Ga对0.3Ga-WO_(x)/SBA-15催化顺式-环辛烯环氧化的促进作用  

Role of Ga in promoting epoxidation of cis-cyclooctene over Ga-WO_(x)/SBA-15

作　　者：李鹏慧 王会香[1,3] 李俊汾 吕宝亮[1,3] LI Peng-hui;WANG Hui-xiang;LI Jun-fen;LÜBao-liang(State Key Laboratory of Coal Conversion,Institute of Coal Chemistry,Chinese Academy of Sciences,Taiyuan 030001,China;University of Chinese Academy of Sciences,Beijing 100049,China;School of Chemistry and Materials Science,Shanxi Normal University,Taiyuan 030031,China)

机构地区：[1]中国科学院山西煤炭化学研究所煤转化国家重点实验室,山西太原03001 [2]中国科学院大学,北京100049 [3]山西师范大学化学与材料科学学院,山西太原030031

出　　处：《燃料化学学报（中英文）》2023年第10期1453-1461,共9页Journal of Fuel Chemistry and Technology

基　　金：supported by the National Natural Science Foundation of China(21972158);Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy(2021017);Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering(2021-K10);Natural Science Foundation of Shanxi Province(SQ2019006);Patent Conversion Foundation of Shanxi Province(202202093)。

摘　　要：本工作研究了镓(Ga)对Ga-WO_(x)/SBA-15催化H_(2)O_(2)与顺式-环辛烯环氧化反应活性的促进作用。最佳催化剂0.3Ga-WO_(x)/SBA-15的TOF为112 h^(-1),是WO_(x)/SBA-15(57 h^(-1))的近两倍。相较于WO_(x)/SBA-15(64.0 kJ/mol),0.3Ga-WO_(x)/SBA-15的低表观反应活化能(49.6 kJ/mol)与其优异的环氧化性能一致。动力学分析表明,H_(2)O_(2)在0.3Ga-WO_(x)/SBA-15表面上的吸附更强,这有助于H_(2)O_(2)的活化。基于催化剂的表征和环氧化的性能表明,Ga添加剂的提升作用归因于Lewis酸位点的增加和亲电性的增强。此外,金属过氧化氢(M-OOH)被鉴定为主要中间体。This article investigates the promoting effect of gallium(Ga)on the activity of Ga-WO_(x)/SBA-15 catalyst for ciscyclooctene epoxidation with H_(2)O_(2).The optimal catalyst of 0.3Ga-WO_(x)/SBA-15 offered a turnover frequency(TOF)of 112 h^(-1),which was nearly two times than that of WO_(x)/SBA-15(57 h^(-1)).The low apparent reaction activation energy for 0.3Ga-WO_(x)/SBA-15(49.6 kJ/mol vs 64.0 kJ/mol for WO_(x)/SBA-15)was also in line with its superior performance.Kinetic analysis demonstrated stronger adsorption of H_(2)O_(2)on 0.3Ga-WO_(x)/SBA-15 surface,facilitating the H_(2)O_(2)activation.Based on the characterizations and catalytic performance,the improvement of Ga was attributed to the increase of Lewis acid sites and the enhancement of electrophilicity.Furthermore,the metal hydrogen peroxide(M-OOH)was identified as the primary intermediate.

关 键 词：环氧化 Ga促进剂 H_(2)O_(2)活化 氧原子转移 

分 类 号：O643.322[理学—物理化学]