Direct Observation of Ammonia Storage in UiO-66 Incorporating Cu(II) Binding Sites

Yujie Ma; Wanpeng Lu; Xue Han; Yinlin Chen; Ivan Da Silva; Daniel Lee; Alena M. Sheveleva; Zi Wang; Jiangnan Li; Weiyao Li; Mengtian Fan; Shaojun Xu; Floriana Tuna; Eric J.L. McInnes; Yongqiang Cheng; Svemir Rudić; Pascal Manuel; Mark D. Frogley; Anibal J. Ramirez-Cuesta; Martin Schröder; Sihai Yang

doi:10.1021/jacs.2c00952

Direct Observation of Ammonia Storage in UiO-66 Incorporating Cu(II) Binding Sites

Yujie Ma, Wanpeng Lu, Xue Han, Yinlin Chen, Ivan Da Silva, Daniel Lee, Alena M. Sheveleva, Zi Wang, Jiangnan Li, Weiyao Li, Mengtian Fan, Shaojun Xu, Floriana Tuna, Eric J.L. McInnes, Yongqiang Cheng, Svemir Rudić, Pascal Manuel, Mark D. Frogley, Anibal J. Ramirez-Cuesta, Martin SchröderSihai Yang

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Abstract

The presence of active sites in metal-organic framework (MOF) materials can control and affect their performance significantly in adsorption and catalysis. However, revealing the interactions between the substrate and active sites in MOFs at atomic precision remains a challenging task. Here, we report the direct observation of binding of NH3 in a series of UiO-66 materials containing atomically dispersed defects and open Cu(I) and Cu(II) sites. While all MOFs in this series exhibit similar surface areas (1111-1135 m2 g-1), decoration of the-OH site in UiO-66-defect with Cu(II) results in a 43% enhancement of the isothermal uptake of NH3 at 273 K and 1.0 bar from 11.8 in UiO-66-defect to 16.9 mmol g-1 in UiO-66-CuII. A 100% enhancement of dynamic adsorption of NH3 at a concentration level of 630 ppm from 2.07 mmol g-1 in UiO-66-defect to 4.15 mmol g-1 in UiO-66-CuII at 298 K is observed. In situ neutron powder diffraction, inelastic neutron scattering, and electron paramagnetic resonance, solid-state nuclear magnetic resonance, and infrared spectroscopies, coupled with modeling reveal that the enhanced NH3 uptake in UiO-66-CuII originates from a {Cu(II)···NH3} interaction, with a reversible change in geometry at Cu(II) from near-linear to trigonal coordination. This work represents the first example of structural elucidation of NH3 binding in MOFs containing open metal sites and will inform the design of new efficient MOF sorbents by targeted control of active sites for NH3 capture and storage.

Original language	English
Journal	Journal of the American Chemical Society
DOIs	https://doi.org/10.1021/jacs.2c00952
State	Accepted/In press - 2022

Funding

The authors thank the EPSRC (EP/I011870, EP/V056409), the Royal Society, and the University of Manchester 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’s Horizon 2020 research and innovation programme (Grant Agreement No. 742401, NANOCHEM). The authors are grateful to Diamond Light Source and the STFC/ISIS Facility for access to Beamlines B22, TOSCA, and WISH. We acknowledge Diamond Light Source beamline staff and the UK catalysis Hub Block Allocation Group (BAG) Programme Mode Application for the provision of beamtime at B18 (Experiment SP19850) for the collection of the data presented in this work and the initial discussion of the data. The UK Catalysis Hub is kindly thanked for the resources and support provided via our membership of the UK Catalysis Hub Consortium and funding by EPSRC Grant: EP/R026939/1, EP/R026815/1, EP/R026645/1, EP/R027129/1, or EP/M013219/1 (biocatalysis). The computing resources were made available through the VirtuES and the ICE-MAN projects, 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, and Y.M. thanks the China Scholarship Council (CSC) for funding.

