Open Access Article
Zineb Bouziane
a,
Fouad Amor
a,
Sara Fatine
a,
Jean-Michel Nunzi
*b and
Abdelaziz Laghzizil
a
aLaboratory of Applied Chemistry of Materials, Faculty of Sciences, Mohammed V University in Rabat, Avenue Ibn Batouta BP.1014 Agdal, Rabat, Morocco
bDepartment of Physics, Engineering Physics and Astronomy, Department of Chemistry, Queen's University, Kingston, ON K7L 3N6, Canada. E-mail: nunzijm@queensu.ca
First published on 28th April 2026
Layered double hydroxides (LDHs) are layered materials of increasing interest for environmental applications due to their tunable chemical composition, structure, and adjustable physicochemical properties. This review presents a critical synthesis of recent advances in LDH-based materials, highlighting the close links between synthesis methods, structural characteristics, and key properties controlling their environmental performance. The main synthesis strategies are discussed in relation to their influence on crystallinity, morphology, specific surface area, metal cation distribution, and the nature of structural defects. Particular attention is paid to the effect of cationic composition, interlayer anions, and structural modifications (doping, exfoliation, composite formation) on adsorption, ion exchange, redox activity, and heterogeneous photocatalysis mechanisms. Environmental applications of LDHs are systematically examined, including the adsorption of inorganic and organic pollutants, the photodegradation of emerging contaminants under UV and visible irradiation, and water treatment. LDH-derived materials, particularly mixed metal oxides and LDH/semiconductor composites, are also discussed due to their improved photocatalytic performance and increased stability. Finally, current challenges and future prospects are addressed, with a particular focus on the recyclability, durability, and scaling up of LDH-based materials for advanced environmental applications.
LDH materials have attracted increasing interest in environmental applications thanks to their exceptional combination of structural, textural, and chemical properties.17 They have demonstrated significant effectiveness in removing emerging polluting species, while also establishing themselves as promising platforms in adsorption, catalysis, and photocatalysis processes.7,18,19 In wastewater treatment, LDHs have demonstrated a remarkable capacity for adsorbing and removing heavy metals through mechanisms combining complexation, precipitation, ion exchange, and electrostatic interactions.20–22 For example, functionalized LDHs have been successfully used to remove ions such as Pb2+, Cd2+, Cr6+, or Cu2+ from aqueous solutions, taking advantage of their large active surface area and available chemical sites for selective adsorption.23 Beyond heavy metals, LDHs are effective at capturing toxic oxyanions such as phosphates and nitrates, which are responsible for eutrophication in aquatic systems.24 In photocatalysis, LDHs are particularly attractive due to their tunable semiconducting properties, their ability to absorb light in the UV-visible spectrum, and their capacity to promote the separation of photogenerated electron–hole pairs,17,25 This makes them suitable for applications such as the degradation of organic pollutants,19,26,27 and the photocatalytic reduction of CO2.28 Modifying LDHs via doping, heterojunctions, defects, or conductive supports enhances light absorption, charge separation, and photocatalytic performance.7,29,30 In this context, this critical and comprehensive overview of layered double hydroxides (LDHs) provides a guide for readers to familiarize with their fundamental principles and environmental relevance. It focuses on LDH synthesis strategies using both commercial and natural precursors, and systematically discusses how synthesis parameters, chemical composition, and thermal treatments influence their structural and physicochemical properties. The review further establishes clear relationships between structure, properties, and performance, with particular emphasis on adsorption and photocatalytic applications for environmental remediation. By highlighting current environmental challenges and recent advances, this work clarifies the key factors governing LDH efficiency and supports the rational design of high-performance and sustainable LDH-based materials for future industrial applications.
