Organic-inorganic Composites Research Articles

Quantitative study of competitive and selective immobilization of Pb(II)-Ni(II)-Zn(II)-MB(I) by biogenic monohydrocalcite composite and its potential environmental effects.

The study of the competitive and selective immobilization properties and mechanisms of pollutants immobilized by metastable biogenic monohydrocalcite is of great importance for the assessment of the eco-environmental effects and applications of hydrated calcite at the Earth's poles. Microbial culture technology was used to induce the synthesis of biogenic monohydrocalcite (BMHC), and mineral characterization, batch adsorption experiments and chemical analyses were further used to investigate the sequestration characteristics, mechanism of action, and environmental effects of BMHC on Pb(II)-Ni(II)-Zn(II)-methylene blue (MB) compound pollution. The results show that BMHC is an organic-inorganic mineral composite (about 3.60 % organic matter, Mg/Ca ≈ 0.07). The adsorption and immobilization processes of Pb(II), Ni(II), Zn(II), and MB(I) by BMHC are all better fitted by the pseudo-second-order kinetic equation. The passivation ability of BMHC for contaminants is ranked as Pb(II) ≫ Zn(II) > Ni(II) > MB(I). BMHC exhibits an excellent selective sequestration capacity of Pb(II) (k ≥ 31.89), which is related to the solubility product of the carbonate minerals, the initial concentration of Pb(II), ion exchange and mineral phase transformation. Studies have shown that the synthesis and transformation of monohydrocalcite at the Earth's poles may regulate the biogeochemical cycling of environmental pollutants. The study provides a theoretical basis for the environmental effects and geochemical action of biogenic monohydrocalcite and its applications.

Research Progress on Solid-State Electrolytes in Solid-State Lithium Batteries: Classification, Ionic Conductive Mechanism, Interfacial Challenges

Solid-state lithium batteries exhibit high-energy density and exceptional safety performance, thereby enabling an extended driving range for electric vehicles in the future. Solid-state electrolytes (SSEs) are the key materials in solid-state batteries that guarantee the safety performance of the battery. This review assesses the research progress on solid-state electrolytes, including polymers, inorganic compounds (oxides, sulfides, halides), and organic–inorganic composites, the challenges related to solid-state batteries in terms of their interfaces, and the status of industrialization research on solid-state electrolytes. For each kind of solid-state electrolytes, details on the preparation, properties, composition, ionic conductivity, ionic migration mechanism, and structure–activity relationship, are collected. For the challenges faced by solid-state batteries, the high interfacial resistance, the side reactions between solid-state electrolytes and electrodes, and interface instability, are mainly discussed. The current industrialization research status of various solid electrolytes is analyzed in regard to relevant enterprises from different countries. Finally, the potential development directions and prospects of high-energy density solid-state batteries are discussed. This review provides a comprehensive reference for SSE researchers and paves the way for innovative advancements in regard to solid-state lithium batteries.

Inorganic‐Organic Composite Cathode Materials for Aqueous Zinc Ion Batteries

AbstractAs potential candidates for large‐scale energy storage systems, aqueous zinc‐ion batteries (AZIBs) have attracted more and more attention from researchers and investors. Tremendous efforts have been devoted to develop high‐efficient cathode materials for improving comprehensive performances of AZIBs. Recently reported inorganic‐organic composite (IOC) cathode materials exhibited excellent electrochemical performance and were generally superior to corresponding inorganic or organic cathode materials. This paper presents a timely review on recent progresses and challenges in IOCs for AZIBs. Preparation strategies of IOCs have been elaborated and categorized, recent advances and main working mechanisms of IOCs are exhibited with a focus on the analysis methods for mechanism studies, outlooks and challenges of IOC cathodes for AZIBs are outlined to guide their future development.

