Phosphate Adsorption Capacity Research Articles

Removal of phosphate from wastewater using zirconium/iron embedded chitosan/alginate hydrogel beads: An experimental and computational perspective

Adsorptive removal of phosphate plays a crucial role in mitigating eutrophication. Herein, the Zr/Fe embedded chitosan/alginate hydrogel bead (Zr/Fe/CS/Alg) is reported as an effective phosphate adsorbent. This polymer nanocomposite is synthesized by the in-situ reduction of the metals on the polymer matrix. The synthesized adsorbent was characterized by the FTIR, SEM-EDX, TGA, BET, and XPS. The adsorbent showed a maximum phosphate adsorption capacity of 221.72 mg/g at pH 3. The experimental data fit well with the Freundlich isotherm and pseudo-second-order kinetics model, indicating a heterogeneous multilayer surface formation and a chemisorption-dominated adsorption process. Density Functional Theory (DFT) and Monte Carlo (MC) calculations revealed high negative adsorption energy due to the chemisorption of phosphate on the adsorbent. Hence, the major interactions such as electrostatic attraction, hydrogen bonding, and inner-sphere complexation of phosphate adsorption and Zr/Fe/CS/Alg hydrogel beads were investigated from the experimental and computational analysis. The negative values of thermodynamic parameters indicated a spontaneous, exothermic, and less random adsorption process. The synthesized adsorbent exhibited excellent selectivity toward phosphate and maintained 73 % efficiency after six adsorption/desorption cycles. The Zr/Fe/CS/Alg hydrogel beads reduced the phosphate concentration in real wastewater samples from 19.02 mg/L to 0.985 mg/L, suggesting that these nanocomposite hydrogel beads could be a promising adsorbent for real-world applications.

Capacitive deionization exploiting La-based LDH composite electrode toward energy efficient and selective removal of phosphate

Capacitive deionization (CDI) is a promising technology for removing phosphate from wastewater. Its practical implementation is however hindered by the constraints on the electrode materials. To boost the adsorption capacity, phosphate selectivity, and cost-effectiveness of the electrode, this study proposed a composite electrode blending Lanthanum-based layered double hydroxide (CaLa LDH) and activated carbon (AC). It capitalizes on the synergistic effects of electric double layer capacitance (EDLC) of AC and the diffusion-controlled charge storage (pseudocapacitive behavior) of CaLa LDH. By optimizing the mass ratios of the constituents and the electrode material loading capacities, the composite electrode AC/Ca-La LDH-5020 was developed, which contains 20 mg of 50 wt% CaLa LDH. This composition achieved a remarkable phosphate adsorption capacity of 34.8 mg P /g and a low energy consumption of 0.0051 kWh/g P in constant voltage (CV) mode. It represented a 241 % increase in adsorption capacity (mg P/g) and 71 % decrease in specific energy consumption (kWh/g P) compared to the electrode made solely of AC. Particularly the moderate inclusion of Lanthanum contributes to its cost-effectiveness. Moreover, further studies extensively examined the impacts of electrical driving force, including applied voltage in constant current (CC) mode and applied current in constant voltage (CV) mode, on the phosphate removal efficiency. The composite electrode remained stable performance with the presence of the high content of coexisting anions (e.g.，Cl−，SO42−, HCO3−, NO3−), obtaining high selectivity coefficient of phosphate over other anions. This study highlighted the practical potential of AC/Ca-La LDH composite electrode for advancing CDI technology for phosphate removal in an efficient, energy-saving and cost-effective manner.

In-situ formation of La2O2CO3 uniformly immobilized on biomass-derived carbon aerogel for enhanced phosphate removal