In biomedical applications, Layered double hydroxides (LDHs) such as MgAl-LDH are used due to their biocompatibility and ability to deliver drugs, genes, and biomolecules, improving bioavailability, controlled release, and anticancer therapy efficiency.38,39 Consequently, LDHs exhibit strong cellular penetration due to their positive charge, which enhances drug delivery efficiency and demonstrates their potential as carriers for genes, proteins, and imaging agents, highlighting their versatility. In addition to biomedicine, LDHs such as MgAl-LDH, ZnAl-LDH, NiAl-LDH, and MgFe-LDH are used as industrial materials including corrosion protection,40,41 barrier coatings,42 polymer nanocomposites,43 and flame-retardants where they enhance mechanical, thermal, and protective properties.44–46
Despite the remarkable performance of layered double hydroxides demonstrated at the laboratory scale, their transition toward industrial applications remains limited. Recent studies highlight that LDHs possess strong potential for large-scale deployment due to their low-cost precursors, structural tunability, and high efficiency in pollutant removal processes.47 However, several critical challenges must be addressed to enable their practical implementation. From a technological perspective, one of the main barriers is the stability of LDH materials under real operating conditions. Under industrial environments, LDHs are exposed to complex physicochemical conditions, including fluctuating pH, high ionic strength, and the presence of competing ions or organic matter. These conditions often lead to structural degradation, metal leaching, and loss of active sites, which significantly reduce their long-term performance and reusability.48 In addition, while many LDH-based systems exhibit excellent efficiency under controlled laboratory conditions, they frequently fail to maintain performance at high flow rates and large-scale continuous operations. This is particularly related to mass transfer limitations, particle aggregation, and poor mechanical stability, which hinder their integration into fixed-bed or membrane-based treatment systems.49 Another important limitation concerns the complexity of real wastewater matrices.50 Unlike synthetic solutions, industrial effluents (e.g., from textile, tannery, or electroplating industries) contain a mixture of heavy metals, dyes, salts, and microorganisms. This complexity can result in competitive adsorption, surface fouling, and reduced selectivity of LDH materials, thereby limiting their efficiency in real applications.51 From an economic and commercial standpoint, challenges include the cost of large-scale synthesis, reproducibility of material properties, and regeneration efficiency. Although LDHs can be synthesized using low-cost or waste-derived precursors (e.g., red mud, slag, or fly ash), scaling up these processes while maintaining consistent quality remains a significant challenge. Nevertheless, the use of industrial waste as a feedstock represents a promising strategy for reducing production costs and improving sustainability. Furthermore, the integration of LDH materials into existing wastewater treatment infrastructures remains underexplored. For industrial adoption, LDHs must be compatible with conventional technologies such as adsorption columns, catalytic reactors, or hybrid advanced oxidation processes. This requires the development of structured or composite materials (e.g., LDH-coated supports, pellets, or membranes) with improved mechanical strength and operational stability. Overall, bridging the gap between laboratory research and industrial implementation requires a shift in focus from maximizing performance under ideal conditions to addressing durability, scalability, and process integration. Future research should prioritize pilot-scale studies, long-term stability assessments, and techno-economic analyses to accelerate the commercialization of LDH-based technologies for wastewater treatment.52
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| Fig. 2 (a) Schematic representation of LDH structure adapted from ref. 53 with permission from MDPI, doi: https://10.3390/catal7090260, copyright 2017 (b) 2D LDH layered materials with a brucite-like structure, composed of M2+/M3+ cations, with interlayer anions and water molecules, adapted from ref. 54 with permission from MDPI, doi: https://10.3390/coatings10070669, copyright 2020. | ||
The partial substitution of M2+ by M3+ generates a net positive charge on the layers, which is compensated by negatively charged interlayer anions and water molecules located in the interlamellar galleries. This layered architecture results in a well-defined lamellar structure, providing LDHs with high anion-exchange capacity, tunable chemical composition, and significant structural flexibility (Fig. 3). The ratio of M2+ to M3+ cations critically influences the charge density of the layers, the distortion of the octahedral sheets, and the interlayer spacing, thereby affecting lattice parameters, porosity, and overall structural stability.26 Interlayer anions, such as CO32−, NO3−, Cl−, SO42−, or organic anions,55 are held by electrostatic forces and hydrogen bonding with hydroxyl groups and water molecules, and they are exchangeable, enabling ion-exchange processes central to the chemical reactivity, adsorption, and functional versatility of LDHs. The nature, charge, and size of these interlayer anions strongly influence the physicochemical properties of LDHs.56 Highly charged anions, such as CO32−, interact strongly with the hydroxide layers, enhancing structural stability and reducing interlayer spacing, whereas bulkier or monovalent anions lead to expanded interlayer galleries and increased flexibility.26,55,56 Structural defects and heterogeneity in the interlayer space further modulate charge distribution, active site accessibility, and the adsorption or catalytic performance of LDH materials, making them versatile for applications in ion exchange, catalysis, and environmental remediation.
