Poor solubility often results in low efficacy of antitumor drugs.Nevertheless,limited research has been conducted on the potential decrease in drug efficacy following the self-assembly of hydrophobic pure drugs into n...Poor solubility often results in low efficacy of antitumor drugs.Nevertheless,limited research has been conducted on the potential decrease in drug efficacy following the self-assembly of hydrophobic pure drugs into nanodrugs,and solutions to this problem are even rarer.Loading water-insoluble antitumor drugs into nanocarriers offers a promising solution.However,intricate carrier preparation,limited drug loading capacity,and carrier-associated safety remain key challenges.In this study,based on the discovery that hydrophobic gambogic acid(GA) self-assembles into nanostructures with diminished antitumor efficacy in aqueous environments,we developed a carrier-free nanodrug system,designated as GA-S-S-AS nanoparticles(NPs),characterized by straightforward preparation,high drug loading,fluorescence imaging,tumor-targeting,and responsive drug release in reducing environments.Specifically,the hydrophobic GA was covalently linked to the hydrophilic aptamer through a disulfide bond and then self-assembled into the nanodrugs.About 92 % of drug was encapsulated in self-assembled NPs,demonstrating remarkable stability under physiological conditions and controlled release of GA in the high-glutathione environment characteristic of tumor sites.Furthermore,by utilizing the synergistic interaction between the enhanced permeability and retention(EPR) effect and ligand-receptor active targeting mechanisms,the nanodrugs significantly increased the accumulation of GA at tumor locations.Consequently,the nanodrugs exhibited optimal therapeutic efficacy against the tumor both in vitro and in vivo,significantly inhibiting tumor growth.Furthermore,the nanodrugs demonstrated enhanced biosafety compared to free GA,effectively reducing GA-induced hepatotoxicity.Taken together,these findings underscore the significant potential of this multifunctional carrier-free nanodrugs for the targeted delivery of GA,thereby laying a foundation for future endeavors aimed at developing novel formulations of hydrophobic antitumor drugs.展开更多
MnO_(x)-CeO_(2)catalysts for the low-temperature selective catalytic reduction(SCR)of NO remain vulnerable to water and sulfur poisoning,limting their practical applications.Herein,we report a hydrophobic-modified MnO...MnO_(x)-CeO_(2)catalysts for the low-temperature selective catalytic reduction(SCR)of NO remain vulnerable to water and sulfur poisoning,limting their practical applications.Herein,we report a hydrophobic-modified MnO_(x)-CeO_(2)catalyst that achieves enhanced NO conversion rate and stability under harsh conditions.The catalyst was synthesized by decorating MnOx crystals with amorphous CeO_(2),followed by loading hydrophobic silica on the external surfaces.The hydrophobic silica allowed the adsorption of NH_(3)and NO and diffusion of H,suppressed the adsorption of H_(2)O,and prevented SO_(2)interaction with the Mn active sites,achieving selective molecular discrimination at the catalyst surface.At 120℃,under H_(2)O and SO_(2)exposure,the optimal hydrophobic catalyst maintains 82%NO conversion rate compared with 69%for the unmodified catalyst.The average adsorption energies of NH_(3),H_(2)O,and SO_(2)decreased by 0.05,0.43,and 0.52 eV,respectively.The NO reduction pathway follows the Eley-Rideal mechanism,NH_(3)^(*)+*→NH_(2)^(*)+H^(*)followed by NH_(2)^(*)+NO^(*)→N_(2)^(*)+H_(2)O^(*),with NH_(3)dehydrogenation being the rate determining step.Hydrophobic modification increased the activation energy for H atom transfer,leading to a minor decrease in the NO conversion rate at 120℃.This work demonstrates a viable strategy for developing robust NH_(3)-S CR catalysts capable of efficient operation in water-and sulfur-rich environments.展开更多
Herein,the surface of Moso bamboo was hydrophobically modified by combining O_(2)/N_(2)plasma treatments with polydimethylsiloxane(PDMS)solution treatment as the hydrophobic solution.The effects of plasma treatment pr...Herein,the surface of Moso bamboo was hydrophobically modified by combining O_(2)/N_(2)plasma treatments with polydimethylsiloxane(PDMS)solution treatment as the hydrophobic solution.The effects of plasma treatment process(power and time),PDMS solution concentration,and maceration time on the hydrophobic performance of bamboo specimens were studied,and the optimal treatment conditions for improving the hydrophobicity were determined.Scanning electron microscopy(SEM),fourier transform infrared(FTIR),X-ray diffraction(XRD),and X-ray photoelectron spectroscopy(XPS)were used to analyze the surface morphology,chemical structure,and functional groups in the specimens before and after the plasma and PDMS solution treatments under optimal conditions.Response surface analysis was also performed to determine the optimal treatment conditions.Results show that the hydrophobic performance of the Moso bamboo surface is effectively improved and the surface energy is reduced after the coordinated treatment.The optimal conditions for improving the hydrophobic performance of Moso bamboo surface are a treatment power of 800 W,treatment time of 15 s,O_(2)flow rate of 1.5 L/min,PDMS solution concentration of 5%,and maceration time of 60 min for O_(2)plasma treatment and a treatment power of 1000 W,treatment time of 15 s,N_(2)flow rate of 1.5 L/min,PDMS solution concentration of 5%,and maceration time of 60 min for N_(2)plasma treatment.After treatment,silicone oil particles and plasma etching traces are observed on the bamboo surface.Moreover,Si-O bonds in the PDMS solution are grafted to the bamboo surface via covalent bonds,thereby increasing the contact angle and decreasing the surface energy to achieve the hydrophobic effect.展开更多
Water often presents significant challenges in catalysts by deactivating active sites,poisoning the reaction,and even degrading composite structure.These challenges are amplified when the water participates as a react...Water often presents significant challenges in catalysts by deactivating active sites,poisoning the reaction,and even degrading composite structure.These challenges are amplified when the water participates as a reactant and is fed as a liquid phase,such as trickle bed-type reactors in a hydrogen-water isotope exchange(HIE)reaction.The key balance in such multiphase reactions is the precise control of catalyst design to repel bulk liquid water while diffusing water vapor.Herein,a platinum-incorporated metal-organic framework(MIL-101)based bifunctional hydrophobic catalyst functionalized with long alkyl chains(C_(12),dodecylamine)and further manufactured with poly(vinylidene fluoride),Pt@MIL-101-12/PVDF,has been developed which can show dramatically improved catalytic activity under multi-phase reactions involving hydrogen gas and liquid water.Pt@MIL-101-12/PVDF demonstrates enhanced macroscopic water-blocking properties,with a notable reduction of over 65%in water adsorption capacity and newly introduced liquid water repellency.while exhibiting a negligible increase in mass transfer resistance,i.e.,bifunctional hydrophobicity.Excellent catalytic activity,evaluated via HIE reaction,and its durability underscore the impact of bifunctional hydrophobicity.In situ DRIFTS analysis elucidates water adsorption/desorption dynamics within the catalyst composite,highlighting reinforced water diffusion at the microscopic level,affirming the catalyst's bifunctionality in different length scales.With demonstrated radiation resistance,Pt@MIL-101-12/PVDF emerges as a promising candidate for isotope exchange reactions.展开更多
CO_(2)reduction reaction(CO_(2)RR)electrolyzers based on gas diffusion electrode(GDE)enable the direct mass transfer of CO_(2)to the catalyst surface for participation in the reaction,thereby establishing an efficient...CO_(2)reduction reaction(CO_(2)RR)electrolyzers based on gas diffusion electrode(GDE)enable the direct mass transfer of CO_(2)to the catalyst surface for participation in the reaction,thereby establishing an efficient three-phase reaction interface that significantly enhances current density.However,current hydrophobic modification methods face difficulties in achieving precise and substantial control over wettability,and the hydrophobic modifiers tend to significantly impair the conductivity of the electrode and ion transport capabilities.This study employs Nafion ionomers to hydrophobically modify the threedimensional catalyst layer,revealing the bifunctionality of Nafion.The fluorinated backbone of Nafion ensures the hydrophobicity of the entire catalyst layer,while its sulfonic acid groups promote ion transport,without significantly affecting the conductivity of the electrode.Furthermore,by employing modifiers with distinct wettability characteristics,a highly efficient and large-scale manipulation of the hydrophilic/hydrophobic properties of the catalyst layer was successfully realized.The electrode,constructed with silver nanopowder as a representative catalyst and modified with the hydrophobic ionomer Nafion,exhibits a substantial enhancement in both catalytic activity and durability.The optimized electrode exhibited exceptional electrocatalytic performance in both flow cell and membrane electrode assembly(MEA)configurations.Notably,in the MEA,the electrode achieved a remarkable CO Faradaic efficiency(FE)of 93.3%at a total current density of 200 mA cm^(-2),while maintaining stable operation for over 62 h.展开更多
