Removal of rubidium from brine by an integrated film of sulfonated polysulfone/graphene/potassium copper ferricyanide

A novel integrated film of sulfonated polysulfone/graphene/potassium copper ferricyanide(KCuFC/SPSG)was used for selectively extracting rubidium ion(Rb^(+))from brine.To form KCuFC/SPSG,the precursor film of sulfonated polysulfone/graphene(SPSG)was synthesized by phase conversion process,which was alternately immersed in 0.1 mol·L^(-1)CuSO_(4)/K_(4)[Fe(CN)_(6)]by in-situ adsorption coupled co-precipitation method.Various data such as nuclear magnetic resonance spectrometer,Fourier transform infrared spectroscope,X-ray photoelectron spectroscope,X-ray diffraction,scanning electron microscope,and energy dispersive spectroscopy all verified that abundant KCuFC were uniformly located on the film.The resulting KCuFC/SPSG was used in film separation system.As the solution was fed into the system,the Rb^(+)could be selectively adsorption by KCuFC/SPSG.After the saturation adsorption,0.5 mol·L^(-1)NH_(4)Cl/HCl was fed into the film cell,Rb^(+)could be quickly desorbed by ion-exchange between Rb^(+)and NH_(4)^(+)in the lattice of KCuFC.The purpose of separating and recovering Rb^(+)from the brine can be achieved after the repeated operation.The effects of pH,adsorption time,and interferential ions on the adsorption capacity of Rb^(+)were investigated by batch experiments.The adsorption behavior fits the pseudo-second order kinetic process,while KCuFC has a higher adsorption capacity(Langmuir maximum sorption 165.4 mg·g^(-1)).In addition,KCuFC/SPSG shows excellent selectivity for Rb^(+)even in complex brine systems.KCuFC/SPSG could maintain 93.5%extraction efficiency after five adsorption/desorption cycles.

Structural optimization and performance trade-off strategies for semi-crystalline sulfonated poly(arylene ether ketone) membranes in high-concentration direct methanol fuel cells

Direct methanol fuel cells(DMFCs) have attracted extensive attention as promising next-generation energy conversion devices. However, commercialized proton exchange membranes(PEMs) hardly fulfill the demand of methanol tolerance for DMFCs employing high-concentration methanol solutions.Herein, we report a series of semi-crystalline poly(arylene ether ketone) PEMs with ultra-densely sulfonic-acid-functionalized pendants linked by flexible alkyl chains, namely, SL-SPEK-x(where x represents the molar ratio of the novel monomer containing multiple phenyl side chain to the bisfluoride monomers). The delicate structural design rendered SL-SPEK-x membranes with high crystallinity and well-defined nanoscale phase separation between hydrophilic and hydrophobic phases. The reinforcement from poly(ether ketone) crystals enabled membranes with inhibited dimensional variation and methanol penetration. Furthermore, microphase separation significantly enhanced proton conductivity. The SL-SPEK-12.5 membrane achieved the optimum trade-off between proton conductivity(0.182 S cm^(-1), 80 ℃), water swelling(13.6%, 80 ℃), and methanol permeability(1.6 × 10^(-7)cm~2 s^(-1)). The DMFC assembled by the SL-SPEK-12.5 membrane operated smoothly with a 10 M methanol solution, outputting a maximum power density of 158.3 mW cm^(-2), nearly twice that of Nafion 117(94.2 mW cm^(-2)). Overall, the novel structural optimization strategy provides the possibility of PEMs surviving in high-concentration methanol solutions, thus facilitating the miniaturization and portability of DMFC devices.

Rheological and physicomechanical properties of rod milling sand-based cemented paste backfill modified by sulfonated naphthalene formaldehyde condensate

Rod milling sand(RMS)—a coarse sand aggregate—was recycled for cemented paste backfill(CPB)for the underground mined area at the Jinchuan nickel deposit,named rod milling sand-based cemented paste backfill(RCPB).The adverse effects of coarse particles on the transportation of CPB slurry through pipelines to underground stopes resulting in weakening of the stability of the backfill system are well known.Therefore,sulfonated naphthalene formaldehyde(SNF)condensate was used for the performance improvement of RCPB.The synergistic effect of solid content(SC),lime-to-sand ratio,and SNF dosage on the rheological and physicomechanical properties,including slump,yield stress,bleeding rate,uniaxial compressive strength(UCS),as well as mechanism analysis of RCPB,have been explored.The results indicate that the effect of SNF on RCPB performance is related to the SNF dosage,lime-to-sand ratio,and SC.The slump of fresh RCPB with 0.1wt%-0.5wt%SNF increased by 2.6%-26.2%,whereas the yield stress reduced by 4.1%-50.3%,indicating better workability and improved cohesiveness of the mix.The bleeding rate of fresh RCPB decreased first and then rose with the increase of SNF dosage,and the peak decrease was 67.67%.UCS of RCPB first increased and then decreased with the increase of SNF dosage.At the optimal SNF addition ratio of 0.3wt%,the UCS of RCPB curing for 7,14 and,28 d ages increased by 31.5%,28.4%,and 29.5%,respectively.The beneficial effects of SNF in enhancing the early UCS of RCPB have been corroborated.However,the later UCS increases at a slower rate.The research findings may guide the design and preparation of RCPB with adequate performance for practical applications.

