Covalent integration of polymers and porous organic frameworks DOI Creative Commons
Md. Amjad Hossain,

Kira Coe-Sessions,

J.W. Ault

et al.

Frontiers in Chemistry, Journal Year: 2024, Volume and Issue: 12

Published: Dec. 18, 2024

Covalent integration of polymers and porous organic frameworks (POFs), including metal-organic (MOFs), covalent (COFs) hydrogen-bonded (HOFs), represent a promising strategy for overcoming the existing limitations traditional materials. This allows combination advantages polymers, i.e., flexibility, processability chemical versatility etc., superiority POFs, like structural integrity, tunable porosity high surface area, creating type hybrid These resulting polymer-POF materials exhibit enhanced mechanical strength, stability functional diversity, thus opening up new opportunities applications across large variety fields, such as gas separation, catalysis, biomedical applications, environmental remediation energy storage. In this review, an overview synthetic routes strategies on how to covalently integrate different with various POFs is discussed, especially particular focus methods polymerization within, among POF structures. To investigate unique properties functions these resultant materials, characterization techniques, nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), transmission electron microscopy (TEM) scanning (SEM), adsorption (BET) computational modeling machine learning, are also presented. The ability polymer-POFs manipulate pore environments at molecular level affords wide range providing versatile platform future advancements in material science. Looking forward, fully realize potential authors highlight scalability, green synthesis methods, stimuli-responsive critical areas research.

Language: Английский

Advanced Porous Aromatic Frameworks: A Comprehensive Overview of Emerging Functional Strategies and Potential Applications DOI

Hamid Ali,

Yasin Orooji, Abdullah Yahya Abdullah Alzahrani

et al.

ACS Nano, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 18, 2025

Porous aromatic frameworks (PAFs) are a fundamental group of porous materials characterized by their distinct structural features and large surface areas. These synthesized from building units linked strong carbon–carbon bonds, which confer exceptional rigidity long-term stability. PAFs functionalities may arise directly the intrinsic chemistry or through postmodification motifs using well-defined chemical processes. Compared to other traditional such as zeolites metallic-organic frameworks, demonstrate superior stability under severe treatments due robust bonding. Even in challenging environments, ease functionalization flexibility specificity. Research on has significantly expanded accelerated over past decade, necessitating comprehensive overview key advancements this field. This review provides an in-depth analysis recent advances synthesis, functionalization, dimensionality PAFs, along with distinctive properties wide-ranging applications. explores innovative methodologies strategies for functionalizing structures, manipulation tailor specific potential Similarly, application areas, including batteries, absorption, sensors, CO2 capture, photo-/electrocatalytic usages, supercapacitors, separation, biomedical discussed detail, highlighting versatility addressing modern scientific industrial challenges.

Language: Английский

Citations

3
Physical Phenomena in Porous Frameworks DOI Creative Commons
Thomas Heine, Mircea Dincă, Guangshan Zhu

et al.