A critical challenge hindering the practical application of lithium–oxygen batteries(LOBs)is the inevitable problems associated with liquid electrolytes,such as evaporation and safety problems.Our study addresses the...A critical challenge hindering the practical application of lithium–oxygen batteries(LOBs)is the inevitable problems associated with liquid electrolytes,such as evaporation and safety problems.Our study addresses these problems by proposing a modified polyrotaxane(mPR)-based solid polymer electrolyte(SPE)design that simultaneously mitigates solvent-related problems and improves conductivity.mPR-SPE exhibits high ion conductivity(2.8×10^(−3)S cm^(−1)at 25℃)through aligned ion conduction pathways and provides electrode protection ability through hydrophobic chain dispersion.Integrating this mPR-SPE into solid-state LOBs resulted in stable potentials over 300 cycles.In situ Raman spectroscopy reveals the presence of an LiO_(2)intermediate alongside Li_(2)O_(2)during oxygen reactions.Ex situ X-ray diffraction confirm the ability of the SPE to hinder the permeation of oxygen and moisture,as demonstrated by the air permeability tests.The present study suggests that maintaining a low residual solvent while achieving high ionic conductivity is crucial for restricting the sub-reactions of solid-state LOBs.展开更多
A radical C−C-coupling reaction of acetonitrile into succinonitrile over hydrophobic TiO_(2) photocatalyst with enhanced catalytic activity was developed.In addition,the usage of a flow reactor further improved the ph...A radical C−C-coupling reaction of acetonitrile into succinonitrile over hydrophobic TiO_(2) photocatalyst with enhanced catalytic activity was developed.In addition,the usage of a flow reactor further improved the photon utilization efficiency for succinonitrile synthesis at room temperature.The space time yield of succinonitrile reached 55.59μmol/(g·h)over hydrophobic TiO_(2) catalyst,which was much higher than that of pristine TiO_(2)(4.23μmol/(g·h)).Mechanistic studies revealed that the hydrophobic modification of TiO_(2) promoted the separation and transfer of photogenerated carriers,as well as suppressed their recombination.Hydrophobic TiO_(2) also enhanced the adsorption of−CH3 of acetonitrile,thus facilitating the activation of C−H bond and the utilization efficiency of photocarriers.展开更多
Aqueous zinc-ion batteries(AZIBs)are pivotal for achieving net-zero goals,yet their commercialization is impeded by zinc dendrites,parasitic reactions,and interfacial instability.Current debates persist on the interpl...Aqueous zinc-ion batteries(AZIBs)are pivotal for achieving net-zero goals,yet their commercialization is impeded by zinc dendrites,parasitic reactions,and interfacial instability.Current debates persist on the interplay between zincophilic-hydrophilic and zincophobic-hydrophobic interactions at the anode-electrolyte interface.Herein,a conceptual framework that decouples these competing effects was proposed,enabling the rational design of a dual-layer architecture with an inner zincophilic layer for Zn^(2+)flux homogenization and an outer hydrophobic layer for water shielding.Through in situ and ex situ analyses,the synergistic mechanism was elucidated.During the cycling process,the zincophilic interface guides uniform Zn deposition,while the hydrophobic coating suppresses H_(2)O-induced side reactions.This dual modification achieves a Zn||Cu cell with an unprecedented 99.89%Coulombic efficiency and 975-cycle stability.This work resolves the long-standing controversy over interfacial affinity design,offering a scalable and industrially viable strategy to enhance AZIBs’durability without sacrificing energy density.展开更多
The waterproof performance,mechanical properties,chemical composition,microstructure,and pore structure of hydrophobically-modified geopolymer concrete are investigated before and after dry-wet cycles,to determine the...The waterproof performance,mechanical properties,chemical composition,microstructure,and pore structure of hydrophobically-modified geopolymer concrete are investigated before and after dry-wet cycles,to determine the long-term feasibility of using hydrophobically-modified geopolymer concrete in wet environments.We use two types of organic modifying agents:polydimethylsiloxane(PDMS)and sodium methyl siliconate(SMS).The experimental results show that incorporating 2%–6%PDMS or 5%–15%SMS can make the concrete hydrophobic,with water absorption and chloride transport rates decreasing by up to 94.3%.We also analyze the bonding modes of organic molecules and geopolymer gels,as well as their evolution mechanisms during dry-wet cycles.PDMS-modified geopolymer concrete is found to exhibit long-term waterproof performance that is not weakened by dry-wet cycles.This is attributed to the robust combination of organic components and the geopolymer gel skeleton formed through phase cross-linking.Meanwhile,PDMS-modified geopolymer concrete’s hydrophobicity,strength,and microstructure are essentially unaffected.In contrast,SMS-modified geopolymer concrete shows higher water sensitivity,although it does maintain efficient waterproof performance.Due to relatively low binding energy,the dry-wet cycles may lead to the detachment of some SMS molecules from the gel network,which results in a decrease of 18.6%in compressive strength and an increase of 37.6%in total porosity.This work confirms the utility of hydrophobically-modified geopolymer concrete as a building material for long-term service in wet environments,for instance,areas with frequent precipitation,or splash and tidal zones.展开更多
Cu(I)based CO adsorbents are prone to oxidation and deactivation owing to the sensitivity of Cu^(+) ions to oxygen and moisture in the humid air.In this study,in order to improve its antioxidant performance,hydrophobi...Cu(I)based CO adsorbents are prone to oxidation and deactivation owing to the sensitivity of Cu^(+) ions to oxygen and moisture in the humid air.In this study,in order to improve its antioxidant performance,hydrophobic Cu(I)based adsorbents were fabricated using polytetrafluoroethylene(PTFE)for the hydrophobic modification,effectively avoiding the contact of CuCl active species with moisture,thereby inhibiting the oxidation of the Cu(I)based adsorbents.The successful introduction of PTFE into the activated carbon(AC)carrier significantly improves the hydrophobicity of the adsorbent.The optimal adsorbent CuCl(6)@AC-PTFE(0.10%)with the CuCl loading of 6 mmol·g^(-1)and the PTFE mass concentration of 0.10%exhibits an excellent CO adsorption capacity of 3.61 mmol·g^(-1)(303 K,500 kPa)as well as high CO/CO_(2)and CO/N_(2)adsorption selectivities of 29 and 203(303 K,100 kPa).Particularly,compared with the unmodified adsorbents,the antioxidant performance of modified adsorbent CuCl(6)@AC-PTFE(0.10%)is significantly improved,holding 86%of CO adsorption performance of fresh one after 24 h of exposure to humid air with a relative humidity of 70%,making the fabricated composite a promising adsorbent for CO separation.展开更多
The formation of segregated structure has been demonstrated as an effective strategy for achieving ex-ceptional electromagnetic interference(EMI)shielding performance at low filler loadings.However,the acquisition of ...The formation of segregated structure has been demonstrated as an effective strategy for achieving ex-ceptional electromagnetic interference(EMI)shielding performance at low filler loadings.However,the acquisition of polymer particles and the formation of interactions with conductive fillers remain signifi-cant challenges for polydimethylsiloxane,which are crucial to the construction of a segregated structure.In this work,MXene sheets were functionalized and assembled onto the surface of polydimethylsilox-ane microspheres via hydrophobic interaction.Subsequently,functionalized MXene/polydimethylsiloxane(FMP)composites with a segregated structure were fabricated by filtration and hot-pressing.The FMP composite containing 8.22 wt.%MXene exhibited a high electrical conductivity of 99.4 S m^(−1)and a sat-isfactory EMI shielding effectiveness/thickness(EMI SE/d)of 31.3 dB mm^(−1).Furthermore,the FMP com-posite demonstrated excellent reliability with over 90%retention of EMI shielding effectiveness under harsh environments such as ultra-high/low temperatures and acidic/alkaline solutions.Additionally,the photothermal conversion performance of FMP composites and the capacitive sensing performance of the sensor based on FMP composites indicated their potential for managing body temperature and moni-toring human movement.Consequently,FMP composites show great promise in wearable electronics for effective electromagnetic interference shielding,thermal management and capacitive sensing.展开更多
