MOF-Composites for adsorption and degradation of contaminants in wastewater

Javier Aguila-Rosas ^ab, Francisco J. Cano ^a, Alan Nagaya ^a, Carlos T. Quirino-Barreda ^b, Ma. de Jesús Martínez Ortiz ^c, Ariel Guzmán Vargas *^c, Ilich A. Ibarra *^a and Enrique Lima *^a
aLaboratorio de Fisicoquímica y Reactividad de Superficies (LaFReS), Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Circuito Exterior s/n, CU, Del. Coyoacán, 04510, Ciudad de México, Mexico. E-mail: lima@iim.unam.mx; Fax: +52-55-5622-4595
^bLaboratorio de Farmacia Molecular y liberación controlada, Universidad Autónoma Metropolitana-Xochimilco, Calzada del Hueso 1100, Col. Villa Quietud, C.P. 04960, CDMX, Mexico
^cESIQIE-IPN, Departamento de Ingeniería Química, Laboratorio de Investigacion en Materiales Porosos, Catalisis Ambiental y Quimica Fina, México, DF 07738, UPALM Edif.7 P.B. Zacatenco, Mexico

First published on 11th July 2025

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1. Introduction

Growing concerns about water pollution have driven the development of innovative technologies for wastewater remediation.^1,2 Among these technologies, metal–organic frameworks (MOFs) have emerged as promising materials due to their high surface area, tuneable porosity, and versatile functionalization.³ A MOF composite is formed by integrating functional materials such as polymers, nanoparticles, or biomolecules into its metal–organic structure to improve its stability, selectivity, and adsorbent or catalytic capacity.⁴ These materials offer effective solutions for the adsorption and degradation of various contaminants in wastewater, including pharmaceuticals, dyes, and heavy metals. Furthermore, their application in biosensors for contaminant detection and their potential for industrial production open new perspectives in water treatment.

MOF composites have established themselves as an innovative and versatile solution for wastewater treatment, standing out for their ability to adsorb and degrade a wide range of persistent and toxic pollutants.⁵ In the case of pharmaceuticals, such as antibiotics, analgesics, and hormones, these materials offer efficient adsorption thanks to their porous structure and high affinity for organic compounds. Similarly, functionalized MOFs have demonstrated remarkable capture efficacy against contamination by synthetic dyes such as methylene blue and methyl orange.^6,7 Furthermore, their architecture allows them to trap highly hazardous heavy metals, such as Pb²⁺, Cd²⁺, Hg²⁺, and As³⁺, with high capacity and selectivity.^8,9 Beyond adsorption, these materials also participate in advanced oxidation processes, generating radicals such as sulfate (SO₄˙⁻) and hydroxyl (˙OH), which break down complex organic pollutants into less harmful byproducts.¹⁰ In parallel, they have been used in the development of biosensors for the selective and ultrasensitive detection of pollutants, taking advantage of their fluorescent and conductive properties to identify metal ions such as Cd²⁺ and Hg²⁺,¹¹ which reinforces their value as a comprehensive tool for environmental monitoring and remediation.

In this paper, we present a review focused on the most recent advances in the use of compounds metal–organic frameworks (MOF-composites) for the adsorption and degradation of contaminants in wastewater. This emerging technology has demonstrated great potential for the efficient removal of various contaminants, which we will address, as well as for advanced chemical processes for contaminant detection using biosensors. Our objective is to provide an updated and critical overview of their applicability, efficacy, and potential for industrial scaling, highlighting their relevance for more sustainable and effective water treatment.

2. Main contaminants in wastewater

Wastewater, generated by domestic, industrial, and agricultural activities, contains a complex mix of pollutants that pose significant risks to human health, aquatic ecosystems, and the environment in general^12,13 (Fig. 1). Among the main pollutants are pharmaceuticals, considered emerging due to their persistence and adverse effects, such as endocrine disruption in aquatic organisms and the generation of bacterial resistance; antibiotics, analgesics, hormones, and antidepressants have been detected in water bodies even at very low concentrations.¹⁴ Synthetic dyes, used in the textile, leather, and food industries, are also persistent and toxic, and their resistance to biodegradation makes conventional treatment difficult.¹⁵ Heavy metals such as lead, mercury, cadmium, and arsenic, from mining and the chemical industry, are highly toxic even in small quantities, accumulating in living beings and entering the food chain, requiring specific processes such as adsorption or bioremediation for their removal.¹⁶ Likewise, the excessive presence of nutrients such as nitrogen and phosphorus, derived primarily from agricultural activity, causes eutrophication, generating dead zones due to the loss of dissolved oxygen.¹⁷ Furthermore, industrial wastewater also includes a wide variety of toxic chemicals such as solvents, pesticides, and organochlorine compounds from the petrochemical, pharmaceutical, and agrochemical sectors, which are difficult to treat and have long-lasting effects.¹⁸ Finally, industries such as nuclear and mining can discharge radioactive substances into aquatic environments, posing serious threats to both the environment and public health by contaminating drinking water sources and affecting nearby communities.¹⁹ All of this underscores the need to update and strengthen wastewater treatment and remediation strategies through more comprehensive approaches and advanced technologies.

The use of micro and nanotechnology in adsorbent materials such as graphene and zeolites has improved the capture of specific contaminants, including pharmaceuticals and heavy metals. However, a technology called MOF is also being incorporated for real-time monitoring and intelligent control systems that optimize treatment based on water conditions. This technology, combined with the combination of other materials, not only improves the quality of treated water but also contributes to sustainable development, allowing its reuse in irrigation and industry in some cases.

3. Characteristics of MOF-composites: advantages and opportunities

MOF composites represent a versatile and powerful platform for a wide range of scientific and industrial applications. Their capacity for custom structural design, high porosity, and functionalization make them unique materials with clear advantages over conventional technologies. As technical barriers are overcome, these materials are expected to play a key role in sustainable development, energy transition, and environmental protection.⁵

Materials of MOFs combined with other compounds, whether organic, inorganic, or biological, to create materials with improved or completely new properties. They leverage the porosity, chemical functionality, and ordered structure of MOFs, along with the complementary properties of the second component, such as conductivity, thermal stability, or catalytic activity.^20,21

MOF composites are typically synthesized through diverse methodologies such as solvothermal, microwave-assisted, sonochemical, and mechanochemical routes,^11,22,23 the latter offering the additional benefit of solvent-free fabrication.²⁴ These techniques afford precise control over morphology, crystallinity, and pore architecture. Furthermore, post-synthetic modification (PSM)—including ligand exchange, metal node substitution, or surface functionalization—enables fine-tuning of the frameworks’ physicochemical attributes, improving hydrolytic stability, affinity, and selectivity for specific targets.²⁵ Collectively, the integration of controlled synthesis and PSM facilitates the rational design of advanced MOF-composites tailored for adsorption and degradation of pollutants in complex aqueous environments.²⁶

A major limitation of pristine MOFs in water treatment is their vulnerability to hydrolytic degradation, which often results in the collapse of the framework and loss of active sites.²⁷ To mitigate this issue, various strategies have been explored, including the design of intrinsically stable frameworks, the formation of composites with hydrophobic materials (e.g., polymers or carbon derivatives), and surface hydrophobization via PSM.²⁸ These adaptations have proven critical for maintaining performance under continuous flow conditions and real-world wastewater matrices.

