Water-stable metal-organic frameworks (MOFs): rational construction and carbon dioxide capture

Abstract

Metal-organic frameworks (MOFs) are considered to be a promising porous material due to their excellent porosity and chemical tailorability. However, due to the relatively weak strength of coordination bonds, the stability (e.g., water stability) of MOFs is usually poor, which severely inhibits their practical applications. To prepare water-stable MOFs, several important strategies such as increasing the bonding strength of building units and introducing hydrophobic units have been proposed, and many MOFs with excellent water stability have been prepared. Carbon dioxide not only causes a range of climate and health problems but also is a by-product of some important chemicals (e.g., natural gas). Due to their excellent adsorption performances, MOFs are considered as a promising adsorbent that can capture carbon dioxide efficiently and energetically, and many water-stable MOFs have been used to capture carbon dioxide in various scenarios, including flue gas decarbonization, direct air capture, and purified crude natural gas. In this review, we first introduce the design and synthesis of water-stable MOFs and then describe their applications in carbon dioxide capture, and finally provide some personal comments on the challenges facing these areas.

Scheme 1. Water stable MOFs based on different strategies. (a) Hard–Soft-Acid–Base engineering (direct preparation of water stable MOFs from hardness matching metals and ligands). (b) Pore engineering (improving the water stability of MOFs through pore modification, including metal metathesis, pore space partition, ligand optimization, and framework interlocking). (c) Hydrophobic engineering (improving the water stability of MOFs through introducing hydrophobic units, including pore hydrophobization and surface hydrophobization).

Scheme 2. The definition and optimization of the thermodynamic stability of MOFs to water. Black line represents the thermodynamic stability of a given MOF to water, which refers to the ΔG¹ of the hydrolysis reaction. The red line represents the optimized thermodynamic stability of the MOF through enhancing its bonding strength (ΔG² > ΔG¹).

Scheme 3. The definition and optimization of the kinetic stability of MOFs to water. Black line represents the kinetic stability of a given MOF to water, which refers to the ΔEa¹ (activation energy) of its hydrolysis reaction. The red line represents the optimized kinetic stability of the MOF through enhancing its activation energy (ΔEa² > ΔEa¹).

Fig. 1. The structures of the MIL series and the used ligands. (a) The H₂BDC ligand. (b) The H₂BDC-NH₂ ligand. (c) The 1,3,5-BTC ligand. (d) MIL-53. (e) MIL-88. (f) MIL-100. (g) MIL-101. Reproduced from ref. with permission from Wiley, Copyright 2018.

Fig. 2. The structures of the UiO series and the used ligands. (a) The H₂BDC ligand. (b) The H₂BPDC ligand. (c) UiO-66. Reproduced from ref. with permission from the American Chemical Society, Copyright 2008. (d) UiO-67. Reproduced from ref. with permission from the American Chemical Society, Copyright 2008. (e) UiO-68. Reproduced from ref. with permission from the American Chemical Society, Copyright 2008.

Fig. 3. The structures of the PCN series and the used ligands. (a) The TPDC-2CH₃ ligand. (b) The TPDC-4CH₃ ligand. (c) The TPDC-2CH₂N₂ ligand. (d) The H₂TCPP ligand. (e) The H₄TCP-1 ligand. (f) The H₄TCP-2 ligand. (g) The H₄TCP-3 ligand. (h) PCN-56. Reproduced from ref. with permission from the American Chemical Society, Copyright 2012. (i) PCN-57. Reproduced from ref. with permission from the American Chemical Society, Copyright 2012. (j) PCN-58. Reproduced from ref. with permission from the American Chemical Society, Copyright 2012. (k) PCN-225. Reproduced from ref. with permission from the American Chemical Society, Copyright 2013. (l) PCN-228. Reproduced from ref. with permission from the American Chemical Society, Copyright 2015. (m) PCN-229. Reproduced from ref. with permission from the American Chemical Society, Copyright 2015. (n) PCN-230. Reproduced from ref. with permission from the American Chemical Society, Copyright 2015.