As an illustrative example from ref. 57 Fig. 4a shows the X-ray diffraction (XRD) patterns of the chloride ZnFe-LDH (ZnFe-Cl), Nitrate ZnFe-LDH (ZnFe-NO3) and Carbonate ZnFe-LDH (ZnFe-CO3). All samples exhibit the characteristic diffraction peaks of layered double hydroxides, indexed along the (003), (006), (012), (015), (110), and (113) planes,58 thus confirming the formation of the LDH structure. A slight decrease in interplanar spacing is observed between ZnFe-Cl (7.9 Å), Zn/Fe-NO3 (7.89 Å), and ZnFe-CO3 (7.8 Å), which can be attributed to the higher charge density of carbonate anions.57 These results indicate that all synthesized ZnFe LDHs possess a well-ordered lamellar structure, regardless of the intercalated anion. The reduced basal spacing in carbonate-intercalated LDH reflects stronger electrostatic interactions between divalent CO32− anions and positively charged hydroxide layers, resulting in a more compact interlayer configuration than in LDH containing monovalent nitrate or chloride ions. Furthermore, FT-IR analysis confirms the structural integrity of the LDH network, as evidenced by similar M-O vibration bands around 1000 cm−1 and characteristic vibrations associated with hydroxyl groups at 1630 cm−1 and 3460 cm−1 for all samples Fig. 4b. Distinct absorption bands corresponding to interlayer anions were observed at approximately 1370 cm−1 for CO32−, 1384 cm−1 for NO3−, and 868 cm−1 for Cl–O, thus confirming the successful and selective intercalation of the respective anions. These anion-dependent structural features are expected to influence the physicochemical properties and potential applications of ZnFe-LDH.
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| Fig. 4 (a) Typical XRD patterns and (b) FTIR spectra of ZnFe-based LDHs with different interlayer anions (Cl−, NO3− and CO32−), adapted from ref. 58 with permission from Elsevier, doi: https://10.1016/j.cej.2011.10.070, copyright 2012. | ||
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| Fig. 5 Typical schematic illustration of LDHs synthesis via co-precipitation and hydrothermal routes. | ||
As shown in Table 1, hydrothermal, solvothermal, sol–gel, and microwave methods produce well-ordered sheets with high surface areas (100–300 m2 g−1) and variable crystallite sizes, while coprecipitation and mechanochemical routes give moderate crystallinity and smaller surface areas (70–150 m2 g−1). Electrochemical synthesis mainly forms uniform films with lower surface areas. The choice of method thus depends on the targeted crystallinity, surface area, and crystallite size, which govern performance in catalysis, adsorption, or other applications.
| Method | Structural features | Interlamellar distance d (Å) | Crystallite size (nm) | Specific surface area (m2 g−1) | Ref. |
|---|---|---|---|---|---|
| Coprecipitation | Uniform lamellar layers, moderate crystallinity | 7.6–8.0 | 10–25 | 80–150 | 59 |
| Hydrothermal | High crystallinity, well-ordered sheets | 7.8–8.2 | 20–40 | 100–200 | 32 |
| Solvothermal | Palmate sheets, solvent-controlled morphology | 7.7–8.3 | 15–35 | 120–220 | 37 |
| Sol–gel | Homogeneous network, regular morphology | 7.6–8.1 | 10–30 | 150–250 | 60 |
| Microwave | Rapid nucleation, thin crystallites | 7.8–8.0 | 5–20 | 180–300 | 61 |
| Electrochemical | Films uniform LDH on substrate | 7.6–8.0 | 15–30 | 50–120 | 62 |
| Mechanochemical | Sheet formation, but low crystallinity | 7.5–7.9 | 10–25 | 70–150 | 58 |
Controlled pH and addition rates during synthesis yield a well-ordered lamellar structure with evenly distributed cations, resulting in enhanced anion exchange capacity and structural stability of MgAl-LDH and ZnAl-LDH.63 Comparatively, hydrothermal synthesis, by involving heat treatment under pressure, significantly increases crystallinity and lamellar order, leading to structures where the basal planes exhibit stronger and sharper XRD peaks.32,37 Table 2 summarizes the effects of hydrothermal operating parameters on the structure of the developed LDH materials. Furthermore, employing solvothermal methods with different solvents alters the morphology of the nanosheets and enhances accessibility to surface active sites, thereby improving the performance of LDHs in demanding applications like selective adsorption and photocatalysis. Meanwhile, alternative methods such as urea hydrolysis produce LDH with finer morphologies and high specific surface areas, well suited for pollutant adsorption and catalysis.61 Microwave-assisted synthesis, although less represented in global reviews, is known to accelerate nucleation and reduce crystallite size, leading to highly reactive nanostructures with large specific surface areas, which is particularly beneficial for electrochemical and catalytic applications,21,64 Finally, sol–gel or mechanochemical approaches affect cation dispersion and sheet size, thus influencing key properties such as specific surface area, thermal stability, or surface reactivity.25
| Operating parameter | Typical values | Structural effects | Ref. |
|---|---|---|---|
| Temperature | 80–120 °C | Dominant nucleation, moderate crystallinity, thin sheets | 65 |
| 150–200 °C | High crystallinity, sheet growth, improved lamellar order | 66 | |
| >180–200 °C | Partial dehydroxylation, LDO formation | 67 | |