One of the most studied types is MOF–polymer composites, in which MOFs are incorporated into or coated with polymer matrices. This combination improves the processability of the materials, enabling the manufacture of flexible membranes, films, and coatings.²⁹ Furthermore, polymers can provide greater mechanical strength and stability in humid or corrosive environments, expanding the use of MOFs in water contaminant separation systems and chemical sensors.³⁰

Another important type is composites with metallic nanoparticles, where MOFs act as matrices that encapsulate or support metals such as gold, silver, platinum, or palladium.³¹ This allows for high dispersion of the nanoparticles and improves catalytic activity, as well as electron transfer. Thanks to this synergy, these materials are highly effective in heterogeneous catalysis and the electrochemical detection of contaminants present in water.³²

Composites between MOFs and metal oxides, such as TiO₂, ZnO, or Fe₃O₄, have also been developed. These oxides provide thermal stability and, in many cases, photocatalytic capacity, opening up opportunities for the degradation of contaminants immersed in water and the development of optical sensors.³³

An area of accelerated growth is the combination of MOFs with carbon materials, including graphene, carbon nanotubes, or activated carbon. These composites significantly improve the electrical conductivity of MOFs and enable their use in energy storage devices, such as supercapacitors or rechargeable batteries.³⁴ Furthermore, the high specific surface area of carbon complements the porosity of MOFs, creating systems with high adsorption capacity for residues present in wastewater.³⁵

Another interesting type of composite includes MOFs integrated with semiconductors³⁶ or photoactive materials such as CdS, ZnS,³⁷ or perovskites,³⁸ and with new materials such as quantum dots³⁹ and Mxenes.⁴⁰ These systems improve light absorption efficiency and the separation of charges generated by irradiation, enabling their use in solar photocatalysis and in energy conversion devices, such as solar cells and visible-light reactors for environmental purification.⁴¹

Finally, mechanochemical methods—such as ball milling—have emerged as a sustainable and scalable route for the synthesis of MOF-based composites. These solvent-free approaches not only reduce environmental impact but also facilitate the direct integration of secondary phases like metal oxides or porous supports, thereby simplifying composite fabrication at industrial scale.²⁴

At a general level, functional composites with MOFs offer significant advantages. They allow combining the properties of MOFs with those of other materials, generating synergies that result in improvements in stability, selectivity, catalytic efficiency, and conductivity.^20,21 Furthermore, these composites are more versatile in terms of processing methods, which is key for industrial and technological applications. This combination of advantages has led to the exploration of MOF-based composites in fields as diverse as the environment and wastewater treatment.

4. MOF-composites as adsorption materials

Among the diverse technologies developed for water purification—such as chemical oxidation, membrane filtration, solvent extraction, and photocatalysis—adsorption remains one of the most efficient and sustainable approaches. This is largely attributable to its operational simplicity, low energy requirements, and broad applicability across a wide range of pollutants.^42,43 In this context, MOF-composites have emerged as a promising class of next-generation adsorbents, offering solutions to the inherent limitations of pristine MOFs while substantially extending their functionality in complex aqueous systems.

The development of MOF-composites involves the deliberate integration of MOF structures with complementary materials that impart enhanced physicochemical properties, including improved structural stability, expanded surface reactivity, and tailored active sites for adsorption.^44,45 This strategic synergy confers superior hydrolytic stability, broadens the spectrum of adsorbable contaminants and activates multiple adsorption mechanisms. Consequently, MOF-composites demonstrate elevated performance in removing a variety of emerging contaminants, such as pharmaceuticals, dyes, heavy metals, and persistent organic pollutants.^46,47

A wide range of functionalization strategies has been explored, each leveraging the intrinsic advantages of the incorporated phase (Fig. 2).⁴⁸ Carbon-based materials (e.g., graphene oxide, carbon nanotubes) introduce high surface area, chemical robustness, and π-electron-rich domains, enhancing interactions such as π–π stacking and hydrogen bonding.⁴⁹ Zeolites, with their crystalline microporous structure and ion-exchange capacity, improve selectivity and provide additional binding sites, especially for ionic species.⁵⁰ Natural clays, such as montmorillonite and bentonite, offer layered morphologies and abundant functional groups that enhance dispersibility and interfacial interactions.⁵¹ Mesoporous silica materials serve as structurally rigid scaffolds, promoting hierarchical porosity and facilitating molecular diffusion.⁵² In particular, silica-based composites incorporating mesoporous matrices such as SBA-15 or MCM-41 impart mechanical stability and facilitate the formation of hierarchically porous MOF architectures. These supports improve diffusion pathways, accelerate adsorption kinetics, and reinforce framework integrity.⁵³ Notably, systems such as UiO-66@SBA-15 have demonstrated enhanced Cr(VI) removal efficiency and reusability, attributed to stabilised active sites and synergistic interfacial interactions.⁵⁴

Additionally, MOF-on-MOF heterostructures—formed via epitaxial growth or modular self-assembly—allow the coexistence of distinct porosities, metal nodes, and surface chemistries within a single system, thus unlocking multifunctional performance and tuneable adsorption characteristics.^48,55

The exceptional adsorption performance of MOF-composites arises from the convergence of four principal attributes: (i) high surface area and porosity, enhancing adsorbate accessibility; (ii) hierarchical pore networks that facilitate diffusion kinetics; (iii) surface chemical heterogeneity enabling multiple interaction modes (electrostatic, coordinative, hydrogen bonding, π–π); and (iv) the simultaneous operation of diverse adsorption mechanisms, including physisorption, chemisorption, redox-driven interactions, and catalytic enhancement.⁵⁶

Overall, MOF composite represent a transformative class of adsorbents, uniting the structural tunability and modular design of MOFs with the functional diversity of auxiliary materials. Their capacity to integrate multiple active sites, maintain structural integrity, and interact with chemically diverse pollutants positions them as leading candidates for advanced, adaptive, and scalable water treatment technologies.

4.1 Mechanisms of adsorption

The remarkable adsorption behaviour of a MOF-composite arises from the convergence of multiple physicochemical mechanisms, which may operate independently or synergistically. These mechanisms are profoundly influenced by the intrinsic characteristics of the adsorbent—such as surface chemistry, porosity, and functional composition—as well as by external environmental factors, including pH, ionic strength, and temperature gradients.⁵⁷ Principal adsorption processes include electrostatic interactions, π–π stacking, hydrogen bonding, pore-filling, and van der Waals or hydrophobic forces (Fig. 3), with their relative contributions varying according to both the nature of the contaminant and the surrounding solution environment.

Electrostatic interactions often dominate the adsorption behaviour of MOF composites, particularly in the uptake of charged species. The strength and direction of these interactions are governed by the ionization state of the adsorbate and the surface charge of the material—both of which are highly pH-dependent.^58,59 For example, Yu et al. (2017) reported enhanced Pb²⁺ uptake onto functionalized MOFs at near-neutral pH due to deprotonation of carboxylate groups, whereas uptake was significantly inhibited under acidic conditions due to proton competition.⁶⁰ A similar pH-dependent trend was observed in the adsorption of Congo Red (CR) by Ce-MOF-4, where adsorption efficiency was maximized at low pH via attractive electrostatic interactions but declined under basic conditions due to charge repulsion. Nevertheless, residual adsorption at high pH suggested the concurrent involvement of non-electrostatic mechanisms, such as π–π stacking and hydrogen bonding. The adsorption of Malachite Green (MG) on Ce-MOF-4 further illustrates this complexity: at acidic pH, MG exists predominantly in a neutral form, reducing the relevance of electrostatic attraction and allowing π–π stacking to prevail. In contrast, under basic conditions, the negatively charged surface of the MOF restored electrostatic attraction, thereby enhancing adsorption performance.⁶¹ These findings underscore the dynamic mechanistic switching in MOF composites, governed by both pH and contaminant speciation. Liu et al. (2023a) substantiated this behaviour using a MIL-101-NH₂(Fe)/biochar composite, where tetracycline adsorption remained effective across a wide pH range, attributed to the system's ability to adapt its surface charge and binding profile under varying electrostatic regimes.⁶²

