Improving the pore properties of porous aromatic frameworks in two aspects via partition strategy

Abstract

Microporous solids are famous for their high surface area and pore size at the molecular scale, which are crucial for the applications of adsorption, separation and catalysis. An ideal porous solid would simultaneously have a high surface area and nanopores with the desired opening size. However, due to the uncontrollable reaction process of porous organic frameworks (POFs), the acquisition of such a solid is still technically limited. Herein, we reported a simple but platform-wide pore partition strategy to improve the porosity of porous aromatic frameworks (PAFs) in two aspects. This strategy was achieved by introducing a partition unit with flexible linkage to segment the original voids of PAFs into multiple micropore domains. The obtained partitioning PAFs have 130%-217% increments in surface area due to the creation of extra accessible surfaces while the pores are segmented into smaller ones. Notably, the partitioning PAFs showed significantly increased adsorption capacity for CO₂ due to their improved surface area. At the same time, the narrowed pore size allowed selective capture of dye molecules by their size differences. Similar to their parent PAFs, the partitioning PAFs retained their high stability in harsh environments. A simple and universal pore partition strategy will be an important step in improving PAF porosity to desired functions.

Keywords

Porous aromatic frameworks / pore partition strategy / size-dependent adsorption

References

[1] Barrer RM.Molecular sieve action at low temperatures.Nature1947;159:508

[2] Li Y.New stories of zeolite structures: their descriptions, determinations, predictions, and evaluations.Chem Rev2014;114:7268-316

[3] Wang Q.State of the art and prospects in metal-organic framework (MOF)-based and MOF-derived nanocatalysis.Chem Rev2020;120:1438-511

[4] Lin JB,Vaidhyanathan R.A scalable metal-organic framework as a durable physisorbent for carbon dioxide capture.Science2021;374:1464-9

[5] Ding SY.Covalent organic frameworks (COFs): from design to applications.Chem Soc Rev2013;42:548-68

[6] Das S,Ben T.Porous organic materials: strategic design and structure-function correlation.Chem Rev2017;117:1515-63

[7] Tian Y.Porous aromatic frameworks (PAFs).Chem Rev2020;120:8934-86

[8] Fan H,Feldhoff A.Covalent organic framework-covalent organic framework bilayer membranes for highly selective gas separation.J Am Chem Soc2018;140:10094-8

[9] Ma Y,Rong H.Continuous porous aromatic framework membranes with modifiable sites for optimized gas separation.Angew Chem Int Ed Engl2022;61:e202113682

[10] Li J,Wang Z.Ultramicroporous covalent organic framework nanosheets with functionality pair for membrane C₂H₂/C₂H₄ separation.Angew Chem Int Ed Engl2023;62:e202216675

[11] Wang P,Jiang Q.High-precision size recognition and separation in synthetic 1D nanochannels.Angew Chem Int Ed Engl2019;58:15922-7

[12] Yue L,Zhou D,Li B.Flexible single-layer ionic organic-inorganic frameworks towards precise nano-size separation.Nat Commun2016;7:10742 PMCID:PMC4773479

[13] Lin RB,Wu H.Optimized separation of acetylene from carbon dioxide and ethylene in a microporous material.J Am Chem Soc2017;139:8022-8

[14] Pang JJ,Zhang K.Real-time in situ volatile organic compound sensing by a dual-emissive polynuclear Ln-MOF with pronounced Ln^III luminescence response.Angew Chem Int Ed Engl2023;62:e202217456

[15] Wang Z,Xu K.Natural oxidase-mimicking copper-organic frameworks for targeted identification of ascorbate in sensitive sweat sensing.Nat Commun2023;14:69 PMCID:PMC9814535

[16] Lim DW,Kitagawa H.Proton transfer in hydrogen-bonded degenerate systems of water and ammonia in metal-organic frameworks.Chem Sci2019;10:16-33 PMCID:PMC6335954

[17] Liu L,Cheng D.Surface-mediated construction of an ultrathin free-standing covalent organic framework membrane for efficient proton conduction.Angew Chem Int Ed Engl2021;60:14875-80

[18] Song J,Cao P.Synergic catalysts of polyoxometalate@cationic porous aromatic frameworks: reciprocal modulation of both capture and conversion materials.Adv Mater2019;31:e1902444

[19] Yuan S,Cai B.Tunable metal hydroxide-organic frameworks for catalysing oxygen evolution.Nat Mater2022;21:673-80

[20] Liu S,Zhang X.Bifunctional {Pb₁₀K₂}–organic framework for high catalytic activity in cycloaddition of CO₂ with epoxides and knoevenagel condensation.ACS Catal2022;12:10373-83

