Boosting the Activity of Ligand‐on Atomically Precise Pd₃Cl Cluster Catalyst by Metal‐Support Interaction from Kinetic and Thermodynamic Aspects

Abstract

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 ] À (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 8C 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 b-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.

Atomically Precise Noble Metal Nanoclusters as Efficient Catalysts: A Bridge between Structure and Properties

“…Zhu's group first developed Pd 3 Cl/TNT (Pd 3 Cl = [Pd 3 (PPh 2 ) 2 (PPh 3 ) 3 Cl] + , TNT = titanate nanotubes), an excellent catalyst for aerobic oxidation promoted by the MSI effect. 482 The composite catalyst exhibits good conversion (68.4−99.3%) with 100% selectivity toward the aldehyde at 30 °C with 1 atm O 2 . Notably, the work presents an atomic-level understanding of the facilitating effect of the MSI on the catalytic properties of the NCs using a combined approach of experiment and theory.…”

“…For nanoparticle catalysts, it is well-known that optimizing the metal–support interaction (MSI) is an astute method to modify their electronic systems for the preparation of catalysts with desired properties. Zhu’s group first developed Pd 3 Cl/TNT (Pd 3 Cl = [Pd 3 (PPh 2 ) 2 (PPh 3 ) 3 Cl] + , TNT = titanate nanotubes), an excellent catalyst for aerobic oxidation promoted by the MSI effect . The composite catalyst exhibits good conversion (68.4–99.3%) with 100% selectivity toward the aldehyde at 30 °C with 1 atm O 2 .…”

“…Results of DFT calculations for the oxidation of benzyl alcohol catalyzed by (A) [Pd 3 (PPh 2 ) 2 (PPh 3 ) 3 Cl] 0 and (B) [Pd 3 (PPh 2 ) 2 (PPh 3 ) 3 Cl] + . Reproduced with permission from ref . Copyright 2018 Wiley-VCH.…”

Designing the electronic and geometric structures of single-atom and nanocluster catalysts

“…77 As a result, the optimisation of the metal-support interaction by choosing an appropriate support material has attracted great research attention which leads to the rational modication of the electronic structures to achieve more superior catalytic performance. 78 Yao et al have engineered the electronic structures of Ru SAs on a series of PtCu alloys via compressive strain to boost the electrocatalytic oxygen evolution reaction. 79 A volcano relation has been reported between the catalytic activity and the lattice constant of the PtCu alloys.…”

C−I Selective Sonogashira and Heck Coupling Reactions Catalyzed by Aromatic Triangular Tri‐palladium

“…[1][2] They are metallic analogous complexes to ordinary organic aromatics. All-metal aromatic complexes had showed various applications in the fields of coordination, [3][4] catalysis [5][6][7] and materials. [8] The continuous developments of all-metal aromatics had indeed expanded the concept and properties of aromaticity.…”