Proton-exchange Sulfonated Poly（ether ether ketone）/Sulfonated Phenolphthalein Poly（ether sulfone） Blend Membranes in DMFCs

A sulfonated poly（ether ether ketone） （SPEEK） membrane with fairly high degree of sulfonation （DS） swells excessively and even dissolves at high temperature. To solve these problems, sulfonated phenolphthalein poly（ether sulfone） （SPES-C, DS= 53.7%） is blended with the SPEEK matrix （DS= 55.1%, 61.7%） to prepare SPEEKJSPES-C blend membrane. The decrease in swelling degree and methanol permeability of the membrane is dose-dependent. Pure SPEEK （DS = 61.7%） membrane dissolves completely in water at 70℃, whereas the swelling degree of the SPEEK （DS = 61.7%）/SPES-C （40%, by mass） membrane is 29.7% at 80℃. From room temperature to 80℃, the methanol permeability of all SPEEK （DS = 55.1%）/SPES-C blend membranes is about one order of magnitude lower than that of Nafion 115. At higher temperature, the addition of SPES-C polymer increases the dimensional stability and greater proton conductivity can be achieved. The SPEEK （DS = 55.1%）/SPES-C （40%, by mass） membrane can withstand temperatures up to 150℃. The proton conductivity of SPEEK （DS = 55.1%）/SPES-C （30%, by mass） membrane approaches 0.16 S·cm^-1, matching that of Nafion 115 at 140℃ and 100% RH, while pure SPEEK （DS = 55.1%） membrane dissolves at 90℃. The SPEEK/SPES-C blend membranes are promising for use in direct methanol fuel cells because of their good dimensional stability, high proton conductivity, and low methanol permeability.

Sulfonated fluorinated multi-block copolymer hybrid containing sulfonated(poly ether ether ketone) and graphene oxide: A ternary hybrid membrane architecture for electrolyte applications in proton exchange membrane fuel cells

A ternary hybrid membrane architecture consisting of sulfonated fluorinated multi-block copolymer （SFMC）, sulfonated （poly ether ether ketone） （SPEEK） and I or 5 wt% graphene oxide （GO） was fabricated through a facile solution casting approach. The simple, but effective monomer sulfonation was performed for SFMC to create compact and rigid hydrophobic backbone structures, while conventional random sulfonation was carried-out for SPEEK. Hydrophilic-hydrophobic-hydrophilic structure of SFMC enhances the compatibility with SPEEK and GO and allows for an unprecedented approach to alter me- chanical strength and proton conductivity of ternary hybrid membrane, as verified from universal test machine （UTM） curves and alternating current （AC） impedance plots. The impact of GO integration on the morphology and roughness of hybrid membrane was scrutinized using field emission scanning electron microscope （FE-SEM） and atomic force microscope （AFM）. Ternary hybrid showed uniform intercalation of GO nanosheets throughout the entire surface of membrane with an increased surface roughness of 8.91 nm. The constructed ternary hybrid membrane revealed excellent water absorption, ion exchange capacity and gas barrier properties, while retaining reasonable dimensional stability. The well-optimized ternary hybrid membrane containing 5 wt% GO revealed a maximum proton conductivity of 111.9 mS/cm, which is higher by a factor of two-fold with respect to that of bare SFMC membrane. The maximum PEMFC power density of 528.07mW/cm2 was yielded by ternary hybrid membrane at a load current density of 1321.1 mA/cm2 when operating the cell at 70 ℃ under 100% relative humidity （RH）. In comparison, a maximum power density of only 182.06 mW/cm2 was exhibited by the bare SFMC membrane at a load current density of 455.56 mA/cm2 under same operating conditions.