| Autogenic pressure | 1–5 MPa | Improved solubility and re-crystallization | 68 |
| Processing time | 6–12 h | LDH with weak crystallization, small crystallite size | 69 |
| 24–48 h | Structural maturation, improved thermal stability | 23 | |
| Initial pH | 8–9 | Partial formation, structural defects | 70 |
| 9–10 | Well-crystallized LDH, stable structure | 71 | |
| >10.5 | Precipitation of simple hydroxides | 72 | |
| Solvent (solvothermal) | Water | Classic lamellar morphology | 73 |
| Eau/Ethanol | Thinner nanosheets, surface ↑ | 51 | |
| Polyols | Advanced morphological control | 62 | |
| Precursor concentration | 0.05–0.1 M | Homogeneous LDH, low aggregation | 74 |
| >0.3 M | Aggregation, structural defects | 57 |
However, the synthesis method plays a crucial role in determining the structural and physicochemical properties of layered double hydroxides (LDHs), which ultimately influence their performance in different applications. For instance, co-precipitation, one of the most commonly used synthesis routes, typically produces LDHs such as MgAl-LDH or ZnAl-LDH with relatively small crystallite sizes and high surface areas. These characteristics are particularly advantageous for applications in adsorption and water treatment, where a high density of active sites is required. In contrast, hydrothermal synthesis often leads to LDHs with improved crystallinity and more ordered layered structures. LDHs such as NiFe-LDH or CoAl-LDH prepared through hydrothermal treatment have demonstrated enhanced electrochemical and catalytic properties, making them promising materials for electrocatalysis and energy-related applications. The increased crystallinity and structural stability obtained by this method can improve electron transfer and catalytic efficiency. Similarly, sol–gel and reconstruction (memory effect) methods allow better control over particle morphology and interlayer composition. These approaches are particularly useful when designing LDHs for drug delivery, controlled release systems, or functional nanocomposites, where precise control of particle size and interlayer chemistry is essential. Overall, recent studies highlight that optimizing the synthesis strategy is essential to tailor LDH properties for specific applications. Rather than considering applications independently, it is important to understand how composition (e.g., MgAl-LDH, ZnAl-LDH, NiFe-LDH), morphology, crystallinity, and interlayer chemistry are directly influenced by the synthesis method and determine the resulting performance. Table 3 summarizes these aspects to illustrate the relationship between the synthesis method and the structure of LDH materials, as well as their main applications.
| Synthesis method | LDH composition | Structural characteristics | Main applications |
|---|---|---|---|
| Co-precipitation | MgAl-LDH, ZnAl-LDH | Small crystallites, high surface area | Adsorption, water treatment |
| Hydrothermal | NiFe-LDH, CoAl-LDH | High crystallinity, ordered layers | Electrocatalysis (OER), energy conversion |
| Sol–gel | MgFe-LDH | Controlled morphology | Catalysis |
| Reconstruction | Various LDHs | Rehydration ability, tunable interlayer chemistry | Drug delivery, functional materials |
Conventional LDH synthesis methods such as co-precipitation and hydrothermal routes are well established, robust, and reproducible, but they often rely on high-purity reagents and controlled conditions, which may limit their sustainability and large-scale applicability. Recently, increasing attention has been given to the synthesis of LDHs from waste-derived precursors as a more sustainable alternative. Although promising in terms of cost reduction and environmental impact, these approaches still face challenges related to variability of raw materials and control over final material properties, requiring further optimization. In this context, natural resources and industrial wastes have emerged as promising substitutes for conventional chemical reagents.80 These materials, including mineral ores, brines, red mud, slag, or other industrial by-products, contain significant amounts of metal ions that can be recovered and utilized for LDH synthesis. The use of such resources not only reduces the overall cost of production but also contributes to waste valorization and environmental protection. Therefore, the synthesis of LDHs from natural and waste-derived precursors has attracted increasing attention, particularly in studies focused on environmental applications, as it aligns with the principles of sustainable chemistry and circular economy. The synthesis of LDH from clays, metallurgical waste or industrial by-products constitutes a sustainable and valuable approach, making it possible to produce functional lamellar materials while reducing the environmental footprint.81,82 Extraction and activation of natural precursors by dissolution, calcination, or hydrothermal processes promotes the formation of crystalline LDH with typical specific surface areas of 50–150 m2 g−1 and crystallites of 10–30 nm.83,84 These studies have shown that synthesizing LDHs from natural resources or waste is not only feasible but also produces functional materials with performance comparable to LDHs developed from commercial reagents, while providing notable environmental and economic advantages.
