A metal-organic framework/inorganic composite(ZIF-8@AMP)was synthesized by the in situ introduction of the active component ammonium phosphomolybdate(AMP)during the ambient solution-phase synthesis of the metal-organi...A metal-organic framework/inorganic composite(ZIF-8@AMP)was synthesized by the in situ introduction of the active component ammonium phosphomolybdate(AMP)during the ambient solution-phase synthesis of the metal-organic framework(ZIF-8).The structure and properties of the composite were characterized using scanning electron microscopy(SEM),X-ray powder diffraction(XRD),X-ray photoelectron spectroscopy(XPS),thermogravimetric analysis(TGA),and Fourier transform infrared spectroscopy(FTIR).Its adsorption performance for Rb^(+)and Cs^(+)in water was investigated.Results indicate that ZIF-8@AMP exhibited adsorption efficiencies of 93.5%and 95.6%for Rb^(+)and Cs^(+)within 30 min,with maximum adsorption capacities of 92.7 and 104.5 mg·g^(-1),respectively.After five adsorption-desorption cycles,it maintained high adsorption capacity and achieved over 84.9%adsorption efficiency for Rb^(+)and Cs^(+)in actual brine samples.The adsorption of ZIF-8@AMP for Rb^(+)and Cs^(+)follows pseudosecond-order kinetics and the Langmuir adsorption isotherm,indicating an endothermic,entropy-increasing,and spontaneous process.The adsorption mechanism involves electrostatic attraction and ion exchange between ZIF-8@AMP and Rb^(+)and Cs^(+).展开更多
In this study,a nickel-based MOF{(NH_(2)(CH_(3))_(2))_(2)[Ni_(3)(O)(L)3(NH(CH_(3))_(2))_(3)]}_(n)(Ni_(3)-MOF),with pore sizes of approximately 1.6 nm×1.6 nm,was synthesized by reacting 4,4′-biphenyldicarboxylic ...In this study,a nickel-based MOF{(NH_(2)(CH_(3))_(2))_(2)[Ni_(3)(O)(L)3(NH(CH_(3))_(2))_(3)]}_(n)(Ni_(3)-MOF),with pore sizes of approximately 1.6 nm×1.6 nm,was synthesized by reacting 4,4′-biphenyldicarboxylic acid(H_(2)L)with Ni(NO_(3))_(2)·6H_(2)O in an N,N-dimethylformamide(DMF)solution.The nanoscale adsorbent Ni_(3)-MOF-N with a particle diameter of approximately 200 nm was prepared using Ni_(3)-MOF.It exhibited a maximum equilibrium tetracycline(TC)adsorption capacity of 358.2 mg·g^(-1)at its isoelectric point(pH=6.50),outperforming most reported MOF-based adsorbents.This exceptional performance is likely attributed to the well-matched pore size of Ni_(3)-MOF-N(1.6 nm×1.6 nm)and the molecular dimensions of TC(0.8 nm×1.2 nm),combined with the presence of partial Ni(Ⅱ)sites on the surface of Ni_(3)-MOF-N.These features collectively facilitate effective TC adsorption through a combination of pore filling,electrostatic attraction,hydrogen bonding,surface complexation,andπ-πinteractions.Recycling experiments demonstrated that Ni_(3)-MOF-N possesses excellent structural stability and consistent adsorption performance.CCDC:2481791,Ni_(3)-MOF.展开更多
To meet the needs of the treatment of Cu^(2+)pollution in aqueous solution,the sodium alginate-modified polyacrylic acid(PAA/SA)composite hydrogel was prepared by solution polymerization with acrylic acid(AA)as monome...To meet the needs of the treatment of Cu^(2+)pollution in aqueous solution,the sodium alginate-modified polyacrylic acid(PAA/SA)composite hydrogel was prepared by solution polymerization with acrylic acid(AA)as monomer,sodium alginate(SA)as filler,N,N’-methylenebisacrylamide(MBA)as crosslinking agent,and potassium persulfate(K2S2O8)as initiator.The characterization results showed that the introduction of SA significantly improved the physical and chemical properties of PAA hydrogel materials.Scanning electron microscopy(SEM)showed that as the SA content increased,the materials gradually evolved from a dense blocky structure to a porous network.When the SA content was 10 wt%,it exhibited a fragmented layered morphology.The Brunauer Emmett Teller(BET)showed that the specific surface area reached 37.65 m2/g and the porosity increased to 12.47%.Fourier transform infrared(FTIR)spectroscopy confirmed that SA was successfully embedded into the PAA network through hydrogen bonding and ion crosslinking,and the carboxyl vibration peak shifted from 2378 to 2352 cm^(-1).Mechanical tests showed that at 10 wt%SA,the maximum stress was 13.1 kPa.The adsorption experiment showed that the equilibrium adsorption capacity of the PAA/SA hydrogel for Cu^(2+)was 11.03 mg/g,with an adsorption efficiency of 42.65%.Dynamics studies showed that the adsorption process follows a first-order kinetic model(R2=0.986-0.997),indicating a physical adsorption mechanism dominated by liquid film diffusion.Theoptimal process conditions were found to be a dosage of 1.5 g/L,and the effect of temperature on adsorption was limited.The material maintained 67.4%of its initial adsorption capacity after six adsorption-desorption cycles.These parameters are generally superior to those of similar materials reported in the literature,indicating broad application prospects.Such a kinetic and isotherm model resulted from the combined effects of functional groups,electrostatic attraction,and chelation.In practical applications,pH,ionic strength,and competing ions will affect the adsorption performance of PAA/SA composite hydrogels.展开更多
Flubendiamide is a commonly used pesticide with low water solubility and a high organic carbon sorption constant,causing it to adhere to soil particles and negatively impact soil ecosystems.First,chili plant stems,typ...Flubendiamide is a commonly used pesticide with low water solubility and a high organic carbon sorption constant,causing it to adhere to soil particles and negatively impact soil ecosystems.First,chili plant stems,typically discarded after the harvest season,represent an abundant local biomass resource with significant potential for utilization,and were converted into biochar through pyrolysis.Here,we describe the synthesis of biochar modified with iron and chitosan to increase the diversity of functions and surface functional groups of biochar.The resulting chitosan-modified magnetic biochar(CMBC)presents a full range of functional groups of chitosan and iron oxide as shown by Fourier-transform infrared spectroscopy.The correlation between flubendiamide concentration and the dose of biochar on adsorption was explored.The flubendiamide adsorption efficiency of CMBC(1%mass ratio of soil)reached 68.03%in 90 min.The highest adsorption capacity achieved was 0.95 mg·g^(−1).The flubendiamide adsorption mechanism by CMBC can be described with a pseudo-second-order kinetic model.The experiment data closely fit a Freundlich isotherm model(R^(2)=0.998),and the low residual sum of squares values demonstrate the high model applicability.In this study,we present a comprehensive overview of pesticides,alongside kinetic and isotherm model studies of flubendiamide adsorption by CMBC.We emphasize the potential of modified biochar to enhance environmental remediation applications.展开更多
To efficiently remove radioactive nuclides from nuclear industry wastewater and minimize the generation of radioactive secondary waste,this study proposes the concept of a magnetically controlled microchannel adsorber...To efficiently remove radioactive nuclides from nuclear industry wastewater and minimize the generation of radioactive secondary waste,this study proposes the concept of a magnetically controlled microchannel adsorber based on magnetic adsorbents.A novel protocol for achieving high adsorption performance in microchannel adsorbers with periodically distributed particles is developed using the particle-resolved computational fluid dynamics (CFD) method,which addresses the limitations of traditional porous media flow models.To align simulation results more closely with practical scenarios,a typical high-efficiency magnetic adsorbent,magnetic sodium alginate/cobalt-based Prussian blue (M-SA/PB-Co),was synthesized.The M-SA/PB-Co microspheres exhibit a uniform size distribution (300–600 μm),and their Cs^(+) adsorption follows the pseudo-second-order kinetic model with a Langmuir saturated adsorption capacity of 124.84 mg·g^(-1).The performance parameters of M-SA/PB-Co,obtained from characterization and adsorption experiments,were integrated into CFD simulations.CFD results indicate that as the flow velocity increases,the flow field gradually transitions with vortices expanding in scale and streamline bifurcation points shifting rearward.The Cs^(+) concentration decreases progressively along the flow direction,with a more pronounced reduction in the vortex regions downstream of particles.The characteristic velocity and characteristic concentration of specific regions surrounding the particles were extracted based on boundary layer distribution.The amount of concentration reduction of Cs^(+) through particle is positively correlated with the characteristic concentration and negatively correlated with the characteristic velocity.The number of microspheres required in the microchannel adsorber was optimized using the response surface method.Compared with industrial fixed-bed adsorbers,microchannel adsorbers exhibit 8–10 times higher processing capacity,demonstrating significant industrial application potential.展开更多
