1.1% and 0.93%, respectively. These values are higher than most of the reported POM materials under similar conditions. The density functional theory (DFT) calculations illuminate the active site of CO2RR and the reduction mechanism. This work provides new insights into the design of stable, high-performance, and low-cost photocatalysts for CO2 reduction.
- Yu, Xiang,Zhao, Cong-Cong,Gu, Jian-Xia,Sun, Chun-Yi,Zheng, Hai-Yan,Yan, Li-Kai,Sun, Min,Wang, Xin-Long,Su, Zhong-Min
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- Sustainable production of formic acid by electrolytic reduction of gaseous carbon dioxide
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A tin (Sn) nanostructure has been applied to a gas diffusion electrode for the direct electro-reduction of carbon dioxide (CO2) in a zero-gap electrolytic cell. A Sn catalyst layer was evenly applied to a carbon substrate by a controlled spraying technique and the efficient catalytic conversion of gas-phase CO2 to formic acid (HCOOH) demonstrated. We observed that the overall mean faradaic efficiency towards HCOOH remained above 5.0% over the entire reduction time. In addition, due to its compact configuration and surroundings at near ambient conditions the approach described is promising in both modularity and scalability. Sustainable energy sources such as solar, wind, or geothermal electricity could be used as a power source to minimize the large-scale operating cost.
- Lee, Seunghwa,Ju, HyungKuk,Machunda, Revocatus,Uhm, Sunghyun,Lee, Jae Kwang,Lee, Hye Jin,Lee, Jaeyoung
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- Stable Heterometallic Cluster-Based Organic Framework Catalysts for Artificial Photosynthesis
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A series of stable heterometallic Fe2M cluster-based MOFs (NNU-31-M, M=Co, Ni, Zn) photocatalysts are presented. They can achieve the overall conversion of CO2 and H2O into HCOOH and O2 without the assistance of additional sacrificial agent and photosensitizer. The heterometallic cluster units and photosensitive ligands excited by visible light generate separated electrons and holes. Then, low-valent metal M accepts electrons to reduce CO2, and high-valent Fe uses holes to oxidize H2O. This is the first MOF photocatalyst system to finish artificial photosynthetic full reaction. It is noted that NNU-31-Zn exhibits the highest HCOOH yield of 26.3 μmol g?1 h?1 (selectivity of ca. 100 %). Furthermore, the DFT calculations based on crystal structures demonstrate the photocatalytic reaction mechanism. This work proposes a new strategy for how to design crystalline photocatalyst to realize artificial photosynthetic overall reaction.
- Dong, Long-Zhang,Zhang, Lei,Liu, Jiang,Huang, Qing,Lu, Meng,Ji, Wen-Xin,Lan, Ya-Qian
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- Photocatalytic CO2 reduction by a mixed metal (Zr/Ti), mixed ligand metal-organic framework under visible light irradiation
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Postsynthetic exchange (PSE) of Ti(iv) into a Zr(iv)-based MOF enabled photocatalytic CO2 reduction to HCOOH under visible light irradiation with the aid of BNAH and TEOA. Use of a mixed-ligand strategy enhanced the photocatalytic activity of the MOF by introducing new energy levels in the band structure of the MOF.
- Lee, Yeob,Kim, Sangjun,Kang, Jeung Ku,Cohen, Seth M.
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- Reductive transformation of CO2 with hydrosilanes catalyzed by simple fluoride and carbonate salts
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Hydrosilylation of CO2 catalyzed by simple fluoride and carbonate salts, such as CsF and K2CO3, is described. Total yields up to 87% for the formylated product were achieved. Mechanistic investigations indicate the reaction proceeds via the formation of an active formate species. This catalytic system was also found to be applicable to formamide synthesis from amines, CO2, and hydrosilane.
- Motokura, Ken,Naijo, Masaki,Yamaguchi, Sho,Miyaji, Akimitsu,Baba, Toshihide
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- CO2 Reduction Catalyzed by Nitrogenase: Pathways to Formate, Carbon Monoxide, and Methane
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The reduction of N2 to NH3 by Mo-dependent nitrogenase at its active-site metal cluster FeMo-cofactor utilizes reductive elimination of Fe-bound hydrides with obligatory loss of H2 to activate the enzyme for binding/reduction of N2. Earlier work showed that wild-type nitrogenase and a nitrogenase with amino acid substitutions in the MoFe protein near FeMo-cofactor can catalytically reduce CO2 by two or eight electrons/protons to carbon monoxide (CO) and methane (CH4) at low rates. Here, it is demonstrated that nitrogenase preferentially reduces CO2 by two electrons/protons to formate (HCOO-) at rates >10 times higher than rates of CO2 reduction to CO and CH4. Quantum mechanical calculations on the doubly reduced FeMo-cofactor with a Fe-bound hydride and S-bound proton (E2(2H) state) favor a direct reaction of CO2 with the hydride ( direct hydride transfer reaction pathway), with facile hydride transfer to CO2 yielding formate. In contrast, a significant barrier is observed for reaction of Fe-bound CO2 with the hydride ( associative reaction pathway), which leads to CO and CH4. Remarkably, in the direct hydride transfer pathway, the Fe-H behaves as a hydridic hydrogen, whereas in the associative pathway it acts as a protic hydrogen. MoFe proteins with amino acid substitutions near FeMo-cofactor (α-70Val→Ala, α-195His→Gln) are found to significantly alter the distribution of products between formate and CO/CH4.