In the face of the dual pressures of eutrophication and phosphorus shortages, it is of utmost importance to efficiently remove and recover phosphate from wastewater. In this study, waste-biomass-derived carbon aerogel (CA) was utilized as a dispersing carrier for lanthanum (La), resulting in the successful in-situ generation of an La2O2CO3 (La3.5-CA-450) phosphate adsorbent on the CA matrix. The results demonstrated that the introduction of CA as an adsorbent led to abundant carbon defects and pore structures, which significantly enhanced its performance. Moreover, through the coordinated pyrolysis of CA and La3+, CO32−, capable of exchanging with PO43−, was generated, thereby contributing to the exceptional phosphate adsorption capacity exhibited by the adsorbent. Specifically, La3.5-CA-450 displayed a high phosphate adsorption capacity of 155.8 mg P/g (272.4 mg P/g La), with the molar ratio of P to La being 1.22:1, indicating a high utilization efficiency for La. The adsorbent exhibited exceptional performances in terms of selectivity, renewability, efficient use in natural water environments, and robust application in a broad range of synthetic availability. This research adheres to the green concept “using waste to treat waste” while providing a novel approach for preparing efficient La-based phosphate adsorbents.

Modification of steel slag and its application for phosphate and ammonia removal in aquatic products processing wastewater

ABSTRACT This study aims to modify different types of steel slag by heating, characterise the material and test its ability for adsorption of phosphate and ammonia from aquatic products processing wastewater. The materials were characterised by SEM, EDS, BET and FT-IR analyses. The effects of the type of steel slag, calcination temperature in steel slag modification, pH, contact time, adsorbent mass and initial pollutant concentration were investigated using the one-factor-at-a-time approach. The results show that the adsorption kinetic of the samples followed the pseudo-second-order model, whereas their adsorption isotherm fitted well with the monomolecular adsorptive Langmuir with a maximum phosphate adsorption capacity of 45.045 mgPO43-/g. Optimisation using Response Surface Methodology was conducted with the independent factors (adsorbent doses, contact time and calcination temperature of steel slag) and response (removal efficiency of phosphate). The temperature and dosage of the material significantly affected phosphate removal efficiency and optimisation conditions were suggested. Validation of one optimum condition at the calcination temperature of 801°C, the adsorbent dosage of 11.9 g/L and the contact time of 72 min using real aquatic products processing wastewater resulted in the removal efficiencies of 86.93, 87.59, 7.76 and 7.58% for phosphate, total phosphorus, ammonia and total nitrogen, respectively.

Study on the adsorption of phosphate by composite biochar of phosphogypsum and rape straw.

Wastewater containing phosphorus is often added by industrial activities, which is bad for the environment. In this study, composite biochar (PG-RS700) was prepared from phosphogypsum (PG) and rape straw (RS) for the treatment of phosphate in wastewater. SEM, FTIR, XRD and XPS characterization results showed that PG and RS were successfully combined. When PG-RS700 was dosed at 1.5g/L and the phosphate solution concentration was 50mg/L and pH = 8, the phosphate removal rate was 100% and the adsorption capacity was three times higher than the corresponding pure PG and RS. The quasi-secondary kinetic model indicated that the adsorption mechanism was chemisorption, and the maximum adsorption capacity for phosphate in the Langmuir isotherm model was 102.25mg/g. Through pot experiment, the phosphorus adsorbed material obviously promoted the growth of plants. PG-RS700 can be used as a powerful adsorbent to treat phosphate in water and return it to soil as phosphate fertilizer.

How do reactive aluminum and iron phases control soil organic carbon and phosphate adsorption capacity in agricultural topsoils across Japan?

