2026-10-12T16:24:30Zhttps://www.radar-service.eu/oai/OAIHandler

10.35097/pnmem7c42eezkx892026-10-09T10:58:21Zradar4kit

https://dx.doi.org/10.35097/pnmem7c42eezkx89 Pauer, Swantje Röse, Philipp Shimizu, Yugo Harada, Juri Shida, Naoki Atobe, Mahito Krewer, Ulrike Model-assisted Identification of the Reaction Mechanism and Kinetics of Cyclohexanone Reduction in a PEM-Cell Karlsruhe Institute of Technology 2026 Engineering dataset Dataset info:eu-repo/semantics/openAccess https://creativecommons.org/licenses/by-sa/4.0/legalcode The kinetics of electroorganic synthesis reactions is usually not analyzed, which prevents knowledge-driven de sign and operation. This study examines the electrochemical cis-selective reduction of 4-tert-butylcyclohexanone to 4-tert-butylcyclohexanol using an Rh/C catalyst in a proton exchange membrane (PEM) cell. The reaction mechanism and kinetics are identified using a combination of experimental cyclic voltammetry (CV) and model based kinetic analysis. Among three proposed reaction mechanisms– one based on Langmuir-Hinshelwood and two based on Eley-Rideal theory– the Langmuir-Hinshelwood-type mechanism (LHM), involving the reaction of adsorbed 4-tert-butylcyclohexanone with adsorbed hydrogen, was identified as the most plausible. Dynamic simulations based on the LHM showed strong agreement with the experimental data, accurately capturing key electrochemical features and reproducing Faradaic efficiencies. The kinetic model accounts for reaction kinetics for the electroreduction and the competitive hydrogen evolution reaction, as well as mass transport processes. Our findings highlight that ketone adsorption influences both catalytic activity and selectivity, whereas alcohol desorption is identified as the rate-limiting step. The accumulation of alcohol at the catalyst surface reduces ac tive site availability and promotes H2 evolution, thereby lowering Faradaic efficiency at higher current densities. Simulations under steady-state conditions predict that increasing ketone concentrations reduces side reactions and increase the Faraday efficiency for the desired product. These insights emphasize the importance of op timizing catalyst properties to enhance overall conversion rate, and of maintaining high ketone concentration to achieve high selectivity, energy efficiency, and Faradaic efficiency. Kinetic analysis is thus shown to be a powerful prerequisite for understanding and improving synthesis processes. The supplied data will enable reproduction of all included figures and is named intuitively. The data includes experimental and simulative datasets. The corresponding publication can be found via: https://doi.org/10.1016/j.electacta.2026.149612 Electrosynthesis Electrochemical reaction kinetics Reaction mechanism Kinetic modeling Process optimization https://publikationen.bibliothek.kit.edu/1000191228 application/x-tar