- Khadka, Nimesh,Dean, Dennis R.,Smith, Dayle,Hoffman, Brian M.,Raugei, Simone,Seefeldt, Lance C.
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- Photocatalytic CO2 reduction using visible light by metal-monocatecholato species in a metal-organic framework
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Metal-organic frameworks (MOFs) with isolated metal-monocatecholato groups have been synthesized via postsynthetic exchange (PSE) for CO2 reduction photocatalyst under visible light irradiation in the presence of 1-benzyl-1,4-dihydronicotinamide and triethanolamine. The Cr-monocatecholato species are more efficient than the Ga-monocatecholato species.
- Lee, Yeob,Kim, Sangjun,Fei, Honghan,Kang, Jeung Ku,Cohen, Seth M.
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- Reductive transformation of CO2: Fluoride-catalyzed reactions with waste silicon-based reducing agents
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CO2 is one of the most important “renewable” carbon sources. To transform CO2 to useful organic compounds, we examined the reactivity of two model silicon-based “waste” materials, disilanes and metallic Si powder, as reducing agents. In these reactions, fluoride salts were found to be active catalysts: CO2 was converted to formic acid at atmospheric pressure in the presence of H2O as a proton source and the silicon-based reducing reagents. Based on in-situ NMR and kinetics analyses, a hydrosilane and penta-coordinate Si species are proposed as the reaction intermediate and active species, respectively.
- Motokura, Ken,Naijo, Masaki,Yamaguchi, Sho,Miyaji, Akimitsu,Baba, Toshihide
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- Highly efficient photoelectrocatalytic reduction of CO2 on the Ti3C2/g-C3N4 heterojunction with rich Ti3+ and pyri-N species
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Photoelectrocatalytic (PEC) reduction of CO2 into chemical fuels in water is a promising route to mitigate the energy crisis and global warming issues. Herein, Ti3C2/g-C3N4 (TCCN) heterojunctions were fabricated by in situ heat treatment and were applied to PEC CO2 reduction. These heterojunctions have narrow band gaps (2.3-2.6 eV) and rich Ti3+ species, which are beneficial to the absorption of solar light and the separation of electrons and holes. Besides this, the abundant pyri-N species in the TCCN heterojunctions can adsorb CO2 molecules, which is favourable for CO2 reduction. The deposition of nanometal particles can accelerate charge transfer. In a two-electrode system of M-TCCNBiVO4, the total formation rate of formate and methanol was as high as 50.2 μM cm-2 h-1 (25.1 mM h-1 g-1), which is tenfold that of pristine g-C3N4. The carbon source of the products was verified by a 13CO2 labeling experiment. These heterojunctions show outstanding PEC performance and stability and are promising candidates in the solar-to-fuel engineering field.
- Xu, Yanjie,Wang, Shuai,Yang, Jun,Han, Bo,Nie, Rong,Wang, Jixian,Dong, Yapeng,Yu, Xiaogang,Wang, Jianguo,Jing, Huanwang
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- Photocatalytic CO2 reduction in N,N-dimethylacetamide/water as an alternative solvent system
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N,N-Dimethylacetamide (DMA) was used for the first time as the reaction solvent in the photocatalytic reduction of CO2. DMA is highly stable against hydrolysis and does not produce formate even if it is hydrolyzed. We report the catalytic activities of [Ru(bpy)2(CO)2](PF 6)2 (bpy = 2,2′-bipyridine) in the presence of [Ru(bpy)3](PF6)2 as a photosensitizer and 1-benzyl-1,4-dihydronicotinamide (BNAH) as an electron donor in DMA/water. In the photochemical CO2 reduction, carbon monoxide (CO) and formate are catalytically produced, while dihydrogen (H2) from the reduction of water is scarcely evolved. We verified that BNAH is oxidized to afford BNA dimers during the photocatalyses in DMA/water. The plots of the production for the CO2 reduction versus the water content in DMA/water show that the 10 vol % water content gives the highest amount of the reduction products, whose reaction quantum yields (φ′) are determined to be 11.6% and 3.2% for CO and formate, respectively. The results are compared with those in the N,N-dimethylformamide (DMF)/water system, which has been typically used as the solvent system for the CO2 reduction.
