Electrolyte Engineering for Efficient Electrochemical Nitrate Reduction to Ammonia on a Titanium Electrode

McEnaney, Joshua M.; Blair, Sarah J.; Nielander, Adam C.; Schwalbe, Jay A.; Koshy, David M.; Cargnello, Matteo; Jaramillo, Thomas F.

doi:10.1021/acssuschemeng.9b05983

Electrolyte Engineering for Efficient Electrochemical Nitrate Reduction to Ammonia on a Titanium Electrode

Journal Article · Fri Feb 07 00:00:00 EST 2020 · ACS Sustainable Chemistry & Engineering

DOI:https://doi.org/10.1021/acssuschemeng.9b05983· OSTI ID:1608699

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Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis
Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis; SLAC National Accelerator Lab., Menlo Park, CA (United States)

Nitrates from agricultural runoff and industrial waste streams are a notorious waste product and hazardous pollutant. Traditional electrochemical water remediation approaches aim to solve this problem by converting nitrates to environmentally benign N₂ while minimizing the production of environmentally hazardous side products such as ammonia and nitrous oxide in a process known as “denitrification”. We modify this concept and outline an opportunity to optimize the conversion of nitrates into ammonia, which is also a key commodity product used as a fertilizer, potential fuel, and chemical precursor. The electrochemical conversion of nitrates to ammonia recycles the fixed nitrogen and offers an appealing and supplementary alternative to the energy- and resource-intensive Haber-Bosch process. In this study, we investigated the effect of varying electrochemical conditions (pH, nitrate concentration, and applied potential) on the selective reduction of nitrate to ammonia at a titanium cathode. We observed that high concentrations of both protons and nitrate ions are needed to achieve high selectivity, reaching a peak of 82% Faradaic efficiency to ammonia at an applied potential of -1 V versus RHE and a partial current density to NH₃ of -22 mA/cm², using 0.4 M [NO₃^–] at pH ~0.77. The Ti electrode, as a poor hydrogen evolution catalyst with notable corrosion resistance, provides a large window of operating conditions to achieve high selectivity in the reduction of nitrate anions. Stability of the system was evaluated, and we found a high Faradaic efficiency throughout the course of an 8 h experiment. After electrochemical testing, titanium hydride was observed at the cathode surface. We also show a preliminary technoeconomic study, indicating that it may be feasible to employ an electrochemical strategy for the production of ammonium nitrate.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1608699

Journal Information:: ACS Sustainable Chemistry & Engineering, Journal Name: ACS Sustainable Chemistry & Engineering Journal Issue: 7 Vol. 8; ISSN 2168-0485

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Ammonia
Anions
Electrodes
Electrolytes
Selectivity
ammonia
electrocatalysis
electrolyte engineering
nitrate reduction
titanium

Electrolyte Engineering for Efficient Electrochemical Nitrate Reduction to Ammonia on a Titanium Electrode

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