Kinetic and Thermodynamic Study of the Dephosphation of Wastewater by Clay Materials from Côte d’Ivoire

Phosphorus is introduced into the aquatic environment from different point sources, mainly by domestic and industrial wastewater;contributing to the eutrophication of water bodies. The most common way for wastewater dephosphation is the injection of expensive chemicals into these bodies of water. Thus, the main objective of this work was to find an alternative to chemicals by using clay materials from Côte d’Ivoire to adsorb phosphate ions from aqueous solutions. The clay samples, taken from various regions were characterized by X-ray diffraction. They have a different mineralogical composition. The influence of various parameters such as the pH of the medium, contact time, the ion force, temperature, etc. on the adsorption was studied. Adsorption is influenced by the temperature, the pH of the medium, valence of the saturated cation and the clay composition. It is described by a kinetic model of the pseudo-second order. The salt of the medium has no significant effect on the process. The thermodynamic study revealed that adsorption is spontaneous, endothermic and that it is done by electrostatic means of physical nature.

Novel interface engineering of LDH-based materials on Mg alloy for efficient photocatalytic systems considering the geometrical linearity of condensed phosphates

This study presents a facile and rapid method for synthesizing novel Layered Double Hydroxide(LDH)nanoflakes,exploring their application as a photocatalyst,and investigating the influence of condensed phosphates'geometric linearity on their photocatalytic properties.Herein,the Mg O film,obtained by plasma electrolysis of AZ31 Mg alloys,was modified by growing an LDH film,which was further functionalized using cyclic sodium hexametaphosphate(CP)and linear sodium tripolyphosphate(LP).CP acted as an enhancer for flake spacing within the LDH structure,while LP changed flake dispersion and orientation.Consequently,CP@LDH demonstrated exceptional efficiency in heterogeneous photocatalysis,effectively degrading organic dyes like Methylene blue(MB),Congo red(CR),and Methyl orange(MO).The unique cyclic structure of CP likely enhances surface reactions and improves the catalyst's interaction with dye molecules.Furthermore,the condensed phosphate structure contributes to a higher surface area and reactivity in CP@LDH,leading to its superior photocatalytic performance compared to LP@LDH.Specifically,LP@LDH demonstrated notable degradation efficiencies of 93.02%,92.89%,and 88.81%for MB,MO,and CR respectively,over a 40 min duration.The highest degradation efficiencies were observed in the case of the CP@LDH sample,reporting 99.99%for MB,98.88%for CR,and 99.70%for MO.This underscores the potential of CP@LDH as a highly effective photocatalyst for organic dye degradation,offering promising prospects for environmental remediation and water detoxification applications.

Effect of safety valve types on the gas venting behavior and thermal runaway hazard severity of large-format prismatic lithium iron phosphate batteries

The safety valve is an important component to ensure the safe operation of lithium-ion batteries(LIBs).However,the effect of safety valve type on the thermal runaway(TR)and gas venting behavior of LIBs,as well as the TR hazard severity of LIBs,are not known.In this paper,the TR and gas venting behavior of three 100 A h lithium iron phosphate(LFP)batteries with different safety valves are investigated under overheating.Compared to previous studies,the main contribution of this work is in studying and evaluating the effect of gas venting behavior and TR hazard severity of LFP batteries with three safety valve types.Two significant results are obtained:(Ⅰ)the safety valve type dominates over gas venting pressure of battery during safety venting,the maximum gas venting pressure of LFP batteries with a round safety valve is 3320 Pa,which is one order of magnitude higher than other batteries with oval or cavity safety valve;(Ⅱ)the LFP battery with oval safety valve has the lowest TR hazard as shown by the TR hazard assessment model based on gray-fuzzy analytic hierarchy process.This study reveals the effect of safety valve type on TR and gas venting,providing a clear direction for the safety valve design.

Predicting the Degradability of Bioceramics through a DFT-based Descriptor

Bioceramics have attracted extensive attention for bone defect repair due to their excellent bioactivity and degradability.However,challenges remain in matching the rate between bioceramic degradation and new bone formation,necessitating a deeper understanding of their degradation properties.In this study,density functional theory(DFT)calculations was employed to explore the structural and electronic characteristics of silicate bioceramics.These findings reveal a linear correlation between the maximum isosurface value of the valence band maximum(VBM_(Fmax))and the degradability of silicate bioceramics.This correlation was subsequently validated through degradation experiments.Furthermore,the investigation on phosphate bioceramics demonstrates the potential of this descriptor in predicting the degradability of a broader range of bioceramics.This discovery offers valuable insights into the degradation mechanism of bioceramics and holds promise for accelerating the design and development of bioceramics with controllable degradation.