- Kuramochi, Yusuke,Kamiya, Masaya,Ishida, Hitoshi
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- Thin-water-film-enhanced TiO2-based catalyst for CO2 hydrogenation to formic acid
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Carbon dioxide (CO2) hydrogenation can not only mitigate global warming, but also produce value-added chemicals. Herein, we report a novel three-phase catalytic system with an in situ generated and dynamically updated thin water film covered on the noble-metal-free TiO2-based catalyst for highly efficient CO2 hydrogenation, realizing a four-time enhancement compared with that with the catalyst suspended in water. The water film plays dual roles by directly participating in the reaction and removing the produced oxygenates (mainly formic acid) from the catalyst surface by dissolution. These results demonstrate an effective design for CO2 hydrogenation, which will open a new door to three-phase catalysis.
- Chen, Shaoqin,Fang, Siyuan,Hu, Yun Hang,Li, Zhangyang,Sun, Zongwei,Wang, Chunling
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supporting information
p. 787 - 790
(2022/02/01)
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- Operando systems chemistry reaction catalysis (OSCR-Cat) for visible light driven CO2conversion
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A systems chemistry approach is taken for compartmentalization of a continuous reaction medium (water and CO2) with induced creation of micro-heterogeneity in the medium by using a SOM (soft-oxometalate) catalyst. The first step involves compartmentalization of an assembled catalyst-photosensitizer duo catalysing the reduction of CO2into formic acid in two reaction spaces: the interior of the compartment and the exterior of the compartment. The exterior compartment obeys typical surface activity driven nanocatalysis principles where the perturbation of the catalyst surface area inversely varies with product yield. The second step of disassembly to disrupt the SOM-catalyst, induced by addition of a base, releases the interior reaction product with total disappearance of the catalyst system. The assembly-disassembly cascade demonstrates the application of systems chemistry principles in perturbation, compartmentalization, catalysis and release of products with well-defined externally controlled stimuli such as concentration, light, and pH. The OSCR-catalyst reported here is an attempt to emulate Golgi bodies in the context of cellular chemistry on a functional level.
- Das, Kousik,De, Ratnadip,Roy, Soumyajit,Verpoort, Francis
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p. 13355 - 13365
(2021/06/16)
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- Development of a panchromatic photosensitizer and its application to photocatalytic CO2reduction
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We designed and synthesized a heteroleptic osmium(ii) complex with two different tridentate ligands,Os.Oscan absorb the full wavelength range of visible light owing to S-T transitions, and this was supported by TD-DFT calculations. Excitation ofOsusing visible light of any wavelength generates the same lowest triplet metal-to-ligand charge-transfer excited state, the lifetime of which is relatively long (τem= 40 ns). Since excitedOscould be reductively quenched by 1,3-dimethyl-2-(o-hydroxyphenyl)-2,3-dihydro-1H-benzo[d]imidazole,Osdisplays high potential as a panchromatic photosensitizer. Using a combination ofOsand a ruthenium(ii) catalyst, CO2was photocatalytically reduced to HCOOHviairradiation with 725 nm light, and the turnover number reached 81; irradiation with light atλex> 770 nm also photocatalytically induced HCOOH formation. These results clearly indicate thatOscan function as a panchromatic redox photosensitizer.
- Irikura, Mari,Ishitani, Osamu,Tamaki, Yusuke
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p. 13888 - 13896
(2021/11/04)
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- MAGNESIUM NANOPARTICLES TO CAPTURE AND CONVERT CO2 TO METHANE, METHANOL OR FORMIC ACID OR OTHER FUELS OR CHEMICALS
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This invention discloses a process of conversion of Carbon Dioxide (CO2) into methane, methanol, formic acids or other fuels or chemicals, characterized by the use of Magnesium (Mg) nanoparticles (NPs) or bulk Mg for the conversion process, wherein Magnesium (Mg) chemisorbs and then activates the Carbon Dioxide (CO2) molecules by electron transfer to facilitate the reduction, using water as a hydrogen source. This conversion of Carbon Dioxide (CO2) is carried out at atmospheric pressure and at room temperature, and without any external energy source, such as thermal, light or electric energy source, or any sacrificial reagent or any co-catalysts. The reaction also facilitates in the production of high yield of Hydrogen.
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(2021/11/26)
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- Homogeneous electrocatalytic CO2 reduction by hexacarbonyl diiron dithiolate complex bearing hydroquinone
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Recently, the hexacarbonyl diiron dithiolate complex ((bdt)Fe2(CO)6, bdt = benzene-1,2-dithiolate) was reported for electrochemical CO2 reduction in CH3OH/CH3CN solution. To further simulate the [NiFe] carbon monoxide dehydrogenase (CODH) active center, another diiron dithiolate complex (1) with phenolic hydroxyl as second coordination sphere group was introduced to catalyze CO2 reduction electrochemically. Cyclic voltammetry measurements revealed that the phenolic hydroxyl group of 1 could lower the onset potential of electrochemical CO2 reduction. Under the best conditions, the maximum turnover frequency (TOFmax) of about 35 s?1 and an almost equal amount of HCOOH, CO, and H2 were obtained. Fourier transform infrared reflectance spectroelectrochemistry (IR-SEC) experiments illuminated the intermediate with terminal coordinated –COOH and the changes of intermolecular hydrogen bonds during the catalytic cycle.
