A graphene@MOFs hybrid based on mechanical force and with the help of a phosphate-containing ligand was obtained for the high efficiency flame retardant of EP
Source abstract
Abstract
The traditional method of preparing graphene flame retardants is expensive, causes serious pollution to the environment, and poses a threat to health. This article adopts a low-cost, environmentally friendly, and sustainable mechanical ball milling method to exfoliate expandable graphite and uses an organic phosphonic acid ligand as a stripping agent aid to obtain a hybrid of multilayer graphene and phosphate-containing organic acid ligand. Using first principles based density functional theory (DFT) to calculate the binding energy between graphene layers, it was confirmed that ligands as stripping agents can significantly improve the stripping efficiency of graphene. A Ni-MOF coated graphene hybrid (G@Ni-MOF) was prepared by hydrothermal method using the phosphate-containing ligands which dispersed on the graphene surface. As expected, G@Ni-MOF has efficient flame retardant and smoke suppression properties. Compared with pure epoxy resin (EP), the peak heat release rate (PHRR) and total heat release (THR) of EP/G@Ni-MOF 5 were reduced by 43% and 23%, respectively. CO production (PCO) decreased by 49%, and CO 2 production (PCO 2 ) decreased by 47%. This study supplies a simple method for the design of large-scale preparation of graphene nano flame retardants, which is of great significance for the application of EP materials.
Source: openalex_inverted_index · Quality: baseline
Research context
OpenAlex topics: Flame retardant materials and properties · Metal-Organic Frameworks: Synthesis and Applications · Magnesium Oxide Properties and Applications
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (66)
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1. Shen Y, Wang B, Li D, Yuan W, Huang Y, Hu Z (2023) Catechol-modified epoxy backbones for multifunctional and ultra-tough thermoset. Chem Eng J. https://doi.org/10.1016/j.cej.2022.14088910.1016/j.cej.2022.140889 ↗
2. Zhou X, Wang J, He L, Qiu S, Pan R (2023) Preparation of an integrated P-N–Si tube containing phosphazene-triazine-silica structure: an efficient flame retardant agent for epoxy resin. Compos Commun. https://doi.org/10.1016/j.coco.2023.10150410.1016/j.coco.2023.101504 ↗
3. Xia L, Miao Z, Dai J, Zhu A, Xu H, Zhong J, Chen Y, Luo W, Xu Y, Yuan C, Zeng B, Cao H, Dai L (2022) Facile fabrication of multifunctional flame retardant epoxy resin by a core–shell structural AgNC@boronate polymer. Chem Eng J. https://doi.org/10.1016/j.cej.2022.13540210.1016/j.cej.2022.135402 ↗
4. Xuan Z, Rongzhi L, Fei F, Minggui S, Qiaoguang L, He L, Xu X, Zhanqian S (2024) A novel efficient flame-retardant curing agent for epoxy resin based on P-N synergistic effect: bio-based benzoxazine phosphate ester. Chem Eng J. https://doi.org/10.1016/j.cej.2024.15644110.1016/j.cej.2024.156441 ↗
5. Liu P, Wang X, Huang J, Jiang X (2024) Halogen-free epoxy flame retardant & promoter with diimidazole skeleton improves overall properties of epoxy resins. Chem Eng J. https://doi.org/10.1016/j.cej.2024.15540810.1016/j.cej.2024.155408 ↗
6. Ruan L, Hu D, Pan Z, Zhang X, Yu K, Ma W (2024) Novel eco-friendly bio-nano flame retardant via the electrostatic-driven hybridization of natural halloysite nanotubes and phytic acid for superior fire safety of epoxy composites. Compos Commun. https://doi.org/10.1016/j.coco.2024.10205510.1016/j.coco.2024.102055 ↗
