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Layered β‐ZrNBr Nitro‐Halide as Multifunctional Photocatalyst for Water Splitting and CO<sub>2</sub> Reduction

Yunfeng Bao, Shiwen Du, Kengo Shibata, Xiangyang Guo, Yoshinobu Kamakura, Zhaochi Feng, Yanqiang Huang, Osamu Ishitani, Kazuhiko Maeda, Fuxiang Zhang

2022Angewandte Chemie International Edition32 citationsDOI

Abstract

Abstract Developing mixed‐anion semiconductors for solar fuel production has inspired extensive interest, but the nitrohalide‐based photocatalyst is still in shortage. Here we report a layered nitro‐halide β‐ZrNBr with a narrow band gap of ca. 2.3 eV and low defect density to exhibit multifunctionalities for photocatalytic water reduction, water oxidation and CO 2 reduction under visible‐light irradiation. As confirmed by the results of electron paramagnetic resonance (EPR) and density functional theory (DFT) calculations, the formation of anion vacancies in the nitro‐halide photocatalyst was inhibited due to its relatively high formation energy. Furthermore, performance of β‐ZrNBr can be effectively promoted by a simple exfoliation into nanosheets to shorten the carrier transfer distance as well as to promote charge separation. Our work extends the territory of functional photocatalysts into the nitro‐halide, which opens a new avenue for fabricating efficient artificial photosynthesis.

Topics & Concepts

PhotocatalysisHalideNitroBand gapPhotochemistryDensity functional theoryMaterials scienceElectron paramagnetic resonancePhotocatalytic water splittingExfoliation jointSemiconductorVisible spectrumWater splittingChemistryCatalysisInorganic chemistryNanotechnologyOptoelectronicsComputational chemistryPhysicsOrganic chemistryNuclear magnetic resonanceAlkylGrapheneAdvanced Photocatalysis TechniquesMXene and MAX Phase MaterialsInorganic Chemistry and Materials