Aqueous zinc-ion batteries(AZIBs) are regarded as one of the most promising energy conversion and storage devices.Nevertheless,side reactions and dendrite growth on the zinc metal anode hinder their widespread applica...Aqueous zinc-ion batteries(AZIBs) are regarded as one of the most promising energy conversion and storage devices.Nevertheless,side reactions and dendrite growth on the zinc metal anode hinder their widespread application.In this study,hemin was employed as a multi-functional artificial interface for the first time to inhibit the disordered growth of zinc dendrites and mitigate side reactions.Theoretical calculations indicate that hemin is preferentially adsorbed onto the zinc anode,thus blocking the interaction between the active zinc anode and electrolyte.Compared with zinc foil,the Hemin@Zn anode demonstrates enhanced corrosion resistance,a decrease in hydrogen evolution,and more orderly deposition of zinc.As expected,the symmetric cell with Hemin@Zn anode can sustain up to 4000 h at 0.2 mA/cm^(2),0.2 mAh/cm^(2).Asymmetric Zn//Cu cells exhibit an average coulombic efficiency exceeding 99.72 % during 500 cycles.Moreover,the full cell Hemin@Zn//NH_(4)V_(4)O_(10) delivers a superior capacity up to 367 m Ah/g and the discharge capacity retention reaches 124 mAh/g after 1200 cycles even at a current density of 5 A/g.This work provides a simple and effective method for constructing a robust artificial interface to promote the application of long-life AZIBs.展开更多
A novel hierarchical porous metal-organic framework(MOF)-based hollow carbon nanofiber mat(CNFM)was prepared through a facile electrospinning process followed by carbonization.Two immiscible polymers,polyacrylonitrile...A novel hierarchical porous metal-organic framework(MOF)-based hollow carbon nanofiber mat(CNFM)was prepared through a facile electrospinning process followed by carbonization.Two immiscible polymers,polyacrylonitrile/polymethyl methacrylate(PAN/PMMA),and porous zeolitic imidazolate framework-8(ZIF-8)particles were selected as components for the electrospinning suspension.The resulting PPZ-CNFM-1–2–2(PAN:PMMA:ZIF8=1:2:2,mass ratio)exhibited a hollow tubular structure with uniformly distributed dense hollow-spheres on the tube walls.The obtained CNFM possessed a high Brunauer-Emmett-Teller specific surface area(SBET)of 1696 m2/g and total pore volume of 2.74 cm^(3)/g,which are comparable to those achieved by traditional physical or chemical activation methods.This MOF-based CNFM demonstrated excellent adsorption performance towards ciprofloxacin(CIP),exhibiting a high static adsorption capacity of approximately 600 mg/g and achieving adsorption equilibrium withing only 1 h.The exceptional adsorption capacity can be attributed to its high SBET and abundant pores that accommodate CIP molecules,while the rapid adsorption rate is facilitated by the presence of hollow-sphere and hollow tubular structures in the carbon nanofibers.Furthermore,the study revealed the significant contributions of pore-filling effect during the adsorption process.Fixed-bed experiments confirmed that this MOF-based hollow CNFM holds great potential for large-scale applications in purifying CIP-contaminated water.展开更多
Economical and sustainable wastewater treatment techniques are highly demanded to alleviate the issues of clearwater scarcity globally.In this work,the acetic acid/H_(2)O_(2) (AHP) was leveraged to enrich oxygenated f...Economical and sustainable wastewater treatment techniques are highly demanded to alleviate the issues of clearwater scarcity globally.In this work,the acetic acid/H_(2)O_(2) (AHP) was leveraged to enrich oxygenated functional groups on the biochar surface for efficient ciprofloxacin (CIP) adsorption and biochar regeneration (In situ degradation of CIP in the spent AHP solution).The AHP-modified biochar exhibited significantly enhanced CIP adsorption capacity,about 22 times that of the pristine biochar.The optimized modification condition (acetic acid/H_(2)O_(2):2.11,temperature:45 ℃,and time:12 h) was screened by the response surface method,reaching the highest CIP adsorption capacity of 86.26 mg·g^(−1).Characterization results revealed that the content of carboxyl —C=O—O was enhanced in AHP-modified biochar,which contributed to efficient CIP adsorption by the electrostatic interaction,hydrogen bonding,and hydrophobic interaction.The adsorption of modified biochar to CIP molecules was a spontaneous endothermic process,and in line with the pseudo-second-order model and the Langmuir isotherm model.Moreover,the biochar modification process enabled the spent AHP solution with a strong oxidizing agent of peracetic acid (PAA),which can be employed to degrade adsorbed CIP for biochar in-situ generation.This work tailored a closed-loop strategy for biochar oxidation,contaminant adsorption,and biochar regeneration,highlighting a viable route for sustainable wastewater treatment.展开更多
In this study,chitosan(CS)was combined with microcrystalline cellulose(MCC)to fabricate composite hydrogel beads.These beads were further modified through blending and grafting with polyethyleneimine(PEI)to develop ch...In this study,chitosan(CS)was combined with microcrystalline cellulose(MCC)to fabricate composite hydrogel beads.These beads were further modified through blending and grafting with polyethyleneimine(PEI)to develop chitosan/microcrystalline cellulose@polyethyleneimine(CS/MCC@PEI)composite gel spheres for the efficient adsorption of diclofenac sodium(DS)from aqueous solutions.The adsorbent was characterized using scanning electron microscopy(SEM),X-ray diffraction(XRD),Fourier-transform infrared spectroscopy(FTIR),X-ray pho-toelectron spectroscopy(XPS),and thermogravimetric analysis(TGA).The CS/MCC@PEI composite exhibited a spherical morphology with a porous structure,abundant surface functional groups,and a high adsorption capac-ity of 274.84 mg/g for DS.Kinetic studies revealed that the adsorption process followed the pseudo-second-order model,dominated by physical adsorption,with both surface and internal diffusion influencing the adsorption rate.The Freundlich isotherm model best described the adsorption behavior,indicating multilayer adsorption on heterogeneous surfaces.Environmental adaptability tests demonstrated minimal interference from co-existing anions and humic acid,while regeneration experiments confirmed excellent reusability(>77%removal after five cycles).The adsorption mechanism involved electrostatic interactions and hydrogen bonding between the hydroxyl/amino groups of the composite and DS.These findings highlight the potential of CS/MCC@PEI as a cost-effective and sustainable adsorbent for DS removal from water.展开更多
The flotation separation of argentite from sphalerite using ammonium dibutyl dithiophosphate(ADD)was studied.Molecular simulation(MS)calculation shows that ADD is chemisorbed on argentite and sphalerite surface in the...The flotation separation of argentite from sphalerite using ammonium dibutyl dithiophosphate(ADD)was studied.Molecular simulation(MS)calculation shows that ADD is chemisorbed on argentite and sphalerite surface in the form of S—P bond.The ADD adsorption on argentite and sphalerite surface in Ag^(+)system was revealed by ICP,Zeta potential and XPS analyses.It is shown that the dissolved Ag^(+)from argentite surface can be absorbed on sphalerite surface in the form of silver hydroxide,and AgOH hydrophilic colloid prevents the adsorption of ADD on sphalerite surface.The ADD adsorption on argentite and sphalerite surface in the pulp containing silver and zinc ions was revealed by adsorption capacity and surface wettability analyses.It is shown that the combined Zn(OH)_(2) and AgOH hydrophilic colloid leads to greater ADD adsorption capacity on argentite surface and stronger surface hydrophobicity than sphalerite.Flotation tests demonstrate that ADD enables efficient separation of argentite from sphalerite in the pulp containing silver and zinc ions.展开更多
This study presents a thorough investigation into the use of single and twin-tailed cationic and anionic surfactant-modified chitosan(SMCS)hydrogel beads as effective adsorbents for the elimination of hazardous polycy...This study presents a thorough investigation into the use of single and twin-tailed cationic and anionic surfactant-modified chitosan(SMCS)hydrogel beads as effective adsorbents for the elimination of hazardous polycyclic aromatic hydrocarbons(PAHs)from aqueous solutions.The Chitosan(CS)hydrogel beads were modified with single/twin-tailed anionic surfactants,sodium dodecyl sulfate(SDS)and sodium bis(2-ethylhexyl)sulfosuccinate(AOT),and cationic surfactants,dodecyltrimethylammonium bromide(DTAB)and didodecyldimethylammonium bromide(DDAB),to enhance their adsorption capacity of PAHs.The CS and SMCS beads were evaluated for their structural,mechanical,and adsorption properties using a range of techniques,including infrared spectroscopy(IR),energy-dispersive X-ray spectroscopy(EDX),rheometry,and field emission scanning electron microscopy(FESEM).Adsorption experiments of naphthalene(Nap),acenaphthene(Ace),and phenanthrene(Phe)on SMCS beads demonstrate that they have significantly higher adsorption capacities than CS beads,due to increase in hydrophobic interactions.Adsorption capacity followed the trend,Phen>Ace>Nap for all the beads revealing that twin-tailed SMCS bead possess much higher adsorption capacities(Qmax)compared to single-tailed SMCS beads.For twin tailed surfactants,the maximum adsorption capacities for Nap,Ace and Phe varied as CS-AOT(CS-DDAB):430.0(323.8)611.60(538.18)633.39(536.99)mg/g respectively,outperforming other reported hydrogel beads.The study highlights the simplicity,eco-friendliness,and enhanced performance of surfactant modification for developing high-efficiency adsorbents,paving the way for cost-effective solutions in water re-mediation.展开更多
