Large electronegativity differences between adjacent atomic sites activate and stabilize ZnIn2S4 for efficient photocatalytic overall water splitting

Xu Xin; Yuke Li; Youzi Zhang; Yijin Wang; Xiao Chi; Yanping Wei; Caozheng Diao; Jie Su; Ruiling Wang; Peng Guo; Jiakang Yu; Jia Zhang; Ana Jorge Sobrido; Maria-Magdalena Titirici; Xuanhua Li

doi:10.1038/s41467-024-44725-1

Large electronegativity differences between adjacent atomic sites activate and stabilize ZnIn₂S₄ for efficient photocatalytic overall water splitting

Nat Commun. 2024 Jan 6;15(1):337. doi: 10.1038/s41467-024-44725-1.

Authors

Xu Xin^#^{1

2}, Yuke Li^#³, Youzi Zhang^{1

2}, Yijin Wang^{1

2}, Xiao Chi⁴, Yanping Wei⁵, Caozheng Diao⁶, Jie Su⁷, Ruiling Wang^{1

2}, Peng Guo^{1

2}, Jiakang Yu¹, Jia Zhang³, Ana Jorge Sobrido⁸, Maria-Magdalena Titirici⁹, Xuanhua Li^{10

11}

Affiliations

¹ State Key Laboratory of Solidification Processing, Center for Nano Energy Materials, School of Materials Science and Engineering, Northwestern Polytechnical University, Xi'an, 710072, China.
² Research & Development Institute of Northwestern Polytechnical University, Shenzhen, 518057, China.
³ Institute of High Performance Computing (IHPC), Agency for Science, Technology and Research (A*STAR), 1 Fusionopolis Way, #16-16 Connexis, Singapore, 138632, Singapore.
⁴ Department of Physics, National University of Singapore, Singapore, 117576, Singapore.
⁵ College of Science, Gansu Agricultural University, Lanzhou, 730070, China.
⁶ Singapore Synchrotron Light Source, National University of Singapore, 5 Research Link, Singapore, 117603, Singapore.
⁷ College of Microelectronics, Xidian University, Xi'an, 710072, China.
⁸ School of Engineering and Materials Science, Faculty of Science and Engineering, Queen Mary University of London, Mile End Road, London, E1 4NS, UK.
⁹ Department of Chemical Engineering, Imperial College London, South Kensington Campus, London, SW7 2AZ, UK.
¹⁰ State Key Laboratory of Solidification Processing, Center for Nano Energy Materials, School of Materials Science and Engineering, Northwestern Polytechnical University, Xi'an, 710072, China. lixh32@nwpu.edu.cn.
¹¹ Research & Development Institute of Northwestern Polytechnical University, Shenzhen, 518057, China. lixh32@nwpu.edu.cn.

^# Contributed equally.

Abstract

Photocatalytic overall water splitting into hydrogen and oxygen is desirable for long-term renewable, sustainable and clean fuel production on earth. Metal sulfides are considered as ideal hydrogen-evolved photocatalysts, but their component homogeneity and typical sulfur instability cause an inert oxygen production, which remains a huge obstacle to overall water-splitting. Here, a distortion-evoked cation-site oxygen doping of ZnIn₂S₄ (D-O-ZIS) creates significant electronegativity differences between adjacent atomic sites, with S₁ sites being electron-rich and S₂ sites being electron-deficient in the local structure of S₁-S₂-O sites. The strong charge redistribution character activates stable oxygen reactions at S₂ sites and avoids the common issue of sulfur instability in metal sulfide photocatalysis, while S₁ sites favor the adsorption/desorption of hydrogen. Consequently, an overall water-splitting reaction has been realized in D-O-ZIS with a remarkable solar-to-hydrogen conversion efficiency of 0.57%, accompanying a ~ 91% retention rate after 120 h photocatalytic test. In this work, we inspire an universal design from electronegativity differences perspective to activate and stabilize metal sulfide photocatalysts for efficient overall water-splitting.

Abstract

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