Controllable Pore Research Articles

Biomineralized metal-organic framework membrane with high-crystallinity for ultrafast molecular separation

Metal-organic frameworks (MOFs) possess uniform and controllable pore structure, holding significant promise for the creation of efficient molecular separation membranes. Nevertheless, the challenge lies in constructing MOF membranes with high crystallinity and effectively utilizing their ordered crystal channels for molecular separation. Drawing inspiration from natural biomineralization processes, an in-situ trace graphene oxide (GO)-mediated crystallization strategy was adopted here to manipulate the crystallization of Zr-MOF (MIP-202(Zr)) membranes. GO nanosheets with abundant oxygen-containing groups could interact with the MOF precursor, furnishing numerous growth sites for the subsequent MOF growth, thereby facilitating the crystallization process during membrane formation within only 60 min. The resultant GO/MIP-202(Zr) composite membrane, composed of highly crystalline MIP-202(Zr) and trace amount of GO nanosheets, overcame the trade-off between MOF crystallinity and membrane formation. Benefiting from the interconnected pore structure, the resulting GO/MIP-202(Zr) membrane presented ultrahigh water permeability (1698.9 L m−2 h−1 bar−1), surpassing that of the pure GO membrane (258.9 L m−2 h−1 bar−1) by 6.5 times, while maintaining a comparable rejection for common dye molecules. Furthermore, the membrane displayed satisfied recyclability and structural stability. This study provides important perspectives for the fabrication of advanced membranes derived from MOFs aimed at enhancing molecular separation processes.

Ultrathin, Stretchable, and Twistable Ferroelectret Nanogenerator for Facial Muscle Detection

Ferroelectret nanogenerators (FENGs) have garnered attention due to their unique porous structure and excellent piezoelectric performance. However, most existing FENGs lack sufficient stretchability and flexibility, limiting their application in the field of wearable electronics. In this regard, we have focused on the development of an ultrathin, stretchable, and twistable ferroelectret nanogenerator (UST-FENG) based on Ecoflex, which is made up of graphene, Ecoflex, and anhydrous ethanol, with controllable pore shape and density. The UST-FENG has a thickness of only 860 µm, a fracture elongation rate of up to 574%, and a Young’s modulus of only 0.2 MPa, exhibiting outstanding thinness and excellent stretchability. Its quasi-static piezoelectric coefficient is approximately 38 pC/N. Utilizing this UST-FENG device can enable the recognition of facial muscle movements such as blinking and speaking, thereby helping to monitor people’s facial conditions and improve their quality of life. The successful application of the UST-FENG in facial muscle recognition represents an important step forward in the field of wearable systems for the human face.

Metal-organic framework-based hybrids with photon upconversion.

Upconversion materials (UCMs) featuring an anti-Stokes type emission establish them as an important category of photoluminescent materials. Metal-organic frameworks (MOFs) are rapidly gaining prominence as a class of versatile materials with favourable physical and chemical properties, including high porosity, controllable pore size, flexible design, and diverse functional sites. To endow MOFs with upconversion capability and improve the properties and performance of UCMs, the hybrids integrating UCMs and MOFs are proven to be successful. This review focuses on the research advancements of upconverting MOF-based hybrids, encompassing classifications, luminescence mechanisms, designs, properties, and applications in energy, catalysis, and biomedical fields. The analyses on the functions of upconversion and MOFs, as well as the advantages and disadvantages of various upconverting MOF-based hybrids, are included. Future research directions spanning from properties and performance to applications are explored. This review will be valuable in highlighting the research accomplishments, inspiring more ideas, facilitating deeper investigations in diverse avenues, and further advancing the research field.

Multifunctional Ti3C2Tx/Fe3O4/glass fiber paper composites for flexible microwave absorption materials with ultralow filling ratio

