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Integration of Anodic and Cathodic Catalysts of Earth-Abundant Materials for Efficient, Scalable CO2 Reduction

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Abstract

A fully integrated electrochemical cell for co-production of formate (HCOO−) and oxygen (O2) from carbon dioxide (CO2) and water using only earth-abundant elements has been developed. The process converts CO2 to formate using electrons derived from anodic water oxidation. A novel cathodic catalyst system, consisting of a tin (Sn) cathode in combination with the soluble heterocycle 2-picoline, was identified for CO2 reduction. Water oxidation takes place at a fluorine-doped tin oxide electrode coated with an electrodeposited cobalt oxide (CoOx) electrocatalyst. Use of 2-picoline as a soluble cathodic co-catalyst lowered the overpotential and enhanced the stability of the Sn-mediated CO2 reduction process. Fluorophosphate served as a redox-stable electrolyte to buffer the anode compartment at mildly acidic pH (~ 5 to 5.5), thereby stabilizing the CoOx electrocatalyst and supporting efficient water oxidation. The complete electrochemical cell maintained a stable cell voltage of less than 3 V over 5 days, with an average formate faradaic yield of 34 %. These results are presented together with an economical analysis of large-scale solar-driven production of formate/formic acid from CO2 and water.

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Notes

  1. Efficiency derived from: (theoretical cell voltage/measured cell voltage) * formate faradaic yield * photovoltaic efficiency. In this case (1.42/2.7)*0.4*0.2 = 4.2 %.

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Acknowledgments

The authors would like to thank Dr. Charles G. Fry for advice on NMR measurements, Dr. Liliana Lopez Aguilar for assistance with IC-MS analysis, and George Leonard for assistance with GC analysis. Research conducted in the Stahl lab was partially supported by an NSF CCI Grant CHE-0802907 and by NMR facility support under NSF Grant CHE-9629688.

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Author notes

  1. Kunttal Keyshar

    Present address: Department of Mechanical Engineering & Materials Science, Rice University, 6100 Main Street, Houston, TX, 77005, USA

  2. Ian Sullivan

    Present address: Department of Chemistry, North Carolina State University, 2620 Yarbrough Drive, Raleigh, NC, 27695, USA

Authors and Affiliations

  1. Liquid Light, Inc., 11 Deer Park Dr., Suite 121, Monmouth Junction, NJ, 08852, USA

    Rishi Parajuli, Kunttal Keyshar, Ian Sullivan, Narayanappa Sivasankar, Kyle Teamey & Emily Barton Cole

  2. Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI, 53706, USA

    James B. Gerken & Shannon S. Stahl

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  1. Rishi Parajuli
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Correspondence to Shannon S. Stahl or Emily Barton Cole.

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Parajuli, R., Gerken, J.B., Keyshar, K. et al. Integration of Anodic and Cathodic Catalysts of Earth-Abundant Materials for Efficient, Scalable CO2 Reduction. Top Catal 58, 57–66 (2015). https://doi.org/10.1007/s11244-014-0345-x

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