- Cheng, Minglun,Fan, Fenglan,Liu, Jinyu,Wang, Lingjuan
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- Photocatalytic CO2 Reduction under Visible-Light Irradiation by Ruthenium CNC Pincer Complexes
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Photocatalytic CO2 reduction using a ruthenium photosensitizer, a sacrificial reagent 1,3-dimethyl-2-(o-hydroxyphenyl)-2,3-dihydro-1H-benzo[d]imidazole (BI(OH)H), and a ruthenium catalyst were carried out. The catalysts contain a pincer ligand, 2,6-bis(alkylimidazol-2-ylidene)pyridine (CNC) and a bipyridine (bpy). The photocatalytic reaction system resulted in HCOOH as a main product (selectivity 70–80 %), with a small amount of CO, and H2. Comparative experiments (a coordinated ligand (NCMe vs. CO) and substituents (tBu vs. Me) of the CNC ligand in the catalyst) were performed. The turnover number (TONHCOOH) of carbonyl-ligated catalysts are higher than those of acetonitrile-ligated catalysts, and the carbonyl catalyst with the smaller substituents (Me) reached TONHCOOH=5634 (24 h), which is the best performance among the experiments.
- Arikawa, Yasuhiro,Horiuchi, Shinnosuke,Miura, Yukari,Sakuda, Eri,Seto, Yudai,Tabata, Itoe,Tajiri, Hiroki,Umakoshi, Keisuke
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supporting information
(2020/04/29)
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- Photocatalytic CO2Reduction Using a Robust Multifunctional Iridium Complex toward the Selective Formation of Formic Acid
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A highly efficient tetradentate PNNP-type Ir photocatalyst, Mes-IrPCY2, was developed for the reduction of carbon dioxide. The photocatalyst furnished formic acid (HCO2H) with 87percent selectivity together with carbon monoxide to achieve a turnover number of 2560, which is the highest among CO2 reduction photocatalysts without an additional photosensitizer. Mes-IrPCY2 exhibited outstanding photocatalytic CO2 reduction activity in the presence of the sacrificial electron source 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH) in CO2-saturated N,N-dimethylacetamide under irradiation with visible light. The quantum yield was determined to be 49percent for the generation of HCO2H and CO. Electron paramagnetic resonance and UV-vis spectroscopy studies of Mes-IrPCY2 with a sacrificial electron donor revealed that the one-electron-reduced species is the key intermediate for the selective formation of HCO2H.
- Fukuzumi, Shunichi,Jung, Jieun,Kamada, Kenji,Morikawa, Takeshi,Saito, Susumu,Sato, Shunsuke,Sekizawa, Keita,Wakabayashi, Taku
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supporting information
p. 10261 - 10266
(2020/07/27)
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- Formation of Glyoxylic Acid in Interstellar Ices: A Key Entry Point for Prebiotic Chemistry
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With nearly 200 molecules detected in interstellar and circumstellar environments, the identification of the biologically relevant α-keto carboxylic acid, glyoxylic acid (HCOCOOH), is still elusive. Herein, the formation of glyoxylic acid via cosmic-ray driven, non-equilibrium chemistry in polar interstellar ices of carbon monoxide (CO) and water (H2O) at 5 K via barrierless recombination of formyl (HCO) and hydroxycarbonyl radicals (HOCO) is reported. In temperature-programmed desorption experiments, the subliming neutral molecules were selectively photoionized and identified based on the ionization energy and distinct mass-to-charge ratios in combination with isotopically labeled experiments exploiting reflectron time-of-flight mass spectrometry. These studies unravel a key reaction path to glyoxylic acid, an organic molecule formed in interstellar ices before subliming in star-forming regions like SgrB2(N), thus providing a critical entry point to prebiotic organic synthesis.
- Eckhardt, André K.,Bergantini, Alexandre,Singh, Santosh K.,Schreiner, Peter R.,Kaiser, Ralf I.
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supporting information
p. 5663 - 5667
(2019/03/29)
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- Base-Free Hydrogenation of Carbon Dioxide to Methyl Formate with a Molecular Ruthenium-Phosphine Catalyst
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Herein, a molecular ruthenium-phosphine catalyst system for the effective base-free methyl formate production from carbon dioxide is described. In detail, the novel [Ru(N-triphosCy)(tmm)] complex, bearing sterically demanding cyclohexyl groups in the triphos-ligand structure, enabled in combination with the Lewis acid Al(OTf)3 the selective transformation of carbon dioxide to methyl formate with unprecedented activity. From a mechanistic perspective, in the initial step formic acid is formed, undergoing a consecutive Lewis acid promoted esterification with methanol to methyl formate. This selective transformation with carbon dioxide paves the way to versatile processes for important C1 building blocks.
