Efficient and stable noble-metal-free catalyst for acidic water oxidation

Sanjiang Pan; Hao Li; Dan Liu; Rui Huang; Xuelei Pan; Dan Ren; Jun Li; Mohsen Shakouri; Qixing Zhang; Manjing Wang; Changchun Wei; Liqiang Mai; Bo Zhang; Ying Zhao; Zhenbin Wang; Michael Graetzel; Xiaodan Zhang

doi:10.1038/s41467-022-30064-6

Efficient and stable noble-metal-free catalyst for acidic water oxidation

Nat Commun. 2022 Apr 28;13(1):2294. doi: 10.1038/s41467-022-30064-6.

Authors

Sanjiang Pan^#^{1

2

3

4

5}, Hao Li^#⁶, Dan Liu⁷, Rui Huang⁸, Xuelei Pan⁹, Dan Ren¹⁰, Jun Li¹⁰, Mohsen Shakouri¹¹, Qixing Zhang^{1

2

3

4

5}, Manjing Wang^{1

2

3

4

5}, Changchun Wei^{1

2

3

4

5}, Liqiang Mai¹², Bo Zhang⁸, Ying Zhao^{1

2

3

4

5}, Zhenbin Wang¹³, Michael Graetzel^{14

15}, Xiaodan Zhang^{16

17

18

19

20}

Affiliations

¹ Institute of Photoelectronic Thin Film Devices and Technology, Renewable Energy Conversion and Storage Center, Solar Energy Research Center, Nankai University, Tianjin, 300350, PR China.
² Key Laboratory of Photoelectronic Thin Film Devices and Technology of Tianjin, Tianjin, 300350, PR China.
³ Haihe Laboratory of Sustainable Chemical Transformations, Tianjin, 300192, PR China.
⁴ Engineering Research Center of Thin Film Photoelectronic Technology of Ministry of Education, Tianjin, 300350, PR China.
⁵ Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin, 300072, PR China.
⁶ Advanced Institute for Materials Research (WPI-AIMR), Tohoku University, Sendai, 980-8577, Japan.
⁷ Institute of Flexible Electronics (IFE), Northwestern Polytechnical University (NPU), Xi'an, 710072, PR China.
⁸ State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai, 200438, PR China.
⁹ State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, International School of Materials Science and Engineering, Wuhan University of Technology, 430070, Wuhan, PR China.
¹⁰ Laboratory of Photonics and Interfaces, Ecole Polytechnique Federale de Lausanne, Lausanne, 1015, Switzerland.
¹¹ Canadian Light Source, Inc. (CLSI), Saskatoon, Saskatchewan, Canada.
¹² State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, School of Materials Science and Engineering, Wuhan University of Technology, 430070, Wuhan, PR China.
¹³ Catalysis Theory Center, Department of Physics, Technical University of Denmark, Lyngby, 2800, Denmark. zwang@fysik.dtu.dk.
¹⁴ Institute of Photoelectronic Thin Film Devices and Technology, Renewable Energy Conversion and Storage Center, Solar Energy Research Center, Nankai University, Tianjin, 300350, PR China. michael.graetzel@epfl.ch.
¹⁵ Laboratory of Photonics and Interfaces, Ecole Polytechnique Federale de Lausanne, Lausanne, 1015, Switzerland. michael.graetzel@epfl.ch.
¹⁶ Institute of Photoelectronic Thin Film Devices and Technology, Renewable Energy Conversion and Storage Center, Solar Energy Research Center, Nankai University, Tianjin, 300350, PR China. xdzhang@nankai.edu.cn.
¹⁷ Key Laboratory of Photoelectronic Thin Film Devices and Technology of Tianjin, Tianjin, 300350, PR China. xdzhang@nankai.edu.cn.
¹⁸ Haihe Laboratory of Sustainable Chemical Transformations, Tianjin, 300192, PR China. xdzhang@nankai.edu.cn.
¹⁹ Engineering Research Center of Thin Film Photoelectronic Technology of Ministry of Education, Tianjin, 300350, PR China. xdzhang@nankai.edu.cn.
²⁰ Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin, 300072, PR China. xdzhang@nankai.edu.cn.

^# Contributed equally.

Abstract

Developing non-noble catalysts with superior activity and durability for oxygen evolution reaction (OER) in acidic media is paramount for hydrogen production from water. Still, challenges remain due to the inadequate activity and stability of the OER catalyst. Here, we report a cost-effective and stable manganese oxybromide (Mn_7.5O₁₀Br₃) catalyst exhibiting an excellent OER activity in acidic electrolytes, with an overpotential of as low as 295 ± 5 mV at a current density of 10 mA cm^-2. Mn_7.5O₁₀Br₃ maintains good stability under operating conditions for at least 500 h. In situ Raman spectroscopy, X ray absorption near edge spectroscopy, and density functional theory calculations confirm that a self-oxidized surface with enhanced electronic transmission capacity forms on Mn_7.5O₁₀Br₃ and is responsible for both the high catalytic activity and long-term stability during catalysis. The development of Mn_7.5O₁₀Br₃ as an OER catalyst provides crucial insights into the design of non-noble metal electrocatalysts for water oxidation.