The electrochemical reduction of CO_(2)(eCO_(2)R)under ambient conditions is crucial for reducing carbon emissions and achieving carbon neutrality.Despite progress with alkaline and neutral electrolytes,their efficien...The electrochemical reduction of CO_(2)(eCO_(2)R)under ambient conditions is crucial for reducing carbon emissions and achieving carbon neutrality.Despite progress with alkaline and neutral electrolytes,their efficiency is limited by(bi)carbonates formation.Acidic media have emerged as a solution,addressing the(bi)carbonates challenge but introducing the issue of the hydrogen evolu-tion reaction(HER),which reduces CO_(2) conversion efficiency in acidic environments.This review focuses on enhancing the selectivity of acidic CO_(2) electrolysis.It commences with an overview of the latest advancements in acidic CO_(2) electrolysis,focusing on product selectivity and electrocatalytic activity enhancements.It then delves into the critical factors shaping selectivity in acidic CO_(2) electrolysis,with a special emphasis on the influence of cations and catalyst design.Finally,the research challenges and personal perspectives of acidic CO_(2) electrolysis are suggested.展开更多
The influence of adipic acid on the formation and corrosion resistance of anodic oxide film fabricated on 2024 aluminum alloy was investigated. The morphology was investigated by scanning electron microscopy (SEM) a...The influence of adipic acid on the formation and corrosion resistance of anodic oxide film fabricated on 2024 aluminum alloy was investigated. The morphology was investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), respectively. The corrosion resistance was evaluated by electrochemical impedance spectroscopy (EIS). The results showed that the adipic acid was absorbed at the electrolyte/anodic layer interface during anodizing. The corrosion rate of anodic film decreased and the film thickness increased. The film was uniform and compact especially at the film/substrate interface. After sealing procedure, anodic film formed with the addition of adipic acid exhibited improved dielectric property and corrosion resistance in aggressive environment.展开更多
A novel SnO2-based gas anode was developed for aluminum electrolysis in molten cryolite at 850 °C to reduce energy consumption and decrease CO2 emissions. Hydrogen was introduced into the anode, participating in...A novel SnO2-based gas anode was developed for aluminum electrolysis in molten cryolite at 850 °C to reduce energy consumption and decrease CO2 emissions. Hydrogen was introduced into the anode, participating in the anode reaction. Carbon and aluminum were used as the cathode and reference electrodes, respectively. Cyclic voltammetry was applied in the cell to investigate the electrochemical behavior of oxygen ion on platinum and SnO2-based materials. The potential for oxygen evolution on these electrode materials was determined. Then, galvanostatic electrolysis was performed on the gas anode, showing a significant depolarization effect (a decrease of ~0.8 V of the anode potential) after the introduction of hydrogen, compared with no gas introduction or the introduction of argon. The results indicate the involvement of hydrogen in the anode reaction (three-phase-boundary reaction including gas, electrolyte and electrode) and give the possibility for the utilization of reducing gas anodes for aluminum electrolysis.展开更多
Boron-doped diamond (BDD) electrocatalysis is combined with photocatalysis using titanium dioxide (TiO2) as a catalyst to improve pollutant-oxidation efficiency. Phenol solution is chosen as model wastewater. Diff...Boron-doped diamond (BDD) electrocatalysis is combined with photocatalysis using titanium dioxide (TiO2) as a catalyst to improve pollutant-oxidation efficiency. Phenol solution is chosen as model wastewater. Different methods involving BDD and/or TiO2 during the degradation processes are compared. Parameters such as the currency density and initial concentration are varied in order to determine their effects on the oxidation process. Moreover, the degradation kinetics of phenol is experimentally studied. The results reveal the superiority of series combination of BDD and TiO2, especially the treatment process of electrocatalysis and succedent photocatalysis, and the optimum working currency density for electrocatalysis is 25.48 mA/cm2. The removal rate decreases with the increase in the initial phenol concentration and the degradation reaction follows quasi-first-order kinetics equation.展开更多
Two organic dyes XSS1 and XS52 derivated from triarylamine and indoline are synthesized for dye-sensitized solar ceils (DSCs) employing cobalt and iodine redox shuttles. The effects of dye structure upon the photoph...Two organic dyes XSS1 and XS52 derivated from triarylamine and indoline are synthesized for dye-sensitized solar ceils (DSCs) employing cobalt and iodine redox shuttles. The effects of dye structure upon the photophysical, electro-chemical characteristics and cell perfor- mance are investigated. XS51 with four hexyloxyl groups on triarylamine performs better steric hindrance and an improvement of photovoltage. X852 provides higher short-circuit photocurrent density due to the strong electron-donating capability of indoline unit. The results from the redox electrolyte on cell performances indicate that the synthesized dyes are more suitable for tris(1,10-phenanthroline)cobalt(II/III) redox couple than I-/I3- redox couple in assembling DSCs. Application of X852 in the cobalt electrolyte yields a DSC with an overall power conversion efficiency of 6.58% under AM 1.5 (100 mW/cm2) irradiation.展开更多