π–π interactions are particularly significant in the adsorption of aromatic compounds, offering selective recognition through electron-rich surfaces. In the M-HAF-2 series, Zhu et al. (2022) demonstrated that the alignment of aromatic linkers enhanced both the structural integrity of the framework and its affinity for aromatic contaminants.⁶³ This concept was extended by Bruno et al. (2021), who developed a Bio-MOF where π–π stacking not only governed adsorption but also played a central role in framework assembly.⁶⁴ More recently, Kopcsik et al. (2025) provided compelling evidence of π–π selectivity by differentiating aromatic solvents based on electronic structure, thereby highlighting the potential of ligand engineering to optimize MOF affinity for specific aromatic targets.⁶⁵

Hydrogen bonding introduces an additional layer of molecular recognition, particularly for polar adsorbates, and often complements other interactions. Liu et al. (2024) reported a Cu-MOF/Ti₃C₂T_x system featuring reversible quadruple hydrogen bonding, which conferred superior mechanical stability and adsorption performance under dynamic aqueous conditions.⁶⁶ Although hydrogen-bonded organic frameworks (HOFs) have been more extensively studied for gas-phase separations, their well-defined bonding motifs, and structural adaptability—exemplified by Lin et al. (2024)—offer valuable insights into designing MOFs with enhanced water compatibility and binding specificity.⁶⁷

Pore-filling and steric confinement mechanisms become particularly relevant when targeting large, weakly interacting molecules. Hierarchical and mesoporous architectures (HP-MOFs) mitigate the diffusion limitations typical of microporous systems by introducing larger channels and facilitating rapid molecular transport. Xiong et al. (2022) and Feng et al. (2020) demonstrated that such structures significantly improve the accessibility of adsorption sites and enhance kinetic performance.^68,69 Arslan et al. (2024) further exemplified this through the rapid adsorption of naproxen—achieved within five minutes—using a micro–mesoporous carbonaceous material, where pore-filling was identified as the dominant uptake mechanism.⁷⁰ Similarly, Attallah et al. (2023) employed spectroscopic techniques to confirm sequential pore occupation during water adsorption, offering direct evidence of diffusion-limited regimes in hierarchically porous MOFs.⁷¹

Although generally weaker, van der Waals and hydrophobic interactions can play a pivotal role in capturing non-polar species, especially in scenarios where electrostatic interactions are suppressed. These interactions are significantly enhanced by the incorporation of hydrophobic moieties—such as reduced graphene or alkyl-functionalized ligands—into the MOF matrix. Such modifications facilitate the partitioning of apolar molecules by displacing water molecules and reducing system free energy.^72,73 In complex water matrices, particularly under neutral pH or in the presence of competing ions, these hydrophobic domains can substantially improve both selectivity and overall adsorption efficiency.

In summary, adsorption in MOF composites is governed by a continuum of coexisting and interdependent mechanisms, whose dominance can be finely tuned through careful material design, environmental adjustment, and contaminant profiling. Rather than relying on a singular interaction type, these systems leverage synergistic processes—including electrostatics, π–π stacking, hydrogen bonding, pore confinement, and hydrophobic effects—to achieve high adsorption capacity, selectivity, and resilience across a diverse range of water treatment applications.

4.2 Adsorption of contaminants in wastewater by MOF-composite

4.2 Adsorption of drugs

Pharmaceutical residues have emerged as high priority micropollutants due to their environmental persistence, low biodegradability, and potential to induce antimicrobial resistance.¹²⁰ Their structural diversity—including ionizable functional groups, varying hydrophobicity, and molecular complexity—renders their removal particularly challenging for conventional treatment systems, especially at trace concentrations.¹²¹ MOF composites, with their tuneable porosity and chemically versatile surfaces, offer a promising platform to overcome these limitations through targeted interactions and enhanced adsorption dynamics.

Functionalization with carbonaceous materials, biopolymers, or functional polymers enables the fine-tuning of MOF performance by improving surface functionality, dispersion, and interaction diversity. These modifications create multivalent domains capable of engaging in π–π stacking, hydrogen bonding, electrostatic attraction, and van der Waals interactions.¹²² Such systems broaden the adsorption spectrum while improving mechanical robustness and reusability.

A prominent example is the UiO-66@Cr-MIL-101 composite developed by Sharafinia et al. (2023), which achieved 99.5% amoxicillin removal within 20 minutes at pH 6. The system followed Langmuir and pseudo-second order (PSO) models, indicative of homogeneous chemisorption on well-defined active sites. The functionalized structure facilitated enhanced site accessibility and mass transfer.¹²³ Similarly, Wang et al. (2023) reported a MOF-199/CNT composite with a capacity of 40.8 mg g⁻¹ for ibuprofen and demonstrated effective drug capture from urine samples—highlighting the translational potential of MOF composite in real biological matrices.¹²⁴

Sustainable synthesis approaches have also yielded promising results. Rivadeneira-Mendoza et al. (2023) fabricated a hydrochar@MIL-53(Al) functionalized from corn cob waste, achieving complete removal of naproxen and ketorolac at concentrations up to 150 ppm. The material retained ∼90% of its capacity over five cycles, and the adsorption was best described by Extended Freundlich and Sips models, suggesting cooperative multilayer binding on heterogeneous surfaces.¹²⁵

Mechanistic insights have been deepened through the integration of modelling and experimentation. Quintero-Álvarez et al. (2023) applied statistical physics models to the uptake of naproxen, diclofenac, and acetaminophen on MIL-100(Fe) and MIL-101(Fe), revealing multimolecular, exothermic adsorption driven by hydrogen bonding, electrostatics, and van der Waals forces. The higher mesoporosity and Fe–O density of MIL-101(Fe) accounted for its superior performance, offering guidance for rational material design.¹²⁶

Functionalization strategies continue to play a central role. Zhang et al. (2023) synthesized MIL-101-ED via ethylenediamine grafting, achieving selective removal of antipsychotic drugs while excluding >90% of proteins. This restricted-access behaviour suggests the potential for drug capture in biofluids and pre-treatment applications.¹²⁷ Likewise, MIL-101(Cr)/activated carbon doped with urea showed enhanced sulfacetamide uptake through Langmuir-type chemisorption, while maintaining high regeneration efficiency.¹²⁸

Computational studies have improved the understanding of structural limitations. Yaicel et al. (2023) demonstrated that standard ZIF-8 models failed to predict the uptake of larger molecules such as caffeine and 5-fluorouracil. Only defective models featuring missing linkers and exposed metal sites aligned with experimental results, underscoring the need for realistic frameworks in simulation workflows.¹²⁹ Surface chemistry modulation has also expanded application versatility. Farrando-Pérez et al. (2023) evaluated UiO-66 derivatives functionalized with –H, –NH₂, and –NO₂ groups for brimonidine tartrate removal. The –NO₂ derivative exhibited the highest adsorption (∼680 mg cm⁻³), though concerns regarding biocompatibility at high loading levels highlight the importance of balancing efficiency with environmental and toxicological safety.¹³⁰

Post-synthetic activation represents an alternative performance-enhancement strategy. Tajahmadi et al. (2023) improved quercetin uptake to 370 mg g⁻¹ by ethanol activation of Gd-MOF, achieving spontaneous thermodynamics without altering the structure of the material.¹³¹ Similarly, Yadav et al. (2023) utilized PEG-coating on MIL-100(Fe) to encapsulate norfloxacin, reaching 20 wt% loading and achieving sustained release over 60 hours—demonstrating dual utility for environmental remediation and drug delivery applications.¹³²

Translational insights have also emerged from biomedical systems. Bikiaris et al. (2023) designed a dual-phase Fe-BTC/PEG–PCL composite capable of loading 40 wt% paclitaxel and achieving complete release within four days. Although intended for therapeutic use, the composite's tuneable interface and controlled release behaviour provide valuable cues for pollutant desorption and diffusion control in environmental systems.¹³³

Table 4 summarizes key findings from recent MOF composites applied to pharmaceutical adsorption, detailing adsorption capacities, target drugs, kinetic and isotherm models, and regeneration performance. Across studies, PSO kinetics and Langmuir or Freundlich isotherms dominate, consistent with chemisorption mechanisms involving electrostatic, hydrogen bonding, and π–π interactions. The increasing application of advanced models—such as Sips and statistical physics approaches—reflects the growing recognition of surface heterogeneity and cooperative binding effects in these systems.