7. Li Q, Song X, Pan Y-T, Sun J, Bifulco A, Yang R (2024) Dual function of carboxymethyl cellulose scaffold: a one-stone-two-birds strategy to prepare double-layer hollow ZIF-67 derivates for flame retardant epoxy composites. J Colloid Interface Sci. https://doi.org/10.1016/j.jcis.2024.06.18910.1016/j.jcis.2024.06.189 ↗
8. Hou B, Song X, Song K, Geng Z, Pan Y-T, Song P, Yang R (2023) Synchronous preparation and modification of LDH hollow polyhedra by polydopamine: synthesis and application. J Colloid Interface Sci. https://doi.org/10.1016/j.jcis.2023.10.00410.1016/j.jcis.2023.10.004 ↗
9. Luo J, Shi C, Yin L, Gong K, Qian X, Zhou K (2023) Killing three birds with one stone: a novel regulate strategy for improving the fire safety of thermoplastic polyurethane. Compos Part A Appl Sci Manuf. https://doi.org/10.1016/j.compositesa.2023.10749110.1016/j.compositesa.2023.107491 ↗
10. Han Z, Zhang W, Song X, Vahabi H, Pan Y-T, Zhang W, Yang R (2023) Fast char formation induced by POSS confining Co-MOF hollow prisms in epoxy composites with mitigated heat and smoke hazards. Chem Eng J. https://doi.org/10.1016/j.cej.2023.14568210.1016/j.cej.2023.145682 ↗
11. He T, Guo J, Qi C, feng R, Yang B, Zhou Y, Tian Li, Cui J (2021) Core–shell structure flame retardant Salen-PZN-Cu@Ni-Mof microspheres enhancing fire safety of epoxy resin through the synergistic effect. J Polym Res. https://doi.org/10.1007/s10965-021-02831-410.1007/s10965-021-02831-4 ↗
12. Ruiping W, Shuo Z, Xinrui H, Yang L, Xiaoli L, Bin T, Miaojun X (2024) Constructing piperazine pyrophosphate@LDH@rGO with hierarchical core-shell structure for improving thermal conductivity, flame retardancy and smoke suppression of epoxy resin thermosets. Compos B Eng. https://doi.org/10.1016/j.compositesb.2024.11187010.1016/j.compositesb.2024.111870 ↗
13. Nie S, Yang K, Yang J, Wang J (2024) Targeted assembly of hierarchical sea-urchin inspired NiPS@LDH architecture for enhanced toughness, wear-resistance and fire-safety of epoxy composites. Chem Eng J. https://doi.org/10.1016/j.cej.2024.15541310.1016/j.cej.2024.155413 ↗
14. Han G, Xue P, Cai Z, Feng Y, Liu C, Shen C (2022) One-step exfoliation and deprotonation of ANF/BNNS suspension for constructing 3D vertically aligned skeleton in epoxy-based thermal management composites. Sci China Technol Sci. https://doi.org/10.1007/s11431-022-2168-310.1007/s11431-022-2168-3 ↗
15. Gaojie H, Di Z, Chuiming K, Bing Z, Yongqian S, Yuezhan F, Chuntai L, De-Yi W (2022) Flexible, thermostable and flame-resistant epoxy-based thermally conductive layered films with aligned ionic liquid-wrapped boron nitride nanosheets via cyclic layer-by-layer blade-casting. Chem Eng J. https://doi.org/10.1016/j.cej.2022.13548210.1016/j.cej.2022.135482 ↗
16. Xue P, Cheng Y, Wang Y, Han G, Zhou B, He C, Liu C, Feng Y (2023) Simultaneous improvement in thermal conductivity and flame retardancy of epoxy resin via constructing 3D BNNS skeleton with assistance of ammonium polyphosphate. Chem Eng J 474(000):10. https://doi.org/10.1016/j.cej.2023.14579110.1016/j.cej.2023.145791 ↗