The cationic guar (CG) is synthesized and the rheological behavior of aqueous solutions of CG in the presence of sodium dodecyl sulfate (SDS) is studied in detail. The steady viscosity measurements show that the z...The cationic guar (CG) is synthesized and the rheological behavior of aqueous solutions of CG in the presence of sodium dodecyl sulfate (SDS) is studied in detail. The steady viscosity measurements show that the zero shear viscosity enhancement can be almost 3 orders of magnitude as the concentration of SDS increases from 0 to 0.043%. The gel-like formation is observed as the concentration of SDS is greater than 0.016%. The oscillatory rheological measurements of CG solutions in the presence of SDS show that the crossover modulus is almost independent of the concentration of SDS whereas the apparent relaxation time increases swiftly upon increasing the concentration of SDS. The experimental results indicate that the strength rather than the number of the cross-links is greatly affected by SDS molecules. The mechanism concerning the effect of SDS upon the rheology of CG solutions can be coined by the two-stage model. Before the formation of cross-links at the critical concentration, the electrostatic interaction between SDS and cationic site of CG chains plays a key role and the SDS molecules bind to CG chains through the electrostatic interaction. After the formation of cross-links at the concentration greater than the critical concentration, the cooperative hydrophobic interaction become dominant and SDS molecules bind to the cross-links through the hydrophobic interaction. The theological behavior of aqueous solutions of CG in the presence of SDS is chiefly determined by the micelle-like cross-links between CG chains. In fact, the flow activation energy of CG solution, obtained from the temperature dependence of the apparent relaxation time, falls in the range of transferring a hydrophobic tail of SDS from the micelle to an aqueous environment.展开更多
A kind of environmental friendly anodizing routine for AZ91D magnesium alloy,based on an alkaline borate-potassium acid phthalate(KAP) electrolyte,was studied.The effect of KAP on the properties of the anodized film...A kind of environmental friendly anodizing routine for AZ91D magnesium alloy,based on an alkaline borate-potassium acid phthalate(KAP) electrolyte,was studied.The effect of KAP on the properties of the anodized film was investigated by scanning electron microscopy(SEM),X-ray diffraction(XRD),energy dispersive spectrometry(EDS),potentiodynamic polarization and electrochemical impedance spectroscopy(EIS),respectively.The results showed that the anodizing process,surface morphology,thickness,phase structure and corrosion resistance of the anodized film were strongly dependent on the concentration of KAP.In the presence of adequate KAP,a compact and smooth anodized film with excellent corrosion resistance was obtained.展开更多
As a raw material,kaolin was modified to prepare a high-performance ammonium ion-exchange material.According to cation-exchange capacity (CEC) measurement,the prepared ammonium ion-exchange material has an ammonium io...As a raw material,kaolin was modified to prepare a high-performance ammonium ion-exchange material.According to cation-exchange capacity (CEC) measurement,the prepared ammonium ion-exchange material has an ammonium ion-exchange capacity greater than 75mg/g and can be used to remove ammonia nitrogen in water treatment.A pharmaceutical extruder-rounder was used to study the effects of granulation process.Polyethylene glycol6000 (PEG-6000) was used as the pore-forming agent and calcining temperature of 650℃ was used as the optimal condition.NMR data indicate that 27 Al is mainly converted from hexa-coordinated Al to tetra-coordinated Al during the modification.Compared with 29 Si in the original kaolin,29 Si in the modified kaolin does not have an obvious change.A comparison of the data with Langmuir and Freundlich isotherm models shows a good correlation.The Freundlich model describes the process more accurately,and the adsorption process of ammonia nitrogen in water with the ammonium ion-exchange material closely matches the pseudo-second-order reaction.展开更多