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Despite these advances, critical challenges persist. Thermodynamic profiling, multicomponent competition, and evaluation under real wastewater conditions are often absent. Additionally, long-term stability, fouling resistance, and cost-effective regeneration strategies remain underexplored. Future work should prioritize the integration of in situ characterization techniques, realistic environmental matrices, and scalable, green synthesis protocols to bridge the gap between laboratory feasibility and field deployment in pharmaceutical pollution control.

4.3 Adsorption of metals

The remediation of heavy metal ions from wastewater presents unique physicochemical challenges distinct from those posed by organic contaminants such as dyes and pharmaceuticals. Metal ions exhibit diverse behaviours arising from their variable oxidation states, hydration shells, coordination geometries, and redox activity.¹³⁴ As such, effective removal requires adsorbents with high selectivity, robust binding affinities, and structural stability across a broad range of aqueous environments.¹³⁵ MOF composites, with their modular design, tuneable surface chemistry, and multifunctional architectures, have emerged as compelling candidates to meet these multifaceted demands.

Despite the growing body of research on MOF composites for the photocatalytic degradation of metal ions, adsorption-specific investigations remain comparatively underdeveloped. Many studies report equilibrium and removal data without in-depth analysis of the underlying mechanisms, thereby limiting the rational design of ion-selective or competitive adsorption systems.

A notable example is the carboxyl-functionalized UiO-66 functionalized with 1,2,4,5-benzenetetracarboxylic acid, which demonstrated preferential uptake of Pb²⁺ (100 mg g⁻¹) over Cd²⁺ (37 mg g⁻¹). This selectivity was attributed to electrostatic interactions influenced by hydration thermodynamics. The ζ-potential (−7.7 mV at pH 7) promoted cation adsorption, and although minor efficiency loss occurred over cycles, the system highlighted the effectiveness of ligand engineering for enhancing metal specificity.¹⁴² Further advances were reported by Wang et al. (2021), who developed a Ni_0.6Fe_2.4O₄-UiO-66-PEI capable of removing Pb²⁺ and Cr(VI) with capacities of 273.2 and 428.6 mg g⁻¹, respectively. XPS and DFT analyses revealed distinct mechanistic pathways: amine-mediated chelation for Pb²⁺ and redox-assisted adsorption for Cr(VI). The composite was magnetically recoverable and retained over 90% efficiency after five regeneration cycles, exemplifying the utility of multifunctional design.¹⁴³

Magnetically responsive MOF composites have also demonstrated efficient multi-metal capture. For instance, magnetite@Fe-BTC removed Cu²⁺, Pb²⁺, Hg²⁺, and As(III) with capacities ranging from 55 to 155 mg g⁻¹, following the selectivity trend Cu²⁺ > Pb²⁺ > Hg²⁺ > As³⁺. While most metals adhered to Langmuir-PSO behaviour, Hg²⁺ adsorption was better represented by the Temkin model, suggesting heterogeneous binding energies.¹⁴⁴

Redox-active systems have proven particularly effective in Cr(VI) remediation. TMPA@MOF-801 aerogels achieved 350.6 mg g⁻¹ uptake through a synergistic mechanism involving electrostatic attraction, ion exchange, and in situ reduction to Cr(III). The material maintained ∼88% removal efficiency over six cycles and exhibited high tolerance to competing ions, expanding the functional scope of MOFs beyond traditional adsorption paradigms. Comparable performance was achieved using nanocellulose–MOF-801 aerogels, which achieved 93.9% Cr(VI) removal in continuous flow columns, treating over 4 L of solution with less than 1 g of adsorbent—highlighting their practical potential.¹⁴⁵

The selective recovery of noble metals has also gained attention. Shi et al. (2025) developed UiO-66-(OH)₂–FA composites embedded in flexible filtration textiles, achieving >99.99% Au³⁺ removal (190.98 mg g⁻¹) while preserving mechanical integrity and reusability. This approach addresses the scalability limitations of powdered MOF systems by enabling integration into robust, application-ready formats.¹⁴⁶ For alkali and alkaline earth metals, WP@PSS@Cu-MOF selectively adsorbed Li⁺ (9.69 mg g⁻¹) in the presence of Na⁺, K⁺, Ca²⁺, and Mg²⁺. The mechanism involved a combination of steric exclusion and sulfonate–Li⁺ coordination. Although capacities were moderate, the material demonstrated promising selectivity and maintained ∼88% efficiency over five cycles under brine-like conditions, offering the potential for lithium recovery from complex matrices.¹⁴⁷

Multicomponent systems have demonstrated high capacities and complex mechanisms. The Co–Al–LDH@Fe₂O₃/3DPCNF exhibited uptake capacities of 400.4 mg g⁻¹ for Cr(VI) and 426.8 mg g⁻¹ for Pb²⁺, through mechanisms including surface complexation, isomorphic substitution, redox processes, and metal precipitation. PSO kinetics and Sips isotherms described the behavior, indicating heterogeneous and cooperative adsorption dynamics.¹⁴⁸ MOF–COF materials have also shown synergistic adsorption behavior. The UiO-66-NH₂@LZU1 composite removed U(VI) at 180.4 mg g⁻¹, outperforming the individual components. This enhancement was ascribed to the complementary coordination environments created by nitrogen- and oxygen-rich sites.¹⁴⁹

Among the highest reported capacities, Zr–MOF–NAC achieved Hg²⁺ uptake of 644 mg g⁻¹via S–Hg and N–Hg coordination, supplemented by electrostatic and film diffusion contributions. Adsorption followed Temkin isotherms and Elovich kinetics, and the material retained 95% of its capacity after four cycles—highlighting its robustness and regeneration efficiency.¹⁵¹

Table 5 presents a comparative overview of recent MOF composites for metal adsorption, detailing adsorption capacities, target ions, kinetic/isotherm models, dominant mechanisms, and recyclability. Collectively, these studies reveal that metal ion adsorption involves far greater structural and mechanistic complexity than the adsorption of organic pollutants. While Langmuir and PSO models remain commonly applied descriptors, they often fail to fully capture the nuanced interplay of redox activity, hydration energetics, speciation, and competitive binding phenomena.

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To advance the rational design of MOF composites for metal remediation, future studies should prioritize multicomponent adsorption systems, in situ spectroscopic analyses, and defect engineering strategies aimed at enhancing selectivity and affinity. Techniques such as solid-state NMR, XPS, and DFT simulations will be instrumental in elucidating metal-specific interactions at the molecular level.¹⁵² Such mechanistic insights will underpin the development of structurally robust, regenerable, and highly selective MOF composites capable of efficiently addressing the complex challenge of heavy metal pollution in real-world environments.