17. Dittrich B, Wartig K-A, Hofmann D, Mülhaupt R, Schartel B (2013) Flame retardancy through carbon nanomaterials: carbon black, multiwall nanotubes, expanded graphite, multi-layer graphene and graphene in polypropylene. Polym Degrad Stab. https://doi.org/10.1016/j.polymdegradstab.2013.04.00910.1016/j.polymdegradstab.2013.04.009 ↗
18. Li H, Liu C, Zhu J, Huan X, Xu K, Geng H, Chen X, Li T, Deng D, Ding W, Zu L, Ge L, Jia X, Yang X (2024) Intrinsically reactive hyperbranched interface governs graphene oxide dispersion and crosslinking in epoxy for enhanced flame retardancy. J Colloid Interface Sci 672:465–476. https://doi.org/10.1016/j.jcis.2024.06.00510.1016/j.jcis.2024.06.005 ↗
19. Hao Q, Liu S, Wang X, Zhang P, Mao Z, Zhang X (2024) Progression from graphene and graphene oxide to high-performance epoxy resin-based composite. Polym Degrad Stabil. https://doi.org/10.1016/j.polymdegradstab.2024.11073110.1016/j.polymdegradstab.2024.110731 ↗
20. Feng Y, He C, Wen Y, Ye Y, Zhou X, Xie X, Mai Y-W (2017) Superior flame retardancy and smoke suppression of epoxy-based composites with phosphorus/nitrogen co-doped graphene. J Hazard Mater. https://doi.org/10.1016/j.jhazmat.2017.12.01910.1016/j.jhazmat.2017.12.019 ↗
21. Zhang C, Xu Z, Sui W, Zang J, Ao Y, Wang L, Shang L (2022) Synergistic effect of novel ionic liquid/graphene complex on the flame retardancy of epoxy nanocomposites. Carbon Lett. https://doi.org/10.1007/s42823-022-00440-910.1007/s42823-022-00440-9 ↗
22. Ming G, Li J, Zhang X, Yue L, Chai Z (2018) The flame retardancy of epoxy resin including the modified graphene oxide and ammonium polyphosphate. Combust Sci Technol. https://doi.org/10.1080/00102202.2018.143772710.1080/00102202.2018.1437727 ↗
23. Xu W, Wang X, Wu Y, Li W, Chen C (2019) Functionalized graphene with Co-ZIF adsorbed borate ions as an effective flame retardant and smoke suppression agent for epoxy resin. J Hazard Mater 363:138–151. https://doi.org/10.1016/j.jhazmat.2018.09.08610.1016/j.jhazmat.2018.09.086 ↗
24. Wang J, Yu S, Huang Y, Zhang Y, Quan Y (2023) MOFs-based core-shell micro-nanostructure covering with curly RGO nanoflakes enabled fire-safe and mechanical-robust EP composites. Appl Surf Sci. https://doi.org/10.1016/j.apsusc.2023.15795310.1016/j.apsusc.2023.157953 ↗
25. Zhang J, Li Z, Qi X, Zhang W, Wang D-Y (2020) Size tailored bimetallic metal-organic framework (MOF) on graphene oxide with sandwich-like structure as functional nano-hybrids for improving fire safety of epoxy. Compos Part B Eng. https://doi.org/10.1016/j.compositesb.2020.10788110.1016/j.compositesb.2020.107881 ↗
26. Zhang J, Li Z, Zhang L, García Molleja J, Wang D-Y (2019) Bimetallic metal-organic frameworks and graphene oxide nano-hybrids for enhanced fire retardant epoxy composites: a novel carbonization mechanism. Carbon 153:407–416. https://doi.org/10.1016/j.carbon.2019.07.00310.1016/j.carbon.2019.07.003 ↗
27. Sturala J, Luxa J, Pumera M, Sofer Z (2018) Chemistry of graphene derivatives: synthesis, applications, and perspectives. Chem Eur J. https://doi.org/10.1002/chem.20170419210.1002/chem.201704192 ↗
28. Jeon I-Y, Shin Y-R, Sohn G-J, Choi H-J, Bae S-Y, Mahmood J, Jung S-M, Seo J-M, Kim M-J, Chang DW, Dai L, Baek J-B (2012) Edge-carboxylated graphene nanosheets via ball milling. Proc Natl Acad Sci U S A. https://doi.org/10.1073/pnas.111689710910.1073/pnas.1116897109 ↗