Improvement of HydrophUicity and Blood Compatibility on Polyethersulfone Membrane by Blending Sulfonated Polyethersulfone

Polyethersulfone(PES) is widely used as biomaterials due to its thermal stability,mechanical strength,and chemical inertness.Nevertheless,their blood compatibility is still not adequate for hemodialysis and blood purification.In this study,the sulfonated polyethersulfone(SPES) was synthesized through an electrophilic substitution reaction,and PES/SPES blending membranes were prepared.The characterization of the SPES was studied by FTIR.The water adsorption and water contact angle experiments show that the hydrophilicity of PES/SPES blend membrane was improved as for the sulfonate group existing in the SPES.Moreover,PES/SPES blend membrane could effectively reduce bovine serum albumin adsorption and prolong the blood coagulation time compared with the PES membrane,thereby improving blood compatibility.

Treatment of drilling wastewater from a sulfonated mud system

Treatment of drilling wastewater from a sulfonated drilling mud system in the Shengli Oilfield, East China, was studied. The wastewater was deeply treated by a chemical coagulationcentrifugal separation-ozone catalytic oxidation combined process. The factors （i.e. pH value, chemical dosage, reaction time, etc.） influencing the treatment effect were investigated, and pH = 7 was determined as optimal for the coagulation; polymeric aluminum chloride （PAC） was selected as the optimal coagulant with a dosage of 18 g/L; cationic polyacrylamide （CPAM） with molecular weight of 8 million was selected as the optimal coagulant aid with an optimum dosage of 8 mg/L; and the optimal condition of catalytic ozonation was found to be a pH of 12 and an oxidation time of 40 min. The results showed that the combined treatment process was effective. The oil content and suspended solids content of the effluent reached the first class discharge standard according to China＇s standard GB 8978-1996 （Integrated Wastewater Discharge Standard） and the chemical oxygen demand （COD） decreased to 195 mg/L from 2.34×10^4 mg/L after coagulation process and ozone oxidation at pH = 12 for 40 min.

Proton-Exchange Sulfonated Poly （ether ether ketone） （SPEEK）/SiOx-S Composite Membranes in Direct Methanol Fuel Cells

A sulfonated poly（ether ether ketone） （SPEEK） membrane with a fairly high degree of sulfonation （DS） can swell excessively and even dissolve at high temperature. To solve these problems, insolvable functionalized silica powder with sulfonic acid groups （SiOx-S） was added into the SPEEK matrix （DS = 55.1%） to prepare SPEEK/ SiOx-S composite membranes. The decrease in both the swelling degree and the methanol permeability of the membranes was a dose-dependent result of addition of the SiOx-S powder. Pure SPEEK membrane swelled 52.6% at 80℃, whereas the SPEEK/SiOx-S （15%, by mass） membrane swelled only 27.3% at the same temperature. From room temperature to 80℃, all SPEEK/SPEEK/SiOx-S composite membranes had methanol permeability of about one order of magnitude lower than that ofNafion115. Compared with pure SPEEK membranes, the addition of the SiOx-S powder not only leads to higher proton conductivity, but also increases the dimensional stability at higher temperatures, and greater proton conductivity can be achieved at higher temperature. The SPEEK/SiO4-S （20%, by mass） membrane could withstand temperature up to 145℃, at which in 100% relative humidity （RH） its proton conductivity exceeded slightly that of Nafion 1 15 membrane and reached 0.17 S·cm^-1, while pure SPEEK membrane dissolved at 90℃. The SPEEK/SiOx-S composite membranes are promising for use in direct methanol fuel cells because of their good dimensional stability, high proton conductivity, and low methanol permeability.

Sulfonated polybenzimidazole/amine functionalized titanium dioxide(s PBI/AFT) composite electrolyte membranes for high temperature proton exchange membrane fuel cells usage

The novel sulfonated polybenzimidazole(sPBI)/amine functionalized titanium dioxide(AFT) composite membrane is devised and studied for its capability of the application of high temperature proton exchange membrane fuel cells(HT-PEMFCs),unlike the prior low temperature AFT endeavors.The high temperature compatibility was actualized because of the filling of free volumes in the rigid aromatic matrix of the composite with AFT nanoparticles which inhibited segmental motions of the chains and improved its thermal stability.Besides,amine functionalization of TiO2 enhanced their dispersion character in the sPBI matrix and shortened the interparticle separation gap which finally improved the proton transfer after establishing interconnected pathways and breeding more phosphoric acid(PA) doping.In addition,the appeared assembled clusters of AFT flourished a superior mechanical stability.Thus,the optimized sPBI/AFT(10 wt%) showed 65.3 MPa tensile strength;0.084 S·cm^-1 proton conductivity(at 160℃;in anhydrous conditions),28.6% water uptake and PA doping level of 23 mol per sPBI repeat unit.The maximum power density peak for sPBI/AFT-10 met the figure of0.42 W·cm^-2 at 160℃(in dry conditions) under atmospheric pressure with 1.5 and 2.5 stoichiometric flow rates of H2/air.These results affirmed the probable fitting of sPBI/AFT composite for HT-PEMFC applications.

