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Title: Understanding Selectivity for the Electrochemical Reduction of Carbon Dioxide to Formic Acid and Carbon Monoxide on Metal Electrodes

Abstract

Increases in energy demand and in chemical production, together with the rise in CO 2 levels in the atmosphere, motivate the development of renewable energy sources. Electrochemical CO 2 reduction to fuels and chemicals is an appealing alternative to traditional pathways to fuels and chemicals due to its intrinsic ability to couple to solar and wind energy sources. Formate (HCOO ) is a key chemical for many industries; however, greater understanding is needed regarding the mechanism and key intermediates for HCOO production. This work reports a joint experimental and theoretical investigation of the electrochemical reduction of CO 2 to HCOO on polycrystalline Sn surfaces, which have been identified as promising catalysts for selectively producing HCOO . Our results show that Sn electrodes produce HCOO , carbon monoxide (CO), and hydrogen (H 2) across a range of potentials and that HCOO production becomes favored at potentials more negative than –0.8 V vs RHE, reaching a maximum Faradaic efficiency of 70% at –0.9 V vs RHE. Scaling relations for Sn and other transition metals are examined using experimental current densities and density functional theory (DFT) binding energies. While *COOH was determined to be the key intermediate for CO productionmore » on metal surfaces, we suggest that it is unlikely to be the primary intermediate for HCOO production. Instead, *OCHO is suggested to be the key intermediate for the CO 2RR to HCOO transformation, and Sn’s optimal *OCHO binding energy supports its high selectivity for HCOO . Lastly, these results suggest that oxygen-bound intermediates are critical to understand the mechanism of CO 2 reduction to HCOO on metal surfaces.« less

Authors:
 [1];  [1];  [2];  [1];  [2];  [2]; ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. Stanford Univ., Stanford, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1390311
Grant/Contract Number:
AC02-76SF00515; 1066515
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 7; Journal Issue: 7; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; carbon monoxide; CO2 reduction; electrocatalysis; formate; Sn; tin

Citation Formats

Feaster, Jeremy T., Shi, Chuan, Cave, Etosha R., Hatsukade, Toru, Abram, David N., Kuhl, Kendra P., Hahn, Christopher, Nørskov, Jens K., and Jaramillo, Thomas F. Understanding Selectivity for the Electrochemical Reduction of Carbon Dioxide to Formic Acid and Carbon Monoxide on Metal Electrodes. United States: N. p., 2017. Web. doi:10.1021/acscatal.7b00687.
Feaster, Jeremy T., Shi, Chuan, Cave, Etosha R., Hatsukade, Toru, Abram, David N., Kuhl, Kendra P., Hahn, Christopher, Nørskov, Jens K., & Jaramillo, Thomas F. Understanding Selectivity for the Electrochemical Reduction of Carbon Dioxide to Formic Acid and Carbon Monoxide on Metal Electrodes. United States. doi:10.1021/acscatal.7b00687.
Feaster, Jeremy T., Shi, Chuan, Cave, Etosha R., Hatsukade, Toru, Abram, David N., Kuhl, Kendra P., Hahn, Christopher, Nørskov, Jens K., and Jaramillo, Thomas F. 2017. "Understanding Selectivity for the Electrochemical Reduction of Carbon Dioxide to Formic Acid and Carbon Monoxide on Metal Electrodes". United States. doi:10.1021/acscatal.7b00687.
@article{osti_1390311,
title = {Understanding Selectivity for the Electrochemical Reduction of Carbon Dioxide to Formic Acid and Carbon Monoxide on Metal Electrodes},
author = {Feaster, Jeremy T. and Shi, Chuan and Cave, Etosha R. and Hatsukade, Toru and Abram, David N. and Kuhl, Kendra P. and Hahn, Christopher and Nørskov, Jens K. and Jaramillo, Thomas F.},
abstractNote = {Increases in energy demand and in chemical production, together with the rise in CO2 levels in the atmosphere, motivate the development of renewable energy sources. Electrochemical CO2 reduction to fuels and chemicals is an appealing alternative to traditional pathways to fuels and chemicals due to its intrinsic ability to couple to solar and wind energy sources. Formate (HCOO–) is a key chemical for many industries; however, greater understanding is needed regarding the mechanism and key intermediates for HCOO– production. This work reports a joint experimental and theoretical investigation of the electrochemical reduction of CO2 to HCOO– on polycrystalline Sn surfaces, which have been identified as promising catalysts for selectively producing HCOO–. Our results show that Sn electrodes produce HCOO–, carbon monoxide (CO), and hydrogen (H2) across a range of potentials and that HCOO– production becomes favored at potentials more negative than –0.8 V vs RHE, reaching a maximum Faradaic efficiency of 70% at –0.9 V vs RHE. Scaling relations for Sn and other transition metals are examined using experimental current densities and density functional theory (DFT) binding energies. While *COOH was determined to be the key intermediate for CO production on metal surfaces, we suggest that it is unlikely to be the primary intermediate for HCOO– production. Instead, *OCHO is suggested to be the key intermediate for the CO2RR to HCOO– transformation, and Sn’s optimal *OCHO binding energy supports its high selectivity for HCOO–. Lastly, these results suggest that oxygen-bound intermediates are critical to understand the mechanism of CO2 reduction to HCOO– on metal surfaces.},
doi = {10.1021/acscatal.7b00687},
journal = {ACS Catalysis},
number = 7,
volume = 7,
place = {United States},
year = 2017,
month = 6
}

