In this work, three MOF-based materials with highly dispersed Rh(I) were synthesized for hydroformylation of n-butene, namely Rh(I)/UiO-66, Rh(I)/MOF-5 and Rh(I)/MIL-101. The defect sites on the metal nodes of MOFs promoted the anchoring of Rh as a single active site. A high-performance Rh(I)/MOF-5 catalyst was obtained with the n-butene conversion and pentanal selectivity of 96.4% and 85.8%, respectively. In addition, it showed a good stability in the recycling tests after five runs. XRD, TEM, XPS, in situ DRIRTS confirmed that the metal nodes in MOFs modified the activity of the coordinated Rh catalyst by influencing the adsorption strength of CO. Combing the DFT results, we predicted that Rh(I)/MOF-5 catalyst with suitable CO adsorption energy could reduce the reaction energy barrier in CO insertion process, which was the rate-determining step of overall reaction, thus improving the selectivity of total aldehydes. This work broadened the application of MOFs as catalyst supports and provided assistance for the development of heterogeneous catalysts in hydroformylation of olefins.

在这项工作中，合成了三种具有高度分散 Rh(I) 的 MOF 基材料用于正丁烯的加氢甲酰化，即 Rh(I)/UiO-66、Rh(I)/MOF-5 和 Rh(I)/MIL -101。MOFs金属节点上的缺陷位点促进了Rh作为单个活性位点的锚定。获得了高性能的 Rh(I)/MOF-5 催化剂，其正丁烯转化率和戊醛选择性分别为 96.4% 和 85.8%。此外，它在五次运行后的回收测试中表现出良好的稳定性。XRD、TEM、XPS、原位 DRIRTS 证实 MOFs 中的金属节点通过影响 CO 的吸附强度来改变配位 Rh 催化剂的活性。结合 DFT 结果，我们预测 Rh(I)/MOF-5 催化剂具有合适的CO吸附能可以降低CO嵌入过程中的反应能垒，这是整个反应的速率决定步骤，从而提高了总醛的选择性。该工作拓宽了 MOFs 作为催化剂载体的应用，并为烯烃加氢甲酰化中多相催化剂的开发提供了帮助。