金属有机框架(MOFs)因具有比表面积大、结构多样、易于功能化等优点,是一类极具潜力的载体材料,广泛应用于气体分离、药物递送、分子传感等研究领域。简要介绍了MOFs材料及其功能化设计,并对其作为载体的不同负载策略进行了综述,为MOFs的发展及载体材料的开发应用提供参考。
As a potential carrier material,metal-organic frameworks (MOFs) have been widely used in molecular sensing,drug delivery,adsorption and separation of gas and other fields due to its large surface area,diverse structure and easy modification.In this paper,MOFs materials and their functional design were introduced.Subsequently,the different loading strategies of MOFs were summarized and discussed,which provided a reference for their development and the application of carrier materials.
[1] Wu X,Huang L,Yang Q,et al.Effective extraction of pyrethroid pesticides from cabbages using Fe3O4@NU-1000 and adsorption mechanism:an experimental and theoretical study[J].Microchemical Journal,2024,204:110979.
[2] Zhang Z,Zhang Y,Jayan H,et al.Recent and emerging trends of metal-organic frameworks (MOFs)-based sensors for detecting food contaminants:a critical and comprehensive review[J].Food Chemistry,2024,448:139051.
[3] Chen X,Argandona S M,Melle F,et al.Advances in surface functionalization of next-generation metal-organic frameworks for biomedical applications:design,strategies,and prospects[J].Chem,2024,10(2):504-543.
[4] Marghade D,Shelare S,Prakash C,et al.Innovations in metal-organic frameworks (MOFs):pioneering adsorption approaches for persistent organic pollutant (POP) removal[J].Environmental Research,2024,258:119404.
[5] Hoang T L G,Doan D T,Nanda S,et al.Development of metal-organic framework-based systems for H2S removal:a comprehensive review[J].Coordination Chemistry Reviews,2025,529:216466.
[6] Kitchamsetti N,Cho J S.A roadmap of MOFs derived porous carbon,oxides,chalcogenides,and phosphides of metals:synthesis,properties,parameter modulation and their utilization as an electrode for Li/Na/K-ion batteries[J].Journal of Energy Storage,2024,84:110947.
[7] Xu K,Zhang S,Zhuang X,et al.Recent progress of MOF-functionalized nanocomposites:from structure to properties[J].Advances in Colloid and Interface Science,2024,323:103050.
[8] Zhao X,Long M,Huang X,et al.Metal-organic framework membranes and their advanced oxidation processes in water treatment:from material regulation to stability evaluation[J].Chemical Engineering Journal,2025,503:158523.
[9] Zhang J P,Zhang Y B,Lin J B,et al.Metal azolate frameworks:from crystal engineering to functional materials[J].Chemical Reviews,2012,112(2):1001-1033.
[10] Wang W,Zhao Q,Zhang X,et al.Geobacter mediated self-assembly preparation of MIL-100(Fe)@Fe3O4 for Fenton-like reaction catalysts[J].Separation and Purification Technology,2024,330:125474.
[11] Bazmi M,Rashidi A,Naderifar A,et al.Simultaneous enhancement of CO2 adsorption capacity and kinetics on a novel micro-mesoporous MIL-101(Cr)-based composite:experimental and DFT study[J].Journal of CO2 Utilization,2024,83:102809.
[12] Zhang X,Wang N,Li H,et al.IRMOF-3 nanosheet-filled glass fiber membranes for efficient separation of hydrogen and carbon dioxide[J].Separation and Purification Technology,2023,318:123908.
[13] Guan Q,Fang Y,Wu X,et al.Stimuli responsive metal organic framework materials towards advanced smart application[J].Materials Today,2023,64:138-164.
[14] Liang J,Liang K.Biocatalytic metal-organic frameworks:prospects beyond bioprotective porous matrices[J].Advanced Functional Materials,2020,30(27):2001648.
[15] Bao S,Li J,Guan B,et al.A green selective water-etching approach to MOF@mesoporous SiO2 Yolk-shell nanoreactors with enhanced catalytic stabilities[J].Matter,2020,3(2):498-508.
[16] Chang X,Yang X F,Qiao Y,et al.Confined heteropoly blues in defected Zr-MOF (bottle around ship) for high-efficiency oxidative desulfurization[J].Small,2020,16(14):1906432.
[17] He W,Lv D,Guan Y,et al.Post-synthesis modification of metal-organic frameworks:synthesis,characteristics,and applications[J].Journal of Materials Chemistry A,2023,11(45):24519-24550.
[18] Payam A F,Khalil S,Chakrabarti S.Synthesis and characterization of MOF-derived structures:recent advances and future perspectives[J].Small,2024,20(32):2310348.
