A Flexible Phosphonate Metal-Organic Framework for Enhanced Cooperative Ammonia Capture

Dukula De Alwis Jayasinghe; Yinlin Chen; Jiangnan Li; Justyna M. Rogacka; Meredydd Kippax−Jones; Wanpeng Lu; Sergei Sapchenko; Jinyue Yang; Sarayute Chansai; Tianze Zhou; Lixia Guo; Yujie Ma; Longzhang Dong; Daniil Polyukhov; Lutong Shan; Yu Han; Danielle Crawshaw; Xiangdi Zeng; Zhaodong Zhu; Lewis Hughes; Mark D. Frogley; Pascal Manuel; Svemir Rudić; Yongqiang Cheng; Christopher Hardacre; Martin Schröder; Sihai Yang

doi:10.1021/jacs.4c12430

A Flexible Phosphonate Metal-Organic Framework for Enhanced Cooperative Ammonia Capture

Dukula De Alwis Jayasinghe, Yinlin Chen, Jiangnan Li, Justyna M. Rogacka, Meredydd Kippax−Jones, Wanpeng Lu, Sergei Sapchenko, Jinyue Yang, Sarayute Chansai, Tianze Zhou, Lixia Guo, Yujie Ma, Longzhang Dong, Daniil Polyukhov, Lutong Shan, Yu Han, Danielle Crawshaw, Xiangdi Zeng, Zhaodong Zhu, Lewis HughesMark D. Frogley, Pascal Manuel, Svemir Rudić, Yongqiang Cheng, Christopher Hardacre, Martin Schröder, Sihai Yang

Chemical Spectroscopy

Research output: Contribution to journal › Article › peer-review

1 Scopus citations

Abstract

Ammonia (NH₃) production in 2023 reached 150 million tons and is associated with potential concomitant production of up to 500 million tons of CO₂ each year. Efforts to produce green NH₃ are compromised since it is difficult to separate using conventional condensation chillers, but in situ separation with minimal cooling is challenging. While metal-organic framework materials offer some potential, they are often unstable and decompose in the presence of caustic and corrosive NH₃. Here, we address these challenges by developing a pore-expansion strategy utilizing the flexible phosphonate framework, STA-12(Ni), which shows exceptional stability and capture of NH₃ at ppm levels at elevated temperatures (100-220 °C) even under humid conditions. A remarkable NH₃ uptake of 4.76 mmol g^-1 at 100 μbar (equivalent to 100 ppm) is observed, and in situ neutron powder diffraction, inelastic neutron scattering, and infrared microspectroscopy, coupled with modeling, reveal a pore expansion from triclinic to a rhombohedral structure on cooperative binding of NH₃ to unsaturated Ni(II) sites and phosphonate groups. STA-12(Ni) can be readily engineered into pellets or monoliths without losing adsorption capacity, underscoring its practical potential.

Original language	English
Journal	Journal of the American Chemical Society
DOIs	https://doi.org/10.1021/jacs.4c12430
State	Accepted/In press - 2024

Funding

We thank the EPSRC (EP/I011870 and EP/V056409), the University of Manchester, National Science Foundation of China, Peking University, and BNLMS for funding. 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 and STFC/ISIS Facility for the access to beamtimes B22 and TOSCA/WISH, respectively. L.G., J.Y., J.M., L.S., and Y.H. thank the China Scholarship Council (CSC) for funding. J.R. is supported by the Polish National Agency for Academic Exchange (decision no. BPN/BEK/2022/1/00053/DEC/1). This research used computing resources 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, as well as resources of the National Energy Research Scientific Computing Centre (NERSC), a U.S. Department of Energy Office of Science User Facility located at Lawrence Berkeley National Laboratory, operated under contract no. DE-AC02-05CH11231 using NERSC award ERCAP0024340. Molecular simulations have been carried out in Wroclaw Center for Networking and Supercomputing ( http://www.wcss.pl ).

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De Alwis Jayasinghe, D., Chen, Y., Li, J., Rogacka, J. M., Kippax−Jones, M., Lu, W., Sapchenko, S., Yang, J., Chansai, S., Zhou, T., Guo, L., Ma, Y., Dong, L., Polyukhov, D., Shan, L., Han, Y., Crawshaw, D., Zeng, X., Zhu, Z., ... Yang, S. (Accepted/In press). A Flexible Phosphonate Metal-Organic Framework for Enhanced Cooperative Ammonia Capture. Journal of the American Chemical Society. https://doi.org/10.1021/jacs.4c12430

@article{8215eab85eb24fa0b789ac45e79ca7d3,

title = "A Flexible Phosphonate Metal-Organic Framework for Enhanced Cooperative Ammonia Capture",

abstract = "Ammonia (NH3) production in 2023 reached 150 million tons and is associated with potential concomitant production of up to 500 million tons of CO2 each year. Efforts to produce green NH3 are compromised since it is difficult to separate using conventional condensation chillers, but in situ separation with minimal cooling is challenging. While metal-organic framework materials offer some potential, they are often unstable and decompose in the presence of caustic and corrosive NH3. Here, we address these challenges by developing a pore-expansion strategy utilizing the flexible phosphonate framework, STA-12(Ni), which shows exceptional stability and capture of NH3 at ppm levels at elevated temperatures (100-220 °C) even under humid conditions. A remarkable NH3 uptake of 4.76 mmol g-1 at 100 μbar (equivalent to 100 ppm) is observed, and in situ neutron powder diffraction, inelastic neutron scattering, and infrared microspectroscopy, coupled with modeling, reveal a pore expansion from triclinic to a rhombohedral structure on cooperative binding of NH3 to unsaturated Ni(II) sites and phosphonate groups. STA-12(Ni) can be readily engineered into pellets or monoliths without losing adsorption capacity, underscoring its practical potential.",