Fig. 4. The structures of the BUT series and the used ligands. (a) The H₃CTTA ligand. (b) The H₃TTNA ligand. (c) The BCQD ligand. (d) The H₄CPTTA ligand. (e) BUT-12. Reproduced from ref. with permission from the American Chemical Society, Copyright 2016. (f) BUT-13. Reproduced from ref. with permission from the American Chemical Society, Copyright 2016. (g) BUT-14. Reproduced from ref. with permission from the American Chemical Society, Copyright 2017. (h) BUT-17. Reproduced from ref. with permission from Springer Nature, Copyright 2019.

Fig. 5. The structures of Ti-MOFs and the used ligands. (a) The 1,3,5-BTC ligand. (b) 5-Aa-IPA ligand. (c) The structures of MIP-207. Reproduced from ref. with permission from Elsevier, Copyright 2020. (d) The structures of MIP-208. Reproduced from ref. with permission from Elsevier, Copyright 2020.

Fig. 6. The structures of representative In(iii)-MOFs and the used ligands. (a) The H₃CTTA ligand. (b) The H₄TCPP ligand. (c) The H₂TCPP ligand. (d) BUT-172. Reproduced from ref. with permission from the Royal Society of Chemistry, Copyright 2020. (e) BUT-173. Reproduced from ref. with permission from the Royal Society of Chemistry, Copyright 2020. (f) In(tcpp). Reproduced from ref. with permission from the Royal Society of Chemistry, Copyright 2021. (g) USTC-8. Reproduced from ref. with permission from the American Chemical Society, Copyright 2018.

Fig. 7. The structures of representative rare-earth MOFs and the used ligands. (a) The 1,3,5-BTC ligand. (b) The 1,4-H₂NDC ligand. (c) The H₂FTZB ligand. (d) The BTBA ligand. (e) The BTB ligand. (f) The BTN ligand. (g) Y-BTC. Reproduced from ref. with permission from the American Chemical Society, Copyright 2010. (h) La-BTN. Reproduced from ref. with permission from the Royal Society of Chemistry, Copyright 2014. (i) La-BTB. Reproduced from ref. with permission from Wiley, Copyright 2013. (j) Eu-1,4-NDC-fcu-MOF. Reproduced from ref. with permission from the American Chemical Society, Copyright 2015. (k) pek-MOF-1. Reproduced from ref. with permission from the American Chemical Society, Copyright 2015. (l) [(CH₃)₂NH₂]₂[Tb₆(μ₃-OH)₈(FTZB)₆(H₂O)₆]·(H₂O)₂₂. Reproduced from ref. with permission from the American Chemical Society, Copyright 2013.

Fig. 8. The structures of representative Zn(ii)-MOFs and the used ligands. (a) The IM ligand. (b) The nIM ligand. (c) The MeIM ligand. (d) The PhIM ligand. (e) The cbIM ligand. (f) The H₂imPim ligand. (g) MAF-stu-1. Reproduced from ref. with permission from Wiley, Copyright 2019. (h) ZIF-8 (MAF-4). Reproduced from ref. with permission from the National Academy of Sciences of the USA, Copyright 2006. (i) ZIF-11. Reproduced from ref. with permission from the National Academy of Sciences of the USA, Copyright 2006. (j) ZIF-61. (k) ZIF-68. (l) ZIF-69. (m) ZIF-70. Reproduced from ref. with permission from The American Association for the Advancement of Science, Copyright 2008.

Fig. 9. The structures of representative Co(ii)-MOFs and the used ligands. (a) The MeIM ligand. (b) The H₂bdpb ligand. (c) The pyz-NH₂ ligand. (d) The H₂bbta ligand. (e) The TPMA ligand. (f) ZJU-75. Reproduced from ref. with permission from Wiley, Copyright 2023. (g) ZIF-67. Reproduced from ref. with permission from The American Association for the Advancement of Science, Copyright 2008. (h) MFU-1. Reproduced from ref. with permission from Wiley, Copyright 2009. (i) MAF-X27-Cl. Reproduced from ref. with permission from the American Chemical Society, Copyright 2016. (j) FJI-H30. Reproduced from ref. with permission from the American Chemical Society, Copyright 2020.

