In the present study, three kinds of copper/titania-silica mixed oxides (Cu/TS) catalysts were prepared using copper chloride, copper nitrate, and copper acetate as copper precursors by the sol-gel method. The catalytic performance was tested in the vapor phase carbonylation of methanol free of halide. The characterization results showed that the interaction between copper and support was the strongest on the 10Cu/TS (Cl) catalyst, leading to the highest copper dispersion and the most surface Cu⁺ species. As a result, the 10Cu/TS (Cl) catalyst obtained the largest absorption capacity of CO and the maximum amount of Lewis acid sites. The catalytic performance results showed that the space time yield (STY) of methyl acetate (MA) was positively correlated with the content of surface Cu⁺ species and the specific surface area of the Cu⁺ cations (S_Cu(I)). Therefore, the 10Cu/TS (Cl) catalyst obtained the highest STY_MA of 1.619 mol/h.kg_cat. Moreover, the STY_MA per Cu⁺ site was inversely proportional to the copper particle size, indicating that the carbonylation of methanol to MA is a structure-sensitive reaction. And the methanol conversion was positively correlated with the amount of surface acid sites. Furthermore, the active sites for the synthesis of methyl formate and dimethyl ether were also studied.

在本研究中，通过溶胶-凝胶法以氯化铜，硝酸铜和乙酸铜为铜前驱体制备了三种铜/二氧化钛-二氧化硅混合氧化物（Cu / TS）催化剂。在不含卤化物的甲醇的气相羰基化中测试了催化性能。表征结果表明，铜与载体之间的相互作用在10Cu / TS（Cl）催化剂上最强，从而导致最高的铜分散度和最大的表面Cu ⁺种类。结果，10Cu / TS（Cl）催化剂获得了最大的CO吸收能力和最大的Lewis酸位。催化性能结果表明，乙酸甲酯（MA）的时空产率（STY）与表面Cu ⁺的含量呈正相关。Cu ⁺阳离子（S _Cu（I））的种类和比表面积。因此，10Cu / TS（Cl）催化剂获得的最高STY _MA为1.619 mol / h.kg _cat。此外，每个Cu ⁺位点的STY _MA与铜的粒径成反比，表明甲醇羰基化成MA是结构敏感的反应。并且甲醇转化率与表面酸性位点的数量呈正相关。此外，还研究了合成甲酸甲酯和二甲醚的活性位点。