Boosting Photocatalytic Overall Water Splitting Activity of Phosphorene Through Five‐Coordinate Passivation Enabled by Carbene Addition
Abstract
ABSTRACT Phosphorene is a promising two‐dimensional semiconductor for solar‐driven redox reactions, yet its practical deployment is severely restricted by rapid degradation under ambient conditions. Conventional covalent functionalization typically forms phosphorus–carbon single bonds (P─C), leaving phosphorus atoms in a four‐coordinate environment and thus failing to fully quench the intrinsic reactivity associated with one residual unpaired electron. Here, we develop a selective strategy to achieve five‐coordinate passivation of phosphorene by constructing phosphorus–carbon double bonds (P═C) through a one‐step photochemical carbene addition reaction. Using a carbene precursor, adamantane groups are grafted onto phosphorene to afford a robust P═C‐bonded architecture. Comprehensive spectroscopic analyses, together with density functional theory (DFT) calculations, validate the preferential formation of the P═C bonds. The resulting P═C‐passivated phosphorene exhibits markedly improved ambient stability compared to the pristine and four‐coordinate‐passivated phosphorene. When utilized as a metal‐free photocatalyst, the P═C‐passivated phosphorene enables highly efficient overall water splitting without sacrificial agents under visible light, delivering record‐high evolution of H 2 and H 2 O 2 with rates of up to 612 and 658 µmol h −1 g −1 , respectively, along with excellent cycling stability.
Article Details
Authors (13)
He Zhang
Yanbo Li
National Synchrotron Radiation Laboratory, University of Science and Technology of China 2 , Hefei 230029, Anhui,
Junchi Xu
Hefei National Research Center for Physical Sciences at the Microscale, School of Chemistry and Materials Science, National Synchrotron Radiation Laboratory
Shengkun Liu
Hefei National Research Center for Physical Sciences at the Microscale Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), School of Chemistry and Materials Science University of Science and Technology of China Hefei China
Taotao Wang
State Key Laboratory of Precision and Intelligent Chemistry Collaborative Innovation Center of Chemistry for Energy Materials (<i>i</i>ChEM) School of Chemistry and Materials Science University of Science and Technology of China Hefei China
Chao Gao
Pingwu Du
State Key Laboratory of Precision and Intelligent Chemistry Collaborative Innovation Center of Chemistry for Energy Materials (<i>i</i>ChEM) School of Chemistry and Materials Science University of Science and Technology of China Hefei China
Hengxing Ji
Hefei National Laboratory for Physical Sciences at the Microscale, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Department of Applied Chemistry
Jun Jiang
State Key Laboratory of Precision and Intelligent Chemistry, Hefei National Research Center for Physical Sciences at the Microscale, School of Chemistry and Materials Science
Guan‐Wu Wang
Key Laboratory of Functional Molecular Solids Ministry of Education Anhui Laboratory of Molecule‐Based Materials, School of Chemistry and Materials Science Anhui Normal University Wuhu China
Yujie Xiong
State Key Laboratory of Advanced Glass Materials, Anhui Engineering Research Center of Carbon Neutrality, The Key Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Laboratory of Molecular-Based Materials, College of Chemistry and Materials Science
Jong‐Beom Baek
Department of Energy and Chemical Engineering Center For Dimension‐Controllable Organic Frameworks Ulsan National Institute of Science and Technology Ulsan South Korea
Shangfeng Yang