Continuous Modulation of Electrocatalytic Oxygen Reduction Activities of Single-Atom Catalysts through p-n Junction Rectification

Zechao Zhuang; Lixue Xia; Jiazhao Huang; Peng Zhu; Yong Li; Chenliang Ye; Minggang Xia; Ruohan Yu; Zhiquan Lang; Jiexin Zhu; Lirong Zheng; Yu Wang; Tianyou Zhai; Yan Zhao; Shiqiang Wei; Jun Li; Dingsheng Wang; Yadong Li

doi:10.1002/anie.202212335

Continuous Modulation of Electrocatalytic Oxygen Reduction Activities of Single-Atom Catalysts through p-n Junction Rectification

Angew Chem Int Ed Engl. 2023 Jan 26;62(5):e202212335. doi: 10.1002/anie.202212335. Epub 2022 Dec 7.

Authors

Zechao Zhuang¹, Lixue Xia², Jiazhao Huang³, Peng Zhu¹, Yong Li⁴, Chenliang Ye¹, Minggang Xia⁵, Ruohan Yu⁶, Zhiquan Lang⁷, Jiexin Zhu⁷, Lirong Zheng⁸, Yu Wang⁹, Tianyou Zhai³, Yan Zhao^{2

10}, Shiqiang Wei¹¹, Jun Li¹, Dingsheng Wang¹, Yadong Li¹

Affiliations

¹ Department of Chemistry, Tsinghua University, Beijing, 100084, China.
² State Key Laboratory of Silicate Materials for Architectures, International School of Materials Science and Engineering, Wuhan University of Technology, Wuhan, 430070, China.
³ State Key Laboratory of Material Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan, 430074, China.
⁴ Institute of Applied and Physical Chemistry and Center for Environmental Research and Sustainable Technology, University of Bremen, 28359, Bremen, Germany.
⁵ Department of Photoelectronic Information Science and Engineering, School of Science, Xi'an Jiaotong University, Xi'an, 710049, China.
⁶ Nanostructure Research Centre, Wuhan University of Technology, Wuhan, 430070, China.
⁷ State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan, 430070, China.
⁸ Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, 100049, China.
⁹ Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201204, China.
¹⁰ The Institute of Technological Sciences, Wuhan University, Wuhan, 430072, China.
¹¹ National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, 230026, China.

PMID: 36380642
DOI: 10.1002/anie.202212335

Abstract

Fine-tuning single-atom catalysts (SACs) to surpass their activity limit remains challenging at their atomic scale. Herein, we exploit p-type semiconducting character of SACs having a metal center coordinated to nitrogen donors (MeN_x ) and rectify their local charge density by an n-type semiconductor support. With iron phthalocyanine (FePc) as a model SAC, introducing an n-type gallium monosulfide that features a low work function generates a space-charged region across the junction interface, and causes distortion of the FeN₄ moiety and spin-state transition in the Fe^II center. This catalyst shows an over two-fold higher specific oxygen-reduction activity than that of pristine FePc. We further employ three other n-type metal chalcogenides of varying work function as supports, and discover a linear correlation between the activities of the supported FeN₄ and the rectification degrees, which clearly indicates that SACs can be continuously tuned by this rectification strategy.

Keywords: Diode Rectification; Oxygen Reduction Reaction; Single-Atom Catalysis; Two-Dimensional Metal Chalcogenide; p-n Junction.

Grants and funding

21890383/National Natural Science Foundation of China