In order to address the evolving emission characteristics of oxygenated volatile organic compounds(OVOCs),it is essential to develop adsorbent materials specifically designed for the efficient adsorption of OVOCs with...In order to address the evolving emission characteristics of oxygenated volatile organic compounds(OVOCs),it is essential to develop adsorbent materials specifically designed for the efficient adsorption of OVOCs with large kinetic diameters.In this study,we used co-pyrolysis to prepare a series of graded porous carbon materials with well-developed micropores by adjusting the doping ratios of root nodules and pretreated cellulose.The material with root nodule to cellulose mass ratio of 1:1(TCC-RN-1)exhibited the highest saturated adsorption capacity for butyl acetate(834 mg/g).This can be attributed to enhanced pore size distribution from nodule doping,which facilitates the development of a micropore-graded structure.Additionally,the nodules acted as auxiliary activating agents that enhanced the KOH micropore regulation effect during the activation stage,resulting in the highest micropore volume(0.863 cm^(3)/g).The doping of root nodules facilitated the formation of additional defects on the surface of the porous carbon material,leading to a more disordered arrangement that improved pollutant adsorption.Furthermore,TCC-RN-1 demonstrated good thermal stability in an air atmosphere,main-taining a butyl acetate adsorption capacity exceeding 95%after five adsorption-desorption cycles.This indicates its favorable potential for industrial applications.展开更多
The severe shuttle effect and sluggish reaction kinetics in room-temperature sodium-sulfur(RT Na-S)batteries have been major bottlenecks hindering their practical application.To overcome these challenges,a straightfor...The severe shuttle effect and sluggish reaction kinetics in room-temperature sodium-sulfur(RT Na-S)batteries have been major bottlenecks hindering their practical application.To overcome these challenges,a straightforward reduction approach was employed to design three bimetallic alloy nanoparticles(FeNi,FeCo,and NiCo)supported on multistage porous carbon substrates.Experimental and theoretical calculations reveal that the charge transfer within the alloy catalyst influences the position of its d-band center and its degree of hybridization with sodium polysulfides(NaPSs).An increased charge transfer leads to a shift of the alloy’s d-band center closer to the Fermi energy level,thereby enhancing its adsorption and catalytic capabilities.Among the three alloy compositions,the FeNi alloy exhibits the highest charge transfer.Consequently,the FeNi alloy demonstrates the superior electrochemical performance,achieving a high reversible specific capacity of 848.2 mA h g^(−1),with an average capacity degradation rate of only 0.037%per cycle over 1000 cycles at 1.2 C.The S/FeNi/NC cathode exhibits a low electrolyte-to-sulfur(E/S)ratio of 6.6µL mg^(−1),while maintaining a high reversible specific capacity of 568.1 mA h g^(−1).This offers valuable insights for the application of alloy catalysts in the S/FeNi/NC cathode of RT Na-S batteries.展开更多
Antibiotics,as an emerging pollutant due to their extensive use and difficulty in biodegradation,can cause harm to health through bioaccumulation.To address this,various photocatalysts have been developed for rapid an...Antibiotics,as an emerging pollutant due to their extensive use and difficulty in biodegradation,can cause harm to health through bioaccumulation.To address this,various photocatalysts have been developed for rapid antibiotic removal.However,their low concentrations limit mass transfer efficiency,resulting in suboptimal performance.Adsorption is crucial for enhancing photocatalytic efficiency.In this study,a series of binary heterojunction catalysts(x%BWO@STHP)were synthesized,consisting of Bi_(2)WO_(6)(BWO)grafted with sulfonated triptycene-based hypercrosslinked polymer(STHP).The high specific surface area of STHP,combined withπ-πconjugation and ionic interactions with antibiotics,significantly enhances adsorption capacity.This facilitates effective contact between low-concentration pollutants in aqueous solutions and the active sites of the catalyst.The formation of a Z-scheme heterojunction between BWO and STHP facilitates photogenerated charge separation,and further significantly improves photocatalytic degradation performance.Specifically,the 20%BWO@STHP catalyst achieved rapid adsorption equilibrium for oxytetracycline(OTC),doxycycline(DOX),and tetracycline(TC)within 2 min and completely degraded them after 15 min of irradiation.Compared to pristine BWO,the photocatalytic reaction rate constants are significantly increased,being 9.69 times higher for OTC and 13.45 times higher for DOX.The catalyst exhibits excellent reusability and holds promising potential for practical applications.展开更多
The protein corona formation has been reported to influence the liposomes’behavioral performance in vivo.Accordingly,the effect of physiologically relevant inorganic ion pairs(sodium chloride,sodium sulfate,magnesium...The protein corona formation has been reported to influence the liposomes’behavioral performance in vivo.Accordingly,the effect of physiologically relevant inorganic ion pairs(sodium chloride,sodium sulfate,magnesium chloride,and magnesium sulfate)was investigated.Bovine serum albumin(BSA)was selected as the model protein.Parameters including particle size and zeta potential were assessed,while various spectroscopic techniques were utilized to elucidate the changes in BSA during its interaction with liposomes.The particle size and light intensity distribution changes indicated that the introduction of inorganic pairs,especially the metal cations,could significantly influence both the adsorption of BSA and the aggregation of particles.Furthermore,spectral characterization elucidated that BSA exhibited more extended peptide chains with enhanced exposure to hydrophobic acid amino residues upon adding ion pairs.Electrostatic adsorption and chelation insertion were proposed as metal ion binding modes and the corresponding BSA corona formation.In the electrostatic adsorption mode,sodium ions can enhance the electrostatic interactions,facilitating the“connection”between BSA and liposomes.Magnesium ions can induce stronger hydrophobic interactions through chelation,effectively“drag”BSA segments into the lipid bilayer.This work highlighted important physiological factors for protein-liposome interaction and provided rational model constructions to lay the foundation for further relevant studies.展开更多
Injecting impure CO_(2)for enhanced gas recovery(CO_(2)-EGR)offers a dual benefit by improving natural gas extraction while enabling CO_(2)sequestration.However,the interactions between CO_(2),N_(2),and CH_(4)under re...Injecting impure CO_(2)for enhanced gas recovery(CO_(2)-EGR)offers a dual benefit by improving natural gas extraction while enabling CO_(2)sequestration.However,the interactions between CO_(2),N_(2),and CH_(4)under reservoir conditions require further investigation.This study employs Grand Canonical Monte Carlo(GCMC)and Molecular Dynamics(MD)simulations to quantify the adsorption and diffusion behaviors of CO_(2),N_(2),and CH_(4)in quartz nanopores over a pressure range of 1-24 MPa under varying water saturations and gas compositions.The results indicate that:(1)CO_(2)exhibits the broadest energy distribution and the strongest adsorption stability,occupying about 20%-30%more adsorption sites than CH_(4)or N_(2)and showing the least sensitivity to water saturation,with only a 30%reduction at 50%saturation,compared to 60%for CH_(4),giving CO_(2)a clear competitive advantage.(2)The adsorption and desorption behaviors are strongly pressure dependent,as increasing pressure reduces the adsorption layer area and shifts gas distribution from adsorption dominated to free phase.Competitive adsorption analysis reveals that while CO_(2)dominates displacement at low pressures,mixtures that contain N_(2)achieve higher CH_(4)desorption efficiency above 13 MPa by mitigating diffusion resistance.(3)A higher N_(2)fraction improves CH_(4)diffusion coefficients,thereby facilitating gas mobility and ensuring superior recovery performance under high-pressure conditions.This study advances the fundamental knowledge of microscale gas behavior in tight sandstones and supports the feasibility of impure CO_(2)injection as a practical strategy for sustainable gas production.展开更多