An innovative strategy was proposed by integration of membrane contactor(MC)with biphasic solvent for efficient CO_(2) capture from flue gas.The accessible fly ash-based ceramic membrane(CM)underwent hydrophobic modif...An innovative strategy was proposed by integration of membrane contactor(MC)with biphasic solvent for efficient CO_(2) capture from flue gas.The accessible fly ash-based ceramic membrane(CM)underwent hydrophobic modification through silane grafting,followed by fluoroalkylsilane decoration,to prepare the superhydrophobic membrane(CSCM).The CSCM significantly improved resistance to wetting by the biphasic solvent,consisting of amine(DETA)and sulfolane(TMS).Morphological characterizations and chemical analysis revealed the notable enhancements in pore structure and hydrophobic chemical groups for the modified membrane.Predictions of wetting/bubbling behavior based on static wetting theory referred the liquid entry pressure(LEP)of CSCM increased by 20 kPa compared to pristine CM.Compared with traditional amine solvents,the biphasic solvent presented the expected phase separation.Performance experiments demonstrated that the CO_(2) capture efficiency of the biphasic solvent increased by 7%,and the electrical energy required for desorption decreased by 32%.The 60-h continuous testing and supplemental characterization of used membrane confirmed the excellent adaptability and durability of the CSCMs.This study provides a potential approach for accessing hydrophobic ceramic membranes and biphasic solvents for industrial CO_(2) capture.展开更多
Sodium alginate(SA)is generally considered highly hydrophilic due to two hydroxyl groups and a carboxylate group on each pyranose ring.However,SA will form a gel after dissolving in water for a certain period.The two ...Sodium alginate(SA)is generally considered highly hydrophilic due to two hydroxyl groups and a carboxylate group on each pyranose ring.However,SA will form a gel after dissolving in water for a certain period.The two properties of SA,hydrophilicity and gelation,seem to be paradoxical.In this study,to explore the mechanism behind these paradoxical properties,the single-chain behaviors of SA in various liquid environments have been investigated by using single-molecule force spectroscopy(SMFS).In nonpolar solvents such as nonane,SA exhibits its single-chain inherent elasticity consistent with the theoretical elasticity derived from quantum mechanical(QM)calculations.Notably,the experimental curve of SA obtained in water shows a long plateau in the low force region.Further research reveals that this phenomenon is driven by the hydrophobic effect.Additionally,SA shows greater rigidity than its inherent elasticity in the middle and high force regions due to electrostatic repulsion between carboxylate groups on adjacent sugar rings.Comparative single-molecule studies suggest that SA exhibits considerable hydrophobicity,offering new insights into the gelation process in water.展开更多
Electrocatalysis has emerged as a sustainable approach for the selective oxidation of fatty alcohols to fatty acids,circumventing the environmental concerns associated with conventional routes.However,the low aqueous ...Electrocatalysis has emerged as a sustainable approach for the selective oxidation of fatty alcohols to fatty acids,circumventing the environmental concerns associated with conventional routes.However,the low aqueous solubility of hydrophobic fatty alcohols presents a major challenge.While nickel hydroxide(Ni(OH)_(2))serves as a cost-effective catalyst for alcohol oxidation,its hydrophilic nature limits substrate accessibility and mass transport,causing sluggish kinetics and competing oxygen evolution.Herein,we propose a hydrophobic interface engineering strategy via co-electrodeposition of Ni(OH)_(2)with polytetrafluoroethylene(PTFE),fabricating the composite electrode(ED-Ni(OH)_(2)-PTFE).The optimized electrode achieves 95%Faradaic efficiency for octanoic acid at 1.5 V vs.RHE,with a production rate 2–3 times higher than pristine Ni(OH)_(2).Mechanistic studies combining in situ Raman spectroscopy,fluorescence imaging,and coarse-grained molecular dynamics simulations reveal that PTFE selectively enriches octanol at the electrode-electrolyte interface by modulating interfacial hydrophobicity.A continuous-flow microreactor integrating anodic octanol oxidation with cathodic hydrogen evolution reduces cell voltage by~100 m V,achieving simultaneous fatty acid and hydrogen production.This work highlights the critical role of hydrophobic interfacial microenvironment design in organic electrosynthesis,offering a promising strategy for upgrading fatty alcohols under mild conditions.展开更多
As the global exploration and development of oil and gas resources advances into deep formations,the harsh conditions of high temperature and high salinity present significant challenges for drilling fluids.In order t...As the global exploration and development of oil and gas resources advances into deep formations,the harsh conditions of high temperature and high salinity present significant challenges for drilling fluids.In order to address the technical difficulties associated with the failure of filtrate loss reducers under high-temperature and high-salinity conditions.In this study,a hydrophobic zwitterionic filtrate loss reducer(PDA)was synthesized based on N,N-dimethylacrylamide(DMAA),2-acrylamido-2-methylpropane sulfonic acid(AMPS),diallyl dimethyl ammonium chloride(DMDAAC),styrene(ST)and a specialty vinyl monomer(A1).When the concentration of PDA was 3%,the FLAPI of PDA-WBDF was 9.8 mL and the FLHTHP(180℃,3.5 MPa)was 37.8 mL after aging at 240℃for 16 h.In the saturated NaCl environment,the FLAPI of PDA-SWBDF was 4.0 mL and the FLHTHP(180℃,3.5 MPa)was 32.0 mL after aging at 220℃ for 16 h.Under high-temperature and high-salinity conditions,the combined effect of anti-polyelectrolyte and hydrophobic association allowed PDA to adsorb on the bentonite surface tightly.The sulfonic acid groups of PDA increased the negative electronegativity and the hydration film thickness on bentonite surface,which enhanced the colloidal stability,maintained the flattened lamellar structure of bentonite and formed an appropriate particle size distribution,resulting in the formation of dense mud cakes and reducing the filtration loss effectively.展开更多
In this study,femtosecond pulsed laser processing was applied to the magnesium alloy,followed by in situ growth of Mg-Al layered double hydroxides(LDHs),and finally modification with low surface energy materials to pr...In this study,femtosecond pulsed laser processing was applied to the magnesium alloy,followed by in situ growth of Mg-Al layered double hydroxides(LDHs),and finally modification with low surface energy materials to prepare a biomimetic of centipede-like superhydrophobic composite coating.The resulting biomimetic coating features a dual-scale structure,comprising a micron-scale laser-etched array and nano-scale LDH sheets,which together create a complex hierarchical architecture.The multistage bionic superhydrophobic coating exhibits exceptional corrosion resistance,with a reduction in corrosion current density by approximately five orders of magnitude compared to the bare magnesium alloy substrate.This remarkable corrosion resistance is attributed to the synergistic effects of the superhydrophobicity with a contact angle(CA)of 154.60°,the densification of the surface LDH nanosheets,and the NO_(3)^(-) exchange capacity.Additionally,compared to untreated AZ91D alloy,the biomimetic coating prolongs ice formation time by 250% at-40℃ and withstands multiple cycles of sandpaper abrasion and repeated tape peeling tests.Furthermore,it demonstrates excellent self-cleaning and anti-fouling properties,as confirmed by dye immersion and dust contamination tests.The construction of the multi-level bionic structured coating not only holds significant practical potential for metal protection but also provides valuable insights into the application of formed LDH materials in functional bionic coating engineering.展开更多