The preparation of multifunctional microwave absorbing materials with the characteristics of stronger absorption, wider bandwidth, lighter weight, higher strength and thinner thickness is an urgent research direction. Due to the difficulty of controllable distribution of absorbers, excellent microwave absorption performance is usually accompanied by large absorber amount and thickness, which can result in microwave absorption composite materials lack flexibility, mechanical properties, and adaptability to the environment. In this study, Ti3C2Tx/Fe3O4/glass fiber paper composite was prepared by vacuum-assisted filtration. The controllable pore structure constructed by glass fiber enables uniform distribution of MXene/Fe3O4 and effectively spreading of MXene monolayer film, enhancing conductivity loss and interface loss. By controlling the diameter of glass fiber, the pore size and the distribution of absorber can be regulated, thereby achieving a minimum reflection loss of up to −57.2 dB at an ultra-low filling ratio of 1.66 wt%. With the addition amount of 1.90 wt%, the effective absorption bandwidth can cover the whole X-band. The ultra-low specific reflection loss exceeds most of fabric materials and MXene-based absorbers. Meanwhile, the composite material exhibited excellent mechanical properties with a tensile strength of 3.054 kN/m and a burst resistance of 290 kPa. In addition, the adhesion between the filler and the glass fiber was increased by adding acrylic resin-based aqueous adhesive, and the surface grafting functional group (-F) made the composite material superhydrophobic. This work provides a new strategy to synthesize multifunctional absorbing material with low filling ratio and strong environmental practicality.

A strong bioceramic microtube and its use in the fabrication of bioceramic implants through flexible deformation and pressure-assisted forming

Bioceramic implants with complex structures, controllable pore size, and excellent mechanical property are hardly manufactured due to high hardness and brittleness of bioceramics. To address the challenge, the study developed a different way to facilitate the fabrication of a strong and tough hydroxyaptite (HA) microtube (HAMT) and ceramic implants. Ceramic implants such as HA bone cage and screw containing microtube were manufactured through flexible deformation and pressure-assisted forming. The compressive strength of HAMT formed by HA filament with 70 carbon fiber(CF) was 132.4 ± 8.4 MPa, which was 73.68 % higher compared to that of HA filament. Furthermore, the HA cage was closely stacked to form dense and uniform structure and had a better mechanical property. The HA bone screw based on the microtube had a compressive strength of 24.5 ± 1.3 MPa and a pullout force of 83.5 ± 1.4 N, which can be used as a bioabsorbable cancellous-bone screw.

Supermolecule-opitimized defect engineering of rich nitrogen-doped porous carbons for advanced zinc-ion hybrid capacitors.

Pitch-based porous carbons with adjustable surface chemical property and controllable pore structure are regarded as promising cathode materials for aqueous zinc-ion hybrid capacitors (ZIHCs), while its disordered carbon matrix and microstructure as well as insufficient surface defects often result in low Zn2+-storage capacity and poor rate capability of ZIHCs. Herein, a synergetic strategy of self-assembled supermolecule and enriched defective carbon engineering was developed to achieve ultrahigh edge-nitrogen doping for ZIHCs. The crystallite defects and surface structure of porous carbon could be effectively achieved through grafting electronegative oxygen-containing small molecules and high-level nitrogen-containing functional groups between modified polycyclic aromatic hydrocarbon and supermolecule framework. The optimized three-dimensional carbon structure delivered high capacity of 218 mAh g-1 at 0.2 A g-1, fast charge/discharge capability, enhanced energy density (165.4 Wh kg-1) and superior cycling stability (95% retention after 10000 cycles as cathode of ZIHCs). This provided new insight into the controllable synthesis of carbon cathodes for ZIHCs and expects to prepare functional porous carbon by supermolecules and special precursors.

Cellulose-Templated Nanomaterials for Nanogenerators and Self-Powered Sensors.

Energy crisis inspires the development of renewable and clean energy sources, along with related applications such as nanogenerators and self-powered devices. Balancing high performance and environmental sustainability in advanced material innovation is a challenging task. Addressing the global challenges of sustainable development and carbon neutrality lead to increasedinterest in biopolymer research. Nanocellulose materials, derived from biopolymers, demonstrate potential as template candidates for advanced materials, due to their unique properties, including high strength, high surface area, controllable pore structures and high-water retention. In recent years, cellulose-templated nanomaterials enable delicate nano-/microscale structural construction, thus promoting developments in the field of nanogenerators and self-powered sensors. However, there is still a limited number of reviews focused on cellulose-templated nanomaterials for applications in nanogenerators and self-powered sensors. This review aims to fill this research gap by introducing various cellulose-templated nanomaterials and providing a detailed analysis of their fashionable applications in nanogenerators and self-powered sensors. The goal is to present cellulose-templated nanomaterials as highly promising template and guest materials for templating technologies, offering sustainable nano-/microscale control over advanced materials for the foreseeable future. This potential is promising for new applications in the fields of nanogenerators and self-powered sensors.