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: 58(3), P. 327 - 329

Published: Feb. 4, 2025

InfoMetricsFiguresRef. Accounts of Chemical ResearchVol 58/Issue 3Article This publication is free to access through this site. Learn More CiteCitationCitation and abstractCitation referencesMore citation options ShareShare onFacebookX (Twitter)WeChatLinkedInRedditEmailJump toExpandCollapse EditorialFebruary 4, 2025Physical Phenomena in Porous FrameworksClick copy article linkArticle link copied!Thomas Heine*Thomas HeineFaculty Chemistry Food Chemistry, TU Dresden, Bergstrasse 66c, 01069 GermanyHelmholtz-Zentrum Dresden-Rossendorf, Centrum for Advanced Systems Understanding, CASUS, Untermarkt 20, 02826 Görlitz, GermanyDepartment Yonsei University IBS center nanomedicine, Seodaemun-gu, Seoul 120-749, Republic Korea*Email: [email protected]More by Thomas Heinehttps://orcid.org/0000-0003-2379-6251Mircea DincaMircea DincaDepartment Massachusetts Institute Technology, Cambridge, 02139, United StatesMore Mircea Dincahttps://orcid.org/0000-0002-1262-1264Guangshan ZhouGuangshan ZhouKey Laboratory Polyoxometalate Reticular Material Ministry Education, School Northeast Normal University, Changchun 130024, ChinaMore Guangshan Zhouhttps://orcid.org/0000-0002-5794-3822Open PDFAccounts ResearchCite this: Acc. Chem. Res. 2025, 58, 3, 327–329Click citationCitation copied!https://pubs.acs.org/doi/10.1021/acs.accounts.4c00835https://doi.org/10.1021/acs.accounts.4c00835Published February 2025 Publication History Received 23 December 2024Published online 4 2025Published issue 2025editorialCopyright © Published American Society. available under these Terms Use. Request reuse permissionsThis licensed personal use The ACS PublicationsCopyright SocietySubjectswhat are subjectsArticle subjects automatically applied from the Subject Taxonomy describe scientific concepts themes article.Electrical conductivityMaterialsMetal organic frameworksQuantum mechanicsTwo dimensional materialsPorous materials characterized a high internal surface area significant pore volume. Natural examples, such as microporous zeolites, have been known humanity since ancient times, but their systematic investigation only started 1930s flourished with discovery synthetic zeolites critical role modern catalysis, molecular sieving, ion exchange. broader family framework compounds was later enriched development coordination networks (1,2) metal–organic frameworks (MOFs). (2) latter distinguished increased stability permanent porosity. (3,4) MOFs, along purely relatives, covalent (COFs) (5) porous aromatic (PAFs), (6) obtained reticular chemistry, "the chemistry linking building blocks strong bonds make crystalline open frameworks". (7) vast structural complexity results plethora crystal nets that materials. (8) Because structure significantly influences physical properties (e.g., see ref (9) tutorial review on two-dimensional systems), targeting particular topologies can be used rational design element new property-tailored materials.Traditional applications take advantage porosity, instance, gas storage, separation, catalysis. However, offer possibilities beyond these, which long-range order, topology, crystallographic nets, dimensionality extended structures. Indeed, range zero-dimensional cages one-dimensional chains or tubular networks, two- three-dimensional networks. Likewise, thought electronic, structurally exhibiting exotic one- electronic properties, instance. (10) Exotic, complex structures often prerequisite structures, Dirac Weyl points, van Hove singularities, flat bands, excite our fellow physicists. combination functionality order beneficial light harvesting optoelectronics. Concerted flexibility result flexible close upon external stimuli which, hence, change dynamically.This special focuses phenomena emerged recent years. A collection 18 experiment theory cover COFs, PAFs, ranging zero three dimensions, well polymer glasses. They feature mechanical flexibility, electrical