Selective perchlorate(ClO_(4)^(−))removal from surface water is a pressing need due to the stringent perchlorate drinking water limits around the world.Herein,we anchored N^(+)–C–H hydrogen bond donors in hydrophobi...Selective perchlorate(ClO_(4)^(−))removal from surface water is a pressing need due to the stringent perchlorate drinking water limits around the world.Herein,we anchored N^(+)–C–H hydrogen bond donors in hydrophobic cavities via interactions of cationic surfactants with montmorillonite to prioritize perchlorate bonding.The prepared adsorbent exhibited high selectivity over commonly occurring competing anions,including SO_(4)^(2−),NO_(3)^(−),PO_(4)^(3−),HCO_(3)^(−),and halide anions.High adsorption capacity,fast adsorption kinetics,and excellent regeneration ability(removal efficiency≥80%after 20 cycles)were confirmed via batch experiments.Unconventional CH···O hydrogen bonding was verified as the primary driving force for perchlorate adsorption,which relies on the higher bond energy(∼80 kcal·mol−1)than conventional bonding.The removal efficiency of anions followed the order of the Hofmeister Series,demonstrating the importance of hydrophobic cavities formed by the tail groups of cationic surfactants.The hydrophobic cavities sheltered the C–H bonds from interacting with anions of low hydration energy(e.g.,perchlorate).Furthermore,a fixed-bed column test demonstrated that about 2900 bed volumes of the feeding streams(∼500μg·L^(−1))can be treated to≤70μg·L^(−1),with an enrichment factor of 10.3.Overall,on the basis of the hydrophobicity-induced hydrogen bonding mechanism,a series of low-cost adsorbents can be synthesized and applied for specific perchlorate removal.展开更多
There have been reports of potential health risks for people from hydrophobic organic pollutants,such as polycyclic aromatic hydrocarbons(PAHs),polychlorinated hydrocarbons(PCHs),and organophosphate flame retardants(O...There have been reports of potential health risks for people from hydrophobic organic pollutants,such as polycyclic aromatic hydrocarbons(PAHs),polychlorinated hydrocarbons(PCHs),and organophosphate flame retardants(OPFRs).When a contaminated site is used for residential housing or public utility and recreation areas,the soil-bound organic pollutantsmight pose a threat to human health.In this study,we investigated the contamination profiles and potential risks to human health of 15 PAHs,6 PCHs,and 12 OPFRs in soils from four contaminated sites in China.We used an in vitro method to determine the oral bioaccessibility of soil pollutants.Total PAHswere found at concentrations ranging from26.4 ng/g to 987 ng/g.PCHs(0.27-14.3 ng/g)and OPFRs(6.30-310 ng/g)were detected,but at low levels compared to earlier reports.The levels of PAHs,PCHs,and OPFRs released from contaminated soils into simulated gastrointestinal fluids ranged from 1.74%to 91.0%,2.51%to 39.6%,and 1.37%to 96.9%,respectively.Based on both spiked and unspiked samples,we found that the oral bioaccessibility of pollutantswas correlated with their logKow andmolecularweight,and the total organic carbon content and pH of soils.PAHs in 13 out of 38 contaminated soil samples posed potential high risks to children.When considering oral bioaccessibility,nine soils still posed potential risks,while the risks in the remaining soils became negligible.The contribution of this paper is that it corrects the health risk of soil-bound organic pollutants by detecting bioaccessibility in actual soils from different contaminated sites.展开更多
Constructing multi-dimensional hydrogen bond(H-bond)regulated single-molecule systems with multiemission remains a challenge.Herein,we report the design of a new excited-state intramolecular proton transfer(ESIPT)feat...Constructing multi-dimensional hydrogen bond(H-bond)regulated single-molecule systems with multiemission remains a challenge.Herein,we report the design of a new excited-state intramolecular proton transfer(ESIPT)featured chromophore(HBT-DPI)that shows flexible emission tunability via the multidimensional regulation of intra-and intermolecular H-bonds.The feature of switchable intramolecular Hbonds is induced via incorporating several hydrogen bond acceptors and donors into one single HBT-DPI molecule,allowing the“turn on/off”of ESIPT process by forming isomers with distinct intramolecular Hbonds configurations.In response to different external H-bonding environments,the obtained four types of crystal/cocrystals vary in the contents of isomers and the molecular packing modes,which are mainly guided by the intermolecular H-bonds,exhibiting non-emissive features or emissions ranging from green to orange.Utilizing the feature of intermolecular H-bond guided molecular packing,we demonstrate the utility of this fluorescent material for visualizing hydrophobic/hydrophilic areas on large-scale heterogeneous surfaces of modified poly(1,1-difluoroethylene)(PVDF)membranes and quantitatively estimating the surface hydrophobicity,providing a new approach for hydrophobicity/hydrophilicity monitoring and measurement.Overall,this study represents a new design strategy for constructing multi-dimensional hydrogen bond regulated ESIPT-based fluorescent materials that enable multiple emissions and unique applications.展开更多
The stability of oil-dominated emulsions,including oil-based drilling fluids and crude oils,is crucial for mitigating gas hydrate risks in the petroleum and natural gas industries.Nanoparticles can stabilize oilwater ...The stability of oil-dominated emulsions,including oil-based drilling fluids and crude oils,is crucial for mitigating gas hydrate risks in the petroleum and natural gas industries.Nanoparticles can stabilize oilwater systems(Pickering emulsions)by residing at the oil-water interface.However,their effects on the kinetics of hydrate formation in these systems remain unclear.To address this,we experimentally investigated how hydrophilic and hydrophobic nano-CaCO_(3) influence CH4 hydrate formation within dynamic oil-water systems.A series of hydrate formation experiments were conducted with varying water cuts and different concentrations of nano-CaCO_(3) at a particle size of 20 nm,under 3℃ and 6 MPa.The induction time,hydrate formation volume,and hydrate growth rate were measured and calculated.The results indicate that hydrophilic nano-CaCO_(3) generally inhibits hydrate formation,particularly at high water cuts,while hydrophobic nano-CaCO_(3) can significantly inhibit or even prevent hydrate formation at low water cuts.Water cut strongly influences the kinetics of hydrate formation,and nanoparticle concentration also impacts the results,likely due to changes in oil-water interface stability caused by nanoparticle distribution.This study will offer valuable insights for designing deepwater oilbased drilling fluids using nanoparticles and ensuring safe multiphase flow in deepwater oil and gas operations.展开更多
基金the National Natural Science Foundation of China (Nos.21907076 and 31901908)the Natural Science Foundation of Tianjin (No.22JCQNJC01570)。
文摘Poor solubility often results in low efficacy of antitumor drugs.Nevertheless,limited research has been conducted on the potential decrease in drug efficacy following the self-assembly of hydrophobic pure drugs into nanodrugs,and solutions to this problem are even rarer.Loading water-insoluble antitumor drugs into nanocarriers offers a promising solution.However,intricate carrier preparation,limited drug loading capacity,and carrier-associated safety remain key challenges.In this study,based on the discovery that hydrophobic gambogic acid(GA) self-assembles into nanostructures with diminished antitumor efficacy in aqueous environments,we developed a carrier-free nanodrug system,designated as GA-S-S-AS nanoparticles(NPs),characterized by straightforward preparation,high drug loading,fluorescence imaging,tumor-targeting,and responsive drug release in reducing environments.Specifically,the hydrophobic GA was covalently linked to the hydrophilic aptamer through a disulfide bond and then self-assembled into the nanodrugs.About 92 % of drug was encapsulated in self-assembled NPs,demonstrating remarkable stability under physiological conditions and controlled release of GA in the high-glutathione environment characteristic of tumor sites.Furthermore,by utilizing the synergistic interaction between the enhanced permeability and retention(EPR) effect and ligand-receptor active targeting mechanisms,the nanodrugs significantly increased the accumulation of GA at tumor locations.Consequently,the nanodrugs exhibited optimal therapeutic efficacy against the tumor both in vitro and in vivo,significantly inhibiting tumor growth.Furthermore,the nanodrugs demonstrated enhanced biosafety compared to free GA,effectively reducing GA-induced hepatotoxicity.Taken together,these findings underscore the significant potential of this multifunctional carrier-free nanodrugs for the targeted delivery of GA,thereby laying a foundation for future endeavors aimed at developing novel formulations of hydrophobic antitumor drugs.
