Influence of Ag Metal Dispersion on the Catalyzed Reduction of CO₂ into Chemical Fuels over Ag–ZrO₂ Catalysts

Metal/metal oxide catalysts reveal unique CO2 adsorption and hydrogenation properties in CO2 electroreduction for the synthesis of chemical fuels. The dispersion of active components on the surface of metal oxide has unique quantum effects, significantly affecting the catalytic activity and selectivity. Catalyst models with 25, 50, and 75% Ag covering on ZrO2, denoted as Ag4/(ZrO2)9, Ag8/(ZrO2)9, and Ag12/(ZrO2)9, respectively, were developed and coupled with a detailed investigation of the electronic properties and electroreduction processes from CO2 into different chemical fuels using density functional theory calculations. The dispersion of Ag can obviously tune the hybridization between the active site of the catalyst and the O atom of the intermediate species CH3O* derived from the reduction of CO2, which can be expected as the key intermediate to lead the reduction path to differentiation of generation of CH4 and CH3OH. The weak hybridization between CH3O* and Ag4/(ZrO2)9 and Ag12/(ZrO2)9 favors the further reduction of CH3O* into CH3OH. In stark contrast, the strong hybridization between CH3O* and Ag8/(ZrO2)9 promotes the dissociation of the C–O bond of CH3O*, thus leading to the generation of CH4. Results provide a fundamental understanding of the CO2 reduction mechanism on the metal/metal oxide surface, favoring novel catalyst rational design and chemical fuel production

Multiscale Simulation of Solid Electrolyte Interface Formation in Fluorinated Diluted Electrolytes with Lithium Anodes

Lithium metal batteries (LMBs) hold great promise in facilitating high-energy batteries due to their merits such as high specific capacity, low reduction potential, and so forth. However, the realizations of practical LMBs are hindered by severe problems such as undesirable dendrite growth, poor Coulombic efficiency, and so forth. A recently proposed fluorinated electrolyte based on 1 M lithium bis­(fluorosulfonyl)­imide (LiFSI) dissolved in designed fluorinated 1,4-dimethoxybutane (FDMB) solvent has attracted significant attention because of its excellent electrochemical performance that origins from its superior physical and chemical properties, especially its unique ability in forming a robust, stable solid electrolyte interphase (SEI). However, the detailed structure and reaction mechanism of the SEI formation in such a novel electrolyte remains unclear. In this work, we carry out a hybrid ab initio and reactive molecular dynamics (HAIR) simulation to investigate the elementary reactions that regulate the formation of the primitive SEI, paying special attention to the process that involves FDMB, the fluorinated solvent. HAIR simulation reveals that both FSI– anion and FDMB provide F that is adequate to form a uniformed LiF layer that resembles the inorganic inner layer (IIL) of the SEI. N and S radicals from the FSI– anion, which do not deposit on the electrode interface to form lithium-containing inorganic substances, promote the polymerization reaction of unsaturated carbon chains produced by FDMB defluorination, forming the organic outer layer (OOL) of the SEI. The combination of the LiF-rich IIL and polymer-rich organic OOL explains the superior performance of the FDMB-based electrolyte in the device. The detailed reaction mechanism and SEI observed in this work provide insights into the atomic scale for the rational design of F-rich electrolytes in the near future

Reaction mechanism on Ni-C₂-NS single-atom catalysis for the efficient CO₂ reduction reaction

Ni-based single-atom catalysis (Ni-SAC) has been experimentally reported with superior performance in reducing CO2 to CO. However, due to the ambiguities in its structures, the active sites of Ni-SAC that are responsible for superior performance have not yet been resolved. This work investigates the CO2 reduction reaction (CO2RR) mechanism on Ni-SAC by carrying out quantum mechanics (QM) simulation to consider both solvation effects. After exploring multiple possible combinations of N, S, and C, we distinguish a Ni-SAC site with two C, one S, and one N, representing the best performance. The predicted formation energy is closely consistent with experimental onset potential. Our prediction also suggests further improvement by finely tuning the electronics state of metal sites by changing the SAC support.</p