- Westhues, Niklas,Belleflamme, Maurice,Klankermayer, Jürgen
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p. 5269 - 5274
(2019/07/12)
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- Light-driven carbon dioxide reduction coupled with conversion of acetylenic group to ketone by a functional Janus catalyst based on keplerate {Mo132}
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Catalysts enabling CO2 reduction coupled with another organic reaction are rare. In this study, we report such a catalyst keplerate {Mo132}, which catalyses photochemical carbon dioxide reduction to formic acid coupled with organic transformation, i.e., hydration of phenylacetylene to acetophenone in visible light. It initially oxidizes water and injects the reducing equivalents for reduction of carbon dioxide at the same time, converting acetylenic group to ketone. Our designed redox Janus catalyst provides an inexpensive pathway to achieve carbon dioxide reduction as well as conversion of phenylacetylene to acetophenone, which is an industrially important precursor.
- Lodh, Joyeeta,Mallick, Apabrita,Roy, Soumyajit
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p. 20844 - 20851
(2018/11/20)
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- Successive C1-C2 bond cleavage: The mechanism of vanadium(v)-catalyzed aerobic oxidation of d-glucose to formic acid in aqueous solution
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Vanadium(v)-catalyzed aerobic oxidation in aqueous solution shows high selectivity in the field of C-C bond cleavage of carbohydrates for chemicals with less carbon atoms. However, the pathway of C-C bond cleavage from carbohydrates and the conversion mechanism are unclear. In this work, we studied the pathway and the mechanism of d-glucose oxidation to formic acid (FA) in NaVO3-H2SO4 aqueous solution using isotope-labeled glucoses as substrates. d-Glucose is first transformed to FA and d-arabinose via C1-C2 bond cleavage. d-Arabinose undergoes similar C1-C2 bond cleavage to form FA and the corresponding d-erythrose, which can be further degraded by C1-C2 bond cleavage. Dimerization and aldol condensation between carbohydrates can also proceed to make the reaction a much more complicated mixture. However, the fundamental reaction, C1-C2 bond cleavage, can drive all the intermediates to form the common product FA. Based on the detected intermediates, isotope-labelling experiments, the kinetic isotope effect study and kinetic analysis, this mechanism is proposed. d-Glucose first reacts with a vanadium(v) species to form a five-membered-ring complex. Then, electron transfer occurs and the C1-C2 bond weakens, followed by C1-C2 bond cleavage (with no C-H bond cleavage), to generate the H3COO-vanadium(iv) complex and d-arabinose. FA is generated from H3COO that is oxidized by another vanadium(v) species. The reduced vanadium species is oxidized by O2 to regenerate to its oxidation state. This finding will provide a deeper insight into the process of C-C bond cleavage of carbohydrates for chemical synthesis and provide guidance for screening and synthesizing new highly-efficient catalyst systems for FA production.
- Niu, Muge,Hou, Yucui,Wu, Weize,Ren, Shuhang,Yang, Ru
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p. 17942 - 17951
(2018/07/14)
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- METHOD FOR PRODUCING METHANOL FROM CARBON DIOXIDE AND HYDROGEN GAS IN HOMOGENEOUSLY CATALYZED REACTIONS AND IN AN AQUEOUS MEDIUM
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The invention relates to a method for producing methanol from hydrogen and carbon dioxide gas in homogeneously catalyzed reactions, composed of the carbon dioxide hydrogenation reaction to formic acid and the formic acid disproportionation reaction into methanol, both being conducted in aqueous media at mild conditions (temperature in the range from 20 to 100 °C, total hydrogen and carbon dioxide gas pressure up to 100 bar).
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Page/Page column 15
(2017/07/12)
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- Carbon Dioxide to Methanol: The Aqueous Catalytic Way at Room Temperature
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Carbon dioxide may constitute a source of chemicals and fuels if efficient and renewable processes are developed that directly utilize it as feedstock. Two of its reduction products are formic acid and methanol, which have also been proposed as liquid organic chemical carriers in sustainable hydrogen storage. Here we report that both the hydrogenation of carbon dioxide to formic acid and the disproportionation of formic acid into methanol can be realized at ambient temperature and in aqueous, acidic solution, with an iridium catalyst. The formic acid yield is maximized in water without additives, while acidification results in complete (98 %) and selective (96 %) formic acid disproportionation into methanol. These promising features in combination with the low reaction temperatures and the absence of organic solvents and additives are relevant for a sustainable hydrogen/methanol economy.
- Sordakis, Katerina,Tsurusaki, Akihiro,Iguchi, Masayuki,Kawanami, Hajime,Himeda, Yuichiro,Laurenczy, Gábor
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supporting information
p. 15605 - 15608
(2016/10/25)
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- SELECTIVE CARBON-CARBON BOND CLEAVAGE BY EARTH ABUNDANT VANADIUM COMPOUNDS UNDER VISIBLE LIGHT PHOTOCATALYSIS
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Provided herein a vanadium(V) complex of formula I, where R1 to R8 are as defined herein. Also provided herein are reactions making use of the vanadium(V) complex of formula I, such as selective sp3-sp3 carbon-carbon bond cleavage under visible light photocatalysis and photodegradation of lignin.
