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Title: CO 2 hydrogenation to formate and methanol as an alternative to photo- and electrochemical CO 2 reduction

Abstract

In this study, carbon dioxide is one of the end products of combustion, and is not a benign component of the atmosphere. The concentration of CO 2 in the atmosphere has reached unprecedented levels and continues to increase owing to an escalating rate of fossil fuel combustion, causing concern about climate change and rising sea levels. In view of the inevitable depletion of fossil fuels, a possible solution to this problem is the recycling of carbon dioxide, possibly captured at its point of generation, to fuels. Researchers in this field are using solar energy for CO 2 activation and utilization in several ways: (i) so-called artificial photosynthesis using photo-induced electrons; (ii) bulk electrolysis of a CO 2 saturated solution using electricity produced by photovoltaics; (iii) CO 2 hydrogenation using solar-produced H 2; and (iv) the thermochemical reaction of metal oxides at extremely high temperature reached by solar collectors. Since the thermodynamics of CO 2 at high temperature (> 1000 ºC) are quite different from those near room temperature, only chemistry below 200 ºC is discussed in this review.

Authors:
 [1];  [2];  [3];  [3];  [3]
+ Show Author Affiliations
  1. Dalian Univ., Panjin (China)
  2. National Inst. of Advanced Industrial Science and Technology, Ibaraki (Japan); JST, ACT-C, Saitama (Japan)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1214520
Report Number(s):
BNL-108316-2015-JA
Journal ID: ISSN 0009-2665; R&D Project: CO026; KC0304030
Grant/Contract Number:
SC00112704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemical Reviews
Additional Journal Information:
Journal Name: Chemical Reviews; Journal ID: ISSN 0009-2665
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wang, Wan -Hui, Himeda, Yuichiro, Muckerman, James T., Manbeck, Gerald F., and Fujita, Etsuko. CO2 hydrogenation to formate and methanol as an alternative to photo- and electrochemical CO2 reduction. United States: N. p., 2015. Web. doi:10.1021/acs.chemrev.5b00197.
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Wang, Wan -Hui, Himeda, Yuichiro, Muckerman, James T., Manbeck, Gerald F., & Fujita, Etsuko. CO2 hydrogenation to formate and methanol as an alternative to photo- and electrochemical CO2 reduction. United States. doi:10.1021/acs.chemrev.5b00197.
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Wang, Wan -Hui, Himeda, Yuichiro, Muckerman, James T., Manbeck, Gerald F., and Fujita, Etsuko. Thu . "CO2 hydrogenation to formate and methanol as an alternative to photo- and electrochemical CO2 reduction". United States. doi:10.1021/acs.chemrev.5b00197. https://www.osti.gov/servlets/purl/1214520.
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@article{osti_1214520,
title = {CO2 hydrogenation to formate and methanol as an alternative to photo- and electrochemical CO2 reduction},
author = {Wang, Wan -Hui and Himeda, Yuichiro and Muckerman, James T. and Manbeck, Gerald F. and Fujita, Etsuko},
abstractNote = {In this study, carbon dioxide is one of the end products of combustion, and is not a benign component of the atmosphere. The concentration of CO2 in the atmosphere has reached unprecedented levels and continues to increase owing to an escalating rate of fossil fuel combustion, causing concern about climate change and rising sea levels. In view of the inevitable depletion of fossil fuels, a possible solution to this problem is the recycling of carbon dioxide, possibly captured at its point of generation, to fuels. Researchers in this field are using solar energy for CO2 activation and utilization in several ways: (i) so-called artificial photosynthesis using photo-induced electrons; (ii) bulk electrolysis of a CO2 saturated solution using electricity produced by photovoltaics; (iii) CO2 hydrogenation using solar-produced H2; and (iv) the thermochemical reaction of metal oxides at extremely high temperature reached by solar collectors. Since the thermodynamics of CO2 at high temperature (> 1000 ºC) are quite different from those near room temperature, only chemistry below 200 ºC is discussed in this review.},
doi = {10.1021/acs.chemrev.5b00197},
journal = {Chemical Reviews},
number = ,
volume = ,
place = {United States},
year = {Thu Sep 03 00:00:00 EDT 2015},
month = {Thu Sep 03 00:00:00 EDT 2015}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI:  10.1021/acs.chemrev.5b00197
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  • ; ; - Journal of the American Chemical Society
    Copper is the only elemental metal that reduces a significant fraction of CO 2 to hydrocarbons and alcohols, but the atomistic reaction mechanism that controls the product distributions is not known because it has not been possible to detect the reaction intermediates on the electrode surface experimentally, or to carry out Quantum Mechanics (QM) calculations with a realistic description of the electrolyte (water). We carry out QM calculations with an explicit description of water on the Cu(100) surface (experimentally shown to be stable under CO 2 reduction reaction conditions) to examine the initial reaction pathways to form CO and formatemore » (HCOO –) from CO 2 through free energy calculations at 298 K and pH 7. We find that CO formation proceeds from physisorbed CO 2 to chemisorbed CO 2 (*CO 2 δ-), with a free energy barrier of ΔG ‡ = 0.43 eV, the rate-determining step (RDS). The subsequent barriers of protonating *CO 2 δ- to form COOH* and then dissociating COOH* to form *CO are 0.37 and 0.30 eV, respectively. HCOO– formation proceeds through a very different pathway in which physisorbed CO 2 reacts directly with a surface H* (along with electron transfer), leading to ΔG ‡ = 0.80 eV. Thus, the competition between CO formation and HCOO – formation occurs in the first electron-transfer step. On Cu(100), the RDS for CO formation is lower, making CO the predominant product. Therefore, to alter the product distribution, we need to control this first step of CO 2 binding, which might involve controlling pH, alloying, or changing the structure at the nanoscale.« less
    Cited by 17

