A review on metal–organic frameworks (MOFs) and MOF–textile composites for personal protection

Abstract

Metal–organic frameworks (MOFs) have become a research hotspot for effective adsorption and degradation of chemical warfare agents (CWAs) and toxic industrial chemicals (TICs) due to their low density, large pore capacity, and customizable structure. However, their further development is seriously hampered by the low stability of MOFs and poor cycle durability. Personal protective equipment (PPE) is the focus of current research as the last barrier to protect people from harm. However, there are still gaps in related research, and the application of MOF–textile composites in personal protection is rarely reported. In this review, the relevant mechanisms of MOFs for the catalysis and adsorption of CWAs are briefly discussed, as well as the research status of MOF adsorption of TICs. Finally, the preparation of MOF–textile composites and their potential for personal protective equipment (PPE) are summarized, and the potential applications of MOFs in chemical protection are prospected.

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1. Introduction

Environmental pollution is now becoming a global concern. Although the Chemical Weapons Convention (CWC) has banned the use of the chemical warfare agents (CWAs), related incidents have continued to occur in recent years. At the same time, toxic and harmful chemicals (e.g. NH₃, H₂S, SO₂, NO_x, etc.) produced by human industrial activities are released into the atmosphere, which affects the quality of human life and health.^1,2 Furthermore, the widespread use of toxic industrial chemicals (TICs) increases the risk of accidental leakage and spillover. Therefore, it is essential to obtain materials that can safely and effectively adsorb or degrade harmful substances under environmental conditions.

Adsorption has been regarded as an excellent purification method in view of its low cost and simplicity. According to different principles, it can be divided into physical and chemical adsorption, respectively.^3,4 Physical adsorption means that the adsorbents isolate or absorb and lock the toxic gas into its pores by physical binding; otherwise, chemical adsorption forms chemical bonds between adsorbents and toxic gas molecules (Fig. 1). Excellent adsorbents should have good performance in terms of adsorption capacity, gas selection and recycling capability. Traditional adsorption materials include activated carbons,⁵ SiO₂,⁶ zeolites,⁷ mesoporous materials,⁸ and so on. Currently, activated carbon is widely used as a commercial adsorbent against poisonous gas. However, the limited adsorption capacity of activated carbon and the weak interaction with toxic substances limit its popularization and application. Therefore, the research for adsorbents that can effectively adsorb toxic and harmful substances is the focus of existing research.

Fig. 1 Diagram of the physical adsorption and chemical adsorption mechanism.

Metal–organic frameworks (MOFs) are constructed from metal (clusters) and organic connectors. Due to their high porosity, adjustable pore size and variable topology, MOFs have excellent adsorption capacity and been widely applied in gas separation,^9,10 energy storage,^11,12 gas sensing,^13,14 drug delivery/biomedicine,^15,16 and other fields. However, the lack of stability and cycle durability of MOFs make it impossible to achieve commercial applications. Researchers found that the ability of MOFs to capture toxic gases, in terms of capacity, can be improved by adjusting the surface area/hole volume,^17,18 regulating the connectivity of the building unit,¹⁹ and increasing open metal sites (OMS) or defect sites.^20,21 Hong et al. modified the organic component of MOF-5²² to contain a carbazole fragment. The carbazole fragment passes through the corner and forms a stable π–π with the phenyl group at the edge of the MOF skeleton, which constructs the structure of the molecular truss beam. This is because of the synergistic interaction generated by the increase in lattice strength and hydrophobicity in the MOF cavity, which greatly improves the stability of the MOFs. Wang et al. used available Cd_SO₄ and H₄L₄ to build MOFs, where the N-coordination site and the introduced SO₄²⁻ optimized the adsorption capability of MOFs for heavy mental ions.²³ The adsorption mechanism of Cd-MOFs was evaluated by relevant models, and it was found that the modified MOFs had the advantage of reusability. It is also expected that Cd-MOFs may become a new option for next-generation post-synthesis modification or functionalization.

Porosity, pore shape and size, and adsorption location are the main factors affecting the effective adsorption of toxic and harmful substances. However, MOFs’ excellent porosity, specific surface area and unique chemical functional groups show high adaptability in the field of harmful gas adsorption. In addition, the ability of MOFs adsorption to eliminate specific gas components in a wide range of environments has great potential. In this review, we first briefly describe the mechanism of the adsorption of CWAs and the catalytic degradation of CWAs by MOFs. In addition, the research status of MOFs on the gas adsorption of TICs (SO_x, NO_x, NH₃, and H₂S) is summarized. Finally, the potential applications of MOFs as adsorption and degradation materials that can adapt to different environments in fibers and fabrics are summarized, and the prospects and challenges of MOFs and MOF–textile composites in the field of personal protection are summarized.

2. CWAs

Since World War I, CWAs have been a continuous threat to human beings. In order to protect the military and civilians from nerve agents, a large number of adsorption materials have been widely explored. Since [Zn₂Ca(BTC)₂(H₂O)₂](DMF)₂ was proved to be the first MOF to capture the nerve agent simulant methylphosphonicn acid (MPA),²⁴ the use of MOFs to adsorb and degrade CWAs has become a hot topic. Commonly used CWAs are shown in Table 1. Simulated molecules with chemical behavior and structure similar to the actual CWAs are usually used in experiments because CWAs are highly toxic. For example, diisopropylfluorophosphate (DFP) structurally resembles sarin (GB) and soman (GD), so it is usually the first choice for G-series simulators.²⁵ Monte Carlo experiments were used to simulate the adsorption efficiency of three simulants (DIMP, DIFP, DMMP) on sarin under selected MOFs conditions, among which DMMP showed the closest behaviour to the active agent, and it is the most simulated agent at present.²⁶ The use of a simulator can restore the experimental results under safe conditions, and also simplifies the operation steps of the experiment. At present, most of the research studies focus on the use of MOF materials to adsorb and detoxify the poisons of the G series and V series.

