TY - JOUR
T1 - A versatile method for the preparation of carbon-rhodium hybrid catalysts on graphene and carbon black
AU - Wong, Chin Min
AU - Walker, D. Barney
AU - Soeriyadi, Alexander H.
AU - Gooding, J. Justin
AU - Messerle, Barbara A.
N1 - Copyright the Author(s) 2016. Version archived for private and non-commercial use with the permission of the author/s and according to publisher conditions. For further rights please contact the publisher.
PY - 2016/3/1
Y1 - 2016/3/1
N2 - Strategies for combining the selectivity and efficiency of homogeneous organometallic catalysts with the versatility of heterogeneous catalysts are urgently needed. Herein a direct and modular methodology is presented that provides rapid access to well-defined carbon-rhodium hybrid catalysts. A pre-synthesized Rh(i) complex containing a carbene-triazole ligand was found to be stable for direct immobilization onto unactivated graphene, carbon black and glassy carbon electrodes. Characterization of the heterogeneous systems using X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), inductively coupled plasma-optical emission spectroscopy/mass spectrometry (ICP-OES/MS), Raman spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) confirmed the well-defined nature of the hybrid catalysts. The hybrid catalysts show excellent activity, comparable to that of the homogeneous system for the hydrosilylation of diphenylacetylene, with turnover numbers ranging from 5000 to 48 000. These catalysts are the best reported to date for the hydrosilylation of diphenylacetylene. In common with conventional heterogeneous catalysts, high reusability, due to a lack of Rh metal leaching, was also observed for all carbon-rhodium complexes under investigation.
AB - Strategies for combining the selectivity and efficiency of homogeneous organometallic catalysts with the versatility of heterogeneous catalysts are urgently needed. Herein a direct and modular methodology is presented that provides rapid access to well-defined carbon-rhodium hybrid catalysts. A pre-synthesized Rh(i) complex containing a carbene-triazole ligand was found to be stable for direct immobilization onto unactivated graphene, carbon black and glassy carbon electrodes. Characterization of the heterogeneous systems using X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), inductively coupled plasma-optical emission spectroscopy/mass spectrometry (ICP-OES/MS), Raman spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) confirmed the well-defined nature of the hybrid catalysts. The hybrid catalysts show excellent activity, comparable to that of the homogeneous system for the hydrosilylation of diphenylacetylene, with turnover numbers ranging from 5000 to 48 000. These catalysts are the best reported to date for the hydrosilylation of diphenylacetylene. In common with conventional heterogeneous catalysts, high reusability, due to a lack of Rh metal leaching, was also observed for all carbon-rhodium complexes under investigation.
UR - http://www.scopus.com/inward/record.url?scp=84959420151&partnerID=8YFLogxK
UR - http://purl.org/au-research/grants/arc/DP130101838
UR - http://purl.org/au-research/grants/arc/DP150103065
U2 - 10.1039/c5sc03787e
DO - 10.1039/c5sc03787e
M3 - Article
C2 - 29899923
AN - SCOPUS:84959420151
SN - 2041-6520
VL - 7
SP - 1996
EP - 2004
JO - Chemical Science
JF - Chemical Science
IS - 3
ER -