In situ study of the low overpotential “dimer pathway” for electrocatalytic carbon dioxide reduction by manganese carbonyl complexes
Literature Information
Gaia Neri, Paul M. Donaldson, Alexander J. Cowan
The electrocatalytic reduction of CO2 using [fac-Mn(bpy)(CO)3Br] (bpy = 2,2′-bipyridine) and its derivatives has been the subject of numerous recent studies. However the mechanisms of catalysis are still debated. Here we carry out in situ vibrational sum-frequency generation (VSFG) spectroelectrochemistry to examine how this catalyst behaves at an electrode surface. In particular, a low overpotential pathway involving a dimeric manganese has been reported in several studies using substituted bipyridine ligands. Here, we find that the “dimer pathway” can also occur with the unsubstuituted bipyridine complexes. Specifically we can observe spectroscopic evidence of the interaction between [Mn2(bpy)2(CO)6] with CO2 in the presence of a suitable acid. Detailed VSFG studies of [Mn2(bpy)2(CO)6], including of the potential dependence of the surface ν(CO) mode, allow us to construct a model of how it accumulates and behaves at the electrode surface under potentiostatic control.
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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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