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High and selective capture of low-concentration CO2 with an anion-functionalized ultramicroporous metal-organic framework

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  • ReceivedMay 19, 2020
  • AcceptedJul 23, 2020
  • PublishedOct 19, 2020

Abstract


Funded by

the National Natural Science Foundation of China(21938011,U1862110,21890764,21725603)

and the National Program for Support of Top-notch Young Professionals(H.,X.)


Acknowledgment

This work was supported by the National Natural Science Foundation of China (21938011, U1862110, 21890764 and 21725603), and the National Program for Support of Top-notch Young Professionals (H. X.).


Interest statement

The authors declare that they have no conflict of interest.


Contributions statement

Zhang Z, Xing H, and Cui X designed the experiments; Ding Q and Cui J performed the experiments; Zhang Z wrote the paper with support from Cui X and Xing H. All authors contributed to the general discussion.


Author information

Zhaoqiang Zhang received his PhD degree from the College of Chemical and Biological Engineering, Zhejiang University in 2019. He is currently working with Prof. Dan Zhao at the National University of Singapore as a post-doctoral fellow. His research interests focus on the design and application of functional ultramicroporous materials in the fields of hydrocarbon adsorption and separation.


Xili Cui obtained her PhD degree from Zhejiang University in 2016. During her postdoctoral research at the University of South Florida from 2018 to 2019, she focused on the syntheses of porous materials for separation and purification of structure-similar mixtures. She joined the College of Chemical and Biological Engineering at Zhejiang University by “Hundred-Talent Program” in 2019. Her current research interest focuses on the design and syntheses of functional porous materials for the separation of hydrocarbons. She has received several awards such as the CPCIF-Clariant Youth Innovation Award for Sustainable Development-Excellent Award.


Supplement

Supplementary information

Experimental details and supporting data are available in the online version of the paper.


References

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  • Figure 1

    Schematic representation of the (a) construction and (b) the pore structure of ZU-16 (TIFSIX-3) materials with pyrazine linker.

  • Figure 2

    (a) CO2 adsorption isotherms on various anion-functionalized ultramicroporous materials at 298 K. (b) Comparison of CO2 uptakes on various anion-functionalized materials at 10,000 ppm. (c) CO2, N2, and CH4 adsorption isotherms on ZU-16-Co at 298 K.

  • Figure 3

    The calculated CO2 adsorption binding configuration in ZU-16-Co by (a) DFT-D and (b) GCMC, revealing the close interactions between CO2 and fluorine atoms of TIFSIX anions (Color code: F, turquoise; Ti, light blue; Co, pink; N, blue; C, Grey; H, white; O, red). Column breakthrough experiments for (c) CO2/N2 (1/99, flow rate: 5 mL min−1) and (d) CO2/CH4 (50/50, flow rate: 4 mL min−1) conducted on ZU-16-Co. CA means the real-time concentration, and C0 means the initial concentration of one gas in mixed mixtures.

  • Table 1   Comparison of the structural information of anion-functionalized ultramicroporous MOFs and CO2 sorption performances

    Material

    Pore size (Å)

    Pore volume (cm3 g−1)

    BET (m2 g−1)

    CO2 uptake at 400 ppm

    (mmol g−1)

    CO2 uptake at 10,000 ppm

    (mmol g−1)

    CO2 uptake at 1 bar

    (mmol g−1)

    ZU-16-Co

    3.62

    0.11

    260a

    1.05

    2.63

    2.87

    SIFSIX-3-Cu [6]

    3.52

    0.10

    325b

    1.24

    2.34

    2.50

    NbOFFIVE-1-Ni [8]

    3.21

    0.095

    280b

    1.30

    1.71

    2.20

    SIFSIX-3-Ni [8]

    3.71

    0.098

    368b

    0.35

    1.9

    2.57

    TIFSIX-3-Ni

    3.4

    0.095

    295b

    0.67

    1.75

    2.32

    SIFSIX-2-Cu-i [37]

    4.9

    0.31

    503c

    0.068

    0.19

    4.71

    SIFSIX-14-Cu-i [38]

    3.6

    0.27

    612a

    Negligible

    1.72

    4.70

    dptz-CuTiF6 [35]

    4.5–6.0

    0.29

    639c

    2.1

    4.51

    BET surface area calculated from CO2 isotherms at 196 K; b) Langmuir surface area calculated from CO2 isotherms at 273 K; c) BET surface area calculated from N2 isotherms at 77 K.

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