Table 1 Summary of CWAs

Types of poisons		Main representatives
Lethal type	Nervous	GA, GB, GD, VX
	Rotten	HD, Louis's agent
	Whole body poisoning	Hydrogen cyanide
	Asphyxiation	Phosgene
Non-lethal type	Incompetent	BZ
	Stimulating	CS, CR

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2.1 Adsorption of CWAs

Zirconium-based MOFs are widely used in the hydrolysis of simulants of nerve agents due to their robustness and the combination of Lewis acid and alkaline hydroxide residues in the center of Zr⁴⁺ to produce biomimetic phosphotriesterase activity.²⁷ The main forms of MOFs that adsorb CWAs are UiO-66, UiO-66-NH₂ and MOF-808.²⁸ The adsorption of CWAs is mainly to increase the active site or defect site of the surface by modifying the surface of MOFs, so as to increase the contact position with harmful gases to increase the adsorption capacity. Sujeong Lee et al. replaced 2,5-dihydroxy-1,4-benzendicarboxylic acid (DHBDC) with hydroxyl-deficient 1,4-benzenedicarboxylic acid (BDC) monomers to construct D-MOF-74, which exhibited effective and stable activity against CWAs mimics (Fig. 2(a)).²⁹ However, too many defect sites will affect the structural stability of the MOFs and cause the structure to collapse. Hong-Hyun Kim et al. prepared a novel UiO-66s with a size of 85 nm, and the reaction time of UiO-66s to DFP was effectively shortened by adjusting the particle size and defect density. The estimated t_1/21.34 h for achieving 2-CEES is the highest reported value of MOF under gas-phase reaction conditions.³⁰ The Fig. 2(b) presents the three Lewis acid sites with different Lewis acidities on UiO-66 and UiO-66s, which suggested the presence of μ₃-OH, -OH₂, and -OH sites. According to calculations, UiO-66s exhibits a higher Lewis acidity than UiO-66. However, the pore accessibility of materials can also vary greatly for specific topologies and surface functional groups. Catalytically induced multifunctional metal nodes at the molecular level can achieve a stable adsorption capacity in wet environments. Relevant studies³¹ have proved that the CWA loading across the MOFs can be effectively increased by adjusting the topology of MOFs which makes CWAs better enter the binding site and effectively improve the adsorption capacity. Ga-Young Cha et al. used a catalyst to form ionic frameworks by gas phase acid–base reactions, which promote the functionalization of hydroxyl species bridging Zr-nodes.³² Researchers demonstrated that triethylenediamine's (TEDA) behavior of selectively depositing μ₃-OH groups on Zr-nodes resulted in the excellent performance of MOF-808 in removing toxic chemicals in wet environments (Fig. 2(c)). The design achieves the excellent performance of MOF-808 to remove toxic chemicals in humid environments. Fig. 2(d) shows the free energy of T-MOF-808 to adsorb CNCl (CK) in a wet environment, and T-MOF-808 exhibits excellent thermodynamic stability. Table 2 summarizes the strategies associated with increasing the adsorption capacity of CWAs.

Fig. 2 (a) Schematic diagram of the synthesis of the defective DMOF-74²⁹ (reproduced with permission from ref. 29, copyright 2023 by The Royal Society of Chemistry), (b) chemical structure of UiO-66s with defect sites³⁰ (reproduced with permission from ref. 30, copyright 2021 by American Chemical Society), (c) schematic diagram of the behavior of the selective deposition of μ₃-OH groups by TEDA, and (d) free energy diagram of T-MOF-808 adsorbed CK (TEDA: orange and black lines and (HTEDA): blue line in humid conditions)³² (reproduced with permission from ref. 32, copyright 2020 Elsevier).

Table 2 Strategies to improve the protection capability of MOFs against CWAs

MOFs	Strategies	Performance	Ref.
D-MOF-74	Hydroxyl-deleted BDCs replaced DHBDCs	DMNP adsorption capacity is 708 mgDMNP gMOF^−1	29
UiO-66s	Controlled the particle size and defect density	Half-lives (t1/2) is 1.34 h against CEES	30
UiO-66/P(MEMA)	A novel polymeric buffer [P(MEMA)43]	t 1/2 is 7.7 min against MPO	33
T-MOF-808	TEDA modified MOF-808	CK adsorption capacity is 1.26 and 4.05 mmol g^−1 in dry and humid conditions	32
PVDF/Ti(OH4)/UiO-66	Created a TEA self-buffering system	t 1/2 is 35 min against GD	34
NU-1000-Cl	Functionalization of linkers	t 1/2 is 1.0 min and 25	35
		Min against CEES in UV LED and blue LED

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As an organic–inorganic hybrid material, MOFs combine the rigidity of inorganic materials with the flexibility of organic materials, and have great prospects for carbohydrate adsorption and decontamination. The unique chemical and thermal stability of zirconium-based MOFs and their functionalized analogues plays a key role in the efficient removal of CWAs and TICs. The surface modification (surface area/pore volume, connector functionalization, increase the active site/metal, site, etc.) of MOFs is widely used to improve the adsorption capacity of CWAs, which effectively broadens the application scenarios of MOFs.

2.2 Catalytic degradation of CWAs

CWA antidote materials should have two important properties: (1) have a certain adsorption capacity and (2) catalyze the degradation of toxic molecules into non-toxic or less toxic molecules. For the porous and reactive materials (MOFs), adsorption and degradation can take place simultaneously. After enhancing the adsorption capacity of MOFs for CWAs, strengthening the catalytic capacity of MOFs is an area of research development. Hydrolysis, dehydrohalogenation, and oxidation are the major routes to detoxification of CWAs. MOFs exhibit excellent catalytic activity in CWA hydrolysis, and the mechanism of hydrolysis of CWAs is mainly through the participation of free water³⁶ and the binding of a secondary building unit (SBU) to CWAs.³⁷ Understanding the properties of the target materials, designing specific MOFs, and applying appropriate functional modifications can further realize the catalytic degradation of CWAs by MOFs.³⁸

Wu et al. prepared MOF-808 by aqueous phase synthesis,³⁹ the results showed that MOF-808 can be used as a highly efficient catalyst for the degradation of high-concentration VX with t_1/2 < 0.5 min. However, for the hydrolysis of high-concentration GD, alkaline buffers are required to maintain the catalytic activity of MOF-808. But the use of small molecule volatile buffers not only contaminates the catalyst and causes it to become inactive, it also hinders its practical application. Kalinovskyy et al. used microblogging-assisted activation and removal of modulators from MOFs and examined the catalytic activity of activated MOFs on CWAs.⁴⁰ The hydrolysis rate of activated MOF-808 with a hydration node was higher than that of un-activated MOF-808, which further demonstrated that the catalytic degradation activity could be improved without buffer reagents. Jin et al. prepared a novel buffer that can enhance the catalytic activity and achieve reusability of MOFs (Fig. 3(a)).³³ The synthesized UiO-66 was used as a hydrolysis catalyst for CWAs and a catalyst system formed by P(MEMA) buffer to achieve complete destruction of MPO within 24 h in a wet environment (Fig. 4(a)).