Excessive phosphorus and arsenic in water bodies not only destroy ecosystems but also pose a serious threat to human health.In this study,a series of Al-doped modified metal-organic frameworks(Zr-Al-MOF)were prepared ...Excessive phosphorus and arsenic in water bodies not only destroy ecosystems but also pose a serious threat to human health.In this study,a series of Al-doped modified metal-organic frameworks(Zr-Al-MOF)were prepared by solvothermal method,which achieved efficient removal of phosphate and arsenate in water.Due to the use of inexpensive Al salts,the material has a lower cost and is more economical.The molar ratio of metal salts,adsorption time,solution pH,initial concentration,temperature and coexisting anions were studied,and it was found that when the molar ratio of Zr:Al was 2,Zr-Al-MOF had the best adsorption performance for phosphate and arsenate,and the maximum adsorption capacity was 93.04 mg P/g and 173.83 mg As/g,respectively.It traps phosphate and arsenate at a fast reaction rate and can be recycled repeatedly.In addition,0.15 g/L of 2Zr-Al-MOF can effectively reduce the phosphate and arsenate content in the contaminated spring water samples of Yangzonghai Lake to the standard range of drinking water,which further confirms the application potential of 2Zr-Al-MOF.By FT-IR and XPS analysis,it was found that the adsorption mechanism was ligand exchange,electrostatic attraction and hydrogen bond formation.The theoretical calculation shows that the adsorption energy is negative,which indicates that 2Zr-Al-MOF is attractive to phosphate and arsenate,and the adsorption state is stable.The results show that 2Zr-Al-MOF is an effective phosphate and arsenate adsorbent and has broad application prospects in eutrophication water treatment.展开更多
The development of aqueous zinc batteries(AZBs)is severely constrained by uncontrolled dendrite growth and parasitic interfacial reactions.Conventional solvation-dominated additives can mitigate these issues by alteri...The development of aqueous zinc batteries(AZBs)is severely constrained by uncontrolled dendrite growth and parasitic interfacial reactions.Conventional solvation-dominated additives can mitigate these issues by altering the Zn^(2+)solvation structure,but they often compromise ion transport.Here,we introduce a molecular design principle for a non-solvating additive(NSA)based on inductive effects.Ethyl trifluoroacetate(ETFA),obtained by introducing an electron-withdrawing–CF_(3) group adjacent to the–C=O moiety of ethyl acetate(EA),participates minimally in the solvation structure but preferentially undergoes Gibbs adsorption at the Zn-electrolyte interface.This process reduces interfacial tension,reconstructs the electrical double layer,and orients ETFA molecules such that the hydrophilic–C=O groups face the electrolyte,modulating hydrogen-bonding networks,while the hydrophobic–CF_(3) groups anchor onto Zn to regulate deposition.As a result,dendrite formation and side reactions are simultaneously suppressed.With only 1 vol%ETFA,Zn-Cu cells achieve over 4000 stable cycles with 99.89%Coulombic efficiency.Zn-I_(2) full cells employing the modified electrolyte maintain stable operation for more than 500 cycles(6.8 mg cm^(-2),10μm Zn,N/P=2.86),and 0.3 Ah Zn-I_(2) pouch cells(30 mg cm^(-2),100μm Zn)can cycle stably for over 200 cycles.These findings highlight the critical role of Gibbs adsorption in interfacial regulation and provide insights for the molecular design of high-performance additives for stable Zn anodes.展开更多
Although extensive research has been conducted on CO_(2)-enhanced coalbed methane(CO_(2)-ECBM)recovery,most prior studies have focused on the impact of gas adsorption-induced swelling on coal permeability under equili...Although extensive research has been conducted on CO_(2)-enhanced coalbed methane(CO_(2)-ECBM)recovery,most prior studies have focused on the impact of gas adsorption-induced swelling on coal permeability under equilibrium conditions.This paper presents a comprehensive thermo-hydro-mechanical-chemical(THMC)model that integrates thermal expansion and heat conduction(T),gas diffusion in the matrix and gas-water two-phase flow in the fractures(H),matrix and fracture deformation due to poroelasticity(M),and non-equilibrium binary gas adsorption-induced matrix swelling(C)during CO_(2)-ECBM recovery.The accuracy of the proposed model was verified through experimental data,and the model was simulated using finite element method(FEM)software.Simulation results indicate that the permeability evolution can be categorized into three stages.Ignoring the impact of water on gas adsorption properties would lead to an overestimation of the influence of adsorption-induced swelling,while disregarding non-equilibrium adsorption underestimates it.An examination of five designed cases identified critical factors influencing permeability.Parametric analysis shows that increases in the injection pressure,the injection temperature,and the initial permeability promote the competitive adsorption-induced swelling between CH_(4)and CO_(2),leading to increased CH_(4)production and CO_(2)storage.Conversely,an increase in initial water saturation reduces available gas flow space,decreasing both CH_(4)production and CO_(2)storage.Higher irreducible water saturation favors early gas recovery,while lower irreducible water saturation is more advantageous for long-term recovery.展开更多
The rational design of high-performance CO_(2)adsorbents remains a critical challenge in addressing global carbon emissions,with metal-organic frameworks(MOFs)emerging as promising candidates due to their tunable pore...The rational design of high-performance CO_(2)adsorbents remains a critical challenge in addressing global carbon emissions,with metal-organic frameworks(MOFs)emerging as promising candidates due to their tunable pore environments.However,the lack of systematic guidelines for functional group selection has hindered their practical implementation in carbon capture applications.Here,this gap was addressed by developing a comprehensive design framework through high-throughput computational screening.Through construction of a topology-directed database of 4797,integrating 10 metal centers with 144 functionalized ligands(18 ligands modified by–NH_(2),–NO_(2),–CH_(3),–CF_(3),–SH_(2),–SO_(2),–OH,and–OLi)across 36 topologies,the fundamental structure–property relationships governing CO_(2)capture performance was established.Multi-metric evaluation reveals that–NO_(2),–SO_(2),and–OLi dramatically enhance CO_(2)selectivity over CH_4/N_(2)via selectivity(S_(ads)),working capacity(ΔN),adsorbent performance score(APS),sorbent selection parameter(S_(sp)),and renewability R.Specially,ΔN rises from 2.34(pristine)to 5.91–7.94 mmol g^(-1)and S_(ads)surges from 24.94/40.36 to 121.11/176.87(–NO_(2)),149.94/215.54(–SO_(2)),and 58.64/267.44(–OLi).Besides,the critical trade-off between adsorption strength and renewability demonstrates that enhanced performance comes at the cost of reduced renewability,where stronger CO_(2)affinity(isosteric heat of-29.15,-29.96,and-30.09 for–NO_(2),–SO_(2),and–OLi)compromises renewability(R reduced by -50%).To resolve this trade-off,a novel energy efficiency(η)metric was introduced,which holistically evaluates both adsorption performance(S_(ads),ΔN,APS,S_(sp),and R)and energy inputs(desorption heat,pressure-swing energy,net loss).This leads to the identification of–SO_(2)as the optimal functional group that balances exceptional CO_(2)capture(η=6.17/12.78 for CO_(2)over CH_4/N_(2)),surpassing the second higher of 4.74/8.80 in–CF_(3)and 0.99/2.18 in non-functionalized counterparts.Adopting high-throughput computational screening methods,this work provides both fundamental insights into host–vip interactions in functionalized MOFs and a practical framework for designing next-generation adsorbents,bridging the gap between materials discovery and process engineering considerations in carbon capture technologies.展开更多
文摘A metal-organic framework/inorganic composite(ZIF-8@AMP)was synthesized by the in situ introduction of the active component ammonium phosphomolybdate(AMP)during the ambient solution-phase synthesis of the metal-organic framework(ZIF-8).The structure and properties of the composite were characterized using scanning electron microscopy(SEM),X-ray powder diffraction(XRD),X-ray photoelectron spectroscopy(XPS),thermogravimetric analysis(TGA),and Fourier transform infrared spectroscopy(FTIR).Its adsorption performance for Rb^(+)and Cs^(+)in water was investigated.Results indicate that ZIF-8@AMP exhibited adsorption efficiencies of 93.5%and 95.6%for Rb^(+)and Cs^(+)within 30 min,with maximum adsorption capacities of 92.7 and 104.5 mg·g^(-1),respectively.After five adsorption-desorption cycles,it maintained high adsorption capacity and achieved over 84.9%adsorption efficiency for Rb^(+)and Cs^(+)in actual brine samples.The adsorption of ZIF-8@AMP for Rb^(+)and Cs^(+)follows pseudosecond-order kinetics and the Langmuir adsorption isotherm,indicating an endothermic,entropy-increasing,and spontaneous process.The adsorption mechanism involves electrostatic attraction and ion exchange between ZIF-8@AMP and Rb^(+)and Cs^(+).