29. Jeon I-Y, Choi H-J, Jung S-M, Seo J-M, Kim M-J, Dai L, Baek J-B (2012) Large-scale production of edge-selectively functionalized graphene nanoplatelets via ball milling and their use as metal-free electrocatalysts for oxygen reduction reaction. J Am Chem Soc 135(4):1386–1393. https://doi.org/10.1021/ja309164310.1021/ja3091643 ↗
30. Leon V, Rodriguez AM, Prieto P, Prato M, Vazquez E (2014) Exfoliation of graphite with triazine derivatives under ball-milling conditions: preparation of few-layer graphene via selective noncovalent interactions. ACS Nano 8(1):563–571. https://doi.org/10.1021/nn405148t10.1021/nn405148t ↗
31. Aparna R, Sivakumar N, Balakrishnan A, Nair AS, Nair SV, Subramanian KRV (2013) An effective route to produce few-layer graphene using combinatorial ball milling and strong aqueous exfoliants. J Renewable Sustainable Energy. https://doi.org/10.1063/1.480979410.1063/1.4809794 ↗
32. Kresse G, Hafner J (1993) Ab initiomolecular dynamics for liquid metals. Phys Rev B 47(1):558–561. https://doi.org/10.1103/PhysRevB.47.55810.1103/PhysRevB.47.558 ↗
33. Kresse G, Hafner J (1994) Ab initiomolecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium. Phys Rev B 49(20):14251–14269. https://doi.org/10.1103/PhysRevB.49.1425110.1103/PhysRevB.49.14251 ↗
34. Steneteg P, Abrikosov IA, Weber V, Niklasson AMN (2010) Wave function extended Lagrangian Born-Oppenheimer molecular dynamics. Phys Rev B. https://doi.org/10.1103/PhysRevB.82.07511010.1103/PhysRevB.82.075110 ↗
35. Kresse F (1996) Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B Condens Matter 54(16):11169–11186. https://doi.org/10.1103/PhysRevB.54.1116910.1103/PhysRevB.54.11169 ↗
36. Blöchl PE (1994) Projector augmented-wave method. Phys Rev B 50(24):17953–17979. https://doi.org/10.1103/PhysRevB.50.1795310.1103/PhysRevB.50.17953 ↗
37. Grimme S, Antony J, Ehrlich S, Krieg H (2010) A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J Chem Phys. https://doi.org/10.1063/1.338234410.1063/1.3382344 ↗
38. Cui H, Tian W, Zhang Y, Liu T, Wang Y, Shan P, Chen Y, Yuan H (2020) Study on the hydrogen storage performance of graphene (N)-Sc-graphene (N) structure. Int J Hydrogen Energy 45(58):33789–33797. https://doi.org/10.1016/j.ijhydene.2020.09.09410.1016/j.ijhydene.2020.09.094 ↗
39. Guo B, Ananth KP, Zhang J, Ji X, Bai J (2020) Investigation of wet-milled graphene nanosheets with sulfur doping for lithium-ion battery. Ionics 26(7):3267–3274. https://doi.org/10.1007/s11581-020-03497-610.1007/s11581-020-03497-6 ↗
40. Qian Y, Qiao P, Li L, Han H, Zhang H, Chang G (2020) Hydrothermal synthesis of lanthanum-doped MgAl-layered double hydroxide/graphene oxide hybrid and its application as flame retardant for thermoplastic polyurethane. Adv Polym Technol 2020:1–10. https://doi.org/10.1155/2020/101809310.1155/2020/1018093 ↗
41. Kumar RV, Vickraman P, Raja TA, Bharathi MSR (2024) Exploratory mass dispersoid rGO in-situ influence on nickel phosphate-trimesic acid metal-organic framework for higher energy density hybrid supercapacitors. J Energy Storage. https://doi.org/10.1016/j.est.2024.11414010.1016/j.est.2024.114140 ↗
42. Guangfei W, Qiang H, Kangmin N (2025) One-step solution self-assembly synthesis of biomass-based flame retardants for constructing epoxy resins with superior flame retardant properties. Constr Build Mater. https://doi.org/10.1016/j.conbuildmat.2025.14170610.1016/j.conbuildmat.2025.141706 ↗