| Composition/parameter | Nature of doping/cation added | Structural effects observed | Physico-chemical properties | Thermal stability | Ref. |
|---|---|---|---|---|---|
| Binary systems: MgAl-LDH | No specific doping agents, main cations | –High crystallinity for MgAl-LDH, and ZnAl-LDH. | Specific surface area 50–200 m2 g−1, moderate porosity, high anion exchange capacity | −400–500 °C for MgAl-LDH, ZnAl-LDH. | 88 |
| ZnAl-LDH | –Octahedral distorsion for NiAl-LDH et FeAl-LDH. | −350–450 °C for (Ni–Al, Fe–Al) | |||
| NiAl-LDH | |||||
| Fe-Al-LDH | |||||
| Ternary/multi-cationic systems | Additional cations: Zn2+, Mg2+, Co2+, Ni2+, Fe3+, Al3+ | Controlled lamellar heterogeneity, modulation of active sites, partial disorder | Specific surface area 70–250 m2 g−1, increased porosity, improved catalytic dispersion | 350–500 °C depending on the composition | 89 |
| Isomorphic substitution/metal doping | Common dopants: Fe3+, Co2+, La3+, Mn2+, Cr3+ | Modification of parameters, introduction of defects, variation in surface reactivity | Increase or decrease in specific surface area depending on the dopant, modification of the basicity/acidity of the sites, adjustable chemical stability | 350–500 °C depending on the doping | 86 |
| Incorporation of functional anions | Interlayer anions: CO32−, NO3−, Cl−, SO42−, organic anions | Variation in interlayer spacing, modulated interlayer interactions | Adjustable specific surface area, modified anion exchange capacity, structural flexibility | 300–450 °C for organic anions, >400 °C for inorganic anions | 87 |
| Effect of the M2+/M3+ ratio | Variation of the ratio Mg2+/Al3+, Zn2+/Al3+, Ni2+/Al3+ | Optimization of charge density, balance between structural stability and accessible surface area | Influence on porosity, specific surface area and reactivity, maximum adsorption capacity for intermediate ratios | 350–500 °C depending on the ratio chosen | 17 |
| LDH type | Operating parameter | Typical values | Structural effects |
|---|---|---|---|
| Carbonated MgAl-LDH | Thermal treatment | 400–500 °C | Reactive amorphous LDO, partially preserved lamellar layers, strongly bound CO32− anions maintain local order |
| >600 °C | Formation of MgAl2O4 spinel, partial loss of lamellar order | ||
| Dehydroxylation/Decarbonation | Controlled thermal process | Collapse of the layers, release of intercalated OH− and CO32− | |
| Memory effect | Rehydration | Partial reconstruction of the lamellar layers, recovery of anion exchange | |
| Specific surface area | 50–150 m2 g−1 | Creation of pores and active sites, adsorption and catalytic reactivity | |
| Sulphated MgAl-LDH | Thermal treatment | 400–500 °C | Amorphous LDO, partially retained leaflets |
| >600 °C | Partial formation of MgAl2O4 spinel, lamellar disorder | ||
| Dehydroxylation/decarbonation | Thermal process | Lamellar collapse and release of OH− and SO42- | |
| Memory effect | Rehydration | Partial reconstruction of lamellar layers, capacity for anion exchange | |
| Specific surface area | 50–160 m2 g−1 | Increased surface area and porosity, improved catalytic activity | |
| Carbonated ZnAl-LDH | Thermal treatment | 400–500 °C | Amorphous LDO, partial retention of leaflets |
| >600 °C | Formation of ZnAl2O4 spinel, loss of lamellar order | ||
| Dehydroxylation/decarbonation | Thermal process | Collapse of the layers and release of intercalated CO32− | |
| Memory effect | Rehydration | Partial restoration of the lamellar layers | |
| Specific surface area | 60–180 m2 g−1 | Increased surface area and porosity, catalytic | |
| Carbonated FeAl-LDH | Thermal treatment | 400–500 °C | Amorphous LDO with partial retention of the lamellar structure |
| >600 °C | Formation of Fe2O3 and FeAl2O4 spinel, lamellar disorder | ||
| Dehydroxylation/decarbonation | Thermal process | Lamellar collapse and release of intercalated anions | |
| Memory effect | Rehydration | Partial reconstruction of the structure, recovery of anion exchange | |
| Specific surface area | 60–170 m2 g−1 | Pore creation and increased surface area, improved adsorption and catalytic activity | |
| Sulphated CoAl-LDH | Thermal treatment | 400–500 °C | Amorphous LDO with partially preserved sheets |
| >600 °C | Crystallization in CoAl2O4 spinel, loss of lamellar order | ||
| Dehydroxylation/decarbonation | Thermal process | Sofa collapse, OH− and SO42− release | |