Efficient Removal of Phosphate from Aqueous Solutions Using Corundum-hollow-spheres Supported Caclined Hydrotalcite Porous Thin Films

Phosphate was removed from aqueous environment by corundum-hollow-spheres supported caclined hydrotalcite (cHT) thin films. Mg-Al-CO3 hydrotalcite (HT) thin films were deposited on corundumhollow-sphere substrates by hydrothermal homogeneous precipitation at 120℃for 30-240 min and cHT thin films were obtained by annealing of the HT thin films at 500℃for 180 min. Their crystal phase, morphology and microstructure were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM).The results show that homogeneous, well-crystallized and hierarchical flower-like thin films were deposited firmly on the surface of the corundum. The mechanism of nucleation and growth of the HT thin films was fitted well with the anion coordination polyhedron growth unit model. To determine the absorption of phosphate by this adsorbent, different bed depth (10-30 cm) and flow rate (1.0-3.0 m L/min) were examined by column experiments. The highest removal efficiency of phosphate amounted to 98.5%under optimum condition (pH=7.2). The adsorption capacity increased as the bed depth increased and decreased as the flow rate increased.

Gadolinium-doped injectable magnesium-calcium phosphate bone cements for noninvasive visualization

Injectable bone cements are used in minimally invasive surgical techniques including vertebroplasty and kyphoplasty.This work is devoted to the development of magnesium-calcium phosphate cements(MCPCs)doped with gadolinium ions(Gd^(3+))for bone defect repair.Interaction between cement powders and a cement liquid resulted in the formation of newberyite and brushite phases,which gave mechanical strength up to 17 MPa without a thermal effect.The introduction of Gd3+into the lattice was confirmed by electron paramagnetic resonance spectroscopy;the doping increased injectivity while giving rise to antibacterial properties against Escherichia coli.Assays of the cement samples soaking in Kokubo’s simulated body fluid revealed the formation of calcium phosphate coatings on the cements’surface.The cements manifested biocompatibility with the MG-63 cell line and significantly enhanced contrast when Gd-MCPC was placed into a bone defect and examined by X-ray micro-computed tomography.For the first time,visualization of a Gd-doped cement material was achieved in a model of a bone defect analyzed by MRI.

Effect of Fluoride on the Ion-association of Calcium Phosphate and Crystallization of Hydroxyapatite

Using a titration setup to accurately control the reaction conditions and in situ monitor the reaction,we showed that fluoride exhibited negligible effects on the ion association process of calcium and phosphate and the formation of ACP nanospheres in a buffer solution with constant ionic strength.However,the stability of ACP increased with increasing fluoride concentration,which was ascribed to the inhibitory effect of fluoride on the aggregation of ACP nanospheres and the nucleation of nanocrystals on the surface of ACP nanospheres.Furthermore,fluoride could inhibit the lateral growth of HAP nanosheets and promote the formation of rod-like crystals.These results further improve our understanding of the crystallization pathway of HAP crystals and the regulatory effects of fluoride.

Surface-neutralization engineered NiCo-LDH/phosphate hetero-sheets toward robust oxygen evolution reaction

Developing highly active oxygen evolution reaction(OER)electrocatalysts with robust durability is essential in producing high-purity hydrogen through water electrolysis.Layered double hydroxide(LDH)based catalysts have demonstrated efficient catalytic performance toward the relatively sluggish OER.By considering the promotion effect of phosphate(Pi)on proton transfer,herein,a facile phosphate acid(PA)surface-neutralization strategy is developed to in-situ construct NiCo-LDH/NiCoPi hetero-sheets toward OER catalysis.OER activity of NiCoLDH is significantly boosted due to the proton promotion effect and the electronic modulation effect of NiCoPi.As a result,the facilely prepared NiCo-LDH/NiCoPi catalyst displays superior OER catalytic activity with a low overpotential of 300 mV to deliver 100 mA cm^(-2)OER and a Tafel slope of 73 mV dec^(-1).Furthermore,no visible activity decay is detected after a 200-h continuous OER operation.The present work,therefore,provides a promising strategy to exploit robust OER electrocatalysts for commercial water electrolysers.

