Tailoring the Selective Oxidation of Hydroxyl-Containing Compounds via Precisely Tuning the Hydrogen-Bond Strength of Catalyst H-Bond Acceptors
Date
2025-02-20
Journal Title
Journal ISSN
Volume Title
Publisher
JACS Au
Abstract
The unique performance of the enzyme is mainly achieved via weak interactions between the “outer coordination sphere” and the substrate. Inspired by this process, we developed 3D encapsulated-structure catalysts with hydrogen-bond engineering on the shell, which mimics the “outer coordination sphere” of an enzyme. Various hydrogen bond acceptors (C═O, S═O, and N–O groups) are imparted in the shell. Concentration-dependent 1H NMR, inverse-phase gas Chromatography (IGC) measurements, and DFT calculations underscore that the hydrogen bond strength between the acceptor groups and alcohol follows the order of C═O < S═O < N–O. The hydroxyl compound oxidation rate vs the hydrogen bond strength follows a volcano behavior, reminiscent of Sabatier’s principle. The performance variation among catalysts is attributed to the adsorption strength of the substrate. The proposed bioinspired design principle expands the scope of encapsulated catalysts, enabling fine regulation of catalytic activity through precise microenvironment control via weak interactions with substrates.
Description
This article was originally published in JACS Au. The version of record is available at: https://doi.org/10.1021/jacsau.4c01262.
Copyright © 2025 The Authors. Published by American Chemical Society. This publication is licensed under CC-BY-NC-ND 4.0 (https://creativecommons.org/licenses/by-nc-nd/4.0/) .
Keywords
enzyme-inspired, encapsulated catalyst, alcohol oxidation, hydrogen bond, Sabatier’s principle
Citation
Feng, Xiao, Piaoping Yang, Yinwei Wang, Jieqi Cao, Jin Gao, Song Shi, and Dionisios G. Vlachos. “Tailoring the Selective Oxidation of Hydroxyl-Containing Compounds via Precisely Tuning the Hydrogen-Bond Strength of Catalyst H-Bond Acceptors.” JACS Au 5, no. 3 (March 24, 2025): 1359–66. https://doi.org/10.1021/jacsau.4c01262.