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Page/Page column 48
(2016/09/22)
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- Mechanism of Br?nsted acid-catalyzed glucose dehydration
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We present the first DFT-based microkinetic model for the Br?nsted acid-catalyzed conversion of glucose to 5-hydroxylmethylfurfural (HMF), levulinic acid (LA), and formic acid (FA) and perform kinetic and isotopic tracing NMR spectroscopy mainly at low conversions. We reveal that glucose dehydrates through a cyclic path. Our modeling results are in excellent agreement with kinetic data and indicate that the rate-limiting step is the first dehydration of protonated glucose and that the majority of glucose is consumed through the HMF intermediate. We introduce a combination of 1) automatic mechanism generation with isotopic tracing experiments and 2) elementary reaction flux analysis of important paths with NMR spectroscopy and kinetic experiments to assess mechanisms. We find that the excess formic acid, which appears at high temperatures and glucose conversions, originates from retro-aldol chemistry that involves the C6 carbon atom of glucose.
- Yang, Liu,Tsilomelekis, George,Caratzoulas, Stavros,Vlachos, Dionisios G.
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p. 1334 - 1341
(2015/05/05)
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- Selective photocatalytic C-C bond cleavage under ambient conditions with earth abundant vanadium complexes
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Selective C-C bond cleavage under ambient conditions is a challenging chemical transformation that can be a valuable tool for organic syntheses and macromolecular disassembly. Herein, we show that base metal vanadium photocatalysts can harvest visible light to effect the chemoselective C-C bond cleavage of lignin model compounds under ambient conditions. Lignin, a major aromatic constituent of non-food biomass, is an inexpensive, accessible source of fine chemical feedstocks such as phenols and aryl ethers. However, existing lignin degradation technologies are harsh and indiscriminately degrade valuable functional groups to produce intractable mixtures. The selective, photocatalytic depolymerization of lignin remains underexplored. In the course of our studies on lignin model compounds, we have uncovered a new C-C activation reaction that takes place under exceptionally mild conditions with high conversions. We present our fundamental studies on representative lignin model compounds, with the aim of expanding and generalizing the substrate scope in the future. Visible light is employed in the presence of earth-abundant vanadium oxo catalysts under ambient conditions. Selective C-C bond cleavage leads to valuable and functionally rich fine chemicals such as substituted aryl aldehydes and formates. Isotope labeling experiments, product analyses, and intermediate radical trapping, together with density functional theory studies, suggest a unique pathway that involves a photogenerated T1 state during the C-C bond cleavage reactions. Our study demonstrates a sustainable approach to harvest sunlight for an unusual, selective bond activation, which can potentially be applied in organic transformations and biomass valorization.
- Gazi, Sarifuddin,Hung Ng, Wilson Kwok,Ganguly, Rakesh,Putra Moeljadi, Adhitya Mangala,Hirao, Hajime,Soo, Han Sen
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p. 7130 - 7142
(2015/11/24)
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- Selective reduction of CO2 with silanes over platinum nanoparticles immobilised on a polymeric monolithic support under ambient conditions
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Here, we demonstrate the use of Pt0 nanoparticles immobilised on a polymeric monolithic support as a ligand-free heterogeneous catalytic system for the reduction of 13CO2 at room temperature and atmospheric pressure. The described system effectively reduces 13CO2 with dihydrosilanes as the hydrogen source to yield a mixture of silylformates, silylacetals and methoxysilanes, which upon further hydrolysis with D2O, produces their respective C1-type products, that is H13COOD, 13CH2(OD)2 and 13CH3OD. If a monohydrosilane was used as the hydrogen source, a selective reduction of 13CO2 to a product mixture of only silylformates was observed. Addition of diethylamine to this reaction mixture results in the formation of H13COOH and Et 2N13CHO. This robust catalytic system is not only maintenance-free and simple to handle, as compared with organometallic and organocatalyst systems, but also shows 3- to 11-fold better catalytic activity and exhibits higher turnover numbers (TONs) up to 21 900 (activity=6.22 kg CO 2 gPt-1 bar-1).
- Taori, Vijay P.,Bandari, Rajendar,Buchmeiser, Michael R.
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supporting information
p. 3292 - 3296
(2014/04/03)
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- Artificial Z-scheme constructed with a supramolecular metal complex and semiconductor for the photocatalytic reduction of CO2
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A hybrid for the visible-light-driven photocatalytic reduction of CO 2 using methanol as a reducing agent was developed by combining two different types of photocatalysts: a Ru(II) dinuclear complex (RuBLRu′) used for CO2 reduction is adsorbed onto Ag-loaded TaON (Ag/TaON) for methanol oxidation. Isotope experiments clearly showed that this hybrid photocatalyst mainly produced HCOOH (TN = 41 for 9 h irradiation) from CO 2 and HCHO from methanol. Therefore, it converted light energy into chemical energy (ΔG = +83.0 kJ/mol). Photocatalytic reaction proceeds by the stepwise excitation of Ag/TaON and the Ru dinuclear complex on Ag/TaON, similar to the photosynthesis Z-scheme.
