Cation-Deficient Perovskites Greatly Enhance the Electrocatalytic Activity for Oxygen Reduction Reaction

Qun Li; Di Zhang; Jiabin Wu; Simin Dai; Heng Liu; Min Lu; Renwen Cui; Wenxi Liang; Dingsheng Wang; Pinxian Xi; Meilin Liu; Hao Li; Liang Huang

doi:10.1002/adma.202309266

Cation-Deficient Perovskites Greatly Enhance the Electrocatalytic Activity for Oxygen Reduction Reaction

Adv Mater. 2024 Feb;36(7):e2309266. doi: 10.1002/adma.202309266. Epub 2023 Dec 7.

Authors

Qun Li^{1

2}, Di Zhang³, Jiabin Wu^{1

4}, Simin Dai¹, Heng Liu³, Min Lu⁵, Renwen Cui¹, Wenxi Liang¹, Dingsheng Wang⁴, Pinxian Xi⁵, Meilin Liu⁶, Hao Li³, Liang Huang¹

Affiliations

¹ Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan, 430074, China.
² CAS Key Laboratory of Nanosystem and Hierarchical Fabrication & CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Beijing, China.
³ Advanced Institute for Materials Research (WPI-AIMR), Tohoku University, Sendai, 980-8577, Japan.
⁴ Department of Chemistry, Tsinghua University, Beijing, 100084, China.
⁵ State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, China.
⁶ School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, GA, 30332-0245, USA.

PMID: 38019100
DOI: 10.1002/adma.202309266

Abstract

Many perovskite oxides (ABO₃ ) are considered the most promising alternatives to noble metal catalysts for oxygen reduction reaction (ORR) due to their high intrinsic activities. However, their electrocatalytic performance is often limited by poor electrical conductivity and low specific surface area. Here an electrochemically induced calcium-leaching process is reported to greatly increase the electrochemical surface area (ECSA) of La_0.6 Ca_0.4 MnO₃ (LCMO64). The ECSA of the activated, Ca-deficient LCMO64 is ≈33.84% higher than that of the unactivated materials, demonstrating superior electrocatalytic ORR performance to the benchmark commercial Pt/C catalyst in an alkaline solution. Theoretical analysis coupled with electrochemical surface state probing and pH-dependent microkinetic modeling suggests that this catalyst with the identified most favorable state under ORR operating conditions reaches the Sabatier optimum of alkaline ORR. This reconstructed LCMO64 is among the best-performing ORR catalysts ever reported, providing new insights into the design of advanced perovskite materials with optimal surface chemistry.

Keywords: ORR catalysis; cation leaching; oxygen reduction reaction; perovskite catalyst; surface reconstruction.

Abstract

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