Fig. 10. The structures of representative Ni(ii)-MOFs and the used ligands. (a) The H₄TPP ligand. (b) The H₄TPPP ligand. (c) The H₃BTP ligand. (d) The H₃TPTA ligand. (e) PCN-601. Reproduced from ref. with permission from the American Chemical Society, Copyright 2016. (f) PCN-602. Reproduced from ref. with permission from the American Chemical Society, Copyright 2017. (g) BUT-32. Reproduced from ref. with permission from the American Chemical Society, Copyright 2020. (h) BUT-33. Reproduced from ref. with permission from the American Chemical Society, Copyright 2020. (i) Ni₃(BTP)₂. Reproduced from ref. with permission from the Royal Society of Chemistry, Copyright 2011.

Fig. 11. The structures of representative Cu/Ag-MOFs and the used ligands. (a) The H₃BTTri ligand. (b) The TBPZ ligand (TBPZ = 3,3′,5,5′-tetraethyl-4,4′-bipyrazolate). (c) The Hetz ligand. (d) The H₂fbdim ligand. (e) The o-H₂mpba ligand. (f) [Ag₂(o-Hmpba)₂(o-H₂mpba)₂]. Reproduced from ref. with permission from Wiley, Copyright 2020. (g) Cu-BTTri. Reproduced from ref. with permission from the American Chemical Society, Copyright 2009. (h) Cu₂TBPZ. Reproduced from ref. with permission from Wiley, Copyright 2014. (i) MAF-2. Reproduced from ref. with permission from the American Chemical Society, Copyright 2008. (j) MAF-41. Reproduced from ref. with permission from Springer Nature, Copyright 2019.

Fig. 12. The structures of representative MOFs based on N-containing carboxylate ligands and the used ligands. (a) The H₂dmcapz ligand. (b) The H₃TZBPDC ligand. (c) The H₂BTTA ligand. (d) The H₂DTBDA ligand. (e) [Zn₄(μ₄-O)-(μ₄-4-carboxy-3,5-dimethyl-4-carboxy-pyrazolato)₃]. Reproduced from ref. with permission from the American Chemical Society, Copyright 2011. (f) USTC-7. Reproduced from ref. with permission from the Royal Society of Chemistry, Copyright 2016. (g) FJI-H14. Reproduced from ref. with permission from Springer Nature, Copyright 2017. (h) FJI-H25Fe. Reproduced from ref. with permission from Wiley, Copyright 2020. (i) FJI-H29. Reproduced from ref. with permission from the American Chemical Society, Copyright 2020. (j) FJI-H36. Reproduced from ref. with permission from Wiley, Copyright 2023.

Fig. 13. The structural components, together with the framework viewed along the c axis. NH₂bdc²⁻ = 2-aminoterephthalate, bpdc²⁻ = biphenyl-4,4′-dicarboxylate), tpt = 2,4,6-tri(4-pyridyl)-1,3,5triazine, tpbz = 1,3,5-tri(4-pyridyl)-benzene, and tppy = 2,4,6-tris(4-pyridyl)pyridine. Reproduced from ref. with permission from the American Chemical Society, Copyright 2021.

Fig. 14. Pore space partition (PSP) through symmetry- and size-matching-regulated ligand insertion. Reproduced from ref. with permission from the American Chemical Society, Copyright 2019.

Fig. 15. Construction of a series of Zr-MOFs by using naphthoate-based tetracarboxylate ligands. (a) 12-Connected Zr₆ clusters; (b) 8-connected Zr₆ clusters; (c) different ligands LA¹, LA², and LA³; (d) configuration of ligands; different topologies (e) and structures (f) of LA²-Zr₆⁸-csq (5), LA²-Zr₆¹²-shp (4), LA¹-Zr₆¹²-shp (3), LA¹-Zr₆⁸-csq (2), LA¹-Zr₆⁸-flu (1), and LA³-Zr₆⁸-flu (6) MOFs, respectively. Reproduced from ref. with permission from the American Chemical Society, Copyright 2019.

Fig. 16. (a) ChemDraw representation of [Zn₂(OH)]³⁺ rod and ball-and-stick view of inter-rod connection. (b) Polyhedral view of the rod and the framework of CPM-74. (c) Comparison between the chains in CPM-74 and MOF-74. (d) Building scheme of CPM-75. Zn1, pink; Zn2, blue; Zn3, green; C, gray; O, red. Reproduced from ref. with permission from the American Chemical Society, Copyright 2019.