Enhancing sustainability in phosphate ore processing:Performance of frying oil as alternative flotation collector for carbonate removal

Recycling waste frying oils for the synthesis of flotation reagents presents a promising avenue for sustainable waste management.Moreover,it offers a cost-effective solution for crafting a specialized collector designed to efficiently remove carbonates and enhance phosphate enrichment in froth flotation processes.This study focuses on the synthesis of an anionic collector using the saponification reaction of a frying oil sample,subsequently applied to the flotation of calcite and dolomite.To elucidate the adsorption mechanisms of the frying oil collector(FrOC)and sodium oleate,a reference collector,on fluorapatite,calcite,dolomite,and quartz surfaces,comprehensive experiments were conducted,including zeta potential measurements and Fourier transform infrared spectroscopy.Results revealed diverse adsorption affinities of the molecules towards these minerals.To assess the practical performance of the collector,flotation tests were conducted using a natural phosphate ore mixture,employing a BoxBehnken experimental design.Notably,under optimized conditions(pH 9,1000 g/t of FrOC,3.5 min of conditioning,and 6 min of flotation),FrOC exhibited excellent performance,with calcite and dolomite recoveries exceeding 80%,while apatite recovery in the concentrate fraction remained below 10%.This work exemplifies both circular economy practices and the distinctive approach to sustainable mineral processing.

In-situ construction of abundant active centers on hierarchically porous carbon electrode toward high-performance phosphate electrosorption: Synergistic effect of electric field and capture sites

Phosphate removal is crucial for eutrophication control and water quality improvement.Electro-assisted adsorption,an eco-friendly elec-trosorption process,exhibited a promising potential for wastewater treatment.However,there are few works focused on phosphate electro-sorption,and reported electrodes cannot attach satisfactory removal capacities and rates.Herein,electro-assisted adsorption of phosphate via in-situ construction of La active centers on hierarchically porous carbon(LaPC)has been originally demonstrated.The resulted LaPC composite not only possessed a hierarchically porous structure with uniformly dispersed La active sites,but also provided good conductivity for interfacial electron transfer.The LaPC electrode achieved an ultrahigh phosphate electrosorption capability of 462.01 mg g^(-1) at 1 V,outperforming most existing electrodes.The superior phosphate removal performance originates from abundant active centers formed by the coupling of electricfield and capture sites.Besides,the stability and selectivity toward phosphate capture were maintained well even under comprehensive conditions.Moreover,a series of kinetics and isotherms models were employed to validate the electrosorption process.This work demonstrates a deep understanding and promotes a new level of phosphate electrosorption.

Preparation and interface state of phosphate tailing-based geopolymers

The long-term storage of phosphate tailings will occupy a large amount of land,pollute soil and groundwater,thus,it is crucial to achieve the harmless disposal of phosphate tailings.In this study,high-performance geopolymers with compressive strength of 38.8 MPa were prepared by using phosphate tailings as the main raw material,fly ash as the active silicon-aluminum material,and water glass as the alkaline activator.The solid content of phosphate tailings and fly ash was 60% and 40%,respectively,and the water-cement ratio was 0.22.The results of XRD,FTIR,SEM-EDS and XPS show that the reactivity of phosphate tailings with alkaline activator is weak,and the silicon-aluminum material can react with alkaline activator to form zeolite and gel,and encapsulate/cover the phosphate tailings to form a dense phosphate tailings-based geopolymer.During the formation of geopolymers,part of the aluminum-oxygen tetrahedron replaced the silicon-oxygen tetrahedron,causing the polycondensation reaction between geopolymers and increasing the strength of geopolymers.The leaching toxicity test results show that the geopolymer has a good solid sealing effect on heavy metal ions.The preparation of geopolymer from phosphate tailings is an important way to alleviate the storage pressure and realize the resource utilization of phosphate tailings.

