Calcium-mediated nitrogen reduction for electrochemical ammonia synthesis

Xianbiao Fu; Valerie A. Niemann; Yuanyuan Zhou; Shaofeng Li; Ke Zhang; Jakob B. Pedersen; Mattia Saccoccio; Suzanne Z. Andersen; Kasper Enemark-Rasmussen; Peter Benedek; Aoni Xu; Niklas H. Deissler; Jon Bjarke Valbæk Mygind; Adam C. Nielander; Jakob Kibsgaard; Peter C.K. Vesborg; Jens K. Nørskov; Thomas F. Jaramillo; Ib Chorkendorff

doi:10.1038/s41563-023-01702-1

Calcium-mediated nitrogen reduction for electrochemical ammonia synthesis

Xianbiao Fu, Valerie A. Niemann, Yuanyuan Zhou, Shaofeng Li, Ke Zhang, Jakob B. Pedersen, Mattia Saccoccio, Suzanne Z. Andersen, Kasper Enemark-Rasmussen, Peter Benedek, Aoni Xu, Niklas H. Deissler, Jon Bjarke Valbæk Mygind, Adam C. Nielander, Jakob Kibsgaard, Peter C.K. Vesborg, Jens K. Nørskov^*, Thomas F. Jaramillo^*, Ib Chorkendorff^*

^*Corresponding author for this work

Research output: Contribution to journal › Journal article › Research › peer-review

Abstract

Ammonia (NH₃) is a key commodity chemical for the agricultural, textile and pharmaceutical industries, but its production via the Haber–Bosch process is carbon-intensive and centralized. Alternatively, an electrochemical method could enable decentralized, ambient NH₃ production that can be paired with renewable energy. The first verified electrochemical method for NH₃ synthesis was a process mediated by lithium (Li) in organic electrolytes. So far, however, elements other than Li remain unexplored in this process for potential benefits in efficiency, reaction rates, device design, abundance and stability. In our demonstration of a Li-free system, we found that calcium can mediate the reduction of nitrogen for NH₃ synthesis. We verified the calcium-mediated process using a rigorous protocol and achieved an NH₃ Faradaic efficiency of 40 ± 2% using calcium tetrakis(hexafluoroisopropyloxy)borate (Ca[B(hfip)₄]₂) as the electrolyte. Our results offer the possibility of using abundant materials for the electrochemical production of NH₃, a critical chemical precursor and promising energy vector.

Original language	English
Journal	Nature Materials
Volume	23
Pages (from-to)	101-107
ISSN	1476-1122
DOIs	https://doi.org/10.1038/s41563-023-01702-1
Publication status	Published - 2024

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Fu, X., Niemann, V. A., Zhou, Y., Li, S., Zhang, K., Pedersen, J. B., Saccoccio, M., Andersen, S. Z., Enemark-Rasmussen, K., Benedek, P., Xu, A., Deissler, N. H., Mygind, J. B. V., Nielander, A. C., Kibsgaard, J., Vesborg, P. C. K., Nørskov, J. K., Jaramillo, T. F., & Chorkendorff, I. (2024). Calcium-mediated nitrogen reduction for electrochemical ammonia synthesis. Nature Materials, 23, 101-107. https://doi.org/10.1038/s41563-023-01702-1

@article{1be66efa5dfa43fb91fc72e19466f354,

title = "Calcium-mediated nitrogen reduction for electrochemical ammonia synthesis",

abstract = "Ammonia (NH3) is a key commodity chemical for the agricultural, textile and pharmaceutical industries, but its production via the Haber–Bosch process is carbon-intensive and centralized. Alternatively, an electrochemical method could enable decentralized, ambient NH3 production that can be paired with renewable energy. The first verified electrochemical method for NH3 synthesis was a process mediated by lithium (Li) in organic electrolytes. So far, however, elements other than Li remain unexplored in this process for potential benefits in efficiency, reaction rates, device design, abundance and stability. In our demonstration of a Li-free system, we found that calcium can mediate the reduction of nitrogen for NH3 synthesis. We verified the calcium-mediated process using a rigorous protocol and achieved an NH3 Faradaic efficiency of 40 ± 2% using calcium tetrakis(hexafluoroisopropyloxy)borate (Ca[B(hfip)4]2) as the electrolyte. Our results offer the possibility of using abundant materials for the electrochemical production of NH3, a critical chemical precursor and promising energy vector.",

