Polymer-based commercial products have been manufactured globally at annual scales of hundreds of millions of tons, occupying an important position in people's daily life and industrial progress, attributed to their light weight, workability, and excellent properties. However, due to their organic composition, polymer materials are sensitive to high temperatures and are easily ignited, frequently leading to serious fire accidents. To address this huge challenge, nano flame retardants with high efficiency and multifunctionality have been regarded as an available approach. First, nano flame retardants significantly increase the melt strength of polymer materials by their extremely large specific surface area and strong interfacial interactions. Second, based on a well-dispersed state, nano flame retardants, especially with layered structures, establish a labyrinth effect to suppress the convective delivery of heat and pyrolysis products. Third, metal-based nano flame retardants chelate with the lone-pair electrons of polymer chains to form a transitional ring structure, thus decreasing the energy barrier to promote the carbonization process. Attracted by these advantages, a large amount of research work has already been dedicated to developing nano flame retardants for enhancing the fire safety of polymer materials.Herein, this Account not only introduces the early discoveries of nano flame retardants but also provides a comprehensive overview of our recent advances in the development of nano flame retardants, the exploration of mechanisms, and applications in emerging frontiers. We first illustrate the initial discovery of nano flame retardants by demonstrating the fundamental mechanisms, synergistic effect with traditional flame retardants, and essential issues in nanocomposite manufacturing. In order to solve the low efficiency of nanomaterials added individually, our research attempts to design nanostructured architectures that integrate multiple nanomaterials with specific mechanisms to produce synergistic effects under complex combustion conditions, thereby further enhancing the flame retardancy efficiency. To enhance sustainability and reduce complex experimental efforts, our research adopts biobased resources and machine learning approaches, respectively, to design novel nano flame retardants. Within the in-depth condensed-phase mechanism, we propose multiple strategies, including the catalytic effect of transition metals and the interfacial charring strategy, which preferentially promote the conversion of pyrolysis products into char layers rather than smoke particles. Building on the intrinsic properties of nanomaterials, our studies further expand the application of nano flame retardants into emerging frontiers such as energy storage, thermal management, and electromagnetic interference shielding, thereby shifting the research perspective from traditional polymer systems toward real-world functional applications. Finally, we outline the future design direction of nano flame retardants, concentrating on artificial intelligence and sustainability, and propose the critical challenges in their practical application.

The large amount of textiles has caused a serious environmental burden. Creative methods should be proposed to solve the long-standing unresolved problem. Herein, waste polyester-cotton blend (PCB) are converted into robust and flame-resistant composite aerogels under the light of ‘Chemical Reengineering’. The compression modulus of the resulting aerogel is up to 23.9 MPa with corresponding specific modulus of 69.92 m2/s2. The in-situ introduction of magnesium-aluminium layered double hydroxide (MgAl LDH) in PCB gel decreases the peak heat release rate (PHRR) by 91.6% and extends the time to peak heat release (tPHRR) to 115 s. Simultaneously, terephthalic acid (TPA) is effectively recovered with a purity as high as 99.7%. Furthermore, a comprehensive sustainability assessment with 4 rating parameters is promoted to evaluate and compare recent recycling methods.

Typical ester-and ether-based polymer electrolytes are semi-crystalline and highly flammable, which brings potential fire risks during their application in lithium metal batteries. In this study, polyrotaxane (PLR)-based flame-retardant solid polymer electrolytes (SPEs) were designed and developed based on polyethylene oxide (PEO) via fully utilizing the dual effects of alpha-cyclodextrin (alpha-CD) as the host (for PLR) and the carbon source in phytic acid-derived charring flame-retardant systems. This work includes the following three aspects: (I) The molecular structure of SPE was tuned by adjusting the feeding order of alpha-CD. Thereinto, the optimized PLR-based electrolytes exhibited better mechanical strength and improved elasticity, which enabled its self-supporting property and improved interfacial compatibility; (II) Lithium phytate (PALi) was introduced for the first time to modify the flame retardancy of polymer electrolytes for lithium batteries by constructing the synergistic charring effect with alpha-CD. With 10 wt% PALi, the modified electrolyte can perform a comparable electrochemical performance with neat electrolyte, whereas the burning intensity has decreased significantly. The apparently reduced burning rate, peak heat release rate, total heat release, total smoke release, and increased char residue formation also proved the improved flame retardancy. In this work, the electrochemical performance and flame retardancy for the PALi-modified PLR-based SPE achieved a balance by a sustainable strategy. This valid synergistic charring effect of PALi and alpha-CD has been proved by systematic flame-retardant mechanism study through FTIR, Raman, and pyrolysis-gas chromatography-mass spectrometry.