ABSTRACT The growing number of studies suggests that the prediction of soil organic carbon (SOC) storage and persistence can be improved by accounting for variations in soil reactive metal phases. Nevertheless, the dataset on reactive metals is often limited at a national scale. In Japan, the phosphate adsorption coefficient (PAC) has been measured for agricultural soils nationwide. PAC is known to be strongly controlled by reactive metals, and hence, it can be used as a surrogate for reactive metal content. However, the relationships between SOC, reactive metals and PAC across a wide range of agricultural soils remain unclear. We thus examined these relationships using agricultural topsoils taken from 115 sites across Japan, covering two major soil great groups, Andosols and Lowland soils, as well as various land uses and soil temperature regimes (7.2–19.1°C). For the whole dataset, PAC was strongly correlated with oxalate-extractable metals (Alox + 0.5Feox: Metalox, r = 0.83) and moderately with pyrophosphate-extractable metals (Alp + 0.5Fep: Metalp, r = 0.68). These results suggest a stronger contribution of short-range-order (SRO) minerals to PAC as the former parameter reflects the content of both SRO minerals and organically complexed metals, while the latter reflects only that of organo-metal complexes. Moreover, Metalp was the best predictor of SOC contents in both Andosols (r = 0.79) and Lowland soils (r = 0.65). When only soils at near neutral soil pH range were considered, the exchangeable Ca content also co-varied with SOC in Lowland soils (n = 17). Of the two metallic elements, reactive Al phases better explained the variation of SOC and PAC in Andosols, whereas reactive Fe phases also showed similar explanatory power for PAC in Lowland soils. Our analyses also suggested that soil group (esp. erosion intensity) and land use likely impacted the SOC-Metalox relationship in Andosols, whereas environmental factors such as soil temperature and soil redox regime affected those relationships in Lowland soils. Overall, we showed that PAC is a useful surrogate for SRO minerals and organo-metal complexes and, with careful considerations of the environmental and pedogenic factors, it is potentially useful to estimate the amounts of SOC stabilized by reactive metal phases in agricultural soils across Japan.

Adsorption of Cr(VI) and phosphate anions by amino-functionalized palm oil fibers.

This work developed a novel sustainable adsorbent (PF-Aq) prepared by the amino-functionalization of palm oil fibers (PF). XPS, SEM/EDS, TGA/DSC, and FT-IR techniques proved the successful functionalization of the PF with the amino group. The PF-Aq adsorbent presents a high adsorption capacity for phosphate and Cr(VI) ions. Adsorption kinetics of the ions onto the PF-Aq followed the general-order models, with 240- and 300-min equilibrium times for phosphate and Cr(VI), respectively. The Freundlich equilibrium model can explain the adsorption of phosphate and Cr(VI) on the PF-Aq. Besides, the maximum adsorption capacities were 151.07mgg-1 for phosphate and 206.08mgg-1 for Cr(VI). The best pH for the adsorption of both ions on PF-Aq was 4.0. Interestingly, adsorption was exothermic for phosphate and endothermic for Cr(VI). The adsorption capacities were reduced by 16% for phosphate and 10% for Cr(VI) after 5 adsorption-desorption cycles, demonstrating the good recyclability of the PF-Aq. It can be concluded that PF-Aq is a relevant adsorbent to uptake phosphate and Cr(VI) from water due to its high adsorption capacity, low cost, recyclability, availability, and fast kinetics. Finally, the excellent adsorption potential results from inserting amino groups in the PF, allowing electrostatic interactions between adsorbent and adsorbate.

Converting large-scale waste paper fibers into lanthanum-modified cellulose carbon aerogel adsorbents for efficient phosphorus removal

This study presents the synthesis of a novel lanthanum-modified cellulose-based carbon aerogel (La-CCA) from waste printing paper, aimed at addressing the issue of phosphate pollution in aquatic environments. The objective was to develop an effective and sustainable adsorbent to mitigate eutrophication caused by excess phosphates in water bodies. La-CCA exhibited a remarkable phosphate adsorption capacity, peaking at 44.32 mg/g under optimal conditions, demonstrating its efficiency as an adsorbent. The novelty of this work lies in the use of waste paper as a raw material, coupled with lanthanum modification, which enhanced adsorption performance through multiple mechanisms, including electrostatic interactions, ligand exchange, and inner-sphere complexation. The study also discussed the retention of the microfibrous structure of cellulose, contributing to the material’s stability and functionality. Comprehensive analyses including zeta potential, FTIR, and XPS elucidate the underlying adsorption mechanisms. La-CCA was demonstrated to be easily separable from solutions with minimal lanthanum leaching, particularly under conditions above pH 3.0, underscoring its potential for practical applications in phosphate removal from nutrient-enriched waters.