The properties of aqueous two-phase system (ATPS) of mixed solution containing gemini cationic surfactant trimethylene-1,3-bis(dodecyldimethyl ammonium) bromide (12-3-12, 2Br-) and traditional anionic surfactant sodiu...The properties of aqueous two-phase system (ATPS) of mixed solution containing gemini cationic surfactant trimethylene-1,3-bis(dodecyldimethyl ammonium) bromide (12-3-12, 2Br-) and traditional anionic surfactant sodium dodecyl sulfate (SDS) with or without added salt have been studied. An ATPS is formed in a narrow region of the ternary phase diagram different from that of traditional aqueous cationic-anionic surfactant systems. In ATPS region, the lowest total concentration of surfactants varies with the mixing ratio of geminis to SDS. Photographs obtained from freeze-etching, negative-staining and transmission electron microscopy show that the microstructures of two phases are different from each other. Micelles and vesicles can coexist in a single phase. The addition of salts can change the phase diagram of ATPS. Furthermore, the added salts promote the aggregation of rod-like micelles to form coarse network structure that increase the viscosity of solutions. The negative ions of the added salts are the determining factor.展开更多
The role of bivalent cations and choline in ATP induced apoptosis via P2Z purinoceptor was investigated in human leukemic lymphocytes. In vitro exposure of leukemic lymphocytes with P2Z rec...The role of bivalent cations and choline in ATP induced apoptosis via P2Z purinoceptor was investigated in human leukemic lymphocytes. In vitro exposure of leukemic lymphocytes with P2Z receptors to 1 mmol/L ATP or 0 1 mmol/L benzoylbenzoic ATP(BzATP) for 8 h in the presence of choline, 1 mmol/L Mg 2+ or other bivalent cations, and ATP induced DNA breaks, associated with apoptosis were quantified by TdT assay. We observed that (1) Extracellular Mg 2+ or Ca 2+ stimulated ATP induced DNA fragmentation in a dose dependent manner, and the compatible evidence was provided by the inhibition of ATP induced DNA fragmentation in the present of EGTA or EDTA; (2) ATP induced DNA fragmentation was completely inhibited by 1 mmol/L Zn 2+ ;(3)ATP induced DNA breaks were not affected by Ba 2+ , Sr 2+ , Co 2+ when they were substituted for extracellular Mg 2+ or Ca 2+ ;(4)Choline, an inhibitor of phospholipase D(PLD) stimulated by ATP through P2Z receptor in human lymphocytes, was also a partial inhibitor of ATP induced DNA fragmentation, and the results were confirmed by flow cytometric analysis (FCA); (5)ATP induced DNA fragmentation was completely obliterated when the temperature was lower than 10℃. These results suggest that the endonuclease and PLD may be involved in ATP induced apoptosis in human lymphocytes via P2Z receptor.展开更多
Ferrocenium monocations as photoinitiators for cationic photopolymerization suffer from a limitation of low absorption and low reactivity under high-pressure Hg lamp. Here, a ferrocenium dication salt, biphenyl bis [...Ferrocenium monocations as photoinitiators for cationic photopolymerization suffer from a limitation of low absorption and low reactivity under high-pressure Hg lamp. Here, a ferrocenium dication salt, biphenyl bis [π-cyclopentadienyl)iron] hexafluorophosphate ([bis(Cp-Fe)-biphenyl] (PF6)2 was synthesized by the ligand exchange reaction between ferrocene and biphenyl. The chemical structure was characterized with FTIR and ^1HNMR. The separation of ferrocenium monocation cyclopentadien-iron-biphenyl hexafluorophosphate ([Cp-Fe-biphenyl] PF6) and dication [bis(Cp-Fe)-biphenyl] (PF6)2 was carried out by column chromatography. The photoactivity of initiating photopolyinerization of epoxide ER14221 was studied as a cationic photoinitiator. [Bis(Cp-Fe)-biphenyl] (PF6)2 can efficiently absorb radiation above 300nm and its photoactivity is higher than that of its monocation.展开更多
The complexation of BDHTD (4-benzylidenamino-4,5-dihydro-lH-l,2,4-triazol-5-one derivatives) by divalent doubly charged metal ions M2+ (M = Mg, Ca, Fe and Cu) has been investigated using the density functional me...The complexation of BDHTD (4-benzylidenamino-4,5-dihydro-lH-l,2,4-triazol-5-one derivatives) by divalent doubly charged metal ions M2+ (M = Mg, Ca, Fe and Cu) has been investigated using the density functional method B3LYP. Two distinct coordination modes (k2-O,O and k2-O,N) have been taken into account. Geometry optimizations have been performed in gas-phase and solution-phase: acetonitrile and DMF (N,N-dimethylformamide) with the basis set 6-31G(d,p). The B3LYP method was also used to calculate the stability and free energies of the 24 complexes of BDHTD with metal ions M2+ (M = Mg, Ca, Fe and Cu) respectively in gas-phase and solution-phase: acetonitrile and DMF. Results indicate that k2-O,N structures are most stable in gas-phase. The influence of substitution on the stability is sensitive in solution-phase. The interaction energies of complexation process in various media have been calculated at B3LYP/6-31G(d,p) and CCSD(T) level. The MIA (metal ion affinity) of BDHTD with M2+ (M = Mg, Ca, Fe and Cu) in various media has been explored. The results show that the M1A highly varies with the coordination mode and substitution effect. From the calculated Gibb energies of complexation in various media, it is revealed that the complexation is possible in gas in acetonitrile. The ligand's affinity toward individual cation M2+ (M = Mg, Ca, Fe and Cu) has been analysed. A significant reduce of BDEs observed confirms the decrease of the antioxidant activity by the metal chelation. The charge transfer induced by metal chelation is examined using the NBO analysis.展开更多
