In Operando Identification of In Situ Formed Metalloid Zincδ+ Active Sites for Highly Efficient Electrocatalyzed Carbon Dioxide Reduction

Xin Yu Zhang; Wen Jing Li; Jiacheng Chen; Xue Feng Wu; Yuan Wei Liu; Fangxin Mao; Hai Yang Yuan; Minghui Zhu; Sheng Dai; Hai Feng Wang; P Hu; Chenghua Sun; Peng Fei Liu; Hua Gui Yang

doi:10.1002/anie.202202298

In Operando Identification of In Situ Formed Metalloid Zinc^δ+ Active Sites for Highly Efficient Electrocatalyzed Carbon Dioxide Reduction

Angew Chem Int Ed Engl. 2022 Jul 11;61(28):e202202298. doi: 10.1002/anie.202202298. Epub 2022 May 9.

Authors

Xin Yu Zhang¹, Wen Jing Li¹, Jiacheng Chen², Xue Feng Wu¹, Yuan Wei Liu¹, Fangxin Mao¹, Hai Yang Yuan¹, Minghui Zhu², Sheng Dai³, Hai Feng Wang⁴, P Hu^{4

5}, Chenghua Sun⁶, Peng Fei Liu¹, Hua Gui Yang¹

Affiliations

¹ Key Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China.
² State Key Laboratory of Chemical Engineering, School of Chemical Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China.
³ Key Laboratory for Advanced Materials and Feringa Nobel Prize Scientist Joint Research Center, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China.
⁴ Key Laboratory for Advanced Materials, Centre for Computational Chemistry and Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China.
⁵ School of Chemistry and Chemical Engineering, The Queen's University of Belfast, Belfast, BT9 5AG, UK.
⁶ Department of Chemistry and Biotechnology, Center for Translational Atomaterials, Swinburne University of Technology, Hawthorn, VIC, 3122, Australia.

PMID: 35389544
DOI: 10.1002/anie.202202298

Abstract

Electrochemical CO₂ -to-CO conversion provides a possible way to address problems associated with the greenhouse effect; however, developing low-cost electrocatalysts to mediate high-efficiency CO₂ reduction remains a challenge on account of the limited understanding of the nature of the real active sites. Herein, we reveal the Zn^δ+ metalloid sites as the real active sites of stable nonstoichiometric ZnO_x structure derived from Zn₂ P₂ O₇ through operando X-ray absorption fine structure analysis in conjunction with evolutionary-algorithm-based global optimization. Furthermore, theoretical and experimental results demonstrated that Zn^δ+ metalloid active sites could facilitate the activation of CO₂ and the hydrogenation of *CO₂ , thus accelerating the CO₂ -to-CO conversion. Our work establishes a critical fundamental understanding of the origin of the real active center in the zinc-based electrocatalysts for CO₂ reduction reaction.

Keywords: CO2 Reduction Reaction; EA Global Optimization Method; Metalloid Znδ+; Operando EXAFS; Zinc Pyrophosphate.

Abstract

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