Efficient electrochemical reduction of nitrate to ammonia over metal-organic framework single-atom catalysts

Lutong Shan; Yujie Ma; Shaojun Xu; Meng Zhou; Meng He; Alena M. Sheveleva; Rongsheng Cai; Daniel Lee; Yongqiang Cheng; Boya Tang; Bing Han; Yinlin Chen; Lan An; Tianze Zhou; Martin Wilding; Alexander S. Eggeman; Floriana Tuna; Eric J.L. McInnes; Sarah J. Day; Stephen P. Thompson; Sarah J. Haigh; Xinchen Kang; Buxing Han; Martin Schröder; Sihai Yang

doi:10.1038/s43246-024-00535-y

Efficient electrochemical reduction of nitrate to ammonia over metal-organic framework single-atom catalysts

Lutong Shan, Yujie Ma, Shaojun Xu, Meng Zhou, Meng He, Alena M. Sheveleva, Rongsheng Cai, Daniel Lee, Yongqiang Cheng, Boya Tang, Bing Han, Yinlin Chen, Lan An, Tianze Zhou, Martin Wilding, Alexander S. Eggeman, Floriana Tuna, Eric J.L. McInnes, Sarah J. Day, Stephen P. ThompsonSarah J. Haigh, Xinchen Kang, Buxing Han, Martin Schröder, Sihai Yang

Chemical Spectroscopy

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Abstract

The design and preparation of efficient catalysts for ammonia production under mild conditions is a desirable but highly challenging target. Here, we report a series of single-atom catalysts [M-SACs, M = Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Mo(II)] derived from UiO-66 containing structural defects and their application to electrochemical reduction of nitrate (NO₃^-) to ammonia (NH₃). Cu-SAC and Fe-SAC exhibit remarkable yield rates for NH₃ production of 30.0 and 29.0 mg h⁻¹ cm⁻², respectively, with a high Faradaic efficiency (FE_NH3) of over 96% at −1.0 V versus the reversible hydrogen electrode. Importantly, their catalytic performance can be retained in various simulated wastewaters. Complementary experiments confirmed the nature of single-atom sites within these catalysts and the binding domains of NO₃^- in UiO-66-Cu. In situ spectroscopic techniques, coupled with density functional theory calculations confirm the strong binding of NO₃^- and the formation of reaction intermediates, thus facilitating the catalytic conversion to NH₃.

Original language	English
Article number	104
Journal	Communications Materials
Volume	5
Issue number	1
DOIs	https://doi.org/10.1038/s43246-024-00535-y
State	Published - Dec 2024

Funding

We thank the EPSRC (EP/I011870, EP/V056409), the Royal Society, the University of Manchester and National Science Foundation of China for funding, and the EPSRC for funding of the EPSRC National EPR Facility at Manchester. This project has received funding from the European Research Council (ERC) under the European Union\u2019s Horizon 2020 research and innovation programme (grant agreement No 742401, NANOCHEM and grant agreement No. 715502 EvoluTEM). We are grateful to the Diamond Light Source for the access to beamtime I11. We acknowledge Diamond Light Source beamline staff and the UK catalysis Hub Block Allocation Group (BAG) Programme Mode Application for provision of beamtime at B18 for collection of the data presented in this work and the initial discussion of the data. The UK Catalysis Hub is kindly thanked for resources and support provided via our membership of the UK Catalysis Hub Consortium and funded by EPSRC grant: EP/R026939, EP/R026815, EP/R026645, EP/R027129 and EP/M013219 (biocatalysis). The computing resources were made available through the VirtuES project, funded by Laboratory Directed Research and Development program and Compute and Data Environment for Science (CADES) at ORNL. A.M.S. is supported by the Royal Society Newton International Fellowship. L.S., Y.M., M.H. and B.T. thank the China Scholarship Council (CSC) for funding. TEM access was supported by the Henry Royce Institute for Advanced Materials, funded through EPSRC grants EP/R00661X, EP/S019367, EP/P025021 and EP/P025498.

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Shan, L., Ma, Y., Xu, S., Zhou, M., He, M., Sheveleva, A. M., Cai, R., Lee, D., Cheng, Y., Tang, B., Han, B., Chen, Y., An, L., Zhou, T., Wilding, M., Eggeman, A. S., Tuna, F., McInnes, E. J. L., Day, S. J., ... Yang, S. (2024). Efficient electrochemical reduction of nitrate to ammonia over metal-organic framework single-atom catalysts. Communications Materials, 5(1), Article 104. https://doi.org/10.1038/s43246-024-00535-y