基金financially sponsored by the National Natural Science Foundation of China(No.52204414)the National Energy-Saving and Low-Carbon Materials Production and Application Demonstration Platform Program,China(No.TC220H06N)+1 种基金the National Key R&D Program of China(No.2021YFC1910504)the Fundamental Research Funds for the Central Universities,China(No.FRFTP-20-097A1Z)。
文摘MnO_(x)-CeO_(2)catalysts for the low-temperature selective catalytic reduction(SCR)of NO remain vulnerable to water and sulfur poisoning,limting their practical applications.Herein,we report a hydrophobic-modified MnO_(x)-CeO_(2)catalyst that achieves enhanced NO conversion rate and stability under harsh conditions.The catalyst was synthesized by decorating MnOx crystals with amorphous CeO_(2),followed by loading hydrophobic silica on the external surfaces.The hydrophobic silica allowed the adsorption of NH_(3)and NO and diffusion of H,suppressed the adsorption of H_(2)O,and prevented SO_(2)interaction with the Mn active sites,achieving selective molecular discrimination at the catalyst surface.At 120℃,under H_(2)O and SO_(2)exposure,the optimal hydrophobic catalyst maintains 82%NO conversion rate compared with 69%for the unmodified catalyst.The average adsorption energies of NH_(3),H_(2)O,and SO_(2)decreased by 0.05,0.43,and 0.52 eV,respectively.The NO reduction pathway follows the Eley-Rideal mechanism,NH_(3)^(*)+*→NH_(2)^(*)+H^(*)followed by NH_(2)^(*)+NO^(*)→N_(2)^(*)+H_(2)O^(*),with NH_(3)dehydrogenation being the rate determining step.Hydrophobic modification increased the activation energy for H atom transfer,leading to a minor decrease in the NO conversion rate at 120℃.This work demonstrates a viable strategy for developing robust NH_(3)-S CR catalysts capable of efficient operation in water-and sulfur-rich environments.
基金Zhejiang Provincial Cooperative Forestry Science and Technology Project(No.2023SY05)Zhejiang Provincial Science and Technology Project(No.2024F1065-2).
文摘Herein,the surface of Moso bamboo was hydrophobically modified by combining O_(2)/N_(2)plasma treatments with polydimethylsiloxane(PDMS)solution treatment as the hydrophobic solution.The effects of plasma treatment process(power and time),PDMS solution concentration,and maceration time on the hydrophobic performance of bamboo specimens were studied,and the optimal treatment conditions for improving the hydrophobicity were determined.Scanning electron microscopy(SEM),fourier transform infrared(FTIR),X-ray diffraction(XRD),and X-ray photoelectron spectroscopy(XPS)were used to analyze the surface morphology,chemical structure,and functional groups in the specimens before and after the plasma and PDMS solution treatments under optimal conditions.Response surface analysis was also performed to determine the optimal treatment conditions.Results show that the hydrophobic performance of the Moso bamboo surface is effectively improved and the surface energy is reduced after the coordinated treatment.The optimal conditions for improving the hydrophobic performance of Moso bamboo surface are a treatment power of 800 W,treatment time of 15 s,O_(2)flow rate of 1.5 L/min,PDMS solution concentration of 5%,and maceration time of 60 min for O_(2)plasma treatment and a treatment power of 1000 W,treatment time of 15 s,N_(2)flow rate of 1.5 L/min,PDMS solution concentration of 5%,and maceration time of 60 min for N_(2)plasma treatment.After treatment,silicone oil particles and plasma etching traces are observed on the bamboo surface.Moreover,Si-O bonds in the PDMS solution are grafted to the bamboo surface via covalent bonds,thereby increasing the contact angle and decreasing the surface energy to achieve the hydrophobic effect.
基金supported by grants from the National Research Foundation of Korea(NRF)under grant No.RS-2022-00155422 and No.2021R1C1C102014。
文摘Water often presents significant challenges in catalysts by deactivating active sites,poisoning the reaction,and even degrading composite structure.These challenges are amplified when the water participates as a reactant and is fed as a liquid phase,such as trickle bed-type reactors in a hydrogen-water isotope exchange(HIE)reaction.The key balance in such multiphase reactions is the precise control of catalyst design to repel bulk liquid water while diffusing water vapor.Herein,a platinum-incorporated metal-organic framework(MIL-101)based bifunctional hydrophobic catalyst functionalized with long alkyl chains(C_(12),dodecylamine)and further manufactured with poly(vinylidene fluoride),Pt@MIL-101-12/PVDF,has been developed which can show dramatically improved catalytic activity under multi-phase reactions involving hydrogen gas and liquid water.Pt@MIL-101-12/PVDF demonstrates enhanced macroscopic water-blocking properties,with a notable reduction of over 65%in water adsorption capacity and newly introduced liquid water repellency.while exhibiting a negligible increase in mass transfer resistance,i.e.,bifunctional hydrophobicity.Excellent catalytic activity,evaluated via HIE reaction,and its durability underscore the impact of bifunctional hydrophobicity.In situ DRIFTS analysis elucidates water adsorption/desorption dynamics within the catalyst composite,highlighting reinforced water diffusion at the microscopic level,affirming the catalyst's bifunctionality in different length scales.With demonstrated radiation resistance,Pt@MIL-101-12/PVDF emerges as a promising candidate for isotope exchange reactions.
基金National Key R&D Program of China(2023YFA1507902,2021YFA1500804)the National Natural Science Foundation of China(22121004,22038009,22250008)+2 种基金the Haihe Laboratory of Sustainable Chemical Transformations(CYZC202107)the Program of Introducing Talents of Discipline to Universities,China(No.BP0618007)the Xplorer Prize,China,for their financial support。
文摘CO_(2)reduction reaction(CO_(2)RR)electrolyzers based on gas diffusion electrode(GDE)enable the direct mass transfer of CO_(2)to the catalyst surface for participation in the reaction,thereby establishing an efficient three-phase reaction interface that significantly enhances current density.However,current hydrophobic modification methods face difficulties in achieving precise and substantial control over wettability,and the hydrophobic modifiers tend to significantly impair the conductivity of the electrode and ion transport capabilities.This study employs Nafion ionomers to hydrophobically modify the threedimensional catalyst layer,revealing the bifunctionality of Nafion.The fluorinated backbone of Nafion ensures the hydrophobicity of the entire catalyst layer,while its sulfonic acid groups promote ion transport,without significantly affecting the conductivity of the electrode.Furthermore,by employing modifiers with distinct wettability characteristics,a highly efficient and large-scale manipulation of the hydrophilic/hydrophobic properties of the catalyst layer was successfully realized.The electrode,constructed with silver nanopowder as a representative catalyst and modified with the hydrophobic ionomer Nafion,exhibits a substantial enhancement in both catalytic activity and durability.The optimized electrode exhibited exceptional electrocatalytic performance in both flow cell and membrane electrode assembly(MEA)configurations.Notably,in the MEA,the electrode achieved a remarkable CO Faradaic efficiency(FE)of 93.3%at a total current density of 200 mA cm^(-2),while maintaining stable operation for over 62 h.