Near-Complete Phosphorus Recovery from Challenging Water Matrices Using Multiuse Ceramsite Made from Water Treatment Residual (WTR)

Water treatment residual (WTR) is a burden for many water treatment plants due to the large volumes and associated management costs. In this study, we transform aluminum-salt WTR (Al-WTR) into ceramsite (ASC) to recover phosphate from challenging waters. ASC showed remarkably higher specific surface area (SSA, 70.53 m2/g) and phosphate adsorption capacity (calculated 47.2 mg P/g) compared to previously reported ceramsite materials (< 40 m2/g SSA and < 20 mg P/g). ASC recovered over 94.9% of phosphate across a wide pH range (3 – 11) and generally sustained > 90% of its phosphate recovery at high concentrations of competing anions (i.e., Cl-, F-, SO42-, or HCO3-) or humic acid (HA). We challenged the material with real municipal wastewater at 10°C and achieved simultaneous phosphate (>97.1%) and COD removal (71.2%). Once saturated with phosphate, ASC can be repurposed for landscaping or soil amendment. The economic analysis indicates that ASC can be a competitive alternative to natural clay-based ceramsite, biochar, or other useful materials. Therefore, ASC is an eco-friendly, cost-effective adsorbent for phosphate recovery from complex waters, shedding light upon a circular economy in the water sector.

Nanoconfinement of MgO in nitrogen pre-doped biochar for enhanced phosphate adsorption: Performance and mechanism

Advanced metal-doped biochar with superior phosphate (P) adsorption capacity plays a crucial role in combating eutrophication, depending on the rational design of the biochar structure for uniform and nanoscale dispersion of metal oxides. Herein, the nanoconfinement of magnesium oxide (MgO) was successfully attained in nitrogen pre-doped biochar (Mg/N-BC). The well-dispersed MgO was confined within nanoscale structure of Mg/N-BC, delivering P adsorption capacity of 108.41 mg g−1 and adsorption rate of 18.01 mg g-1h−1. More importantly, its adsorption performance at equilibrium 0.5 mg P/L was 17.70 times higher. Results suggested the decrease in pore size was positively correlated with the increase of N, confirming the role of N pre-doping in structure shaping and MgO confinement. The enhanced P adsorption was attributed to the well-dispersed MgO nanoparticles within the biochar. This study introduced a facile synthesis approach for biochar-incorporated nanoscale MgO, offering a new strategy for enhanced P removal.

Mechanistic insight into the simultaneous removal of Cr(VI) and phosphate by a novel versatile bimetallic material

Industrial wastewater containing hexavalent chromium Cr(VI) and phosphate poses a great threat to human health and the aquatic ecological environment. In this study, a novel La(OH)3- and CaO2-fabricated CNT (La-Ca-CNT) material was developed for the simultaneous and highly effective removal of aqueous Cr(VI) and phosphate. Characterization results showed that synergistic effects existed between the CNT support and La and Ca species. La-Ca-CNT showed high phosphate and Cr(VI) removal rates in acidic conditions with high stability. Kinetic study suggested that the fast adsorption of phosphate on La-Ca-CNT was controlled by intraparticle diffusion. The removal of Cr(VI) and phosphate interacted with each other, and the removal of Cr(VI) went through a slow-fast-slow reaction, reaching a Cr(VI) removal rate of over 97% within 180min. La-Ca-CNT had a high phosphate adsorption capacity (174.3mg/g), and over 70% of the adsorbed phosphate could be recovered. The presence of co-existing anions showed negative effects on phosphate adsorption but negligible effects on Cr(VI) reduction, while organic carbon in natural water showed no effect on phosphate and Cr(VI) removal. A mechanistic study revealed that phosphate was removed by physical-chemical adsorption (outer-sphere complexation and ligand exchange) over La-Ca-CNT, while Cr(VI) was reduced by H2O2 generated from CaO2 or directly by surface CaO2.

Dual-functional MnS nanomaterials: Efficient adsorbent for phosphate removal and sonocatalyst for textile dye degradation

