A Versatile Method for Ammonia Detection in a Range of Relevant Electrolytes via Direct Nuclear Magnetic Resonance Techniques

Adam C. Nielander, Joshua M. McEnaney, Jay A. Schwalbe, Jon G. Baker, Sarah J. Blair, Lei Wang, Jeffrey G. Pelton, Suzanne Zamany Andersen, Kasper Enemark-Rasmussen, Viktor Colic, Sungeun Yang, Stacey F. Bent, Matteo Cargnello, Jakob Kibsgaard, Peter Christian Kjærgaard Vesborg, Ib Chorkendorff, Thomas F. Jaramillo*

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

Electrocatalytic N-2 reduction to ammonia has recently attracted a great deal of interest as a possible renewable energy-driven alternative to the Haber-Bosch process. However, the detection of NH3 after attempting electrocatalytic reduction of N-2 can be hampered by low NH3 yields, ambient NH3 contamination, and the need for multistep chemical separation of NH3 from the electrolyte. Herein, we report a frequency-selective pulse nuclear magnetic resonance (NMR) method and quantify the efficacy of this method to measure the concentration of NH3 (present in the assay as NH4+) in an electrolyte after electrocatalysis. This NMR method was demonstrated to be effective in a variety of nondeuterated, nonaqueous and aqueous electrolytes, and did not require the separation of NH3 from the electrolyte. NH3 sensitivity down to 1 mu M was readily achieved with isotopic and chemical specificity. Compatible electrolytes and solvents included ethanol, tetrahydrofuran, dimethyl sulfoxide, acetonitrile, propylene carbonate, diethyl either, hexanes, and water. The efficacy of the commonly employed Berthelot method was also quantified and compared to the NMR method in a range of nonaqueous and aqueous electrolytes, including ethanol, THF, propylene carbonate, and water.
Original languageEnglish
JournalACS Catalysis
Volume9
Issue number7
Pages (from-to)5797-5802
Number of pages6
ISSN2155-5435
DOIs
Publication statusPublished - 2019

Keywords

  • Nitrogen reduction
  • Ammonia detection
  • NMR
  • Electrocatalysis
  • Nonaqueous electrochemistry

Cite this

Nielander, A. C., McEnaney, J. M., Schwalbe, J. A., Baker, J. G., Blair, S. J., Wang, L., ... Jaramillo, T. F. (2019). A Versatile Method for Ammonia Detection in a Range of Relevant Electrolytes via Direct Nuclear Magnetic Resonance Techniques. ACS Catalysis, 9(7), 5797-5802. https://doi.org/10.1021/acscatal.9b00358
Nielander, Adam C. ; McEnaney, Joshua M. ; Schwalbe, Jay A. ; Baker, Jon G. ; Blair, Sarah J. ; Wang, Lei ; Pelton, Jeffrey G. ; Andersen, Suzanne Zamany ; Enemark-Rasmussen, Kasper ; Colic, Viktor ; Yang, Sungeun ; Bent, Stacey F. ; Cargnello, Matteo ; Kibsgaard, Jakob ; Vesborg, Peter Christian Kjærgaard ; Chorkendorff, Ib ; Jaramillo, Thomas F. / A Versatile Method for Ammonia Detection in a Range of Relevant Electrolytes via Direct Nuclear Magnetic Resonance Techniques. In: ACS Catalysis. 2019 ; Vol. 9, No. 7. pp. 5797-5802.
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title = "A Versatile Method for Ammonia Detection in a Range of Relevant Electrolytes via Direct Nuclear Magnetic Resonance Techniques",
abstract = "Electrocatalytic N-2 reduction to ammonia has recently attracted a great deal of interest as a possible renewable energy-driven alternative to the Haber-Bosch process. However, the detection of NH3 after attempting electrocatalytic reduction of N-2 can be hampered by low NH3 yields, ambient NH3 contamination, and the need for multistep chemical separation of NH3 from the electrolyte. Herein, we report a frequency-selective pulse nuclear magnetic resonance (NMR) method and quantify the efficacy of this method to measure the concentration of NH3 (present in the assay as NH4+) in an electrolyte after electrocatalysis. This NMR method was demonstrated to be effective in a variety of nondeuterated, nonaqueous and aqueous electrolytes, and did not require the separation of NH3 from the electrolyte. NH3 sensitivity down to 1 mu M was readily achieved with isotopic and chemical specificity. Compatible electrolytes and solvents included ethanol, tetrahydrofuran, dimethyl sulfoxide, acetonitrile, propylene carbonate, diethyl either, hexanes, and water. The efficacy of the commonly employed Berthelot method was also quantified and compared to the NMR method in a range of nonaqueous and aqueous electrolytes, including ethanol, THF, propylene carbonate, and water.",
keywords = "Nitrogen reduction, Ammonia detection, NMR, Electrocatalysis, Nonaqueous electrochemistry",
author = "Nielander, {Adam C.} and McEnaney, {Joshua M.} and Schwalbe, {Jay A.} and Baker, {Jon G.} and Blair, {Sarah J.} and Lei Wang and Pelton, {Jeffrey G.} and Andersen, {Suzanne Zamany} and Kasper Enemark-Rasmussen and Viktor Colic and Sungeun Yang and Bent, {Stacey F.} and Matteo Cargnello and Jakob Kibsgaard and Vesborg, {Peter Christian Kj{\ae}rgaard} and Ib Chorkendorff and Jaramillo, {Thomas F.}",
year = "2019",
doi = "10.1021/acscatal.9b00358",
language = "English",
volume = "9",
pages = "5797--5802",
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Nielander, AC, McEnaney, JM, Schwalbe, JA, Baker, JG, Blair, SJ, Wang, L, Pelton, JG, Andersen, SZ, Enemark-Rasmussen, K, Colic, V, Yang, S, Bent, SF, Cargnello, M, Kibsgaard, J, Vesborg, PCK, Chorkendorff, I & Jaramillo, TF 2019, 'A Versatile Method for Ammonia Detection in a Range of Relevant Electrolytes via Direct Nuclear Magnetic Resonance Techniques', ACS Catalysis, vol. 9, no. 7, pp. 5797-5802. https://doi.org/10.1021/acscatal.9b00358

