Pd-Catalyzed Electrohydrogenation of Carbon Dioxide to Formate: High Mass Activity at Low Overpotential and Identification of the Deactivation Pathway
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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Further studies on OD Au demonstrated a large presence of grain boundaries (GB), which was linearly correlated with surface-area-normalized activity for CO2RR.
“Further studies on OD Au demonstrated a large presence of grain boundaries (GB), which was linearly correlated with surface-area-normalized activity for CO2RR (Figure .5B). [79]”
From Electrochemical CO <sub>2</sub> Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design (2019) · cites this paper as [79]
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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.
- ORCID
- Kanan, Matthew W.
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- 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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