Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University , Xiamen 361005, PR China.
Department of Chemistry, University of Chicago , 929 East 57th Street, Chicago, Illinois 60637, United States.
J Am Chem Soc. 2017 Mar 15;139(10):3834-3840. doi: 10.1021/jacs.7b00058. Epub 2017 Mar 2.
The interfaces of Cu/ZnO and Cu/ZrO play vital roles in the hydrogenation of CO to methanol by these composite catalysts. Surface structural reorganization and particle growth during catalysis deleteriously reduce these active interfaces, diminishing both catalytic activities and MeOH selectivities. Here we report the use of preassembled bpy and Zr(μ-O)(μ-OH) sites in UiO-bpy metal-organic frameworks (MOFs) to anchor ultrasmall Cu/ZnO nanoparticles, thus preventing the agglomeration of Cu NPs and phase separation between Cu and ZnO in MOF-cavity-confined Cu/ZnO nanoparticles. The resultant Cu/ZnO@MOF catalysts show very high activity with a space-time yield of up to 2.59 g kg h, 100% selectivity for CO hydrogenation to methanol, and high stability over 100 h. These new types of strong metal-support interactions between metallic nanoparticles and organic chelates/metal-oxo clusters offer new opportunities in fine-tuning catalytic activities and selectivities of metal nanoparticles@MOFs.
Cu/ZnO 和 Cu/ZrO 的界面在这些复合催化剂将 CO 加氢转化为甲醇的过程中起着至关重要的作用。在催化过程中，表面结构的重组和颗粒的生长会严重破坏这些活性界面，降低催化活性和甲醇选择性。在这里，我们报告了在 UiO-bpy 金属有机骨架 (MOF) 中使用预先组装的 bpy 和 Zr(μ-O)(μ-OH) 位点来锚定超小的 Cu/ZnO 纳米颗粒，从而防止 Cu NPs 的团聚和 MOF 腔限 Cu/ZnO 纳米颗粒中 Cu 和 ZnO 之间的相分离。所得的 Cu/ZnO@MOF 催化剂表现出非常高的活性，时空产率高达 2.59 g kg h，对 CO 加氢制甲醇具有 100%的选择性，在 100 h 以上具有高稳定性。金属纳米颗粒和有机螯合物/金属氧簇之间的这种新型强金属-载体相互作用为调整金属纳米颗粒@MOF 的催化活性和选择性提供了新的机会。
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