Department of Chemistry, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, 200433, P. R. China.
Laboratory for Catalysis Engineering School of Chemical and Biomolecular Engineering, The University of Sydney, New South Wales, 2006, Australia.
ChemSusChem. 2020 Sep 18;13(18):5073-5079. doi: 10.1002/cssc.202001377. Epub 2020 Aug 13.
Metal-organic frameworks (MOFs) as solid acid catalysts provide active sites with definite structures. Here, Zr -based MOF-808 and its derivatives were studied as catalysts for glycerol dehydration, the products of which (acrolein vs. acetol) are very sensitive to the nature of the catalytic acid sites. Evolving MOF-808 into MOF-808-S with a 120 % increase in the number of Brønsted OH /H O coordinated to Zr and a vanished Lewis acidity by steam treatment, the post-synthetically modified catalyst presented 100 % conversion of glycerol, 91 % selectivity to acrolein, and 0 % selectivity to acetol within the active window. Real-time analysis of the product composition indicated the in situ MOF structural evolution. Overall, the specific MOF-substrate interaction characterized by the probe reaction provides more understandings on the structural evolution of the MOFs and their impact on the performance as solid acid catalysts.
金属-有机骨架（MOFs）作为固体酸催化剂提供了具有确定结构的活性位。在这里，研究了基于 Zr 的 MOF-808 及其衍生物作为甘油脱水的催化剂，其产物（丙烯醛与乙缩醛）对催化酸性位的性质非常敏感。将 MOF-808 通过蒸汽处理演变成 MOF-808-S，Zr 配位的 Brønsted OH/H2O 数量增加了 120%，Lewis 酸度消失，后合成修饰的催化剂在活性窗口内实现了甘油的 100%转化率、91%丙烯醛选择性和 0%乙缩醛选择性。产物组成的实时分析表明了原位 MOF 结构的演变。总的来说，探针反应所表征的特定 MOF-底物相互作用提供了对 MOFs 结构演变及其对固体酸催化剂性能影响的更多理解。
