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 Maria
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, Chris
AU - Schröder, Martin
AU - Yang, Sihai
PY - 2024/11/20
Y1 - 2024/11/20
N2 - Ammonia (NH3) production in 2023 reached 150 million tons and is associated with concomitant production of 500 million tons of CO2 each year. Efforts to produce greenNH3 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 (MOF) 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 utilising 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 microbar (equivalent to 100 ppm) is observed, and in situ neutron powder diffraction, inelastic neutron scattering, and infrared microspectroscopy, coupled with modelling, reveal a pore expansion from triclinic to rhombohedral structures 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 concomitant production of 500 million tons of CO2 each year. Efforts to produce greenNH3 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 (MOF) 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 utilising 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 microbar (equivalent to 100 ppm) is observed, and in situ neutron powder diffraction, inelastic neutron scattering, and infrared microspectroscopy, coupled with modelling, reveal a pore expansion from triclinic to rhombohedral structures 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.
KW - Adsorption
KW - Materials
KW - Metal organic frameworks
KW - Noncovalent interactions
KW - Sorbents
U2 - 10.1021/jacs.4c12430
DO - 10.1021/jacs.4c12430
M3 - Article
SN - 0002-7863
VL - 146
SP - 32040
EP - 32048
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 46
ER -