A balanced enhancement of anti-flammability, smoke suppression and mechanical property of thermosetting epoxy merely via a phosphorus/nitrogen-free catalytic mode was a vigorous challenge. To attain this goal, we put forward a simultaneous optimizing strategy via integrating the vapor/condensed-phase sensitive dual-effect ironcatalytic structures into polymeric supermolecule. A radical co-polymerization was executed on specific hostguest vinyl cyclodextrin/ferrocene (VCD@Ferr) and co-monomer acrylic acid, followed by a complexation with Fe3+ to synthesize a bio-based iron-derived supermolecule (VCD@Ferr-AA-Fe). Various characterizations verified the target structure. An incorporation of merely 2 wt% VCD@Ferr-AA-Fe4:1 (iron loading 0.085 wt%) resulted in a UL-94 V-1 and a LOI of 27.9 % with total smoke production and peak smoke production rate decreased by 31.3 % and 33.6 %, respectively. A series of experiments evidenced a presence of intra-molecular synergistic effect between VCD@Ferr and AA-Fe component. In a proposed mechanism, iron ions of VCD@FerrAA-Fe4:1 coordinated with degraded products of epoxy to increase the melt viscosity, followed by a combined catalytic charring behavior. Additionally, the released ferrocene participated into the vapor-phase flame inhibition and smoke suppression. Besides, flexural and unnotched impact strength were respectively increased by 37.3 % and 39.5 % without a loss of tensile strength. Prospectively, a bio-based dual-effect structure exploited a P/N-free highly efficient route towards fire-safe polymers.

Chloroprene rubber (CR) is one of the widely used materials due to its excellent performance. However, it will evolve large amounts of smoke and toxic gas during its combustion, which may cause smoke inhalation even human deaths in the populated enclosed spaces like rail transit, etc. Aiming to improving the fire safety of CR, the effects of zinc borate (ZnB) and antimony trioxide (Sb2O3) alone and their combination on the flame retardancy, smoke suppression, and toxicity inhibition of CR are investigated. The performances of CR/ZnB, CR/Sb2O3 and CR/ZnB/Sb2O3 were analyzed by limiting oxygen index (LOI), UL94 rating and cone data. The results showed that the combination of ZnB and Sb2O3 can integrate their advantages to exhibit the higher LOI and flame retardancy index (FRI) values as well as toxicity inhibition ability, indicating their good fire retardancy feature. The corresponding mechanism including the flame retardant mechanism and Lewis acid function was discussed in detail.

High ionic conductivity, fire safety, and broad electrochemical windows are crucial considerations for the next generation of solid polymer electrolytes (SPEs) employed in solid-state lithium-ion batteries. Based on these factors, we design a novel nanohybrid filler by loading a phosphazene-based flame retardant into halloysite nanotubes (HNT@FPPN). A 36 % reduction in the peak heat release rate (pHRR) confirms the enhanced fire safety of poly(ethylene oxide) (PEO)-based PEO-5HNT@FPPN SPE. Besides, the PEO-5HNT@FPPN electrolyte exhibits an enhanced ionic conductivity of 1.82 x 10(-4) S cm(-1) at 45 degrees C. The improved ionic conductivity is attributed to the plasticization effect of nanohybrids, which reduces the crystallinity and aids the motion of PEO chains. After 100 cycles, the as-fabricated Li/PEO-5HNT@FPPN/LiFePO4 cell shows stable cycling at 0.1C with a specific discharge capacity of 145 mAh/g. These findings demonstrate the unique properties of modified PEO SPEs, which may open new pathways for designing safer electrolytes.

