School of Materials Science and Engineering, Liaocheng University, Liaocheng 252059, China
wangliping5@163.com (L.P.W.)
lglzsd@126.com (G. L.)
收稿:2026-04-22,
录用:2026-05-16,
网络首发:2026-07-09,
纸质出版:2026-08-15
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Li, H. Y.; Wang, Z. A.; Wang, L. P.; Li, G. Surface functionalization modification of metal organic frameworks with polymer via metal-free atom transfer radical polymerization for oil-water separation. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3667-9
Hong-Ye Li, Zi-An Wang, Li-Ping Wang, et al. Surface Functionalization Modification of Metal Organic Frameworks with Polymer
Li, H. Y.; Wang, Z. A.; Wang, L. P.; Li, G. Surface functionalization modification of metal organic frameworks with polymer via metal-free atom transfer radical polymerization for oil-water separation. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3667-9 DOI:
Hong-Ye Li, Zi-An Wang, Li-Ping Wang, et al. Surface Functionalization Modification of Metal Organic Frameworks with Polymer
We present a method for modifying metal organic frameworks (MOFs) surface functionalization using metal-free atom transfer radical polymerization (ATRP). Amino-functionalized zeolitic imidazolate frameworks-8 (ZIF-8-NH
2
) was synthesized at room temperature
and ZIF-8-Br was obtained by the reaction of the amino group in ZIF-8-NH
2
with the acyl bromide group in 2-bromoisobutyl bromide (BIBB)
thereby introducing secondary bromine groups onto the surface of ZIF-8-NH
2
. Then
ZIF-8-
g
-polymethyl methacrylate (ZIF-8-
g
-PMMA) hybrid materials were synthesized using ZIF-8-Br as an initiator
via
surface-initiated metal-free atom transfer radical polymerization (metal-free ATRP). The structural and morphological evolutions were monitored using Fourier transform infrared spectroscopy (FTIR)
X-ray photoelectron spectroscopy (XPS)
X-ray powder diffraction (XRD) and scanning electron microscopy (SEM) measurements. Thermogravimetry (TG) analysis verified that ZIF-8-
g-
PMMA had excellent thermal stability
and the water stability test demonstrated that after grafting PMMA from the ZIF-8-NH
2
surface
the hydrophobicity and water stability were improved significantly. The BET results proved that ZIF-8-
g-
PMMA ha
d a high specific surface area of 835.24 m
2
/g. By immobilizing ZIF-8-
g
-PMMA hybrid material on fabrics
the modified fabrics exhibit excellent superhydrophobicity
with the water contact angle as high as 159.2
o
. Attributed to the synergistic effect of the micro- and nano-graded porous structure and low-surface-energy PMMA coatings
ZIF-8-
g
-PMMA hybrid material modified fabrics achieves highly efficient oil-water separation
with excellent adsorption effects on both light and heavy oils. Among them
the heavy oil can pass through the modified fabric within seconds with an oil-water separation efficiency of 96%. This method will further expand the scope of application of metal-free ATRP technology and MOFs materials.
Jiang, C.; Wang, X.; Ouyang, Y.; Lu, K.; Jiang, W.; Xu, H.; Wei, X.; Wang, Z.; Dai, F.; Sun, D. Recent advances in metal–organic frameworks for gas adsorption/separation. Nanoscale Adv. 2022 , 4 , 2077−2089..
Yang, X. H.; Yao, Y. Q.; Huang, M. H.; Chai, C. P. Preparation and characterization of poly (vinyl alcohol)/ZIF-8 porous composites by ice-templating method with high ZIF-8 loading amount. Chinese J. Polym. Sci. 2020 , 38 , 638−643..
Zhang, Y.; Yu, X.; Hou, Y.; Liu, C.; Xie, G.; Chen, X. Current research status of MOF materials for catalysis applications. Mol. Catal. 2024 , 555 , 113851..