Fig. 3 (a) Schematic diagram of the hydrolysis of MPO by UiO-66 under a catalyst system³³ (reproduced with permission from ref. 33, copyright 2023 by American Chemical Society), (b) schematic diagram of lithium alkoxide inserted into a zirconia cluster⁴¹ (reproduced with permission from ref. 41, copyright 2023 by Wiley), and (c) schematic diagram of photocatalytic oxidation of NU-1000 of a pyrene linker and MOFs of different excited states³⁵ (reproduced with permission from ref. 35, 2023 by American Chemical Society).

Fig. 4 (a) DFT-calculated SO₂ binding sites on DMOF-TM (the distances are given in Å)⁴² (reproduced with permission from ref. 42, copyright 2021 by Wiley), and (b) view of the hydrophobic drum-like Co₂₄U₆ cage⁴³ (reproduced with permission from ref. 43, copyright 2021 by Clarivate).

López-Maya et al. inserted lithium alkoxides into zirconia clusters which can improve the catalytic activity of phosphotriesterase to prepare a material for self-detoxifying CWAs (Fig. 3(b)).⁴¹ With the increase of active sites/or missing linker defects, the induction catalytic capacity of MOFs to CWAs continues to increase, and lithium alkoxides in UiO-66 improve the activity of phosphatase hydrolysis P–F, P–O and C–Cl, However, unlike the traditional reaction mechanism, dehydrohalogenation and oxidation are the main reaction routes of composite materials. But the rate of dehydrohalogenation and oxidation reaction is slow, and catalytic degradation is more difficult because HD is insoluble in water. In addition, the oxidation conditions are too harsh, making it easy to produce a mixture of equally toxic sulfoxide and sulfone products during the degradation process. Therefore, in recent years, photocatalytic oxidation has become an emerging pathway for MOF-catalyzed degradation of CWAs, which provides an opportunity for “soft” oxidation.^44,45 Ann et al. synthesized several different NU-1000 variants (MOF-R, R = –Cl, –NO₂, –CH₃) with functional groups located at the ortho or metasite of the carboxylic acids on the linker.³⁵ The linker of the ortho-substituent has a small pyrene twist angle, and the conjugation between the event rings enhances and promotes reactivity under blue light conditions. From Fig. 3(c), it can be seen that the pyrene linker structure in MOFs is excited into a singlet state under different catalytic light conditions, and is excited into a triplet state in the crossover system, and then interacts with the ground state triplet oxygen to produce active singlet oxygen.

Zr–MOFs is one of the most effective porous functional materials for catalyzing CWAs, and it has great expectations in achieving catalytic degradation of CWAs. Different synthesis strategies,⁴⁶ usage environments,⁴⁷ and functionalized materials⁴⁸ have been widely studied to improve the catalytic degradation of CWAs by MOFs. This study lays a foundation for the application of MOFs as adsorbents and catalysts for catalytic degradation of CWAs.

3. TICs

Toxic air pollutants generated by human activities, which are accompanied by serious problems such as global climate change, ozone depletion, acid rain and forest damage, are the key to environmental pollution. The adsorption material can be fine-tuned according to the different characteristics of the gases (Table 3) to improve capture ability. MOFs are some of the materials commonly used for the adsorption and separation of toxic gases, and the stability and reusability of MOFs can be realized by achieving coordination strength and metal bond strength, oxidation state of metal center, robustness of metal clusters, and mutual application of superconductors. A considerable number of research studies are devoted to modifying MOFs by controlling the aperture, increasing the functional group, and compounding with other materials to improve the adsorption capacity. This article summarizes the studies on the use of MOFs to adsorb TICs in recent years.

Table 3 Physical properties and toxicity of TICs

Gas	Kinetic diameter (pm)	Normal boiling point (K)	Dipole moment (D)	IDLH (ppm)
IDLH^49 represents a directly dangerous air concentration value for life or health.
Acetone	430	329.22	2.88	2500
NH3	290	239.82	1.4718	300
H2S	362.3	212.84	0.97	100
Methanol	362.6	337.69	1.69	6000
SO2	411.2	263	1.62	100
NO2	401–512	302.22	0.316	20
NO	349.2	121.38	0.15872	100
Toluene	525	383.79	0.375	500
H2O	264.1	373.13	1.8546	—

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3.1 Capture of SO_x

Sulfur oxides (SO_x) are one of the main atmospheric pollutants, among which SO₂ mainly comes from the combustion of sulfur-containing fuels. In an atmospheric environment, SO₂ will be oxidized into sulfuric acid fog or sulfate aerogel, becoming the precursor of acid rain. A large number of studies on the use of MOF materials to adsorb and remove SO₂ have become the focus. In this review, we will introduce the recent work of adsorption and removal of SO₂ from the atmospheric environment. Improving the affinity of MOFs for SO₂ under low pressure conditions is the key to achieving the large-capacity adsorption capacity of MOFs. Since SO₂ is corrosive, ensuring the chemical and thermal stability of the adsorbent is the basis for capturing toxic gases. The adsorption capacity of MOFs for SO₂ at 1 bar and 293 K is related to the specific surface area and pore volume, and independent of the surface micropores.⁵⁰ At the same time, the absorption of SO₂ was inversely proportional to the expansion of pores.⁵¹ The commonly used methods to improve the affinity of MOFs for SO₂ are: opening metal sites on MOF structures and using polar amino groups on MOFs as polar sites. For the absorption of low-pressure SO₂, it is theoretically believed that the pores in the range of 4–8 Å have a high affinity for SO₂. NH₂-MIL-53 (Al) is treated to be the material that shows the highest avidity for SO₂, while CTF-1 (600) and SAPO-34 are considered to be the materials with positive development prospects under wet conditions.^52–54 A study proved that a MOF composite nanostructure shows broad-spectrum removal activity for toxic gases with different chemical properties (acid gases, alkaline gases and nitrogen oxides).⁵⁵

To achieve high affinity for SO₂ at low pressure, the CB6@MIL-101-Cl composite structure was synthesized by wet impregnation and ligand exchange method, and CB6@MIL-101-Cl almost completely retained its crystallinity and porosity under exposure to dry and wet SO₂, exhibiting the capture of high-capacity SO₂ under low pressure conditions.⁵⁶ In addition, Zhang et al. introduced aliphatic amines into MOFs to achieve reversible and durable capture of SO₂.⁵⁷ Compared with MIL-101(Cr), the SO₂ adsorption site in the mmen-MIL-101(Cr) is transferred from Cr to the N atom.

