141-53-7Relevant articles and documents
Lundsted, L. G.
, p. 323 - 324 (1949)
Iron-catalyzed hydrogenation of bicarbonates and carbon dioxide to formates
Zhu, Fengxiang,Zhu-Ge, Ling,Yang, Guangfu,Zhou, Shaolin
, p. 609 - 612 (2015)
The catalytic hydrogenation of carbon dioxide and bicarbonate to formate has been explored extensively. The vast majority of the known active catalyst systems are based on precious metals. Herein, we describe an effective, phosphine-free, airand moisture-
Catena-Poly[disodium [[diformato-tricopper(II)]-di-μ3- formato-tetra-μ2-formato]]: A new mode of bridging between binuclear and mononuclear formate-copper(II) units
Golobic, Amalija,Malekovic, Martina,Segedin, Primoz
, p. m102-m104 (2006)
The novel title polymeric copper(II) complex, {Na2[Cu 3-(CHO2)8]}n, consists of sodium cations and infinite anionic chains, in which neutral dinuclear [Cu 2(O2CH)4] moieties alternate with dianionic [Cu(O2CH)4]2- units. Both metal-containing moieties are located on crystallographic inversion centers. The syn-syn bridging configuration between the mononuclear and dinuclear components yields a structure that is significantly more dense than the structures previously reported for mononuclear-dinuclear copper(II) carboxylates with syn-anti or anti-anti bridging modes.
Mesoporous Silica-Encaged Ultrafine Bimetallic Nanocatalysts for CO2 Hydrogenation to Formates
Sun, Qiming,Fu, Xinpu,Si, Rui,Wang, Chi-Hwa,Yan, Ning
, p. 5093 - 5097 (2019)
CO2 hydrogenation to formic acid/formate has been recognized as a key reaction to realizing the CO2-mediated hydrogen energy cycle. Herein, ultrafine and well-dispersed Pd?CoO nanoparticles (～1.8 nm) were encapsulated within mesoporous silica nanospheres (MSNs) via a facile one-pot ligand-protected synthesis strategy. The MSN-encaged bimetallic nanocatalysts exhibit excellent catalytic activity and stability for the formate production from CO2 hydrogenation, showing high turnover frequency value up to 1824 h?1 at 373 K, which is among the top-level reported for heterogeneous catalysts.
A MOF-assisted phosphine free bifunctional iron complex for the hydrogenation of carbon dioxide, sodium bicarbonate and carbonate to formate
Coufourier, Sébastien,Gaillard, Sylvain,Clet, Guillaume,Serre, Christian,Daturi, Marco,Renaud, Jean-Luc
, p. 4977 - 4980 (2019)
The hydrogenation of carbon dioxide into formic acid (FA) with Earth-abundant metals is a vibrant research area because FA is an attractive molecule for hydrogen storage. We report a cyclopentadienyl iron tricarbonyl complex that provides up to 3000 turnover number for carbon dioxide hydrogenation when combined with a catalytic amount of the chromium dicarboxylate MOF MIL-53(Cr). To date, this is the highest turnover number reported in the presence of a phosphine-free iron complex.
PERFLUORO- AND POLYFLUOROCHLOROKETONES IN HALOFORM CLEAVAGE REACTION
Saloutina, L. V.,Zapevalov, A. Ya.,Kodess, M. I.,Kolenko, I. P.,German, L. S.
, p. 1023 - 1025 (1984)
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Nanoporous Ag-Sn derived from codeposited AgCl-SnO2 for the electrocatalytic reduction of CO2 with high formate selectivity
Wang, Xiaoyan,Xiao, Wei,Zhang, Jichen,Wang, Zhiyong,Jin, Xianbo
, p. 52 - 56 (2019)
Nanoporous Ag-Sn was prepared by direct electroreduction of a codeposited AgCl-SnO2 mixture in 0.1 M HCl, and evaluated as an electrode catalyst for the reduction of CO2 in 0.5 M KHCO3. A volcano-type correlation between selectivity for the formate product and the atomic ratio of Ag to Sn in the nanoporous catalysts was revealed. It was found that the bimetallic catalyst with a Ag:Sn ratio of 3:2, mainly composed of the Ag4Sn alloy, showed excellent catalytic performance for the conversion of CO2 to formate. This catalyst delivered a current of about 10 mA cm?2 with a high formate faradaic efficiency of about 85% at ?0.8 V vs. the reversible hydrogen electrode. Moreover, the catalytic activity remained reasonably stable during a 13.5-hour electrolysis.
