Rational Design of Core–Shell Structured Pd@MIL-100(Fe) for Efficient Visible Light-Initiated Syntheses of Secondary Amines from Nitro Aromatics and Benzyl Alcohols

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL ACS Catalysis Pub Date : 2025-01-24 DOI:10.1021/acscatal.4c06074

Liangliang Hu, Hurunqing Liu, Zhaohui Li

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Abstract

A rational design of MNPs@MOFs (MNPs = metal nanoparticles, MOFs = metal–organic frameworks) nanocomposites is important for their application as multifunctional catalysts for light-initiated one-pot tandem/cascade reactions. Herein, the Pd@MIL-100(Fe) nanocomposite with a core–shell structure, in which Pd colloids of ca. 3 nm are encapsulated inside the matrix of MIL-100(Fe), was constructed successfully via self-assembly of MIL-100(Fe) in preformed PVP-capped Pd colloids (PVP = polyvinylpyrrolidone) at room temperature. Via a successful combination of MOF-based photocatalysis with Pd-based hydrogenation, Pd_rpvp@MIL-100(Fe), with PVP partially removed, exhibited superior performance for the reaction between nitro aromatics and benzyl alcohols to produce secondary amines. Comparison of activity over Pd_rpvp@MIL-100(Fe) with that of the other two types of MNPs/MIL-100(Fe) nanocomposites suggests that its superior activity can be attributed to the presence of well-stabilized stable Pd nanoparticles (NPs) for hydrogenation and the unoccupied cavities in MOFs to promote the mass diffusion, especially in the case of larger substrates, as well as an efficient charge transfer from the MOF to Pd NPs for their cooperation. This study indicates that a rational strategy in the construction of metal NPs/MOFs nanocomposites is important for their application as multifunctional catalysts for light-initiated one-pot tandem/cascade reactions.

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.