43. Feng Y, Li X, Zhao X, Ye Y, Zhou X, Liu H, Liu C, Xie X (2018) synergetic improvement in thermal conductivity and flame retardancy of epoxy/silver nanowires composites by incorporating “branch-like” flame-retardant functionalized graphene. ACS Appl Mater Interfaces. https://doi.org/10.1021/acsami.8b0522110.1021/acsami.8b05221 ↗
44. Wang J, Wang J, Yang S, Xu R, Ding G, Liu W, Sun J, Chen K, Duan L, Zhou G, Liu X, Huo S (2025) Metal-phosphorus-imidazole synergistic complexes for enhancing latency and fire safety in single-component epoxy resins. Polym Degrad Stabil. https://doi.org/10.1016/j.polymdegradstab.2025.11138310.1016/j.polymdegradstab.2025.111383 ↗
45. Pan D, Dong J, Yang G, Su F, Chang BaoBao, Liu C, Zhu CY, Guo Z (2021) Ice template method assists in obtaining carbonized cellulose/boron nitride aerogel with 3D spatial network structure to enhance the thermal conductivity and flame retardancy of epoxy-based composites. Adv Compos Hybrid Mater. https://doi.org/10.1007/s42114-021-00362-610.1007/s42114-021-00362-6 ↗
46. Pan D, Luo S, Feng Y, Zhang X, Su F, Liu H, Liu C, Mai X, Naik N, Guo Z (2021) Highly thermally conductive 3D BN/MWCNTs/C spatial network composites with improved electrically insulating and flame retardancy prepared by biological template assisted method. Compos Part B Eng. https://doi.org/10.1016/j.compositesb.2021.10903910.1016/j.compositesb.2021.109039 ↗
47. Chen Q, Liu L, Zhang A, Wang W, Wang Z, Zhang J, Feng J, Huo S, Zeng X, Song P (2022) An iron phenylphosphinate@graphene oxide nanohybrid enabled flame-retardant, mechanically reinforced, and thermally conductive epoxy nanocomposites. Chem Eng J. https://doi.org/10.1016/j.cej.2022.14042410.1016/j.cej.2022.140424 ↗
48. Shi X-H, Liu Q-Y, Li X-L, Yang S-Y, Wang D-Y (2022) Simultaneously improving the fire safety and mechanical properties of epoxy resin with iron phosphonated grafted polyethylenimine. Polym Degrad Stabil. https://doi.org/10.1016/j.polymdegradstab.2022.11017310.1016/j.polymdegradstab.2022.110173 ↗
49. Lei J, Han Z, Xiang L, Pan D, Liu H, Shen C (2025) The preparation of SiO2/SWCNT@Ni composite film with sandwich structure and its excellent electromagnetic shielding and thermal insulation performances in extreme environment. Adv Compos Hybrid Mater. https://doi.org/10.1007/s42114-025-01235-y10.1007/s42114-025-01235-y ↗
50. Pan D, Han Z, Lei J, Niu Y, Liu H, Shin S, Liu C, Guo Z (2025) Core-shell structured BN/SiO2 nanofiber membrane featuring with dual-effect thermal management and flame retardancy for extreme space thermal protection. Sci Bull. https://doi.org/10.1016/j.scib.2025.01.00510.1016/j.scib.2025.01.005 ↗
51. Schartel B, Bartholmai M, Knoll U (2006) Some comments on the main fire retardancy mechanisms in polymer nanocomposites. Polym Adv Technol 17(9–10):772–777. https://doi.org/10.1002/pat.79210.1002/pat.792 ↗
52. Inagaki M, Kang F (2014) Graphene derivatives: graphane, fluorographene, graphene oxide, graphyne and graphdiyne. J Mater Chem A 2(33):13193–13206. https://doi.org/10.1039/c4ta01183j10.1039/c4ta01183j ↗
53. Perumal S, Atchudan R, Cheong IW (2021) Recent studies on dispersion of graphene–polymer composites. Polymers. https://doi.org/10.3390/polym1314237510.3390/polym13142375 ↗
54. Ma Z, Zhang J, Liu L, Zheng H, Dai J, Tang L-C, Song P (2022) A highly fire-retardant rigid polyurethane foam capable of fire-warning. Compos Commun. https://doi.org/10.1016/j.coco.2021.10104610.1016/j.coco.2021.101046 ↗