5. MOF-composite for degradation of contaminants in wastewater

When adsorption of contaminants is not feasible, their conversion to smaller and harmless products is preferred. Advanced oxidation processes (AOPs) are a special class of wastewater treatment technologies aiming at the conversion of the contaminants to CO₂, water, and inorganic substances (by mineralization).¹⁵³ Their potential to degrade stable and bio-refractory compounds under ambient conditions makes them prominent in the field of water purification research. The denomination AOP comprises a large variety of different technologies, all of which involve the generation of hydroxyl radicals (˙OH), which rapidly attack most organic species.^154,155 The AOPs are divided in two groups (Fig. 7) non-photomechanical and photomechamical.^155–157 The MOF composites are used as heterogeneous photocatalyst, in this type of photocatalyst, the catalyst and the reaction system are in a different phase.^155,158 The process consists of five elementary steps: migration of the analyte from the liquid bulk phase to the photocatalyst surface; adsorption; surface reaction; desorption of the products; transfer of the products to the liquid bulk phase.^153,155

The Fig. 8 schematizes the photocatalytic mechanism, in this process the MOF can be used as semiconductor material due to the ligands, or metal ion/metal oxide clusters. It starts when a photon with energy, h_ν matches or exceeds the band gap energy, h_ν ≥ E_g. Conduction electrons, e_CB⁻, are promoted from the valence band into the conduction band (CB), leaving a hole, h_VB⁺, behind. The resulting e⁻–h⁺ pairs within the semiconductor particle can be separated, diffused to the surface of the semiconductor and thus participate in the oxidation and reduction reactions of the organic and inorganic compounds or are subjected for the recombination process by decreasing the quantum yield of the reaction. The electrons in conduction band can react with oxygen, O₂ to yield super oxide anion, then in reaction with water can form hydrogen peroxide ˙O₂⁻ and then give a hydroxyl radical, ˙OH. The hole can either oxidize a compound directly or react with electron donors like water to form OH radicals, which in turn react with pollutants. The resulting ˙OH radicals are very strong oxidizing agents.^155,159

In degradation processes the MOF is used as a semiconductor material, due to the organic linker ligand and metal ion. The organic ligands can donate many unpaired electrons to the metal ions to fill up the vacant orbital shells. So, metal ions can easily accept these unpaired electrons to form MOF materials. Is common the use of aromatic carboxylic acid ligand, that exhibits an intense UV-absorption peak near 250 nm due to the excess electron density. A feasible strategy is to design a suitable band gap by changing the functional groups on the aromatic ligands, such as NH₂ or hydroxyl groups, introducing some dye chromophores or regulating metal ion/metal oxide clusters.^155,160,161 The AOPs not only depend on irradiation wavelength and nature and morphology of the photocatalyst, in addition, it depends on irradiation intensity, concentration of analyte, photocatalyst concentration, solution pH, temperature of the reaction.¹⁵³

To improve the photocatalyst performance in the removal of various types of organic and chemical contaminants in wastewater, the MOF composites emerge as a suitable alternative. The Table 6 summarize recent MOF composites used with this finality. Different types of materials are coupled with MOFs. MOFs coupled with metal, metal-containing nanoparticles,^155,162,163 polymers,^164–167 graphene oxides,¹⁶⁸ MXenes,¹⁶⁹ implantation of quantum dots,¹⁷⁰ Layered double hydroxides,¹⁷¹ COFs,^172,173 due to the combination of different materials and MOFs can reduce the recombination rate of photogenerated electron and hole pairs and simplifies the interfacial charge transfers. Another major advantage of doped incorporated MOF is tuneable pore size, adsorption capacities, dispersibility and interfacial compatibility.

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Li et al.¹⁷⁴ synthesised Cu dopped ZIF-7 with a molar ratio 1:1 of Cu²⁺ to Zn²⁺. Under visible light irradiation, Cu@ZIF-7 serves as a Fenton-like catalyst. With the addition of 9.8 mmol H₂O₂ and exposure to visible light for 30 min, 10 mg of Cu@ZIF-7 can completely decompose RhB solution. Han et al.¹⁷⁵ designed Au doped PCN 224 as bi-functional wastewater treatment agents to absorb and decompose organics molecules efficiently under light irradiation. This MOF composites performs better in absorbing organic compounds consisted of S contained heterocyclic ring (such as methylene blue). Mehrehjedy et al.¹⁷⁶ synthetised a Co doped ZIF-8 using visible light for degradation methylene blue achievement 97% of efficiency.

Hu et al.¹⁷⁷ prepared SNP-TiO₂ by loading non-noble metal modified on the surface of Cu-MOF to photocatalyst Karenia mikimotoi under visible light using concentration of 100 mg L⁻¹ and reaction times 6 h, the visible the reported efficiency was 93.75%. Roy et al.¹⁷⁸ incorporated ZnO with Cu-MOF for degradation of Rose Bengal exhibit an efficiency of 97.4% in 45 min under natural sunlight with catalyst dosage of 320 mg L⁻¹, showed that the degradation followed first-order kinetics with a rate constant of 0.077869 min⁻¹. The addition metal oxide not only improved the photocatalytic quality, Mehrehjedy et al.¹⁷⁶ additionally doped the Co@ZIF-8 with Fe₃O₄ and microcrystalline cellulose (MCC) to enhance the reusability of the MOF composite through the application of an external magnetic field, and without the modification of the efficiency.

Ishfaq et al.¹⁷⁹ made nanocomposites of chitosan and MnO₂ with MOF-801 for degradation of Rh B. Li et al.¹⁸⁰ integrated Cu-MOFs into an alginate substrate to offer environmentally friendly, sustainable, facile separation, and high-performance MOF-based hydrogel photocatalysis platforms for Cr(IV) and Congo red dye combined. Wang et al.¹⁸¹ and Wang et al.¹⁸² used NH₂-UiO-66 composites for the photo-catalytic degradation of sulphonamides and Cr(IV) respectively using polyimide and p-type polypyrrole. Wani et al.,¹⁸³ integrate Ni-MOF in chitosan and g-C₃N₄ for degradation of tetracycline and antibacterial activities, using polymers and nanoparticles with MOFs.

Wang et al.¹⁸⁴ prepared nanocomposites to inactivate Microsystis aeruginosa and degradate microcystin under visible light irradiation, doping with g-C₃N₄ a Cu-MOF. Wang et al.¹⁸⁵ synthetized a Bi₂MoO₆/NH₂-UiO-66(Zr) for photocatalytic degradation under visible light conditions.

The efficiency for photocatalytic degradation of tetracycline reaches 81.72% in 90 min. Bouider et al.¹⁸⁶ and Zao et al.¹⁸⁷ incorporate MOF with graphene oxide (GO) for degradation of methylene blue, obtained a degradation of 92% in 360 min under sunlight radiation and 94.8% in 30 min under visible light radiation.

Far et al.¹⁸⁹ grown the UiO-66 on Ti₃C₂T_x MXene nanosheets enhanced the degradation of methylene blue and direct red 31 dyes efficiency to 78% and 56% within 60 min of UV-visible irradiation. Li et al.¹⁹⁸ using solvothermal synthesis for create a composite Ti₃C₂T_x MXene and PCN-224 for degradation of tetracycline and Rhodamine B obtained 91.2% and 97.4% efficiency under sunlight irradiation during 60 min. Eslaminejad et al.¹⁹⁷ combined palladium nano particles with Ti₃C₂T_x MXene for the degradation of ofloxacin achievement almost 100% of efficiency under visible light during 30 min.