Calcium Carbonate as an Ionic Molecular Lock for Ultrastrong Fluorescence of Single Organic Molecules

Locking molecular conformation are widely applied in molecular engineering for improved performance. However, locking via organic functional groups often changes the original molecular properties. Following the rigidity and stability of ionic interaction in ionic compounds, we suggested the use of a molecular‐scale ionic compound, calcium carbonate oligomer, as a robust molecular segment to functionalize organic molecules. The rigid structure of the ionic molecular segments locked the organic molecules, which could remarkably limit the intramolecular motion and intermolecular interactions. This ensured a stable and ultrastrong fluorescence of the single organic molecule while preserving its original maximum emission wavelength. The locking strategy was general and extendable to multiple organic molecules. Additionally, the ultrastrong single‐molecular fluorescence can be maintained in inorganic solids with even higher quantum yields and almost unchanged maximum emission wavelength. The highest quantum yield of the investigated molecules reached 99.9%, superior to all reported organic‒inorganic fluorescent composite under air conditions. This work demonstrates a general strategy to restrict intramolecular motion and intermolecular interactions by using ionic oligomers as molecular locks, providing an alternative method for realizing ultraemissive molecules. This further demonstrates a fascinating example of molecular engineering in the presence of inorganic ionic molecules.

Calcium Carbonate as an Ionic Molecular Lock for Ultrastrong Fluorescence of Single Organic Molecules.

Locking molecular conformation are widely applied in molecular engineering for improved performance. However, locking via organic functional groups often changes the original molecular properties. Following the rigidity and stability of ionic interaction in ionic compounds, we suggested the use of a molecular-scale ionic compound, calcium carbonate oligomer, as a robust molecular segment to functionalize organic molecules. The rigid structure of the ionic molecular segments locked the organic molecules, which could remarkably limit the intramolecular motion and intermolecular interactions. This ensured a stable and ultrastrong fluorescence of the single organic molecule while preserving its original maximum emission wavelength. The locking strategy was general and extendable to multiple organic molecules. Additionally, the ultrastrong single-molecular fluorescence can be maintained in inorganic solids with even higher quantum yields and almost unchanged maximum emission wavelength. The highest quantum yield of the investigated molecules reached 99.9%, superior to all reported organic‒inorganic fluorescent composite under air conditions. This work demonstrates a general strategy to restrict intramolecular motion and intermolecular interactions by using ionic oligomers as molecular locks, providing an alternative method for realizing ultraemissive molecules. This further demonstrates a fascinating example of molecular engineering in the presence of inorganic ionic molecules.

Cryogels Composites: Recent Improvement in Bone Tissue Engineering.

Autogenous bone grafts have long been considered the optimal choice for bone reconstruction due to their excellent biocompatibility and osteogenic properties. However, their limited availability and associated donor site morbidity have led to exploration of alternative bone substitutes. Cryogels, with their interconnected porosity, shape recovery, and enhanced mass transport capabilities, have emerged as a promising polymer-based solution. By incorporating bioactive glasses and nanofillers, cryogel composites offer bioactivity, cost-efficiency, and easy cell integration. This approach not only enhances bone regeneration but also underscores the broader role of nanotechnology in regenerative medicine. This mini-review discusses the advancement of organic-inorganic composites, focusing on biopolymeric cryogels and inorganic elements for reinforcement. We highlight how cryogels can be integrated into minimally invasive procedures, reducing patient distress and complications, and advanced 3D-printing techniques that enable further customization of these materials to mimic bone tissue architecture, offering potential for patient-specific treatments.