Metal-organic frameworks (MOFs) are crystalline porous materials constructed by metal nodes and organic linkers. A series of key features such as high surface area, catalytic performance provide a platform for preparing MOF-based fire retardants (FRs). However, understanding the role of the porous structure and catalytic metal species remains a key issue towards the fire retardant mechanism of MOFs. This work systematically studied the difference between the performance of a zirconium based MOF(UiO-66), its derived porous zirconium oxide (U-ZrO2), and commercial ZrO2 (C-ZrO2), in imparting fire retardancy, suppressing smoke and charring property towards epoxy. With the presence of 3wt% porous U-ZrO2, EP/3U-ZrO2 sample showed better performance in suppressing heat (10% reduction) and toxic carbon monoxide (14% reduction) than that of EP/3C-ZrO2 due to the “tortuous path” effect and formation of a compact char. Moreover, a greater number of exposed catalytic sites on MOF compared with thermally treated metal oxide significantly reduced total smoke production (TSP) of the EP/MOF sample by 38%. Catalytic carbonization attributed to the great number of metal sites on MOF is crucial in providing compact char residue, thereby suppressing smoke for EP. In perspective, this work opens a window for understanding the fire retardant mechanism of MOF-based FR towards polymers.

High-performance and multifunctional epoxy resins (EP) hold significant promise for diverse applications, yet grappling with the flammability, low thermal stability and mechanical property. In this work, a hierarchical core-shell-dot nanostructure (PDH@beta-CD-AA-Fe) was designed via the in-situ polymerization of dopamine hydrochloride (DOPA) on the surface of halloysite nanotube (HNT), then hybriding with aminobenzeneboronic acid (AA), cyclodextrins (beta-CD) and transition metal iron ions (Fe). Only 2.5 wt% PDH@beta-CD-AA-Fe imparted EP with UL-94 V-0 level at a LOI of 29.3 %, a 52.8 % decreased of peak heat release rate (pHRR), accompanied by a higher proportion of graphitized char layer via the interface-catalyzed charring process. Remarkably, the tensile strength and flexural strength concurrently increased by 40.0 % and 24.9 % comparing to that of neat EP, respectively. Furthermore, a significant reduction in temperature directly above the standard room's ceiling within 500 s of ignition, accompanied by substantial decreases in CO concentration and smoke emission according to the Fire Dynamics Simulator. Prospectively, the rational strategy of constructing an interface catalysis charring and active organic surface of HNT exploits a highly efficient strategy for developing high-performance EP.

Inspired by the significant synergistic effect of transition metals and ammonium polyphosphate (APP) on flame reatrdancy, a nickel/cobalt-layered double hydroxide derived from a selected zeolitic imidazolate framework-67 (APP@NiCo) was constructed onto the surface of APP to enhance the fire safety of thermoplastic polyurethane (TPU). The results demonstrated that TPU containing 6 wt% APP@NiCo exhibited a LOI value of 27.7% and achieved UL-94 V-0 rating. Furthermore, there was a significant reduction in the peak heat release rate, heat release rate, and total smoke production by 72.8%, 37.5% and 56.9%, respectively. The remarkable improvement in flame retardancy was contributed to the highly synergistic charring catalysis of APP and dual transition metals cobalt and nickel, which effectively promoted the formation of robust char layers during TPU combustion for enhancing fire safety.

Preventing aggregation and inducing homogeneous dispersion of flame retardant nanofillers is critical to enhance the fire safety and mechanical properties of nanocomposites. Although chemical modifications are commonly used to improve the filler's compatibility with the polymer chain, such methods are often cumbersome and limited. Herein, porous liquids (PLs) with flame retardant function were constructed in which porous defect-Co-LDH@ZIF-67 (d-LDH@ZIF) heterostructure particles were converted into liquid materials by electrostatic interaction with a large-volume solvent. This is also the first report of PLs in the field of flame retardant. Specifically, the d-LDH@ZIF heterostructure was designed by defect engineering and in situ growth strategy to compensate for the low catalytic activity and specific surface area of Co-LDH, and to serve as a rigid porous framework for PLs. Numerous cobalt/oxygen vacancies and lattice defects in the d-LDH@ZIF heterostructure have also been proven to confer higher flame retardancy relative to Co-LDH. d-LDH@ZIF porous liquids (PLs-dL@Z) presents favorable liquid characteristics and achieves a monodisperse state in the polyurea matrix. The limiting oxygen index of polyurea composites blended with 20 wt% PLs-d-L@Z (3 wt% d-LDH@ZIF content) can be increased to 24.2 % and pass the V-0 rating in the UL-94 test. Moreover, the peak of heat release rate, total heat release, and total smoke production are reduced by around 40.4, 27.0, and 39.9 %, respectively, compared to neat polyurea. Emphatically, the PLs-modified polyurea composites exhibit significantly improved mechanical and impact resistance properties, as well as favorable chemical resistance. This strategy of liquefying solid flame retardant fillers will open an avenue to the design of functional nanomaterials for fire safety and other potential applications.

