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., ...Daha Fazla

ACS APPLIED MATERIALS & INTERFACES, cilt.9, sa.39, ss.33511-33520, 2017 (SCI-Expanded) identifier identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 9 Sayı: 39
  • Basım Tarihi: 2017
  • Doi Numarası: 10.1021/acsami.7b03858
  • Dergi Adı: ACS APPLIED MATERIALS & INTERFACES
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.33511-33520
  • Anahtar Kelimeler: 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
  • İstanbul Teknik Üniversitesi Adresli: Hayır

Özet

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.