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Ultrasmall Platinum Stabilized on Triphenylphosphine‐Modified Silica for Chemoselective Hydrogenation
Author(s) -
Jayakumar Sanjeevi,
Modak Arindam,
Guo Miao,
Li He,
Hu Xiangping,
Yang Qihua
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201700980
Subject(s) - chemoselectivity , phenylacetylene , triphenylphosphine , platinum , catalysis , acetophenone , x ray photoelectron spectroscopy , chemistry , adsorption , styrene , fourier transform infrared spectroscopy , platinum nanoparticles , selectivity , inorganic chemistry , photochemistry , materials science , organic chemistry , chemical engineering , copolymer , polymer , engineering
Chemoselective hydrogenation of substrates with more than one functional group that could be hydrogenated is quite challenging and is of fundamental importance. Here, the enhanced chemoselectivity of ultrasmall (<1 nm) platinum nanoparticles (NPs) stabilized on silica modified with triphenylphosphine (PSiO 2 ) in hydrogenation reactions is reported. Platinum NPs on PSiO 2 exhibit much higher selectivity than those on SiO 2 in the hydrogenation of acetophenone to 1‐phenylethanol (99.9 versus 36 %) and hydrogenation of phenylacetylene to styrene (85 versus 52 %). The results of NMR spectroscopy, X‐ray photoelectron spectroscopy, and in situ CO adsorption FTIR spectroscopy indicate the existence of strong interactions between triphenylphosphine and Pt NPs. Consequently, Pt NPs on PSiO 2 have smaller particle sizes and more positive Pt 4 f binding energy than those of Pt/SiO 2 ; these are the main contributors to the superior chemoselectivity of Pt NPs. The organically modified silica could act as an efficient solid ligand for tuning the catalytic performance of metal NPs.