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

Ammonia (NH<sub>3</sub>) production in 2023 reached 150 million tons and is associated with potential concomitant production of up to 500 million tons of CO<sub>2</sub> each year. Efforts to produce green NH<sub>3</sub> 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 NH<sub>3</sub>. 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 NH<sub>3</sub> at ppm levels at elevated temperatures (100-220 °C) even under humid conditions. A remarkable NH<sub>3</sub> uptake of 4.76 mmol g<sup>-1</sup> 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 NH<sub>3</sub> 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.

Authors

Institutions

Publication Details

Journal
Journal of the American Chemical Society
Published
2024-11-08
DOI
https://doi.org/10.1021/jacs.4c12430
Citations
19
Primary Topic
Ammonia Synthesis and Nitrogen Reduction
Type
article
Field-Weighted Citation Impact
2.03

Funders

Controls
|||
ALL TIME
JAN
FEB
MAR
APR
MAY
JUN
JUL
AUG
SEP
OCT
article

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

Wanpeng Lu, Svemir Rudić, Meredydd Kippax‐Jones, Mark D. Frogley et al.
19 citations
Journal of the American Chemical Society
Ammonia Synthesis and Nitrogen Reduction
2.03
article

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

Wanpeng Lu, Svemir Rudić, Meredydd Kippax‐Jones, Mark D. Frogley, Justyna Rogacka, Yongqiang Q. Cheng, Long‐Zhang Dong, Lutong Shan, Zhaodong Zhu, Xiangdi Zeng, Sihai Yang⧫, Lewis Hughes, Dukula De Alwis Jayasinghe, Lixia Guo, Christopher Hardacre, Martin Schröder, Danielle Crawshaw, Pascal Manuel, Yujie Ma, Jiangnan Li, Yinlin Chen, Daniil M. Polyukhov, Yu Han, Tianze Zhou, Jinyue Yang, Sergei Sapchenko
article en
19 citations

Abstract

Ammonia (NH<sub>3</sub>) production in 2023 reached 150 million tons and is associated with potential concomitant production of up to 500 million tons of CO<sub>2</sub> each year. Efforts to produce green NH<sub>3</sub> 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 NH<sub>3</sub>. 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 NH<sub>3</sub> at ppm levels at elevated temperatures (100-220 °C) even under humid conditions. A remarkable NH<sub>3</sub> uptake of 4.76 mmol g<sup>-1</sup> 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 NH<sub>3</sub> 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.

Journal of the American Chemical SocietyVol. 146(46)
Micron (United States) (US), Wrocław University of Science and Technology (PL), Rutherford Appleton Laboratory (GB), Oak Ridge National Laboratory (US), Peking University (CN), Diamond Light Source (GB), University of Manchester (GB), Beijing National Laboratory for Molecular Sciences (CN), AGH University of Krakow (PL)
National Science Foundation, Diamond Light Source, National Energy Research Scientific Computing Center, European Commission, National Natural Science Foundation of China, China Scholarship Council, Peking University, Narodowa Agencja Wymiany Akademickiej, Office of Science, Engineering and Physical Sciences Research Council, Science and Technology Facilities Council, Beijing National Laboratory for Molecular Sciences, Oak Ridge National Laboratory, Lawrence Berkeley National Laboratory, H2020 European Research Council
Openalex Percentile: Top 12%
Ammonia Synthesis and Nitrogen Reduction
2.03
DOIOpen Access PDFOpenAlex
AI Navigator

Ask Laika to Summarize, Analyze, and Connect papers live on the map.

Summarize Papers & Methodologies

Extract key findings, datasets, and comparative methods across publications.

Benchmark Rankings & Visual Analytics

Rank top research institutions, authors, funders, topics, and journals by Field-Weighted Citation Impact (FWCI) and paper volume with instant charts.

Connect Distant Disciplines

Bridge topological clusters on the map to find hidden collaborative intersections.