A mild route to solid-supported rhodium nanoparticle catalysts and their application to the selective hydrogenation reaction of substituted arenes

Abstract

A clean route is described for the preparation of 1.3 % (w/w) supported rhodium nanoparticle (3.0 ± 0.7 nm) catalysts onto commercial ion-exchange resins. Their application to the liquid-phase hydrogenation reaction of C=C bonds shows the most active species are obtained under catalytic conditions at room temperature and 1 bar H2. The heterogeneous catalyst shows excellent activity, selectivity and reusability in the hydrogenation reaction of alkenes and substituted arenes under very undemanding conditions. The results are discussed in terms of support effect on the catalytic efficiency.

Chemoselective hydrogenation of arenes by PVP supported Rh nanoparticles

“…30 In terms of TOF the catalytic performance of the prepared RhNP/ PVP catalyst is similar to the results obtained by Barbaro and co-workers with resin-supported RhNP catalysts under mild reaction conditions (1 bar and RT). 31 Other RhNP-based catalytic systems have been reported to be more active in the hydrogenation of arenes than the one presented in this work, but usually the reaction conditions are more harsh in terms of temperature (>60°C) and H 2 pressure (>10 bar). Moreover, the present work uses water as the solvent making the overall process greener than other reported catalytic systems.…”

“…Moreover, the present work uses water as the solvent making the overall process greener than other reported catalytic systems. [31][32][33] Encouraged by the good performance of the RhNP/PVP catalyst in the selective hydrogenation of arenes, the hydrogenation of levulinic acid and methyl levulinate was further explored as a plausible route to obtain γ-valerolactone from biomass (Scheme 1). The reaction conditions were selected on the basis of our recently developed catalytic system with Au core and Pt shell NPs stabilized on graphitized carbon black (Au@Pt/G-CB).…”

Metal nanoparticles immobilized on ion-exchange resins: A versatile and effective catalyst platform for sustainable chemistry

“…Following the same strategy described above for the immobilization of PdNP, rhodium NPs were recently prepared within the pores of a gel-type, cation-exchange sulfonic resin Dowex, using [Rh(NBD)2]BF4 as the soluble metal precursor [102]. Choice of the precursor was motivated by the known propensity to H2 metal reduction via norbornene elimination [103].…”

“…In-situ prepared Rh@Dowex catalysts (Table 1, entry 14) efficiently catalyse the hydrogenation of arenes under the very undemanding conditions of H2 ((1-10  10 5 Pa) at room temperature in the liquid phase, providing excellent chemo-and cis/trans selectivity to the corresponding cyclohexane derivatives at full substrate conversion. However, this reaction has very poor tolerance for ketone groups toward hydrogenation (Table 5) [102].…”

Metal Nanoparticles Supported on Perfluorinated Superacid Polymers: A Family of Bifunctional Catalysts for the Selective, One‐Pot Conversion of Vegetable Substrates in Water

“…A representative example is shown in Figure for Rh@PW65SM‐OTf. Notably, Pd@PW65SM‐H2 and Rh@PW65SM‐H2 show activities comparable to those of the parent Pd@Dowex and Rh@Dowex catalysts based on a gel‐type polymeric support. This indicates the full site‐accessibility of the Aquivion catalysts thanks to the microporosity that developed upon swelling.…”