基金supported by a National Research Foundation of Korea(NRF)Grant funded by the Ministry of Science and ICT(2021R1A2C1014294,2022R1A2C3003319)the BK21 FOUR(Fostering Outstanding Universities for Research)through the National Research Foundation(NRF)of Korea.
文摘A critical challenge hindering the practical application of lithium–oxygen batteries(LOBs)is the inevitable problems associated with liquid electrolytes,such as evaporation and safety problems.Our study addresses these problems by proposing a modified polyrotaxane(mPR)-based solid polymer electrolyte(SPE)design that simultaneously mitigates solvent-related problems and improves conductivity.mPR-SPE exhibits high ion conductivity(2.8×10^(−3)S cm^(−1)at 25℃)through aligned ion conduction pathways and provides electrode protection ability through hydrophobic chain dispersion.Integrating this mPR-SPE into solid-state LOBs resulted in stable potentials over 300 cycles.In situ Raman spectroscopy reveals the presence of an LiO_(2)intermediate alongside Li_(2)O_(2)during oxygen reactions.Ex situ X-ray diffraction confirm the ability of the SPE to hinder the permeation of oxygen and moisture,as demonstrated by the air permeability tests.The present study suggests that maintaining a low residual solvent while achieving high ionic conductivity is crucial for restricting the sub-reactions of solid-state LOBs.
基金supported by the National Key R&D Program of China(2021YFF0500703)Natural Science Foundation of Shanghai(22JC1404200)+3 种基金Program of Shanghai Academic/Technology Research Leader(20XD1404000)Natural Science Foundation of China(U22B20136,22293023)Science and Technology Major Project of Inner Mongolia(2021ZD0042)the Youth Innovation Promotion Association of CAS。
文摘A radical C−C-coupling reaction of acetonitrile into succinonitrile over hydrophobic TiO_(2) photocatalyst with enhanced catalytic activity was developed.In addition,the usage of a flow reactor further improved the photon utilization efficiency for succinonitrile synthesis at room temperature.The space time yield of succinonitrile reached 55.59μmol/(g·h)over hydrophobic TiO_(2) catalyst,which was much higher than that of pristine TiO_(2)(4.23μmol/(g·h)).Mechanistic studies revealed that the hydrophobic modification of TiO_(2) promoted the separation and transfer of photogenerated carriers,as well as suppressed their recombination.Hydrophobic TiO_(2) also enhanced the adsorption of−CH3 of acetonitrile,thus facilitating the activation of C−H bond and the utilization efficiency of photocarriers.
基金supported by the National Natural Science Foundation of China(U2130204)the Joint Funds of the National Key R&D Program of China(2022YFB2502102)+1 种基金the Young Elite Scientists Sponsorship Program by CAST(YESS20200364)the Beijing Outstanding Young Scientists Program(BJJWZYJH01201910007023)。
文摘Aqueous zinc-ion batteries(AZIBs)are pivotal for achieving net-zero goals,yet their commercialization is impeded by zinc dendrites,parasitic reactions,and interfacial instability.Current debates persist on the interplay between zincophilic-hydrophilic and zincophobic-hydrophobic interactions at the anode-electrolyte interface.Herein,a conceptual framework that decouples these competing effects was proposed,enabling the rational design of a dual-layer architecture with an inner zincophilic layer for Zn^(2+)flux homogenization and an outer hydrophobic layer for water shielding.Through in situ and ex situ analyses,the synergistic mechanism was elucidated.During the cycling process,the zincophilic interface guides uniform Zn deposition,while the hydrophobic coating suppresses H_(2)O-induced side reactions.This dual modification achieves a Zn||Cu cell with an unprecedented 99.89%Coulombic efficiency and 975-cycle stability.This work resolves the long-standing controversy over interfacial affinity design,offering a scalable and industrially viable strategy to enhance AZIBs’durability without sacrificing energy density.
基金supported by the National Natural Science Foundation of China(Nos.52101328 and 52171277)the National Key Research and Development Program of China(No.2022YFE0109200)+1 种基金the Foundation of the Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering(No.2022SZ-TD006)the Postdoctoral Fellowship Program of China Postdoctoral Science Foundation(CPSF)(No.GZB20230653)。
文摘The waterproof performance,mechanical properties,chemical composition,microstructure,and pore structure of hydrophobically-modified geopolymer concrete are investigated before and after dry-wet cycles,to determine the long-term feasibility of using hydrophobically-modified geopolymer concrete in wet environments.We use two types of organic modifying agents:polydimethylsiloxane(PDMS)and sodium methyl siliconate(SMS).The experimental results show that incorporating 2%–6%PDMS or 5%–15%SMS can make the concrete hydrophobic,with water absorption and chloride transport rates decreasing by up to 94.3%.We also analyze the bonding modes of organic molecules and geopolymer gels,as well as their evolution mechanisms during dry-wet cycles.PDMS-modified geopolymer concrete is found to exhibit long-term waterproof performance that is not weakened by dry-wet cycles.This is attributed to the robust combination of organic components and the geopolymer gel skeleton formed through phase cross-linking.Meanwhile,PDMS-modified geopolymer concrete’s hydrophobicity,strength,and microstructure are essentially unaffected.In contrast,SMS-modified geopolymer concrete shows higher water sensitivity,although it does maintain efficient waterproof performance.Due to relatively low binding energy,the dry-wet cycles may lead to the detachment of some SMS molecules from the gel network,which results in a decrease of 18.6%in compressive strength and an increase of 37.6%in total porosity.This work confirms the utility of hydrophobically-modified geopolymer concrete as a building material for long-term service in wet environments,for instance,areas with frequent precipitation,or splash and tidal zones.
基金supported by the Natural Science Foundation of Shandong Province(ZR2021MB135)the Major Scientific and Technological Innovation Project of Shandong Province(2021ZDSYS13).
文摘Cu(I)based CO adsorbents are prone to oxidation and deactivation owing to the sensitivity of Cu^(+) ions to oxygen and moisture in the humid air.In this study,in order to improve its antioxidant performance,hydrophobic Cu(I)based adsorbents were fabricated using polytetrafluoroethylene(PTFE)for the hydrophobic modification,effectively avoiding the contact of CuCl active species with moisture,thereby inhibiting the oxidation of the Cu(I)based adsorbents.The successful introduction of PTFE into the activated carbon(AC)carrier significantly improves the hydrophobicity of the adsorbent.The optimal adsorbent CuCl(6)@AC-PTFE(0.10%)with the CuCl loading of 6 mmol·g^(-1)and the PTFE mass concentration of 0.10%exhibits an excellent CO adsorption capacity of 3.61 mmol·g^(-1)(303 K,500 kPa)as well as high CO/CO_(2)and CO/N_(2)adsorption selectivities of 29 and 203(303 K,100 kPa).Particularly,compared with the unmodified adsorbents,the antioxidant performance of modified adsorbent CuCl(6)@AC-PTFE(0.10%)is significantly improved,holding 86%of CO adsorption performance of fresh one after 24 h of exposure to humid air with a relative humidity of 70%,making the fabricated composite a promising adsorbent for CO separation.
基金supported by the Fundamental Research Funds for the Central Universities(No.D5000220252)the funds for Ministry of Industry and Information Technology(No.MJZ44N22)Shaanxi Undergraduate Training Program for Innovation and Entrepreneurship(No.S202310699509).
