Tuning the activity and selectivity of electroreduction of CO<sub>2</sub> to synthesis gas using bimetallic catalysts.

Lee, Ji Hoon; Kattel, Shyam; Jiang, Zhao; Xie, Zhenhua; Yao, Siyu; Tackett, Brian M; Xu, Wenqian; Marinkovic, Nebojsa S et al. · Nat Commun · 2019

basic_science · Level V

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Abstract

The electrochemical carbon dioxide reduction reaction to syngas with controlled CO/H<sub>2</sub> ratios has been studied on Pd-based bimetallic hydrides using a combination of in situ characterization and density functional theory calculations. When compared with pure Pd hydride, the bimetallic Pd hydride formation occurs at more negative potentials for Pd-Ag, Pd-Cu, and Pd-Ni. Theoretical calculations show that the choice of the second metal has a more significant effect on the adsorption strength of *H than *HOCO, with the free energies between these two key intermediates (i.e., ΔG(*H)-ΔG(*HOCO)) correlating well with the carbon dioxide reduction reaction activity and selectivity observed in the experiments, and thus can be used as a descriptor to search for other bimetallic catalysts. The results also demonstrate the possibility of alloying Pd with non-precious transition metals to promote the electrochemical conversion of CO<sub>2</sub> to syngas.