Cu-BTC衍生的CuO_(x)/C催化甲醇氧化羰基化合成碳酸二甲酯性能  

Performance of Cu-BTC-derived CuO_(x)/C for methanol oxidative carbonylation to dimethyl carbonate

作　　者：李文杰 高山林 赖春波 肖婉婧 李心灵 林慧博 王馨雨 徐成华[1] 邓志勇 LI Wenjie;GAO Shanlin;LAI Chunbo;XIAO Wanjing;LI Xinling;LIN Huibo;WANG Xinyu;XU Chenghua;DENG Zhiyong(Air Environmental Modeling and Pollution Controlling Key Laboratory of Sichuan Higher Education Institutes,China-Serbia"the Belt and Road"Joint Laboratory on Environment and Energy,College of Resources and Environment,Chengdu University of Information Technology(CUIT),Chengdu 610225,China;Shanghai Engineering Research Center of Coal-based Polygeneration,Shanghai Huayi Holding Group CO.,LTD.,Shanghai 200040,China)

机构地区：[1]成都信息工程大学资源环境学院,中-塞环境与能源“一带一路”联合实验室,大气环境模拟与污染控制四川省高校重点实验室,成都610225 [2]上海华谊控股集团有限公司上海煤基多联产工程技术研究中心,上海200040

出　　处：《复合材料学报》2024年第7期3620-3629,共10页Acta Materiae Compositae Sinica

基　　金：四川省科技计划(2022ZYD0049,2021YFG0225);上海煤基多联产工程技术研究中心开放课题(GZKF-MJDLC-03);成都信息工程大学科研基金资助成果(KYTZ202118)。

摘　　要：碳基材料负载Cu是一类高效的甲醇氧化羰基化合成碳酸二甲酯催化剂,但存在Cu纳米颗粒易团聚和氧化等问题。采用溶剂热法制备了Cu-BTC,并以其为前驱体,在N2气氛下热解,制备了碳负载Cu及其氧化物(CuOx/C)催化剂。考察了热解温度对Cu纳米颗粒粒径、Cu的价态以及甲醇氧化羰基化合成碳酸二甲酯性能的影响。表征结果显示,升高热解温度有利于Cu^(2+)还原为(Cu^(0)+Cu^(+)),但会导致Cu纳米颗粒团聚。催化剂活性随着热解温度升高而降低,当热解温度为300℃时,制备的CuOx/C-300具有最优的催化活性,碳酸二甲酯的时空收率为1209 mg·g^(-1)·h^(-1),归因于Cu纳米颗粒的粒径最小(7.5 nm)。经过6次循环实验后,碳酸二甲酯的时空收率降至468 mg·g^(-1)·h^(-1),催化剂失活的主要原因是(Cu^(0)+Cu^(+))的氧化和Cu纳米颗粒团聚。Carbon-based material supported Cu is an efficient catalyst for methanol oxidative carbonylation to dimethyl carbonate,but Cu nanoparticles are prone to agglomeration and oxidation.Cu-BTC were prepared by hydrothermal method.And then CuO_(x)/C catalysts was prepared by pyrolysis Cu-BTC under N_(2) atmosphere.The effect of pyrolysis temperature on Cu nanoparticle size,Cu valence state and performance for methanol oxidative carbonylation to dimethyl carbonate were investigated.The characterization results show that increasing the pyrolysis temperature is beneficial to the reduction of Cu^(2+)to(Cu^(0)+Cu^(+)),but would lead to the agglomeration of Cu nanoparticles.Catalytic activity decreases with the increasing of pyrolysis temperature.CuO_(x)/C-300,prepared by pyrolysis of Cu-BTC at 300℃,shows the optimized catalytic activity and the space-time yield of dimethyl carbonate is 1209 mg·g^(-1)·h^(-1).This is attributed to the smallest particle size of Cu nanoparticles(7.5 nm).In addition,the space-time yield of dimethyl carbonate decreased to 468 mg·g^(-1)·h^(-1) after 6 cycle experiments.The main reasons for catalyst inactivation are the oxidation of(Cu^(0)+Cu^(+))and the agglomeration of Cu nanoparticles.

关 键 词：催化剂 碳基材料 Cu纳米颗粒 碳酸二甲酯 MOFS 热解 氧化羰基化 

分 类 号：TB333[一般工业技术—材料科学与工程] TQ225[化学工程—有机化工]