Naturally abundant, environmentally friendly alternatives for replacing the expensive lanthanum-based phosphate removal technique are sought after. Solocatalysis is an emerging area for water remediation. This study introduces a dual-functional MnS nanomaterial for removing phosphate ions and Congo Red textile dye. MnS nanomaterials were synthesized via a hydrothermal route. Batch adsorption experiments revealed a phosphate adsorption capacity of 160.73 mg P/g, commendable for adsorbent in its bare form. Thermodynamic parameters of the process indicated a spontaneous, exothermic process, confirming favourable adsorption. FTIR analysis confirmed the adsorption mechanism, which includes electrostatic attraction, surface complexation, and ion exchange. MnS maintained its adsorption capacity despite competing ions, demonstrating a selective affinity for phosphate ions. MnS showed high sonocatalytic efficiency, degrading Congo Red dye within 10 min of ultrasonic irradiation. The degradation mechanism of Congo Red dye in the sonocatalytic process is proposed. This novel metal chalcogenide material exhibits exceptional affinity for phosphate ions and Congo Red dye molecules, surpassing La-based adsorbents in efficacy. The results suggest that MnS nanomaterials are promising for practical applications in phosphate removal and textile dye degradation from wastewater.

Corn stover waste preparation cerium-modified biochar for phosphate removal from pig farm wastewater: Adsorption performance and mechanism

The high phosphorus content in livestock and poultry wastewater is a significant factor contributing to water eutrophication. It is imperative to seek an economically efficient method for phosphate recovery. This study employed cerium-modified biochar to recover phosphate from pig farm wastewater. An investigation was conducted to examine the adsorption performance and removal mechanism of phosphate. Among the different samples, 0.1CeB-500℃ was selected for subsequent experiments. It exhibited a phosphate adsorption capacity of 9.58 mg/g and a removal efficiency of 95.75 %. The results showed that the phosphate adsorption process followed not only the pseudo-second-order kinetic model, but also the Langmuir isotherm model. It suggested that the adsorption of phosphate onto the biochar occurred in a monolayer chemical manner, with a maximum adsorption capacity of 10.86 mg/g. Phosphate adsorption was minimally affected within the pH range of 2–9, with Cl- having negligible impact, NO3- slightly inhibiting, and HCO3- and CO32- significantly hindering phosphate adsorption. A series of characterization results indicated that phosphate removal occurred through surface precipitation forming CePO4, ligand exchange between carbonate and phosphate, inner-sphere complexation, and electrostatic attraction. The phosphate removal efficiency from pig farm wastewater was 43.25 %, demonstrating promising potential for practical application.

Development of the Diffusive Gradient in Thin Film (DGT) Method with CaO/Biochar Binding Agent from Eggshells and Rice Straw Waste for Determining the Concentration of Phosphate

Phosphorus, often found in the form of phosphate in the environment, especially aquatic environments, has been identified as the primary contaminant that causes algae blooms and eutrophication. Phosphate adsorption in the aquatic environment was carried out by comparing the adsorption capabilities of eggshell (CaO), rice straw (BC) and CaO/biochar materials at mass variations of 1:1, 1:2 and 2:1 from the use of eggshell and rice straw waste. Each material was synthesized using ball milling and pyrolysis methods. The adsorption isotherm and kinetics of the material are by the Langmuir adsorption isotherm and are pseudo-second-order (PSO) adsorption kinetics. The CaO/biochar 1:2 material shows the highest phosphate adsorption capacity at pH 12 with a contact time of 24 hours. CaO/biochar 1:2 was applied in the phosphate adsorption process using the Diffusive Gradient in Thin Film method as a binding agent, which acts as an adsorbent. The DGT technique is an in situ sample preparation technique for identifying the presence of phosphate, a labile species. The binding agent material was characterized using FTIR, XRD, and BJH-BET instruments. The success of synthesizing CaO/biochar 1:2 binding gel and ferrihydrite was demonstrated by the appearance of the same adsorption as the diffusive gel using FTIR. The CaO/biochar binding gel demonstrated that it is a better material compared to the ferrihydrite binding gel for phosphate adsorption, achieving CDGT values of 10.1727 mg/L and 2.5959 mg/L at pH 5 and 3, respectively, with a phosphate concentration of 10 mg/L. These findings underscore the potential of CaO/biochar as a more effective material for phosphate removal applications.

