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用于高效苯甲醇选择性氧化的硫化镍/红磷复合材料中的可调界面电荷转移:硫化镍晶相的影响

Tunable interfacial charge transfer in a nickel sulfide/red phosphorus composite for efficient benzyl alcohol selective oxidation: Effect of nickel sulfide crystal phase.

作者信息

Jin Xin, Lin Haili, Jia Xuemei, Li Shuang, Li Xinyue, Wang Qianlong, Chen Shifu, Cao Jing

机构信息

Key Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, Anhui Key Laboratory of Synthetic Chemistry and Applications, College of Chemistry and Materials Science, Huaibei Normal University, Huaibei, Anhui 235000, PR China.

Key Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, Anhui Key Laboratory of Synthetic Chemistry and Applications, College of Chemistry and Materials Science, Huaibei Normal University, Huaibei, Anhui 235000, PR China.

出版信息

J Colloid Interface Sci. 2025 Jul 15;690:137315. doi: 10.1016/j.jcis.2025.137315. Epub 2025 Mar 15.

DOI:10.1016/j.jcis.2025.137315
PMID:40117883
Abstract

Red phosphorus (RP) has recently attracted considerable attention in the field of photocatalysis owing to its remarkable optical properties. However, the rapid recombination of photogenerated carriers presents a substantial challenge for the application of RP in the selective photocatalytic oxidation of benzyl alcohol. Herein, a series of nickel sulfide (NiS) materials with different crystal phase, including α-NiS, β-NiS and α-β-NiS, were employed to modulate the interfacial charge transfer in RP for photocatalytic oxidation of benzyl alcohol (BA) coupled with H evolution. A comprehensive array of experimental and theoretical analyses has demonstrated that the Ohmic junction formed between β-NiS and RP is more conducive to enhancing the separation and migration of carriers in comparison to the Schottky junction formed between α-NiS and RP. As expected, the β-NiS/RP exhibited superior photocatalytic performance, achieving higher yields of benzaldehyde (6.79 μmol g h) and H (7.16 μmol g h) compared to α-NiS/RP, α-β-NiS(glo)/RP and α-β-NiS(fla)/RP. The observed enhancement in photocatalytic activity can primarily be attributed to the distinct carrier separation mechanisms, specifically the Ohmic contact in the β-NiS/RP system and the Schottky junction in the α-NiS/RP system. This study introduces an effective strategy for optimizing carrier migration mechanisms in composite catalysts via crystal phase modulation, thereby providing valuable insights into the design of highly efficient photocatalysts for energy and environmental applications.

摘要

红磷(RP)因其卓越的光学性能,近年来在光催化领域备受关注。然而,光生载流子的快速复合对RP在苯甲醇选择性光催化氧化中的应用构成了重大挑战。在此,一系列具有不同晶相的硫化镍(NiS)材料,包括α-NiS、β-NiS和α-β-NiS,被用于调节RP中的界面电荷转移,以实现苯甲醇(BA)光催化氧化与析氢反应的耦合。一系列全面的实验和理论分析表明,与α-NiS和RP之间形成的肖特基结相比,β-NiS和RP之间形成的欧姆结更有利于增强载流子的分离和迁移。正如预期的那样,β-NiS/RP表现出优异的光催化性能,与α-NiS/RP、α-β-NiS(glo)/RP和α-β-NiS(fla)/RP相比,实现了更高的苯甲醛产率(6.79 μmol g h)和氢气产率(7.16 μmol g h)。观察到的光催化活性增强主要归因于不同的载流子分离机制,特别是β-NiS/RP体系中的欧姆接触和α-NiS/RP体系中的肖特基结。本研究介绍了一种通过晶相调制优化复合催化剂中载流子迁移机制的有效策略,从而为能源和环境应用中的高效光催化剂设计提供了有价值的见解。

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