1633-56-3Relevant articles and documents
Isolated Single-Atomic Ru Catalyst Bound on a Layered Double Hydroxide for Hydrogenation of CO2 to Formic Acid
Mori, Kohsuke,Taga, Tomohisa,Yamashita, Hiromi
, p. 3147 - 3151 (2017)
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).
A photocatalyst-enzyme coupled artificial photosynthesis system for solar energy in production of formic acid 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.
, p. 11455 - 11461 (2012)
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.
Silicone wastes as reducing agents for carbon dioxide transformation: Fluoride-catalyzed formic acid synthesis from CO2, H2O, and disilanes
Motokura, Ken,Naijo, Masaki,Yamaguchi, Sho,Miyaji, Akimitsu,Baba, Toshihide
, p. 1464 - 1466 (2015)
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.
Gold(III)-induced oxidation of glycinet
Zou, Juan,Guo, Zijian,Parkinson, John A.,Yu, Chen,Sadler, Peter J.
, p. 1359 - 1360 (1999)
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.
Visible-Light Photocatalytic Reduction of CO2 to Formic Acid with a Ru Catalyst Supported by N,N″-Bis(diphenylphosphino)-2,6-diaminopyridine Ligands
Hameed, Yasmeen,Rao, Gyandshwar Kumar,Ovens, Jeffrey S.,Gabidullin, Bulat,Richeson, Darrin
, p. 3453 - 3457 (2019)
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
Semiconductive Amine-Functionalized Co(II)-MOF for Visible-Light-Driven Hydrogen Evolution and CO2 Reduction
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
, p. 11436 - 11442 (2018)
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.
Sustainable production of formic acid by electrolytic reduction of gaseous carbon dioxide
Lee, Seunghwa,Ju, HyungKuk,Machunda, Revocatus,Uhm, Sunghyun,Lee, Jae Kwang,Lee, Hye Jin,Lee, Jaeyoung
, p. 3029 - 3034 (2015)
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.
Photocatalytic CO2 reduction by a mixed metal (Zr/Ti), mixed ligand metal-organic framework under visible light irradiation
Lee, Yeob,Kim, Sangjun,Kang, Jeung Ku,Cohen, Seth M.
, p. 5735 - 5738 (2015)
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.
CO2 Reduction Catalyzed by Nitrogenase: Pathways to Formate, Carbon Monoxide, and Methane
Khadka, Nimesh,Dean, Dennis R.,Smith, Dayle,Hoffman, Brian M.,Raugei, Simone,Seefeldt, Lance C.
, p. 8321 - 8330 (2016)
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.
Reductive transformation of CO2: Fluoride-catalyzed reactions with waste silicon-based reducing agents
Motokura, Ken,Naijo, Masaki,Yamaguchi, Sho,Miyaji, Akimitsu,Baba, Toshihide
, p. 434 - 439 (2017)
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.
Photocatalytic CO2 reduction in N,N-dimethylacetamide/water as an alternative solvent system
Kuramochi, Yusuke,Kamiya, Masaya,Ishida, Hitoshi
, p. 3326 - 3332 (2014)
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.
Operando systems chemistry reaction catalysis (OSCR-Cat) for visible light driven CO2conversion
Das, Kousik,De, Ratnadip,Roy, Soumyajit,Verpoort, Francis
, p. 13355 - 13365 (2021/06/16)
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.
Homogeneous electrocatalytic CO2 reduction by hexacarbonyl diiron dithiolate complex bearing hydroquinone
Cheng, Minglun,Fan, Fenglan,Liu, Jinyu,Wang, Lingjuan
, (2021/10/12)
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.