Rahmani et al.¹⁹⁶ modified MOF-808 with sulphured and nitrogen co-doped carbon quantum dots (S,N-CQDs) using a simple solvothermal technique, MOF-808 was not photo-active in visible light region because of its large band gap energy (3.85 eV), the prepared composites exhibited photocatalytic activity in Rhodamine B degradation up to 89% under visible light and 95% under sunlight irradiation in optimal conditions. Ghasemzadeh & Akhbari studied the degradation of acid blue 41 with two different modified MOFs with quantum dots, with ZnO quantum dots doped MOF-801 obtained an efficiency of 42.7% using UV light¹⁹¹ and carbon quantum dots doped MOF-808 obtained an efficiency of 86.62% under visible light.¹⁹³

Bhuyan & Ahmaruzzaman¹⁹⁰ loaded Ni/Co-LDH@ MOF-5 composite with metal-oxide quantum dots (ZNCQD) was via ultrasonication, towards the degradation of methylene blue, rose Bengal and malachite green (MG). The maximum percentage degradation was 96.2%, 95.8%, and 99.6%, respectively. Wang et al.¹⁹⁵ constructed UiO-66 MOF with layered Mg/Al-LDH in a hydrothermal synthesis strategy for the highly efficient photodegradation of diclofenac reached 100% mineralization using solar energy. Pirkarami et al.¹⁸⁸ decorated MIL-177-LT with Ni/Fe LDH for degradation of the Acid Red 18 from water.

Zhang et al.¹⁹² prepared Zr-MOF@TzDa-COF for degradation of Potassium butyl xanthate, Potassium amyl xanthane, Ethyl zanthane and Sodium isopropyl xanthane using visible light, obtained of 100%, 100%, 92.61% and 80.32% respectively. Li et al.¹⁹⁹ fabricated hollow heterojunction of W-Zr-MOF-NH₂@TpTt-COF synthesized through acid etching and hydrothermal methods for tetracycline degradation, it showed 87% degradation of tetracycline under 300 W Xenon lamp irradiation. Zhou et al.¹⁹⁴ customized MIL-68@COF-V which realize the efficient degradation, up to 95%, of tetracycline within 15 min, rhodamine 6G within 25 min, and phenol within 40 min using sunlight. Finally, it is worth noting that Gan et al. investigated the removal of the organophosphate herbicide glyphosate (GP) from water using a Zr-based MOF (mCB-MOF-2), which combines high adsorption capacity (11.4 mmol g⁻¹) with selective photodegradation. This MOF converts 69% of GP into non-toxic products such as sarcosine, while effectively preventing the formation of aminomethylphosphonic acid (AMPA).²⁰⁰ This research stands out, since in recent years various material modification strategies have been described to improve the photocatalytic degradation performance of pesticides²⁰¹ and and it has also been investigated that the metal center of MOFs gives it properties for the adsorption and photodegradation of herbicides.²⁰²

6. MOF-composites based biosensors of wastewater pollutants

Biosensors are devices for detecting the specific analyte that combines a biological element with the transducer or the detector element (Fig. 9).^203,204 The fundamental function of a sensor is to convert a signal into information that can be measured, displayed, and processed directly.^205,206 The sensitive biological species can be microorganisms, tissue, cells, receptors, enzymes, antibodies, nucleic acids, etc., which are biologically derived materials or bio-mimetic components that bind with the transducer.^{203,205,207,208} Biosensors usually divided in two types, electrochemical sensors, the sensing strategy utilizes changes in various electrical parameters, techniques such as cyclic voltammetry (CV), chronoamerometry, square wave voltammetry (SWV), electrochemical impedance spectroscopy (EIS) and differential pulse voltammetry (DPV) are employed. The other type are the optical sensors with techniques as fluorescence, surface plasmon resonance (SPR), surface enhanced Raman scattering (SERS) and optical fibers.^{204,208–210}

The rapid industrialization results a water pollution to causes ecological imbalance and threatens human health. The detection of contaminants such as pesticides, antibiotics, nitro-explosives, heavy metals, etc.²⁰⁶ The design and development of effective and sensitive analytical strategies for precise pretreatment and determination of different water contaminants in various aqueous solutions are critical. More interestingly, selectivity and sensitivity are essential to accurately determine the concentration of water contaminants because they are usually present at low concentrations.^204,211

The realization of MOF composites provides a platform to strength MOFs in the biosensor's realm. MOFs properties including high pore volume, large surface area, and good thermal stability. Besides, MOFs can conjugate biomolecules through electrostatic interaction, π–π stacking, coordination bonding, chemical bonding, etc. Therefore, MOF composites-based biosensors with superior properties are expected to be sensitive in the detection.^203,204,212 The main advantages of using MOFs for sensing materials stem from their distinct and highly modifiable physical, chemical, and structural (and thus functional) properties, such as regular porosity and adjustable pore size, multivariate structures with multiple metal centres and diverse organic linkers. Post-synthetic modifications (PSM) can also be utilized to functionalize MOFs (external surface and interior pore space) and provide new functions. Selectivity is determined by pore and aperture sizes, and MOF surface chemistry, such as specific (bio)chemical interactions of the analyte with functional groups or opens metal sites (OMS). The rate of analyte diffusion to the interaction site, is related to MOF particle size and pore diameters, nanosized MOFs, which have faster diffusion rates and consequently faster analyte responses than micrometer-sized MOFs, are often preferred to ensure rapid analyte uptake and equilibration with better sensitivity.^203,213

The Table 7 summarizes important parameter of recent MOF composite to detected wastewaters pollutants. Nanoparticles formed common composites with MOFs to create biosensors. Liang et al.²¹⁴ characterize a Fe-MOF@YAU-101/GCE sensor that can efficiently and synchronously identify Hg²⁺, Pb²⁺ and Cd²⁺ limits of detection (LOD) are 1.33 × 10⁻⁸ M, 6.67 × 10⁻¹⁰ M and 3.33 × 10⁻¹⁰ M respectively. The detection limits are superior to the permissible limits set by the National Environmental Protection Agency, using DVP sensing method. Menon et al.²¹⁵ grown MOF-5 in situ over the tannic acid-capped gold nanoparticles (AuNPs) of plasmonic U-bent fiber optic sensor (U-FOS) probes. The Pb²⁺ ion binding to MOF-5 was detected and quantified as an increase in the plasmonic absorption of the light by AuNPs due to significant refractive index changes at the AuNP surface. Bodkhe et al.²¹⁶ fabricated selective and sensitive Hg²⁺ion electrochemical sensor using a solvothermally synthesised composite of silver nanoparticles (AgNPs) and zinc benzene dicarboxylate (ZnBDC) MOF. The electrochemical sensor was fabricated by drop-casting the Ag@ZnBDC composite onto a glassy carbon electrode. Remarkably, the sensor exclusively and highly selectively responded to Hg²⁺ions among Cd²⁺, Cr³⁺, Cu²⁺, Fe³⁺, and Pb²⁺ ions at a concentration of 1 μM. Saravanakumar et al.²¹⁷ fabricated Cu-MOF@Pd-500 modified glassy carbon (GC) electrode was for the sensing of Bisphenol A (BPA).

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Other technologies to create sensing MOFs are the addition of dots. Yan et al.²¹⁸ prepared Eu doped NH₂-UiO-66 MOF complexed with S-containing carbon dots (CDs) exhibited dual-emission fluorescence. The MOF composite could bind specifically to Hg²⁺and Pb²⁺ with enhanced sensitivity. Jain et al.²¹⁹ designed a fluorescence-based biosensor for the selective and sensitive detection of Pb²⁺ with boron and nitrogen carbon dots (BNCDs)-doped carboxyl functionalized-terbium metal–organic framework (COOH-Tb MOF) as a fluorescent tag and quencher-modified catalytic NH₃-GR5 DNAzyme as a bioreceptor molecule. Sonowal et al.²²⁰ synthesized NH₂-UiO-66 using in situ solvothermal synthetic technique for fluorescence sensing of Hg²⁺ in water. The well-distributed graphitic carbon nitride quantum dots on the MOF improve Hg²⁺ sensing activity in water owing to their great electronic and optical properties.

