采用共沉淀法分别制备锰掺杂钨、钒、铋3种双金属复合氧化物载体,以氯化钯为活性组分制备负载型催化剂,并用于苯酚氧化羰基化合成碳酸二苯酯（DPC）。通过气相色谱（GC）、X射线衍射（XRD）、氢气程序升温还原（H₂-TPR）、X射线光电子能谱（XPS）等表征手段,对催化剂结构和性能进行表征。结果表明:钨-锰载体随掺杂比例和焙烧温度升高,逐步形成四氧化三锰晶粒,同时钨渗入锰氧化物晶格中,在掺杂比（物质的量比）为1:1、焙烧温度为600 ℃条件下制备的催化剂性能最佳,DPC收率为5.20%;钒-锰载体在焙烧温度为400 ℃、掺杂比为1:5条件下形成二氧化锰晶相,催化剂性能明显提高,DPC收率为10.46%,而较高的焙烧温度会破坏晶型的完整;铋-锰载体在掺杂比为1:5、焙烧温度为400 ℃条件下制备的催化剂催化效果最好,DPC单程收率可达到13.13%。

The Mn-doped W,V and Bi bimetallic oxide supports were prepared by co-precipitation method.PdCl₂ was used as the active component to prepare supported catalysts for synthesis of DPC by heterogeneous catalytic oxidation of phenol.The structure and properties were characterized by means of gas chromatography,X-ray diffraction,hydrogen temperature programmed reduction and X-ray photoelectron spectroscopy etc..Results showed that with the increase of tungsten-manganese doping ratio and calcination temperature,MnO grew into Mn₃O₄ grains gradually and infiltrated into the lattice of MnO_x.Finally,the catalytic activity was best and the yield of DPC was 5.20% at a doping ratio（amount-of-substance ratio） of 1:1 and calcination at 600 ℃.For vanadium manganese oxide,higher calcination temperature will destroy the integrity of the crystal form,and formation of MnO₂ at a doping ratio of 1:5 at 400 ℃ can significantly improve the property of activity,and the yield of DPC was 10.46%.The bismuth-manganese bimetallic oxide catalyst with doping ratio of 1:5 and calcination at 400 ℃ had the best catalytic effect,the one-way yield of DPC was 13.13%.