Designing low-cost and high-performance photoelectrodes with improved light harvesting and charge separation rates is significant in photoelectrochemical water splitting.Here,a novel TiO2/Cu2O/Al/Al2O3 photoelectrode ...Designing low-cost and high-performance photoelectrodes with improved light harvesting and charge separation rates is significant in photoelectrochemical water splitting.Here,a novel TiO2/Cu2O/Al/Al2O3 photoelectrode is manufactured by depositing plasmonic nanoparticles of the non-noble metal Al on the surface of a TiO2/Cu2O core/shell heterojunction for the first time.The Al nanoparticles,which exhibit a surface plasmon resonance(SPR)effect and are substantially less expensive than noble metals such as Au and Ag,generate hot electron-hole pairs and amplify the electromagnetic field at the interface under illumination.The as-prepared TiO2/Cu2O/Al/Al2O3 photoelectrodes have an extended absorption range and enhanced carrier separation and transfer.Their photocurrent density of 4.52 mA·cm^-2 at 1.23 V vs.RHE represents an 1.84-fold improvement over that of TiO2/Cu2O.Specifically,the ultrathin Al2O3 passivation layer spontaneously generated on the surface of Al in air could act as a protective layer to significantly increase its stability.In this work,the synergistic effect of the heterojunctions and the SPR effect of the non-noble metal Al significantly improve the photoelectrode performance,providing a novel concept for the design of electrodes with good properties and high practicability.展开更多
To degrade the organic compounds in the electroplating wastewater,magnetic field was tentatively introduced into electrocatalytic oxidation on Ti-PbO2 anode.The magnetic field assisted electrocatalytic oxidation can p...To degrade the organic compounds in the electroplating wastewater,magnetic field was tentatively introduced into electrocatalytic oxidation on Ti-PbO2 anode.The magnetic field assisted electrocatalytic oxidation can promote anion movement and the generation of active species,resulting more organic compounds to be oxidized and degraded.Oxidation parameters such as treatment time,current density and initial pH of the wastewater were systematically discussed and optimized.The mineralization of organic compounds is improved by over 15% under a magnetic density of 22 mT while the current density is 50 A/m2,pH is 1.8 and the reaction time is 1.5 h.The results indicate that the magnetic field assisted electrocatalytic oxidation has considerable potential in electroplating wastewater treatment.展开更多
A systematic study was conducted on current efficiency (CE), corrosion and structural changes in SnO2-based inert anodes (made of 96wt%SnO2+2wt%Sb2O3+2wt%CuO) on a laboratory Hall-Heroult aluminium cell. The inf...A systematic study was conducted on current efficiency (CE), corrosion and structural changes in SnO2-based inert anodes (made of 96wt%SnO2+2wt%Sb2O3+2wt%CuO) on a laboratory Hall-Heroult aluminium cell. The influence of operating parameters and electrolyte composition on the CE and corrosion process were evaluated. The CE was found to be more than 90% and catastrophic corrosion took place at low percent of Al2O3, high percent of LiF, low cryolite ratio and high current densities. From all the structural changes that took place in the SnO2-based inert anodes, we assumed that the most important contribution was due to the migration of CuO towards the outer limits of the constituent grains of SnO2 based ceramic. The complex process occurred during the formation of various phases and their sintering ability both directly depended on Cu/Sb molar ratio.展开更多
Consumable carbon anodes are used in the electrowinning of aluminium by the Hall-Heroult process. Emissions of CO2 may be eliminated by introducing an inert oxygen evolving anode, which however will require a higher a...Consumable carbon anodes are used in the electrowinning of aluminium by the Hall-Heroult process. Emissions of CO2 may be eliminated by introducing an inert oxygen evolving anode, which however will require a higher anode potential. An alternative approach is to use a natural gas or hydrogen gas anode to reduce the CO2 emissions and lower the anode potential. Preliminary laboratory experiments were carried out in an alternative molten salt electrolyte consisting of CaCl2-CaO-NaCl at 680℃ Porous anodes of platinum and tin oxide were tested during electrolysis at constant current. The behaviour of inert anode candidate materials such as tin oxide and nickel ferrite were also studied.展开更多
CO2 is not only the most important greenhouse gas but also an important resource of elemental carbon and oxygen.From the perspective of resource and energy strategy,the conversion of CO2 to chemicals driven by renewab...CO2 is not only the most important greenhouse gas but also an important resource of elemental carbon and oxygen.From the perspective of resource and energy strategy,the conversion of CO2 to chemicals driven by renewable energy is of significance,since it can not only reduce carbon emission by the utilization of CO2 as feedstock but also store low-grade renewable energy as high energy density chemical energy.Although studies on photoelectrocatalytic reduction of CO2 using renewable energy are increasing,artificial bioconversion of CO2 as an important novel pathway to synthesize chemicals has attracted more and more attention.By simulating the natural photosynthesis process of plants and microorganisms,the artificial bioconversion of CO2 can efficiently synthesize chemicals via a designed and constructed artificial photosynthesis system.This review focuses on the recent advancements in artificial bioreduction of CO2,including the key techniques,and artificial biosynthesis of compounds with different carbon numbers.On the basis of the aforementioned discussions,we present the prospects for further development of artificial bioconversion of CO2 to chemicals.展开更多