conductivity, magnetism, methodological work synthesis, assembly, theoretical description. It contains fine examples where control enables superior performance chemistry-related applications, sensing photocatalysis.One core material conductivity. Most insulators semiconductors. Even if band gap narrow, conductivity hindered largely ionic metal–ligand act charge traps decrease mobility. Hopping transport likewise large distances across wide pores. Recent advances synthesis electrically conductive picture avenues applications. For example, smart route involving nonplanar linkers achieve conjugated 2D MOFs electric described Liu, Xing, Chen. (11) Jeong colleagues discuss strategies fabricate large-area MOF films. (12) Electrical controlled electron hopping achieved manipulating oxidation state metal nodes MOFs. Li Ott how factors redox-conductive frameworks. (13)Enhanced either in-plane conjugation COFs suitably embedded nodes, coupled active groups framework, chemiresistors enable selective sensing, discussed Benedetto Mirica. (14) Electric photocatalytic energy conservation. Fang et al. it via morphology also defects. Moreover, they tune Fermi level proper selection utilize donor–acceptor block pairs facilitate separation. (15) Beyond spin opens door utilization spintronics quantum To this, Lu, Samori, Feng highlight challenges experimental realization, large-scale decoupling out-of-plane manipulation dynamics. (16) Combination chemical sensitivity together local spins noses, qubits allowing specific recognition molecules spin–spin interactions, Yamauchi Yanai. (17)The lattice subject contributions. Chen Jiang emphasize impact transfer separation possibility fine-tune light-harvesting COF photocatalysis. (18) Creating thus establishing nanotubes, allows constrained 1D. (19) An intriguing property some them suffer changes stimuli. If carry lattice-dependent then change. Such responsive serve basis multiferroic (20)The processability structuring relatively hard polycrystalline materials, remains challenging. Two interesting approaches shown here: transformation glasses improves stability. (21) parallel approach overall crystallinity controlling orientation during growth using magnetic fields. (22)On side, Hardiagon summarize predict density-functional theory, machine learning, data-based preselection hierarchical refinement. (23)Framework made ingredients, turn give additional contributions issue. include metal–phosphonate frameworks, construction, properties. (24) capture CO2 molecule unit form stable As pointed out Kadota Horike, may reservoirs potentially even upgrading. (25) Wang, Su, Zuo tetrathiafulvalene (TTF) its analogues remarkable focus TTF-MOFs TTF-COFs, fuel cells, batteries, photo- electrocatalysts sensors crossover devices, among others. (26) entirely blocks, developed centers, introducing coupling reactions. Another novelty PAF research enhanced facilitated variants two different units. (27) Finally, built triangulenes explored means predictive theory. Functionalization diamagnetic tunable including effective carrier masses, gap, positions. exploited create photocatalysts operating without overpotentials. spin-carrying instead, surprisingly crystal, cases couplings, resulting Stoner ferromagnetism, predicted. (28)The compiled suggest will both potential nanotechnology technology. These opportunities twist motivating many more consider stem unique properties.Author InformationClick section linkSection copied!Corresponding AuthorThomas Heine, Faculty Germany; Helmholtz-Zentrum Department Korea, https://orcid.org/0000-0003-2379-6251, Email: protected]AuthorsMircea Dinca, States, https://orcid.org/0000-0002-1262-1264Guangshan Zhou, Key China, https://orcid.org/0000-0002-5794-3822NotesViews expressed editorial those authors not necessarily views ACS.ReferencesClick copied! references 28 other publications. 