The dipole interaction and hydrogen bonding between N atoms and S (SO₂) atoms improve the adsorption of SO₂ at low pressure. Mmen-MIL101(Cr) exhibits excellent gas adsorption performance and high cycling stability, and shows that aliphatic amine modification strategies can effectively improve the effective capture performance of MOFs for SO₂. Xing et al. used a pre-synthetic pore environment customization strategy to improve the affinity for SO₂ under low pressure by controlling the methyl density of stable isomorphic methyl functionalized MOFs⁴² (Fig. 4(a)). The increase in spatial resistance and hydrophobicity improves the stability of DMOFs to SO₂. Researchers have proved that the presence of H₂O will reduce the adsorption capacity of SO₂, and the high stability of MOF when exposed to air, immersed in distilled water and even boiling water further promotes the practicability of MOF (e.g., CAU-10 and InOF-1).^58,59 At the same time, in addition to pressure, the temperature in the atmospheric environment is also an important factor affecting gas adsorption. The MOF-type Mg₂(dobpdc) exhibits high SO₂ capture and high chemical stability to dry and wet SO₂, and it has excellent cycling properties and is easy to regenerate.⁶⁰ Fan et al. prepared a drum-shaped nanocage templated from a propyl molten imidazolic acid dicarboxylic acid ligand.⁴³ The MOFs of the nanocage exhibit high thermal and chemical stability in water and weakly acidic/alkaline solutions, as well as excellent hydrophobicity. Fig. 4(b) presents the nanocage structure, which is rich in open metal sites for transition metal ions and actinides, resulting in stronger coordination with SO₂.

3.2 Capture of NH₃

Ammonia (NH₃) is a colorless gas with a strong pungent smell, which is weakly alkaline. When the concentration of ammonia reaches 500 mg m⁻³, it can cause skin burns, mucous membranes of the eyes and respiratory organs, and prolonged inhalation can even lead to swelling and death of the lungs. NH₃ mainly comes from electronics, food, chemicals, and liquid NH₃ manufacturing processes. Commonly used materials including activated carbon, zeolite, and MOFs have shown potential for NH₃ adsorption, but the progressive properties of NH₃ absorption remain a challenging problem. Among them, there has been a great deal of interest in the adsorption of NH₃ by selecting appropriate modification strategies for building blocks or objective functions to create customized binding sites.^61–63 The unique microporous composition of the high pore framework enhances the physical adsorption, and the chemisorption type achieved by the interaction of the effective functional groups in the porous structure with NH₃ is an important component of the high-efficiency adsorbent. By exploring the effect of MOFs on toxic gases, it was found that the existence of electronic structures of metal ions and active sites was the main influencing factor for NH₃ adsorption.⁶⁴ Wang et al. proposed a MOF multi-site ligand screening strategy for efficient and reversible adsorption of NH₃.⁶² The abundant active sites in the MOF structure enhance the interaction of hydrogen bonds between Fe-NU-1000, which is the basis for large-capacity adsorption and excellent reversibility (Fig. 5(a)). A direct and effective guest incorporation strategy was used to prepare metal chloride functionalized MOFs at room temperature.⁶⁵ Through the synergistic effect of multiple and open metal sites, the adsorption and selective separation of NH₃ in universities were realized (Fig. 5(b)). Li et al. used the gas intermediate reaming strategy to prepare MOF-derived catalysts, which realized a large and uniform diffusion of metal substances into the MOF pores, and the synthesized catalysts showed excellent catalytic performance of low-temperature NH₃-SCR. On this basis, it is also a major research direction to use cheap, easily available, low-toxic/non-toxic ligands and different solvents to build MOFs to achieve efficient adsorption of NH₃.

Fig. 5 (a) Schematic diagram of a multi-site ligand screening strategy⁶² (reproduced with permission from ref. 62, copyright 2021 by American Chemical Society), and (b) capture and selective separation of NH₃ by metal-functionalized MOF-253 (Al)⁶⁵ (reproduced with permission from ref. 65, copyright 2023 by Elsevier).

3.3 Capture of H₂S

Hydrogen sulfide (H₂S) is a colorless, highly toxic, low concentration with the smell of rotten eggs, soluble in water, flammable toxic gas. It is usually found in natural gas, oil and biogas. Even at very low concentrations (300 ppm) it can be extremely harmful to human health, deactivate catalysts and corrode equipment. MOFs with certain structural flexibility have become the materials for the current efficient adsorption of compounds^66–68 (Table 4). Further progress has been made in the adsorption of H₂S gas by copper-based,⁶⁹ iron-based⁷⁰ and bimetal-based^71,72 MOF materials under exploratory environmental conditions. MOF-199 is a copper-based, microporous MOF that is commonly used in gas separation, storage, and capture, and is one of the most studied MOFs. In the process of thermal conversion of MOF-199 particles to CuO nanoparticles, the adsorption of H₂S gas under environmental conditions is realized, and an alternative green method is proposed for the secondary use of depleted adsorbent materials.⁷³ Polyvinylpyrrolidone was used as a coordination agent, nucleating agent and template agent to synthesize small-crystalline porous MOF-199 in an aqueous system through PVP regulation.⁷⁴ The adsorption of H₂S is a weak coordination and physical interaction, which makes MOF-199 maintain its intact structure even after desulfurization and has a good reversible adsorption ability. The small crystalline size leads to the exposure of the active site, and the layered porous structure improves the diffusion of H₂S. This structural strategy provides a new research direction for the adsorption of sulfides (Fig. 6(a)). It is a common method to improve the performance by controlling the crystal structure of MOFs or the morphological structure of composite materials. The core/shell nanostructures of the novel Sc-MOF@SiO₂ were synthesized under mild conditions using ultrasound-assisted microwave pathways.⁷⁵ This unique sandwich core–shell structure exhibits high hydrogen sulfide reduction and stability in the application. For example, the high specific surface area is 3700 m² g⁻¹, the porosity is greater than 2 nm, and the high stability of 328 °C can be achieved. In addition, the COF layer co-modified the sandwich structure composite with SiO₂ nanospheres fixed inside and iron oxide nanoparticles coated outside.⁷⁶ The core–shell structure exhibits high H₂S reduction performance and application stability (Fig. 6(b)). The structure of metal oxide nanoparticles sandwiched between a MOF and materials with specific morphologies has good prospects in the field of H₂S adsorption and photocatalysis.