[19] Yan J W,Liu Z Y,Song S,et al.Two In-MOFs based on pore size control strategy for highly selective separation of SF6[J].Chemical Engineering Science,2025,302:120871.
[20] Li G,Zhang W,Liu R,et al.Dual-ligand strategies to assemble S,N-containing metal organic framework nanoflowers for hybrid supercapacitors[J].New Journal of Chemistry,2022,46(18):8489-8499.
[21] Sun Y,Quan K,He J,et al.Regulation and synthesis of metal-organic frameworks through mixed-ligand strategy:a pathway to enhance adsorption of perfluoroalkyl acids[J].Chemical Engineering Journal,2024,495:153621.
[22] Du M,Wang Y,Cao Y,et al.Defect-Engineered MOF-801/sodium alginate aerogel beads for boosting adsorption of Pb(Ⅱ)[J].ACS Applied Materials & Interfaces,2024,16(42):57614-57625.
[23] Gu Y,Anjali B A,Yoon S,et al.Defect-engineered MOF-801 for cycloaddition of CO2 with epoxides[J].Journal of Materials Chemistry A,2022,10(18):10051-10061.
[24] Zhang Y,Lei Y,Yan T,et al.Efficient adsorption removal of 2,4-dichlorophenoxyacetic acid using amine-functionalized metal-organic frameworks (MOFs):performance and mechanisms[J].Separation and Purification Technology,2024,334:126120.
[25] Ajayan P,Wang W,Chen Y,et al.Ultrastable carboxyl-functionalized pore-space-partitioned metal-organic frameworks for gas separation[J].Advanced Materials,2024,36(41):2408042.
[26] Qiu P F,Tan X N,Huang Z Y,et al.Thiol-functionalized conductive Co-MOF and its derivatives S-doped Co(OH)2 nanoflowers for high-performance supercapacitors[J].Journal of Colloid and Interface Science,2025,679:995-1006.
[27] Yu J,Jiang X,Zhou Z,et al.A novel mercapto-functionalized bimetallic Zn/Ni-MOF adsorbents for efficient removal of Hg(Ⅱ) in wastewater[J].Journal of Environmental Chemical Engineering,2024,12(4):113258.
[28] He W,Lv D,Guan Y,et al.Post-synthesis modification of metal-organic frameworks:synthesis,characteristics,and applications[J].Journal of Materials Chemistry A,2023,11(45):24519-24550.
[29] Liu Y,Zhao Y,Jiang L.Spiropyran-decorated nanoporous metal-organic frameworks for reversible light-controlled adsorption of multiple salts from water:implications for water purification[J].ACS Applied Nano Materials,2023,6(19):17996-18004.
[30] Yang C,Xia Y.Trifluoromethyl-modified hierarchical nanoporous metal-organic framework nanoparticles for adsorption of fluorine-containing pesticides[J].ACS Applied Nano Materials,2022,5(4):5268-5277.
[31] Li J,Zhang Q,Chen Z,et al.Postsynthetic modification of thermo-treated metal-organic framework for combined photothermal/photodynamic antibacterial therapy[J].ACS Applied Materials & Interfaces,2024,16(7):8459-8473.
[32] Qin X,Yang W,Yang W,et al.Covalent modification of ZIF-90 for uranium adsorption from seawater[J].Microporous and Mesoporous Materials,2021,323:111231.
[33] Shen Y,Kang J,Guo L,et al.Recent progress on the application of MOFs and their derivatives in adsorbing emerging contaminants[J].Separation and Purification Technology,2024,350:127955.
[34] Xue Y,Wang J,Wang M,et al.Magnetic porous material derived from Ni-MOF for the removal of tetracycline from aqueous solution[J].ACS Applied Nano Materials,2024,7(7):7614-7621.
[35] Zhao H,Chang G,Wang Y,et al.Highly efficient utilization of sodium storage sites for MOF-derived carbon by rapid carbonization[J].Chemical Communications,2023,59(28):4205-4208.
[36] Wu D,Lin H,Ren X,et al.ZIF-8 derived spherical porous carbon as an efficient sustained-release carrier for nitroimidazole drugs[J].Materials Today Chemistry,2024,38:102057.
[37] Zhao B,Yang H,Mao J,et al.Mof-derived hollow-open hierarchically porous carbon spheres for enzyme encapsulation and biocatalysis[J].Chemical Engineering Journal,2025,505:158972.
[38] Nie L,Yang Y,Xin S,et al.Easy-regeneration Mn-doped ZIF-67 derivate adsorbent with ultra-high adsorption capacity for tetracycline hydrochloride in wastewater[J].Separation and Purification Technology,2024,338:126429.
[39] Xu C,Cao L,Liu T,et al.pH-responsive copper-doped ZIF-8 MOF nanoparticles for enhancing the delivery and translocation of pesticides in wheat plants[J].Environmental Science:Nano,2023,10(9):2578-2590.