Co-adsorption performance and mechanism of ammonium and phosphate by iron-modified biochar in water

To recover nitrogen and phosphorus from water bodies and reduce their potential risk of causing eutrophication, high-temperature pyrolysis-produced biochar (HBC) modified by ferric chloride (Fe-HBC) was adopted to investigate its surface modification on the co-adsorption performance of nitrogen and phosphate. In comparison to HBC, Fe-HBC exhibited superior specific surface area, well-developed pore structure, and enriched surface functional groups while successfully loading Fe2+ and Fe3+. It has been determined that the co-adsorption mechanism of ammonium and phosphate by Fe-HBC involves a combination of pore filling, ion exchange, functional group coordination, electrostatic attraction, and coprecipitation. The results from the batch adsorption experiments indicate that the ammonium adsorption capacities for Fe-HBC1, Fe-HBC2, and Fe-HBC3 were 10.59 mg/g, 10.38 mg/g, and 7.59 mg/g, respectively, while the phosphate adsorption capacities were 13.46 mg/g, 10.46 mg/g, and 15.22 mg/g, respectively. The results of the column adsorption experiments showed that too high or too low biochar percentage and flow rate were not conducive to improving the adsorption capacity of the adsorption column, and the maximum adsorption capacity of the adsorption column was achieved at a biochar percentage of 1 % and a flow rate of 1 mL/min. This study demonstrates the potential of this iron-modified biochar derived from agricultural wastes for practical application in the removal of ammonium and phosphate from wastewater.

Functionalized biobased carbon electrodes for selective phosphorus removal by capacitive deionization: Application and theory study

Capacitive deionization (CDI) emerges as a viable and efficient strategy for the removal and recovery of phosphorus from wastewater. However, the economic feasibility and complex synthesis of current electrode materials restrict its broader industrial application. To overcome the limitation, we fabricated aminated biobased electrode materials (MRSCN) from rice straw, forming active sites and hydrogen bonding interaction interfaces throughout the bulk phase by the nitrogen sites and peripheral amino groups in MRSCN, thereby enhancing the rapid enrichment and selective adsorption of phosphates. The phosphate adsorption capacity of MRSCN electrode reached up to 5.03 mg P/g at 1.2 V. In the presence of competing anions (Cl-, NO3– and SO42-), MRSCN exhibited markedly improved selective adsorption for phosphorus. Furthermore, density functional theory (DFT) calculations revealed that the incorporation of nitrogen active sites optimized the electronic structure of MRSCN. Meanwhile, H2PO4- and HPO42- anions served as hydrogen bond donors to the amino groups, leading to a more robust binding affinity between MRSCN and phosphates relative to other anions. The synergistic interaction between nitrogen sites and amino groups in facilitating selective phosphate removal was validated at the molecular scale. This study demonstrated the considerable potential of modified biobased carbon materials for the application in phosphate removal utilizing the CDI technique.

Recycle of Fe/Ca-rich fly ash in preparation of modified porous ceramsite for selective and efficient phosphate recovery

Although wastewater management has systematically developed globally, the removal efficiency of phosphates still posed a serious challenge and attracted worldwide concerns. On the other side, the discharge of fly ash (FA) from sludge incineration also caused serious environmental problems. In this study, Fe/Ca-rich FA was recycled to synthesize a porous ceramsite (modified CFA) through a non-sintered method. It could be an efficient adsorbent for phosphate recovery in virtue of abundant adsorption sites, accompanied by its low-cost and environmental friendliness. The phosphate adsorption capacity was 26.31 mg-P·g-1 for modified CFA, and its average adsorption rate could reach 1.344 mg-P·(g·day)-1 in the first 2 days. While it could also efficiently immobilize phosphate for a quite long period in the dynamic system effluent. According to electron microscopic and spectroscopic characterizations, modified CFA was indicated to chemisorb and immobilize phosphates via multiple interface interactions. Phosphates were firstly H-bonded with the surface Fe/Ca-OH of modified CFA and then rapidly coordinate with active Fe sites through a ligand exchange mechanism. When the exposed Fe sites had been saturated-adsorbed, inner-sphere Ca-O-P coordination would be further formed. In summary, this study provides a promising FA-derived adsorbent and realizes the efficient P pollution management with low cost and minimal environmental risks, which would be a potential waste-to-wealth strategy for further applications.