Table 4 A summary of MOFs and their derivatives to remove H₂S

MOFs	Uptake (mg g^−1)	Flow rate (mL min^−1)	C o (ppm)	Ref.
Cu(BDC)0.5(BDC-NH2)0.5	128.4	100	500	69
NaCoxOy	168.2	100	500	72
a-Fe2O3	36.2	300	500	70
Ag–Cu-trimesate MOF	69.7	200	500	71
MOF-199	77.1	200	500	73
MOF-199-P2	74.3	100	700	74

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Fig. 6 (a) Schematic diagram of the synthesis of hierarchical porous MOF-199⁷⁴ (reproduced with permission from ref. 74, copyright 2022 by Elsevier), and (b) SiO₂@α-Fe₂O₃@COF core–shell structured photocatalysts⁷⁶ (reproduced with permission from ref. 76, copyright 2023 by Elsevier).

In order to achieve efficient conversion of H₂S to polysulfides, the selectivity of MOF provides a new perspective. Due to the nature of the accessible metal sites, the polysulfide pathway mechanisms may exhibit different properties: open metal sites or semi-(non-permanent) sites,⁷⁷i.e. for some MOFs, the metal connection bond is highly dynamic. We believe that controlling and regulating the thin balance between dynamic metal linker binding and MOF instability through different external stimuli (e.g., temperature and molecular inclusion) is one of the most relevant challenges for the scientific community across multiple disciplines to improve and develop new and exciting applications.⁷⁸ The in situ conversion of H₂S to polysulfides within MOF micropores is an exciting new strategy that holds great promise for the permanent sequestration of toxic H₂S for the involvement of novel sulfur battery electrodes. Experimentally, SU-101 was used in a lithium–sulfur battery to attract H₂S to spontaneously convert to polysulfide at room temperature and pressure, independently of maintaining the crystal structure of the frame.⁷⁹ This approach is a promising candidate for the implementation of toxic waste valorization strategies and subsequent applications in electrochemical energy storage applications.

3.4 Capture of NO_x

Nitrogen oxides (NO_x) mainly come from the combustion of fossil raw materials, the production and use of nitric acid etc. They are an important cause of acid rain and photochemical smog, and bring great harm to human life and the environment. Common nitrogen oxides include nitrogen dioxide (NO₂), nitric oxide (NO), nitrous oxide (N₂O), nitrous oxide trioxide (N₂O₃), etc. At present, the main treatment method of nitrogen oxides is the selective catalytic reduction (SCR) method, which refers to the chemical reaction of reducing agents (NH₃, urea, alkanes, etc.) with nitrogen oxides to form nitrogen and water. This method has the advantages of less secondary pollution and high purification efficiency. There are two reaction mechanisms of SCR: one is Langmuir–Hinshelwood (L–H), which means that NH₃ reacts with NO_x adsorbed at the same or adjacent active site; the other is Eley–Rideal (E–R), which refers to the reaction of adsorbed NH₃ reacting with NO_x in the air. According to the commonly used forms of MOF adsorption NO_x materials, they can be divided into monometallic, bimetallic and MOF-derived materials. At low temperatures, the catalyst generally has shortcomings such as poor activity, sulfur resistance and water resistance. Therefore, the development of SCR catalysts with strong low temperature and sulfur resistance has always been a research hotspot.^80–83

3.4.1 Monometallic MOFs as NO_x SCR catalysts. SCR includes a wide range of methods for nitrogen oxide conversion, but the commonly used catalysts have disadvantages such as high toxicity, poor stability, high cost, and complex production. The abundant and ordered porosity and controllable active sites of MOFs have made it a new application in the field of gas molecule transformation. Based on iron-based MOFs, a single-atom Fe-modified n-doped carbon catalyst (Fe₁–N₄-c) with abundant Fe₁–N₄ positions was developed for the oxidation of NO and SO₂.⁸⁴ The catalyst has rich sites for the oxidation of NO. Relative research shows that it has ultra-high catalytic activity and strong sulfur resistance at low and room temperature. This work not only effectively realizes the catalytic reduction of a variety of pollutants, but also provides a direction for practical application. The introduction of amines in the MOFs structure is able to increase the OMS of the surface, which are beneficial for the removal of toxic gases under dry conditions. Ebrahim et al. synthesized amine-modified copper-based MOFs (CuBTC) with different surface chemical and structural characteristics using melamine and urea as amine sources.⁸⁵ The addition of melamine prevents the growth of crystals. Whereas, urea addition maintains the octahedral shape of the parent body and has more pore sizes (Fig. 7(a)). The urea-modified samples exhibited good NO₂ adsorption performance in a humid environment, but the reactivity and physical properties of the melamine-modified samples provided a favorable environment for H₂S removal. However, the results show that neither the changes in temperature can overcome the shortcomings of poor thermal stability of MOFs in the field of denitrification. A series of manganese-containing MOFs nanorods were prepared by a solvothermal method and two-stage calcination method.⁸⁶ The abundant oxygen vacancies, unique hierarchical porous structure and semi-metallic properties in the nanorods successfully overcome the shortcomings of the poor SO₂ resistance of manganese-based catalysts, and SO₂ also promotes the reaction of NH₃ at the B acid site, thereby improving the regeneration ability of the catalyst. The in situ drift method was used to study the reaction of E–R and L–H, and it was found that both B and L acid sites were involved in the reaction (Fig. 7(b)). Gopalsamy et al. systematically evaluated the NO_x adsorption performance of caged UiO-66 nanoporous MOFs functionalized by metal(II) catecholate CatM(II) at very low concentrations (ppm-ppb level).⁸⁷ The calculation shows that the reaction mechanism of the two NO_x SCRs of UiO-66-CatFe(II) also has excellent capture effects.