Ligand assisted carbon dioxide activation and hydrogenation using molybdenum and tungsten amides
Chakraborty, Subrata,Blacque, Olivier,Berke, Heinz
, p. 6560 - 6570 (2015)
The hepta-coordinated isomeric M(NO)Cl3(PNHP) complexes {M = Mo, 1a(syn,anti); W, 1b(syn,anti), PNHP = (iPr2PCH2CH2)2NH, (HN atom of PNHP syn and anti to the NO ligand)} and the paramagnetic species M(NO)Cl2(PNHP) (M = Mo, 2a(syn,anti); W, 2b(syn,anti)) could be prepared via a new synthetic pathway. The pseudo trigonal bipyramidal amides M(NO)(CO)(PNP) {M = Mo, 3a; W, 3b; [PNP]- = [(iPr2PCH2CH2)2N]-} were reacted with CO2 at room temperature with CO2 approaching the MN double bond in the equatorial (CO,NO,N) plane trans to the NO ligand and forming the pseudo-octahedral cyclic carbamates M(NO)(CO)(PNP)(OCO) (M = Mo, 4a(trans); W = 4b(trans)). DFT calculations revealed that the approach to form the 4b(trans) isomer is kinetically determined. The amine hydrides M(NO)H(CO)(PNHP) {M = Mo, 5a(cis,trans); W, 5b(cis,trans)}, obtained by H2 addition to 3a,b, insert CO2 (2 bar) at room temperature into the M-H bond generating isomeric mixtures of the η1-formato complexes M(NO)(CO)(PNHP)(η1-OCHO), (M = Mo, 6a(cis,trans); M = W, 6b(cis,trans)). Closing the stoichiometric cycles for sodium formate formation the 6a,b(cis,trans) isomeric mixtures were reacted with 1 equiv. of Na[N(SiMe3)2] regenerating 3a,b. Attempts to turn the stoichiometric formate production into catalytic CO2 hydrogenation using 3a,b in the presence of various types of sterically congested bases furnished yields of formate salts of up to 4%. This journal is
Facile hydrogenation of bicarbonate to formate in aqueous medium by highly stable nickel-azatrane complex
Sivanesan, Dharmalingam,Seo, Bongkuk,Lim, Choong-Sun,Kim, Hyeon-Gook
, p. 121 - 128 (2020)
Molecular catalyst-based direct hydrogenation of bicarbonate to formate in aqueous medium is a challenging research topic for the H2 storage. Finding a green and effective method for the bicarbonate to formate conversion with non-precious metal-based catalyst is vital to the practical application. We report the direct hydrogenation of bicarbonate to formate using a water soluble nickel-azatrane complex. Catalysts 1–5, designed and synthesized, were screened for the hydrogenation of bicarbonate to formate in aqueous medium; the best TON of 121 was obtained for catalyst 4 at 120 °C (60 bar). Introduction of isopropyl (2) and methyl (3 and 4) groups in the coordination environment of the metal center enhances the production of formate. Further, the hydrogenation of bicarbonate with CO2 promoted the formate production for catalyst 4 with a TON of 92 (3 h). The use of green solvent and non-precious metal catalyst makes this catalytic method environmentally sustainable.
Efficient and Mild Carbon Dioxide Hydrogenation to Formate Catalyzed by Fe(II) Hydrido Carbonyl Complexes Bearing 2,6-(Diaminopyridyl)diphosphine Pincer Ligands
Bertini, Federica,Gorgas, Nikolaus,St?ger, Berthold,Peruzzini, Maurizio,Veiros, Luis F.,Kirchner, Karl,Gonsalvi, Luca
, p. 2889 - 2893 (2016)
Fe(II) hydrido carbonyl complexes supported by PNP pincer ligands based on the 2,6-diaminopyridine scaffold were found to promote the catalytic hydrogenation of CO2 and NaHCO3 to formate in protic solvents in the presence of bases, r
Conversion of CO2 from air into formate using amines and phosphorus-nitrogen PN3P-Ru(ii) pincer complexes
Guan, Chao,Pan, Yupeng,Ang, Eleanor Pei Ling,Hu, Jinsong,Yao, Changguang,Huang, Mei-Hui,Li, Huaifeng,Lai, Zhiping,Huang, Kuo-Wei
, p. 4201 - 4205 (2018)
Well-defined ruthenium(ii) PN3P pincer complexes were developed for the hydrogenation of carbon dioxide. Excellent product selectivity and catalytic activity with TOF (turnover frequency) and TON (turnover number) up to 13000 h-1 and 33000, respectively, in a THF/H2O biphasic system were achieved. Notably, effective conversion of carbon dioxide from air into formate was conducted in the presence of an amine, allowing easy product separation and catalyst recycling.
Cu AND Cu-BASED AMORPHOUS ALLOY ELECTRODES FOR ANODIC FORMALDEHYDE ELECTRO-OXIDATION
Machida, Ken-ichi,Enyo, Michio
, p. 75 - 78 (1985)
The electrodes of Cu and Cu-based amorphous alloys, a-Cu35Ti65 and a-Cu33Zr67, were very active for the HCHO electro-oxidation in alkaline solutions.The oxidation started at electrode potentials as low as 0.1 V (RHE) and the HF-treated amorphous alloys exhibited high current densities around 40 mA cm-2 (app.) at 0.2 V.
Direct Formation of Formic Acid from Carbon Dioxide and Dihydrogen using the 2>-Ph2P(CH2)4PPh2 Catalyst System
Graf, Elisabeth,Leitner, Walter
, p. 623 - 624 (1992)
Formic acid, isolable as sodium formate from the reaction mixture, is produced directly from hydrogen and carbon dioxide with yields up to 1150 moles per mole of rhodium using a homogeneous catalyst formed in situ from 2> and Ph2P(CH2)4PPh2; the precious metal is recovered during work-up in a catalytically active form.