Upcycling Waste Polyethylene Terephthalate to Produce Nitrogen-Doped Porous Carbon for Enhanced Capacitive Deionization

Porous carbon with a high surface area and controllable pore size is needed for energy storage. It is still a significant challenge to produce porous carbon in an economical way. Nitrogen-doped porous carbon (N-PC) was prepared through carbonization of a mixture of waste PET-derived metal–organic frameworks (MOFs) and ammonium. The obtained N-PC exhibits a large surface area and controlled pore size. When utilized as an electrode material for supercapacitors, the N-PC exhibits a specific capacitance of 224 F g−1, significantly surpassing that of commercial activated carbon (AC), which has a capacitance of 111 F g−1. In the subsequent capacitive deionization (CDI) tests, the N-PC demonstrated a maximum salt adsorption capacity of 19.9 mg g−1 at 1.2 V in a NaCl electrolyte (0.5 g L−1), and the salt adsorption capacity increased to 24.7 mg g−1 at 1.4 V. The N-PC electrode also exhibited superior regeneration. The present work not only presents a potential approach to develop cost-effective electrodes for seawater purification but also paves the way for recycling of waste plastics into high value-added products.

Construction of PTFE/PI-PI/PANI-PA composite nanofibrous membrane for efficient photothermal membrane distillation and VOCs interception

Water-soluble volatile organic compounds (VOCs) are one of the difficult substances in seawater and industrial wastewater treatment. Photothermal membrane distillation (PMD) technology has great advantages in solving the problems of low energy conversion efficiency and serious pollution of traditional membrane distillation (MD) technology, but it still faces the challenge that VOCs cannot be effectively removed.To solve this problem, we prepared photothermal Polytetrafluoroethylene/Polyimide-Polyimide/Polyaniline-Polyamide (PTFE/PI-PI/PANI-PA) composite membranes with VOCs interception. The composite membrane was fabricated by applying the previously studied PTFE/PI-PI/PANI/PANI membrane by interfacially polymerising an ultrathin PA layer with controllable pore sizes. Among them, the PTFE/PI-PI/PANI base membrane in the composite membrane not only provides strong support and durability as a backbone structure, but the PANI photothermal layer also provides photothermal conversion for effective PMD operation. In addition, the ultra-thin PA layer acts as a molecular sieve separator to effectively intercept VOCs in the feed solution. When the feed solution was 35 g⋅L−1 NaCl, the average permeate flux of the #M-PA-0.1 membrane was 1.44 ± 0.02 L⋅m−2⋅h−1 with a salt interception rate of 99.99 % or more after 80 h of PMD testing. Meanwhile, when 50 mg⋅L−1 of VOCs was added to the feed solution, the VOCs retention rate >99.35 %, and the concentration of VOCs on the permeate side was much lower than the corresponding concentration in the drinking water standards recommended by the World Health Organisation (WHO) and the US Environmental Protection Agency (EPA). This study effectively combines the molecular sieve effect with the solar-powered evaporation process, which provides a research basis for the preparation of high-performance PMD membranes that can effectively remove volatile organic compounds.

Solubility-controlled early age hydration of carbonate-activated slag: Underlying mechanisms and acceleration via seeding

The low environmental impacts and good performance of carbonate-activated binders have attracted substantial interest, while their intrinsically delayed reaction and prolonged setting times constrain widespread implementation. This study aims to investigate the early-age reaction kinetics of carbonate-activated binders, elucidate the underlying mechanisms and propose controlling methods. Results reveal that hydrotalcite and C-A-S-H gel precursors rapidly reach supersaturation within hours, yet precipitation of these phases remains absent. This phenomenon, coupled with high Si/Ca ratios in the pore solution, exhibits characteristics that may contribute to the observed reaction delays. A prolonged induction period and lethargic strength development are observed owing to the lack of strength-giving phases. The hydrotalcite and C-A-S-H concentrations surpass their theoretical solubility thresholds due to rising ionic strength and salt-in effects. The addition of a pH-neutral layered double hydroxide salt accelerates the reaction, confirming seeding impacts control pore solution saturation limits, constituting the underlying accelerator mechanism.

The Chemistry of Metal-Organic Frameworks for Multicomponent Gas Separation.

