Dopant-tuned stabilization of intermediates promotes electrosynthesis of valuable C3 products.

Zhuang, Tao-Tao; Nam, Dae-Hyun; Wang, Ziyun; Li, Hui-Hui; Gabardo, Christine M; Li, Yi; Liang, Zhi-Qin; Li, Jun et al. · Nat Commun · 2019

basic_science · Level V

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Abstract

The upgrading of CO<sub>2</sub>/CO feedstocks to higher-value chemicals via energy-efficient electrochemical processes enables carbon utilization and renewable energy storage. Substantial progress has been made to improve performance at the cathodic side; whereas less progress has been made on improving anodic electro-oxidation reactions to generate value. Here we report the efficient electroproduction of value-added multi-carbon dimethyl carbonate (DMC) from CO and methanol via oxidative carbonylation. We find that, compared to pure palladium controls, boron-doped palladium (Pd-B) tunes the binding strength of intermediates along this reaction pathway and favors DMC formation. We implement this doping strategy and report the selective electrosynthesis of DMC experimentally. We achieve a DMC Faradaic efficiency of 83 ± 5%, fully a 3x increase in performance compared to the corresponding pure Pd electrocatalyst.