Wang, J.; Zhang, X.; Wang, X.; Liu, J.; Li, S.; Nie, Y.; Zong, K.; Zhang, X.; Meng, H.; Jin, M. Activation of MOF catalysts with low steric hindrance via undercoordination chemistry for efficient polysulfide conversion in lithium–sulfur battery. Adv. Energy Mater. 2024 , 14 , 2402072..
Felix Sahayaraj, A.; Joy Prabu, H.; Maniraj, J.; Kannan, M.; Bharathi, M.; Diwahar, P.; Salamon, J. Metal–organic frameworks (MOFs): the next generation of materials for catalysis, gas storage, and separation. J. Inorg. Organomet. Polym. Mater. 2023 , 33 , 1757−1781..
Ma, D.; Wang, G.; Lu, J.; Zeng, X.; Cheng, Y.; Zhang, Z.; Lin, N.; Chen, Q. Multifunctional nano MOF drug delivery platform in combination therapy. Eur. J. Med. Chem. 2023 , 261 , 115884..
Rahaman, S. J.; Samanta, A.; Mir, M. H.; Dutta, B. Metal-organic frameworks (MOFs): a promising candidate for stimuli-responsive drug delivery. ES Mater. Manuf. 2022 , 19 , 792..
Si, Y.; Luo, H.; Zhang, P.; Zhang, C.; Li, J.; Jiang, P.; Yuan, W.; Cha, R. CD-MOFs: From preparation to drug delivery and therapeutic application. Carbohydr. Polym. 2024 , 323 , 121424..
Cheng, Y.; Lan, D.; Jia, Z.; Gao, Z.; Liu, X.; Shi, X.; He, M.; Guo, H.; Wu, G. MOF derivatives anchored to multichannel hollow carbon fibers with gradient structures for corrosion resistance and efficient electromagnetic wave absorption. J. Mater. Sci. Technol. 2025 , 216 , 150−164..
Fan, X. X.; Wang, Z. Z.; Zhang, X. C.; Li, L.; Cao, M. S. High-performance MOF-based electromagnetic wave absorption materials: design and performance optimization. Mater. Chem. Front. 2025 , 9 , 403−417..
Jia, Z.; Zhang, X.; Gu, Z.; Wu, G. MOF-derived Ni-Co bimetal/porous carbon composites as electromagnetic wave absorber. Adv. Compos. Hybrid Mater. 2023 , 6 , 28..
Zhao, X.; Wang, Y.; Li, D. S.; Bu, X.; Feng, P. Metal–organic frameworks for separation. Adv. Mater. 2018 , 30 , 1705189..
Duan, Y.; Li, L.; Shen, Z.; Cheng, J.; He, K. Engineering metal-organic-framework (MOF)-based membranes for gas and liquid separation. Membranes 2023 , 13 , 480..
Yang, M.; Wang, Y.; Li, H.; Bo, P.; Liu, B.; Ge, B.; Wang, L.; Li, G. Preparation and properties of UiO-66 based hybrid materials via surface initiated metal-free ATRP. Eur. Polym. J. 2024 , 202 , 112612..
Mallakpour, S.; Nikkhoo, E.; Hussain, C. M. Application of MOF materials as drug delivery systems for cancer therapy and dermal treatment. Coord. Chem. Rev. 2022 , 451 , 214262..
Hayat, A.; Rauf, S.; Al Alwan, B.; El Jery, A.; Almuqati, N.; Melhi, S.; Amin, M. A.; Al-Hadeethi, Y.; Sohail, M.; Orooji, Y. Recent advance in MOFs and MOF-based composites: synthesis, properties, and applications. Mater. Today Energy 2024 , 41 , 101542..
Jiao, L.; Seow, J. Y. R.; Skinner, W. S.; Wang, Z. U.; Jiang, H.-L. Metal–organic frameworks: Structures and functional applications. Mater. Today 2019 , 27 , 43−68..
García-Salcido, V.; Mercado-Oliva, P.; Guzmán-Mar, J. L.; Kharisov, B. I.; Hinojosa-Reyes, L. MOF-based composites for visible-light-driven heterogeneous photocatalysis: Synthesis, characterization and environmental application studies. J. Solid State Chem. 2022 , 307 , 122801..
