A theoretical study of the effect of a non-aqueous proton donor on electrochemical ammonia synthesis
Literature Information
Aayush R. Singh, Brian A. Rohr, Yanjing Su, Lijie Qiao
Ammonia synthesis is one of the most studied reactions in heterogeneous catalysis. To date, however, electrochemical N2 reduction in aqueous systems has proven to be extremely difficult, mainly due to the competing hydrogen evolution reaction (HER). Recently, it has been shown that transition metal complexes based on molybdenum can reduce N2 to ammonia at room temperature and ambient pressure in a non-aqueous system, with a relatively small amount of hydrogen output. We demonstrate that the non-aqueous proton donor they have chosen, 2,6-lutidinium (LutH+), is a viable substitute for hydronium in the electrochemical process at a solid surface, since this donor can suppress the HER rate. We also show that the presence of LutH+ can selectively stabilize the *NNH intermediate relative to *NH or *NH2via the formation of hydrogen bonds, indicating that the use of non-aqueous solvents can break the scaling relationship between limiting potential and binding energies.
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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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