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Vol. 14 (2022)

Electron-Deficient Zn-N6 Configuration Enabling Polymeric Carbon Nitride for Visible-Light Photocatalytic Overall Water Splitting

https://doi.org/10.1007/s40820-022-00962-x
Daming Zhao
International Research Center for Renewable Energy, State Key Laboratory of Multiphase Flow in Power Engineering, Xi’an Jiaotong University, Xi’an 710049, People’s Republic of China
Yiqing Wang
International Research Center for Renewable Energy, State Key Laboratory of Multiphase Flow in Power Engineering, Xi’an Jiaotong University, Xi’an 710049, People’s Republic of China
Chung‑Li Dong
Department of Physics, Tamkang University, New Taipei City 25137, Taiwan, People’s Republic of China
Fanqi Meng
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, People’s Republic of China
Yu‑Cheng Huang
Department of Physics, Tamkang University, New Taipei City 25137, Taiwan, People’s Republic of China
Qinghua Zhang
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, People’s Republic of China
Lin Gu
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, People’s Republic of China
Lan Liu
International Research Center for Renewable Energy, State Key Laboratory of Multiphase Flow in Power Engineering, Xi’an Jiaotong University, Xi’an 710049, People’s Republic of China
Shaohua Shen
International Research Center for Renewable Energy, State Key Laboratory of Multiphase Flow in Power Engineering, Xi’an Jiaotong University, Xi’an 710049, People’s Republic of China

Corresponding Author: Shaohua Shen

shshen_xjtu@mail.xjtu.edu.cn

Nano-Micro Letters, Vol. 14 (2022), Article Number: 223

Abstract

Despite of suitable band structures for harvesting solar light and driving water redox reactions, polymeric carbon nitride (PCN) has suffered from poor charge transfer ability and sluggish surface reaction kinetics, which limit its photocatalytic activity for water splitting. Herein, atomically dispersed Zn-coordinated three-dimensional (3D) sponge-like PCN (Zn-PCN) is synthesized through a novel intermediate coordination strategy. Advanced characterizations and theoretical calculations well evidence that Zn single atoms are coordinated and stabilized on PCN in the form of Zn-N6 configuration featured with an electron-deficient state. Such an electronic configuration has been demonstrated contributive to promoted electron excitation, accelerated charge separation and transfer as well as reduced water redox barriers. Further benefited from the abundant surface active sites derived from the 3D porous structure, Zn-PCN realizes visible-light photocatalysis for overall water splitting with H2 and O2 simultaneously evolved at a stoichiometric ratio of 2:1. This work brings new insights into the design of novel single-atom photocatalysts by deepening the understanding of electronic configurations and reactive sites favorable to excellent photocatalysis for water splitting and related solar energy conversion reactions.


Highlights:


1 Atomically dispersed Zn-anchored 3D sponge-like polymeric carbon nitride (Zn-PCN) characteristic of a unique Zn-N6 electron-deficient configuration is synthesized via an intermediate coordination strategy.
2 The electron-deficient Zn-N6 configuration contributes to enhanced electron excitation, accelerated charge separation and transfer as well as reduced overpotentials of water redox reactions.
3 The obtained Zn-PCN realizes photocatalytic overall water splitting to stoichiometrically produce H2 and O2 with good durability under visible light.

Keywords

Zn single atoms Polymeric carbon nitride Overall water splitting Photocatalysis
Zhao, Daming, Yiqing Wang, Chung‑Li Dong, Fanqi Meng, Yu‑Cheng Huang, Qinghua Zhang, Lin Gu, Lan Liu, and Shaohua Shen. 2022. “Electron-Deficient Zn-N6 Configuration Enabling Polymeric Carbon Nitride for Visible-Light Photocatalytic Overall Water Splitting”. Nano-Micro Letters 14 (November):223. https://doi.org/10.1007/s40820-022-00962-x.
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