Journal Article:
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  • The prospects for the electrochemical reduction of carbon dioxide to methanol were examined by investigating the intermediate reactions. The reduction of carbon dioxide was carried out in a neutral electrolyte at a mercury electrode. The high overvoltage observed for carbon dioxide reduction to the formate anion reflects a low value for the efficiency of electric energy utilization for this process. Formic acid can be reduced to methanol in a perchloric acid electrolyte (at a lead electrode) or in a buffered formic acid electrolyte (at a tin electrode). The faradaic efficiency for methanol formation is close to 100% at the tinmore » electrode in a narrow potential region corresponding to a low current density. The potential dependence of formic acid reduction to methanol suggests that the adsorption of formic acid on the electrode, near the pzc, may be the rate-controlling step in the over-all reaction. The reduction of formaldehyde to methanol occurs with a faradaic efficiency exceeding 90% in a basic solution. The Tafel slope decreases when either the formaldehyde concentration is increased (at constant pH) or when the pH of the solution is increased (at constant concentration). The polyoxymethylene glycols present as impurities in formaldehyde solutions may influence the mechanism of the electrode process through interaction with formaldehyde molecules and/or other adsorbed species resulting in small changes of the Tafel slope.« less
  • Simultaneous reduction of carbon dioxide and nitrate ions was examined at gas-diffusion electrodes with various catalysts (Cr, Mo, Mn, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, An, Cd, In, Tl, Sn and Pb). The formation of urea, CO, formic acid, nitrite ions, and ammonia at the gas-diffusion electrodes with groups 11--14 catalysts, except for Au, was found in the simultaneous reduction. The maximum faradaic efficiency of urea formation on Zn catalysts is approximately 35% at {minus}1.75 V. The formation of urea at the gas-diffusion electrodes with groups 6--10 catalysts was not found in the simultaneous reduction ofmore » CO{sub 2} and nitrate. Relationship of the ability for urea formation to the ability for CO and NH{sub 3} formation was investigated with various catalysts. The ability for urea formation with the catalysts depends on the ability for CO and NH{sub 3} formation. The catalysts with high ability for CO and NU{sub 3} formation could form large amounts of CO-like and ammonia-like precursors. The faradaic efficiency of urea formation for simultaneous reduction with nitrate ions is lower than that with nitrite ions. This result seems to be related to the ability for ammonia-like precursor formation.« less
  • This paper investigates the influence of the material of the electro-catalyst, the electrode composition, the type and concentration of the electrolyte, the temperature and the potential of the electrode on the electroreduction of carbon monoxide in aqueous electrolytes. The following metal powders were used as electrocatalysts: Co, Ni, Fe, Nb, Pt, W, Cu, Cd, Pb, Zn, and Raney nickel. A large series of tests showed that no organic products were synthesized in the electroysis in the presence of CO on the metals Pt, Nb, Cd, W, Cu, Pb, and Zn. The only product in the whole potential range was hydrogen,more » derived from the decomposition of the electrolyte. Methane, ethane, and traces of ethylene were obtained on Ni, Co, Fe, and Raney nickel. With respect to the other hydrocarbons the methane content was equal to 95%. Best results were obtained on nickel electrodes.« less