Fig. 17. (a) The ligand and the structure of PCN-426-Mg; (b) the metal exchange routes for PCN-426. Reproduced from ref. with permission from the American Chemical Society, Copyright 2014.

Fig. 18. Packing diagram of MOF 1 along the c-axis direction (top); design concept for creating a polyMOF analogue of MOF 1 via replacing dangling groups by polymer chains (bottom). Reproduced from ref. with permission from the American Chemical Society, copyright 2016.

Fig. 19. (a) Structure of the ligand H₈tdhb, (b) crystal structure of BUT-155a, and (c) octahedral cage (cage A) and (d) cuboctahedral cage (cage B) in BUT-155a (color code: C, black; O, red; Cu, blue; H atoms on ligands are omitted for clarity). Reproduced from ref. with permission from the American Chemical Society, copyright 2017.

Fig. 20. Fluorinated functional group introduction into the confined pore space. Reproduced from ref. with permission from Wiley, Copyright 2023.

Fig. 21. Preparation of super-hydrophobic NH₂-UiO-66(Zr)-shp. Reproduced from ref. with permission from Wiley, Copyright 2019.

Fig. 22. The modification process used to prepare hydrophobic MOF@PDA-SF composites. Reproduced from ref. with permission from the Royal Society of Chemistry, Copyright 2019.

Fig. 23. Preparative route for Pd/UiO-66@PDMS. Reproduced from ref. with permission from Wiley, Copyright 2016.

Fig. 24. Fabrication of epn-MOF@SBS, Ti mesh@epn-MOF@SBS, Filter@epn-MOF@SBS, and AC@epn-MOF@SBS composites. Reproduced from ref. with permission from Elsevier, Copyright 2022.

Scheme 4. Physical and chemical properties of CO₂ (a), N₂ (b), and CH₄ (c).

Fig. 25. Carbon dioxide adsorption on open metal ions through coordination interactions. (a) The Ni(ii)–CO₂ interactions in CPO-27-Ni. Reproduced from ref. with permission from the Royal Society of Chemistry, Copyright 2008. (b) The Co(ii)–CO₂ interactions in Co-MOF-74. Reproduced from ref. with permission from the Royal Society of Chemistry, Copyright 2017. (c) The Zn(ii)–CO₂ interactions in UTSA-74. Reproduced from ref. with permission from the American Chemical Society, Copyright 2016. (d) The Cu(ii)–CO₂ interactions in FJI-H14. Reproduced from ref. with permission from Springer Nature, Copyright 2017.

Fig. 26. Carbon dioxide adsorption on electrically rich atoms through dipole interactions. (a) The N⋯CO₂ dipole interactions in Zn₂(Atz)₂(ox). Reproduced from ref. with permission from the American Association for the Advancement of Science, Copyright 2010. (b) The N⋯CO₂ dipole interactions in [Zn₂(btm)₂]. Reproduced from ref. with permission from the American Chemical Society, Copyright 2012. (c) The O⋯CO₂ dipole interactions in MFM-102-NO₂. Reproduced from ref. with permission from the Royal Society of Chemistry, Copyright 2020. (d) The O⋯CO₂ dipole interactions in FJI-H38. Reproduced from ref. with permission from Wiley, Copyright 2023. (e) The F⋯CO₂ dipole interactions in NbOFFIVE-1-Ni. Reproduced from ref. with permission from the American Chemical Society, Copyright 2016. (f) The F⋯CO₂ dipole interactions in dptz-CuTiF₆. Reproduced from ref. with permission from Elsevier, Copyright 2019.

Fig. 27. Carbon dioxide adsorption on electron-deficient H atoms through hydrogen-bonding interactions. (a) The OH⋯O hydrogen-bonding interactions in UTSA-16. Reproduced from ref. with permission from Springer Nature, Copyright 2012. (b) The OH⋯O hydrogen-bonding interactions in NOTT-300. Reproduced from ref. with permission from Springer Nature, Copyright 2012. (c) The NH/CH⋯O hydrogen-bonding interactions in MFM-188a. Reproduced from ref. with permission from Springer Nature, Copyright 2017. (d) The CH⋯O hydrogen-bonding interactions in MFM-102-NO₂. Reproduced from ref. with permission from the Royal Society of Chemistry, Copyright 2020.