Charge-transfer salt (dbtf),HGeW12O40. 4H2O(C84H57O44S24GeW12)was synthesized by electrocrystallization and characterized by IR and electronic spectra.Its magnetic and conducting properties and crystal structure were ...Charge-transfer salt (dbtf),HGeW12O40. 4H2O(C84H57O44S24GeW12)was synthesized by electrocrystallization and characterized by IR and electronic spectra.Its magnetic and conducting properties and crystal structure were determined. The titlesalt crystallized in triclinic system with P1 space group. Its cell parameters are reflexions展开更多
文摘The electrochemical reduction of CO_(2)(eCO_(2)R)under ambient conditions is crucial for reducing carbon emissions and achieving carbon neutrality.Despite progress with alkaline and neutral electrolytes,their efficiency is limited by(bi)carbonates formation.Acidic media have emerged as a solution,addressing the(bi)carbonates challenge but introducing the issue of the hydrogen evolu-tion reaction(HER),which reduces CO_(2) conversion efficiency in acidic environments.This review focuses on enhancing the selectivity of acidic CO_(2) electrolysis.It commences with an overview of the latest advancements in acidic CO_(2) electrolysis,focusing on product selectivity and electrocatalytic activity enhancements.It then delves into the critical factors shaping selectivity in acidic CO_(2) electrolysis,with a special emphasis on the influence of cations and catalyst design.Finally,the research challenges and personal perspectives of acidic CO_(2) electrolysis are suggested.
基金Project(51271012)supported by the National Natural Science Foundation of China
文摘The influence of adipic acid on the formation and corrosion resistance of anodic oxide film fabricated on 2024 aluminum alloy was investigated. The morphology was investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), respectively. The corrosion resistance was evaluated by electrochemical impedance spectroscopy (EIS). The results showed that the adipic acid was absorbed at the electrolyte/anodic layer interface during anodizing. The corrosion rate of anodic film decreased and the film thickness increased. The film was uniform and compact especially at the film/substrate interface. After sealing procedure, anodic film formed with the addition of adipic acid exhibited improved dielectric property and corrosion resistance in aggressive environment.
基金Project(51404001)supported by the National Natural Science Foundation of ChinaProject([2014]1685)supported by the Scientific Research Foundation for the Returned Overseas Chinese Scholars,Ministry of Education,China
文摘A novel SnO2-based gas anode was developed for aluminum electrolysis in molten cryolite at 850 °C to reduce energy consumption and decrease CO2 emissions. Hydrogen was introduced into the anode, participating in the anode reaction. Carbon and aluminum were used as the cathode and reference electrodes, respectively. Cyclic voltammetry was applied in the cell to investigate the electrochemical behavior of oxygen ion on platinum and SnO2-based materials. The potential for oxygen evolution on these electrode materials was determined. Then, galvanostatic electrolysis was performed on the gas anode, showing a significant depolarization effect (a decrease of ~0.8 V of the anode potential) after the introduction of hydrogen, compared with no gas introduction or the introduction of argon. The results indicate the involvement of hydrogen in the anode reaction (three-phase-boundary reaction including gas, electrolyte and electrode) and give the possibility for the utilization of reducing gas anodes for aluminum electrolysis.
基金The Key Project of Chinese Ministry of Education (No.108601)Major Projects of National Water Pollution Control and Management Technology (No.2009ZX07101-011)Specialized Research Fund for the Doctoral Program of Higher Education (No.20060286010)
文摘Boron-doped diamond (BDD) electrocatalysis is combined with photocatalysis using titanium dioxide (TiO2) as a catalyst to improve pollutant-oxidation efficiency. Phenol solution is chosen as model wastewater. Different methods involving BDD and/or TiO2 during the degradation processes are compared. Parameters such as the currency density and initial concentration are varied in order to determine their effects on the oxidation process. Moreover, the degradation kinetics of phenol is experimentally studied. The results reveal the superiority of series combination of BDD and TiO2, especially the treatment process of electrocatalysis and succedent photocatalysis, and the optimum working currency density for electrocatalysis is 25.48 mA/cm2. The removal rate decreases with the increase in the initial phenol concentration and the degradation reaction follows quasi-first-order kinetics equation.