Adsorbents-based gas separation technologies are regarded as the potential energy-efficient alternatives towards current thermal-driven methods, and the study on multi-component gas separation is essential to deepen our understanding of the adsorbents for practical use. Relative to the ideal two-component mixtures, both the adsorption behavior and separation mechanisms are obviously more complex in multiple gas mixtures due to their close or even overlapped sizes and properties. The emergence of metal-organic frameworks with controllable pore size and pore chemistry provides the platform for the tailor-made pore structure to satisfy the harsh requirements of multi-component gas separation. This minireview highlights the recent advance of multi-component gas separation using metal-organic frameworks, including multiple impurities removal and selective molecular capture. Combining with the typical cases of hydrocarbon separations (C2, C4, and C8), the detailed discussion about the developed strategies (e.g. self-adaptive binding sites, multiple binding spaces, synergistic binding sites, synergistic sorbent separation technology, gate-opening effect, size and thermodynamic combine effect) that are adaptive to different scenarios would be provided. The review will conclude with our perspective on the existing barriers and the future direction of this topic.

The Chemistry of Metal–Organic Frameworks for Multicomponent Gas Separation

AbstractAdsorbents‐based gas separation technologies are regarded as the potential energy‐efficient alternatives towards current thermal‐driven methods, and the study on multi‐component gas separation is essential to deepen our understanding of the adsorbents for practical use. Relative to the ideal two‐component mixtures, both the adsorption behavior and separation mechanisms are obviously more complex in multiple gas mixtures due to their close or even overlapped sizes and properties. The emergence of metal–organic frameworks with controllable pore size and pore chemistry provides the platform for the tailor‐made pore structure to satisfy the harsh requirements of multi‐component gas separation. This minireview highlights the recent advance of multi‐component gas separation using metal–organic frameworks, including multiple impurities removal and selective molecular capture. Combining with the typical cases of hydrocarbon separations (C2, C4, and C8), the detailed discussion about the developed strategies (e.g. self‐adaptive binding sites, multiple binding spaces, synergistic binding sites, synergistic sorbent separation technology, gate‐opening effect, size and thermodynamic combine effect) that are adaptive to different scenarios would be provided. The review will conclude with our perspective on the existing barriers and the future direction of this topic.

Self-exothermic reaction behavior and pore structures of Ni-Al intermetallics with more than 70% porosity

Abstract In this study, high-porosity Ni-Al alloys with complete shape and controllable pore structures were prepared by combining the self-exothermic reaction with the space holder method. The observations show that porous Ni-Al sintered discs appeared to melt and deform after a violent reaction without adding space holder particles. The link between the volume content of urea particles and macroscopic morphology, combustion behavior, phase composition and pore structures of porous Ni-Al compounds were studied. The space holder pores acts as a heat absorber, greatly increasing the open porosity to 76.0% when adding 50 vol% urea particles. This leachable space holder method can be an effective strategy to regulate the sample shape and pore characteristics of porous Al-containing intermetallics.

Cell migration within porous electrospun nanofibrous scaffolds in a mouse subcuticular implantation model.

Cellular infiltration into electrospun nanofibers (NFs) is limited due to the dense structure and small pore sizes. We developed a programmed NF collector that can fabricate porous NFs with desired pore sizes and thickness. Previously we demonstrated improved cellular proliferation and differentiation of osteoblasts, osteoclasts, and fibroblasts with increased pore sizes of polycaprolactone (PCL) NF in-vitro. This study investigated in-vivo host cell migration and vascular ingrowth within porous NF sheets implanted subcutaneously in a mouse model. Two types of PCL NFs with well-defined pore sizes were created using varying speeds of the NF collector: NF-zero (no movement, pore size 14.4 ± 8.9 µm2) and NF-high (0.232 mm/min, pore size 286.7 ± 381.9 µm2). The NF obtained by using classical flat NF collector (2D NF, pore size 1.09 ± 1.7 µm2) was a control. The three formulae of NFs were implanted subcutaneously in 18 BALB/cJ mice. Animals were killed 7 and 28-days after implantation (n = 3 per group per time point). The tissue with implanted NFs were collected for histologic analysis. Overall, 7-day samples showed little inflammatory response. At 28-days, the degree of tissue penetration of PCL NF sheet matrices was linked to pore size and area. NFs with the largest pore area had more efficient tissue migration and new blood vessel formation compared to those with smaller pore sizes. No newly formed blood vessels were observed in the 2D NF group. A porous NF scaffold with controllable pore size has potential for tissue repair/regeneration in situ with potential for many applications in orthopaedics.