1Hoskins, B. F.; Robson, R. Design construction class scaffolding-like comprising infinite polymeric 3D-linked rods. reappraisal zinc cyanide cadmium diamond-related [N(CH3)4][CuIZnII(CN)4] CuI[4,4′,4″,4″″-tetracyanotetraphenylmethane]BF4.xC6H5NO2. J. Am. Soc. 1990, 112 (4), 1546– 1554, DOI: 10.1021/ja00160a038 Google Scholar1Design CuI[4,4',4'',4'''-tetracyanotetraphenylmethane]BF4.xC6H5NO2Hoskins, RichardJournal Society (1990), 1546-54CODEN: JACSAT; ISSN:0002-7863. proposed extensive afforded centers tetrahedral an octahedral array valences rodlike connecting Some simple general principles concerning presented reasons expecting show unusual useful simplest conceivable systems type isomorphous Zn(CN)2 Cd(CN)2 whose were reexamd. single-crystal x-ray diffraction, confirming earlier description based powder diffraction data 2 interpenetrating frameworks: cubic, space group P‾43m, Z = 2; 5.9002(9) Å (Zn(CN)2) 6.301(1) (Cd(CN)2); 1 surrounded tetrahedrally 4C 4N donors; MCNM rods linear; Zn-C 1.923(6), Zn-N 2.037(5), Cd-C 2.099(5), Cd-N 2.196(4), C-N 1.150(5) Zn(CN)2, 1.162(5) Cd(CN)2. interpenetration sep. demonstrated archetypal likely major concern future studies scaffolding [N(CH3)4][CuZn(CN)4] deliberately designed demonstrate one way preventing interpenetration; F‾43m, 11.609(3) Å; 4. single alternating Cu(I) Zn(II) linear very CuCNZn bond Cu-C 1.877(8) 2.069(15) Å, Z(CH3)4+ ions occupy half adamantane cavities generated remaining being vacant. CuI[4,4',4'',4'''-tetracyanotetraphenylmethane]BF4·xC6H5NO2 (x ≥ 7.7) represents first attempt generate 3-dimensional complexity. tetragonal, I‾4m2, 13.620(2) c 22.642(2) 2. cationic C·C6H4·CN·Cu length 8.856(2) Å. tetragonally elongated axis apparently nonbonded interactions between 8 ortho-H atoms around methane C centers. There no interpenetration. generates adamantane-like occupied disordered C6H5NO2 (at least 7.7 mols. per Cu) BF4- ions. crystals undergo ready anion approx. thirds vol. what undoubtedly effectively liq. provide confidence solids should prove accessible. >> SciFinder ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK3cXovVOjtw%253D%253D&md5=2a9efabcd93072e8668a50199c51320c2Yaghi, O. M.; Sun, Z.; Richardson, D. A.; Groy, T. L. Directed Transformation Molecules Solids: Synthesis Microporous Sulfide Molecular Germanium Cages. 1994, 116 (2), 807– 808, 10.1021/ja00081a067 Scholar2Directed CagesYaghi, L.Journal (1994), 807-8CODEN: Ge4S104- mol. sulfide network, MnGe4S10·2(CH3)4N, at room temp. X-ray anal. starting Ge4S10[(CH3)4N]4 [cubic, 19.554(2), P43n, Z=8] revealed presence discrete anions, each contg. four germanium Ge linked doubly-bridging sulfides terminal sulfide. Addn. copolymn. Mn(II) formation solid, cryst. form. performed solid [tetragonal, 9.513(1), 14.281(2) I‾4, Z=2] showed present cage manganese channel system, channels tetramethylammonium cations. Pro. ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2cXhsFaisr0%253D&md5=ae60ea31c8068de18751d7f78ac1bfda3Yaghi, Li, G.; H. Selective binding removal guests framework. Nature 1995, 378 (6558), 703– 706, 10.1038/378703a0 Scholar3Selective metal-organic frameworkYaghi, Guangming; HailianNature (London) (1995), 703-6CODEN: NATUAS; ISSN:0028-0836. (Macmillan Magazines) inorg. find widespread application heterogeneous adsorption ion-exchange processes. rigidity allow shape- size-selective inclusion org. Analogous precise design, shape, size functionalization Here we report metal-org. bind arom. guest selectively. basic sym. mol., binds layers compd. compn. detd. selectively bound. We formed thermally up 350°C, after included mols., inclusions readsorbed. ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2MXhtVSnt7rP&md5=b0f48a6fa756cb3acc150b91b847516e4Li, H.; Eddaoudi, O'Keeffe, Yaghi, M. exceptionally highly 1999, 402 (6759), 276– 279, 10.1038/46248 Scholar4Design frameworkLi, Hailian; Mohamed; M.Nature (1999), 276-279CODEN: Open widely regarded promising sepn., storage recognition. Compared conventionally architecture So far, inability support porosity avoid collapsing absence solvents, has further progress field. Zn4O(BDC)3.(DMF)8.