Electrochemical hydrogeneration (ECH) of biomass-derived platform molecules, which avoids the disadvantages in utilizing fossil fuel and gaseous hydrogen, is a promising route toward value-added chemicals production. Herein, we reported a CoO/Co heterostructure-supported Pt single atoms electrocatalyst (Pt-CoO/Co) that exhibited an outstanding performance with a high conversion (>99%), a high Faradaic efficiency (87.6%), and robust stability (24 recyclability) at -20 mA/cm for electrochemical phenol hydrogenation to high-valued KA oil (a mixture of cyclohexanol and cyclohexanone). Experimental results and the density functional theory calculations demonstrated that Pt-CoO/Co presented strong adsorption of phenol and hydrogen on the catalyst surface simultaneously, which was conducive to the transfer of the adsorbed hydrogen generated on the single atom Pt sites to activated phenol, and then, ECH of phenol with high performance was achieved instead of the direct hydrogen evolution reaction. This work described that the multicomponent synergistic single atom catalysts could effectively accelerate the ECH of phenol, which could help the achievement of large-scale biomass upgrading.
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http://dx.doi.org/10.1021/acs.inorgchem.3c03338 | DOI Listing |
J Am Chem Soc
January 2025
CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
Well-defined single-atom catalysts (SACs) serve as ideal model systems for directly comparing experimental results with theoretical calculations, offering profound insights into heterogeneous catalytic processes. However, precisely designing and controllably synthesizing SACs remain challenging due to the unpredictable structure evolution of active sites and generation of embedded active sites, which may bring about steric hindrance during chemical reactions. Herein, we present the precious nonpyrolysis synthesis of Re SACs with a well-defined phenanthroline coordination supported by NiO (Re-phen/NiO).
View Article and Find Full Text PDFLangmuir
January 2025
Centre for Energy (M473), The University of Western Australia, 35 Stirling Highway, Crawley, WA 6009, Australia.
The mechanisms of NO reduction by CO over nitrogen-doped graphene (N-graphene)-supported single-atom Ni catalysts in the presence of O, HO, CO, and SO have been studied via density functional theory (DFT) modeling. The catalyst is represented by a single Ni atom bonded to four N atoms on N-graphene. Several alternative reaction pathways, including adsorption of NO on the Ni site, direct reduction of NO by CO, decomposition of NO to NO followed by reduction of NO to N, formation of active oxygen radical O*, and reduction of O* by CO, were hypothesized and the energy barrier corresponding to each of the reaction steps was calculated using DFT.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
Université Paris-Saclay, CNRS, Institut des Sciences Moléculaires d'Orsay UMR 8214, 91405 Orsay, France.
This study deals with the understanding of hydrogen atom scattering from graphene, a process critical for exploring C-H bond formation and energy transfer during atom surface collision. In our previous work [Shi, L.; 2023, 159, 194102], starting from a cell with 24 carbon atoms treated periodically, we have achieved quantum dynamics (QD) simulations with a reduced-dimensional model (15D) and a simulation in full dimensionality (75D).
View Article and Find Full Text PDFACS Nano
January 2025
Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive, Los Angeles, California 90095-1569, United States.
Dimension-engineered synthesis of atomically thin II-VI nanoplatelets (NPLs) remains an open challenge. While CdSe NPLs have been made with confinement ranging from 2 to 11 monolayers (ML), CdTe NPLs have been significantly more challenging to synthesize and separate. Here we provide detailed mechanistic insight into the layer-by-layer growth kinetics of the CdTe NPLs.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2025
Theoretical Physics Section, Bhabha Atomic Research Centre, Mumbai-400085, India.
Extensive research on ultrashort laser-induced melting of noble metals like Au, Ag and Cu is available. However, studies on laser energy deposition and thermal damage of their alloys, which are currently attracting interest for energy harvesting and storage devices, are limited. This study investigates the melting damage threshold (DT) of three intermetallic alloys of Au and Cu (AuCu, AuCu and AuCu) subjected to single-pulse femtosecond laser irradiation, comparing them with their constituent metals.
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