author = "{De Alwis Jayasinghe}, Dukula and Yinlin Chen and Jiangnan Li and Rogacka, {Justyna M.} and Meredydd Kippax−Jones and Wanpeng Lu and Sergei Sapchenko and Jinyue Yang and Sarayute Chansai and Tianze Zhou and Lixia Guo and Yujie Ma and Longzhang Dong and Daniil Polyukhov and Lutong Shan and Yu Han and Danielle Crawshaw and Xiangdi Zeng and Zhaodong Zhu and Lewis Hughes and Frogley, {Mark D.} and Pascal Manuel and Svemir Rudi{\'c} and Yongqiang Cheng and Christopher Hardacre and Martin Schr{\"o}der and Sihai Yang",

note = "Publisher Copyright: {\textcopyright} 2024 The Authors. Published by American Chemical Society.",

year = "2024",

doi = "10.1021/jacs.4c12430",

language = "English",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

}

De Alwis Jayasinghe, D, Chen, Y, Li, J, Rogacka, JM, Kippax−Jones, M, Lu, W, Sapchenko, S, Yang, J, Chansai, S, Zhou, T, Guo, L, Ma, Y, Dong, L, Polyukhov, D, Shan, L, Han, Y, Crawshaw, D, Zeng, X, Zhu, Z, Hughes, L, Frogley, MD, Manuel, P, Rudić, S, Cheng, Y, Hardacre, C, Schröder, M & Yang, S 2024, 'A Flexible Phosphonate Metal-Organic Framework for Enhanced Cooperative Ammonia Capture', Journal of the American Chemical Society. https://doi.org/10.1021/jacs.4c12430

TY - JOUR

T1 - A Flexible Phosphonate Metal-Organic Framework for Enhanced Cooperative Ammonia Capture

AU - De Alwis Jayasinghe, Dukula

AU - Chen, Yinlin

AU - Li, Jiangnan

AU - Rogacka, Justyna M.

AU - Kippax−Jones, Meredydd

AU - Lu, Wanpeng

AU - Sapchenko, Sergei

AU - Yang, Jinyue

AU - Chansai, Sarayute

AU - Zhou, Tianze

AU - Guo, Lixia

AU - Ma, Yujie

AU - Dong, Longzhang

AU - Polyukhov, Daniil

AU - Shan, Lutong

AU - Han, Yu

AU - Crawshaw, Danielle

AU - Zeng, Xiangdi

AU - Zhu, Zhaodong

AU - Hughes, Lewis

AU - Frogley, Mark D.

AU - Manuel, Pascal

AU - Rudić, Svemir

AU - Cheng, Yongqiang

AU - Hardacre, Christopher

AU - Schröder, Martin

AU - Yang, Sihai

PY - 2024

Y1 - 2024

N2 - Ammonia (NH3) production in 2023 reached 150 million tons and is associated with potential concomitant production of up to 500 million tons of CO2 each year. Efforts to produce green NH3 are compromised since it is difficult to separate using conventional condensation chillers, but in situ separation with minimal cooling is challenging. While metal-organic framework materials offer some potential, they are often unstable and decompose in the presence of caustic and corrosive NH3. Here, we address these challenges by developing a pore-expansion strategy utilizing the flexible phosphonate framework, STA-12(Ni), which shows exceptional stability and capture of NH3 at ppm levels at elevated temperatures (100-220 °C) even under humid conditions. A remarkable NH3 uptake of 4.76 mmol g-1 at 100 μbar (equivalent to 100 ppm) is observed, and in situ neutron powder diffraction, inelastic neutron scattering, and infrared microspectroscopy, coupled with modeling, reveal a pore expansion from triclinic to a rhombohedral structure on cooperative binding of NH3 to unsaturated Ni(II) sites and phosphonate groups. STA-12(Ni) can be readily engineered into pellets or monoliths without losing adsorption capacity, underscoring its practical potential.

AB - Ammonia (NH3) production in 2023 reached 150 million tons and is associated with potential concomitant production of up to 500 million tons of CO2 each year. Efforts to produce green NH3 are compromised since it is difficult to separate using conventional condensation chillers, but in situ separation with minimal cooling is challenging. While metal-organic framework materials offer some potential, they are often unstable and decompose in the presence of caustic and corrosive NH3. Here, we address these challenges by developing a pore-expansion strategy utilizing the flexible phosphonate framework, STA-12(Ni), which shows exceptional stability and capture of NH3 at ppm levels at elevated temperatures (100-220 °C) even under humid conditions. A remarkable NH3 uptake of 4.76 mmol g-1 at 100 μbar (equivalent to 100 ppm) is observed, and in situ neutron powder diffraction, inelastic neutron scattering, and infrared microspectroscopy, coupled with modeling, reveal a pore expansion from triclinic to a rhombohedral structure on cooperative binding of NH3 to unsaturated Ni(II) sites and phosphonate groups. STA-12(Ni) can be readily engineered into pellets or monoliths without losing adsorption capacity, underscoring its practical potential.

UR - http://www.scopus.com/inward/record.url?scp=85209394772&partnerID=8YFLogxK

U2 - 10.1021/jacs.4c12430

DO - 10.1021/jacs.4c12430

M3 - Article

C2 - 39513623

AN - SCOPUS:85209394772

SN - 0002-7863

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

ER -

A Flexible Phosphonate Metal-Organic Framework for Enhanced Cooperative Ammonia Capture

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