- Sekizawa, Keita,Maeda, Kazuhiko,Domen, Kazunari,Koike, Kazuhide,Ishitani, Osamu
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supporting information
p. 4596 - 4599
(2013/05/23)
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- Partial oxidation of ethane to oxygenates using Fe- and Cu-containing ZSM-5
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Iron and copper containing ZSM-5 catalysts are effective for the partial oxidation of ethane with hydrogen peroxide giving combined oxygenate selectivities and productivities of up to 95.2% and 65 mol kgcat -1 h-1, respectively. High conversion of ethane (ca. 56%) to acetic acid (ca. 70% selectivity) can be observed. Detailed studies of this catalytic system reveal a complex reaction network in which the oxidation of ethane gives a range of C2 oxygenates, with sequential C-C bond cleavage generating C1 products. We demonstrate that ethene is also formed and can be subsequently oxidized. Ethanol can be directly produced from ethane, and does not originate from the decomposition of its corresponding alkylperoxy species, ethyl hydroperoxide. In contrast to our previously proposed mechanism for methane oxidation over similar zeolite catalysts, the mechanism of ethane oxidation involves carbon-based radicals, which lead to the high conversions we observe.
- Forde, Michael M.,Armstrong, Robert D.,Hammond, Ceri,He, Qian,Jenkins, Robert L.,Kondrat, Simon A.,Dimitratos, Nikolaos,Lopez-Sanchez, Jose Antonio,Taylor, Stuart H.,Willock, David,Kiely, Christopher J.,Hutchings, Graham John
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supporting information
p. 11087 - 11099
(2013/08/23)
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- Trapping formaldehyde in the homogeneous catalytic reduction of carbon dioxide
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Formaldehyde detectives: Evidence for the production of formaldehyde during a ruthenium-catalyzed CO2 reduction process, and for its involvement in the formation of the resulting C2 compound, is disclosed. Ultimately, formaldehyde can be recovered by methanol trapping. HBPin=pinacolborane. Copyright
- Bontemps, Sebastien,Sabo-Etienne, Sylviane
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supporting information
p. 10253 - 10255
(2013/10/21)
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- Direct conversion of glycerol into formic acid via water stable Pd(II) catalyzed oxidative carbon-carbon bond cleavage
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Using our tridentate NHC-amidate-alkoxide Pd(II) complex, we developed a catalytic method for oxidative C-C bond cleavage of glycerol. The glycerol was degraded exclusively to formic acid and CO2. Two possible degradation pathways were proposed through 13C labeled studies.
- Pullanikat, Prasanna,Lee, Joo Ho,Yoo, Kyung Soo,Jung, Kyung Woon
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supporting information
p. 4463 - 4466
(2013/07/26)
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- A polymeric-semiconductor-metal-complex hybrid photocatalyst for visible-light CO2 reduction
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A polymeric carbon nitride semiconductor is demonstrated to photocatalyse CO2 reduction to formic acid under visible light (λ > 400 nm) with a high turnover number (>200 for 20 hours) and selectivity (>80%), when coupled with a molecular ruthenium complex as a catalyst. The Royal Society of Chemistry 2013.
- Maeda, Kazuhiko,Sekizawa, Keita,Ishitani, Osamu
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supporting information
p. 10127 - 10129
(2013/10/22)
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- Copper-catalyzed formic acid synthesis from CO2 with hydrosilanes and H2O
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A copper-catalyzed formic acid synthesis from CO2 with hydrosilanes has been accomplished. The Cu(OAc)2?H 2O-1,2-bis(diphenylphosphino)benzene system is highly effective for the formic acid synthesis under 1 atm of CO2. The TON value approached 8100 in 6 h. The reaction pathway was revealed by in situ NMR analysis and isotopic experiments.
- Motokura, Ken,Kashiwame, Daiki,Miyaji, Akimitsu,Baba, Toshihide
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experimental part
p. 2642 - 2645
(2012/08/13)
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- Carbon nanoparticles as visible-light photocatalysts for efficient CO 2 conversion and beyond
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Increasing atmospheric CO2 levels have generated much concern, driving the ongoing carbon sequestration effort. A compelling CO2 sequestration option is its photocatalytic conversion to hydrocarbons, for which the use of solar irradiation represents an ultimate solution. Here we report a new strategy of using surface-functionalized small carbon nanoparticles to harvest visible photons for subsequent charge separation on the particle surface in order to drive the efficient photocatalytic process. The aqueous solubility of the catalysts enables photoreduction under more desirable homogeneous reaction conditions. Beyond CO2 conversion, the nanoscale carbon-based photocatalysts are also useful for the photogeneration of H 2 from water under similar conditions.
