氯氧铋@纳米纤维素复合材料中氧空位对苄胺C-N偶联的光催化促进作用  

Photocatalytic promotion of benzylamine C-N coupling by oxygen vacancies in bismuth oxychloride@nanocellulose composites

作　　者：王晓霞 孙龙 秦鹂 苏静[1] 王佳佳[1] WANG Xiaoxia;SUN Long;QIN Li;SU Jing;WANG Jiajia(Department of Chemistry,Changzhi University,Changzhi 046011,China)

机构地区：[1]长治学院化学系,山西长治046011

出　　处：《燃料化学学报（中英文）》2024年第6期864-872,共9页Journal of Fuel Chemistry and Technology

基　　金：山西省基础研究项目(202203021212172,202203021222333);山西省高等学校科技创新项目(2022L505,2022L506)资助。

摘　　要：本工作采用纳米纤维素(CNC)为载体,与BiOCl在室温搅拌下制备了复合光催化剂BiOCl@CNC。XRD、FT-IR、SEM、TEM、XPS等系列表征表明,CNC中大量羟基可以与BiOCl通过氢键紧密结合,并在材料中构造丰富的氧空位,从而显著提升其可见光催化性能。以可见光下催化苄胺C-N偶联为目标反应评估BiOCl@CNC的性能并对机理进行研究。首先对反应条件进行优化,得最优条件为1.0 mmol苄胺作为底物,20 mg BiOCl@CNC作催化剂,以30 W白色LED灯为光源,在CH3CN中氧气氛围下室温反应20 h。底物扩展实验表明,BiOCl@CNC对含有不同取代基的反应物均表现出良好的适应性,且具有优异的稳定性。通过自由基捕获实验表明,电子在氧空位的辅助下产生超氧自由基,并与胺阳离子自由基中间体形成最终产物。这一工作不仅丰富了Bi基复合半导体的应用,也为N-苄烯丁胺的合成提供了新思路。In this study,a composite photocatalyst BiOCl@CNC was prepared by simple stirring with BiOCl at room temperature using nanocellulose(CNC)as a carrier.Comprehensive characterizations(XRD,FT-IR,SEM,TEM,XPS)reveal that the abundant hydroxyl groups in CNC can form strong hydrogen bonds with BiOCl,leading to the creation of numerous oxygen vacancies in the material and thereby significantly enhancing its visible lightdriven photocatalytic performance.The performance of the BiOCl@CNC was evaluated using the C-N coupling reaction of benzylamine as the target reaction under visible light,and the underlying mechanism was investigated.The results show that the optimal reaction process is that 1.0 mmol of benzylamine and 20 mg of BiOCl@CNC are added to CH3CN under an oxygen atmosphere to react for 20 hours using a 30 W white LED lamp as the light source.In the substrate expansion experiments,the BiOCl@CNC exhibits remarkable adaptability and exceptional stability towards reactants with diverse substituents.The free radical capture experiments demonstrate that the electrons can effectively generate superoxide radicals in the presence of oxygen vacancies and subsequently form the ultimate product through amine cation radical intermediates.This study not only expands the application potential of Bi-based composite semiconductors but also presents novel insights for synthesizing N-benzylene butylamine.

关 键 词：氯氧铋 纳米纤维素 氧空位 可见光催化 苄胺氧化 

分 类 号：O643[理学—物理化学]