Rh2P Nanoparticles Stabilized by Carbon Patches for Hydroformylation of Olefins

Rh2P nanoparticles (NPs) have been identified as suitable mimics of [RhI(Ph3P)3]+, the benchmark of homogeneous catalysts in liquid-phase hydroformylation. For this reason, a fitted synthetic strategy is required to develop catalysts based exclusively on Rh2P NPs. To attain this, two synthetic pathways have been devised. In the first one, two separate sources of Rh and P were used. In the second one, the Wilkinson complex was employed as a unique source of Rh and P to probe the positive influence of the well-defined molecular organization on the preparation of dispersed and controlled Rh2P nanoparticles, stabilized by carbon patches formed during the pyrolysis treatment from PPh3. In addition, metallic Rh nanoparticles were also synthesized to be used as reference. All catalysts have been compared by means of: transmission electron microscopy, X-ray diffraction, and X-ray adsorption spectroscopy. The application of XAS to the study of Rh2P NPs is unusual and has been essential in the discussion of the results. Starting with a well-defined metal precursor leads to the exclusive formation of Rh2P NPs with excellent catalytic activity for the liquid-phase hydroformylation. The role of P is to modulate the particle size and the electronic configuration of Rh species, resulting in the improvement of the catalytic performance and the obtention of turnover frequencies of 5236 h-1 at 60 °C and 17,788 h-1 at 100 °C.Program Severo Ochoa SEV-2016-0683 is gratefully acknowledged. C.G.-R. thanks MINECO for her FPU Ph.D. contract FPU17/04172. The authors thank the financial support by the Spanish Government (RTI2018-096399-A-I00). The authors thank J.G.M. for his technical support. We also thank the Electron Microscopy Service of the UPV for TEM facilities. C.W.L. thanks PRH 50.1 – ANP/FINEP Human Resources Program for the Visiting Researcher Fellowship. This research used resources of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by the Argonne National Laboratory and was supported by the U.S. DOE under contract no. DE-AC02-06CH11357 and the Canadian Light Source and its funding partners.Peer reviewe