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title = "Efficient electrochemical reduction of nitrate to ammonia over metal-organic framework single-atom catalysts",

abstract = "The design and preparation of efficient catalysts for ammonia production under mild conditions is a desirable but highly challenging target. Here, we report a series of single-atom catalysts [M-SACs, M = Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Mo(II)] derived from UiO-66 containing structural defects and their application to electrochemical reduction of nitrate (NO3-) to ammonia (NH3). Cu-SAC and Fe-SAC exhibit remarkable yield rates for NH3 production of 30.0 and 29.0 mg h−1 cm−2, respectively, with a high Faradaic efficiency (FENH3) of over 96% at −1.0 V versus the reversible hydrogen electrode. Importantly, their catalytic performance can be retained in various simulated wastewaters. Complementary experiments confirmed the nature of single-atom sites within these catalysts and the binding domains of NO3- in UiO-66-Cu. In situ spectroscopic techniques, coupled with density functional theory calculations confirm the strong binding of NO3- and the formation of reaction intermediates, thus facilitating the catalytic conversion to NH3.",

author = "Lutong Shan and Yujie Ma and Shaojun Xu and Meng Zhou and Meng He and Sheveleva, {Alena M.} and Rongsheng Cai and Daniel Lee and Yongqiang Cheng and Boya Tang and Bing Han and Yinlin Chen and Lan An and Tianze Zhou and Martin Wilding and Eggeman, {Alexander S.} and Floriana Tuna and McInnes, {Eric J.L.} and Day, {Sarah J.} and Thompson, {Stephen P.} and Haigh, {Sarah J.} and Xinchen Kang and Buxing Han and Martin Schr{\"o}der and Sihai Yang",

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year = "2024",

month = dec,

doi = "10.1038/s43246-024-00535-y",

language = "English",

volume = "5",

journal = "Communications Materials",

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Shan, L, Ma, Y, Xu, S, Zhou, M, He, M, Sheveleva, AM, Cai, R, Lee, D, Cheng, Y, Tang, B, Han, B, Chen, Y, An, L, Zhou, T, Wilding, M, Eggeman, AS, Tuna, F, McInnes, EJL, Day, SJ, Thompson, SP, Haigh, SJ, Kang, X, Han, B, Schröder, M & Yang, S 2024, 'Efficient electrochemical reduction of nitrate to ammonia over metal-organic framework single-atom catalysts', Communications Materials, vol. 5, no. 1, 104. https://doi.org/10.1038/s43246-024-00535-y

TY - JOUR

T1 - Efficient electrochemical reduction of nitrate to ammonia over metal-organic framework single-atom catalysts

AU - Shan, Lutong

AU - Ma, Yujie

AU - Xu, Shaojun

AU - Zhou, Meng

AU - He, Meng

AU - Sheveleva, Alena M.

AU - Cai, Rongsheng

AU - Lee, Daniel

AU - Cheng, Yongqiang

AU - Tang, Boya

AU - Han, Bing

AU - Chen, Yinlin

AU - An, Lan

AU - Zhou, Tianze

AU - Wilding, Martin

AU - Eggeman, Alexander S.

AU - Tuna, Floriana

AU - McInnes, Eric J.L.

AU - Day, Sarah J.

AU - Thompson, Stephen P.

AU - Haigh, Sarah J.

AU - Kang, Xinchen

AU - Han, Buxing

AU - Schröder, Martin

AU - Yang, Sihai

PY - 2024/12

Y1 - 2024/12

N2 - The design and preparation of efficient catalysts for ammonia production under mild conditions is a desirable but highly challenging target. Here, we report a series of single-atom catalysts [M-SACs, M = Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Mo(II)] derived from UiO-66 containing structural defects and their application to electrochemical reduction of nitrate (NO3-) to ammonia (NH3). Cu-SAC and Fe-SAC exhibit remarkable yield rates for NH3 production of 30.0 and 29.0 mg h−1 cm−2, respectively, with a high Faradaic efficiency (FENH3) of over 96% at −1.0 V versus the reversible hydrogen electrode. Importantly, their catalytic performance can be retained in various simulated wastewaters. Complementary experiments confirmed the nature of single-atom sites within these catalysts and the binding domains of NO3- in UiO-66-Cu. In situ spectroscopic techniques, coupled with density functional theory calculations confirm the strong binding of NO3- and the formation of reaction intermediates, thus facilitating the catalytic conversion to NH3.

AB - The design and preparation of efficient catalysts for ammonia production under mild conditions is a desirable but highly challenging target. Here, we report a series of single-atom catalysts [M-SACs, M = Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Mo(II)] derived from UiO-66 containing structural defects and their application to electrochemical reduction of nitrate (NO3-) to ammonia (NH3). Cu-SAC and Fe-SAC exhibit remarkable yield rates for NH3 production of 30.0 and 29.0 mg h−1 cm−2, respectively, with a high Faradaic efficiency (FENH3) of over 96% at −1.0 V versus the reversible hydrogen electrode. Importantly, their catalytic performance can be retained in various simulated wastewaters. Complementary experiments confirmed the nature of single-atom sites within these catalysts and the binding domains of NO3- in UiO-66-Cu. In situ spectroscopic techniques, coupled with density functional theory calculations confirm the strong binding of NO3- and the formation of reaction intermediates, thus facilitating the catalytic conversion to NH3.

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U2 - 10.1038/s43246-024-00535-y

DO - 10.1038/s43246-024-00535-y

M3 - Article

AN - SCOPUS:85196387046

SN - 2662-4443

VL - 5

JO - Communications Materials

JF - Communications Materials

IS - 1

M1 - 104

ER -

Efficient electrochemical reduction of nitrate to ammonia over metal-organic framework single-atom catalysts

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