Kinetic Analysis of Electroless Deposition of Copper
Schumacher, R.,Pesek, J. J.,Melroy, O. R.
, p. 4338 - 4342 (1985)
Kinetic data on elelctroless copper deposition from a formaldehyde/EDTA solution are analyzed and discussed in terms of a formal kinetic rate law.The derived rate equation shows first-order dependence on the methylene glycol anion and zeroth order on cupric ion.Kinetic preexponential factors evaluated from temperature dependencies of reaction rates indicate that the rate-determining step involves an adsorbed species.A primary kinetic isotope effect kH/kD = 5 upon substitution of deuterium for protium in formaldehyde indicates that cleavage of the carbon-hydrogen bond of the adsorbed methylene glycol anion is rate determining.
A Raman spectral study of the kinetics of deuterium-hydrogen exchange on the formate anion at elevated temperatures and pressures
Bartholomew, Richard J.,Stevenson, Wendy J.,Irish, Donald E.
, p. 1695 - 1701 (1996)
Raman spectra of the hydrogen-deuterium exchange reaction occurring in the HCOO--D2O system at elevated temperatures and pressures are reported. The rate constants at four temperatures have been measured and from these an activation energy of around 170 kJ mol-1 has been calculated. Exchange also takes place in the DCOO--H2O system. The rate constants at four temperatures indicate an activation energy of 93 kJ mol-1.
Carbon dioxide conversion into the reaction intermediate sodium formate for the synthesis of formic acid
Masood, Muhammad Hanan,Haleem, Noor,Shakeel, Iqra,Jamal, Yousuf
, p. 5165 - 5180 (2020)
Increased carbon dioxide (CO2) emissions from anthropogenic activities are a contributing factor to the growing global warming worldwide. The economical method to recover and effectively reuse CO2 is through adsorption and absorption. In this study, CO2 is absorbed into the solution of sodium hydroxide having various concentrations (0.01, 0.1, 0.5, 1.0, 3.0 and 5.0?N), and the impact of the solution pH on the various product formation was observed. The resultant products formed at different pH of the absorbing solution are sodium carbonate at pH 10, Trona at pH 9, and sodium hydrogen carbonate at pH 8. The products formed are confirmed through X-ray diffraction analysis. After pH optimization, the sodium hydrogen carbonate formed at pH 8 is converted into sodium formate through hydrogenation in the presence of nickel ferrite catalyst at 80 °C and atmospheric pressure. The sodium formate produced is then used as a precursor to synthesize formic acid upon simple reaction with sulfuric acid. A reaction % age yield of 79 ± 0.2% formic acid is noted. Condensed formic acid vapors are later analyzed, using a high performance?liquid chromatography for the qualitative analysis.
Kinetics and mechanisms of the catalytic reactions of formaldehyde with copper oxides and a copper ion complex in aqueous alkali
Demchenko,Belkin
, p. 26 - 33 (2011)
The kinetics of the autocatalytic reactions of formaldehyde with copper(II) and copper(I) oxides and with the Cu2+ ion of the copper EDTA complex, as well as formaldehyde disproportionation in the presence of copper metal, have been investigated in aqueous solutions of sodium hydroxide. Two likely reaction mechanisms are presented. The difference between these mechanisms does not alter the observed kinetics of the processes, whose rate is determined by their first, slow step, namely, the oxidation of the methylene glycol anion adsorbed on the copper surface into formic acid. In the slow step of the first mechanism, a hydride ion is abstracted from the methylene glycol anion and is transferred to copper. In the slow step of the second mechanism, the methylene glycol anion undergoes anodic oxidation, releasing a hydrogen atom and an electron. In the rapid steps of the first mechanism, the hydride ion undergoes anodic oxidation to hydrogen, the copper compound undergoes cathodic reduction to copper metal, and, simultaneously, the electron and hydrogen are transferred to a nonionized formaldehyde molecule to yield methanol. Mathematical models are suggested for the reactions. The effective rate constants and activation energies of the slow steps of the reactions have been determined. The effective rate constants of the noncatalytic reduction reactions of the copper compounds and the ratios of the rates of the rapid hydrogen and methanol formation reactions have been estimated.
Homogeneous hydrogenation of saturated bicarbonate slurry to formates using multiphase catalysis
Filonenko, Georgy A.,Pidko, Evgeny A.,Rebreyend, Christophe
supporting information, p. 8848 - 8852 (2021/11/23)
Formic acid and formate salts are key intermediates along the pathways for CO2utilization and hydrogen storage. Herein we report a highly efficient multiphase catalytic system utilizing a ruthenium PNP pincer catalyst for converting supersaturated bicarbonate solutions and slurries to aqueous formate solutions up to 12 M in molarity. The biphasic catalytic system delivers turnover frequencies up to 73?000 h?1and remains stable for up to 474?000 turnovers once reaction conditions are optimized.
