Doped Transition Metal Nitrides As Efficient Electrocatalysts for Electrochemical Reduction of CO2

Electrochemical reduction of CO 2 to hydrocarbons and alcohols using intermittent renewable energy sources is a promising approach to store energy into chemical bonds for automotive and industrial applications. 1 Among many known catalysts, very few, such as copper, are capable of reducing CO 2 to significant amount of hydrocarbons and oxygenates, albeit at high overpotentials. 2 In the past, numerous experimental and theoretical efforts have been dedicated to understand CO 2 reduction reaction mechanism as well as identify efficient catalysts. 3–6 Transition metal nitrides have attracted a lot of attention for electrochemical reactions such as oxygen reduction reaction, ammonia synthesis and hydrogen evolution in recent years. 7–9 In the present study, we employ Density Functional Theory (DFT) calculations to study a wide range of transition metal nitrides with and without heteroatom dopants for CO 2 reduction reaction. We identify several stable and active catalysts. This study suggests that transition metal nitrides are promising catalysts for electrochemical reduction of CO 2 . References: Verma, S., Kim, B., Jhong, H.-R. “Molly”, Ma, S. & Kenis, P. J. A. A Gross-Margin Model for Defining Technoeconomic Benchmarks in the Electroreduction of CO 2 . ChemSusChem 9 , 1972–1979 (2016). Hori, Y. Electrochemical CO 2 Reduction on Metal Electrodes. in CO2 Reduction on Metal Electrodes. Modern Aspects of Electrochemistry (eds. Vayenas, C. G., White, R. E. & Gamboa-Aldeco, M. E.) 89–189 (Springer New York, 2008). Kuhl, K. P. et al. Electrocatalytic conversion of carbon dioxide to methane and methanol on transition metal surfaces. J. Am. Chem. Soc. 136 , 14107–14113 (2014). Peterson, A. A., Abild-Pedersen, F., Studt, F., Rossmeisl, J. & Nørskov, J. K. How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels. Energy Environ. Sci. 3 , 1311 (2010). Karamad, M., Hansen, H. A., Rossmeisl, J. & Nørskov, J. K. Mechanistic Pathway in the Electrochemical Reduction of CO 2 on RuO 2 . ACS Catal. 5 , 4075–4081 (2015). Li, Y. & Sun, Q. Recent Advances in Breaking Scaling Relations for Effective Electrochemical Conversion of CO 2 . Adv. Energy Mater. 6 , 1600463 (2016). Abroshan, H. et al. Ultrathin Cobalt Oxide Overlayer Promotes Catalytic Activity of Cobalt Nitride for the Oxygen Reduction Reaction. J. Phys. Chem. C 122 , 4783–4791 (2018). Abghoui, Y. et al. Enabling electrochemical reduction of nitrogen to ammonia at ambient conditions through rational catalyst design. Phys. Chem. Chem. Phys. 17 , 4909–4918 (2015). Abghoui, Y. & Skúlason, E. Hydrogen Evolution Reaction Catalyzed by Transition-Metal Nitrides. J. Phys. Chem. C 121 , 24036–24045 (2017).