A series of ternary copper-cerium-zirconium catalysts containing two kinds of copper species, surface CuO and Cu-Ce-Zr solid solution, are prepared and studied for catalytic properties of CO₂ hydrogenation to methanol. The copper-cerium- zirconium catalyst calcined at 450 °C (CCZ-450) is much more favorable for improving the nature of surface CuO species and forming Cu-Ce-Zr solid solution than others. The best catalytic behavior in terms of methanol selectivity (T = 280 °C, S_CH3OH = 71.8%), turnover frequency (TOF_CO2 = 13.4 × 10⁻² s⁻¹) and activation energy (E_a = 28.5 kJ/mol) are achieved using CCZ-450. The excellent catalytic performance of CCZ-450 is attributed to the stronger H₂ adsorption ability arising from highly dispersed surface CuO specie with higher copper surface area and higher concentration of active bi/m-HCOO* intermediate caused by the formation of Cu-Ce-Zr solid solution. Both the dispersion and surface area of active sites and the activation abilities of CO₂ are critical for catalyst activity and product selectivity. In situ diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) experiments at 3 MPa confirm that both bi-HCOO* and m-HCOO* are the active intermediates for CO₂ hydrogenation to methanol. The accumulation of m-HCOO* on the catalyst surface is the crucial step of CO₂ hydrogenation to methanol.

制备了一系列含铜表面CuO和Cu-Ce-Zr固溶体两种铜的三元铜-铈-锆催化剂，并研究了CO ₂加氢制甲醇的催化性能。与其他方法相比，在450°C下煅烧的铜-铈-锆催化剂（CCZ-450）更有利于改善表面CuO种类的性质并形成Cu-Ce-Zr固溶体。就甲醇选择性（T  = 280°C，S _CH3OH  = 71.8％），周转频率（TOF _CO2  = 13.4×10 ^-2 s ^-1）和活化能（E _a）而言，最佳的催化行为 = 28.5 kJ / mol）是使用CCZ-450实现的。CCZ-450优异的催化性能归因于高度分散的表面CuO物种具有更高的H ₂吸附能力，而CuO物种具有较高的铜表面积和较高的活性Bi / m-HCOO *中间体浓度，这是由于形成Cu-Ce- Zr固溶体。活性位点的分散度和表面积以及CO ₂的活化能力对于催化剂活性和产物选择性都至关重要。在3 MPa下进行的原位漫反射红外傅里叶变换光谱（DRIFTS）实验证实，bi-HCOO *和m-HCOO *都是CO ₂的活性中间体加氢成甲醇。m-HCOO *在催化剂表面的积累是CO ₂加氢为甲醇的关键步骤。