| «Memory effect» | Rehydration | Partial restoration of the lamellar structure | |
| Specific surface area | 60–180 m2 g−1 | Pore creation and surface area increase, catalytic |
| LDH | Pollutant | Key conditions | Capacity qmax (mg g−1) | Adsorption mechanism | Ref. |
|---|---|---|---|---|---|
| MgLa-LDH | PO43− | Batch, pH 6–7, contact 25–60 min, 25 °C | 87.23 | Chemisorption monolayer, ion- exchange, surface complexation | 91 |
| MgAl-LDH@Biochar | Cu2+, Co2+, Pb2+, PO43− | pH 5–7, 30–120 min, dose 0.5–1 g L−1 | Cu2+: 25.8; Co2+: 15.0; Pb2+: 40.4; PO43−: 21.8 | Ion-exchange + surface complexation | 89 |
| FeMg-LDH@ Bentonite | Pb2+, Cd2+ | Batch, pH 6, 2 h, 2 g L−1 | Pb2+: 1397.6; Cd2+: 510.2 | Surface complexation + ion exchange + precipitation | 95 |
| Activated carbon@ MgAl-LDH (composite) | PO43− | Batch, pH 6, 22 °C, 1 h | 209.8–337.2 | Electrostatic + ion-exchange + inner-sphere complexation | 96 |
| (CO3/Cl) MgZnAl-LDH | Textile dye IDB | pH 4.6, 6 h, dose 2 g L−1 | 94.5 | Chemisorption | 97 |
| MgAl-LDH | Reactive Black 5 | 30 °C, pH 5–6, 4 h | 61.3 | Anion exchange + surface adsorption | 68 |
| MgAl-LDH | Methylene blue, amoxicillin | pH 11, 50 mg L−1 adsorbent, 120 min | 114.94 | H-bonding + Van der Waals | 93 |
| 48.08 | |||||
| Cellulose@CoFe LDH composite | Sulfamethoxazole cefixime | pH 5, 0.1 g adsorbent | 272.13 | Surface Binding, complexation | 98 |
| 208.00 | |||||
| MgFe-LDH@ Biochar | Tetracycline, ciprofloxacin | Batch, wide pH range | 77.04 | Complexation + H-bonds | 99 |
| Batch, wide pH range | 66.74 | ||||
| Activated carbon@ MgFe-LDH composite | Phenol | — | 138.69 | Chemical bonding + π–π interactions | 100 |
| Carbon-LDH materials | Methylene blue | T∼30 °C, pH 6.8 | 328.95 (MO); ∼80–122 (MB) | Langmuir adsorption | 101 |
| Methyl orange, congo red, crystal violet | Varied | 100–400 | Electrostatic+ π–π + H-bonding | 102 |
The primary mechanism is ion exchange, where interlayer anions of LDH, such as CO32−, NO3−, or Cl−, are replaced by anions present in the solution (Fig. 6). This interaction is particularly effective for capturing heavy metals and organic anions (dyes, pharmaceuticals). The efficiency of the exchange is highly dependent on pH, the nature and charge of the anion, and the availability of interlayer sites within the lamellar structure. Simultaneously, surface adsorption occurs via electrostatic interactions. Hydroxyl groups in LDH layers can interact with metal cations through chemical complexation, or with polar organic molecules through hydrogen bonding and electrostatic interactions. For Pb2+, Cd2+ or Cu2+ ions, they can bind directly to hydroxyl sites, while negatively charged organic molecules are attracted to the positively charged surfaces of LDH. Certain molecules or ions can also be trapped in the interlayer spaces. This intercalation mechanism is often observed for organic or neutral anions and allows for partial confinement of contaminants, thus increasing adsorption capacity. The size and polarity of the contaminant, as well as the expansion of the interlayer space, strongly influence this type of adsorption. LDHs can be combined with other materials to form composites, for example with carbon (LDH@C) or semiconducting oxides (LDH@TiO2, LDH@ZnO), which introduces synergistic mechanisms. In LDH@C composites, π–π and electrostatic interactions enhance the adsorption of aromatic molecules, while LDH@oxide enables the photodegradation of organic pollutants while maintaining complementary adsorption. Finally, several factors influence the adsorption performance on LDH: the pH of the solution, which determines the surface charge and the ionic species of the contaminant; the temperature, which affects the kinetics and equilibrium of adsorption; the LDH dosage, which conditions the maximum capacity; and the structural composition of LDH, including the M2+/M3+ cation ratio, the nature of the interlayer anions and the specific surface area. In summary, contaminant adsorption on LDHs results from a combination of ion exchange, surface adsorption, intercalation, and, in the case of composites, synergistic mechanisms, making these materials particularly effective for treating a wide range of inorganic and organic pollutants. Understanding and modulating these mechanisms is essential for optimizing the environmental performance of LDHs.
