温和条件下新型铜基磷酸盐在氧化反应中的高催化活性  

Novel Copper Phosphates with High Catalytic Activities under Mild Conditions

作　　者：孟祥举[1] 肖丰收[1] 

机构地区：[1]吉林大学化学学院,无机合成与制备化学国家重点实验室,长春130012

出　　处：《物理化学学报》2004年第F08期939-945,共7页Acta Physico-Chimica Sinica

基　　金：国家自然科学基金(20173022;20121103);国家基础研究重大项目计划(G2000077507)资助~~

摘　　要：系统综述了以新型铜基磷酸盐(Cu2(OH)PO4)为代表的催化剂在一些典型的氧化反应中的活性.本文涉及的反应类型主要包括以过氧化氢为氧化剂,苯、苯酚、2,3,6-三甲基苯酚的羟化,烯烃的环氧化反应和以氧气为氧化剂,烯烃和醇的氧化反应,结果显示Cu2(OH)PO4的比表面积较小,但是在这一系列的反应中展示了很高的催化活性.同时利用电子自旋共振(ESR)、红外(IR)等表征手段对催化反应的机理和反应路径进行了讨论,羟基自由基和铜的过氧物种被认为是催化反应的重要中间体.Conventionally,heterogeneous catalysts are mainly focused on the mate rials with large surface area such as TS-1(350m 2 ·g -1 ),and the materials with relatively s mall surface area(<10m 2 ·g -1 )are generally ignored.This review summarized the catalytic activities and mechanism in a series of oxidations by H 2 O 2 or oxy-gen as oxidants over novel copper pho sphates with very small surface area less than 1.4m 2 ·g -1 .In the hydroxy-lation of phenol and benzene by H 2 O 2 ,the high activities of this catalyst are comparable to those of TS-1.In e pox-idation of styrene by H 2 O 2 ,the selectivity for epoxide is much higher than that of TS-1.In hydroxyl ation of 2,3,6-trimethylphenol by H 2 O 2 ,it showed good activity and high selectivity for trimethylhydroquinon e.In oxidation of olefins and alcohols by O 2 ,the catalysts exhibited remarkabl e catalytic results.The characterization of ESR and IR spectroscopies shows that hydroxyl radicals and peroxide species are im portant intermediates in these oxid ations.

关 键 词：磷酸铜 过氧化氢 氧气 苯酚羟化 烯烃环氧化 醇的氧化 羟基自由基 过氧物种 

分 类 号：O643[理学—物理化学]