Sahoo, R.; Ghosh, S.; Chand, S.; Pal, S. C.; Kuila, T.; Das, M. C. Highly scalable and pH stable 2D Ni-MOF-based composites for high performance supercapacitor. Compos. Part B 2022 , 245 , 110174..
Hwang, Y. K.; Hong, D. Y.; Chang, J. S.; Jhung, S. H.; Seo, Y. K.; Kim, J.; Vimont, A.; Daturi, M.; Serre, C.; Férey, G. Amine grafting on coordinatively unsaturated metal centers of MOFs: consequences for catalysis and metal encapsulation. Angew. Chem. 2008 , 120 , 4144−4148..
Liu, Z.; Chen, Y.; Sun, J.; Lang, H.; Gao, W.; Chi, Y. Amine grafting on coordinatively unsaturated metal centers of MIL-101 Cr for improved water absorption characteristics. Inorg. Chim. Acta 2018 , 473 , 29−36..
Kim, M.; Cahill, J . F.; Fei, H.; Prather, K. A.; Cohen, S. M. Postsynthetic ligand and cation exchange in robust metal–organic frameworks. J. Am. Chem. Soc. 2012 , 134 , 18082−18088..
[Taddei, M.; Wakeham, R. J.; Koutsianos, A.; Andreoli, E.; Barron, A. R. Post-synthetic ligand exchange in zirconium-based metal–organic frameworks: beware of the defects! Angew. Chem. Int. Ed . 2018, 57 , 11706-11710..
Wang, D.; Li, T. Toward MOF@ polymer core–shell particles: design principles and potential applications. Acc. Chem. Res. 2023 , 56 , 462−474..
He, S.; Wang, H.; Zhang, C.; Zhang, S.; Yu, Y.; Lee, Y.; Li, T. A generalizable method for the construction of MOF@ polymer functional composites through surface-initiated atom transfer radical polymerization. Chem. Sci. 2019 , 10 , 1816−1822..
Yang, X.; Cheng, T. C.; Morris, A. J. Polymer-grafted Metal-Organic frameworks: design, synthesis, and application. J. Mater. Chem. C 2024 , 12 , 4562−4592..
Ding, M.; Jiang , H.-L. Improving water stability of metal–organic frameworks by a general surface hydrophobic polymerization. CCS Chem. 2021 , 3 , 2740−2748..
Sun, H.; Tang, B.; Wu, P. Development of hybrid ultrafiltration membranes with improved water separation properties using modified superhydrophilic metal–organic framework nanoparticles. ACS Appl. Mater. Interfaces 2017 , 9 , 21473−21484..
Singh, N.; Qutub, S.; Khashab, N. M. Biocompatibility and biodegradability of metal organic frameworks for biomedical applications. J. Mater. Chem. B 2021 , 9 , 5925−5934..
Liu, S.; Zhai, L.; Li, C.; Li, Y.; Guo, X.; Zhao, Y.; Wu, C. Exploring and exploiting dynamic noncovalent chemistry for effective surface modification of nanoscale Metal–organic frameworks. ACS Appl. Mater. Interfaces 2014 , 6 , 5404−5412..
Liu, H.; Zhu, H.; Zhu, S. Reversibly Dispersible/Collectable Metal-Organic Frameworks Prepared by Grafting Thermally Responsive and Switchable Polymers. Macromol. Mater. Eng. 2015 , 300 , 191−197..
Allegretto, J. A.; Giussi, J. M.; Moya, S. E.; Azzaroni, O.; Rafti, M. Synthesis and characterization of thermoresponsive ZIF-8@PNIPAm-co-MAA microgel composites with enhanced performance as an adsorption/release platform. RSC Adv. 2020 , 10 , 2453−2461..