文摘In this study,a nickel-based MOF{(NH_(2)(CH_(3))_(2))_(2)[Ni_(3)(O)(L)3(NH(CH_(3))_(2))_(3)]}_(n)(Ni_(3)-MOF),with pore sizes of approximately 1.6 nm×1.6 nm,was synthesized by reacting 4,4′-biphenyldicarboxylic acid(H_(2)L)with Ni(NO_(3))_(2)·6H_(2)O in an N,N-dimethylformamide(DMF)solution.The nanoscale adsorbent Ni_(3)-MOF-N with a particle diameter of approximately 200 nm was prepared using Ni_(3)-MOF.It exhibited a maximum equilibrium tetracycline(TC)adsorption capacity of 358.2 mg·g^(-1)at its isoelectric point(pH=6.50),outperforming most reported MOF-based adsorbents.This exceptional performance is likely attributed to the well-matched pore size of Ni_(3)-MOF-N(1.6 nm×1.6 nm)and the molecular dimensions of TC(0.8 nm×1.2 nm),combined with the presence of partial Ni(Ⅱ)sites on the surface of Ni_(3)-MOF-N.These features collectively facilitate effective TC adsorption through a combination of pore filling,electrostatic attraction,hydrogen bonding,surface complexation,andπ-πinteractions.Recycling experiments demonstrated that Ni_(3)-MOF-N possesses excellent structural stability and consistent adsorption performance.CCDC:2481791,Ni_(3)-MOF.
基金funded by Quality Engineering Project Fund of Anhui University of Applied Technology,grant numbers 2024xjjxyjy41 and 2024xjjpkc05.
文摘To meet the needs of the treatment of Cu^(2+)pollution in aqueous solution,the sodium alginate-modified polyacrylic acid(PAA/SA)composite hydrogel was prepared by solution polymerization with acrylic acid(AA)as monomer,sodium alginate(SA)as filler,N,N’-methylenebisacrylamide(MBA)as crosslinking agent,and potassium persulfate(K2S2O8)as initiator.The characterization results showed that the introduction of SA significantly improved the physical and chemical properties of PAA hydrogel materials.Scanning electron microscopy(SEM)showed that as the SA content increased,the materials gradually evolved from a dense blocky structure to a porous network.When the SA content was 10 wt%,it exhibited a fragmented layered morphology.The Brunauer Emmett Teller(BET)showed that the specific surface area reached 37.65 m2/g and the porosity increased to 12.47%.Fourier transform infrared(FTIR)spectroscopy confirmed that SA was successfully embedded into the PAA network through hydrogen bonding and ion crosslinking,and the carboxyl vibration peak shifted from 2378 to 2352 cm^(-1).Mechanical tests showed that at 10 wt%SA,the maximum stress was 13.1 kPa.The adsorption experiment showed that the equilibrium adsorption capacity of the PAA/SA hydrogel for Cu^(2+)was 11.03 mg/g,with an adsorption efficiency of 42.65%.Dynamics studies showed that the adsorption process follows a first-order kinetic model(R2=0.986-0.997),indicating a physical adsorption mechanism dominated by liquid film diffusion.Theoptimal process conditions were found to be a dosage of 1.5 g/L,and the effect of temperature on adsorption was limited.The material maintained 67.4%of its initial adsorption capacity after six adsorption-desorption cycles.These parameters are generally superior to those of similar materials reported in the literature,indicating broad application prospects.Such a kinetic and isotherm model resulted from the combined effects of functional groups,electrostatic attraction,and chelation.In practical applications,pH,ionic strength,and competing ions will affect the adsorption performance of PAA/SA composite hydrogels.
基金supported by research funds of Jeonbuk National University in 2024 and partly supported by the National Research Foundation of Korea(NRF-2019R1A2C1006441)from the Ministry of Education.
文摘Flubendiamide is a commonly used pesticide with low water solubility and a high organic carbon sorption constant,causing it to adhere to soil particles and negatively impact soil ecosystems.First,chili plant stems,typically discarded after the harvest season,represent an abundant local biomass resource with significant potential for utilization,and were converted into biochar through pyrolysis.Here,we describe the synthesis of biochar modified with iron and chitosan to increase the diversity of functions and surface functional groups of biochar.The resulting chitosan-modified magnetic biochar(CMBC)presents a full range of functional groups of chitosan and iron oxide as shown by Fourier-transform infrared spectroscopy.The correlation between flubendiamide concentration and the dose of biochar on adsorption was explored.The flubendiamide adsorption efficiency of CMBC(1%mass ratio of soil)reached 68.03%in 90 min.The highest adsorption capacity achieved was 0.95 mg·g^(−1).The flubendiamide adsorption mechanism by CMBC can be described with a pseudo-second-order kinetic model.The experiment data closely fit a Freundlich isotherm model(R^(2)=0.998),and the low residual sum of squares values demonstrate the high model applicability.In this study,we present a comprehensive overview of pesticides,alongside kinetic and isotherm model studies of flubendiamide adsorption by CMBC.We emphasize the potential of modified biochar to enhance environmental remediation applications.
基金Dalian distinguished young scholars program(2022RJ17)the Dalian excellent young talents program(2023RY037)provided funding for this study.
文摘To efficiently remove radioactive nuclides from nuclear industry wastewater and minimize the generation of radioactive secondary waste,this study proposes the concept of a magnetically controlled microchannel adsorber based on magnetic adsorbents.A novel protocol for achieving high adsorption performance in microchannel adsorbers with periodically distributed particles is developed using the particle-resolved computational fluid dynamics (CFD) method,which addresses the limitations of traditional porous media flow models.To align simulation results more closely with practical scenarios,a typical high-efficiency magnetic adsorbent,magnetic sodium alginate/cobalt-based Prussian blue (M-SA/PB-Co),was synthesized.The M-SA/PB-Co microspheres exhibit a uniform size distribution (300–600 μm),and their Cs^(+) adsorption follows the pseudo-second-order kinetic model with a Langmuir saturated adsorption capacity of 124.84 mg·g^(-1).The performance parameters of M-SA/PB-Co,obtained from characterization and adsorption experiments,were integrated into CFD simulations.CFD results indicate that as the flow velocity increases,the flow field gradually transitions with vortices expanding in scale and streamline bifurcation points shifting rearward.The Cs^(+) concentration decreases progressively along the flow direction,with a more pronounced reduction in the vortex regions downstream of particles.The characteristic velocity and characteristic concentration of specific regions surrounding the particles were extracted based on boundary layer distribution.The amount of concentration reduction of Cs^(+) through particle is positively correlated with the characteristic concentration and negatively correlated with the characteristic velocity.The number of microspheres required in the microchannel adsorber was optimized using the response surface method.Compared with industrial fixed-bed adsorbers,microchannel adsorbers exhibit 8–10 times higher processing capacity,demonstrating significant industrial application potential.