  • ; ; ; ... - Energy Sources
    The electrochemical reduction of CO{sub 2} in tetraethylammonium perchlorate + methanol electrolyte was investigated with a copper wire electrode at an extremely low temperature ({minus}30 C). The main products from CO{sub 2} by the electrochemical reduction were methane, ethylene, carbon monoxide, and formic acid. Under the optimum experimental conditions, 28.1% faradaic efficiency methane, 7.2% ethylene, 67.8% carbon monoxide, and 23.2% formic acid were produced from CO{sub 2} by the electrochemical reduction. The maximum partial current densities for CO{sub 2} reduction and hydrocarbons were 4.5 and 1.6 mA/cm{sup 2} at {minus}4.0 V vs SCE, respectively. At {minus}30 C, the efficiency ofmore » hydrogen formation, being a competitive reaction against CO{sub 2} reduction, was suppressed to less than 10.1%.« less

  • ; ; ; ... - Energy Sources
    The electrochemical reduction of carbon dioxide in 0.1 M KOH-methanol electrolyte was investigated with a copper electrode at {minus}30, {minus}15, 0, and 15 C. The main products from carbon dioxide by electrochemical reduction were carbon monoxide, formic acid, ethylene, and methane. Under the optimum experimental conditions, 56% Faradaic efficiency carbon monoxide, 23% formic acid, and 10% methane were produced from carbon dioxide by electrochemical reduction. The best ethylene formation (12%) was obtained at {minus}2.2 V and 0 C.

  • ; ; ; ... - Industrial and Engineering Chemistry Research
    Ternary copper-based catalysts of type CuO/ZnO/Al{sub 2}O{sub 3}, CuO/ZnO/Cr{sub 2}O{sub 3}, and CuO/ZnO/La{sub 2}O{sub 3} have been advantageously used in the hydrogenolysis of methyl and ethyl formate to methanol. The catalysts are active under mild conditions (150--185 C; 5--10 MPa) both in gas-solid and in gas-liquid-solid phases with high selectivities to methanol (80--90%). The decarbonylation of the formic ester is the only side reaction, but the catalysts, different from other copper-based systems, do not suffer from the presence of Co in the reaction gases. Accordingly the hydrogenolysis may be carried out with a hydrogen feed containing CO without any poisoningmore » of the catalyst or decrease of the selectivity to methanol. A preliminary screening of different copper catalysts points out that the insensitivity to CO might be related to the presence of basic sites on the catalysts.« less

  • ; ; - Inorganic Chemistry
    Electroreduction of [Ru(bpy){sub 2}(CO){sub 2}]{sup 2+} in CH{sub 3}CN induces deposition of a [Ru{sup 0}(bpy)(CO){sub 2}{sub n}] film on the electrode. The authors used cyclic voltammetry to study the electrocatalytic effects of this film in the reduction of CO{sub 2}.