| Step | Key process | Mechanistic description | Specific role of LDH |
|---|---|---|---|
| 1 | Light absorption | Under UV or visible irradiation, LDH or the LDH/semiconductor composite absorbs photons and generates electron–hole pairs (e−/h+) | Bandgap adjustment by doping or heterojunction |
| 2 | Generation of charges | Excitation of electrons from the valence band to the conduction band | Lamellar structure facilitating charge migration |
| 3 | Separation of charges | Directional transfer of electrons and holes at the LDH/semiconductor interface, limiting their recombination | Formation of efficient heterojunctions |
| 4 | Pollutant adsorption | Adsorption of pharmaceutical molecules on the surface or within the interlayer space | Positively charged leaves and high adsorption capacity |
| 5 | Oxygen reduction | Electrons react with O2 to form superoxide radicals (˙O2−) | Redox active sites (Fe, co, Ni, Cu…) |
| 6 | Oxidation of water/OH− | The holes oxidize H2O or OH− to generate hydroxyl radicals (˙OH) | Hydroxylated surface rich in –OH groups |
| 7 | ROS generation | Formation of highly reactive ROS (˙OH, ˙O2−, 1O2) | Stabilization and amplification of reactive species |
| 8 | Radical attack | ROS attack the aromatic and functional bonds of pollutants | Proximity between surface and pollutant is favored by adsorption |
| 9 | Mineralization | Final oxidation to CO2, H2O and inorganic ions | Maintenance of catalytic activity and recyclability |
Under UV or visible light, LDHs or LDH-semiconductor composites absorb photons to generate electron–hole pairs, initiating the photocatalytic process. The lamellar structure of LDHs facilitates charge separation and migration to the surface, where redox reactions occur. In pure LDHs, rapid electron–hole recombination can limit efficiency, but in composites, heterojunctions promote directional charge transfer and extend the lifetime of active charges. Photoexcited electrons reduce oxygen to superoxide radicals, while holes oxidize water or hydroxyl ions to hydroxyl radicals. These reactive species degrade pollutants, and the adsorption of contaminants on the LDH surface enhances their interaction with radicals, improving overall photocatalytic performance. The degradation of drug residues then occurs through a series of non-selective radical reactions. Hydroxyl and superoxide radicals attack the most reactive bonds of polluting molecules, such as aromatic rings, amine groups, or alkyl side chains. This attack leads to the progressive disruption of the molecular structure, the formation of lower molar mass intermediates, and their subsequent oxidation until partial or total mineralization into carbon dioxide, water, and inorganic ions. In certain doped or modified LDH systems, the presence of redox-active metal cations can also contribute to additional electron transfers, enhancing the generation of oxidizing species and accelerating the degradation kinetics. Thus, the photodegradation mechanism of pollutants by LDH relies on a synergy between adsorption, photo-induced excitation, efficient charge separation, and the production of reactive oxygen species. This combination gives LDHs and their composites a particular effectiveness for the degradation of persistent pharmaceutical pollutants, while offering great design flexibility for optimizing activity under visible light and realistic environmental conditions. Fig. 7 illustrates the generation of photo-excited electron–hole pairs upon light absorption by the LDH material, the subsequent formation of reactive oxygen species (ROS) such as ˙OH and ˙O2−, and their role in oxidizing adsorbed organic pollutants. The LDH structure facilitates charge separation and provides active sites for adsorption, enhancing the overall photocatalytic efficiency.