Fig. 28. Carbon dioxide adsorption on phenyl groups through π–π interaction. (a) and (b) The potential π–π interaction between adsorbed CO₂ and phenyl rings based on MS. Reproduced from ref. with permission from the American Chemical Society, Copyright 2013. Reproduced from ref. with permission from Springer Nature, Copyright 2019. (c) The π–π/p–π interactions between adsorbed CO₂ and phenyl groups in CaSDB. Reproduced from ref. with permission from Wiley, Copyright 2013. (d) The π–π/p–π interactions between adsorbed CO₂ and phenyl groups in MFM-300(V^IV). Reproduced from ref. with permission from Springer Nature, Copyright 2017.

Fig. 29. Carbon dioxide adsorption on nitrogen atoms through the formation of ammonium carbamate/carbamic acid. (a) The ammonium carbamate chain in mmen-Mn₂(dobpdc). Reproduced from ref. with permission from Springer Nature, Copyright 2015. (b) The carbamic acid and ammonium carbamate in IRMOF-74-III-(CH₂NH₂)₂. Reproduced from ref. with permission from the American Chemical Society, Copyright 2017. (c) The carbamate pairs in dmpn-Zn₂(dobpdc). Reproduced from ref. with permission from the American Chemical Society, Copyright 2017. (d) The mixture of carbamic acid and ammonium carbamate in dmpn-Mg₂(dobpdc). Reproduced from ref. with permission from the American Chemical Society, Copyright 2018.

Fig. 30. Carbon dioxide adsorption on oxygen atoms through the formation of carbonate. (a) The alkyl carbonates in CD-MOF-2. Reproduced from ref. with permission from the American Chemical Society, Copyright 2011. (b) The bicarbonate in KOH CD-MOF. Reproduced from ref. with permission from Wiley, Copyright 2022. (c) The bicarbonate in MAF-X25ox. Reproduced from ref. with permission from the Royal Society of Chemistry, Copyright 2015. (d) The bicarbonate in [Zn(ZnOH)₄(bibta)₃]. Reproduced from ref. with permission from the American Chemical Society, Copyright 2018.

Fig. 31. The structure and CO₂ adsorption performance of ALF. Reproduced from ref. with permission from the Advancement of Science, Copyright 2022. (a) The structure of ALF. (b) The CO₂/N₂ sorption isotherms of ALF at 298 K. (c) The breakthrough curves of ALF at 323 K. (d) 130 cycles of adsorption and desorption.

Fig. 32. (a) The structure of NKMOF-3-Ln. (b)–(d) The CO₂/N₂ adsorption isotherms, CO₂ adsorption enthalpy, and breakthrough curves of CO₂/N₂ (15/85) mixtures at 298 K. Reproduced from ref. with permission from the American Chemical Society, Copyright 2019.

Fig. 33. (a) The structure of SIFSIX-2-Cu-i and SIFSIX-3-Zn. (b) PXRD patterns of SIFSIX-2-Cu-i after breakthrough experiments, high-pressure absorption, and water adsorption. (c) and (d) The CO₂ sorption isotherms of SIFSIX-3-Zn (c) and SIFSIX-2-Cu-i at different temperatures. Reproduced from ref. and with permission from Springer Nature, Copyright 2015.

Fig. 34. (a) The CO₂ and N₂ adsorption isotherms for FJI-H14 at 298 K. (b) The isosteric heat of CO₂ adsorption (Q_st) for FJI-H14. (c) The IAST selectivity of FJI-H14 for CO₂/N₂ (15 : 85). (d) 5 Cycles of CO₂ adsorption for FJI-H14 at 298 K. Reproduced from ref. with permission from Springer Nature, Copyright 2017.

Fig. 35. (a) The structure of CALF-20. (b) The CO₂ and N₂ isotherms of CALF-20 at different temperatures. Reproduced from ref. with permission from the Advancement of Science, Copyright 2021.

