1. Identification of active catalysts for the acceptorless dehydrogenation of alcohols to carbonyls
- Author
-
Wang, Tao, Sha, Jin, Sabbe, Maarten, Sautet, Philippe, Pera-Titus, Marc, Michel, Carine, Institute for Advanced Biosciences / Institut pour l'Avancée des Biosciences (Grenoble) (IAB), Centre Hospitalier Universitaire [Grenoble] (CHU)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Etablissement français du sang - Auvergne-Rhône-Alpes (EFS)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Universiteit Gent = Ghent University (UGENT), University of California [Los Angeles] (UCLA), University of California (UC), Eco-Efficient Products & Processes Laboratory (E2P2L), RHODIA-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-13-CDII-0004,SHAPes,Nouveaux procédés d'amination sélective pour la synthèse de monomères biosourcés(2013), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Universiteit Gent = Ghent University [Belgium] (UGENT), University of California, Eco-Efficient Products &Processes Laboratory (E2PL2), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-RHODIA, Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Michel, Carine, Chimie Durable – Industries, Innovation - Nouveaux procédés d'amination sélective pour la synthèse de monomères biosourcés - - SHAPes2013 - ANR-13-CDII-0004 - CD2I - VALID, and École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL)
- Subjects
inorganic chemicals ,OXIDANT-FREE DEHYDROGENATION ,SITES ,Heterogeneous catalysis ,Technology and Engineering ,CATALYSIS ,organic chemicals ,Science ,Reaction mechanisms ,METAL-CATALYSTS ,OXIDATION ,Article ,COOPERATIVE ,[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry ,DENSITY-FUNCTIONAL THEORY ,[CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry ,C-H ,HETEROGENEOUS CATALYST ,ACID-BASE ,METHANOL DECOMPOSITION ,Density functional theory ,RATIONAL DESIGN - Abstract
Acceptorless dehydrogenation into carbonyls and molecular hydrogen is an attractive strategy to valorize (biobased) alcohols. Using 2-octanol dehydrogenation as benchmark reaction in a continuous reactor, a library of metal-supported catalysts is tested to validate the predictive level of catalytic activity for combined DFT and micro-kinetic modeling. Based on a series of transition metals, scaling relations are determined as a function of two descriptors, i.e. the surface binding energies of atomic carbon and oxygen. Then, a volcano-shape relation based on both descriptors is derived, paving the way to further optimization of active catalysts. Evaluation of 294 diluted alloys but also a series of carbides and nitrides with the volcano map identified 12 promising candidates with potentially improved activity for alcohol dehydrogenation, which provides useful guidance for experimental catalyst design. Further screening identifies β-Mo2N and γ-Mo2N exposing mostly (001) and (100) facets as potential candidates for alcohol dehydrogenation., Identifying active catalysts for the conversion of alcohols into aldehydes or ketones and molecular hydrogen is highly desirable. Here the authors develop and validate against experiments a screening model based on DFT calculations and scaling relationships for identifying alcohol dehydrogenation catalysts.
- Published
- 2021