A theoretical study of the effect of a non-aqueous proton donor on electrochemical ammonia synthesis
Abstract
We report that 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. Finally, 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.
- Authors:
-
- University of Science and Technology Beijing (China). Corrosion and Protection Center, Key Laboratory for Environmental Fracture (MOE); SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis
- SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis; Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering; Univ. of Southern California, Los Angeles, CA (United States). Mork Family Department of Chemical Engineering and Materials Science
- Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering
- University of Science and Technology Beijing (China). Corrosion and Protection Center, Key Laboratory for Environmental Fracture (MOE)
- SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis; Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE; National Science Foundation (NSF)
- OSTI Identifier:
- 1423520
- Grant/Contract Number:
- AC02-76SF00515; 9455; DGE-1656518
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Chemistry Chemical Physics. PCCP
- Additional Journal Information:
- Journal Volume: 20; Journal Issue: 7; Journal ID: ISSN 1463-9076
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Zhang, Linan, Mallikarjun Sharada, Shaama, Singh, Aayush R., Rohr, Brian A., Su, Yanjing, Qiao, Lijie, and Nørskov, Jens K. A theoretical study of the effect of a non-aqueous proton donor on electrochemical ammonia synthesis. United States: N. p., 2018.
Web. doi:10.1039/c7cp05484j.
Zhang, Linan, Mallikarjun Sharada, Shaama, Singh, Aayush R., Rohr, Brian A., Su, Yanjing, Qiao, Lijie, & Nørskov, Jens K. A theoretical study of the effect of a non-aqueous proton donor on electrochemical ammonia synthesis. United States. https://doi.org/10.1039/c7cp05484j
Zhang, Linan, Mallikarjun Sharada, Shaama, Singh, Aayush R., Rohr, Brian A., Su, Yanjing, Qiao, Lijie, and Nørskov, Jens K. Wed .
"A theoretical study of the effect of a non-aqueous proton donor on electrochemical ammonia synthesis". United States. https://doi.org/10.1039/c7cp05484j. https://www.osti.gov/servlets/purl/1423520.
@article{osti_1423520,
title = {A theoretical study of the effect of a non-aqueous proton donor on electrochemical ammonia synthesis},
author = {Zhang, Linan and Mallikarjun Sharada, Shaama and Singh, Aayush R. and Rohr, Brian A. and Su, Yanjing and Qiao, Lijie and Nørskov, Jens K.},
abstractNote = {We report that 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. Finally, 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.},
doi = {10.1039/c7cp05484j},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 7,
volume = 20,
place = {United States},
year = {Wed Jan 17 00:00:00 EST 2018},
month = {Wed Jan 17 00:00:00 EST 2018}
}
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Figures / Tables:
Fig. 1: 2,6-Lutidinium adsorption configurations on Pt(111) – (a) parallel to the surface and (b) perpendicular to the surface. (1) indicates side view and (2) is the top view. The solid line represents the size of one unit cell.
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