文摘The formation of segregated structure has been demonstrated as an effective strategy for achieving ex-ceptional electromagnetic interference(EMI)shielding performance at low filler loadings.However,the acquisition of polymer particles and the formation of interactions with conductive fillers remain signifi-cant challenges for polydimethylsiloxane,which are crucial to the construction of a segregated structure.In this work,MXene sheets were functionalized and assembled onto the surface of polydimethylsilox-ane microspheres via hydrophobic interaction.Subsequently,functionalized MXene/polydimethylsiloxane(FMP)composites with a segregated structure were fabricated by filtration and hot-pressing.The FMP composite containing 8.22 wt.%MXene exhibited a high electrical conductivity of 99.4 S m^(−1)and a sat-isfactory EMI shielding effectiveness/thickness(EMI SE/d)of 31.3 dB mm^(−1).Furthermore,the FMP com-posite demonstrated excellent reliability with over 90%retention of EMI shielding effectiveness under harsh environments such as ultra-high/low temperatures and acidic/alkaline solutions.Additionally,the photothermal conversion performance of FMP composites and the capacitive sensing performance of the sensor based on FMP composites indicated their potential for managing body temperature and moni-toring human movement.Consequently,FMP composites show great promise in wearable electronics for effective electromagnetic interference shielding,thermal management and capacitive sensing.
基金supported by the National Key R&D Program of China(2023YFF0614301,2023YFC3707004,and 2018YFB0604302)Fundamental Research Funds for the Central Universities(No.2022MS041)+1 种基金National Natural Science Foundation of China(No.22106084)Tsinghua University Initiative Scientific Research Program(2023Z02JMP001).
文摘An innovative strategy was proposed by integration of membrane contactor(MC)with biphasic solvent for efficient CO_(2) capture from flue gas.The accessible fly ash-based ceramic membrane(CM)underwent hydrophobic modification through silane grafting,followed by fluoroalkylsilane decoration,to prepare the superhydrophobic membrane(CSCM).The CSCM significantly improved resistance to wetting by the biphasic solvent,consisting of amine(DETA)and sulfolane(TMS).Morphological characterizations and chemical analysis revealed the notable enhancements in pore structure and hydrophobic chemical groups for the modified membrane.Predictions of wetting/bubbling behavior based on static wetting theory referred the liquid entry pressure(LEP)of CSCM increased by 20 kPa compared to pristine CM.Compared with traditional amine solvents,the biphasic solvent presented the expected phase separation.Performance experiments demonstrated that the CO_(2) capture efficiency of the biphasic solvent increased by 7%,and the electrical energy required for desorption decreased by 32%.The 60-h continuous testing and supplemental characterization of used membrane confirmed the excellent adaptability and durability of the CSCMs.This study provides a potential approach for accessing hydrophobic ceramic membranes and biphasic solvents for industrial CO_(2) capture.
基金financially supported by the National Natural Science Foundation of China(No.22273079)。
文摘Sodium alginate(SA)is generally considered highly hydrophilic due to two hydroxyl groups and a carboxylate group on each pyranose ring.However,SA will form a gel after dissolving in water for a certain period.The two properties of SA,hydrophilicity and gelation,seem to be paradoxical.In this study,to explore the mechanism behind these paradoxical properties,the single-chain behaviors of SA in various liquid environments have been investigated by using single-molecule force spectroscopy(SMFS).In nonpolar solvents such as nonane,SA exhibits its single-chain inherent elasticity consistent with the theoretical elasticity derived from quantum mechanical(QM)calculations.Notably,the experimental curve of SA obtained in water shows a long plateau in the low force region.Further research reveals that this phenomenon is driven by the hydrophobic effect.Additionally,SA shows greater rigidity than its inherent elasticity in the middle and high force regions due to electrostatic repulsion between carboxylate groups on adjacent sugar rings.Comparative single-molecule studies suggest that SA exhibits considerable hydrophobicity,offering new insights into the gelation process in water.
基金Financial supports from the National Natural Science Foundation(No.21991104 and No.22,278,235)。
文摘Electrocatalysis has emerged as a sustainable approach for the selective oxidation of fatty alcohols to fatty acids,circumventing the environmental concerns associated with conventional routes.However,the low aqueous solubility of hydrophobic fatty alcohols presents a major challenge.While nickel hydroxide(Ni(OH)_(2))serves as a cost-effective catalyst for alcohol oxidation,its hydrophilic nature limits substrate accessibility and mass transport,causing sluggish kinetics and competing oxygen evolution.Herein,we propose a hydrophobic interface engineering strategy via co-electrodeposition of Ni(OH)_(2)with polytetrafluoroethylene(PTFE),fabricating the composite electrode(ED-Ni(OH)_(2)-PTFE).The optimized electrode achieves 95%Faradaic efficiency for octanoic acid at 1.5 V vs.RHE,with a production rate 2–3 times higher than pristine Ni(OH)_(2).Mechanistic studies combining in situ Raman spectroscopy,fluorescence imaging,and coarse-grained molecular dynamics simulations reveal that PTFE selectively enriches octanol at the electrode-electrolyte interface by modulating interfacial hydrophobicity.A continuous-flow microreactor integrating anodic octanol oxidation with cathodic hydrogen evolution reduces cell voltage by~100 m V,achieving simultaneous fatty acid and hydrogen production.This work highlights the critical role of hydrophobic interfacial microenvironment design in organic electrosynthesis,offering a promising strategy for upgrading fatty alcohols under mild conditions.
基金supported by State Key Laboratory of Deep Oil and Gas(No.SKLDOG2024-ZYRC-03)supported by the Excellent Young Scientists Fund of the National Natural Science Foundation of China(No.52322401)the National Natural Science Foundation of China(52288101).
文摘As the global exploration and development of oil and gas resources advances into deep formations,the harsh conditions of high temperature and high salinity present significant challenges for drilling fluids.In order to address the technical difficulties associated with the failure of filtrate loss reducers under high-temperature and high-salinity conditions.In this study,a hydrophobic zwitterionic filtrate loss reducer(PDA)was synthesized based on N,N-dimethylacrylamide(DMAA),2-acrylamido-2-methylpropane sulfonic acid(AMPS),diallyl dimethyl ammonium chloride(DMDAAC),styrene(ST)and a specialty vinyl monomer(A1).When the concentration of PDA was 3%,the FLAPI of PDA-WBDF was 9.8 mL and the FLHTHP(180℃,3.5 MPa)was 37.8 mL after aging at 240℃for 16 h.In the saturated NaCl environment,the FLAPI of PDA-SWBDF was 4.0 mL and the FLHTHP(180℃,3.5 MPa)was 32.0 mL after aging at 220℃ for 16 h.Under high-temperature and high-salinity conditions,the combined effect of anti-polyelectrolyte and hydrophobic association allowed PDA to adsorb on the bentonite surface tightly.The sulfonic acid groups of PDA increased the negative electronegativity and the hydration film thickness on bentonite surface,which enhanced the colloidal stability,maintained the flattened lamellar structure of bentonite and formed an appropriate particle size distribution,resulting in the formation of dense mud cakes and reducing the filtration loss effectively.