Fig. 36. (a) Introducing hydrophobic polynaphthylene (PN) into MOF-5 through the polymerization of DEB. (b) The CO₂ adsorption isotherms of MOF-5 and PN@MOF-5 at different temperatures. (c) The IAST selectivity of MOF-5 and PN@MOF-5 for a CO₂/N₂ mixture (14 : 86) at 273 K. Reproduced from ref. with permission from the American Chemical Society, Copyright 2016.

Fig. 37. (a) The structure of NJU-Bai52 and NJU-Bai53. (b) The N₂ sorption isotherms of NJU-Bai53 (77 K) before and after water treatment. (c) The CO₂ adsorption isotherms of NJU-Bai52 and NJU-Bai53 at 298 K. (d) The adsorption enthalpy of NJU-Bai52 and NJU-Bai53 for CO₂. Reproduced from ref. with permission from the American Chemical Society, Copyright 2019.

Fig. 38. (a) The structure of NbOFFIVE-1-Ni. (b) The CO₂ sorption isotherms of NbOFFIVE-1-Ni at different temperatures. (c) The CO₂ adsorption sites in NbOFFIVE-1-Ni. (d) The breakthrough curves with the mixed-gas CO₂/N₂ (1/99) at 1 bar and 298 K in both dry and humid environments. Reproduced from ref. with permission from the American Chemical Society, Copyright 2016.

Fig. 39. (a) The structure of FJI-H38. (b) The CO₂ sorption isotherms of FJI-H38 at different temperatures. (c) The IAST selectivity of FJI-H38 for CO₂/N₂ at various partial pressures. (d) The breakthrough curves of FJI-H38 for CO₂/N₂ (1 : 99) under different humid conditions. Reproduced from ref. with permission from Wiley, Copyright 2023.

Fig. 40. (a) Introducing N₂H₄ into pores of Mg₂(dobdc). (b) The CO₂ sorption isotherms of (Mg₂(dobdc)(N₂H₄)_1.8) at different temperatures. (c) The breakthrough curves of (Mg₂(dobdc)(N₂H₄)_1.8) for CO₂/N₂ (1 : 999) under different humid conditions. Reproduced from ref. with permission from the Royal Society of Chemistry, Copyright 2016.

Fig. 41. (a) Coating HPMCP on SIFSIX-3-Ni. (b) The breakthrough curves of SIFSIX-3-Ni and HPMCP/SIFSIX-3 for CO₂/N₂ (1 : 99) under different humid conditions. (c) The HPMCP/SIFSIX-3-Ni recyclability tests for humid 1% CO₂/99% N₂ and 15% CO₂/85% N₂ gas mixtures (regeneration at 80 °C). Reproduced from ref. with permission from the American Chemical Society, Copyright 2020.

Fig. 42. (a) The structure of UTSA-280. (b) The CO₂/CH₄ sorption isotherms of UTSA-280 at 273 and 298 K. (c) and (d) The breakthrough curves and cycles of UTSA-280 for CO₂/CH₄ (1 : 1). Reproduced from ref. with permission from Wiley, Copyright 2020.

Fig. 43. (a) The framework of AlFFIVE-1-Ni. (b) The breakthrough experiments using a CO₂/H₂S/CH₄:5/5/90 gas mixture on AlFFIVE-1-Ni at 298 K and 323 K (1 bar). (c) The breakthrough trials using a fresh sample under the same parameters (298 K) after optimal activation (105 °C) and after five breakthrough cycles. (d) The breakthrough experiments under humid conditions (65% RH). Reproduced from ref. with permission from the American Association for the Advancement of Science, Copyright 2017. Reproduced from ref. with permission from Springer Nature, Copyright 2018.

Fig. 44. (a) The structure of MUF-16. (b) The CO₂ adsorption isotherms of MUF-16s at 293 K. (c) The IAST selectivity of MUF-16 for CO₂/CH₄ (50 : 50) at 293 K. (d) The CO₂ adsorption isotherms of MUF-16 at 293 K, after 4 consecutive sorption cycles, 12 months of exposure to air with 80% RH, and 24 hours of immersion in water. Reproduced from ref. with permission from Springer Nature, Copyright 2021.