Design and optimization of pore structure in three-dimensional micro-nano hierarchical SnOx supercapacitor electrodes for enhanced ion diffusion

This paper introduced a novel continuous electrochemical synthesis strategy to address the challenges of slow ion/electron transport rates and low electrode reaction efficiency in Sn-based electrode materials. This approach leveraged the induction and confinement of bubble templates to assist atoms deposition, generating micron-sized tin skeletons. Subsequently, these skeletons were transformed into a secondary nanoporous structure through dissolution-deposition etching effects. From liquid-phase ions to metal skeletons to porous oxides, the sequential material transformations realized the innovative design of three-dimensional (3D) hierarchical structures. This strategy ingeniously exploited the diffusion advantages of the electrolyte in the micro-nano hierarchical structure to achieve the diffusion enhancement of ions, thus solving the “dead surface” problem in the energy storage process. This study revealed the thermodynamic and kinetic feasibility of the constructed 3D micro-nano hierarchical structure through electrochemical evaluations and theoretical calculations, and elucidated the constitutive relationship in which the electrochemical performance of the electrode materials was enhanced with decreasing pore size. In addition, design optimization of pore structures and modelling exploration of pore size limit values were conducted based on density functional theory (DFT) simulations. These simulations demonstrated the advantages of hierarchical structures with controllable pore sizes in facilitating electrolyte ion diffusion, predicting an optimal pore size of 55 μm for 3D hierarchical porous SnOx electrodes. The integration of this innovative structural design with simulation insights offered significant implications for enhancing the sluggish electrode reaction kinetics of metal oxide electrode materials, advancing the controllable fabrication of high-performance energy storage devices.

Wrinkled hierarchical porous carbon spheres with interconnected multi-cavity for ultrahigh capacitive deionization

As one of the most promising electrode materials for capacitive deionization (CDI), the development of carbon materials with controllable pore structure and continuous mass production is essential for their practical application. Herein, a facile ultrasonic spray pyrolysis method was developed to synthesize surface-functionalized wrinkled hierarchical porous carbon spheres (HCS) with unique interconnected multi-cavity structures. The wrinkled and interconnected multi-cavity hierarchical pores of the HCS play a crucial role in providing accessible ion adsorption sites and promoting ion diffusion and storage in the “multi-cavity warehouse”. The carboxyl groups on the surface of HCS generate a negative charge that promotes the adsorption of cations. The optimized HCS possesses outstanding desalination capacity (114.25 mg g−1), fast adsorption rate (6.57 mg g−1 min−1), and superior cycling stability (95%). Meanwhile, the HCS exhibited impressive desalination capacities in brackish water. Furthermore, the density functional theory calculation results confirmed that the synergistic effect of carboxyl groups and defects significantly enhanced the Na+ adsorption capacity and facilitated ion diffusion. This study extends the synthesis method of surface-functionalized hierarchical porous carbon, which is expected to facilitate the development of CDI electrode materials.

Pore engineering of Porous Materials: Effects and Applications.

Porous materials, characterized by their controllable pore size, high specific surface area, and controlled space functionality, have become cross-scale structures with microenvironment effects and multiple functions and have gained tremendous attention in the fields of catalysis, energy storage, and biomedicine. They have evolved from initial nanopores to multiscale pore-cavity designs with yolk-shell, multishells, or asymmetric structures, such as bottle-shaped, multichambered, and branching architectures. Various synthesis strategies have been developed for the interfacial engineering of porous structures, including bottom-up approaches by using liquid-liquid or liquid-solid interfaces "templating" and top-down approaches toward chemical tailoring of polymers with different cross-linking degrees, as well as interface transformation using the Oswald ripening, Kirkendall effect, or atomic diffusion and rearrangement methods. These techniques permit the design of functional porous materials with diverse microenvironment effects, such as the pore size effect, pore enrichment effect, pore isolation and synergistic effect, and pore local field enhancement effect, for enhanced applications. In this review, we delve into the bottom-up and top-down interfacial-oriented synthesis approaches of porous structures with advanced structures and microenvironment effects. We also discuss the recent progress in the applications of these collaborative effects and structure-activity relationships in the areas of catalysis, energy storage, electrochemical conversion, and biomedicine. Finally, we outline the persisting obstacles and prospective avenues in terms of controlled synthesis and functionalization of porous engineering. The perspectives proposed in this paper may contribute to promote wider applications in various interdisciplinary fields within the confined dimensions of porous structures.