基金financially supported by the National Natural Science Foundation of China (No.52372188)Natural Science Foundation of Henan (Nos.242300421625,252300421333)+4 种基金CAS Henan Industrial Technology Innovation & Incubation Center (No.2024121)Key Scientific Research Project of Education Department of Henan Province (Nos.22A150042,23A150038,and 24A150019)2023 Introduction of studying abroad talent programthe China Postdoctoral Science Foundation (No.2019 M652546)Key Project of Science and Technology of Henan Province (No.252102240007)。
文摘Aqueous zinc-ion batteries(AZIBs) are regarded as one of the most promising energy conversion and storage devices.Nevertheless,side reactions and dendrite growth on the zinc metal anode hinder their widespread application.In this study,hemin was employed as a multi-functional artificial interface for the first time to inhibit the disordered growth of zinc dendrites and mitigate side reactions.Theoretical calculations indicate that hemin is preferentially adsorbed onto the zinc anode,thus blocking the interaction between the active zinc anode and electrolyte.Compared with zinc foil,the Hemin@Zn anode demonstrates enhanced corrosion resistance,a decrease in hydrogen evolution,and more orderly deposition of zinc.As expected,the symmetric cell with Hemin@Zn anode can sustain up to 4000 h at 0.2 mA/cm^(2),0.2 mAh/cm^(2).Asymmetric Zn//Cu cells exhibit an average coulombic efficiency exceeding 99.72 % during 500 cycles.Moreover,the full cell Hemin@Zn//NH_(4)V_(4)O_(10) delivers a superior capacity up to 367 m Ah/g and the discharge capacity retention reaches 124 mAh/g after 1200 cycles even at a current density of 5 A/g.This work provides a simple and effective method for constructing a robust artificial interface to promote the application of long-life AZIBs.
基金supported by the Natural Science Foundation of Xiamen,China(No.3502Z20227238)the National Natural Science Foundation of China(Nos.22276181 and 52300143)+3 种基金the Science and Technology Planning project of Fujian Province,China(Nos.2022H0045 and 2023I0035)the Youth Innovation Promotion Associ-ation CAS(No.2019307)China Postdoctoral Science Foundation(No.2022M723082)the Youth Science and Technology Innovation Pro-gram of Xiamen Ocean and Fisheries Development Special Funds(No.23ZHZB032QCA20).
文摘A novel hierarchical porous metal-organic framework(MOF)-based hollow carbon nanofiber mat(CNFM)was prepared through a facile electrospinning process followed by carbonization.Two immiscible polymers,polyacrylonitrile/polymethyl methacrylate(PAN/PMMA),and porous zeolitic imidazolate framework-8(ZIF-8)particles were selected as components for the electrospinning suspension.The resulting PPZ-CNFM-1–2–2(PAN:PMMA:ZIF8=1:2:2,mass ratio)exhibited a hollow tubular structure with uniformly distributed dense hollow-spheres on the tube walls.The obtained CNFM possessed a high Brunauer-Emmett-Teller specific surface area(SBET)of 1696 m2/g and total pore volume of 2.74 cm^(3)/g,which are comparable to those achieved by traditional physical or chemical activation methods.This MOF-based CNFM demonstrated excellent adsorption performance towards ciprofloxacin(CIP),exhibiting a high static adsorption capacity of approximately 600 mg/g and achieving adsorption equilibrium withing only 1 h.The exceptional adsorption capacity can be attributed to its high SBET and abundant pores that accommodate CIP molecules,while the rapid adsorption rate is facilitated by the presence of hollow-sphere and hollow tubular structures in the carbon nanofibers.Furthermore,the study revealed the significant contributions of pore-filling effect during the adsorption process.Fixed-bed experiments confirmed that this MOF-based hollow CNFM holds great potential for large-scale applications in purifying CIP-contaminated water.
基金supported by the National Natural Science Foundation of China(22478266 and 32472027)the National Key Research&Development Program of China(2022YFE0207100)the Department of Science and Technology of Sichuan Province(2024ZYD0080 and 2022YFN0027).
文摘Economical and sustainable wastewater treatment techniques are highly demanded to alleviate the issues of clearwater scarcity globally.In this work,the acetic acid/H_(2)O_(2) (AHP) was leveraged to enrich oxygenated functional groups on the biochar surface for efficient ciprofloxacin (CIP) adsorption and biochar regeneration (In situ degradation of CIP in the spent AHP solution).The AHP-modified biochar exhibited significantly enhanced CIP adsorption capacity,about 22 times that of the pristine biochar.The optimized modification condition (acetic acid/H_(2)O_(2):2.11,temperature:45 ℃,and time:12 h) was screened by the response surface method,reaching the highest CIP adsorption capacity of 86.26 mg·g^(−1).Characterization results revealed that the content of carboxyl —C=O—O was enhanced in AHP-modified biochar,which contributed to efficient CIP adsorption by the electrostatic interaction,hydrogen bonding,and hydrophobic interaction.The adsorption of modified biochar to CIP molecules was a spontaneous endothermic process,and in line with the pseudo-second-order model and the Langmuir isotherm model.Moreover,the biochar modification process enabled the spent AHP solution with a strong oxidizing agent of peracetic acid (PAA),which can be employed to degrade adsorbed CIP for biochar in-situ generation.This work tailored a closed-loop strategy for biochar oxidation,contaminant adsorption,and biochar regeneration,highlighting a viable route for sustainable wastewater treatment.
基金supported by the Open Project Funding of Key Laboratory of Intelligent Health Perception and Ecological Restoration of Rivers and Lakes,Ministry of Education,Hubei University of Technology(No.HGKFZ03).
文摘In this study,chitosan(CS)was combined with microcrystalline cellulose(MCC)to fabricate composite hydrogel beads.These beads were further modified through blending and grafting with polyethyleneimine(PEI)to develop chitosan/microcrystalline cellulose@polyethyleneimine(CS/MCC@PEI)composite gel spheres for the efficient adsorption of diclofenac sodium(DS)from aqueous solutions.The adsorbent was characterized using scanning electron microscopy(SEM),X-ray diffraction(XRD),Fourier-transform infrared spectroscopy(FTIR),X-ray pho-toelectron spectroscopy(XPS),and thermogravimetric analysis(TGA).The CS/MCC@PEI composite exhibited a spherical morphology with a porous structure,abundant surface functional groups,and a high adsorption capac-ity of 274.84 mg/g for DS.Kinetic studies revealed that the adsorption process followed the pseudo-second-order model,dominated by physical adsorption,with both surface and internal diffusion influencing the adsorption rate.The Freundlich isotherm model best described the adsorption behavior,indicating multilayer adsorption on heterogeneous surfaces.Environmental adaptability tests demonstrated minimal interference from co-existing anions and humic acid,while regeneration experiments confirmed excellent reusability(>77%removal after five cycles).The adsorption mechanism involved electrostatic interactions and hydrogen bonding between the hydroxyl/amino groups of the composite and DS.These findings highlight the potential of CS/MCC@PEI as a cost-effective and sustainable adsorbent for DS removal from water.
基金the support from the National Key Research and Development Program of China (No. 2022YFC2904504)the Science and Technology Research Project of Jiangxi Provincial Department of Education, China (No. GJJ2200864)the Gansu Provincial Key Research and Development Project, China (No. 22YF7GA073)。
文摘The flotation separation of argentite from sphalerite using ammonium dibutyl dithiophosphate(ADD)was studied.Molecular simulation(MS)calculation shows that ADD is chemisorbed on argentite and sphalerite surface in the form of S—P bond.The ADD adsorption on argentite and sphalerite surface in Ag^(+)system was revealed by ICP,Zeta potential and XPS analyses.It is shown that the dissolved Ag^(+)from argentite surface can be absorbed on sphalerite surface in the form of silver hydroxide,and AgOH hydrophilic colloid prevents the adsorption of ADD on sphalerite surface.The ADD adsorption on argentite and sphalerite surface in the pulp containing silver and zinc ions was revealed by adsorption capacity and surface wettability analyses.It is shown that the combined Zn(OH)_(2) and AgOH hydrophilic colloid leads to greater ADD adsorption capacity on argentite surface and stronger surface hydrophobicity than sphalerite.Flotation tests demonstrate that ADD enables efficient separation of argentite from sphalerite in the pulp containing silver and zinc ions.
基金the Department of Science and Technology(DST),Govt.of India for providing funds under the FIST program and PURSE grant vide No.SR/PURSE/2020/31 to the department of Chemistry,University of Kashmir.
