Selective CO2 reduction to C3 and C4 oxyhydrocarbons on nickel phosphides at overpotentials as low as 10 mV

Karin U.D. Calvinho, Anders B. Laursen, Kyra M.K. Yap, Timothy A. Goetjen, Shinjae Hwang, Nagarajan Murali, Bryan Mejia-Sosa, Alexander Lubarski, Krishani M. Teeluck, Eugene S. Hall, Eric Garfunkel, Martha Greenblatt, G. Charles Dismukes

Research output: Contribution to journalArticlepeer-review

49 Citations (Scopus)


We introduce five nickel phosphide compounds as electro-catalysts for the reduction of carbon dioxide in aqueous solution, that achieve unprecedented selectivity to C3 and C4 products (the first such report). Three products: formic acid (C1), methylglyoxal (C3), and 2,3-furandiol (C4), are observed at potentials as low as +50 mV vs. RHE, and at the highest half-reaction energy efficiencies reported to date for any >C1 product (99%). The maximum selectivity for 2,3-furandiol is 71% (faradaic efficiency) at 0.00 V vs. RHE on Ni2P, which is equivalent to an overpotential of 10 mV, with the balance forming methylglyoxal, the proposed reaction intermediate. P content in the series correlates closely with both the total C products and product selectivity, establishing definitive structure-function relationships. We propose a reaction mechanism for the formation of multi-carbon products, involving hydride transfer as the potential-determining step to oxygen-bound intermediates. This unlocks a new and more energy-efficient reduction route that has only been previously observed in nickel-based enzymes. This performance contrasts with simple metallic catalysts that have poor selectivity between multi-carbon products, and which require high overpotentials (>700 mV) to achieve comparable reaction rates.

Original languageEnglish
Pages (from-to)2550-2559
Number of pages10
JournalEnergy and Environmental Science
Issue number9
Publication statusPublished - Sep 2018

ASJC Scopus subject areas

  • Environmental Chemistry
  • Renewable Energy, Sustainability and the Environment
  • Nuclear Energy and Engineering
  • Pollution

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