Ionic Pairs-Engineered Fluorinated Covalent Organic Frameworks Toward Direct Air Capture of CO2

Qiu, Liqi; Lei, Ming; Wang, Caiqi; Hu, Jianzhi; He, Lilin; Ivanov, Alexander S.; Jiang, De‐en; Lin, Hongfei; Popovs, Ilja; Song, Yanpei; Fan, Juntian; Li, Meijia; Mahurin, Shannon M.; Yang, Zhenzhen; Dai, Sheng

doi:10.1002/smll.202401798

Title: Ionic Pairs-Engineered Fluorinated Covalent Organic Frameworks Toward Direct Air Capture of CO₂

Journal Article · 02 May 2024 · Small

DOI: https://doi.org/10.1002/smll.202401798 · OSTI ID:2439832

Qiu, Liqi ^[1]; Lei, Ming ^[2]; Wang, Caiqi ^[3]; Hu, Jianzhi ^[4]; He, Lilin ^[5]; Ivanov, Alexander S. ^[5]; Jiang, De‐en ^[2]; Lin, Hongfei ^[3]; Popovs, Ilja ^[5]; Song, Yanpei ^[5]; Fan, Juntian ^[5]; Li, Meijia ^[5]; Mahurin, Shannon M. ^[5]; Yang, Zhenzhen ^[5];

^[6]

Univ. of Tennessee, Knoxville, TN (United States)
Vanderbilt Univ., Nashville, TN (United States)
Washington State Univ., Pullman, WA (United States)
Washington State Univ., Pullman, WA (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

The covalent organic frameworks (COFs) possessing high crystallinity and capability to capture low-concentration CO₂ (400 ppm) from air are still underdeveloped. The challenge lies in simultaneously incorporating high-density active sites for CO₂ insertion and maintaining the ordered structure. Herein, a structure engineering approach is developed to afford an ionic pair-functionalized crystalline and stable fluorinated COF (F-COF) skeleton. The ordered structure of the F-COF is well maintained after the integration of abundant basic fluorinated alcoholate anions, as revealed by synchrotron X-ray scattering experiments. The breakthrough test demonstrates its attractive performance in capturing (400 ppm) CO₂ from gas mixtures via O$$-$$C bond formation, as indicated by the in situ spectroscopy and operando nuclear magnetic resonance spectroscopy using ¹³C-labeled CO₂ sources. Both theoretical and experimental thermodynamic studies reveal the reaction enthalpy of ≈-40 kJ mol^-1 between CO₂ and the COF scaffolds. This implies weaker interaction strength compared with state-of-the-art amine-derived sorbents, thus allowing complete CO₂ release with less energy input. The structure evolution study from synchrotron X-ray scattering and small-angle neutron scattering confirms the well-maintained crystalline patterns after CO₂ insertion. In conclusion, the as-developed proof-of-concept approach provides guidance on anchoring binding sites for direct air capture (DAC) of CO₂ in crystalline scaffolds.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC05-00OR22725; AC05-76RL01830; SC0012704

OSTI ID:: 2439832

Report Number(s):: PNNL-SA--198363

Journal Information:: Small, Journal Name: Small Journal Issue: 36 Vol. 20; ISSN 1613-6810

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Ionic Pairs-Engineered Fluorinated Covalent Organic Frameworks Toward Direct Air Capture of CO2

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