Cation-Radius-Controlled Sn-O Bond Length Boosting CO2 Electroreduction over Sn-Based Perovskite Oxides

Mingfa Chen; Kuan Chang; Yu Zhang; Zhenbao Zhang; Yuming Dong; Xiaoyu Qiu; Heqing Jiang; Yongfa Zhu; Jiawei Zhu

doi:10.1002/anie.202305530

Cation-Radius-Controlled Sn-O Bond Length Boosting CO₂ Electroreduction over Sn-Based Perovskite Oxides

Angew Chem Int Ed Engl. 2023 Oct 26;62(44):e202305530. doi: 10.1002/anie.202305530. Epub 2023 Aug 9.

Authors

Mingfa Chen¹, Kuan Chang¹, Yu Zhang^{2

3}, Zhenbao Zhang⁴, Yuming Dong¹, Xiaoyu Qiu⁵, Heqing Jiang^{2

3}, Yongfa Zhu⁶, Jiawei Zhu^{1

2

3}

Affiliations

¹ Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, 214122, Wuxi, China.
² Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, 266101, Qingdao, China.
³ Shandong Energy Institute, 266101, Qingdao, China.
⁴ School of Chemistry and Chemical Engineering, Linyi University, 276005, Linyi, China.
⁵ School of Chemistry and Materials Science, Nanjing Normal University, 210023, Nanjing, China.
⁶ Department of Chemistry, Tsinghua University, 100084, Beijing, China.

PMID: 37533227
DOI: 10.1002/anie.202305530

Abstract

Despite the intriguing potential shown by Sn-based perovskite oxides in CO₂ electroreduction (CO₂ RR), the rational optimization of their CO₂ RR properties is still lacking. Here we report an effective strategy to promote CO₂ -to-HCOOH conversion of Sn-based perovskite oxides by A-site-radius-controlled Sn-O bond lengths. For the proof-of-concept examples of Ba_1-x Sr_x SnO₃ , as the A-site cation average radii decrease from 1.61 to 1.44 Å, their Sn-O bonds are precisely shortened from 2.06 to 2.02 Å. Our CO₂ RR measurements show that the activity and selectivity of these samples for HCOOH production exhibit volcano-type trends with the Sn-O bond lengths. Among these samples, the Ba_0.5 Sr_0.5 SnO₃ features the optimal activity (753.6 mA ⋅ cm^-2 ) and selectivity (90.9 %) for HCOOH, better than those of the reported Sn-based oxides. Such optimized CO₂ RR properties could be attributed to favorable merits conferred by the precisely controlled Sn-O bond lengths, e.g., the regulated band center, modulated adsorption/activation of intermediates, and reduced energy barrier for *OCHO formation. This work brings a new avenue for rational design of advanced Sn-based perovskite oxides toward CO₂ RR.

Keywords: A-Site Cation Radius; CO2 Electroreduction; HCOOH Production; Sn-Based Perovskite Oxide; Sn−O Bond Length.

Abstract

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