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

Bernales V., Yang D., Yu J., Gumuslu G., Cramer C. J. , Gates B. C. , ...More

ACS APPLIED MATERIALS & INTERFACES, vol.9, no.39, pp.33511-33520, 2017 (SCI-Expanded) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 9 Issue: 39
  • Publication Date: 2017
  • Doi Number: 10.1021/acsami.7b03858
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.33511-33520
  • Keywords: metal-organic framework nodes, ethylene dimerization, ethylene hydrogenation, rhodium complexes, supported catalyst, density functional theory, ATOMIC-LAYER-DEPOSITION, SURFACE-CHEMISTRY, BASIS-SETS, MOF, NUCLEARITY, MECHANISM, CLUSTERS, ETHENE, STEPS, SITES
  • Istanbul Technical University Affiliated: No


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.