[21] Li H,Wang Y.Pore structure unveiling effect to boost lithium-selenium batteries: selenium confined in hierarchically porous carbon derived from aluminum based MOFs.Chem Synth2023;3:30

[22] Wang L,Li Z.PAF-6 doped with phosphoric acid through alkaline nitrogen atoms boosting high-temperature proton-exchange membranes for high performance of fuel cells.Adv Mater2023;35:e2303535

[23] Yuan Y.Porous aromatic frameworks as a platform for multifunctional applications.ACS Cent Sci2019;5:409-18 PMCID:PMC6439448

[24] Liu L,Qi M,Ren H.Facile synthesis of heteroporous covalent organic frameworks with dual linkages: a “three-in-one” strategy.Chem Synth2024;4:10

[25] Deng L,Ye X.Covalent organic frameworks: chemistry of pore interface and wall surface perturbation and impact on functions.Acc Mater Res2022;3:879-93

[26] Lu W,Yuan D,Fordham S.Rational design and synthesis of porous polymer networks: toward high surface area.Chem Mater2014;26:4589-97

[27] Ben T,Ma S.Targeted synthesis of a porous aromatic framework with high stability and exceptionally high surface area.Angew Chem Int Ed Engl2009;48:9457-60

[28] Zhou DD,Wang C.Intermediate-sized molecular sieving of styrene from larger and smaller analogues.Nat Mater2019;18:994-8

[29] Zeng H,Wang T.Orthogonal-array dynamic molecular sieving of propylene/propane mixtures.Nature2021;595:542-8

[30] Dong Q,Wan J.Confining water nanotubes in a Cu₁₀O₁₃-based metal-organic framework for propylene/propane separation with record-high selectivity.J Am Chem Soc2023;145:8043-51

[31] Lin RB,Zhou HL.Molecular sieving of ethylene from ethane using a rigid metal-organic framework.Nat Mater2018;17:1128-33

[32] Zhai QG,Zhao X,Feng P.Pore space partition in metal-organic frameworks.Acc Chem Res2017;50:407-17

[33] Wei YS,Liao PQ.Coordination templated [2+2+2] cyclotrimerization in a porous coordination framework.Nat Commun2015;6:8348 PMCID:PMC4595715

[34] Xiao Y,Hong AN,Feng P.Solvent-free Synthesis of multi-module pore-space-partitioned metal-organic frameworks for gas separation.Angew Chem Int Ed Engl2023;62:e202300721

[35] Xu X,Xu K,Chen H.Pore partition in two-dimensional covalent organic frameworks.Nat Commun2023;14:3360 PMCID:PMC10250421

[36] Hao M,Lei M.Pore space partition synthetic strategy in imine-linked multivariate covalent organic frameworks.J Am Chem Soc2024;146:1904-13

[37] Zhang Z,Dou Z.Multivariate porous aromatic frameworks with high porosity and hierarchical structures for enzyme immobilization.ACS Cent Sci2023;9:488-93 PMCID:PMC10037458

[38] Jing Y,Chen Y.Crystallinity regulation and defects passivation for efficient and stable perovskite solar cells using fully conjugated porous aromatic frameworks.Angew Chem Int Ed Engl2023;62:e202301234

[39] Liu Y,Meng X,Song X.Increasing the surface area and CO₂ uptake of conjugated microporous polymers via a post-knitting method.Mater Chem Front2021;5:5319-27

[40] Jing X,Cui P,Zhu G.Facile synthesis of cost-effective porous aromatic materials with enhanced carbon dioxide uptake.J Mater Chem A2013;1:13926-31

[41] Rozyyev V,Ullah R.High-capacity methane storage in flexible alkane-linked porous aromatic network polymers.Nat Energy2019;4:604-11

[42] Yuan Y,Ren H.Targeted synthesis of a porous aromatic framework with a high adsorption capacity for organic molecules.J Mater Chem2011;21:13498-502

[43] Xiao J,Xie Z,Song Y.Environmentally friendly reduced graphene oxide as a broad-spectrum adsorbent for anionic and cationic dyes via π–π interactions.J Mater Chem A2016;4:12126-35

[44] Hasan Z.Removal of hazardous organics from water using metal-organic frameworks (MOFs): plausible mechanisms for selective adsorptions.J Hazard Mater2015;283:329-39

[45] Chen T,Li B.Adsorptive separation of aromatic compounds from alkanes by π-π interactions in a carbazole-based conjugated microporous polymer.ACS Appl Mater Interfaces2020;12:56385-92

[46] Durán-jiménez G,Stevens L,Dodds C.Microwave pyrolysis of waste biomass and synthesis of micro-mesoporous activated carbons: the role of textural properties for CO₂ and textile dye adsorption.Chem Eng J2024;488:150926