A Versatile Method for Ammonia Detection in a Range of Relevant Electrolytes via Direct Nuclear Magnetic Resonance Techniques. / Nielander, Adam C.; McEnaney, Joshua M.; Schwalbe, Jay A.; Baker, Jon G.; Blair, Sarah J.; Wang, Lei; Pelton, Jeffrey G.; Andersen, Suzanne Zamany; Enemark-Rasmussen, Kasper; Colic, Viktor; Yang, Sungeun; Bent, Stacey F.; Cargnello, Matteo; Kibsgaard, Jakob; Vesborg, Peter Christian Kjærgaard; Chorkendorff, Ib; Jaramillo, Thomas F.

In: ACS Catalysis, Vol. 9, No. 7, 2019, p. 5797-5802.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - A Versatile Method for Ammonia Detection in a Range of Relevant Electrolytes via Direct Nuclear Magnetic Resonance Techniques

AU - Nielander, Adam C.

AU - McEnaney, Joshua M.

AU - Schwalbe, Jay A.

AU - Baker, Jon G.

AU - Blair, Sarah J.

AU - Wang, Lei

AU - Pelton, Jeffrey G.

AU - Andersen, Suzanne Zamany

AU - Enemark-Rasmussen, Kasper

AU - Colic, Viktor

AU - Yang, Sungeun

AU - Bent, Stacey F.

AU - Cargnello, Matteo

AU - Kibsgaard, Jakob

AU - Vesborg, Peter Christian Kjærgaard

AU - Chorkendorff, Ib

AU - Jaramillo, Thomas F.

PY - 2019

Y1 - 2019

N2 - Electrocatalytic N-2 reduction to ammonia has recently attracted a great deal of interest as a possible renewable energy-driven alternative to the Haber-Bosch process. However, the detection of NH3 after attempting electrocatalytic reduction of N-2 can be hampered by low NH3 yields, ambient NH3 contamination, and the need for multistep chemical separation of NH3 from the electrolyte. Herein, we report a frequency-selective pulse nuclear magnetic resonance (NMR) method and quantify the efficacy of this method to measure the concentration of NH3 (present in the assay as NH4+) in an electrolyte after electrocatalysis. This NMR method was demonstrated to be effective in a variety of nondeuterated, nonaqueous and aqueous electrolytes, and did not require the separation of NH3 from the electrolyte. NH3 sensitivity down to 1 mu M was readily achieved with isotopic and chemical specificity. Compatible electrolytes and solvents included ethanol, tetrahydrofuran, dimethyl sulfoxide, acetonitrile, propylene carbonate, diethyl either, hexanes, and water. The efficacy of the commonly employed Berthelot method was also quantified and compared to the NMR method in a range of nonaqueous and aqueous electrolytes, including ethanol, THF, propylene carbonate, and water.

AB - Electrocatalytic N-2 reduction to ammonia has recently attracted a great deal of interest as a possible renewable energy-driven alternative to the Haber-Bosch process. However, the detection of NH3 after attempting electrocatalytic reduction of N-2 can be hampered by low NH3 yields, ambient NH3 contamination, and the need for multistep chemical separation of NH3 from the electrolyte. Herein, we report a frequency-selective pulse nuclear magnetic resonance (NMR) method and quantify the efficacy of this method to measure the concentration of NH3 (present in the assay as NH4+) in an electrolyte after electrocatalysis. This NMR method was demonstrated to be effective in a variety of nondeuterated, nonaqueous and aqueous electrolytes, and did not require the separation of NH3 from the electrolyte. NH3 sensitivity down to 1 mu M was readily achieved with isotopic and chemical specificity. Compatible electrolytes and solvents included ethanol, tetrahydrofuran, dimethyl sulfoxide, acetonitrile, propylene carbonate, diethyl either, hexanes, and water. The efficacy of the commonly employed Berthelot method was also quantified and compared to the NMR method in a range of nonaqueous and aqueous electrolytes, including ethanol, THF, propylene carbonate, and water.

KW - Nitrogen reduction

KW - Ammonia detection

KW - NMR

KW - Electrocatalysis

KW - Nonaqueous electrochemistry

U2 - 10.1021/acscatal.9b00358

DO - 10.1021/acscatal.9b00358

M3 - Journal article

VL - 9

SP - 5797

EP - 5802

JO - A C S Catalysis

JF - A C S Catalysis

SN - 2155-5435

IS - 7

ER -