Differential roles of C-3 and C-6 phosphate monoesters in affecting potato starch properties

The effects of starch phosphate monoester content(SPC),namely C-3(C3P)and C-6 phosphate monoesters(C6P),on the starch properties were investigated using four potato starches with varied SPC/C3P/C6P and two nonphosphorylated maize starches with a similar range of amylose content(AC)as controls.The starch property results showed that a higher SPC is associated with lower turbidity,storage and loss modulus after storage,and water solubility,but higher swelling power(SP)and pasting viscosities.These findings suggested that SPC inhibited molecular rearrangement during storage and starch leaching during heating,and enhanced swelling and viscosities due to increased hydration and water uptake caused by the repulsion effect of phosphate groups and a less ordered crystalline structure.Increased SPC also resulted in lower resistant starch(RS)content in a native granular state but higher RS after retrogradation.Pearson correlations further indicated that SPC/C3P/C6P were positively correlated with peak(r^(2)=0.925,0.873 and 0.930,respectively),trough(r^(2)=0.994,0.968 and 0.988,respectively),and final viscosities(r^(2)=0.981,0.968 and 0.971,respectively).Notably,SPC,mainly C3P,exhibited a significantly positive correlation with SP(r^(2)=0.859)and setback viscosity(r^(2)=0.867),whereas SPC,mainly C6P,showed a weak positive correlation with RS after retrogradation(r^(2)=0.746).However,SPC had no significant correlations with water solubility,turbidity and rheology properties,which were more correlated with AC.These findings are helpful for the food industry to select potato starches with desired properties based on their contents of SPC,C3P,or C6P.

Immunomodulatory activity of polycaprolactone nanoparticles with calcium phosphate salts against Leishmania infantum infection

Objective:To prepare and characterize polycaprolactone(PCL)nanoparticles loaded with sonicator fragmented(SLA)and freeze-thaw Leishmania antigens(FTLA)and to investigate the in vitro immunogenicity of antigen-encapsulated nanoparticles with calcium phosphate adjuvant.Methods:The water/oil/water binary emulsion solvent evaporation method was used to synthesize antigen-loaded PCL nanoparticles.Particles were characterized by scanning electron microscopy and zeta potential measurements.Their cytotoxicity in J774 macrophages in vitro was determined by MTT analysis.In addition,the amount of nitric oxide and the level of cytokines produced by macrophages were determined by Griess reaction and ELISA method,respectively.The protective effect of the developed formulations was evaluated by determining the infection index percentage in macrophages infected with Leishmania infantum.Results:Compared to the control group,SLA PCL and FTLA PCL nanoparticles with calcium phosphate adjuvant induced a 6-and 7-fold increase in nitric oxide,respectively.Additionally,the vaccine formulations promoted the production of IFN-γand IL-12.SLA PCL and FTLA PCL nanoparticles combined with calcium phosphate adjuvant caused an approximately 13-and 11-fold reduction in infection index,respectively,compared to the control group.Conclusions:The encapsulation of antigens obtained by both sonication and freeze-thawing into PCL nanoparticles and the formulations with calcium phosphate adjuvant show strong in vitro immune stimulating properties.Therefore,PCL-based antigen delivery systems and calcium phosphate adjuvant are recommended as a potential vaccine candidate against leishmaniasis.

Research,application and development of inorganic binder for casting process

Inorganic binder used in casting process has the advantages of low odor,labor-friendly conditions,and relatively low cost,which is one of the main development directions for casting molding materials in the future.However,compared to organic binders(such as resin binders),inorganic binders exhibit lower bonding strength and are more sensitive to environmental humidity.This sensitivity poses challenges,particularly in the reclamation of used sand,thus limiting their broader application.In this paper,the research and application status of inorganic binders(mainly silicate inorganic binders)and their curing methods are summarized.In addition,the research and application of phosphate inorganic binders and 3D printing inorganic binders that are being developed are introduced.Meanwhile,a detailed comparative analysis is conducted on the challenging issue of“reclamation for used sand”in the application of inorganic binders.Finally,the development direction of inorganic binders is clarified.