文摘Two organic dyes XSS1 and XS52 derivated from triarylamine and indoline are synthesized for dye-sensitized solar ceils (DSCs) employing cobalt and iodine redox shuttles. The effects of dye structure upon the photophysical, electro-chemical characteristics and cell perfor- mance are investigated. XS51 with four hexyloxyl groups on triarylamine performs better steric hindrance and an improvement of photovoltage. X852 provides higher short-circuit photocurrent density due to the strong electron-donating capability of indoline unit. The results from the redox electrolyte on cell performances indicate that the synthesized dyes are more suitable for tris(1,10-phenanthroline)cobalt(II/III) redox couple than I-/I3- redox couple in assembling DSCs. Application of X852 in the cobalt electrolyte yields a DSC with an overall power conversion efficiency of 6.58% under AM 1.5 (100 mW/cm2) irradiation.
文摘The cationic guar (CG) is synthesized and the rheological behavior of aqueous solutions of CG in the presence of sodium dodecyl sulfate (SDS) is studied in detail. The steady viscosity measurements show that the zero shear viscosity enhancement can be almost 3 orders of magnitude as the concentration of SDS increases from 0 to 0.043%. The gel-like formation is observed as the concentration of SDS is greater than 0.016%. The oscillatory rheological measurements of CG solutions in the presence of SDS show that the crossover modulus is almost independent of the concentration of SDS whereas the apparent relaxation time increases swiftly upon increasing the concentration of SDS. The experimental results indicate that the strength rather than the number of the cross-links is greatly affected by SDS molecules. The mechanism concerning the effect of SDS upon the rheology of CG solutions can be coined by the two-stage model. Before the formation of cross-links at the critical concentration, the electrostatic interaction between SDS and cationic site of CG chains plays a key role and the SDS molecules bind to CG chains through the electrostatic interaction. After the formation of cross-links at the concentration greater than the critical concentration, the cooperative hydrophobic interaction become dominant and SDS molecules bind to the cross-links through the hydrophobic interaction. The theological behavior of aqueous solutions of CG in the presence of SDS is chiefly determined by the micelle-like cross-links between CG chains. In fact, the flow activation energy of CG solution, obtained from the temperature dependence of the apparent relaxation time, falls in the range of transferring a hydrophobic tail of SDS from the micelle to an aqueous environment.
基金Projects (50771092,21073162) supported by the National Natural Science Foundation of ChinaProject (08JC1421600) supported by the Science and Technology Commission of Shanghai,ChinaProject (2008AZ2018) supported by the Science and Technology Bureau of Jiaxing,China
文摘A kind of environmental friendly anodizing routine for AZ91D magnesium alloy,based on an alkaline borate-potassium acid phthalate(KAP) electrolyte,was studied.The effect of KAP on the properties of the anodized film was investigated by scanning electron microscopy(SEM),X-ray diffraction(XRD),energy dispersive spectrometry(EDS),potentiodynamic polarization and electrochemical impedance spectroscopy(EIS),respectively.The results showed that the anodizing process,surface morphology,thickness,phase structure and corrosion resistance of the anodized film were strongly dependent on the concentration of KAP.In the presence of adequate KAP,a compact and smooth anodized film with excellent corrosion resistance was obtained.
基金Supported by Natural Science Foundation of Tianjin(No.06YFGPSH04300)
文摘As a raw material,kaolin was modified to prepare a high-performance ammonium ion-exchange material.According to cation-exchange capacity (CEC) measurement,the prepared ammonium ion-exchange material has an ammonium ion-exchange capacity greater than 75mg/g and can be used to remove ammonia nitrogen in water treatment.A pharmaceutical extruder-rounder was used to study the effects of granulation process.Polyethylene glycol6000 (PEG-6000) was used as the pore-forming agent and calcining temperature of 650℃ was used as the optimal condition.NMR data indicate that 27 Al is mainly converted from hexa-coordinated Al to tetra-coordinated Al during the modification.Compared with 29 Si in the original kaolin,29 Si in the modified kaolin does not have an obvious change.A comparison of the data with Langmuir and Freundlich isotherm models shows a good correlation.The Freundlich model describes the process more accurately,and the adsorption process of ammonia nitrogen in water with the ammonium ion-exchange material closely matches the pseudo-second-order reaction.
基金the National Natural Science Foundation of China (No. 20025618, No. 20236010) Shanghai Municipal Education Commission of China.
