Cited by 541CO2 Reduction Techniques and CatalystsCarbon dioxide utilization in catalysisElectrocatalysts for Energy Conversion

Pd-Catalyzed Electrohydrogenation of Carbon Dioxide to Formate: High Mass Activity at Low Overpotential and Identification of the Deactivation Pathway

Min, Xiaoquan, Kanan, Matthew W.·2015·Journal of the American Chemical Society

Abstract

Electrochemical reduction of CO2 to formate (HCO2(-)) powered by renewable electricity is a possible carbon-negative alternative to synthesizing formate from fossil fuels. This process is energetically inefficient because >1 V of overpotential is required for CO2 reduction to HCO2(-) on the metals currently used as cathodic catalysts. Pd reduces CO2 to HCO2(-) with no overpotential, but this activity has previously been limited to low synthesis rates and plagued by an unidentified deactivation pathway. Here we show that Pd nanoparticles dispersed on a carbon support reach high mass activities (50-80 mA HCO2(-) synthesis per mg Pd) when driven by less than 200 mV of overpotential in aqueous bicarbonate solutions. Electrokinetic measurements are consistent with a mechanism in which the rate-determining step is the addition of electrochemically generated surface adsorbed hydrogen to CO2 (i.e., electrohydrogenation). The electrodes deactivate over the course of several hours because of a minor pathway that forms CO. Activity is recovered, however, by removing CO with brief air exposure.

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Crossref · 10.1021/ja511890h

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Authors
Min, X., & Kanan, M. W.
Affiliations
  • Department of Chemistry, Stanford University, Stanford, California 94305, United States
  • Stanford University (US)
Corresponding author
Kanan, Matthew W.
Venue
Journal of the American Chemical Society
Published
2015-04-06
Volume
137
Issue
14
Pages
4701-4708
ISSN
  • 0002-7863 (ISSN-L)
  • 1520-5126
OpenAlex
W2093202328
Cited by
541
References
51
Citations by year
2026: 30 · 2025: 42 · 2024: 49 · 2023: 40 · 2022: 34 · 2021: 62 · 2020: 58 · 2019: 61 · 2018: 52 · 2017: 67 · 2016: 31 · 2015: 15
FWCI
16.26
Type
journal article
Language
en
Open access
closed
Locations
  • Journal of the American Chemical Society (publishedVersion)
  • PubMed (publishedVersion)
Funders
  • Division of Chemistry (CHE-1266401)
  • Stanford University
  • Hellman Foundation
Topics
  • Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › CO2 Reduction Techniques and Catalysts
  • Physical Sciences › Chemical Engineering › Process Chemistry and Technology › Carbon dioxide utilization in catalysis
  • Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Electrocatalysts for Energy Conversion
Keywords
electrohydrogenation, electrochemical CO2 reduction, formate production, palladium nanoparticles, low overpotential, catalyst deactivation, bicarbonate electrolyte, rate-determining step, CO formation, catalyst regeneration, mass activity

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