文摘This study presents a thorough investigation into the use of single and twin-tailed cationic and anionic surfactant-modified chitosan(SMCS)hydrogel beads as effective adsorbents for the elimination of hazardous polycyclic aromatic hydrocarbons(PAHs)from aqueous solutions.The Chitosan(CS)hydrogel beads were modified with single/twin-tailed anionic surfactants,sodium dodecyl sulfate(SDS)and sodium bis(2-ethylhexyl)sulfosuccinate(AOT),and cationic surfactants,dodecyltrimethylammonium bromide(DTAB)and didodecyldimethylammonium bromide(DDAB),to enhance their adsorption capacity of PAHs.The CS and SMCS beads were evaluated for their structural,mechanical,and adsorption properties using a range of techniques,including infrared spectroscopy(IR),energy-dispersive X-ray spectroscopy(EDX),rheometry,and field emission scanning electron microscopy(FESEM).Adsorption experiments of naphthalene(Nap),acenaphthene(Ace),and phenanthrene(Phe)on SMCS beads demonstrate that they have significantly higher adsorption capacities than CS beads,due to increase in hydrophobic interactions.Adsorption capacity followed the trend,Phen>Ace>Nap for all the beads revealing that twin-tailed SMCS bead possess much higher adsorption capacities(Qmax)compared to single-tailed SMCS beads.For twin tailed surfactants,the maximum adsorption capacities for Nap,Ace and Phe varied as CS-AOT(CS-DDAB):430.0(323.8)611.60(538.18)633.39(536.99)mg/g respectively,outperforming other reported hydrogel beads.The study highlights the simplicity,eco-friendliness,and enhanced performance of surfactant modification for developing high-efficiency adsorbents,paving the way for cost-effective solutions in water re-mediation.
基金supported by the National Natural Science Foundation of China(No.52370112).
文摘In order to address the evolving emission characteristics of oxygenated volatile organic compounds(OVOCs),it is essential to develop adsorbent materials specifically designed for the efficient adsorption of OVOCs with large kinetic diameters.In this study,we used co-pyrolysis to prepare a series of graded porous carbon materials with well-developed micropores by adjusting the doping ratios of root nodules and pretreated cellulose.The material with root nodule to cellulose mass ratio of 1:1(TCC-RN-1)exhibited the highest saturated adsorption capacity for butyl acetate(834 mg/g).This can be attributed to enhanced pore size distribution from nodule doping,which facilitates the development of a micropore-graded structure.Additionally,the nodules acted as auxiliary activating agents that enhanced the KOH micropore regulation effect during the activation stage,resulting in the highest micropore volume(0.863 cm^(3)/g).The doping of root nodules facilitated the formation of additional defects on the surface of the porous carbon material,leading to a more disordered arrangement that improved pollutant adsorption.Furthermore,TCC-RN-1 demonstrated good thermal stability in an air atmosphere,main-taining a butyl acetate adsorption capacity exceeding 95%after five adsorption-desorption cycles.This indicates its favorable potential for industrial applications.
基金supported by Shaanxi Fundamental Science Research Project for Chemistry and Biology(23JHQ011)Natural Science Foundation of Shaanxi(2024JC-YBMS-115)Natural Science Basic Research Plan in Shaanxi Province of China(2025JC-YBMS-141)。
文摘The severe shuttle effect and sluggish reaction kinetics in room-temperature sodium-sulfur(RT Na-S)batteries have been major bottlenecks hindering their practical application.To overcome these challenges,a straightforward reduction approach was employed to design three bimetallic alloy nanoparticles(FeNi,FeCo,and NiCo)supported on multistage porous carbon substrates.Experimental and theoretical calculations reveal that the charge transfer within the alloy catalyst influences the position of its d-band center and its degree of hybridization with sodium polysulfides(NaPSs).An increased charge transfer leads to a shift of the alloy’s d-band center closer to the Fermi energy level,thereby enhancing its adsorption and catalytic capabilities.Among the three alloy compositions,the FeNi alloy exhibits the highest charge transfer.Consequently,the FeNi alloy demonstrates the superior electrochemical performance,achieving a high reversible specific capacity of 848.2 mA h g^(−1),with an average capacity degradation rate of only 0.037%per cycle over 1000 cycles at 1.2 C.The S/FeNi/NC cathode exhibits a low electrolyte-to-sulfur(E/S)ratio of 6.6µL mg^(−1),while maintaining a high reversible specific capacity of 568.1 mA h g^(−1).This offers valuable insights for the application of alloy catalysts in the S/FeNi/NC cathode of RT Na-S batteries.
基金the financial support provided by the National Natural Science Foundation of China(22478267,22438009,U24A20535)Basic Research Program of Jiangsu province(BK20243002)+1 种基金Prospective Application Research Project of Suzhou(SYC2022042)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD).
文摘Antibiotics,as an emerging pollutant due to their extensive use and difficulty in biodegradation,can cause harm to health through bioaccumulation.To address this,various photocatalysts have been developed for rapid antibiotic removal.However,their low concentrations limit mass transfer efficiency,resulting in suboptimal performance.Adsorption is crucial for enhancing photocatalytic efficiency.In this study,a series of binary heterojunction catalysts(x%BWO@STHP)were synthesized,consisting of Bi_(2)WO_(6)(BWO)grafted with sulfonated triptycene-based hypercrosslinked polymer(STHP).The high specific surface area of STHP,combined withπ-πconjugation and ionic interactions with antibiotics,significantly enhances adsorption capacity.This facilitates effective contact between low-concentration pollutants in aqueous solutions and the active sites of the catalyst.The formation of a Z-scheme heterojunction between BWO and STHP facilitates photogenerated charge separation,and further significantly improves photocatalytic degradation performance.Specifically,the 20%BWO@STHP catalyst achieved rapid adsorption equilibrium for oxytetracycline(OTC),doxycycline(DOX),and tetracycline(TC)within 2 min and completely degraded them after 15 min of irradiation.Compared to pristine BWO,the photocatalytic reaction rate constants are significantly increased,being 9.69 times higher for OTC and 13.45 times higher for DOX.The catalyst exhibits excellent reusability and holds promising potential for practical applications.
基金supported by the National Natural Science Foundation of China(No.82373800)Guangdong Basic and Applied Basic Research Foundation(No.2024A1515011236)Continuation Project of Excellent Doctors,Guangzhou Basic and Applied Basic Research Foundation(No.2025A04J5082).
文摘The protein corona formation has been reported to influence the liposomes’behavioral performance in vivo.Accordingly,the effect of physiologically relevant inorganic ion pairs(sodium chloride,sodium sulfate,magnesium chloride,and magnesium sulfate)was investigated.Bovine serum albumin(BSA)was selected as the model protein.Parameters including particle size and zeta potential were assessed,while various spectroscopic techniques were utilized to elucidate the changes in BSA during its interaction with liposomes.The particle size and light intensity distribution changes indicated that the introduction of inorganic pairs,especially the metal cations,could significantly influence both the adsorption of BSA and the aggregation of particles.Furthermore,spectral characterization elucidated that BSA exhibited more extended peptide chains with enhanced exposure to hydrophobic acid amino residues upon adding ion pairs.Electrostatic adsorption and chelation insertion were proposed as metal ion binding modes and the corresponding BSA corona formation.In the electrostatic adsorption mode,sodium ions can enhance the electrostatic interactions,facilitating the“connection”between BSA and liposomes.Magnesium ions can induce stronger hydrophobic interactions through chelation,effectively“drag”BSA segments into the lipid bilayer.This work highlighted important physiological factors for protein-liposome interaction and provided rational model constructions to lay the foundation for further relevant studies.
基金supported by the National Natural Science Foundation of China(Grant No.U23A2022)the National Natural Science Foundation of China(Grant No.52474047)+2 种基金the Natural Science Foundation of Chongqing(Grant No.CSTB2024NSCQ-MSX0951)the Natural Science Foundation of Sichuan Province(Grant No.2025ZNSFSC1357)the National Science and Technology Major Project(Grant No.2025ZD1404307).
文摘Injecting impure CO_(2)for enhanced gas recovery(CO_(2)-EGR)offers a dual benefit by improving natural gas extraction while enabling CO_(2)sequestration.However,the interactions between CO_(2),N_(2),and CH_(4)under reservoir conditions require further investigation.This study employs Grand Canonical Monte Carlo(GCMC)and Molecular Dynamics(MD)simulations to quantify the adsorption and diffusion behaviors of CO_(2),N_(2),and CH_(4)in quartz nanopores over a pressure range of 1-24 MPa under varying water saturations and gas compositions.The results indicate that:(1)CO_(2)exhibits the broadest energy distribution and the strongest adsorption stability,occupying about 20%-30%more adsorption sites than CH_(4)or N_(2)and showing the least sensitivity to water saturation,with only a 30%reduction at 50%saturation,compared to 60%for CH_(4),giving CO_(2)a clear competitive advantage.(2)The adsorption and desorption behaviors are strongly pressure dependent,as increasing pressure reduces the adsorption layer area and shifts gas distribution from adsorption dominated to free phase.Competitive adsorption analysis reveals that while CO_(2)dominates displacement at low pressures,mixtures that contain N_(2)achieve higher CH_(4)desorption efficiency above 13 MPa by mitigating diffusion resistance.(3)A higher N_(2)fraction improves CH_(4)diffusion coefficients,thereby facilitating gas mobility and ensuring superior recovery performance under high-pressure conditions.This study advances the fundamental knowledge of microscale gas behavior in tight sandstones and supports the feasibility of impure CO_(2)injection as a practical strategy for sustainable gas production.