Sulfonated carbon catalyzed oxidation of aldehydes to carboxylic acids by hydrogen peroxide

Sulfonated carbon as a strong and stable solid acid catalyst exhibited excellent catalytic performance in various acid-catalyzed reactions. Here, sulfonated carbon, as catalyst for oxidation reaction, was prepared via the carbonization of starch followed by sulfonation with concentrated sulfuric acid. N2 physisorption, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray fluorescence and acid-base titration were used to characterize the obtained materials. The catalytic activity of sulfonated carbon was studied in the oxidation of aldehydes to carboxylic acids using 30 wt% H2O2 as oxidant. This oxidation protocol works well for various aldehydes including aromatic and aliphatic aldehydes. The sulfonated carbon can be recycled for three times without obvious loss of activity.

Quinone-mediated decolorization of sulfonated azo dyes by cells and cell extracts from Sphingomonas xenophaga

The effects of various quinone compounds on the decolorization rates of sulfonated azo dyes by Sphingomonas xenophaga QYY were investigated. The results showed that anthraquinone-2-sulfonate （AQS） was the most effective redox mediator and AQS reduction was the rate-limited step of AQS-mediated decolorization of sulfonated azo dyes. Based on AQS biological toxicity tests, it was assumed that AQS might enter the cells and kill them. In the cytoplasmic extracts from strain QYY, AQS more effectively increased decolorization rates of sulfonated azo dyes than other quinone compounds. In addition, we found a NADH/FMN-dependent AQS reductase using nondenaturing polyacrylamide gel electrophoresis （Native-PAGE）.

One Step Preparation of Sulfonated Solid Catalyst and Its Effect in Esterification Reaction

A carbon-based sulfonated catalyst was prepared by direct sulfonation and carbonization （in moderate conditions：200 ＆#176;C, 12 h） of red liquor solids, a by-product of paper-making process. The prepared sulfonated cata-lyst （SC） had aromatic structure, composed of carbon enriched inner core, and oxygen-containing （SO3H, COOH, OH） groups enriched surface. The SO3H, COOH, OH groups amounted to 0.74 mmol·g^-1, 0.78 mmol·g^-1, 2.18 mmol·g^-1, respectively. The fresh SC showed much higher catalytic activity than that of the traditional solid acid catalysts （strong^-acid 732 cation exchange resin, hydrogen type zeolite socony mobile-five （HZSM-5）, sulfated zir-conia） in esterification of oleic acid. SC was deactivated during the reactions, through the mechanisms of leaching of sulfonated species and formation of sulfonate esters. Two regeneration methods were developed, and the catalytic activity can be mostly regenerated by regeneration Method 1 and be fully regenerated by regeneration Method 2, respectively.

Kinetic and thermodynamic studies of the esterification of acidified oil catalyzed by sulfonated cation exchange resin

This study describes the kinetics and thermodynamics of the esterification of acidified oil with methanol catalyzed by sulfonated cation exchange resins（SCER）. The effects of the mass ratio of methanol to acidified oil,reaction temperature,and catalyst loading were studied to optimize the conditions for maximum conversion of free fatty acids（FFAs）. The results showed that the optimal conversion rate of FFAs was 91.87% at the mass ratio of methanol to acidified oil of 2.5：1.0,reaction temperature of 65.0 °C,catalyst loading of 5.0 g and reaction time of 8.0 h. The external and internal mass transfer resistances were negligible based on the experimental results and a pseudo-homogeneous kinetic model was proposed for the esterification. The activation energy and thermodynamic parameters including G,S and H were determined. The conversion rates of FFAs obtained from the established model were in good agreement with the experimental data.