Real-time observation of crystals growth under optical microscopy: A self-assembly process of organic-inorganic intercalation composites driven by electrostatic interaction

The utilization of self-assembly through non-covalent forces such as electrostatic interactions and hydrogen bonds offers an effective strategy for the construction of organic-inorganic intercalation composite materials. Although self-assembly strategies hold significant potential, the embedding of organic guest molecules within inorganic host materials through self-assembly processes remains unexplored. In this work, the real-time observation of the self-assembly process of organic-inorganic intercalation composite materials has been achieved using confocal microscopy. We found that methylene blue intercalated molybdenum oxide (MB-MoO3-x) can be synthesized using a mild solution-phase self-assembly reaction and proposed a potential crystal growth model. Our findings indicate that the intercalation of MB remarkably increases the interlayer spacing of MoO3, that causes a transition from an amorphous to a more ordered crystalline structure. Adjusting UV irradiation and N-Methyl-2-pyrrolidone (NMP) content, the particle size of MB-MoO3-x could be controlled, ranging from 400 nm to 500 μm. Characterization techniques such as XPS, FTIR and Raman spectroscopy revealed that the self-assembly of MB with MoO3 is driven by non-covalent electrostatic interactions. Our research provides significant insights into the self-assembly mechanism of organic-inorganic intercalation composite materials, aiding the development of materials that combine the stability and electronic utility of inorganic metal oxides with the chemical diversity and functionality of organic molecules.

Petal-like ammonia phosphotungstate/polyimides for enhanced photocatalysis

The profound influence of morphology on photocatalysis is clear. This study synthesized a polyimide composite, DMBD-PW, via solid phase thermal polymerization, ammonium phosphotungstate as a precursor, and monomolecular terminator phthalic anhydride (PA) for modulating its morphology. Transmission electron microscopy revealed its petal-like structure. DMBD-PW showed improved visible light absorption and enhanced photogenerated electron transfer, compared with the bulk BD-PW without PA. Under visible light irradiation, DMBD-PW could be used for photocatalytic degradation of three neonicotinoid insecticides: imidacloprid, acetamiprid, and thiacloprid, and exhibited remarkable photocatalytic activity. The test results confirmed that the structure of DMBD-PW remained intact after multiple uses without substantial alterations. A potential photocatalytic mechanism was proposed during the research. This study would help to understand the application of modulating the morphology of inorganic–organic composites in photocatalysis.

Stabilization of arsenic-cadmium co-contaminated soil with the iron-manganese sludge derived amendment: Effects and mechanisms

An iron-manganese sludge-derived amendment was proposed to remediate arsenic (As) and cadmium (Cd) co-contaminated soil, with a strong adsorptive capacity across pH 4 to 10. The Langmuir model defined maximum adsorption at 78.17 mg/g for As(III), 110.48 mg/kg for As(V), and 65.77 mg/g for Cd(II). The X-ray photoelectron spectroscopy (XPS) spectra provided insights into the chemical interactions: As was predominantly complexed or ligand exchanged with iron(hydr)oxides. In contrast, cadmium exhibited a tendency to bond with acylamino and carboxyl groups, in addition to the ferric hydroxyl groups. Notably, 42.15% of the adsorbed As(III) was oxidized into As(V) by Mn(IV) oxides present in the amendment. The soil-verification experiment demonstrated that an amendment dosage of 40 g/kg was efficacious in reducing the leaching concentration of As and Cd to maintained below the safety thresholds of 0.1 mg/L and 0.01 mg/L, respectively, for pH levels 4 to 11, meeting the Chinese Surface Water Quality Standard V (GB3838-2002). After the stabilization, the exchangeable fractions of As and the acid-soluble fractions of Cd were significantly reduced, with these elements being transformed into more stable forms. The amendment maintained the soil's neutral pH and adjusted the soil physicochemical properties. This article presents a holistic approach by examining the organic-inorganic composite of iron-manganese oxides with polyacrylamide, modified as a stabilizing amendment for As and Cd co-contaminated soil. This innovative amendment adeptly navigates the previously conflicting stabilization mechanisms for anionic and cationic metals. Offering dual advantages, the amendment not only remediates soil but also addresses the disposal of waste, presenting a win-win solution for environmental management.