基金supported by the NSFC-Yunnan Joint Fund(No.U2102210)the National Natural Science Foundation of China(No.22168044)+1 种基金Yunnan Provincial Department of Science and Technology(No.202201BF070001-013)the Research Innovation Fund for Graduate Students of Yunnan University(No.KC-23234004).
文摘Excessive phosphorus and arsenic in water bodies not only destroy ecosystems but also pose a serious threat to human health.In this study,a series of Al-doped modified metal-organic frameworks(Zr-Al-MOF)were prepared by solvothermal method,which achieved efficient removal of phosphate and arsenate in water.Due to the use of inexpensive Al salts,the material has a lower cost and is more economical.The molar ratio of metal salts,adsorption time,solution pH,initial concentration,temperature and coexisting anions were studied,and it was found that when the molar ratio of Zr:Al was 2,Zr-Al-MOF had the best adsorption performance for phosphate and arsenate,and the maximum adsorption capacity was 93.04 mg P/g and 173.83 mg As/g,respectively.It traps phosphate and arsenate at a fast reaction rate and can be recycled repeatedly.In addition,0.15 g/L of 2Zr-Al-MOF can effectively reduce the phosphate and arsenate content in the contaminated spring water samples of Yangzonghai Lake to the standard range of drinking water,which further confirms the application potential of 2Zr-Al-MOF.By FT-IR and XPS analysis,it was found that the adsorption mechanism was ligand exchange,electrostatic attraction and hydrogen bond formation.The theoretical calculation shows that the adsorption energy is negative,which indicates that 2Zr-Al-MOF is attractive to phosphate and arsenate,and the adsorption state is stable.The results show that 2Zr-Al-MOF is an effective phosphate and arsenate adsorbent and has broad application prospects in eutrophication water treatment.
基金financially supported by the Science and Technology Foundation of Henan Province(252102230017)the Doctoral Foundation of Henan University of Technology(2019BS005)+2 种基金the Talent Research Start-up Fund Project of Tongling University(2021tlxyrc23)the Natural Science Research Project of the Anhui Educational Committee(2023AH040234)the Scientific Research Projects of Tongling University(2022tlxyszZD04)。
文摘The development of aqueous zinc batteries(AZBs)is severely constrained by uncontrolled dendrite growth and parasitic interfacial reactions.Conventional solvation-dominated additives can mitigate these issues by altering the Zn^(2+)solvation structure,but they often compromise ion transport.Here,we introduce a molecular design principle for a non-solvating additive(NSA)based on inductive effects.Ethyl trifluoroacetate(ETFA),obtained by introducing an electron-withdrawing–CF_(3) group adjacent to the–C=O moiety of ethyl acetate(EA),participates minimally in the solvation structure but preferentially undergoes Gibbs adsorption at the Zn-electrolyte interface.This process reduces interfacial tension,reconstructs the electrical double layer,and orients ETFA molecules such that the hydrophilic–C=O groups face the electrolyte,modulating hydrogen-bonding networks,while the hydrophobic–CF_(3) groups anchor onto Zn to regulate deposition.As a result,dendrite formation and side reactions are simultaneously suppressed.With only 1 vol%ETFA,Zn-Cu cells achieve over 4000 stable cycles with 99.89%Coulombic efficiency.Zn-I_(2) full cells employing the modified electrolyte maintain stable operation for more than 500 cycles(6.8 mg cm^(-2),10μm Zn,N/P=2.86),and 0.3 Ah Zn-I_(2) pouch cells(30 mg cm^(-2),100μm Zn)can cycle stably for over 200 cycles.These findings highlight the critical role of Gibbs adsorption in interfacial regulation and provide insights for the molecular design of high-performance additives for stable Zn anodes.
基金the support from the National Natural Science Foundation of China(No.52079077)Natural Science Foundation of Hubei Provincial(2025AFB358).
文摘Although extensive research has been conducted on CO_(2)-enhanced coalbed methane(CO_(2)-ECBM)recovery,most prior studies have focused on the impact of gas adsorption-induced swelling on coal permeability under equilibrium conditions.This paper presents a comprehensive thermo-hydro-mechanical-chemical(THMC)model that integrates thermal expansion and heat conduction(T),gas diffusion in the matrix and gas-water two-phase flow in the fractures(H),matrix and fracture deformation due to poroelasticity(M),and non-equilibrium binary gas adsorption-induced matrix swelling(C)during CO_(2)-ECBM recovery.The accuracy of the proposed model was verified through experimental data,and the model was simulated using finite element method(FEM)software.Simulation results indicate that the permeability evolution can be categorized into three stages.Ignoring the impact of water on gas adsorption properties would lead to an overestimation of the influence of adsorption-induced swelling,while disregarding non-equilibrium adsorption underestimates it.An examination of five designed cases identified critical factors influencing permeability.Parametric analysis shows that increases in the injection pressure,the injection temperature,and the initial permeability promote the competitive adsorption-induced swelling between CH_(4)and CO_(2),leading to increased CH_(4)production and CO_(2)storage.Conversely,an increase in initial water saturation reduces available gas flow space,decreasing both CH_(4)production and CO_(2)storage.Higher irreducible water saturation favors early gas recovery,while lower irreducible water saturation is more advantageous for long-term recovery.
基金supported by The National Natural Science Foundation of China(22471289 and 22478430)Shandong Natural Science Foundation(ZR2022ME105 and ZR2023ME004)+4 种基金Qingdao Natural Science Foundation(23-2-1-232-zyyd-jch)Geological body description and key technologies of reservoir engineering of CCUS oil displacement(2021ZZ01-03)Science and Technology Major Project on New Oil and Gas Exploration and Development:Research on Comprehensive Control Technology for CO_(2)-Enhanced Miscible and Immiscible Displacement(2024ZD1406601)State Key Laboratory of Enhanced Oil Recovery of Open Fund Funded Project(2024-KFKT-19)the Fundamental Research Funds for the Central Universities(24CX06042A and 24CX06070A)。
文摘The rational design of high-performance CO_(2)adsorbents remains a critical challenge in addressing global carbon emissions,with metal-organic frameworks(MOFs)emerging as promising candidates due to their tunable pore environments.However,the lack of systematic guidelines for functional group selection has hindered their practical implementation in carbon capture applications.Here,this gap was addressed by developing a comprehensive design framework through high-throughput computational screening.Through construction of a topology-directed database of 4797,integrating 10 metal centers with 144 functionalized ligands(18 ligands modified by–NH_(2),–NO_(2),–CH_(3),–CF_(3),–SH_(2),–SO_(2),–OH,and–OLi)across 36 topologies,the fundamental structure–property relationships governing CO_(2)capture performance was established.Multi-metric evaluation reveals that–NO_(2),–SO_(2),and–OLi dramatically enhance CO_(2)selectivity over CH_4/N_(2)via selectivity(S_(ads)),working capacity(ΔN),adsorbent performance score(APS),sorbent selection parameter(S_(sp)),and renewability R.Specially,ΔN rises from 2.34(pristine)to 5.91–7.94 mmol g^(-1)and S_(ads)surges from 24.94/40.36 to 121.11/176.87(–NO_(2)),149.94/215.54(–SO_(2)),and 58.64/267.44(–OLi).Besides,the critical trade-off between adsorption strength and renewability demonstrates that enhanced performance comes at the cost of reduced renewability,where stronger CO_(2)affinity(isosteric heat of-29.15,-29.96,and-30.09 for–NO_(2),–SO_(2),and–OLi)compromises renewability(R reduced by -50%).To resolve this trade-off,a novel energy efficiency(η)metric was introduced,which holistically evaluates both adsorption performance(S_(ads),ΔN,APS,S_(sp),and R)and energy inputs(desorption heat,pressure-swing energy,net loss).This leads to the identification of–SO_(2)as the optimal functional group that balances exceptional CO_(2)capture(η=6.17/12.78 for CO_(2)over CH_4/N_(2)),surpassing the second higher of 4.74/8.80 in–CF_(3)and 0.99/2.18 in non-functionalized counterparts.Adopting high-throughput computational screening methods,this work provides both fundamental insights into host–vip interactions in functionalized MOFs and a practical framework for designing next-generation adsorbents,bridging the gap between materials discovery and process engineering considerations in carbon capture technologies.
