Confinement of Ultrasmall Cu/ZnOx Nanoparticles in Metal-Organic Frameworks for Selective Methanol Synthesis from Catalytic Hydrogenation of CO2
Confinement of Ultrasmall Cu/ZnOx Nanoparticles in Metal-Organic Frameworks for Selective Methanol Synthesis from Catalytic Hydrogenation of CO2
复制标题
金属有机框架中超小的 Cu/ZnOx 纳米颗粒的限制用于 CO2 催化加氢选择性合成甲醇
DOI：
10.1021/jacs.7b00058
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发表时间：
2017-03-15
影响因子：
15
通讯作者：
Lin, Wenbin
中科院分区：
文献类型：
--
作者：
An, Bing;Zhang, Jingzheng;Lin, Wenbin
Cu/ZnO和Cu/ZrO_2界面在这些复合催化剂的CO_2加氢制甲醇反应中起着重要作用。催化过程中的表面结构重组和颗粒生长有害地减少了这些活性界面，降低了催化活性和MeH选择性。本文报道了在UiO-bpy金属有机骨架（MOFs）中使用预组装的bpy和Zr-6（mu（3）-O）（4）（mu（3）-O）（4）位点来锚超小的Cu/ZnO纳米颗粒，从而防止Cu纳米颗粒的团聚和MOFs腔限制的Cu/ZnOx纳米颗粒中Cu和ZnOx之间的相分离。所得Cu/ZnOx@MOF催化剂显示出非常高的活性，时空产率高达2.59 gMeOH kgCu（-1）h（-1），CO2加氢为甲醇的选择性为100%，并且在100 h内具有高稳定性。金属纳米颗粒与有机螯合物/金属-氧簇之间的这些新型强金属载体相互作用为微调金属纳米颗粒@MOFs的催化活性和选择性提供了新的机会。
interfaces of Cu/ZnO and Cu/ZrO2 play vital roles in the hydrogenation of CO2 to methanol by these composite catalysts. Surface structural reorganization and particle growth during catalysis deleteriously reduce these active interfaces, diminishing both catalytic activities and MeH selectivities. Here we report the use of preassembled bpy and Zr-6(mu(3)-O)(4)(mu(3)-O)(4) sites in UiO-bpy metal-organic frameworks (MOFs) to anchor ultrasmall Cu/ZnO nano particles, thus preventing the agglomeration of Cu NPs and phase separation between Cu and ZnOx in MOF-cavity-confined Cu/ZnOx nanoparticles. The resultant Cu/ZnOx@MOF catalysts show very high activity with a space-time yield of up to 2.59 gMeOH kgCu(-1) h(-1), 100% selectivity for CO2 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.