Molecular Rhodium Complexes Supported on the Metal-Oxide-Like Nodes of Metal Organic Frameworks and on Zeolite HY: Catalysts for Ethylene Hydrogenation and Dimerization

作者：Bernales Varinia; Yang Dong; Yu Jun; Gumuslu Gamze; Cramer Christopher J; Gates Bruce C^*; Gagliardi Laura^*

来源：ACS Applied Materials & Interfaces, 2017, 9(39): 33511-33520.

DOI：10.1021/acsami.7b03858

• metal-organic framework nodes
• ethylene dimerization
• ethylene hydrogenation
• rhodium complexes
• supported catalyst
• density functional theory

Metal-organic frameworks (MOFs) with nodes consisting of zirconium oxide clusters (Zr-6) offer new opportunities as supports for catalysts with-defined, essentially molecular, structures. We used the precursor Rh(C2H4)(2) (acac) (acac is acetylacetonate) to anchor Rh(l) complexes to the nodes of the MOF UiO-67 and, for comparison, to the zeolite dealuminated HY. (DAY). These were characterized experimentally by measurement of catalytic activities and selectivities for ethylene hydrogenation and dimerization Iii-a once-through flow reactor at 298 K and 1 bar. The catalyst performance data are complemented with structural information determined by infrared and extended X-ray absorption fine structure spectroscopies and by calculations at the level of density functional theory, the latter carried out also to extend ithe investigation to a related MOF, NU-1000. The agreement between the experimental and calculated structural metrics is good, and the calculations have led to predictions of reaction mechanisms and associated energetics. The data demonstrate a correlation between the catalytic activity and selectivity and the electron-donor tendency of the supported rhodium (as measured by the frequencies of CO ligands bonded as probes to the Rh(l) centers), which is itself a measure of the electron-donor tendency of the support.

• 出版日期2017-10-4