Xie, K.; Fu, Q.; He, Y.; Kim, J.; Goh, S. J.; Nam, E.; Qiao, G.; Webley, P. Synthesis of well dispersed polymer grafted metal–organic framework nanoparticles. Chem. Commun. 2015 , 51 , 15566−15569..
Su, H.; Yang, M.; Liu, Y.; Gao, J.; Ge, B.; Wang, L.; Li, G. Preparation of SiO 2 - g -PMMA hybrid materials employing different photocatalysts of metal-free ATRP and its application for oil-water separation. Appl. Surf. Sci. 2023 , 615 , 156288..
Kaur, R.; Rana, S.; Mehra, P.; Kaur, K. Surface-Initiated Reversible Addition–Fragmentation Chain Transfer Polymerization (SI-RAFT) to Produce Molecularly Imprinted Polymers on Graphene Oxide for Electrochemical Sensing of Methylparathion. ACS Appl. Mater. Interfaces 2024 , 16 , 49889−49901..
Hou, Y.; Zhang, Z.; Harrisson, S.; Sèbe, G. SI-ATRP grafting of polymers from polydopamine-modified cellulose nanocrystals. Carbohydr. Polym. 2024 , 341 , 122346..
Tizro, N.; Moniri, E.; Saeb, K.; Ahmad Panahi, H.; Sobhanardakani, S. Grafting β-Cyclodextrin/allyle glycidyl ether/thermosensitive containing polymer onto modified Fe3O4@ SiO 2 for adsorption of diazinon from aqueous solution. Int. J. Environ. Anal. Chem. 2023 , 103 , 123−139..
Song, G. X.; Miao, T. F.; Cheng, X. X.; Ma, H. T.; He, Z. X.; Zhang, W.; Zhang, Z. B.; Zhu, X. L. Construction of chiroptical switch on silica nanoparticle surface via chiral self-assembly of side-chain azobenzene-containing polymer. Chinese J. Polym. Sci . 2021 , 39 , 1528−1537..
Liu, Y.; Wang, Z.; Zhao, Y.; Hou, G.; Jiang, R.; Bockstaller, M. R.; Qin, X.; Zhang, L.; Matyjaszewski, K. SiO- g -polyisoprene particle brush reinforced advanced elastomer nanocomposites prepared via ARGET ATRP. Adv. Funct. Mater. 2024 , 34 , 2315741..
Yin, Y.; Tian, X.; Jiang, X.; Zhu, P. Modification of cellulose nanocrystals via surface-initiated ARGET ATRP and their reinforcement of poly(lactic acid)-based biocomposites. Ind. Crops Prod. 2022 , 188 , 115575..
Almeida, A.; Gaspar, R.; Ferreira-Dias, S.; Costa, M. R. P.; Dias, R. C. Pyridyl-functionalized and surface molecularly imprinted cellulose particles to target bioactive compounds in olive leaf. React. Funct. Polym. 2025 , 214 , 106338..
McDonald, K. A.; Feldblyum, J. I.; Koh, K.; Wong-Foy, A. G.; Matzger, A. J. Polymer@ MOF@ MOF: “grafting from” atom transfer radical polymerization for the synthesis of hybrid porous solids. Chem. Commun. 2015 , 51 , 11994−11996..
Katayama, Y.; Kalaj, M.; Barcus, K. S.; Cohen, S. M. Self-assembly of metal–organic framework (MOF) nanoparticle monolayers and free-standing multilayers. J. Am. Chem. Soc. 2019 , 141 , 20000−20003..
Wu, M.; Wu, M.; Pan, M.; Jiang, F.; Hui, B.; Zhou, L. Synthesization and characterization of lignin-graft-poly (lauryl methacrylate) via arget atrp. Int. J. Biol. Macromol. 2022 , 207 , 522−530..
Li, S.; Colaco, R.; Staubitz, A. ARGET ATRP of methyl acrylate and methyl methacrylate with diazocine-derived initiators. ACS Appl. Polym. Mater. 2022 , 4 , 6825−6833..