Metal-organic frameworks (MOFs) are favored in the field of flame retardancy due to the catalytic effect of metal nodes on char layer formation and the synergistic flame-retardant effect of organic ligands containing elements such as nitrogen and phosphorus. However, the inherent microporosity of MOFs limits their adsorption efficiency for toxic smoke and flammable gases. In this work, an organic phosphorus-modified MOF with a distinctive nanostructure of hierarchically porous (P-Co-MOF/ZIF) was successfully synthesized. In brief, an aminofunctionalized zeolitic imidazolate framework (NH2-ZIF) was initially synthesized through a ligand substitution reaction with ZIF-67. Subsequently, organic phosphorus flame retardants were grafted on NH2-ZIF, and the acidic substances generated during this process were used to synchronously half etch ZIF, resulting in a ZIF with a high specific surface area and unique nanostructure. Through this simple synthetic method, the catalytic ability of transition metals in ZIF is preserved, and organic phosphorus flame retardants are incorporated into ZIF, resulting in the synergistic flame-retardant effect of phosphorus and nitrogen. Additionally, its unique hierarchically porous nanostructure can effectively enhance the adsorption of volatile products during the combustion process, thereby offering outstanding flame retardancy and smoke suppression effects for epoxy resin (EP). The results indicate that adding 2 wt% P-Co-MOF/ZIF to EP can increase the limiting oxygen index value to 29.5%. Furthermore, the peak of heat release rate, total heat release, and total smoke production of the composite material can decrease by 43.3%, 37.9%, and 38.1%, respectively, compared to EP. Therefore, this work will provide new inspiration for designing functional nanostructures and synthesizing efficient flame retardants.

Toward addressing the aesthetic demand, IR emissivity, and fire hazards of radiative cooling materials in the practical application, chameleon-inspired is tactfully employed, dipole moment-increasing, and fire-retardant strategies to manufacture an advanced polyurea-based composite coating through incorporating thermochromic microcapsules, boron nitride nanosheets, and montmorillonite nanosheets. The chameleon-inspired thermochromic microcapsules and admirable IR emissivity (supported by the original IR emittance spectra) realized by the increasing dipole moment allow the composite coatings to spontaneously adjust the solar absorption and reflection during hot daytime, while enabling high-efficiency radiative cooling throughout the day. The IR emissivity higher than most literature is attributed to the strong interfacial interactions within polyurea composite coatings which improve the dipole moment of C & horbar;O & horbar;C, Si & horbar;O, and B & horbar;N bonds by increasing the distance between the centers of positive and negative charges, thus producing more IR emissions. Furthermore, the thermally melted montmorillonite nanosheets can form a ceramic protective layer enhanced by boron nitride nanosheets, further suppressing combustion behavior to improve the fire safety performance of polyurea coatings. The integration of thermochromic functionality, high fire safety, and admirable IR emissivity not only contribute to promoting the practical application of radiative cooling materials, but also provide a precious reference route to design high IR emissivity. The table of contents entry: Chameleon-inspired, dipole moment-increasing, and fire-retardant strategies are employed to address the aesthetic demand, high cooling efficiency, and fire safety issue of radiative cooling materials in the practical application. Most importantly, IR emissivity higher than reported most literature is achieved in polyurea composite coatings by increasing change of dipole moment of chemical bonds with strong interfacial interactions. image

The fire hazard of polymers presents a remarkable threat to life and property. In response to this challenge, the pursuit of highly efficient and reliable flame retardants is of paramount significance. Hyperbranched oligomers/polymers, featuring specific and tailorable molecular architectures, demonstrate an intensive potential in imparting diverse polymer matrices with flame retardancy and other functionalities via flame-retardant-targeted structural design. Recently, numerous studies have reported the design and application of hyperbranched flame-retardant molecules, yet a progress-relevant comprehensive summary of the molecule design, fire properties, and mode of action of hyperbranched fire retardants is still lacking. In this case, this review summarizes the state-of-the-art research progress of hyperbranched fire-retardant molecules or structures, concentrating on revealing the highly efficient design principle, structure-property relationship, and multifunctional reinforcement fundamentals. The review proceeds from various flame-retardant structural units such as phosphorus-containing, phosphorus-nitrogen bond-containing borates, silicates, and triazines, accompanied by their synthesis routes, behavior, and flame-retardant mode of action in polymers. Also, the enhancement of multifunctionality such as heat resistance, transparency, and processability is specified. The review provides comprehensive guidance for a rational design of hyperbranched flame-retardant fire-fighting molecules with high efficiency, reliability, and multifunctionality.