Novel electrochromic-supercapacitor device based on P(TPACz)/WO3-PDA nanocomposite film

Organic–inorganic composites of (E)-3,5-di(9 H-carbazol-9-yl)-N-(4-(diphenylamino)benzylidene)aniline/dopamine-modified WO3 (P(TPACz)/WO3-PDA) were prepared by electrochemical polymerisation. The as-prepared P(TPACz)/WO3-PDA composites showed good electrochromic and electrochemical performance. The prominent electrochemical performance of P(TPACz)/WO3-PDA represents a high areal capacitance (32.15 mF cm−2 at 0.1 mA cm−2) and wide range of potential windows (-2.0−1.6 V). Additionally, symmetric supercapacitor devices based on P(TPACz)/WO3-PDA composite films were successfully constructed, which exhibited a high specific capacitance (13.88 mF cm−2 at 0.02 mA cm−2) and an energy density of 7.71 × 10−3 mWh cm−2 in n-doped station. The remarkable electrochromic and electrochemical performances are due to the synergy between the organic polymer and WO3-PDA. A complete large-area composite film structure with high conductivity promises fast electronic transport. This study provides a method for preparing multifunctional composite electrode materials, offering technical support for intelligent displays and energy storage technologies.

Mechanically robust and flexible antireflection coatings from UV-cured organic-inorganic composites

It is a good choice to mix hollow SiO2 nanoparticles with organic resins to prepare mechanically robust and flexible anti-reflective coating. In this paper, hollow SiO2 nanoparticles with adjustable size, good dispersion and homogeneity were prepared by polyacrylic acid template, in which the size of the hollow silica nanoparticles can be adjusted between 60 and 370 nm. Hollow SiO2 nanoparticles were compounded with UV-cured silsesquioxanes sol to prepare four sets of composite coatings with refractive indices of 1.11, 1.20, 1.27 and 1.36. Each of these coatings can result in a significant reduction in the reflectance of the PET substrate and can result in the lowest reflectance of the PET substrate to 1.63 %, 1.26 %, 0.96 % and 1.45 %, respectively. Among them, the coating with the lowest reflectance result can reduce the average reflectivity of the PET substrate in the 400–1000 nm band from 5.92 % to 2.02 %. In addition, the organic resins can connect the hollow SiO2 nanoparticles together to improve the mechanically robust of the coating. The results of the pencil hardness tester showed that the mechanical properties of the composite coating were significantly improved. The composite anti-reflective coating with hollow SiO2 nanoparticles and organic resin not only has excellent anti-reflective performance in flexible substrate materials, but also has great application prospects in photovoltaic glass, architectural glass and other fields.

Preparation and performance studies on organic-inorganic phase change composites based on zeolitic imidazolate and paraffin for reducing gun barrel erosion

With the increasing requirements of tank guns for higher muzzle velocity and faster firing rate, some high energetic additives, such as cyclotrimethylene trinitramine (RDX) and cyclotetramethylene tetranitramine (HMX), have been widely used in high energy gun propellants. Consequently, the gun barrel erosion induced by the burning of high energy gun propellants has been an important issue that affects the lifespan of gun barrels. In order to address this problem, erosion reducing additives, including TiO2, paraffin, polyurethane or a combination of these, were introduced into the gun propellant or propellant charge system to alleviate the gun barrel erosion. In this study, a novel organic-inorganic phase change composite paraffin/ZIF-67 with solid paraffin (SP) as the phase change component and zeolitic imidazolate framework-67 (ZIF-67) as the matrix was designed and prepared as anti-erosion additives. The designed composite has a high thermal storage capacity of 93.88 J/g when the ZIF-67 content is 5 wt%. The erosion reducing effect of paraffin/ZIF-67 was determined by erosion tube test. The results show that the introduction of paraffin/ZIF-67 can improve the erosion-reducing efficiency of gun propellants. Compared with the control sample, the erosion-reducing efficiency of paraffin/ZIF-67 exhibited a faster increase with the increase of their contents, having the maximum erosion-reducing efficiency of 39.2 % when the addition of paraffin/ZIF-67 is 3.2 wt%. The incorporation of paraffin/ZIF-67 in the composites has a cooperative effect of each component on reducing gun barrel erosion. The developed organic-inorganic phase change composites exhibit great potential in the application of reducing gun barrel erosion, providing a new way for the development of erosion reducing additives.