Upcycling the spent graphite/LiCoO_(2) batteries for high-voltage graphite/LiCoPO_(4)-co-workable dual-ion batteries

The worldwide proliferation of portable electronics has resulted in a dramatic increase in the number of spent lithium-ion batteries(LIBs).However,traditional recycling methods still have limitations because of such huge amounts of spent LIBs.Therefore,we proposed an ecofriendly and sustainable double recycling strategy to concurrently reuse the cathode(LiCoO_(2))and anode(graphite)materials of spent LIBs and recycled LiCoPO_(4)/graphite(RLCPG)in Li^(+)/PF^(-)_(6) co-de/intercalation dual-ion batteries.The recycle-derived dualion batteries of Li/RLCPG show impressive electrochemical performance,with an appropriate discharge capacity of 86.2 mAh·g^(-1) at25 mA·g^(-1) and 69%capacity retention after 400 cycles.Dual recycling of the cathode and anode from spent LIBs avoids wastage of resources and yields cathode materials with excellent performance,thereby offering an ecofriendly and sustainable way to design novel secondary batteries.

Natural variation in ZmGRF10 regulates tolerance to phosphate deficiency in maize by modulating phosphorus remobilization

Phosphorus is a limiting factor in agriculture due to restricted availability in soil and low utilization efficiency of crops.The identification of superior haplotypes of key genes responsible for low-phosphate(Pi)tolerance and their natural variation is important for molecular breeding.In this study,we conducted genome-wide association studies on low-phosphate tolerance coefficients using 152 maize inbred lines,and identified a significant association between SNPs on chromosome 7 and a low-phosphate tolerance coefficient.ZmGRF10 was identified as a candidate gene involved in adaptation of maize to Pi starvation.Expression of ZmGRF10 is induced by Pi starvation.A mutation in ZmGRF10 alleviated Pi starvation stress.RNA-seq analyses revealed significant upregulation of genes encoding various phosphatases in the zmgrf10-1 mutant,suggesting that ZmGRF10 negatively regulates expression of these genes,thereby affecting low-Pi tolerance by suppressing phosphorus remobilization.A superior haplotype with variations in the promoter region exhibited lower transcription activity of ZmGRF10.Our study unveiled a novel gene contributing to tolerance to low-Pi availability with potential to benefit molecular breeding for high Pi utilization.

Solid-state impedance spectroscopy studies of dielectric properties and relaxation processes in Na_(2)O–V_(2)O_(5)–Nb_(2)O_(5)–P_(2)O_(5) glass

Solid-state impedance spectroscopy(SS-IS)was used to investigate the influence of structural modifications resulting from the addition of Nb2O5 on the dielectric properties and relaxation processes in the quaternary mixed glass former(MGF)system 35Na_(2)O–10V_(2)O_(5)–(55-x)P_(2)O_(5)–xNb_(2)O_(5)(x=0–40,mol%).The dielectric parameters,including the dielectric strength and dielectric loss,are determined from the frequency and temperature-dependent complex permittivity data,revealing a significant dependence on the Nb2O5 content.The transition from a predominantly phosphate glass network(x<10,region I)to a mixed niobate–phosphate glass net-work(10≤x≤20,region II)leads to an increase in the dielectric parameters,which correlates with the observed trend in the direct-cur-rent(DC)conductivity.In the predominantly niobate network(x≥25,region III),the highly polarizable nature of Nb5+ions leads to a fur-ther increase in the dielectric permittivity and dielectric strength.This is particularly evident in Nb-40 glass-ceramic,which contains Na_(13)Nb_(35)O_(94) crystalline phase with a tungsten bronze structure and exhibits the highest dielectric permittivity of 61.81 and the lowest loss factor of 0.032 at 303 K and 10 kHz.The relaxation studies,analyzed through modulus formalism and complex impedance data,show that DC conductivity and relaxation processes are governed by the same mechanism,attributed to ionic conductivity.In contrast to glasses with a single peak in frequency dependence of imaginary part of electrical modulus,M″(ω),Nb-40 glass-ceramic exhibits two distinct contributions with similar relaxation times.The high-frequency peak indicates bulk ionic conductivity,while the additional low-fre-quency peak is associated with the grain boundary effect,confirmed by the electrical equivalent circuit(EEC)modelling.The scaling characteristics of permittivity and conductivity spectra,along with the electrical modulus,validate time-temperature superposition and demonstrate a strong correlation with composition and modification of the glass structure upon Nb_(2)O_(5) incorporation.

