1633-56-3Relevant academic research and scientific papers
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).
Toward solar-driven photocatalytic CO2 reduction using water as an electron donor
Sato, Shunsuke,Arai, Takeo,Morikawa, Takeshi
, p. 5105 - 5113 (2015)
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.
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.
Surface Engineering of a Supported PdAg Catalyst for Hydrogenation of CO2 to Formic Acid: Elucidating the Active Pd Atoms in Alloy Nanoparticles
Mori, Kohsuke,Sano, Taiki,Kobayashi, Hisayoshi,Yamashita, Hiromi
, p. 8902 - 8909 (2018)
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.
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.
Highly efficient, selective, and durable photocatalytic system for CO2 reduction to formic acid
Tamaki, Yusuke,Koike, Kazuhide,Ishitani, Osamu
, p. 7213 - 7221 (2015)
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.
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.
Photochemical Reduction of Carbon Dioxide to Formic Acid using Ruthenium(II)-Based Catalysts and Visible Light
Rosas-Hernández, Alonso,Junge, Henrik,Beller, Matthias
, p. 3316 - 3321 (2015)
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.
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
Matrix Infrared Spectra and Photolysis and Pyrolysis of Isotopic Secondary Ozonides of Ethylene
Hawkins, Michael,Kohlmiller, Christopher K.,Andrews, Lester
, p. 3154 - 3166 (1982)
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.
