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Boosting the Activity of Ligand‐on Atomically Precise Pd 3 Cl Cluster Catalyst by Metal‐Support Interaction from Kinetic and Thermodynamic Aspects
Author(s) -
Yun Yapei,
Sheng Hongting,
Yu Jie,
Bao Linquan,
Du Yuanxin,
Xu Fengqing,
Yu Haizhu,
Li Peng,
Zhu Manzhou
Publication year - 2018
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201800603
Subject(s) - nanoclusters , catalysis , chemistry , x ray photoelectron spectroscopy , calcination , dissociation (chemistry) , metal , heterogeneous catalysis , bimetallic strip , selectivity , chemical engineering , organic chemistry , engineering
Atomically precise nanoclusters (APNCs), as ideal model catalysts, revealed great advantages to deep‐understand of reaction mechanisms in heterogeneous catalysis. Boosting the activity of APNCs is the most critical issue under the premise of maintaining structure invariance. Herein, utilizing Metal‐Support Interaction (MSI) strategy, we prepared an excellent and recyclable catalyst for aerobic oxidation by combination of an otherwise inert nanocluster [Pd 3 Cl(PPh 2 ) 2 (PPh 3 ) 3 ] + [SbF 6 ] − (denoted as Pd 3 Cl) with functional titanate nanotubes (TNT). The promising Pd 3 Cl/TNT composite gives rise to excellent conversion with 100% selectivity without any additives at 30 °C under an oxygen pressure. This result is unprecedented in ligand‐on nanocluster catalysts without high temperature calcination. The distinct difference between their activities of Pd 3 Cl/TNT composite and fresh Pd 3 Cl nanocluster is explained by the presence of the MSI effect, as confirmed using X‐ray photoelectron spectroscopy (XPS) analysis. Theoretical simulations are further carried out to elucidate the catalytic mechanism, indicating the MSI effect promotes the crucial β‐H elimination step in both kinetic and thermodynamic aspects. This work presents the example of atomic‐level understanding of the effect of MSI on facilitating the APNCs catalytic properties.