Efficiency of Fulvic Acid for Improving Physico-Chemical Properties of Albic Black, Gansu Desert and Shahjiang Black Soils

Fulvic acids are a crucial component of soil that influence various chemical, biological, and physical aspects of soils as well as increase nutrient availability. We examined that application of plant-derived liquid (PDL) fulvic acid on three low obstacle, typical Chinese soil can improve the soil fertility and enhance the plant growth and nutrients uptake. The pot experiments were carried out on three different Albic (AL), Irrigated Desert (IR) and Shahjiang Black (SH) soils, the Plant-derived Liquid (PDL) fulvic acid (FA) was applied at rates of 0.50% as well as control applied at 0% along with three replications. The results showed that PDL FA significantly increases the SOC content in three soils highest SOC was detected at SH, however the SOC fractions were significantly decreased in AL, SH and no-significant difference was recorded at IR. Similarly, the soil pH was significantly increased in AL and decreased at IR and SH, however, the electrical conductivity of IR decreased and increased in AL and SH comparing with initial soil pH and electrical conductivity. The results also examine that available nitrogen, phosphorus of AL, IR and SH soils were increased, however, available potassium content was decreased in IR and increased at AL and SH comparing with initial values. The highest Ca and Mg content was observed in SH and organic degree compound were found 26.7% AL, 49.2% IR and 18.2%, SH soil, conversely the organic-inorganic composite was observed lower. This study suggests that the PDL FA significantly increases the nutrient content of AL, IR and SH soils comparing with initial soil properties.

Preparation of Photocurable Organic-Inorganic Hybrid Composites for Continuous Manufacturing of 3D-Patterned Abrasive.

Photocurable hybrid organic-inorganic composites were prepared via surface modification and 3D-patterned structures were fabricated by utilizing a continuous roll-to-roll manufacturing strategy. The surfaces of nanocrystals were engineered with a bifunctional ligand that is a 2-carboxyethyl acrylate, which possesses a carboxylic acid moiety at one end and an acrylate functionality moiety at the other end, yielding acrylate-functionalized nanocrystals. Micro-scale 3D patterns (protruding pyramidal shapes with each side measuring 147 μm) were continuously manufactured at a speed of 2.5 m/min via UV curing with a soft engraved mold. The surface properties of the functionalized nanocrystals and their UV curing condition were explored with Fourier transform infrared spectroscopy. The morphology of the 3D film was measured using scanning electron microscopy. A pin-on-disk tribometer measurement revealed an improved interaction between the functionalized particles and resins.

Polydopamine-induced biomimetic mineralization strategy to generate hydroxyapatite for the preparation of carbon fiber composites with excellent mechanical properties

Living organisms have developed a miraculous biomineralization strategy to form multistage organic-inorganic composites through the orderly assembly of hard/soft substances, achieving mechanical enhancement of materials from the nanoscale to the macroscale. Inspired by biominerals, this study used polydopamine (PDA) coating as a template to induce the growth of hydroxyapatite (HAP) on the surface of carbon fibers (CFs) for enhancing the interfacial properties of the CF/epoxy resin composites. This polydopamine-assisted hydroxyapatite formation (pHAF) biomimetic mineralization strategy constructs soft/hard ordered structure on the CF surface, which not only improves the chemical reaction activity of the CFs but also increases the fiber surface roughness. This, in turn, enhances the interaction and loading delivery among the fibers and the matrix. Compared to the untreated carbon fiber/epoxy resin (CF/EP) composites, the prepared composites showed a substantial enhancement in interlaminar shear strength (ILSS), flexural strength, and interfacial shear strength (IFSS), with improvements of 45.2 %, 46.9 %, and 60.5 %, respectively. This can be attributed to the HAP nanolayers increasing the adhesion and mechanical interlocking with the CFs to the matrix. This study provides an interface modification method of biomimetic mineralization for the preparation of high strength CF composites.