[40] Xu Z,Jiang T,Zhang J,et al.A novel self-reactivated and stable MOF-derived Mg-doped CaO sorbent for high-temperature CO2 capture[J].Separation and Purification Technology,2025,359:130827.
[41] Xiang Y,Liu Z,Cheng Z L.Diatomite supported highly-dispersed ZnO/Zn-co-embedded ZIF-8 derived porous carbon composites for adsorption desulfurization[J].Journal of Hazardous Materials,2024,471:134399.
[42] Berekute A K,Wang A Y,Lin K Y,et al.A novel MOF-on-MOF-derived carbon-encapsulated CeO2/Co/Co3O4 humidity-resistant heterojunction with abundant oxygen vacancies for efficient ozone removal[J].Environmental Research,2025,268:120775.
[43] Li X,Lu X,Liang X,et al.Preparation and extraction property study of corn cob-like magnetic mosaic carbon materials derived from MOF-on-MOF composites[J].Analytica Chimica Acta,2024,1287:342112.
[44] Xu K,Zhang S,Zhuang X,et al.Recent progress of MOF-functionalized nanocomposites:from structure to properties[J].Advances in Colloid and Interface Science,2024,323:103050.
[45] Vaz R C A,Lopez M A R,Ferreira G M D.Unlocking the potential of MOF-biochar composites:advanced functional materials for adsorption,catalysis,and energy storage[J].Materials Today Chemistry,2024,42:102383.
[46] Li Y,Qin W,Chen S,et al.Iron-based metal organic framework (Fe-MOF)-doped sesame stalk biochar enhances antibiotic degradation:important role of free radicals and comparison of multiple degradation processes[J].Separation and Purification Technology,2025,353:128464.
[47] Wang Z,Gu X,Zhang X,et al.New easily recycled carrier based polyurethane foam by loading Al-MOF and biochar for selective removal of fluoride ion from aqueous solutions[J].Science of The Total Environment,2023,901:166312.
[48] Zhou Q,Yu C,Meng L,et al.Research progress of applications for nano-materials in improved QuEChERS method[J].Critical Reviews in Food Science and Nutrition,2024,64(28):10517-10536.
[49] Xu F,Fan S,Li Y,et al.Removal and recycling of aqueous selenite anions using cobalt-based metal-organic-framework coated on multi-walled carbon nanotubes composite membrane[J].Journal of Colloid and Interface Science,2024,653:493-503.
[50] Ci E,Chen Q,Wang Y,et al.The hyper-crosslinked aniline polymer@MOFs hybrid materials reinforced with active ionic sites for efficient and fast Cr(Ⅵ) removal[J].Separation and Purification Technology,2025,352:128144.
[51] Chen K,Ni L,Guo X,et al.Introducing pyrazole-based MOF to polymer of intrinsic microporosity for mixed matrix membranes with enhanced CO2/CH4 separation performance[J].Journal of Membrane Science,2023,688:122110.
[52] Tajwar M A,Qi L.Dual stimulus-responsive enzyme@metal-organic framework-polymer composites toward enhanced catalytic performance for visual detection of glucose[J].ACS Applied Bio Materials,2024,7(1):325-331.
[53] Safarpour R,Pooresmaeil M,Namazi H.Folic acid functionalized Ag@MOF(Ag) decorated carboxymethyl starch nanoparticles as a new doxorubicin delivery system with inherent antibacterial activity[J].International Journal of Biological Macromolecules,2024,282:137096.
[54] Liu Z,Liao M,Wang L,et al.Recent advancements in PFAS adsorptive removal using MOFs and COFs:a review[J].Reviews in Environmental Science and Bio/Technology,2024.https://doi.org/10.1007/s11157-024-09715-1.
[55] Feng H,Liu J,Mu Y,et al.Hybrid ultrafiltration membranes based on PES and MOFs@carbon quantum dots for improving anti-fouling performance[J].Separation and Purification Technology,2021,266:118586.
[56] Long H,Li X,Liu X,et al.Immobilization of laccase by alkali-etched bimetallic CoCu-MOF to enhance enzyme loading and congo red degradation[J].Langmuir,2023,39(24):8404-8413.
[57] Vikal A,Maurya R,Patel P,et al.Exploring metal-organic frameworks (MOFs) in drug delivery:a concise overview of synthesis approaches,versatile applications,and current challenges[J].Applied Materials Today,2024,41:102443.
[58] Binaeian E,Rohani S.pH-responsive prodrug containing Zr-based MOF and aldehyde-based drug; anionic hydrogel coating as a smart delivery system[J].Advanced Powder Technology,2024,35(1):104316.