Zaborniak, I.; Chmielarz, P. How we can improve ARGET ATRP in an aqueous system: Honey as an unusual solution for polymerization of (meth) acrylates. Eur. Polym. J. 2023 , 183 , 111735..
Yang, T.; Li, R.; Ding, M.; Yu, H.; Zhang, L.; Xie, H. Aldehyde-functionalization of chitin nanocrystals via SI-ARGET ATRP of lignin-derived monomers. Carbohydr. Polym. 2025 , 348 , 122892..
Wang, S.; Zhang, H.; Ma, J.; Liu, D.; Zhang, T.; Li, Y.; Li, G. Construction of cross-linked PEO grafting copolymer for high-performance gel electrolyte. Polym. Test. 2025 , 142 , 108655..
Wang, X.; Wang, S.; Fan, X.; Yuan, W.; Zhang, T.; Li, Y. Controllable construction of zwitterionic polymer grafting modified polyvinylidene fluoride (PVDF) microfiltration membrane. React. Funct. Polym. 2024 , 200 , 105925..
Zhang, F. J.; Liu, X. H. ICAR ATRP of acrylonitrile utilizing a moderate temperature radical initiator. Chinese J. Polym. Sci. 2013 , 31 , 1613−1622..
Luan, M.; Shen, D.; Zhou, P.; Li, D.; Li, P.; Shi, B.; Wang, G. One-pot synthesis of block copolymer dispersant by ICAR ATRP with ppm copper catalyst and the dispersibility on pigment. Prog. Org. Coat. 2022 , 169 , 106914..
Rezende, T. C.; Silvestre, J. C.; Mendonça, P. V.; Moniz, J.; Serra, A. C.; Coelho, J. F. Efficient dispersion of TiO 2 in water-based paint formulation using well-defined poly[oligo (ethylene oxide) methyl ether acrylate ] synthesized by ICAR ATRP. Prog. Org. Coat. 2022 , 165 , 106734..
Mosnáček, J.; Ilčíková, M. t. Photochemically mediated atom transfer radical polymerization of methyl methacrylate using ppm amounts of catalyst. Macromolecules 2012 , 45 , 5859−5865..
Pathiwada, D.; Annušová, A. H.; Machata, P.; Shaalan, M.; Halahovets, Y.; Mosnáček, J. Fully open-air surface initiated photochemically induced atom transfer radical polymerization of renewable α-methylene-γ-butyrolactone with potential in biomedical applications via post–functionalization. Eur. Polym. J. 2025 , 234 , 114023..
Flejszar, M.; Chmielarz, P.; Sme nda, J.; Wolski, K. Following principles of green chemistry: Low ppm photo-ATRP of DMAEMA in water/ethanol mixture. Polymer 2021 , 228 , 123905..
Treat, N. J.; Sprafke, H.; Kramer, J. W.; Clark, P. G.; Barton, B. E.; Read de Alaniz, J.; Fors, B. P.; Hawker, C. J. Metal-free atom transfer radical polymerization. J. Am. Chem. Soc. 2014 , 136 , 16096−16101..
Ma, A.; Zhang, J.; Wang, N.; Bai, L.; Chen, H.; Wang, W.; Yang, H.; Yang, L.; Niu, Y.; Wei, D. Surface-initiated metal-free photoinduced ATRP of 4-vinylpyridine from SiO 2 via visible light photocatalysis for self-healing hydrogels. Ind. Eng. Chem. Res. 2018 , 57 , 17417−17429..
Liu, X.; Shen, J.; Wang, Y.; Li, M.; Fu, S. Photoinduced metal-free atom transfer radical polymerization for the modification of cellulose with poly(n-isopropylacrylamide) to create thermo-responsive injectable hydrogels. Int. J. Mol. Sci. 2024 , 25 , 2867..
Iqbal, M. A.; Akhter, T.; Faheem, M.; Mahmood, A.; Al-Masry, W.; Nadeem, S.; Hassan, S. U.; Park, C. H. Metal-free, visible light-mediated atom transfer radical polymerization of hydroxypropyl cellulose-graft-poly(methyl methacrylate) s: effect of polymer side chains on thermo-resp onsive behavior of hydroxypropyl cellulose. Cellulose 2023 , 30 , 7519−7533..