Organic-inorganic light-absorbing composites for near infrared part of spectrum

Organic-inorganic light-absorbing composites for near infrared part of spectrum

Promoting neurovascularized bone regeneration with a novel 3D printed inorganic-organic magnesium silicate/PLA composite scaffold

Critical-size bone defect repair presents multiple challenges, such as osteogenesis, vascularization, and neurogenesis. Current biomaterials for bone repair need more consideration for the above functions. Organic-inorganic composites combined with bioactive ions offer significant advantages in bone regeneration. In our work, we prepared an organic-inorganic composite material by blending polylactic acid (PLA) with 3-aminopropyltriethoxysilane (APTES)-modified magnesium silicate (A-M2S) and fabricated it by 3D printing. With the increase of A-M2S proportion, the hydrophilicity and mineralization ability showed an enhanced trend, and the compressive strength and elastic modulus were increased from 15.29MPa and 94.61MPa to 44.30MPa and 435.77MPa, respectively. Furthermore, A-M2S/PLA scaffolds not only exhibited good cytocompatibility of bone marrow mesenchymal stem cells (BMSCs), human umbilical vein endothelial cells (HUVECs), and Schwann cells (SCs), but also effectively promoted osteogenesis, angiogenesis, and neurogenesis in vitro. After implanting 10% A-M2S/PLA scaffolds in vivo, the scaffolds showed the most effective repair of cranium defects compared to the blank and control group (PLA). Additionally, they promoted the secretion of proteins related to bone regeneration and neurovascular formation. These results provided the basis for expanding the application of A-M2S and PLA in bone tissue engineering and presented a novel concept for neurovascularized bone repair.

Molecularly imprinted Ag2S quantum dots with high photocatalytic activity for dye removal: Experimental and DFT insights

Molecular imprinted polymers (MIPs) were developed by carrying out the cocktail solution of Template ((Salata, 2004)-Gingerol), monomer, crosslinker, and Ag2S Quantum Dots (QDs) by ex-situ dissolved in an appropriate solvent, resulting in an efficient crosslinked polymer composite. Degradation of Alizarin red S (ARS) dye and yellowish sunset (SY) azo dye under visible light irradiation was reported first time by the introduction of prepared MIPs composite. In this research, the result shows efficient photocatalyt activity of Ag2S-MIPs composite for the degradation of AR and SY dye with degradation% (80%) and (84%) in the aqueous wastewater. The degradation efficiency of the Ag2S-MIPs composite and the Ag2S QD associated with non-imprinted polymers (NIPs) (i.e.Ag2S-NIPs composite) were calculated by using different parameters such as catalyst dose, pH value, optimum time and concentration variation and the observations are evocative. Moreover, the density functional theory (DFT) approach was also used to analyze the structural, stability/energetics, and electronic features of the organic-inorganic hybrid composites of the Ag2S QD with the MIPs based on (Salata, 2004)-gingerol extract. The proposed QD and MIPs (EGDMA and (Salata, 2004)-Gingerol) composite model has been detected to be the most stable because it shows the largest binding energy (BE) among the three chosen composite models. It was found out that imprinted polymers were superior in enhancing the degradation of dyes when compared to non imprinted polymers. Introducing MIPs into the valence band accelerates the catalysis properties to stabilize newly fashioned excitons that are basically generated as a result of light excitation in presence of Ag2S Quantum Dots (QDs) and molecular imprinted polymer (MIPs). Motivation behind this work is to address the challenges related to environmental pollution causing by organic dyes. These toxins are known to cause diverse symptoms (e.g., skin irritation, eye infection, respiratory disorders, and even cancer) once exposed through ingestion and inhalation. Through incorporation of Ag2S QD into MIP,the purpose of this research is to enhance the selectivity, specificity and photocatalytic activity for dyes and that work holds a potential towards environmental remediation by developing a cost effective and sustainable method for controlling pollution in water.

