Hydrogen radical-boosted electrocatalytic CO2 reduction using Ni-partnered heteroatomic pairs

Zhibo Yao; Hao Cheng; Yifei Xu; Xinyu Zhan; Song Hong; Xinyi Tan; Tai-Sing Wu; Pei Xiong; Yun-Liang Soo; Molly Meng-Jung Li; Leiduan Hao; Liang Xu; Alex W Robertson; Bingjun Xu; Ming Yang; Zhenyu Sun

doi:10.1038/s41467-024-53529-2

Hydrogen radical-boosted electrocatalytic CO₂ reduction using Ni-partnered heteroatomic pairs

Nat Commun. 2024 Nov 14;15(1):9881. doi: 10.1038/s41467-024-53529-2.

Authors

Zhibo Yao^#¹, Hao Cheng^#², Yifei Xu^#³, Xinyu Zhan¹, Song Hong¹, Xinyi Tan⁴, Tai-Sing Wu⁵, Pei Xiong⁶, Yun-Liang Soo⁷, Molly Meng-Jung Li⁶, Leiduan Hao¹, Liang Xu¹, Alex W Robertson⁸, Bingjun Xu³, Ming Yang⁹, Zhenyu Sun¹⁰

Affiliations

¹ State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing, PR China.
² Department of Applied Physics, The Hong Kong Polytechnic University, Hung Hom, Hong Kong SAR, PR China.
³ College of Chemistry and Molecular Engineering, Peking University, Beijing, PR China.
⁴ School of Materials Science and Engineering, Beijing Institute of Technology, Beijing Key Laboratory of Environmental Science and Engineering, Beijing, PR China. [email protected].
⁵ National Synchrotron Radiation Research Center, Hsinchu, Taiwan.
⁶ Department of Applied Physics, The Hong Kong Polytechnic University, Hong Kong, PR China.
⁷ Department of Physics, National Tsing Hua University, Hsinchu, Taiwan.
⁸ Department of Physics, University of Warwick, Coventry, UK.
⁹ Department of Applied Physics, The Hong Kong Polytechnic University, Hung Hom, Hong Kong SAR, PR China. [email protected].
¹⁰ State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing, PR China. [email protected].

^# Contributed equally.

PMID: 39543091
DOI: 10.1038/s41467-024-53529-2

Abstract

The electrocatalytic reduction of CO₂ to CO is slowed by the energy cost of the hydrogenation step that yields adsorbed *COOH intermediate. Here, we report a hydrogen radical (H•)-transfer mechanism that aids this hydrogenation step, enabled by constructing Ni-partnered hetero-diatomic pairs, and thereby greatly enhancing CO₂-to-CO conversion kinetics. The partner metal to the Ni (denoted as M) catalyzes the Volmer step of the water/proton reduction to generate adsorbed *H, turning to H•, which reduces CO₂ to carboxyl radicals (•COOH). The Ni partner then subsequently adsorbs the •COOH in an exothermic reaction, negating the usual high energy-penalty for the electrochemical hydrogenation of CO₂. Tuning the H adsorption strength of the M site (with Cd, Pt, or Pd) allows for the optimization of H• formation, culminating in a markedly improved CO₂ reduction rate toward CO production, offering 97.1% faradaic efficiency (FE) in aqueous electrolyte and up to 100.0% FE in an ionic liquid solution.