Funders	Funder number
Catalysis Hub Consortium	EP/M013219/1, EP/R026645/1, EP/R027129/1, EP/R026815/1, EP/R026939/1
Compute and Data Environment for Science
Laboratory Directed Research and Development
Horizon 2020 Framework Programme	742401
Engineering and Physical Sciences Research Council	EP/V056409, EP/I011870
Royal Society
University of Manchester
European Research Council
China Scholarship Council

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10.1021/jacs.2c00952

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Ma, Y., Lu, W., Han, X., Chen, Y., Da Silva, I., Lee, D., Sheveleva, A. M., Wang, Z., Li, J., Li, W., Fan, M., Xu, S., Tuna, F., McInnes, E. J. L., Cheng, Y., Rudić, S., Manuel, P., Frogley, M. D., Ramirez-Cuesta, A. J., ... Yang, S. (Accepted/In press). Direct Observation of Ammonia Storage in UiO-66 Incorporating Cu(II) Binding Sites. Journal of the American Chemical Society. https://doi.org/10.1021/jacs.2c00952

@article{98999b2be06744f28e2c0b817c39867c,

title = "Direct Observation of Ammonia Storage in UiO-66 Incorporating Cu(II) Binding Sites",

abstract = "The presence of active sites in metal-organic framework (MOF) materials can control and affect their performance significantly in adsorption and catalysis. However, revealing the interactions between the substrate and active sites in MOFs at atomic precision remains a challenging task. Here, we report the direct observation of binding of NH3 in a series of UiO-66 materials containing atomically dispersed defects and open Cu(I) and Cu(II) sites. While all MOFs in this series exhibit similar surface areas (1111-1135 m2 g-1), decoration of the-OH site in UiO-66-defect with Cu(II) results in a 43% enhancement of the isothermal uptake of NH3 at 273 K and 1.0 bar from 11.8 in UiO-66-defect to 16.9 mmol g-1 in UiO-66-CuII. A 100% enhancement of dynamic adsorption of NH3 at a concentration level of 630 ppm from 2.07 mmol g-1 in UiO-66-defect to 4.15 mmol g-1 in UiO-66-CuII at 298 K is observed. In situ neutron powder diffraction, inelastic neutron scattering, and electron paramagnetic resonance, solid-state nuclear magnetic resonance, and infrared spectroscopies, coupled with modeling reveal that the enhanced NH3 uptake in UiO-66-CuII originates from a {Cu(II)···NH3} interaction, with a reversible change in geometry at Cu(II) from near-linear to trigonal coordination. This work represents the first example of structural elucidation of NH3 binding in MOFs containing open metal sites and will inform the design of new efficient MOF sorbents by targeted control of active sites for NH3 capture and storage.",

author = "Yujie Ma and Wanpeng Lu and Xue Han and Yinlin Chen and {Da Silva}, Ivan and Daniel Lee and Sheveleva, {Alena M.} and Zi Wang and Jiangnan Li and Weiyao Li and Mengtian Fan and Shaojun Xu and Floriana Tuna and McInnes, {Eric J.L.} and Yongqiang Cheng and Svemir Rudi{\'c} and Pascal Manuel and Frogley, {Mark D.} and Ramirez-Cuesta, {Anibal J.} and Martin Schr{\"o}der and Sihai Yang",

note = "Publisher Copyright: {\textcopyright} 2022 The Authors. Published by American Chemical Society.",

year = "2022",

doi = "10.1021/jacs.2c00952",

language = "English",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

}

Ma, Y, Lu, W, Han, X, Chen, Y, Da Silva, I, Lee, D, Sheveleva, AM, Wang, Z, Li, J, Li, W, Fan, M, Xu, S, Tuna, F, McInnes, EJL, Cheng, Y, Rudić, S, Manuel, P, Frogley, MD, Ramirez-Cuesta, AJ, Schröder, M & Yang, S 2022, 'Direct Observation of Ammonia Storage in UiO-66 Incorporating Cu(II) Binding Sites', Journal of the American Chemical Society. https://doi.org/10.1021/jacs.2c00952

TY - JOUR

T1 - Direct Observation of Ammonia Storage in UiO-66 Incorporating Cu(II) Binding Sites

AU - Ma, Yujie

AU - Lu, Wanpeng

AU - Han, Xue

AU - Chen, Yinlin

AU - Da Silva, Ivan

AU - Lee, Daniel

AU - Sheveleva, Alena M.