Efficient construction of self-assembled starch colloidosomes for controlled-release of pesticides

Biodegradable colloidosomes have attracted increasing attention for their applications to enhance the efficacy and reduce wastage of pesticides in agriculture. In this study, we present a continuous and highly efficient method for production of starch colloidosomes. The starch particles with an average particle size of 230.2 nm and good dispersibility were prepared using surface modification technology, and then used as environment-friendly shell materials to form self-assembled starch colloidosomes using spray drying technology. The influences of inlet temperature, feed rate and air flow rate on the morphologies of colloidosomes were also studied. This strategy enables the construction of starch colloidosomes with uniform spherical morphology and controllable pore sizes under different pH, and can be used for pesticide encapsulation. After loading pyraclostrobin (PYR), the regular spherical colloidosomes not only achieve a small mean diameter of 2.35 µm, but also realize a high encapsulation efficiency of 82 %. The release performance of PYR has an obvious pH response and follows the segmented Ritger-Pepapes model of sustained-release. The colloidosomes were used to prevent the photodegradation of pesticides. The PYR loaded colloidosomes exhibit excellent UV resistance with a retention rate of 72.7 %. In addition, the loading of Fe3O4 nanoparticles and the embedding of carbon dots were also explored.

In-situ growth of novel iron oxide/iron organic framework composites as efficient electroactive materials of battery supercapacitor hybrids

Iron oxide (Fe2O3) with a high theoretical capacitance, wide potential ranges and easy availability has attracted much attentions as the electrode material of battery supercapacitor hybrids (BSH). Metal–organic framework (MOF) is one of the promising potential energy storage materials due to its large surface area and controllable pore structures. In this work, novel iron oxide/iron organic framework composites (Fe2O3/FeMOF) are in-situ grown on the Ni foam as efficient energy storage electrodes of BSH. By tuning the solvothermal durations, the morphology changes from random sizes of sheets, regular grown vertical sheets, to flower-like structures. The d-spacing also increases for the Fe2O3/FeMOF synthesized using longer solvothermal durations. The optimal Fe2O3/FeMOF electrode synthesized using 9 h shows a high areal capacitance of 10.97 F/cm2 along with an areal capacity of 5.49 F/cm2 at the current density of 35 mA/cm2, owing to the most regular growth of sheets, the large d-spacing, and the smallest charge-transfer resistances. A BSH composed of the Fe2O3/FeMOF positive electrode and a graphene negative electrode shows a maximum energy density of 0.76 mWh/cm2 at 22.5 mW/cm2. The excellent long-term cycling stability with the capacitance retention of 85% and Coulombic efficiency of 98% are also achieved after 10,000 charge/discharge cycles.

Functionalized Zr‐MOFs for Enhancing Flame Retardancy and Smoke Suppression Performance on TPU

AbstractMetal‐Organic Framework (MOF) materials can be used as flame‐retardants and smoke suppressants for polymers. As a MOF material, UIO‐66(Zr) possesses higher thermal stability and controllable pore size. In this paper, UIO‐66(Zr), NH2‐UIO‐66(Zr), and SiO2, MWCNT, and GO functionalized NH2‐UIO‐66(Zr) was fabricated to improve the flame retardant and smoke suppression performance of thermoplastic polyurethanes (TPU). The experimental results show that compared with neat TPU (LOI value 19.1 %), 2 % usage of UIO‐66(Zr) and NH2‐UIO‐66(Zr) can endow TPU with 26 % LOI value and vertical combustion rating of V‐1. Moreover, SiO2, MWCNT, and GO functionalized NH2‐UIO‐66(Zr) provide TPU with above 27.8 % LOI value and vertical combustion rating of V‐0. Meanwhile, the CCT results showed that the peak heat release rate and total heat release of TPU‐U5 (added 2 % GO‐modified NH2‐UIO‐66(Zr)) are 299.52 Kw ⋅ m−2 and 68.21 MJ m−2, much lower than that of neat TPU, which are 1180.05 Kw ⋅ m−2and 104.87 MJ m−2, respectively. The TGA, char residue EDS and XRD analysis show that SiO2, MWCNT, and GO functionalized NH2‐UIO‐66(Zr) could generate zirconium metal oxide during the combustion process, which acts as a physical barrier to prevent the TPU matrix by promoting the generation of carbonization layer. The zirconium metal oxide and carbonization layer also can confine flammable gases, which can delay the ignition time and hinder the overflow of gas. In addition, NH2‐UIO‐66(Zr) could generate non‐flammable N2 diluting the concentration of flammable gases. The mechanical properties of TPU composites can maintain more than 87 % of the neat TPU after the addition of 2 % SiO2, MWCNT, and GO functionalized NH2‐UIO‐66(Zr). These results indicate that functionalized Zr‐MOFs composites could act as excellent flame‐retardants in TPU.