A rational design of manganese electrocatalysts for Lewis acid-assisted carbon dioxide reduction
文献信息
Xiaoli Wang, Haiyan Ma, Caiyun Meng, Dezhan Chen, Fang Huang
Herein, the mechanisms of Brønsted acid- and Lewis acid-assisted CO2 electroreduction by Mn(mesbpy)(CO)3Br (1) were investigated by density functional theory calculations. Our results indicate that for the Lewis acid-assisted cycle, an energy sink (13) is present owing to the interaction between Mg(OTf)2 and activated CO2, which is disadvantageous to the apparent activation energy (ΔG≠). Moreover, a series of substituted 13 counterparts were investigated to reduce the energy sink and decrease ΔG≠. Based on our study on the substituent effect, an excellent linear relationship was found between 2e reduction potentials and LUMO energies of substituted 1, and a moderate linear relationship was observed between ΔG of substituted 13 and the 2e reduction potential of substituted 1 counterparts. Moreover, for the CO2 reduction assisted by a Lewis acid, the formyl-substituted complex R8 has been predicted to be a more effective catalyst with lower overpotential and higher catalytic activity than its parent complex 1.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.












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