In this work, an aerogel with excellent flame retardancy, enhanced compression modulus, and efficient thermal insulation was developed from poly(vinyl alcohol) (PVA), biobased phytic acid (PA), and single-walled carbon nanohorns (SWCNHs). The microstructural evolution of the freeze-dried PVA/PA/SWCNH composite aerogels revealed that varied amounts of phytic acid could influence the three-dimensional architecture. Especially, when the concentration of PA was 1.5%, the PVA/PA/SWCNHs composite aerogel with a tightly arranged "short tubes" structure had a high compressive modulus of 2.02 MPa, corresponding to the specific modulus of 20.2 MPa cm(3)/g. Compared to the PVA/SWCNHs aerogel, the PVA/PA/SWCNHs composite aerogels showed better fire retardancy, as confirmed by limited oxygen index (LOI) tests and cone calorimetry (CC) tests. Notably, the introduction of phytic acid at 1.5% resulted in LOI values up to 49.8 +/- 0.1% and the pHRR and THR of the PVA/PA/SWCNHs composite aerogel were dramatically reduced by 74.3 and 81.0%, respectively. In addition, PVA/PA/SWCNHs composite aerogels with different concentrations of phytic acid exhibited excellent thermal insulation performance with a slightly lower thermal conductivity (32.2-46.9 mW/(m K)) and resisted the similar to 1300 degrees C flame. Meanwhile, the synergistic flame retardancy between SWCNHs and phytic acid was also confirmed by the analysis of the char residues and gas-phase products. These unique characteristics make the aerogel a promising multifunctional candidate for applications in aviation, aerospace, and other fields.

Ultrasensitive and stretchable strain sensors based on graphene nanoplatelet (GNP) doped poly(ethylene glycol) diglycidyl ether (PEGDGE) for human motion monitoring purposes with remote tracking by using Internet of Things (IoT) technologies are synthesized. The quasi–static and cycling responses under both tensile and compression conditions of nanocomposites are studied in detail. On one hand, quasi-static analysis shows very high values of the gauge factor, reaching values around 50–100 at low strain levels (1–2%) and 1000–2500 at high strain levels (10%) in tensile mode, with increasing sensitivity with decreasing GNP content. In addition, electromechanical response under 500 tensile and compression load cycles up to 1%, 2.5%, and 5% strain levels proves their high stability and as a result, their high sensitivity to detect a low degree of strain levels. Three general proofs–of–concept demonstrate that these sensors can detect several types of deformations such as pressure, bending, and twisting. Finally, human breathing is monitored with the sensor attached to a conventional mask. Different breath rhythms combining the calm and excited states of a person walking are remotely sent and monitored on the internet by using different IoT platforms.

Epoxy resin (EP) is one kind of widely applicated thermosetting resin with excellent manufacturability, mechanical performance and chemical resistance, but its flammability seriously limited its widely application. In this work, the flame-retarding curing agent (BIPD) with was prepared by a simple one-step substitution reaction between benzimidazole (BI) and phenylphosphonyl dichloride (PD). When the mass fraction of BIPD is 10 %, the flexural strength and impact strength are 174.7 MPa and 14.9 KJ/m2, respectively, which are 15.5 % and 69 % higher than those of EP/BI10. The EP/BIPD10 passed the UL-94 V-0 rating with a limiting oxygen index (LOI) reaching to 33 %. Meanwhile, the peak of heat release rate (PHRR) and total heat release rate (THR) of EP/BIPD10 decreased by 50.2 % and 37.8 %, the total smoke production (TSP) and the mass percentage of residues increased by 10.4% and 204.1 % than that of EP/BI10 in the cone calorimeter (CC) measurement, showing a jointly flame-retarding process in the condensed and gas phase. Furthermore, the results of Raman spectrum, the thermogravimetric infrared spectroscopy (TG-FTIR) and pyrolysis-gas chromatography/mass spectrometry (PY-GC/MS) confirmed the conclusion.

