第 52 卷第 5 期 Vol. 52 No. 5 2022 年 10 月 Oct 2022

所属栏目：功能材料 P掺杂C3N4的制备及其在碱催化反应中的应用

陈 琨，肖 广，兰东辉*，沈 静*，区泽堂，易 兵* （湖南工程学院 材料与化工学院，环境催化与废弃物再生化湖南省重点实验室，湖南 湘潭 411104）

摘　要：基于酸碱协同催化设计思想，以结构类似的三聚氰胺和六氯环三磷腈热缩聚制备了P掺杂的C3N4材料。利用SEM和BET分析P掺入前后材料的结构，发现P掺入后材料变为直径约为5 μm的球状结构，比表面积由8.2 m2/g增加至11.9 m2/g。采用XPS和31P MAS NMR证明P以P-OH和P=O键形式进入三嗪结构骨架中。将P掺杂的C3N4材料作为无金属多相催化剂应用于碱催化反应中。采用硝酸将部分P-OH氧化为P=O，探讨了P种类和数量对环氧丙烷与CO2环加成反应、碳酸丙烯酯与甲醇酯交换反应以及苯甲醛与丙二腈Knoevenagel反应的影响，结合XPS和31P MAS NMR表征结果发现P-OH的引入有利于CO2环加成反应、酯交换反应和Knoevenagel反应的进行。

关键词：多相催化剂；碳三氮四；碱催化；CO2环加成反应；酯交换反应；Knoevenagel反应

中图分类号：O530.24　　文献标识码：A　　文章编号：1009-9212（2022）05-0050-07

Facile Synthesis of P-doped C3N4 for Base-catalyzed Reactions

CHEN Kun, XIAO Guang, LAN Dong-hui*, SHEN Jing*, AU Chak-tong, YI Bing* (Hunan Provincial Key Laboratory of Environmental Catalysis and Waste Rechemistry, College of Materials and Chemical Engineering, Hunan Institute of Engineering, Xiangtan 411104, China)

Abstract：Based on the synergic catalytic effects between Base and Acid, P doped carbon nitride were facilely synthesized by thermal polycondensation of hexachlorotriphosphazene and melamine. Based on the results of SEM and BET analyses, P-C3N4 show a spheroidal structure with 11.9 m2/g. As characterized by XPS and 31P MAS NMR analyses, there is substitution of P atoms for C atoms which located at the bay and edge terminal positions. Partial P-OH bonds of P doped carbon nitride were oxidized to P=O by HNO3. The P doped carbon nitride was used as easy-to-handle and metal-free heterogeneous catalyst for base-catalyzed reactions such as cycloaddition of CO2 with propylene oxide, transesterification of propylene carbonate with methanol, Knoevenagel reaction between benzaldehyde and malononitrile. The relation between catalytic performance and the type and amount of P were investigated. The excellent performance of P-C3N4 for CO2 cycloaddition, transesterification and Knoevenagel reaction is owing to the synergetic effect of P-OH and uncondensed amino groups.

Key words：heterogeneous catalysts; C3N4; base-catalyzed reaction; CO2 cycloaddition; transesterification; Knoevenagel reaction

基金项目：湖南省教育厅优秀青年项目（18B379），湖南省自然科学基金项目（2018JJ3099），大学生创新创业项目（202211342015），湖南省研究生科技创新项目（CX20221295）。

作者简介：陈 琨（1999—），男，湖南岳阳人，硕士，研究方向：多相催化（E-mail：756932363@qq.com）。

联 系 人：兰东辉，副教授，博士，研究方向：多相催化、CO2资源化、碳酸酯合成（E-mail：donghuilan@hnu.edu.cn）；沈 静，讲师，博士，研究方向：功能材料；易 兵，教授，博士，研究方向：绿色合成，催化与不对称合成。

收稿日期：2022-08-14