基金supported by the National Natural Science Foundation of China(No.52331004,U2106216)the Natural Science Foundation of Shandong Province(No.ZR2022ZD12)+2 种基金the Key R&D Program of Shandong Province,China(2023ZLGX05,2023CXGC010406)Key Program of Natural Science Foundation of Shandong Province of China(No.ZR2022ZD12,ZR2024ZD14)the Taishan Scholarship of Climbing Plan(No.tspd20230603)。
文摘In this study,femtosecond pulsed laser processing was applied to the magnesium alloy,followed by in situ growth of Mg-Al layered double hydroxides(LDHs),and finally modification with low surface energy materials to prepare a biomimetic of centipede-like superhydrophobic composite coating.The resulting biomimetic coating features a dual-scale structure,comprising a micron-scale laser-etched array and nano-scale LDH sheets,which together create a complex hierarchical architecture.The multistage bionic superhydrophobic coating exhibits exceptional corrosion resistance,with a reduction in corrosion current density by approximately five orders of magnitude compared to the bare magnesium alloy substrate.This remarkable corrosion resistance is attributed to the synergistic effects of the superhydrophobicity with a contact angle(CA)of 154.60°,the densification of the surface LDH nanosheets,and the NO_(3)^(-) exchange capacity.Additionally,compared to untreated AZ91D alloy,the biomimetic coating prolongs ice formation time by 250% at-40℃ and withstands multiple cycles of sandpaper abrasion and repeated tape peeling tests.Furthermore,it demonstrates excellent self-cleaning and anti-fouling properties,as confirmed by dye immersion and dust contamination tests.The construction of the multi-level bionic structured coating not only holds significant practical potential for metal protection but also provides valuable insights into the application of formed LDH materials in functional bionic coating engineering.
基金supported by the National Key Research and Development Program of China(2023YFC3207904).
文摘Selective perchlorate(ClO_(4)^(−))removal from surface water is a pressing need due to the stringent perchlorate drinking water limits around the world.Herein,we anchored N^(+)–C–H hydrogen bond donors in hydrophobic cavities via interactions of cationic surfactants with montmorillonite to prioritize perchlorate bonding.The prepared adsorbent exhibited high selectivity over commonly occurring competing anions,including SO_(4)^(2−),NO_(3)^(−),PO_(4)^(3−),HCO_(3)^(−),and halide anions.High adsorption capacity,fast adsorption kinetics,and excellent regeneration ability(removal efficiency≥80%after 20 cycles)were confirmed via batch experiments.Unconventional CH···O hydrogen bonding was verified as the primary driving force for perchlorate adsorption,which relies on the higher bond energy(∼80 kcal·mol−1)than conventional bonding.The removal efficiency of anions followed the order of the Hofmeister Series,demonstrating the importance of hydrophobic cavities formed by the tail groups of cationic surfactants.The hydrophobic cavities sheltered the C–H bonds from interacting with anions of low hydration energy(e.g.,perchlorate).Furthermore,a fixed-bed column test demonstrated that about 2900 bed volumes of the feeding streams(∼500μg·L^(−1))can be treated to≤70μg·L^(−1),with an enrichment factor of 10.3.Overall,on the basis of the hydrophobicity-induced hydrogen bonding mechanism,a series of low-cost adsorbents can be synthesized and applied for specific perchlorate removal.
基金supported by the National Key Research and Development Program of China(No.2019YFC1804604)Basic and Applied Basic Research Foundation of Guangdong Province(No.2021A1515010018).
文摘There have been reports of potential health risks for people from hydrophobic organic pollutants,such as polycyclic aromatic hydrocarbons(PAHs),polychlorinated hydrocarbons(PCHs),and organophosphate flame retardants(OPFRs).When a contaminated site is used for residential housing or public utility and recreation areas,the soil-bound organic pollutantsmight pose a threat to human health.In this study,we investigated the contamination profiles and potential risks to human health of 15 PAHs,6 PCHs,and 12 OPFRs in soils from four contaminated sites in China.We used an in vitro method to determine the oral bioaccessibility of soil pollutants.Total PAHswere found at concentrations ranging from26.4 ng/g to 987 ng/g.PCHs(0.27-14.3 ng/g)and OPFRs(6.30-310 ng/g)were detected,but at low levels compared to earlier reports.The levels of PAHs,PCHs,and OPFRs released from contaminated soils into simulated gastrointestinal fluids ranged from 1.74%to 91.0%,2.51%to 39.6%,and 1.37%to 96.9%,respectively.Based on both spiked and unspiked samples,we found that the oral bioaccessibility of pollutantswas correlated with their logKow andmolecularweight,and the total organic carbon content and pH of soils.PAHs in 13 out of 38 contaminated soil samples posed potential high risks to children.When considering oral bioaccessibility,nine soils still posed potential risks,while the risks in the remaining soils became negligible.The contribution of this paper is that it corrects the health risk of soil-bound organic pollutants by detecting bioaccessibility in actual soils from different contaminated sites.
基金supported by the National Key R&D Program of China(No.2021YFC2103600)the National Natural Science Foundation of China(Nos.21878156,21978131,22275085,and 22278224)+2 种基金the Natural Science Foundation of Jiangsu Province(Nos.BK20200089 and BK20200691)the Project of Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)the State Key Laboratory of Materials-Oriented Chemical Engineering(No.KL21-08).
文摘Constructing multi-dimensional hydrogen bond(H-bond)regulated single-molecule systems with multiemission remains a challenge.Herein,we report the design of a new excited-state intramolecular proton transfer(ESIPT)featured chromophore(HBT-DPI)that shows flexible emission tunability via the multidimensional regulation of intra-and intermolecular H-bonds.The feature of switchable intramolecular Hbonds is induced via incorporating several hydrogen bond acceptors and donors into one single HBT-DPI molecule,allowing the“turn on/off”of ESIPT process by forming isomers with distinct intramolecular Hbonds configurations.In response to different external H-bonding environments,the obtained four types of crystal/cocrystals vary in the contents of isomers and the molecular packing modes,which are mainly guided by the intermolecular H-bonds,exhibiting non-emissive features or emissions ranging from green to orange.Utilizing the feature of intermolecular H-bond guided molecular packing,we demonstrate the utility of this fluorescent material for visualizing hydrophobic/hydrophilic areas on large-scale heterogeneous surfaces of modified poly(1,1-difluoroethylene)(PVDF)membranes and quantitatively estimating the surface hydrophobicity,providing a new approach for hydrophobicity/hydrophilicity monitoring and measurement.Overall,this study represents a new design strategy for constructing multi-dimensional hydrogen bond regulated ESIPT-based fluorescent materials that enable multiple emissions and unique applications.
基金supported by the National Natural Science Foundation of China(No.42402319,51704266)the Anhui Provincial Natural Science Foundation(No.2308085QE151)+3 种基金the Natural Science Research Project of Anhui Educational Committee(No.2023AH051222)Young Talent Nurturing Program of Anhui Association For Science and Technology(No.RCTJ202403)the Open Foundation of the Innovation Base of Fine Mine Prospecting and Intelligent Monitoring Technology(No.2023-MPIM-01)partly supported by the Open Fund of Engineering Research Center of Rock-Soil Drilling&Excavation and Protection(No.202407).
文摘The stability of oil-dominated emulsions,including oil-based drilling fluids and crude oils,is crucial for mitigating gas hydrate risks in the petroleum and natural gas industries.Nanoparticles can stabilize oilwater systems(Pickering emulsions)by residing at the oil-water interface.However,their effects on the kinetics of hydrate formation in these systems remain unclear.To address this,we experimentally investigated how hydrophilic and hydrophobic nano-CaCO_(3) influence CH4 hydrate formation within dynamic oil-water systems.A series of hydrate formation experiments were conducted with varying water cuts and different concentrations of nano-CaCO_(3) at a particle size of 20 nm,under 3℃ and 6 MPa.The induction time,hydrate formation volume,and hydrate growth rate were measured and calculated.The results indicate that hydrophilic nano-CaCO_(3) generally inhibits hydrate formation,particularly at high water cuts,while hydrophobic nano-CaCO_(3) can significantly inhibit or even prevent hydrate formation at low water cuts.Water cut strongly influences the kinetics of hydrate formation,and nanoparticle concentration also impacts the results,likely due to changes in oil-water interface stability caused by nanoparticle distribution.This study will offer valuable insights for designing deepwater oilbased drilling fluids using nanoparticles and ensuring safe multiphase flow in deepwater oil and gas operations.