The use of aptamer, synthetic of ssDNA, ssRNA or peptides that bind to some target with high specificity and affinity,²²¹ in MOFs for selectivity is wide extended. Wang et al.²²² developed a personal glucose meter (PGM)-based aptasensor utilizing a porous spherical cerium-based metal–organic framework (Ce-MOF) as a loading platform for glucose oxidase (GOx) and an aptamer, oligonucleotide sequences (cDNA), for the sensing of ofloxacin, a widely used antibiotic, is of particular concern due to its potential for contamination in milk and surface water. Zhang et al.²²³ fabricated a Ni-MOF that carrier aptamers of Bisphenol A (BPA), that immobilizing the aptamers inside its array channels under Mg²⁺ regulation. Due to the in-hole fixation strategy of aptamers, Ni-MOF played protection aptamers not only the activity of BPA aptamer@Ni-MOF composite was maintained more than 50% in complex environments such as pH 3.0–11.0, 30 70 °C and organic solvents, but also the aptamer was protected from nuclease hydrolysis under physiological conditions. Wang et al.²²⁴ constructed an electrochemiluminescence (ECL) aptamer sensor based on Ru@Zn-oxalate MOF composites is for sensitive detection of sulfadimethoxine (SDM). The prepared Ru@Zn-oxalate MOF composites with the three-dimensional structure provide good ECL performance. The use of the aptamer improves the selectivity of the sensor. Thus, high-sensitivity detection of SDM specificity is realized through the specific affinity between SDM and its aptamer.

Carbon derivates as Carbon nanotubes (CNT) are used to enhanced conductivity or controlled pore size. Wang et al.²²⁵ report a 2D Ce-MOF nanosheets grown on carbon nanotube substrates. The construction of layered MOF nanosheet materials is based on CNTs as the backbone and relies on the low ligand–metal ratios which is controlled by the loaded organic ligands on the surface of CNTs.

The synthesized layered CNTs@Ce-MOF nanosheet composite material uses Ce as the centre ion and electrocatalytic active material for nitrite sensing. Guo et al.²²⁶ fabricated an electrochemical sensor for methyl parathion electrochemical sensor from UiO-66 and Ketjen black-CNTs. For the KB-CNTs@UiO-66 composite, Zr-based UiO-66 with Zr–OH groups possessed good affinity for phosphate groups on methyl parathion molecules, which enhanced the selective recognition and enrichment capability. The KB-CNTs possessed three-dimensional interconnected carbon conductive network with synergistic point-line carbon conductive contact, which showed excellent electrical conductivity. Zhao et al.²²⁷ using a ZIF-67 derived cobalt/nitrogen-doped carbon (NC) composite polyhedrons linked with multi-walled carbon nanotubes (MWCNTs), for the simultaneous monitoring of Cd²⁺ and Pb²⁺. Nanoporous ZIF-67 was first in situ grown on the MWCNTs, followed by carbonization, endowing the composite with good electrical conductivity and a large specific surface area, providing more active sites for subsequent metal ion attachment.

Graphene composites can amplify the electron transfer rate in electrochemical biosensors. Sun et al.²²⁸ modified with Au nanoparticles the composite Zr-MOF@Graphene as the electrode modification material for detecting sunset yellow and Sudan I. The prepared AuNPs/Zr-MOF@Graphene composites presented electrochemical an improving accumulation efficiency, electrocatalytic activity and promoting charge transfer. Liu et al.²²⁹ presents the development of Sn-MOF-650@rGO, created by carbonizing reduced graphene oxide (rGO) on the surface of Sn-MOF after in situ encapsulation. The Sn-MOF-650@rGO modified glassy carbon electrode was successfully constructed for the electrochemical detection of catechol. Karazmi et al.²³⁰ combined polymers, LDH and graphene oxide to synthetised polyvinyl alcohol (PVA)/poly acrylic acid (PAA)/MOF NiCoZn-LDH@graphene oxide (GO) electrospun nanofiber for multiple drugs. The combination of MOF NiCoZn-LDH@GO with a highly porous structure and rich functional groups in the PVA/PAA substrate casing significantly improves the absorption properties of the nanofibers.

The composites MOF and polymers was used to improve usage properties. Gao et al.²³¹ prepared a Zn-luminescent MOF-based sensor with poly(methyl methacrylate) polymer, the polymer matrix provided the chemical protection for MOF particles. The as fabricated Zn-LMOF@PMMA exhibited strong blue emission under ultraviolet light irradiation, which can act as luminescent probe for detecting antibiotics and pesticides and exhibited visual, real-time detection of antibiotics ornidazole (ODZ) and pesticides 2,6-dichloro-4-nitrobenzenamine (DCN). Ghost et al.²³² designed a formamide functionalized Zr-MOF, was used for the selective and fast fluorescence sensing anti-microbial drug nitroxoline (NTX) and herbicide 2,4-dichlorophenoxyaceticacid (2,4-D). For rapid and on-site naked eye detection, a cheap, handy, reusable, and biocompatible, they fabricated a chitosan@cotton@MOF composite. The composite was capable to change its colour up to nanomolar-level concentrations. Rozenberga et al.²³³ immobilize Eu-MOF, EnMTA, in a cross-linked poly(2 hydroxyethyl methacrylate) (PHEMA) matrix resulted in a significant enhancement in the ligand stability, as well as an increase in the Fe³⁺ sensing range (2–120 ppm). Compared to native EuMTA powder (0.16–4 ppm). The PHEMA matrix also functioned to protect the embedded MOF, improving the stability of the sensor under acidic conditions, while enhancing Fe³⁺ ion selectivity compared to a EuMTA powder suspension.

The Ti₃C₂T_x Mxene improves sensitivity of MOFs sensors. Zhang et al.²³⁴ sensed L-Tryptophan using a Ce-doped Ti₃C₂T_x@MOF-199 nanocomposite. Density functional theory (DFT) calculation suggested that the doping of Ce can effectively enhance the electronic structure of MOF-199 and improve its adsorption capacity for L-Trp. Additionally, the integration of Ce-doped MOF-199 with Ti₃C₂T_x MXene substantially improves the conductivity of MOFs, resulting in enhanced electrocatalytic activity of the nanocomposite material. Chen et al.²³⁵ introduces a FeS_x@MOF-808/Ti₃C₂T_x for detection of As³⁺. The composite enhances the sensitivity and selectivity detection. The sensor demonstrated exceptional sensitivity with a detection limit of 0.02 ng mL⁻¹ and a broad linear response range of 0.05–100 ng mL⁻¹, surpassing World Health Organization guidelines. And notably exhibited minimal interference from common heavy metals.

The heterostructure of MOF@COF improve photoactivity and interaction between sensor and analyte. Li et al.²³⁶ developed a fluorescence sensor based on dual-emissions NH₂-UiO-66@TpTt-COF composite by an interfacial growth method for detecting tetracycline. The import of NH₂-UiO-66 attenuates the aggregation-caused quenching (ACQ) of TpTt-COF. Tetracycline is recognized by the MOF composite through π–π stacking and interacts. The MOF-composite has a detection limit of 7.4 nmol L⁻¹ and is applied for the detection of tetracycline in soil and river water. The same MOF composite was used for Yang et al.²³⁷ for determination of dibutyl phthalate (DBP). However, for improve the sensing performance, molecularly imprinted polymer (MIP) was developed by sol–gel polymerization method as the recognition component photoelectrochemical sensor (PEC). The NH₂-UiO-66/TpPa-1-COF was synthesized using a simple one-step solvothermal method, which improved photocurrent response owing to heterojunction formation, favourable energy-band configuration and strong light absorption capacity. Song et al.²³⁸ employed Cu-MOF material was employed as a substrate, and its conductivity and catalytic properties were then enhanced by incorporating Tp-BD-DBd COF within the pores. Tp-COF@Cu-BDC introduced not only extensive π-conjugated systems but also the mutual electron-donating amino and carboxylate electron-with drawing groups that may help improve the adsorption capability of 2-aminophenol (AP).