Surface engineered waterworks sludge embedded PAN electrospun membrane for efficient and selective removal of phosphate in actual surface water

Advanced adsorbents for selective removal of excessive phosphorus in actual surface water bodies and safe disposal of waterworks sludge are essential due to environmental risks and resource wastes. Herein, a strategy of killing two birds with one stone was proposed to design a La(OH)3/iron-based waterworks sludge/polyacrylonitrile (La(OH)3/IS/PAN) membrane for selective removal of phosphate. In this strategy, nano-La(OH)3 was well-dispersed on IS surface to realize functionalization of IS, and PAN electrospun nanofibers prevented powdered La(OH)3/IS from loss. The membrane showed a maximum adsorption capacity of 19.89 mg/L at 25 °C and remained relatively stable phosphate adsorption capacity under various anions interference. More importantly, after adsorption, the total phosphorus (TP) of the actual surface water from Yudai river was reduced to meet the requirement of the surface water standard of China, Ⅱ (GB 3838–2002). The work provides a novel way to overcome the challenges posed by eutrophication and sludge problems for industrial applications.

Structural insights into amino-modified defective UiO-67: Enhancing phosphate adsorption through multiple active sites synergistic interactions

Zirconium-based Metal-Organic Frameworks (Zr-MOFs) have attracted significant attention for phosphate removal due to their large specific surface area and abundant active sites. In this study, amino-modified Zr-MOFs were synthesized and used for phosphate removal, with a focus on investigating the relationship between the physicochemical structure of the amino-modified Zr-MOFs and phosphate adsorption, as well as the role of the amino groups. A series of amino-modified Zr-MOFs (UiO-67) were synthesized and characterized, with particular emphasis on the variant with one amino group functionalization on a defect-rich framework, designated as DUN. The results reveal that amino modification of defective UiO-67 (DUN) increases the number of phosphate adsorption sites per unit mass and specific surface area, thereby enhancing phosphate adsorption capacity, which is significantly higher than that of other synthesized UiO-67 variants. The role of amino group not only enhances the affinity for phosphate and the adsorption efficiency at low phosphate concentrations but also accelerates the phosphate adsorption rate. Through comprehensive characterization and DFT simulations, the superior performance of DUN is primarily attributed to the synergistic effects of its structural defects, carboxyl groups, and introduced amino functionalities. The defects at Zr nodes in DUN contribute significantly to phosphate adsorption by providing Zr-OH groups and oxygen vacancies. Concurrently, the carboxyl groups present in the DUN's ligand linkers engage in hydrogen bonding interactions with phosphate. The amino groups, a novel addition to the DUN structure, not only provide additional adsorption sites but also significantly enhance the strength of the existing hydrogen bonds and the Zr-O-P coordination interactions. This study sheds light on the intricate relationship between the physicochemical structure of Zr-MOFs and their phosphate adsorption capacity, providing a theoretical basis and practical approach for developing efficient Zr-MOF-based adsorbents for water purification.

Stable Magnetite@La-Fe Oxide Core-Shell Nanostructures Prepared via Lattice Lock for Reusable Extraction of Phosphate Anions.

Stable magnetic core-shell nanostructures are developed by lattice locking lanthanide-iron (La-Fe) oxide shells with magnetite cores to prevent the release of La from the surfaces of the magnetite nanostructures. The resulting core-shell nanostructures demonstrate excellent outstanding regeneration performance and high adsorption capacity for phosphate (115 mg P·g-1). These nanostructures release minimal La from the magnetite core surfaces after adsorbent regeneration, with a La loss of only 20% compared to the control sample, Mag@La(OH)3. La3+ ions were released at concentrations ranging from 1 to 2.3 μg·L-1 at pH levels of 4 to 8, which is within the metal content range found in natural aquatic environments. These results demonstrate the high stability of the nanostructures after regeneration. Furthermore, the adsorbent exhibits high extraction capacity across a wide pH range of 4 to 10 and performs well even in the presence of interfering anions at phosphate-to-anion molar ratios of 1:5, 1:25, and 1:100. Microscopic and spectroscopic analyses reveal that the primary extraction mechanism of phosphate in the La-containing shells is surface precipitation. This approach not only improves the use of magnetic core-shell nanostructures as adsorbents but also demonstrates the creation of a broad range of stable magnetic functional materials for diverse applications.