Investigating the synergetic effect of tungsten oxide doping into the 1,3-dicarbonyl moiety grafted chitosan and phytic acid impregnated sodium alginate for efficient U(VI) adsorption

In this work, chemical modification of the chitosan with ethyl acetoacetate was performed through a base-catalyzed reaction in which epichlorohydrin facilitated the insertion as well as nucleophilic substitution reaction to graft the 1,3-dioxo moiety across the linear chains of the base biopolymer to establish specificity and selectivity for U(VI) removal. The modified chitosan (EAA-CS) was intercalated into phosphate rich alginate matrix (PASA). Later on, the WO3-doped composites with different WO3 to PASA mass ratio were prepared and characterized using FTIR, XPS, SEM-EDS, XRD, and elemental mapping analysis. WO3 significantly contributed to chemically stable inorganic-organic composites with improved porous texture. Among the prepared composites, MCPS-3 microspherical beads, having mass ratio of 30.0 % w/w, exhibited excellent sorption capacity for U(VI) at an optimal pH 4.5. The successful U(VI) sorption was validated by the existence of two U4f peaks at 392.25 and 381.36 eV due to U4f5/2 and U4f7/2 sub-peaks with an intensity ratio of 3:4, respectively. Batch mode sorption kinetics followed pseudo-second-order rate equation (R2 ≈ 0.99, qe,th ≈ 116.88 mg/g, k2 = 0.86 × 10−4 g/mg.min−1) and equilibrium sorption data aligns with Langmuir (R2 = 0.99, qm = 343.85 mg/g at 310 K and pH = 4.5, KL = 2.00 × 10−2 L/mg) and Temkin models (R2 ≈ 0.99). Thermodynamic parameters ΔHo (30.51 kJ/mol), ΔSo (0.19 kJ/mol.K) and ΔGo (−25.64, −26.89, and − 27.91 kJ/mol) at 298, 305, and 310 K, respectively, suggested that the uptake process is feasible, endothermic and spontaneous. Based on these findings, it is reasonable to conclude that MCPS-3 could be a better hydrogel-based biomaterial for appreciable uranium recovery.

Understanding Zinc Transport in Estuarine Environments: Insights from Sediment Composition

Sediments are sources and sinks of heavy metals in water, and estuaries are heavily influenced by human production and life. Therefore, it is of great significance to study the composition of estuarine sediments and the relationship between their components to understand the transport and transformation pathways of heavy metals in the environment. In this research, we investigated the characteristics and patterns of Zn adsorption by organic–inorganic composites, organic–clay mineral composites, and iron oxide–clay mineral composites in eight estuarine sediment samples from Dianchi Lake. The results show that both Langmuir and Freundlich isothermal models can describe the adsorption behaviour of the adsorbent better. The order of the adsorption capacity of the three groups of samples for zinc was organic–inorganic composites > organic–clay mineral composites > iron oxide–clay mineral composites. Through FTIR and XRD analyses, the adsorption of Zn2+ on the three groups of samples was dominated by electrostatic attraction and coordination adsorption, accompanied by the occurrence of ion exchange and co-precipitation. After FTIR semi-quantitative analysis, it was found that the source of the differences in the high and low Zn adsorption of the three types of samples may be mainly due to the content of phenolic functional groups in the organic matter. This may be related to the low redox site of the phenolic hydroxyl group, which, as an electron donor, is susceptible to electrostatic attraction and complexation with heavy metal cations. The organic–inorganic composite has a higher adsorption capacity for Zn when the ratio of the active fraction of organic matter to the free iron oxide content is 0.65–0.70. In this range, the organic matter can provide enough negative charge without making the sample surface too dense. Iron oxides can also activate the sample by providing sufficient contact between the clay minerals and the organic matter. When this ratio is too high or too low, it will be unfavourable for Zn adsorption.