Fig. 7 (a) Reactive adsorption pathways of amine-modified MOFs⁸⁵ (reproduced with permission from ref. 85, copyright 2022 by Elsevier), and (b) reaction mechanisms of Mn-BTC, including E–R (a) and L–H (b) mechanisms (blue and red represent different pathways for standard and fast SCR reactions, respectively)⁸⁶ (reproduced with permission from ref. 86, copyright 2023 by American Chemical Society).

3.4.2 Bimetallic MOFs as NO_x SCR catalysts. Reducibility, acid sites, and the synergistic interaction between the two are important influencing factors of NO_x and have been extensively studied in a series of SCR reactions. The bimetallic MOF catalyst prepared by simple solvothermal method and two-stage calcination treatment is suitable for catalytic reduction reactions.⁸⁸ By adjusting the ratio of Fe and Mn, the pore structure and specific surface area of the catalyst were changed, and the synergistic effect of the difference in charge transport caused by the difference in electronegativity between metal particles was improved. Similarly, by pyrolysis of similar MOF-74 containing Fe and Mn and immobilized on carbon nanotubes (CNTs), the prepared catalyst has higher sulfur and water resistance under the conditions of selective reduction of NO_x in water vapor at high SO₂ concentration and low temperature.⁸⁹ The advanced scholars used the hydrothermal method to synthesize the MOF catalyst to study the effect of doped Ti cation as a catalyst to catalyze the performance of nitrogen oxides under synergistic action (Fig. 8).⁹⁰ Ti cations enhance the bimetallic interaction with Ce metal and accelerate the oxygen mobility. At the same time, the concentration and activity of Ce³⁺ were reduced to balance and regulate the synergistic catalytic reaction and enhance the strength of Lewis acid, which improved the reactivity of the catalyst. Zhang et al. applied CO selective catalytic reduction of NO (CO-SCR) through the synthetic modification method with a Ag_x–Ni–MOF-7 catalyst.⁹¹ The addition of Ag is beneficial to enrich the active sites of the catalyst and improve the rate of catalysis and transmission. Compared with monometallic catalysts, bimetallic catalysts have better low-temperature CO-SCR.

Fig. 8 Mechanism of synergistic removal of NOx by catalysts⁹⁰ (reproduced with permission from ref. 90, copyright 2023 by Elsevier).

3.4.3 MOF-derived NO_x SCR catalysts. The catalysts derived from MOFs have been proven to increase the specific surface area and enhance the catalytic activity, which has wide application in the field of NH₃-SCR. Yang et al. prepared CuO_x/C catalysts by calcination on the basis of the synthesis of MOFs at room temperature. The CuO_x/C catalyst has both CuO and Cu₂O crystal phase structures at different roasting times and temperatures. Furthermore, the increase in temperature gradually reduces the Cu₂O crystal phase, then an appropriate amount of Cu⁺ and Cu²⁺ coexist to form electron pairs, thereby improving the denitrification activity of the catalyst. Du et al. synthesized MnTi–MOF by solvent thermal method and evaluated the derived MnTi-I catalyst in NH₃-SCR. The MnTi-I catalyst shows excellent catalytic performance and anti-SO₂ performance. The high specific surface area and skeleton structure of the MOF precursors make the active site of the catalyst more dispersed.

4. MOF–textile composites

From the above, it can be seen that the unique pore structure and superior adsorption performance of MOFs have been widely studied in CWAs and TICs. However, due to the fact that MOFs mostly exist in the form of powders, their practical application is limited. The combination of MOFs and textile materials is an effective way to expand the application of MOFs. The synergistic effect between composites and textiles is regulated at the molecular structure scale, and the comprehensive properties of composites at the macroscopic level are affected. At present, a common strategy for the integration of MOFs and textiles is in situ growth and covalent modification for interfacial binding. Electrospinning,⁴¹ hot pressing,⁹² inkjet printing⁹³ and other methods are used to achieve the composite of performance; alternatively, solvothermal synthesis⁹⁴ and coating⁹⁵ can be used to directly enhance the interfacial synthesis strength. It is commonly used to realize interlayer interactions, including hydrogen bond interaction, electrostatic interaction, coordination interaction, etc. The integration of MOFs into textiles enables the preparation of MOF-based solid catalysts for practical protection applications such as CWAs and TICs catalytic adsorption. Although MOF–textile composites show promise for adsorption and degradation of toxic and harmful gases under relevant conditions, it is critical to optimize the preparation of these composites for maximum catalytic activity, capture capacity, and overall protection.

Ru et al. used a combination of electrospinning, in situ growth, and carbonization as a Zn_xCo_3−xO₄/carbon nanofiber (CNF) adsorbent (Fig. 9(a)).⁹⁶ The Zn_xCo_3−xO₄ nanoparticles derived from the MOFs were uniformly loaded on the carbon nanofibers, which effectively exceeded the sulfur adsorption capacity (12.4 g S/100 g) and the good utilization rate of active components (83.2%). The synergistic effect of the layered structure and wide distribution of nanoparticles on the fiber surface not only produces oxide nuclei, but also forms a carbon grid on the surface to achieve physical isolation and avoid oxide aggregation. Chemical protection relies on two possible and complementary processes, namely adsorption and/or decontamination of CWAs.⁹⁷ Therefore, a lightweight and multi-functional hybrid film was prepared in macroporous nonwovens by electrospinning/electrospray technology, which also used nanofiber and MOF particles as the matrix, which has outstanding performance in the physical screening of particulate matter and the capture of toxic gases (NH₃, H₂S).⁹⁸ The bifunctional personal protective equipment (PPE) manufacturing route proposed in the study that can be scaled and directly processed; as well as the optimal structure establishment of the MOFs and CNF hybrid platform, it provides a development direction for the comfort and multi-functionality of personal protection. There are related problems in the preparation of MOF–textile composites prepared by a mixing method and in situ growth: (1) MOFs are adhered or encapsulated in polymers during the molding process, and (2) MOFs have poor dispersion in emulsions, and the pores are easily blocked. Schwotzer et al. successfully synthesized a two-dimensional MOF material assembled into a carpet-like structure by interfacial synthesis.⁹⁹ The two-dimensional independent mesostructure layer provides a large number of surface-exposed open metal sites for chemical adsorption of porous materials, which significantly improves the adsorption capacity of H₂S. In order to further avoid the problems of inhomogeneity and low loading of composites prepared by a one-step in situ growth method, Lan et al. used a layer-by-layer immersion (LBL) growth method to achieve high-density uniform growth of MOFs on polyamide–polyethylenimine (PA–PEI) substrates (Fig. 9(b)).¹⁰⁰ Among them, the hierarchical pore structure and the formation of multi-position hydrogen bond interactions that are conducive to adsorption and mass transfer of composites have laid the foundation for efficient adsorption of NH₃.