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| Fig. 7 Schematic representation of the photocatalytic degradation mechanism of organic pollutants on LDHs under light irradiation. | ||
Table 8 summarizes the type of catalyst, the target pollutant, the optimized operating conditions and the degradation efficiency or removal rate along with the reaction time reported in the literature. LDHs and their composites have proven effective for the degradation of organic pollutants such as pharmaceuticals and dyes under UV or visible light irradiation. Carbonated ZnCr-LDH or modified LDHs (carbon doped ZnCr-LDH) have shown high degradation rates (77–90%) in relatively short times, thanks to improved light absorption, efficient separation of photoexcited charges, and enhanced adsorption of pollutants on the catalyst surface.108 Composites incorporating semiconductors, conductive supports (g-C3N4, MXene, h-BN), or S-scheme heterojunctions promote electron–hole separation, extending the lifetime of active charges and increasing the production of reactive radicals responsible for pollutant degradation. These advances not only allow the efficient treatment of pharmaceutical residues such as ibuprofen, ciprofloxacin, tetracycline, gemifloxacin and oxytétracycline, but also extend the application of LDHs to other emerging contaminants. The performance of LDHs strongly depends on their metal composition, lamellar structure, the presence of dopants or conductive supports, and their adsorption capacity, making these materials a versatile and promising catalytic platform for the remediation of contaminated water.
| Catalyst | Pollutanta | Optimized operating conditions | Degradation/time | Ref. |
|---|---|---|---|---|
| a Tetracycline (TC), gemifloxacin (GEM), sulfamethoxazole (SUL), oxytétracycline (OXY), ibuprofen (IBU), rifampicine (RIF), methylene blue (MB). Red phosphorus (RP). | ||||
| g-C3N4@ZnFe-LDH | TC | UV light + oxone (peroxymonosulfate) to generate SO4˙− and ˙OH, combined with LDH composite | 92.4% in 30 min | 109 |
| Zn-Co-LDH@ Biochar | GEM | UV light irradiation, catalyst loading optimized | ∼92.7% in 200 min | 110 |
| LDH@Fe3O4-Ag | TC | Irradiation visible, 90 min, pH 9, initial TC 35 ppm, photocatalyst 0.05 g L−1 | 96.4% in 200 min | 111 |
| Zn-TMU-5@30%Ni-Ti -LDH | SUL | Natural solar light, 0.1 g L−1 catalyst | >98% in 45 min | 112 |
| g- C3N4/@ZnFe-LDH | TC | UV + oxone (persulfate source) (US assist) | 100% TC in 25 min | 113 |
| g-C3N4/MgZnAl-LDO | TC | Visible light | 100% in 120 min) | 114 |
| La-NiAl-LDH@hematene composite | RIF | Visible light, charge separation improved | ≈ 89.2% in 120 min | 94 |
| RP@ZnAl-LDH | TC | Visible light | 89% in 90 min | 91 |
| MgAl-LDH@g- C3N4@Ag3PO45 | MB | Visible light (150 W mercury lamp), pH = 11, catalyst 0.05 g/100 mL, dark adsorption step, 45 min irradiation | 99% in 45 min | 115 |
| O-doped g- C3N4@LDH | MB | Visible light, catalyst dose & pH increased to maximize ˙OH radicals | ≈98.5% | 96 |
| ZnAl-LDH@POM | MB | Visible light irradiation, catalyst loading 0.6 g L−1, [MB] ∼7.5 mg L−1, pH ∼6 | ∼78% (varies with composition) | 116 |
The thermal stability of LDHs remains a critical parameter for their reuse as adsorbents or catalysts. Calcination, for example at 600 °C, can sometimes lead to the formation of LDOs, resulting in the loss of lamellar structure and porosity, which reduces their efficiency. To address this issue, it is preferable to use LDHs as they are while enhancing their thermal stability, allowing their reuse by burning residual molecules and/or by-products at 600 °C without altering the structure or surface. Strategies such as the careful selection of cations, metal doping, and the integration of stable supports help reinforce thermal robustness. Thermally stable LDHs can thus be efficiently recycled, maintaining their performance and enabling the safe destruction of by-products, thereby optimizing their role in environmental applications.
Overall, the above discussion highlights that while LDH-based materials demonstrate remarkable environmental performance and significant application potential, addressing the remaining challenges is essential to fully bridge the gap between laboratory research and real-world industrial implementation. These considerations provide a solid basis for the general conclusions of this review. Layered double hydroxides are highly promising materials for environmental applications due to their tunable composition, high surface area, and strong anion-exchange capacity, which enable efficient adsorption and photocatalytic degradation of pollutants. After suitable modification or coupling with semiconductors, they exhibit enhanced visible-light activity, improved charge separation, and higher generation of reactive species, making them effective for water and air purification. Their low cost, structural flexibility, and easy synthesis further strengthen their application potential. However, challenges such as scalability of synthesis, structural stability, particle recovery, and cost of some doped systems still limit their industrial deployment. Overall, LDHs remain strong candidates for environmental remediation, provided that efforts focus on improving large-scale production, durability, and practical implementation.
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