(PhCl) (named MOF-5, BDC 1,4-benzenedicarboxylate), cryst., evidenced analyses, when fully desolvated heated 300°. borrowing ideas carboxylate cluster chem., dicarboxylate linker reaction gives supertetrahedron clusters capped monocarboxylates. rigid divergent character added articulation into higher apparent than most zeolites. universal strategy currently pursued phases composites, gas-storage ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK1MXnvFSiuro%253D&md5=68f27e20a7e4e15ea2c2f49a2a61e98a5Côté, A. P.; Benin, I.; Ockwig, N. W.; Matzger, J.; Porous, crystalline, Science (New York, N.Y.) 2005, 310 (5751), 1166– 1170, 10.1126/science.1120411 ScholarThere corresponding record reference.6Ben, T.; Ren, Ma, S.; Cao, D.; Lan, Jing, X.; Xu, Deng, Simmons, Qiu, Zhu, G. Targeted area. Angewandte Chemie (International ed. English) 2009, 48 (50), 9457– 9460, 10.1002/anie.200904637 reference.7Yaghi, Chemistry-Construction, Properties, Precision Reactions Frameworks. 2016, 138 (48), 15507– 15509, 10.1021/jacs.6b11821 Scholar7Reticular FrameworksYaghi, Omar M.Journal (2016), 15507-15509CODEN: (American Society) expanded reference. ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhvFOgtbnJ&md5=aeeb3573f65a2cb69bb61ed7bcf623038O'Keeffe, Peskov, Ramsden, S. Structure Resource (RCSR) database of, symbols for, nets. 2008, 41 (12), 1782– 1789, 10.1021/ar800124u Scholar8The netsO'Keeffe, Michael; Maxim Stuart M.Accounts Research (2008), 1782-1789CODEN: ACHRE4; ISSN:0001-4842. During past decade, interest grown tremendously constructed atoms. notable (MOFs), polyat. metal-contg. joined polytopic linkers. (Although sometimes referred polymers, prefer differentiate them, because linkages yield robust frameworks.) realization could synthesized led emergence discipline call chem.MOFs represented kind graph called periodic net. descriptions date back earliest crystallog. become much common recently thousands hundreds underlying reported. In diamond), vertices net, links (edges) connect them. case edges net.Because explosive area, need arisen system nomenclature, classification, identification, retrieval topol. identification interest, now use. Account, explain methodol. assigning (RCSR), about 1600 collected illustrated searched symbol, name, keywords, attributes. resource searchable polyhedra layers.The entries come enumerations chem. compds. both. case, refs. occurrences provided. crystallog., topol., attributes reported database. tool Assocd. net natural tiling, partition space-filling tiles. export analyze illustrate tilings. ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXht1SgsrjF&md5=392c624f403dd8457460a7649aa496f39Springer, T.-J.; Kuc, Topological polymers. Rev. 2020, 49 (7), 2007– 2019, 10.1039/C9CS00893D Scholar9Topological polymersSpringer, Maximilian Tsai-Jung; Agnieszka; ThomasChemical Reviews (2020), 2007-2019CODEN: CSRVBR; ISSN:0306-0012. (Royal Chemistry) review. 200 (2D) topologies. network defines structure. Including rise cones, bands insulators. Tutorial Review, calcd. tight-binding approach, 2nd-neighbor spin-orbit included. det. whether features signatures calcn. Chern nos., Z2 invariants, nanoribbon approach. suggestions realized explicit atomistic given substituted properly selected stitched π-conjugation retained. ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXlsVegtrY%253D&md5=bc4bd69f131da50fc781af3e8f97580b10Skorupskii, Le, K. N.; Cordova, Yang, L.; Chen, Hendon, C. Arguilla, Q.; Dincă, lanthanide metallic Proc. Natl. Acad. Sci. U.S.A. 2022, 119 (34), e2205127119 10.1073/pnas.2205127119 reference.11Liu, Conjugated Metal-Organic Frameworks: Defined Tailor-Made Functions. 2024, 57 1032– 1045, 10.1021/acs.accounts.3c00788 reference.12Jeong, Park, Jeon, Fabricating Large-Area Thin Films Conductive (16), 2336– 2346, 10.1021/acs.accounts.4c00292 reference.13Li, Ott, Redox-Conductive (19), 2836– 2846, 10.1021/acs.accounts.4c00430 reference.14Benedetto, Mirica, Framework Materials Chemiresistive Detection Differentiation Toxic Gases. 2775– 2789, 10.1021/a

