Cation-Deficiency-Dependent CO2 Electroreduction over Copper-Based Ruddlesden-Popper Perovskite Oxides

Jiawei Zhu; Yanying Wang; Aomiao Zhi; Zitao Chen; Lei Shi; Zhenbao Zhang; Yu Zhang; Yinlong Zhu; Xiaoyu Qiu; Xuezeng Tian; Xuedong Bai; Ying Zhang; Yongfa Zhu

doi:10.1002/anie.202111670

Cation-Deficiency-Dependent CO₂ Electroreduction over Copper-Based Ruddlesden-Popper Perovskite Oxides

Angew Chem Int Ed Engl. 2022 Jan 17;61(3):e202111670. doi: 10.1002/anie.202111670. Epub 2021 Nov 22.

Authors

Jiawei Zhu¹, Yanying Wang¹, Aomiao Zhi², Zitao Chen², Lei Shi³, Zhenbao Zhang⁴, Yu Zhang⁵, Yinlong Zhu⁶, Xiaoyu Qiu⁷, Xuezeng Tian², Xuedong Bai², Ying Zhang¹, Yongfa Zhu⁸

Affiliations

¹ School of Chemical and Material Engineering, Jiangnan University, Wuxi, Jiangsu, 214122, China.
² Beijing National Laboratory for Condensed Matter Physics and Institute of Physics, Chinese Academy of Sciences, Beijing, 100190, China.
³ College of Materials Science and Engineering, Nanjing Forestry University, Nanjing, 210037, China.
⁴ Department of Chemistry, College of Chemistry and Materials Science, Jinan University, Guangzhou, 510632, China.
⁵ School of Mechanical and Power Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China.
⁶ Department of Chemical Engineering, Monash University, Clayton, Victoria, 3800, Australia.
⁷ School of Chemistry and Materials Science, Nanjing Normal University, Nanjing, 210023, China.
⁸ Department of Chemistry, Tsinghua University, Beijing, 100084, China.

PMID: 34668284
DOI: 10.1002/anie.202111670

Abstract

We report an effective strategy to enhance CO₂ electroreduction (CER) properties of Cu-based Ruddlesden-Popper (RP) perovskite oxides by engineering their A-site cation deficiencies. With La_2-x CuO_4-δ (L_2-x C, x=0, 0.1, 0.2, and 0.3) as proof-of-concept catalysts, we demonstrate that their CER activity and selectivity (to C₂₊ or CH₄ ) show either a volcano-type or an inverted volcano-type dependence on the x values, with the extreme point at x=0.1. Among them, at -1.4 V, the L_1.9 C delivers the optimal activity (51.3 mA cm^-2 ) and selectivity (41.5 %) for C₂₊ , comparable to or better than those of most reported Cu-based oxides, while the L_1.7 C exhibits the best activity (25.1 mA cm^-2 ) and selectivity (22.1 %) for CH₄ . Such optimized CER properties could be ascribed to the favorable merits brought by the cation-deficiency-induced oxygen vacancies and/or CuO/RP hybrids, including the facilitated adsorption/activation of key reaction species and thus the manipulated reaction pathways.

Keywords: A-site cation deficiencies; CO2 electroreduction; CuO/perovskite hybrid; Ruddlesden-Popper perovskite oxide; oxygen vacancies.

Abstract

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