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Pyrene‐Thiol‐modified Pd Nanoparticles on Carbon Support: Kinetic Control by Steric Hinderance and Improved Stability by the Catalyst‐Support Interaction
Author(s) -
Yoshii Takeharu,
Umemoto Daiki,
Yamamoto Masanori,
Kuwahara Yasutaka,
Nishihara Hirotomo,
Mori Kohsuke,
Kyotani Takashi,
Yamashita Hiromi
Publication year - 2020
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.202000987
Subject(s) - catalysis , steric effects , chemistry , thiol , imine , dehydrogenation , photochemistry , nanoparticle , combinatorial chemistry , inorganic chemistry , organic chemistry , materials science , nanotechnology
Aerobic oxidative dehydrogenation of amines to imines by thiol‐modified Pd nanoparticle (NP) catalysts on carbon supports is reported herein. Whereas conventional non‐modified Pd NP catalysts are nearly inactive, the carbon‐supported Pd catalysts modified with thiol ligands efficiently catalyze the reaction with high selectivity. Kinetic studies and DFT calculations reveal that the rate‐limiting imine product desorption step is significantly boosted on the thiol ligands‐modified Pd surface compared to the non‐modified Pd surface due to the steric hindrance of the ligands. Furthermore, the catalytic activity is dramatically enhanced in the presence of both pyrene‐functionalized thiol modifiers and graphene‐based carbon supports; 96 % conversion is attained after 4 h at 110 °C. The π – π interactions between pyrene groups and the highly crystallized carbon surface suppress the leaching of ligands, which offers improved catalyst stability even under O 2 atmosphere at 110 °C, thereby resulting in high activity.