- Cao, Li,Sahu, Sushant,Anilkumar, Parambath,Bunker, Christopher E.,Xu, Juan,Fernando, K. A. Shiral,Wang, Ping,Guliants, Elena A.,Tackett, Kenneth N.,Sun, Ya-Ping
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body text
p. 4754 - 4757
(2011/06/21)
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- An unusual carbon-carbon bond cleavage reaction during phosphinothricin biosynthesis
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Natural products containing phosphorus-carbon bonds have found widespread use in medicine and agriculture. One such compound, phosphinothricin tripeptide, contains the unusual amino acid phosphinothricin attached to two alanine residues. Synthetic phosphi
- Cicchillo, Robert M.,Zhang, Houjin,Blodgett, Joshua A. V.,Whitteck, John T.,Li, Gongyong,Nair, Satish K.,Van Der Donk, Wilfred A.,Metcalf, William W.
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experimental part
p. 871 - 874
(2010/06/14)
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- Bio-inspired oxidation of methane in water catalyzed by N-bridged diiron phthalocyanine complex
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A stable μ-nitrido diiron phthalocyanine activates H2O 2 to oxidize CH4 in water at 25-60 °C to methanol, formaldehyde and formic acid as evidenced using 13C and 18O labelling. The Royal Society of Chemistry.
- Sorokin, Alexander B.,Kudrik, Evgeny V.,Bouchu, Denis
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supporting information; body text
p. 2562 - 2564
(2009/02/04)
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- Synthesis and Characterization of Chiral Oxazolidine-2-selones: A General One-Step Procedure from Readily Available Oxazolines
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The synthesis of a wide variety of chiral oxazolidine-2-selones from readily available 2-oxazolines has been accomplished in one step with yields ranging from 82 to 98percent.A mechanistic investigation of the formation of these selones has indicated the presence of intermediate anions which have been characterized by 13C and 77Se NMR spectroscopy.X-ray crystallographic data suggest the chiral selones exists as dimeric pairs or networks linked by unusual selenium hydrogen bonds.These chiral reagents exhibit extraordinary 77Se chemical shift sensitivity and are useful for the detection and quantitation of chirality at remotely disposed chiral centers.
- Peng, Jie,Barr, Mary E.,Ashburn, David A.,Odom, Jerome D.,Dunlap, R. Bruce,Silks, Louis A.
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p. 4977 - 4987
(2007/10/02)
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- REACTION BETWEEN NO3 AND CH2O IN AIR: A DETERMINATION OF THE RATE CONSTANT AT 295+/-2 K.
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The reaction between NO3 and CH2O was studied in a 450-L glass/Teflon chamber by using FT-IR spectroscopy as the analytical technique.NO3 was obtained in equilibrium with N2O5 introduced from evaporation of the solid phase into the cell or generated in the cell itself by reacting NO2 with O3.Experiments were performed in both cases at 295+/-2 K and 740 Torr in purified air. (13)CH2O was used to avoid spurious effects on the measured CO; (13)C(18)O was introduced to estimate the OH radical concentration in the system from the buildup of the oxidation product (16)O(13)C(18)O. (13)CH2O, (13)C(16)O, N2O5, O3, NO2, and H(13)COOH time-dependent concentrations were measured and the data fitted on the basis of a model involving 31 reactions, with the aid of the FACSIMILE computer program.A rate constant for the reaction NO3+CH2O equal to (5.4+/-1.1)*1E-16 cm3 molecule-1 s-1, at 295+/-2 K and 740 Torr, has been obtained assuming for the reactions N2O5NO3+NO2 an equilibrium constant equal to 5.3*1E10 molecules cm-3.Significant differences have been found between the measured concentrations of OH and HCOOH with respect to those predicted by the model.In the framework of this study, the absolute strength of the ν6 band of H(12)COOH (1045-1150 cm-1) has been measured equal to (3.48+/-0.5)*1E-17 cm molecule-1.
- Hjorth, J,Ottobrini, G.,Restelli, G.
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p. 2669 - 2672
(2007/10/02)
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- NMR VISUALIZATION OF FREE ASPARAGINE IN POTATO TISSUE USING ADDUCT FORMATION WITH FORMALDEHYDE
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The free asparagine in potato (Solanum tuberosum) tuber tissue has been observed by 13C NMR, using labelled formaldehyde as a marker; formaldehyde-asparagine adduct formation is specific and leads to characteristic 13C resonances.In addition, metabolism of formaldehyde to methanol and formate by potato tissue has been observed by 13C and deuterium NMR.Metabolism of formaldehyde-d2 leads to 3 : 1 mixture of CD3OH and CD2HOH.
- Mason, Ralph P.,Sanders, Jeremy K. M.,Gidley, Michael J.
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p. 1567 - 1572
(2007/10/02)
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