Department of Ecological Engineering for Environmental Sustainability, College of the Environment and Ecology , Xiamen University , Xiamen 361102 , P. R. China.
Department of Chemical and Biochemical Engineering, College of Chemistry and Chemical Engineering, National Laboratory for Green Chemical Productions of Alcohols, Ethers and Esters, Key Lab for Chemical Biology of Fujian Province , Xiamen University , Xiamen 361005 , P. R. China.
ACS Appl Mater Interfaces. 2019 Sep 11;11(36):33263-33272. doi: 10.1021/acsami.9b11547. Epub 2019 Aug 29.
Metal-organic frameworks have been exploited as excellent solid precursors and templates for the preparation integrated nanocatalysts with multicomponent and hierarchical structures. Herein, a novel synthetic protocol has been developed to fabricate versatile Zr-based solid solutions (such as ZnO-ZrO, CoO-ZrO, and CuO-ZrO) via pyrolysis of Schiff base-modified UiO-66 octahedrons (size <100 nm), which were then utilized as efficient catalysts for CO hydrogenation. The Schiff base serves as an effective bridge to dope secondary metal ions into UiO-66 frameworks with controlled amounts of 0.13-8.8 wt %, which are initially hard to achieve. Interestingly, by simply changing the loading metal ions, the selectivity of C hydrogenation products can be facilely tuned. For instance, the maximum CO conversion of ZnO-ZrO, CoO-ZrO, and CuO-ZrO solid solutions were 5.8, 11.4, and 22.5%, with the main product selectivity of 70% CHOH, 92.5% CH, and 86.7% CO, respectively. Moreover, in situ diffuse reflectance infrared Fourier transform spectra characterization reveals that the significant difference in C product selectivity is mainly determined by the balance of *HCOO, *CHO, and *CO intermediate species over the Zr-based solid solutions.
金属-有机骨架已被开发为用于制备具有多组分和分级结构的集成纳米催化剂的优秀固体前体和模板。在此，开发了一种新颖的合成方案，通过热解席夫碱修饰的 UiO-66 八面体（<100nm）来制备多功能 Zr 基固溶体（如 ZnO-ZrO、CoO-ZrO 和 CuO-ZrO），然后将其用作 CO 加氢的高效催化剂。席夫碱作为一种有效的桥联剂，可以将二次金属离子掺杂到 UiO-66 骨架中，掺杂量为 0.13-8.8wt%，这在初始阶段是很难实现的。有趣的是，通过简单地改变负载金属离子，可以轻松地调节 C 加氢产物的选择性。例如，ZnO-ZrO、CoO-ZrO 和 CuO-ZrO 固溶体的最大 CO 转化率分别为 5.8%、11.4%和 22.5%，主要产物的选择性分别为 70% CHOH、92.5% CH 和 86.7% CO。此外，原位漫反射红外傅里叶变换光谱表征表明，C 产物选择性的显著差异主要取决于 Zr 基固溶体上 *HCOO、*CHO 和 *CO 中间物种的平衡。
