Discovering Partially Charged Single-Atom Pt for Enhanced Anti-Markovnikov Alkene Hydrosilylation

Abstract

The hydrosilylation reaction is one of the largest-scale application of homogeneous catalysis and is widely used to enable the commercial manufacture of silicon products. However, considerable issues including disposable platinum consumption, undesired side reactions and unacceptable catalyst residues still remain. Here, we synthesize a heterogeneous partially charged single-atom platinum supported on anatase TiO (Pt/TiO) catalyst via an electrostatic-induction ion exchange and two-dimensional confinement strategy, which can catalyze hydrosilylation reaction with almost complete conversion and produce exclusive adduct. Density functional theory calculations reveal that unexpected property of Pt/TiO originates from atomic dispersion of active species and unique partially positive charge Pt electronic structure that conventional nanocatalysts do not possess. The fabrication of single-atom Pt/TiO catalyst accomplishes a reasonable use of Pt through recycling and maximum atom-utilized efficiency, indicating the potential to achieve a green hydrosilylation industry.

Ultrathin Metal–Organic Framework Nanosheets with Ultrahigh Loading of Single Pt Atoms for Efficient Visible‐Light‐Driven Photocatalytic H2 Evolution

“…Zuschriften those of Pt II and Pt 0 ,indicating that the incorporated Pt atoms are partially in oxidation state. [14] TheP tc ontent is determined to be 12.0 wt %byinductively coupled plasma optical emission spectrometry (ICP-OES). It is worth noting that such ah igh loading surpasses those of most reported singleatom catalysts (Supporting Information, Table S1).…”

“…[12b] Thes ingle peak attributed to the PtÀNb onding in the N1sX PS spectrum ( Figure 1e;Supporting Information, Figure S9) coupled with ac haracteristic peak for Pt species in the Pt 4f spectrum (Figure 1f)confirms the presence of Pt À Ncoordination in the porphyrin units of the MOF nanosheets. [14] TheP tc ontent is determined to be 12.0 wt %byinductively coupled plasma optical emission spectrometry (ICP-OES). [14] TheP tc ontent is determined to be 12.0 wt %byinductively coupled plasma optical emission spectrometry (ICP-OES).…”

One‐Pot Cooperation of Single‐Atom Rh and Ru Solid Catalysts for a Selective Tandem Olefin Isomerization‐Hydrosilylation Process

“…[2] Their cationic nature,m onoatomicity and defined coordination environment make oxide-supported SACs excellent candidates to bridge the gap between the disciplines of heterogeneous and homogeneous catalysis, [3] particularly in an umber of areas which have been traditionally dominated by molecular complex catalysts applied in solution. Hence, SACs have been recently explored for reactions classically catalyzed by cationic metal salts or complexes,i ncluding olefin hydroformylation, [5] olefin hydrosilylation, [6] alkyne hydrochlorination, [7] or C À Ccoupling. [8] Arelevant area where SACs can have aprofound impact is tandem catalysis,that is,the integration of two catalysts in as ingle pot to achieve sequential transformations in adirect manner.…”

Stable Discrete Pt1(0) in Crown Ether with Ultra‐High Hydrosilylation Activity

“…The high activity of Pt 1 @[15]crown‐5 can be attributed to the electron deficient of Pt 1 δ+ center and the easy leaving of oxygen ligands compared to dvtms . The weakly coordinating ether oxygens of [15]crown‐5 can be easily replaced by olefin coordination compared to the dvtms coordinated Pt complexes .…”

“…The products yield and selectivity were determined by 1 no deactivation was observed in three catalyst reuse evaluations ( Figure S4). The high activity of Pt 1 @ [15]crown-5 can be attributed to the electron deficient of Pt 1 δ + center [33] and the easy leaving of oxygen ligands compared to dvtms. [6] The weakly coordinating ether oxygens of [15]crown-5 can be easily replaced by olefin coordination compared to the dvtms coordinated Pt complexes.…”