Impact of H-termination on the nitrogen reduction reaction of molybdenum carbide as an electrochemical catalyst

Literature Information

Publication Date 2018-08-24
DOI 10.1039/C8CP04474K
Impact Factor 3.676
Authors

Qinye Li, Siyao Qiu, Lizhong He, Xiwang Zhang


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Abstract

Transition metal molybdenum (Mo) exhibits a strong capacity to adsorb nitrogen (N2), but the Mo–N2 interaction is too strong and thus it is difficult for ammonia (NH3) to be released from the catalyst surface. Bonding with nonmetals with strong electronegativity is helpful to weaken the Mo–N2 interaction, while the effect of hydrogen termination on catalyst surfaces needs to be evaluated given that the hydrogen evolution reaction (HER) is a key side reaction. This computational work aims to explore α-molybdenum carbide (Mo2C, orthorhombic phase) as an electrochemical catalyst for the full nitrogen reduction reaction (NRR). Our density functional theory (DFT) calculations focus on a (100) surface and demonstrate that (i) surface molybdenum and carbon can be terminated by hydrogen via the Volmer step and (ii) the NRR can occur on H-terminated Mo2C(100) with an energy requirement of 1.0–1.4 eV, depending on H-coverage. Although C–Mo bonding can remarkably reduce difficulty in NH3 release from a Mo-site, H-terminals result in performance deterioration. These results provide new insights into the development of NRR catalysts.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

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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