文摘The properties of aqueous two-phase system (ATPS) of mixed solution containing gemini cationic surfactant trimethylene-1,3-bis(dodecyldimethyl ammonium) bromide (12-3-12, 2Br-) and traditional anionic surfactant sodium dodecyl sulfate (SDS) with or without added salt have been studied. An ATPS is formed in a narrow region of the ternary phase diagram different from that of traditional aqueous cationic-anionic surfactant systems. In ATPS region, the lowest total concentration of surfactants varies with the mixing ratio of geminis to SDS. Photographs obtained from freeze-etching, negative-staining and transmission electron microscopy show that the microstructures of two phases are different from each other. Micelles and vesicles can coexist in a single phase. The addition of salts can change the phase diagram of ATPS. Furthermore, the added salts promote the aggregation of rod-like micelles to form coarse network structure that increase the viscosity of solutions. The negative ions of the added salts are the determining factor.
文摘The role of bivalent cations and choline in ATP induced apoptosis via P2Z purinoceptor was investigated in human leukemic lymphocytes. In vitro exposure of leukemic lymphocytes with P2Z receptors to 1 mmol/L ATP or 0 1 mmol/L benzoylbenzoic ATP(BzATP) for 8 h in the presence of choline, 1 mmol/L Mg 2+ or other bivalent cations, and ATP induced DNA breaks, associated with apoptosis were quantified by TdT assay. We observed that (1) Extracellular Mg 2+ or Ca 2+ stimulated ATP induced DNA fragmentation in a dose dependent manner, and the compatible evidence was provided by the inhibition of ATP induced DNA fragmentation in the present of EGTA or EDTA; (2) ATP induced DNA fragmentation was completely inhibited by 1 mmol/L Zn 2+ ;(3)ATP induced DNA breaks were not affected by Ba 2+ , Sr 2+ , Co 2+ when they were substituted for extracellular Mg 2+ or Ca 2+ ;(4)Choline, an inhibitor of phospholipase D(PLD) stimulated by ATP through P2Z receptor in human lymphocytes, was also a partial inhibitor of ATP induced DNA fragmentation, and the results were confirmed by flow cytometric analysis (FCA); (5)ATP induced DNA fragmentation was completely obliterated when the temperature was lower than 10℃. These results suggest that the endonuclease and PLD may be involved in ATP induced apoptosis in human lymphocytes via P2Z receptor.
基金Supported by the National Natural Science Foundation of China (20676012).
文摘Ferrocenium monocations as photoinitiators for cationic photopolymerization suffer from a limitation of low absorption and low reactivity under high-pressure Hg lamp. Here, a ferrocenium dication salt, biphenyl bis [π-cyclopentadienyl)iron] hexafluorophosphate ([bis(Cp-Fe)-biphenyl] (PF6)2 was synthesized by the ligand exchange reaction between ferrocene and biphenyl. The chemical structure was characterized with FTIR and ^1HNMR. The separation of ferrocenium monocation cyclopentadien-iron-biphenyl hexafluorophosphate ([Cp-Fe-biphenyl] PF6) and dication [bis(Cp-Fe)-biphenyl] (PF6)2 was carried out by column chromatography. The photoactivity of initiating photopolyinerization of epoxide ER14221 was studied as a cationic photoinitiator. [Bis(Cp-Fe)-biphenyl] (PF6)2 can efficiently absorb radiation above 300nm and its photoactivity is higher than that of its monocation.
文摘The complexation of BDHTD (4-benzylidenamino-4,5-dihydro-lH-l,2,4-triazol-5-one derivatives) by divalent doubly charged metal ions M2+ (M = Mg, Ca, Fe and Cu) has been investigated using the density functional method B3LYP. Two distinct coordination modes (k2-O,O and k2-O,N) have been taken into account. Geometry optimizations have been performed in gas-phase and solution-phase: acetonitrile and DMF (N,N-dimethylformamide) with the basis set 6-31G(d,p). The B3LYP method was also used to calculate the stability and free energies of the 24 complexes of BDHTD with metal ions M2+ (M = Mg, Ca, Fe and Cu) respectively in gas-phase and solution-phase: acetonitrile and DMF. Results indicate that k2-O,N structures are most stable in gas-phase. The influence of substitution on the stability is sensitive in solution-phase. The interaction energies of complexation process in various media have been calculated at B3LYP/6-31G(d,p) and CCSD(T) level. The MIA (metal ion affinity) of BDHTD with M2+ (M = Mg, Ca, Fe and Cu) in various media has been explored. The results show that the M1A highly varies with the coordination mode and substitution effect. From the calculated Gibb energies of complexation in various media, it is revealed that the complexation is possible in gas in acetonitrile. The ligand's affinity toward individual cation M2+ (M = Mg, Ca, Fe and Cu) has been analysed. A significant reduce of BDEs observed confirms the decrease of the antioxidant activity by the metal chelation. The charge transfer induced by metal chelation is examined using the NBO analysis.