author = "Xianbiao Fu and Niemann, {Valerie A.} and Yuanyuan Zhou and Shaofeng Li and Ke Zhang and Pedersen, {Jakob B.} and Mattia Saccoccio and Andersen, {Suzanne Z.} and Kasper Enemark-Rasmussen and Peter Benedek and Aoni Xu and Deissler, {Niklas H.} and Mygind, {Jon Bjarke Valb{\ae}k} and Nielander, {Adam C.} and Jakob Kibsgaard and Vesborg, {Peter C.K.} and N{\o}rskov, {Jens K.} and Jaramillo, {Thomas F.} and Ib Chorkendorff",

note = "Publisher Copyright: {\textcopyright} 2023, The Author(s), under exclusive licence to Springer Nature Limited.",

year = "2024",

doi = "10.1038/s41563-023-01702-1",

language = "English",

volume = "23",

pages = "101--107",

journal = "Nature Materials",

issn = "1476-1122",

publisher = "Nature Publishing Group",

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Fu, X, Niemann, VA, Zhou, Y, Li, S, Zhang, K, Pedersen, JB, Saccoccio, M, Andersen, SZ, Enemark-Rasmussen, K, Benedek, P, Xu, A, Deissler, NH, Mygind, JBV, Nielander, AC, Kibsgaard, J , Vesborg, PCK , Nørskov, JK, Jaramillo, TF & Chorkendorff, I 2024, 'Calcium-mediated nitrogen reduction for electrochemical ammonia synthesis', Nature Materials, vol. 23, pp. 101-107. https://doi.org/10.1038/s41563-023-01702-1

TY - JOUR

T1 - Calcium-mediated nitrogen reduction for electrochemical ammonia synthesis

AU - Fu, Xianbiao

AU - Niemann, Valerie A.

AU - Zhou, Yuanyuan

AU - Li, Shaofeng

AU - Zhang, Ke

AU - Pedersen, Jakob B.

AU - Saccoccio, Mattia

AU - Andersen, Suzanne Z.

AU - Enemark-Rasmussen, Kasper

AU - Benedek, Peter

AU - Xu, Aoni

AU - Deissler, Niklas H.

AU - Mygind, Jon Bjarke Valbæk

AU - Nielander, Adam C.

AU - Kibsgaard, Jakob

AU - Vesborg, Peter C.K.

AU - Nørskov, Jens K.

AU - Jaramillo, Thomas F.

AU - Chorkendorff, Ib

PY - 2024

Y1 - 2024

N2 - Ammonia (NH3) is a key commodity chemical for the agricultural, textile and pharmaceutical industries, but its production via the Haber–Bosch process is carbon-intensive and centralized. Alternatively, an electrochemical method could enable decentralized, ambient NH3 production that can be paired with renewable energy. The first verified electrochemical method for NH3 synthesis was a process mediated by lithium (Li) in organic electrolytes. So far, however, elements other than Li remain unexplored in this process for potential benefits in efficiency, reaction rates, device design, abundance and stability. In our demonstration of a Li-free system, we found that calcium can mediate the reduction of nitrogen for NH3 synthesis. We verified the calcium-mediated process using a rigorous protocol and achieved an NH3 Faradaic efficiency of 40 ± 2% using calcium tetrakis(hexafluoroisopropyloxy)borate (Ca[B(hfip)4]2) as the electrolyte. Our results offer the possibility of using abundant materials for the electrochemical production of NH3, a critical chemical precursor and promising energy vector.

AB - Ammonia (NH3) is a key commodity chemical for the agricultural, textile and pharmaceutical industries, but its production via the Haber–Bosch process is carbon-intensive and centralized. Alternatively, an electrochemical method could enable decentralized, ambient NH3 production that can be paired with renewable energy. The first verified electrochemical method for NH3 synthesis was a process mediated by lithium (Li) in organic electrolytes. So far, however, elements other than Li remain unexplored in this process for potential benefits in efficiency, reaction rates, device design, abundance and stability. In our demonstration of a Li-free system, we found that calcium can mediate the reduction of nitrogen for NH3 synthesis. We verified the calcium-mediated process using a rigorous protocol and achieved an NH3 Faradaic efficiency of 40 ± 2% using calcium tetrakis(hexafluoroisopropyloxy)borate (Ca[B(hfip)4]2) as the electrolyte. Our results offer the possibility of using abundant materials for the electrochemical production of NH3, a critical chemical precursor and promising energy vector.

U2 - 10.1038/s41563-023-01702-1

DO - 10.1038/s41563-023-01702-1

M3 - Journal article

C2 - 37884670

AN - SCOPUS:85174889377

SN - 1476-1122

VL - 23

SP - 101

EP - 107

JO - Nature Materials

JF - Nature Materials

ER -

Calcium-mediated nitrogen reduction for electrochemical ammonia synthesis

Abstract

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