Fig. 9 (a) The mechanism diagram of Zn_xCo_3−xO₄/carbon nanofiber adsorbent⁹⁶ (reproduced with permission from ref. 96, copyright 2022 by American Chemical Society); (b) the mechanism diagram of PA-PEI-MOF-303(Al) composites¹⁰⁰ (reproduced with permission from ref. 100, copyright 2023 by the authors).

The comprehensive tunable properties and intrinsic porosity of conductive MOFs make them promising materials for electrical signal transduction and toxic gas detection. In order to achieve effective device integration, two criteria must be met: (i) effective contact between the chemical resistance material and the electrode; and (ii) a reliable charge permeation path through the device.¹⁰¹ Therefore, the development of effective and scalable methods for the integration of MOFs into electronic devices is essential for the effective monitoring of toxic gases. The mixture of MOFs and graphite is generated using a solvent-free ball milling program that is integrated into the device to produce a functional sensor. An array of chemical resistors consisting of four conductive MOFs is capable of effectively detecting and differentiating NH₃, H₂S, and NO at parts per million concentrations (Fig. 10(a)). Using this method, the selectivity of low-conductivity MOFs for the desired analyte at parts per million and parts per thousand concentrations can be quickly demonstrated.¹⁰² However, this method is limited to the detection limits of analytes and is currently not comparable to the detection limits of chemical resistors using materials such as metal oxides and conductive polymers. Mirica et al. used simple molecular building blocks to integrate conductive two-dimensional (2D) MOFs into fabrics to prepare e-textiles. These e-textiles offer reliable electrical conductivity, enhanced porosity, flexibility, and washability stability. Fig. 10(b) shows how the textile self-organizing framework (SOFT) device can detect and distinguish important gaseous analytes (NO, H₂S, and H₂O) at ppm levels and maintain their chemical resistance capabilities at humidity (5000 ppm, 18% RH). In addition to sensing, these devices are capable of capturing and filtering analytes (Fig. 10(c)), enabling real-time gas detection in wearable systems of electronically accessible adsorption layers in protective equipment.¹⁰³ A new gentle, robust, and rapid oxidative recombination method directly reconstructs Cu₀ features into MOFs with multifunctional properties, and then integrates Cu₃(HHTP)₂ MOFs into flexible porous substrates as electronic textile sensors.¹⁰⁴ Oxidative remodeling as a means to install conductive MOF materials at the fiber level (Fig. 10(d)) effectively realizes the selectivity and sensitivity of copper-based MOF e-textiles for simultaneous detection and detoxification of toxic gases. MOF provides filtration and detoxification capabilities, as well as real-time chemical testing, paving the way for the next generation of personal protection systems.

Fig. 10 (a) Sensing performance of M₃HHTP₂/graphite blends as chemiresistors when exposed to gaseous analytes, and statistical analysis of the sensing response¹⁰² (reproduced with permission from ref. 102 copyright 2017 by the authors), (b) breakthrough studies for the simultaneous detection and capture of analytes and (c) breakthrough studies for the simultaneous detection and capture of analytes¹⁰³ (reproduced with permission from ref. 103 copyright 2017 by the American Chemical Society). (d) Proposed mechanism of oxidative restructuring of Cu⁰ metal into a Cu₃(HHTP)₂ MOF¹⁰⁴ (reproduced with permission from ref. 104, copyright 2022 by the authors).

5. Mechanism

The unique adsorption behavior of MOFs is explained by the fact that the heterogeneous surface of MOFs consists of hydrophilic (SBUs) and hydrophobic (linker) regions, resulting in the so-called “bridging effect”.¹⁰⁵ The intrinsic properties of MOF can be adapted through the design of organic linkers, the creation of open inorganic sites, and/or post-synthesis modifications (PSMs) to achieve chemical and physical transformation of the MOF backbone to enhance the interaction between the backbone and the adsorbate.¹⁰⁶ Cheng et al. prepared a unique ZIF-67-on-InOF-1 heterostructure by growing secondary Co-based ZIF-67 on initial InOF-1 nanorods¹⁰⁷ (Fig. 11(a)). The abundant heterogeneous interfaces expose the active sites that enable the composites to produce rapid electron transfer under light irradiation, thus endowing the structure with excellent photocatalytic activity. In addition, the study shows that the rational design of the heterostructure gives full play to the synergistic effect between different components (Fig. 11(b)), which paves the way for the rational design and structural control of MOF precursors and their derivatives as efficient and durable catalysts in pollutant degradation, water splitting, fuel cell and other applications. Qian et al. synthesized a MOF with a chiral 4₁In(OH)(CO₂)₂ helix chain under solvothermal conditions, which used hydroxide anion as a bridging ligand and BPTC⁴⁻ ligand to the In(III) center to form a rare chiral 4₁In((OH)(CO)₂)₂ helical chain, which cooperated with a carboxylate ligand to produce a microporous InOF-1 with a cylindrical channel.⁵⁹ MOF maintains a high degree of structural stability at a certain humidity and even in boiling water, while having excellent gas selectivity and adsorption capacity. It further lays a foundation for MOFs as a substitute for gas adsorption in special environments.

