journal article·2024-10-15

Manipulation of d-Orbital Electron Configurations in Nonplanar Fe-Based Electrocatalysts for Efficient Oxygen Reduction

Tong Liu, Hui Huang, Airong Xu, Zhiguo Sun, Dong Liu, Shuaiwei Jiang, Li Xu, Yudan Chen, Xiaokang Liu, Qiquan Luo, Tao Ding, Tao Yao

ACS Nano· Volume 18· Issue 41
Publisher page

Abstract

Manipulation of the spin state holds great promise to improve the electrochemical activity of transition metal-based catalysts. However, the underlying relationship between the nonplanar metal coordination environment and spin states remains to be explored. Herein, we report the precise regulation of nonplanar Fe atomic d-orbital energy level into an irregular tetrahedral crystal field configuration by introducing P atoms. With the increase of P coordination number, the spin magnetic moment decreases linearly from 3.8 μB to 0.2 μB, and the high spin content decreases linearly from 31% to 5%. Significantly, a volcanic curve between the spin states of Fe-based catalysts (Fe–N x P y ) and oxygen reduction reaction (ORR) activity has been unequivocally established based on the thermodynamic results. Thus, the Fe–N 3 P 1 catalyst with a 19% medium spin state experimentally exhibits the optimal reaction activity with a high half-wave potential of 0.92 V. These findings indicate that regulating electron spin moments through coordination engineering is a promising catalyst design strategy, providing important insights into spin catalysis.
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Research context

OpenAlex topics: Electrocatalysts for Energy Conversion · Electrochemical Analysis and Applications · Fuel Cells and Related Materials

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Key Laboratory of Precision and Intelligent Chemistry, School of Nuclear Science and Technology, Hefei National Research Center for Physical Sciences at the Microscale, National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230026, P. R. China

College of Science, National University of Defense Technology, Changsha 410073, China

Institutes of Physical Science and Information Technology, Anhui University, Hefei 230601, China

Funding

University of Science and Technology of China · National Key Research and Development Program of China · China Postdoctoral Science Foundation · Youth Innovation Promotion Association of the Chinese Academy of Sciences · Fundamental Research Funds for the Central Universities · National Natural Science Foundation of China · Chinese Academy of Sciences · University of China Innovation Program of Anhui Province

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