Metal-organic frameworks (MOFs), as a new family of nanomaterials with multiple dimensions, present enormous potential in different applications due to their high specific surface area and porosity, easy chemical functionalization, and excellent designability of nanostructure. These peculiar properties make MOFs promising alternatives as nanofillers for the fabrication of high-performance and multifunctional composites. In the past five years from 2017 to 2022, many researchers have investigated the flame retardant effects and mechanisms of MOFs in various polymeric materials. Statistical analysis based on bibliometrics showed that the research of MOFs flame retardant epoxy composites accounts for about 40% of the flame retardant field of MOFs, which is also very necessary to be sorted out separately. And to our knowledge there is no comprehensive report on MOFs flame retardant epoxy composites. Here, this review provides the latest advances of MOFs in flame retardant epoxy composites using pure MOFs, MOFs derivatives, functionalized MOFs, and synergistic systems based on MOFs and other functional components. The modification strategies and flame retardant efficiency of MOFs-based flame retardants are analyzed with special emphasis on the flame retardant mechanisms of different components. In addition, most MOFs-based flame retardant composites exhibit multiple functions that benefit from their inherent properties such as wave absorption as well as mechanical enhancement, thus promising in some high-end applications. Finally, the opportunities and challenges for the future development of MOFs-based flame retardants were summarized and prospected. This work is also expected to facilitate researchers to quickly understand the latest developments in this field and guide their effective design.

Thermoplastic polyurethane elastomer (TPU) is an easily flammable materials with serious droplets and smoke toxicity, which critically restrict its practical application. In order to improve the flame retardancy of TPU, the present work designed a halogen free flame retardant (AL-APP) containing phosphorus and nitrogen elements via the modification of ammonium polyphosphate (APP) with sodium alendronate (Al). It was found that the limiting oxygen index of TPU/AL-APP5 composites increased from 20.7 % to 26.5 % and got past the V-0 rating without any droplets in the UL-94 vertical measurement. Meanwhile, the peak heat release rate (PHRR) and total heat release (THR) of TPU/AL-APP5 system reduced from 1021 to 255 kW/m2 and 87.5-61.2 MJ/m2 in cone calo-rimeter (CC) measurement when comparing to that of purchased TPU. According the thermogravimetric-infrared and Raman spectroscopy results, the production of the inert gas and formation of continuous carbon layer of AL-

In this work, the highly-efficient multifunctional bio-based fire retardant phenylphosphonic difurfurylamine (PPDF) was prepared successfully for poly(lactic acid) using furfurylamine and phenylphosphonic dichloride. Moreover, the structure of PPDF was analyzed by NMR, FTIR and MS. The fire safety, thermal, crystallization, rheological and mechanical properties of PLA/PPDF compounds were systematically tested by LOI, UL94, cone calorimeter test, TGA, DSC, polarizing optical microscope, rheometer, DMA and tensile properties. Surprisingly, only a very small loading of 0.8 wt% loading of bio-fire retardant PPDF could increase the LOI value of PLA from 19.0 % to 30.0 % and achieve V-0 rating in UL-94 vertical burning test. Moreover, PPDF not only reduced the molecular entanglement and viscosity of PLA, but also acted as a nucleating agent to increase crystallinity and crystallization rate of PLA matrix. More importantly, in the gas phase phosphorus, the PLA/PPDF compounds based on highly reactive benzene, phosphorus, phosphooxygen and phosphooxygen benzene radicals from the pyrolysis of PPDF had a highly-efficient fire safety. In the condensed phase, a relative stable residual char layer played a secondary role in the barrier. Thus, the total heat release and ignition time of PLA/PPDF compounds were evidently declined by 8.3 % and 10 s with only 0.8 wt% of PPDF loading.

Hollow nanocages derived from metal-organic frameworks (MOFs) feature more exposed active sites, stronger interactions, and better compatibility within the polymer matrix than solid blocks. Nevertheless, the preparation always requires the sacrifice of MOFs as a self-template. Herein, using step-by-step carving in the sequence of organic phytic acid and inorganic boric acid, MOFs can be retained in the form of nanodots with high-energy plane decorated on the hollow shells, endowing the hybrid superstructure product (ZNs-B/CP) with a relatively high surface area and enhanced catalytic properties. Owing to the ingeniously designed chemical composition and nanostructures, a load of 2 wt% ZNs-B/CP into epoxy resin improved the limiting oxygen index to 28.4% and decreased the peak of heat release rate and total heat release by 43.1% and 11.9%, respectively, assisted by the fast char formation mechanism, with slight influence on the mechanical strengths of the composites. Under the background of burgeoning investigations for MOFs, this work supplements a feasible synthetic artifice for MOF nanodots and proposes a potential application as a flame retardant for epoxy resin.