[59] Chen J R,Zhou D,Liu Y,et al.Luminescent cyclometalated gold(Ⅲ) complexes covalently linked to metal-organic frameworks for heterogeneous photocatalysis[J].Chemical Science,2025,16(5):2202-2214.
[60] Justin A,Espín J,Pougin M J,et al.Post-synthetic covalent grafting of amines to NH2-MOF for post-combustion carbon capture[J].Advanced Functional Materials,2024,34(7):2307430.
[61] Wu P H,Cheng P F,Kaveevivitchai W,et al.MOF-based nanozyme grafted with cooperative Pt(Ⅳ) prodrug for synergistic anticancer therapy[J].Colloids and Surfaces B:Biointerfaces,2023,225:113264.
[62] Amenaghawon A N,Anyalewechi C L,Osazuwa O U,et al.A comprehensive review of recent advances in the synthesis and application of metal-organic frameworks (MOFs) for the adsorptive sequestration of pollutants from wastewater[J].Separation and Purification Technology,2023,311:123246.
[63] Zhang G,Yin Z Z,Zuo X,et al.Carboxymethyl potato starch hydrogels encapsulated cyclodextrin metal-organic frameworks for enantioselective loading of S-naproxen and its programmed release[J].International Journal of Biological Macromolecules,2024,262:130013.
[64] Han G,Huang H,Guo M,et al.Rational design of the double hydrogen-bonds sites in IL@MOF composites for efficient and selective formaldehyde capture[J].Separation and Purification Technology,2024,328:125116.
[65] Safarpour R,Pooresmaeil M,Namazi H.Folic acid functionalized Ag@MOF(Ag) decorated carboxymethyl starch nanoparticles as a new doxorubicin delivery system with inherent antibacterial activity[J].International Journal of Biological Macromolecules,2024,282:137096.
[66] Ke Q,Jiang K,Li H,et al.Hierarchically micro-,meso-,and macro-porous MOF nanosystems for localized cross-scale dual-biomolecule loading and guest-carrier cooperative anticancer therapy[J].ACS Nano,2024,18(33):21911-21924.
[67] Wang T,Fu J,Gao X,et al.Pore engineering of MOF-808 for effective adsorption of roxarsone[J].Separation and Purification Technology,2024,348:127724.
[68] Luo Q,Liu P,Bi L,et al.Selective and efficient removal of ciprofloxacin from water by bimetallic MOF beads:mechanism quantitative analysis and dynamic adsorption[J].Separation and Purification Technology,2024,332:125832.
[69] Alvarado-Ramírez L,Machorro-García G,López-Legarrea A,et al.Metal-organic frameworks for enzyme immobilization and nanozymes:a laccase-focused review[J].Biotechnology Advances,2024,70:108299.
[70] Lam P K,Vo T H,Chen J H,et al.A green and ultrafast one-pot mechanochemical approach for efficient biocatalyst encapsulation in MOFs:insights from experiments and computation[J].Journal of Materials Chemistry A,2023,11(45):24678-24685.
[71] Jiao J,Yang H,Zhou X,et al.Ultrathin 2D Cu-porphyrin MOF Nanosheet loaded Fe3O4 Nanoparticles As A Multifunctional Nanoplatform For Synergetic Chemodynamic And Photodynamic Therapy Independent of O2[J].ACS Applied Materials & Interfaces,2025,17(5):7438-7448.
[72] Liu X,Wang Y,Wang L,et al.Enzymatic nanomotors surviving harsh conditions enabled by metal organic frameworks encapsulation[J].Small,2024,20(14):2305800.
[73] Wang B,Chen J,Wu S,et al.Reusable carboxylesterase immobilized in ZIF for efficient degradation of chlorpyrifos in enviromental water[J].Pesticide Biochemistry and Physiology,2023,194:105519.
[74] Liang J,Huang Z,Wang K,et al.Ultrasensitive visual detection of the food-borne pathogen via MOF encapsulated enzyme[J].Talanta,2023,259:124503.
[75] Wang X,Singh S P,Zhang T,et al.Amino functionality enables aqueous synthesis of carboxylic acid-based MOFs at room temperature by biomimetic crystallization[J].Inorganic Chemistry,2024,63(21):9801-9808.
[76] Wang L,Zhi W,Wan J,et al.Recyclable β-glucosidase by one-pot encapsulation with Cu-MOFs for enhanced hydrolysis of cellulose to glucose[J].ACS Sustainable Chemistry & Engineering,2019,7(3):3339-3348.
[77] Sun Z,Li T,Mei T,et al.Nanoscale MOFs in nanomedicine applications:from drug delivery to therapeutic agents[J].Journal of Materials Chemistry B,2023,11(15):3273-3294.
基金资助
国家自然科学基金(32302219);上海市优秀学术/技术带头人计划项目(22XD1434700)