A Flexible Phosphonate Metal Organic Framework for Enhanced Cooperative Ammonia Capture

Dukula De Alwis Jayasinghe, Yinlin Chen, Jiangnan Li, Justyna Maria 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, Chris Hardacre, Martin Schröder, Sihai Yang

Research output: Contribution to journalArticlepeer-review

Abstract

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.
Original languageEnglish
Pages (from-to)32040–32048
JournalJournal of the American Chemical Society
Volume146
Issue number46
Early online date8 Nov 2024
DOIs
Publication statusPublished - 20 Nov 2024

Keywords

  • Adsorption
  • Materials
  • Metal organic frameworks
  • Noncovalent interactions
  • Sorbents

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