Rhodium nanoparticles stabilized by sulfonic acid functionalized metal-organic framework for the selective hydrogenation of phenol to cyclohexanone


ERTAS I. E. , Gülcan M. , BULUT A., YURDERI M., Zahmakıran M.

JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, vol.410, pp.209-220, 2015 (Journal Indexed in SCI) identifier identifier

  • Publication Type: Article / Article
  • Volume: 410
  • Publication Date: 2015
  • Doi Number: 10.1016/j.molcata.2015.09.025
  • Title of Journal : JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
  • Page Numbers: pp.209-220
  • Keywords: Metal-organic framework, MIL-101, Rhodium, Phenol, Hydrogenation, RUTHENIUM(0) NANOCLUSTERS, SYNERGISTIC CATALYSIS, ZEOLITE FRAMEWORK, SUPERB CATALYST, FORMIC-ACID, DEHYDROGENATION, BENZENE, SOLVENT, MIL-101, PORES

Abstract

Rhodium(0) nanoparticles stabilized by sulfonic acid functionalized metal-organic framework (Rh@SMIL-101) were prepared, for the first time, by using a direct cationic exchange approach and subsequent reduction with sodium borohydride at room temperature. The characterization of the resulting Rh@SMIL-101 material was done by using multi pronged analyses including ICP-OES, EA, P-XRD, XPS, DR-UV-vis, BFFEM, HRTEM, STEM-EDX and N2-adsorption-desorption technique, which revealed that the formation of rhodium(0) nanoparticles (2.35 +/- 0.9 nm) stabilized by the framework of S-MIL-101 by keeping the host framework intact (Rh@S-MIL-101). The catalytic performance of Rh@S-MIL-101 in terms of activity, selectivity and stability was demonstrated in the hydrogenation of phenol under mild conditions (at 50 degrees C and 5 bar initial H-2 pressure). We found that Rh@S-MIL-101 catalyst selectively hydrogenated phenol to cyclohexanone with high activity (initial TOF= 78 mol cyclohexanone/mol Rh x h) and selectivity (>92%) at almost complete conversion (>95%). Moreover, the resulting rhodium nanopartides were found to be highly stable against leaching and sintering, which makes Rh@S-MIL-101 reusable heterogeneous catalyst without losing of significant activity and selectivity. (C) 2015 Elsevier B.V. All rights reserved.