The binary MOF composite (2) i.e., the sensor exhibited excellent limit of detection (LOD) value of 2.4 nmol L⁻¹ for Hg^{2 +}. The sensor also exhibited excellent performance for mercury(II) detection in real water samples. The characterizations of the synthesized materials were done using various spectroscopic techniques and the fluorescence sensing mechanism was studied.

7. Current perspectives and prospects for MOF-composites in water contaminant applications

Currently, the systematic investigation of MOF composites for the adsorption of dyes, pharmaceuticals, and metal ions has firmly established them as versatile platforms for aqueous pollutant remediation. Their consistently superior performance arises from a unique combination of properties: high densities of chemically accessible active sites, hierarchical and tunable porosity, and synergistic multivalent binding mechanisms—including electrostatic interactions, π–π stacking, hydrogen bonding, coordination chemistry, and, when applicable, redox-mediated processes.

Nevertheless, despite their significant potential, MOF composites still face several challenges. Key aspects such as scalable synthesis, long-term stability under real-world conditions, and cost-effective production must be optimized to enable wider industrial implementation. In addition, further advancements are required in processing techniques that facilitate their integration into solid matrices or membranes—an essential step for many water treatment applications. Nevertheless, recent developments in green synthesis and post-synthetic modification methods offer a promising outlook. The integration of artificial intelligence is expected to accelerate the design of highly efficient MOFs tailored to specific environmental targets.

A comparative evaluation of recent adsorption studies (Table 8) reveals that MOF composites consistently outperform conventional materials across a wide range of contaminants, including dyes, pharmaceuticals, and heavy metals. For cationic dyes such as methylene blue, composites such as functionalized Fe-MOF/GO (387.0 mg g⁻¹) and Al-MOF/GO (336.0 mg g⁻¹) exhibit significantly higher adsorption capacities than traditional carbonaceous, clay-based, or biopolymeric composites, which seldom exceed 200 mg g⁻¹.^105,239 This superiority is even more pronounced for Rhodamine B, where a ZIF–MIL-4 composite achieved an exceptional capacity of 1181.0 mg g⁻¹, orders of magnitude greater than that of conventional polymer–inorganic composites.¹⁰¹

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Similar trends are observed for anionic dyes, pharmaceutical residues, and metal ions. MOF composites such as Ni-BDC, Cu-BDC, and Zn-BDC surpass 700 mg g⁻¹ in the adsorption of Alizarin Yellow, far exceeding the performance of layered double hydroxides and biogenic oxide nanoparticles.¹¹¹ In the case of pharmaceutical adsorption, Gd-MOF-based composite and HKUST-1/ZIF-8 composites outperform sol–gel-derived carbon aerogels and molecularly imprinted polymers, achieving capacities an order of magnitude higher.^131,138,240 For metal ion capture, UiO-66-NH₂@LZU1 demonstrates a U(VI) uptake of 180.4 mg g⁻¹, substantially superior to conventional clay or bio-based composites.^149,241 Nevertheless, each pollutant class imposes distinct physicochemical demands. Dyes have long served as model compounds for probing the interplay between pore architecture and functional site accessibility, emphasizing the role of molecular size, charge, and diffusion pathways. In contrast, pharmaceutical adsorption introduces complexities related to dynamic speciation, co-solute interference, and biofluid-like matrices, requiring materials capable of balancing strong uptake with controlled release. The adsorption of metal ions presents an additional layer of mechanistic complexity—arising from redox sensitivity, multivalent speciation, and competitive binding in polymetallic environments—which necessitates a highly tailored material design and more precise mechanistic elucidation. Moreover, the modularity of MOF frameworks allows precise functionalization strategies to target specific pollutants, providing fine control over selectivity, adsorption kinetics, and capacity even under complex, competitive conditions. By contrast, traditional composites, although advantageous in terms of cost and ease of production, are limited by lower surface areas, poorly defined active site distributions, and reduced chemical resilience under challenging environmental conditions, restricting their efficiency and versatility in practical applications.

While considerable strides have been made in the synthesis, characterization, and benchmarking of MOF composites, several critical gaps remain. Adsorption studies on metal ions remain largely empirical, often lacking integration with advanced spectroscopic, thermodynamic, or computational techniques to verify proposed mechanisms. Across all contaminant classes, the continued reliance on static batch experiments under idealized conditions limits the predictive relevance of laboratory findings, underscoring the urgent need for in situ characterization and performance validation under realistic, multicomponent, and flow-based scenarios. To overcome these limitations, future research must adopt an integrated, mechanism-based approach to materials development.

Furthermore, advanced analytical methods capable of capturing in situ adsorption dynamics, such as time-resolved spectroscopy, solid-state NMR, and ambient TEM, will be essential to resolve mechanistic ambiguities. On the other hand, designing scalable synthesis routes, ensuring long-term material stability, and validating performance under real-world water treatment conditions are all imperative to unlock the full potential of MOF composites.

Finally, MOF composites are clearly promising for the degradation of water pollutants (Table 9), as are the uses of pure MOFs or individual materials such as polymers, oxides, nanoparticles, MXenes, or quantum dots. This is because MOF composites overcome critical limitations of each material when used separately, providing unique synergies that enhance processes such as photocatalysis, peroxide activation, and Fenton-type reactions. While pure MOFs offer high porosity and adsorption capacity, they typically exhibit low stability in aqueous media and limited catalytic activity. On the other hand, materials such as metal oxides, QDs, or MXenes can be good conductors or photocatalysts, but lack the porous structure and molecular selectivity of MOFs. When combined in composites, functional integration is achieved, enabling, for example, improved electron–hole charge separation, accelerated generation of reactive oxygen species (ROS), enhanced structural and hydrolytic stability, and facilitated material reuse. Composites such as MOF@TiO₂, MOF@MXene, or MOF@g-C₃N₄ have demonstrated superior efficiency in the degradation of emerging contaminants such as pharmaceuticals, dyes, and pesticides, even under visible light. Furthermore, some MOF composites enable magnetic separation or even simultaneous detection of the contaminant. Therefore, MOF composites offer an optimal balance of adsorption, reactivity, stability, and processability, positioning them as one of the most advanced and versatile technologies for treating contaminated water in the near future.

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8. Conclusions

MOF-composites represent a promising technology for the adsorption, degradation, and sensing of contaminants in wastewater. Their high adsorption capacity, catalytic properties, and versatility by functional modification make them ideal candidates to address current environmental challenges. With continued advances in their development and production, MOF-composites have the potential to transform wastewater treatment, contributing to environmental protection and public health.

We describe how the combination of other materials provides further expanded the potential for metal–organic frameworks (MOFs), as they have demonstrated to be promising tools in environmental remediation applications, such as wastewater, thanks to their inherent properties and structural versatility. In the case of adsorption, these combinations favour greater capacity and selectivity, to trap contaminants at low concentrations. For degradation, especially in photocatalysis, MOF-composites act as active platforms capable of accelerating the decomposition of contaminants under visible or ultraviolet light. Regarding sensing, the composites enable the precise and early detection of specific contaminants due to their high sensitivity and rapid response. Together, these advances consolidate MOF-composite as a promising technology for advanced wastewater monitoring and remediation.

Author contributions

J. Aguila-Rosas, Francisco J. Cano and Alan Nagayaa wrote the paper with input from all authors. T. Quirino-Barreda and Ma. De Jesús Martínez were involved in managing information and commented on the manuscript. J. Aguila-Rosas, Ariel Guzmán, I. Ibarra and E. Lima designed and directed the project.

Conflicts of interest

There are no conflicts to declare.

Data availability

All the data supporting this article have been included in the main text.

Acknowledgements

This work was supported by the SECIHTI Mexico (CBF2023-2024-227).

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