55. Shi Y, Wang Z, Zhou JA (2018) Facile synthesis of a flame retardant melamine phenylphosphate and its epoxy resin composites with simultaneously improved flame retardancy, smoke suppression and water resistance. RSC Adv 8(68):39214–39221. https://doi.org/10.1039/c8ra08696f10.1039/c8ra08696f ↗
56. Zhou K, Gong K, Gao F, Yin L (2022) Facile strategy to synthesize MXene@LDH nanohybrids for boosting the flame retardancy and smoke suppression properties of epoxy. Compos Part A Appl Sci Manuf. https://doi.org/10.1016/j.compositesa.2022.10691210.1016/j.compositesa.2022.106912 ↗
57. Song I-H, Park T (2017) PMMA solution assisted room temperature bonding for PMMA–PC hybrid devices. Micromachines. https://doi.org/10.3390/mi809028410.3390/mi8090284 ↗
58. Kokulnathan T, Manikandan R, Chen S-M, Ponnusamy VK (2018) Synthesis and characterization of nanostructured nickel phosphate as a robust electrocatalyst for the highly sensitive voltammetric determination of chlorpromazine in biological sample. J Taiwan Inst Chem Eng 93:11–20. https://doi.org/10.1016/j.jtice.2018.07.00110.1016/j.jtice.2018.07.001 ↗
59. Xie R, Qu B (2001) Expandable graphite systems for halogen-free flameretarding of polyolefins. II. Structures of intumescent char and flame-retardant mechanism. J Appl Polym Sci 80(8):1190–1197. https://doi.org/10.1002/app.120310.1002/app.1203 ↗
60. Chen S, Liang F, Jin L, Ji C, Xu N, Qian K, Guo W (2024) A molecularly engineered fully bio-derived phosphorylated furan-based flame retardant for biomass-based fabrics. Int J Biol Macromol. https://doi.org/10.1016/j.ijbiomac.2024.12983610.1016/j.ijbiomac.2024.129836 ↗
61. Lai H, Wu Q, Zhao J, Shang L, Li H, Che R, Lyu Z, Xiong J, Yang L, Wang X, Hu Z (2016) Mesostructured NiO/Ni composites for high-performance electrochemical energy storage. Energy Environ Sci 9(6):2053–2060. https://doi.org/10.1039/c6ee00603e10.1039/c6ee00603e ↗
62. Fereja SL, Li P, Zhang Z, Guo J, Fang Z, Li Z, Chen W (2022) Construction of NiCo2S4/Fe2O3 hybrid nanostructure as a highly efficient electrocatalyst for the oxygen evolution reaction. Electrochim Acta. https://doi.org/10.1016/j.electacta.2021.13979310.1016/j.electacta.2021.139793 ↗
63. Zhou H, Zhou Y, Cao Y, Wang Z, Wang J, Zhang Y, Pan W (2023) Hollow LDH cage covering with ultra-thin MXenes veil: integrated micro-nano structure upon heat release suppression and toxic effluents elimination for polymer. Chem Eng J. https://doi.org/10.1016/j.cej.2023.14203510.1016/j.cej.2023.142035 ↗
64. Yin L, Gong K, Zhou K, Qian X, Shi C, Gui Z, Qian L (2022) Flame-retardant activity of ternary integrated modified boron nitride nanosheets to epoxy resin. J Colloid Interface Sci 608:853–863. https://doi.org/10.1016/j.jcis.2021.10.05610.1016/j.jcis.2021.10.056 ↗
65. Yu S, Cheng C, Li K, Wang J, Wang Z, Zhou H, Wang W, Zhang Y, Quan Y (2023) Fire-safe epoxy composite realized by MXenes based nanostructure with vertically arrayed MOFs derived from interfacial assembly strategy. Chem Eng J. https://doi.org/10.1016/j.cej.2023.14303910.1016/j.cej.2023.143039 ↗
66. Chen C, Bai X, Xiao G, Wang B, Chen C, Mou C, Zhong F, Yang Z, Wang M (2024) Phosphorus-nitrogen co-modification of floral hydrotalcite synergized with zinc hydroxystannate for enhancing fire resistance of waterborne epoxy coatings. Colloids Surf A Physicochem Eng Asp. https://doi.org/10.1016/j.colsurfa.2024.13484010.1016/j.colsurfa.2024.134840 ↗