Selective CO2 reduction to C3 and C4 oxyhydrocarbons on nickel phosphides at overpotentials as low as 10 mV. Issue 9 (29th June 2018)

• Record Type: Journal Article
• Authors: Calvinho, Karin U. D.; Laursen, Anders B.; Yap, Kyra M. K.; Goetjen, Timothy A.; Hwang, Shinjae; Murali, Nagarajan; Mejia-Sosa, Bryan; Lubarski, Alexander; Teeluck, Krishani M.; Hall, Eugene S.; Garfunkel, Eric; Greenblatt, Martha; Dismukes, G. Charles
• Is Part Of: Energy & environmental science. Volume 11:Issue 9(2018)
• Page Start: 2550
• Page End: 2559
• Publication Date: 2018-06-29
• Subjects: Energy conversion -- Periodicals; Fuel switching -- Periodicals; Environmental sciences -- Periodicals; Environmental chemistry -- Periodicals; 333.79
• DOI: 10.1039/c8ee00936h
• Languages: English
• ISSNs: 1754-5692

Abstract

Abstract : Bioinspired nickel phosphide electrocatalysts achieve breakthrough efficiency and selectivity for C3 and C4 products. Abstract : 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 Ni2 P, 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.