Work

Understanding Heterogeneously Catalyzed Hydrogenation of Carbonyl Compounds Through Keto‐Enol Tautomerization

Year: 2025

Type: article

Abstract: The possibility of low-barrier hydrogenation of carbonyl compounds via keto-enol tautomerization as the initial step is a highly debated question in catalysis research. Here, a comprehensive description is provided, supported by theoretical and experimental techniques, of surface-assisted keto-enol tautomerization and subsequent hydrogenation of carbonyl compounds to alcohols. The crucial role of the ketone-ketone dimers as key reaction intermediates is elucidated, in which one ketone species undergoes a low-barrier tautomerization to form a stable ketone-enol dimer. This phenomenon arises from the strong intermolecular interactions within the dimers and the substantial charge-transfer between the adsorbates and the surface. Remarkably, the reduction of the barrier is primarily attributed to the charge-transfer from the inner HOMO-1 orbital. This work explores the atomic details underlying the tautomerization reaction, contributing to the rational design of high-performance metal catalysts for low-barrier hydrogenation of carbonyl compounds.

Source: Small

DOI: 10.1002/smll.202504104

Authors: Jingtai Li, Carsten Schröder, Marvin Schmidt, Jan Smyczek, Swetlana Schauermann, Wei Liu

Institutions: Chinese Academy of Sciences, Changchun Institute of Applied Chemistry, State Key Laboratory of Rare Earth Resources Utilization, Christian-Albrechts-Universität zu Kiel

Language: English

Topic: Nanomaterials for catalytic reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: bronze

Funders: People's Government of Jilin Province, Chinesisch-Deutsche Zentrum für Wissenschaftsförderung, National Key Research and Development Program of China

Awards: G6354121392, G6435936047