A theoretical study of the effect of a non-aqueous proton donor on electrochemical ammonia synthesis

Zhang, Linan; Mallikarjun Sharada, Shaama; Singh, Aayush R.; Rohr, Brian A.; Su, Yanjing; Qiao, Lijie; Nørskov, Jens K.

doi:10.1039/c7cp05484j

Title: A theoretical study of the effect of a non-aqueous proton donor on electrochemical ammonia synthesis

Journal Article · Wed Jan 17 00:00:00 EST 2018 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/c7cp05484j· OSTI ID:1423520

Zhang, Linan ^[1]; Mallikarjun Sharada, Shaama ^[2]; Singh, Aayush R. ^[3]; Rohr, Brian A. ^[3]; Su, Yanjing ^[4]; Qiao, Lijie ^[4]; Nørskov, Jens K. ^[5]

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

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.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE; National Science Foundation (NSF)

Grant/Contract Number:: AC02-76SF00515; 9455; DGE-1656518

OSTI ID:: 1423520

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Vol. 20, Issue 7; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 76 works

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