State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, 222 South Tianshui Road, Lanzhou, Gansu 730000, P. R. China.
Dalton Trans. 2014 Jan 21;43(3):1011-8. doi: 10.1039/c3dt51987b. Epub 2013 Oct 28.
A series of metal ion doped TiO2 nanoparticles (M-TiO2, M = Cr(3+), Mn(2+), Fe(3+), V(5+), Zn(2+), Ni(2+), Ag(+), Cu(2+) and Co(2+)) were prepared by a facile co-precipitation approach and characterized by means of ICP-AES, N2 adsorption-desorption isotherms, XRD, TEM and HRTEM. Their catalytic performance was investigated via the oxidation of organic compounds. The variation of metal ion species and doping contents allowed tuning the catalytic properties of the M-TiO2. Among them, the catalyst Cu-10 displayed excellent activity (97.5%) in the oxidation of styrene and the selectivity of benzaldehyde was as high as 99.4%. Surprisingly, the product distribution of styrene oxidation experienced a reverse trend over the Co-TiO2 catalysts with different doping amounts of cobalt ions: Co-10 was in favor of forming benzaldehyde (80.2% selectivity), in contrast with Co-15, which produced styrene oxide as the dominant product (84.7% selectivity). The M-TiO2 catalysts also showed catalytic activities for the oxidation of benzyl alcohol and toluene to generate chlorine-free benzaldehyde in excellent selectivities (>99%).
采用简单的共沉淀法制备了一系列金属离子掺杂的 TiO2 纳米粒子（M-TiO2，M = Cr(3+)、Mn(2+)、Fe(3+)、V(5+)、Zn(2+)、Ni(2+)、Ag(+)、Cu(2+)和 Co(2+)）。通过 ICP-AES、N2 吸附-脱附等温线、XRD、TEM 和 HRTEM 对其进行了表征。通过氧化有机化合物考察了它们的催化性能。金属离子种类和掺杂含量的变化可以调节 M-TiO2 的催化性能。其中，催化剂 Cu-10 在苯乙烯氧化中表现出优异的活性（97.5%），苯甲醛的选择性高达 99.4%。令人惊讶的是，不同钴离子掺杂量的 Co-TiO2 催化剂上苯乙烯氧化的产物分布呈现相反的趋势：Co-10 有利于形成苯甲醛（选择性 80.2%），而 Co-15 则生成氧化苯乙烯作为主要产物（选择性 84.7%）。M-TiO2 催化剂也表现出对苯甲醇和甲苯氧化的催化活性，以优异的选择性（>99%）生成无氯苯甲醛。
