甲醇在Cu_(4)-C_(5)N_(2)H_(2)表面吸附和裂解机理的DFT研究  

DFT Study on Adsorption and Cracking Mechanism of Methanol on the Cu_(4)-C_(5)N_(2)H_(2)Surface

作　　者：王婉楠 任瑞鹏[1,2] 吕永康 WANG Wannan;REN Ruipeng;LÜYongkang(State Key Laboratory of Clean and Efficient Coal Utilization,Taiyuan University of Technology,Taiyuan 030024,China;Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering,Taiyuan 030024,China)

机构地区：[1]太原理工大学省部共建煤基能源清洁高效利用国家重点实验室,山西太原030024 [2]山西浙大新材料与化工研究院,山西太原030024

出　　处：《分子催化(中英文)》2025年第1期34-40,I0002,共8页Journal of Molecular Catalysis(China)

基　　金：国家自然科学基金项目(21776196、51778397);山西省自然科学基金项目(202203021211181);山西浙大新材料与化工研究院项目(2021SXFR001、2021SX-AT004)。

摘　　要：开发高效稳定的甲醇制甲醛催化剂意义重大,但催化剂稳定性差和甲醛选择性低的问题仍然存在.以嵌入氮化碳中的铜四原子团簇(Cu_(4)-C_(5)N_(2)H_(2))催化剂作为模型,基于DFT-D3探索了甲醇在催化剂表面吸附和裂解反应机理.结果表明,Cu_(4)-C_(5)N_(2)H_(2)具有优异的稳定性和高的甲醛选择性,甲醇在Cu_(4)-C_(5)N_(2)H_(2)表面裂解的最优路径为CH_(3)OH→CH_(3)O→CH_(2)O,电荷分析结果显示催化剂与甲醇之间的电子转移使得甲醇得以活化.这些结果为合理设计高效甲醇制甲醛催化剂提供了理论指导.It is of great significance to develop an efficient and stable catalyst for methanol to formaldehyde,but the problems of poor stability and low selectivity for formaldehyde still exist.The mechanism of methanol adsorption and cleavage on the catalyst surface was explored based on DFT-D3,using Cu_(4) cluster catalyst embedded in carbon nitride(Cu_(4)-C_(5)N_(2)H_(2))as a model.The results show that Cu_(4)-C_(5)N_(2)H_(2)exhibits excellent stability and high formaldehyde selectivity.The optimal path of methanol pyrolysis is CH_(3)OH→CH_(3)O→CH_(2)O on the Cu_(4)-C_(5)N_(2)H_(2)surface.The charge analysis results show that the electron specialization between the catalyst and methanol can activate methanol.These results provide theoretical guidance for rational design of efficient methanol to formaldehyde catalysts.

关 键 词：甲醇 甲醛 DFT Cu_(4)-C_(5)N_(2)H_(2) 裂解机理 

分 类 号：O643.32[理学—物理化学]