AU - Wang, Zi

AU - Li, Jiangnan

AU - Li, Weiyao

AU - Fan, Mengtian

AU - Xu, Shaojun

AU - Tuna, Floriana

AU - McInnes, Eric J.L.

AU - Cheng, Yongqiang

AU - Rudić, Svemir

AU - Manuel, Pascal

AU - Frogley, Mark D.

AU - Ramirez-Cuesta, Anibal J.

AU - Schröder, Martin

AU - Yang, Sihai

PY - 2022

Y1 - 2022

N2 - The presence of active sites in metal-organic framework (MOF) materials can control and affect their performance significantly in adsorption and catalysis. However, revealing the interactions between the substrate and active sites in MOFs at atomic precision remains a challenging task. Here, we report the direct observation of binding of NH3 in a series of UiO-66 materials containing atomically dispersed defects and open Cu(I) and Cu(II) sites. While all MOFs in this series exhibit similar surface areas (1111-1135 m2 g-1), decoration of the-OH site in UiO-66-defect with Cu(II) results in a 43% enhancement of the isothermal uptake of NH3 at 273 K and 1.0 bar from 11.8 in UiO-66-defect to 16.9 mmol g-1 in UiO-66-CuII. A 100% enhancement of dynamic adsorption of NH3 at a concentration level of 630 ppm from 2.07 mmol g-1 in UiO-66-defect to 4.15 mmol g-1 in UiO-66-CuII at 298 K is observed. In situ neutron powder diffraction, inelastic neutron scattering, and electron paramagnetic resonance, solid-state nuclear magnetic resonance, and infrared spectroscopies, coupled with modeling reveal that the enhanced NH3 uptake in UiO-66-CuII originates from a {Cu(II)···NH3} interaction, with a reversible change in geometry at Cu(II) from near-linear to trigonal coordination. This work represents the first example of structural elucidation of NH3 binding in MOFs containing open metal sites and will inform the design of new efficient MOF sorbents by targeted control of active sites for NH3 capture and storage.

AB - The presence of active sites in metal-organic framework (MOF) materials can control and affect their performance significantly in adsorption and catalysis. However, revealing the interactions between the substrate and active sites in MOFs at atomic precision remains a challenging task. Here, we report the direct observation of binding of NH3 in a series of UiO-66 materials containing atomically dispersed defects and open Cu(I) and Cu(II) sites. While all MOFs in this series exhibit similar surface areas (1111-1135 m2 g-1), decoration of the-OH site in UiO-66-defect with Cu(II) results in a 43% enhancement of the isothermal uptake of NH3 at 273 K and 1.0 bar from 11.8 in UiO-66-defect to 16.9 mmol g-1 in UiO-66-CuII. A 100% enhancement of dynamic adsorption of NH3 at a concentration level of 630 ppm from 2.07 mmol g-1 in UiO-66-defect to 4.15 mmol g-1 in UiO-66-CuII at 298 K is observed. In situ neutron powder diffraction, inelastic neutron scattering, and electron paramagnetic resonance, solid-state nuclear magnetic resonance, and infrared spectroscopies, coupled with modeling reveal that the enhanced NH3 uptake in UiO-66-CuII originates from a {Cu(II)···NH3} interaction, with a reversible change in geometry at Cu(II) from near-linear to trigonal coordination. This work represents the first example of structural elucidation of NH3 binding in MOFs containing open metal sites and will inform the design of new efficient MOF sorbents by targeted control of active sites for NH3 capture and storage.

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U2 - 10.1021/jacs.2c00952

DO - 10.1021/jacs.2c00952

M3 - Article

C2 - 35533381

AN - SCOPUS:85130645632

SN - 0002-7863

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

ER -

Direct Observation of Ammonia Storage in UiO-66 Incorporating Cu(II) Binding Sites

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