College of Chemical Engineering, Northwest University

以焙烧商用氢氧化锆（Zr(OH)4）得到的ZrO2为载体，通过沉积-沉淀法制备了ZnO-ZrO2催化剂，并在873 K下对该催化剂上CO2辅助的乙烷氧化脱氢反应（CO2-ODHE）的催化性能进行了评价。利用X射线衍射（XRD）、扫描电镜（SEM）、拉曼光谱（Raman）、高分辨透射电镜（HRTEM）、X射线光电子能谱（XPS）、CO2程序升温脱附（CO2-TPD）等技术对ZnO-ZrO2催化剂的表面物理化学性质和形貌进行了表征。结果表明，在5%ZnO-ZrO2催化剂上，ZnO掺入到了ZrO2的表面晶格之中，在催化剂表面产生了高度分散的ZnO物种和氧缺陷区域。5%ZnO-ZrO2催化剂可以选择性地剪裁乙烷C−H键，抑制C−C键的断裂，具备良好的催化性能。210 µmol/(gcat·min)的C2H4形成率可以与贵金属和过渡金属碳化物催化剂的报道数据接近。此外，还对ZnO-ZrO2催化剂上CO2-ODHE反应可能的反应机制进行了讨论。

The ZnO-ZrO2 catalyst was prepared by the deposition-precipitation method using ZrO2 as the carrier obtained from calcining commercial zirconium hydroxide (Zr(OH)4). And the catalytic performance was evaluated at 873 K in CO2-assisted ethane oxidative dehydrogenation reaction (CO2-ODHE). The physical-chemical properties and morphology were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), Raman spectra, High-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectra (XPS), CO2 temperature-programmed desorption (CO2-TPD). The results show that ZnO were doped into the surface lattice of ZrO2 on the 5%ZnO-ZrO2 catalyst, generating highly dispersed ZnO species and oxygen-deficient regions on catalyst surface. 5%ZnO-ZrO2 catalyst could selectively breaking C−H bond instead of C−C bond, delivering excellent catalytic performance. 210 μmol/(gcat·min) of C2H4 formation rate could compare favorably with the data reported on noble metal and transition metal carbides. Additionally, the possible mechanism is discussed.

廖多华, 杨亮, 宋庚哲, 马雪冬, 李爽. ZnO-ZrO2催化剂上CO2辅助乙烷氧化脱氢制乙烯的研究[J]. 燃料化学学报（中英文）, 2023, 51(10): 1421-1431.

LIAO Duo-hua, YANG Liang, SONG Geng-zhe, MA Xue-dong, LI Shuang. CO2-assisted oxidative dehydrogenation of ethane to ethylene over the ZnO-ZrO2 catalyst[J]. Journal of Fuel Chemistry and Technology, 2023, 51(10): 1421-1431.