Bioinspired Hydrophobic Single-Atom Catalyst with Flexible Sulfur Motif for Aqueous-Phase Hydrogenative Transformation

作者：Wengang Liu, Jiachang Liu, Jiachang Liu, Xilu Liu, Haonan Zheng, Jian Liu, Jian Liu · 发表于：ACS Catalysis · 年份：2022 · DOI：10.1021/acscatal.2c05862 · 被引用次数：32 · 研究领域：Nanomaterials for catalytic reactions、Asymmetric Hydrogenation and Catalysis、Advanced Photocatalysis Techniques

Metalloenzyme-like metal–nitrogen–carbon (M–N–C) single-atom catalysts (SACs) have received increasing attention in the synthesis of fine chemicals because of the abundant atomic sites and versatile catalytic properties. However, the organic transformations with high atom efficiency over SACs in aqueous media were less investigated. Inspired by the hydrophobic pockets of the metalloenzyme, herein we introduced a hydrophobic, atomically dispersed Pd catalyst (Pd 1 –S–C) in the sulfur-doped carbon based on metal–sulfur coordination chemistry. This hydrophobic Pd-based SAC displayed satisfying catalytic performance for aqueous-phase semihydrogenation of terminal alkynes with high chemoselectivity, friendly substrate scope, and fairly good stability. Molecular dynamics simulations revealed that the hydrophobicity of the Pd 1 –S–C catalyst could contribute to accelerated reaction kinetics by enriching the organic alkynes around the catalytic sites in aqueous media. Furthermore, the electron-rich PdS 4 single sites were demonstrated to promote activation of H 2 molecules and desorption of C═C intermediates, which outperformed the electron-deficient PdN 4 single sites. The current work highlights the potential of enzyme-inspired hydrophobic SACs in the conversion of organic substrates in aqueous media.