Language: Английский

Citations

0
Construction of ionic cavities in porous aromatic frameworks for palladium immobilization and effective catalysis DOI

Yuhui Zhai,

Zhaofu Zhang,

Hengtao Lei

et al.

Journal of Materials Chemistry A, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A strategy is presented to construct a porous aromatic framework (PAF-282) with ionic cavities for palladium immobilization and effective Suzuki–Miyaura coupling reactions.

Language: Английский

Citations

0
Progress and prospect of covalent organic framework-based membranes for sustainable alkali metal batteries: A brief review DOI
Yuan Zhong, Xin Liu, Boying He

et al.

Journal of Energy Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

Language: Английский

Citations

0
An Imidazole‐Based Halogen‐Bonded Organic Framework for the High‐Sensitive Detection of Nitrofuran Antibiotics DOI
Shumeng Wang, Zhen‐Nan Tian,

Guanfei Gong

et al.

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 25, 2025

Comprehensive Summary Nitrofuran antibiotics threaten human health and the environment due to their toxicity persistence. Their detection is challenging low concentrations interference, while fluorescence sensing offers superior sensitivity selectivity for effective monitoring. In this work, a novel halogen‐bonded organic framework, XOF‐TPEM , was introduced, constructed using an imidazole‐based ligand AIE molecule, TPEM . The framework successfully characterized by various techniques, including 1 H NMR, PXRD, XPS, FT‐IR, HRTEM, SAED, SEM EDS, confirming its excellent crystalline structure. As electron‐donating fluorophore, fluorescent demonstrates potential as selective sensor electron‐deficient nitrofuran antibiotics. Experimental results show that it exhibits high detecting nitrofurans such NFT, FZD, FLD, NFZ, with LODs of 9.7 ppb, 11.0 19.7 236.1 respectively. Mechanistic studies indicate outstanding performance attributed inner‐filter effect occurring between Through comparison pyridine‐based XOF, superiority imidazole ligands in constructing XOFs demonstrated. This study presents luminescent highlights frameworks, underscoring significant expanding functional applications.

Language: Английский

Citations

0
Facile preparation of fluorine-functionalized covalent organic frameworks@SiO2 as stationary phase for chromatographic separation of pharmaceutical molecules DOI
Xuerui Zhang, Shuo Wang, Yixin Ren

et al.

Microchemical Journal, Journal Year: 2024, Volume and Issue: unknown, P. 112513 - 112513

Published: Dec. 1, 2024

Language: Английский

Citations

0
Covalent integration of polymers and porous organic frameworks DOI Creative Commons
Md. Amjad Hossain,

Kira Coe-Sessions,

J.W. Ault

et al.

Frontiers in Chemistry, Journal Year: 2024, Volume and Issue: 12

Published: Dec. 18, 2024

Covalent integration of polymers and porous organic frameworks (POFs), including metal-organic (MOFs), covalent (COFs) hydrogen-bonded (HOFs), represent a promising strategy for overcoming the existing limitations traditional materials. This allows combination advantages polymers, i.e., flexibility, processability chemical versatility etc., superiority POFs, like structural integrity, tunable porosity high surface area, creating type hybrid These resulting polymer-POF materials exhibit enhanced mechanical strength, stability functional diversity, thus opening up new opportunities applications across large variety fields, such as gas separation, catalysis, biomedical applications, environmental remediation energy storage. In this review, an overview synthetic routes strategies on how to covalently integrate different with various POFs is discussed, especially particular focus methods polymerization within, among POF structures. To investigate unique properties functions these resultant materials, characterization techniques, nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), transmission electron microscopy (TEM) scanning (SEM), adsorption (BET) computational modeling machine learning, are also presented. The ability polymer-POFs manipulate pore environments at molecular level affords wide range providing versatile platform future advancements in material science. Looking forward, fully realize potential authors highlight scalability, green synthesis methods, stimuli-responsive critical areas research.

Language: Английский

Citations

0