文摘Designing low-cost and high-performance photoelectrodes with improved light harvesting and charge separation rates is significant in photoelectrochemical water splitting.Here,a novel TiO2/Cu2O/Al/Al2O3 photoelectrode is manufactured by depositing plasmonic nanoparticles of the non-noble metal Al on the surface of a TiO2/Cu2O core/shell heterojunction for the first time.The Al nanoparticles,which exhibit a surface plasmon resonance(SPR)effect and are substantially less expensive than noble metals such as Au and Ag,generate hot electron-hole pairs and amplify the electromagnetic field at the interface under illumination.The as-prepared TiO2/Cu2O/Al/Al2O3 photoelectrodes have an extended absorption range and enhanced carrier separation and transfer.Their photocurrent density of 4.52 mA·cm^-2 at 1.23 V vs.RHE represents an 1.84-fold improvement over that of TiO2/Cu2O.Specifically,the ultrathin Al2O3 passivation layer spontaneously generated on the surface of Al in air could act as a protective layer to significantly increase its stability.In this work,the synergistic effect of the heterojunctions and the SPR effect of the non-noble metal Al significantly improve the photoelectrode performance,providing a novel concept for the design of electrodes with good properties and high practicability.
基金Project(2008ZX07101-006-09) supported by the Major Science and Technology Program for Water Pollution Control and Treatment of China
文摘To degrade the organic compounds in the electroplating wastewater,magnetic field was tentatively introduced into electrocatalytic oxidation on Ti-PbO2 anode.The magnetic field assisted electrocatalytic oxidation can promote anion movement and the generation of active species,resulting more organic compounds to be oxidized and degraded.Oxidation parameters such as treatment time,current density and initial pH of the wastewater were systematically discussed and optimized.The mineralization of organic compounds is improved by over 15% under a magnetic density of 22 mT while the current density is 50 A/m2,pH is 1.8 and the reaction time is 1.5 h.The results indicate that the magnetic field assisted electrocatalytic oxidation has considerable potential in electroplating wastewater treatment.
文摘A systematic study was conducted on current efficiency (CE), corrosion and structural changes in SnO2-based inert anodes (made of 96wt%SnO2+2wt%Sb2O3+2wt%CuO) on a laboratory Hall-Heroult aluminium cell. The influence of operating parameters and electrolyte composition on the CE and corrosion process were evaluated. The CE was found to be more than 90% and catastrophic corrosion took place at low percent of Al2O3, high percent of LiF, low cryolite ratio and high current densities. From all the structural changes that took place in the SnO2-based inert anodes, we assumed that the most important contribution was due to the migration of CuO towards the outer limits of the constituent grains of SnO2 based ceramic. The complex process occurred during the formation of various phases and their sintering ability both directly depended on Cu/Sb molar ratio.
文摘Consumable carbon anodes are used in the electrowinning of aluminium by the Hall-Heroult process. Emissions of CO2 may be eliminated by introducing an inert oxygen evolving anode, which however will require a higher anode potential. An alternative approach is to use a natural gas or hydrogen gas anode to reduce the CO2 emissions and lower the anode potential. Preliminary laboratory experiments were carried out in an alternative molten salt electrolyte consisting of CaCl2-CaO-NaCl at 680℃ Porous anodes of platinum and tin oxide were tested during electrolysis at constant current. The behaviour of inert anode candidate materials such as tin oxide and nickel ferrite were also studied.
基金supported by the National Natural Science Foundation of China (91745114, 21802160)the National Key R&D Program of China (2016YFA0202800)+2 种基金Shanghai Sailing Program (18YF1425700)Shanghai Advanced Research Institute Innovation Research Program (Y756812ZZ1(172002),Y756803ZZ1(171003))the support from the Hundred Talents Program of the Chinese Academy of Sciences~~
文摘CO2 is not only the most important greenhouse gas but also an important resource of elemental carbon and oxygen.From the perspective of resource and energy strategy,the conversion of CO2 to chemicals driven by renewable energy is of significance,since it can not only reduce carbon emission by the utilization of CO2 as feedstock but also store low-grade renewable energy as high energy density chemical energy.Although studies on photoelectrocatalytic reduction of CO2 using renewable energy are increasing,artificial bioconversion of CO2 as an important novel pathway to synthesize chemicals has attracted more and more attention.By simulating the natural photosynthesis process of plants and microorganisms,the artificial bioconversion of CO2 can efficiently synthesize chemicals via a designed and constructed artificial photosynthesis system.This review focuses on the recent advancements in artificial bioreduction of CO2,including the key techniques,and artificial biosynthesis of compounds with different carbon numbers.On the basis of the aforementioned discussions,we present the prospects for further development of artificial bioconversion of CO2 to chemicals.
文摘Charge-transfer salt (dbtf),HGeW12O40. 4H2O(C84H57O44S24GeW12)was synthesized by electrocrystallization and characterized by IR and electronic spectra.Its magnetic and conducting properties and crystal structure were determined. The titlesalt crystallized in triclinic system with P1 space group. Its cell parameters are reflexions