Ma, L.; Li, N.; Zhu, J.; Chen, X. Visible light-induced metal free surface initiated atom transfer radical polymerization of methyl methacrylate on SBA-15. Polymers 2017 , 9 , 58..
Su, H. L.; Yang, M. M.; Liu, M.; Fu, J. W.; Wang, Y. H.; Yao, M. X.; Yang, D. H.; Wang, L. P.; Li, G. PH and thermo dual-sensitive copolymers with fluorescent properties grafted mesoporous silica SBA-15 via metal-free ATRP. Eur. Polym. J. 2022 , 167 , 111064..
Xu, X.; He, J.; Zeng, Y.; Yu, C.; Zhang, F. Controllable surface-initiated metal-free atom transfer radical polymerization of methyl methacrylate on mesoporous SBA-15 via reductive quenching. Eur. Polym. J. 2020 , 131 , 109724..
Xu, X.; Zou, Y.; He, J.; Zeng, Y.; Yu, C.; Zhang, F. Insight into the effects of reaction conditions on metal-free surface-initiated atom-transfer radical polymerization of methyl methacrylate from SBA-15. J. Appl. Phys. 2020 , 127 , 115102..
Zeng, G.; Liu, M.; Jiang, R.; Heng, C.; Huang, Q.; Mao, L.; Hui, J.; Deng, F.; Zhang, X.; Wei, Y. Surface grafting of Eu 3+ doped luminescent hydroxyapatite nanomaterials through metal free light initiated atom transfer radical polymerization for theranostic applications. Mater. Sci. Eng. C 2017 , 77 , 420−426..
Zeng, G.; Liu, M.; Heng, C.; Huang, Q.; Mao, L.; Huang, H.; Hui, J.; Deng, F.; Zhang, X.; Wei, Y. Surface polyPEGylation of Eu 3+ doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization. Appl. Surf. Sci. 2017 , 399 , 499−505..
Zhang, F.; Ma, N.; He, L.; Lin, H.; Wei, S.; Zhao, X.; You, C.; Cai, L.; Wang, F. Efficient adsorption of flavonoids on amino-functionalized ZIF-8/chitosan aerogels. Int. J. Biol. Macromol. 2024 , 282 , 136928..
Hoop, M.; Walde, C. F.; Riccò, R.; Mushtaq, F.; Terzopoulou, A.; Chen, X.-Z.; deMello, A. J.; Doonan, C. J.; Falcaro, P.; Nelson, B. J. Biocompatibility characteristics of the metal organic framework ZIF-8 for therapeutical applications. Appl. Mater. Today 2018 , 11 , 13−21..
Li, H. Y.; Wang , Z. A.; Yang, M. M.; Ge, B.; Wang, L. P.; Li, G. Polymer decorated Zn-MOF (ZIF-8-NH 2 ) for the fabrication of superhydrophobic material via metal-free atom transfer radical polymerization. Chinese J. Polym. Sci. 2025 , 43 , 1−13..
Elaouni, A.; El Ouardi, M.; Zbair, M.; BaQais, A.; Saadi, M.; Ait Ahsaine, H. ZIF-8 metal organic framework materials as a superb platform for the removal and photocatalytic degradation of organic pollutants: a review. RSC Adv. 2022 , 12 , 31801−31817..
Zhang, H.; Zhao, M.; Lin, Y. Stability of ZIF-8 in water under ambient conditions. Micropor. Mesopor. Mat. 2019 , 279 , 201−210..
Xiong, Y.; Deng, N.; Wu, X.; Zhang, Q.; Liu, S.; Sun, G. De novo synthesis of amino-functionalized ZIF-8 nanoparticles: Enhanced interfacial compatibility and pervaporation performance in mixed matrix membranes applying for ethanol dehydration. Sep. Purif. Technol. 2022 , 285 , 120321..
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