Fluid-Related Performances and Compressive Strength of Clinker-Free Cementitious Backfill Material Based on Phosphate Tailings

Phosphate tailings are usually used as backfill material in order to recycle tailings resources.This study considers the effect of the mix proportions of clinker-free binders on the fluidity,compressive strength and other key performances of cementitious backfill materials based on phosphate tailings.In particular,three solid wastes,phosphogypsum(PG),semi-aqueous phosphogypsum(HPG)and calcium carbide slag(CS),were selected to activate wet ground granulated blast furnace slag(WGGBS)and three different phosphate tailings backfill materials were prepared.Fluidity,rheology,settling ratio,compressive strength,water resistance and ion leaching behavior of backfill materials were determined.According to the results,when either PG or HPG is used as the sole activator,the fluidity properties of the materials are enhanced.Phosphate tailings backfill material activated with PG present the largest fluidity and the lowest yield stress.Furthermore,the backfill material’s compressive strength is considerably increased to 2.9 MPa at 28 days after WGGBS activation using a mix of HPG and CS,all with a settling ratio of only 1.15 percent.Additionally,all the three ratios of binder have obvious solidification effects on heavy metal ions Cu and Zn,and P in phosphate tailings.

Non-flammable long chain phosphate ester based electrolyte via competitive solventized structures for high-performance lithium metal batteries

Safety remains a persistent challenge for high-energy-density lithium metal batteries(LMBs).The development of safe and non-flammable electrolytes is especially important in harsh conditions such as high temperatures.Herein,a flame-retardant,low-cost and thermally stable long chain phosphate ester based(tributyl phosphate,TBP)electrolyte is reported,which can effectively enhance the cycling stability of highly loaded high-nickel LMBs with high safety through co-solvation strategy.The interfacial compatibility between TBP and electrode is effectively improved using a short-chain ether(glycol dimethyl ether,DME),and a specially competitive solvation structure is further constructed using lithium borate difluorooxalate(LiDFOB)to form the stable and inorganic-rich electrode interphases.Benefiting from the presence of the cathode electrolyte interphase(CEI)and solid electrolyte interphase(SEI)enriched with LiF and Li_(x)PO_(y)F_(z),the electrolyte demonstrates excellent cycling stability assembled using a 50μm lithium foil anode in combination with a high loading NMC811(15.4 mg cm^(-2))cathode,with 88%capacity retention after 120 cycles.Furthermore,the electrolyte exhibits excellent high-temperature characteristics when used in a 1-Ah pouch cell(N/P=0.26),and higher thermal runaway temperature(238℃)in the ARC(accelerating rate calorimeter)demonstrating high safety.This novel electrolyte adopts long-chain phosphate as the main solvent for the first time,and would provide a new idea for the development of extremely high safety and high-temperature electrolytes.

Preparation and Reinforcement Adaptability of Jute Fiber Reinforced Magnesium Phosphate Cement Based Composite Materials

To improve the brittleness characteristics of magnesium phosphate cement-based materials(MPC)and to promote its promotion and application in the field of structural reinforcement and repair,this study aimed to increase the toughness of MPC by adding jute fiber,explore the effects of different amounts of jute fiber on the working and mechanical properties of MPC,and prepare jute fiber reinforced magnesium phosphate cement-based materials(JFRMPC)to reinforce damaged beams.The improvement effect of beam performance before and after reinforcement was compared,and the strengthening and toughening mechanisms of jute fiber on MPC were explored through microscopic analysis.The experimental results show that,as the content of jute fiber(JF)increases,the fluidity and setting time of MPC decrease continuously;When the content of jute fiber is 0.8%,the compressive strength,flexural strength,and bonding strength of MPC at 28 days reach their maximum values,which are increased by 18.0%,20.5%,and 22.6%compared to those of M0,respectively.The beam strengthened with JFRMPC can withstand greater deformation,with a deflection of 2.3 times that of the unreinforced beam at failure.The strain of the steel bar is greatly reduced,and the initial crack and failure loads of the reinforced beam are increased by 192.1%and 16.1%,respectively,compared to those of the unreinforced beam.The JF added to the MPC matrix dissipates energy through tensile fracture and debonding pull-out,slowing down stress concentration and inhibiting the free development of cracks in the matrix,enabling JFRMPC to exhibit higher strength and better toughness.The JF does not cause the hydration of MPC to generate new compounds but reduces the amount of hydration products generated.