Fig. 11 (a) Stepwise fabrication of MOF-on-MOF-derived hollow bimetallic photocatalyst H-Co₃O₄/In₂O₃ for the CO₂RR, (b) diagram of inorganic SBUs and organic linkers¹⁰⁷ (reproduced with permission from ref. 107 copyright 2023 by the authors), (c) scheme for the dip-coating process¹⁰⁸ (reproduced with permission from ref. 108 copyright 2024 by American Chemical Society), and (d) schematic of PCN-222-PP fiber composite and its functional performance for catalytic degradation of chemical warfare agents, including phosphonate hydrolysis and thioether partial oxidation¹⁰⁹ (reproduced with permission from ref. 109 copyright 2020 by Wiley).

The chemistry and structure of textile materials are key design considerations in the formation of MOF textile composites. The polymer composition of textiles affects the self-assembly of MOFs on the textile surface by forming covalent interactions between molecules (e.g., hydrogen bonds, van der Waals interactions, electrostatic interactions).¹¹⁰ The latest innovations in filtration and decontamination applications of MOF–textile composites are mainly focused on gaseous threatening agents or liquid-phase contaminants. Saptasree et al. developed an industrially feasible dip coating process in which multiple MOFs are incorporated into a single flexible textile fiber matrix.¹⁰⁸ This method provides composites with the flexibility of heterogeneous catalysis, chemical sensing, adsorption of toxic gases, and in addition, composites have been shown to provide an excellent barrier to CWAs (including the nerve agents GD and VX) as well as the blowing agent HD, with the ability to destroy these highly toxic compounds (Fig. 11(c)). Studies have shown that the introduction of hydrogen bonding donors can stabilize the transition of sulfoxide intermediates and thus improve the selectivity of sulfoxide.¹¹¹ Catalytic metal–organic framework/polymer textile composites using simple template-free low-temperature synthesis of unfolded structures.¹⁰⁹ The composites show rapid hydrolysis and oxidation of multiple reactive chemical warfare agents GD and HD and their mimics due to the oxidation of the active metal node sites that significantly improves the visible GD hydrolytic photoactivation (Fig. 11(d)), while at the same time confirming that the MOF-fabric is as effective or better at degrading than similar MOF powders in terms of agent degradation, especially in terms of oxidation. This strategy provides a promising new scheme for high-level protective military uniforms and other personal protective equipment.

6. Summary and outlook

In summary, this paper reviews the latest progress in the adsorption and elimination of toxic and harmful substances in MOFs and MOF textile composites. MOFs have proven to be the strongest material for the adsorption of harmful gases, with an inexhaustible environmental adsorption capacity. At the same time, MOF textile composites are also widely used in the field of personal protection. Over the past few years, the study of MOFs has become more and more in-depth, indicating that there is a strong interest in this field from the scientific community. Here, we highlight the adsorption and catalytic degradation mechanisms of CWAs by MOFs, as well as extensive studies on the adsorption of TIC gases, and conclude with a summary that materials using MOF-based properties exhibit higher porosity, specific surface area, and adsorption capacity in terms of harmful gas adsorption, while MOFs have been shown to outperform other materials. MOF textile composites show high functionality and cycle durability in the field of personal protection, and have a broad application space in the field of personal protection. The author firmly believes that MOFs occupy a dominant position in the adsorption of harmful gases, because they are superior to other adsorbents in adsorption, removal of toxic and harmful gases, functionality, etc., and MOF–textile composite materials have a wide range of applications in the field of chemical protection, and the following aspects need special attention.

Strategies such as increasing active sites/defect sites, topology, and building units are often used to modify MOFs to achieve efficient adsorption and catalytic degradation of CWAs and TICs. Through the micro-regulation of MOF structure, the stability of macrostructure and the protection performance against toxic and harmful substances are improved.¹¹² Realizing the instantaneous detoxification of CWAs and the efficient adsorption of TICs are the focus of current research,^113,114 and in the future, MOF adsorbents should focus on the recycling¹¹⁵ and stable recovery of materials under the premise of achieving efficient catalytic adsorption. In addition, it is the goal of research to promote the industrialization process of MOFs for toxic and harmful substances.

Secondly, the existence form of MOFs is mainly powdered. Due to low load, insufficient load stability and low actual washing durability, MOFs cannot be popularized. Effective integration of MOF particles into fibers or textiles is conducive to promoting the practical application in PPEs.^98,116–118 In addition, when choosing MOF adsorbents for use in individual protective equipment, attention should be paid to the problem of desorption in practical applications to prevent secondary pollution and greater harm. Intelligent protective clothing with high adsorption capacity,^119,120 excellent cycling stability and integrated self-detoxification function is also a potential application for MOFs.

Finally, the current literature ignores the problem of the cost of MOF synthesis.^121,122 The actual estimated production cost is less than US$ 10 k per ton.¹²³ However, this cost estimate is overly optimistic, as the reference price for activated carbon is only US$ 1.44 k per ton.¹²⁴ The current cost of producing MOF-5, MOF-177 and MOF-210 is estimated at US$ 200 k per ton, US$ 130 M per ton and US$ 200 M per ton. Therefore, the excessively high cost price makes it difficult to promote the industrial application of MOFs.

In addition, many new MOF-based adsorbents must still be developed to provide lasting research interest for current and future applications. The application of MOF–textile composites can provide more comprehensive protection for the personnel involved. With continuous development, MOFs are recognized as a viable alternative in the field of gas adsorption. They have a promising future in the field of gas adsorption of CWAs and TICs, and composite materials provide strong support in the field of chemical protection.

The development and application of this new material will be fascinating in the coming years.

Author contributions

Junmei Li: conceptualization, investigation, visualization, writing – original draft. Yinan Fan, Ruigan Zhang, Demao Ban, Zhixuan Duan and Xiaoyuan Liu: visualization, writing – review & editing. Lifang Liu: project administration, supervision, writing – review & editing.

Data availability

Data sharing is not applicable to this article as no new data were created or analyzed in this study.

Conflicts of interest

There are no conflicts to declare.

Acknowledgements

The work was supported by the “National Key R&D Program of China (2023YFC3011603)”, the “Taishan Industrial Experts Program (TSCX202306163)” and the “Technical Standard Project of Shanghai Science and Technology Innovation Action Plan (22DZ2201400)”.

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Footnote

† These authors contributed to the work equally.

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