SYNTHESIS AND PROPERTIES OF SULFONATED POLY(ARYLENE ETHER) CONTAINING TRIPHENYL METHANE MOIETIES FROM ISOCYNATE MASKED BISPHENOL

A novel sulfonated poly（arylene ether） containing triphenylmethane moieties was synthesized by the sulfonation of a designed parent polymer using chlorosulfonic acid as sulfonation agent. The sulfonation took place at the para position of the pendant phenyl rings because of the specially designed parent polymer. The position and degree of sulfonation were characterized by ^1H-NMR and elemental analysis. The sulfonated polymers are highly soluble in common organic solvents, such as dimethylsulfoxide, N,N＇-dimethylacetamide, dimethylformamide, ethylene glycol monomethyl ether, and can be readily cast into tough and smooth films from solutions. The films showed good thermal and hydrolysis stabilities. Moreover, Fenton＇s reagent test revealed that the films exhibited superior stability to oxidation. The proton conductivities of the films were comparable with Nation 117 under same conditions. The membrane electrode assembly （MEA） prepared with the asmade film （706 EW, 100 μm dry thickness） shows better cell performance than Nation 115-MEA in the whole current density range.

STUDY ON LIGHTLY SULFONATED SYNDIOTACTIC POLYSTYRENE IONOMERS

Sulfonated syndiotactic polystyrene ionomers (SsPS) with 1.8 mol% degree of sulfonation have been studied. WAXD shows that the crystallinity of SsPS ionomers was decreased with increasing diameter size of the counter ions and sPS > SsPS-H > SsPS-K > SsPS-Zn. Moreover, SsPS ionomers only have alpha crystal form, while original sPS has two crystal forms: alpha and beta crystal form. TGA shows that the thermal stability of SsPS ionomers is higher than that of the original sPS and SsPS-Zn > SsPS-K > SsPS-H. DSC shows that all the glass transition temperatures (T-g) of SsPS ionomers are higher than that of the neat sPS and SsPS-Zn > SsPS-Na > SsPS-K > SsPS-H. However, the melting temperature (T-m) and crystallization peak temperature (T-p) of SsPS ionomers are lower and SsPS-H > SsPS-Zn > SsPS-K > SsPS-Na, while the crystallinity (X-c) of SsPS-Zn is the lowest. Nonisothermal crystallization kinetics shows that the Avrami index of sPS and SsPS-H are both about 4, suggesting the nucleation growth of SsPS-H with lower degree of sulfonation still keeps its three-dimension form. FTIR spectra of SsPS ionomers show a splitting absorption band for asymmetric stretching vibration of sulfonation group. The CH in-plane bending vibration of benzene ring shifted to higher wavenumber and the symmetric stretching vibration of sulfonation group changed slightly with different counter ion neutralized SsPS ionomers.

Proton Conducting Composite Membranes from Sulfonated Polyether Ether Ketone and SiO_2

Proton conducting composite membranes from sulfonated polyether ether ketone and SiO2 for direct methanol fuel cell （DMFC） application were prepared with sulfonated polyether ether ketone（SPEEK） and tetracethoxy silane（TEOS） by sol-gel method. The covalent crosslinking structure was formed between —SO3H of SPEEK via SiO2. The SEM images show that the interfacial compatibility of SPEEK and SiO2 is improved obviously and SiO2 disperses uniformly in the polymer matrix and the particle diameter of SiO2 does not exceed 40 nm. The proton conductivity of composite membranes decreases slightly compared with the SPEEK membrane while the methanol permeability and swelling of composite membrane are improved remarkablely owing to covalent cross-linking between —SO3H and SiO2 .

Synthesis and Characterization of Ion-exchange Sulfonated Poly (ether sulfone)

N,N＇-Bis（3-hydroxyphenyl）-1,8,4,5-naphthalenetetracarboxylic bisimide was prepared from the reaction of 1,8,4,5-naphthalenetetrcarboxylic acid dianhydride and 2-aminophenol in N, N-dimethylformamide. Polymerization of this bisimide with 4,4＇-difluorodiphenylsulfone and disodium 3,3＇-disulfonate4,4＇-difluorodiphenylsulfone gave ion-exchange sulfonated poly（ether sulfone）. The structure of the title compound was characterized with H-NMR and its polymer was characterized with FT-IR.

Friction-reducing,Anti-wear and Self-repairing Properties of Sulfonated Graphene

The friction reducing properties of sulfonated graphene as a lubricating additive were investigated using a four-ball machine tester with high carbon chromium bearing steels GCr15（SAE52100） friction pairs. The microscopic morphology, elemental composition, and self-repairing properties were observed and analyzed by using scanning electronic microscopy（SEM）, X-ray diffraction（XRD） and digital microscopy. The relationships among sulfonated graphene ethanol solution concentration, friction coefficient, and abrasion loss were revealed. It was found that the optimal concentration of ethanol solution with the addition of sulfonated graphene was 0.15g/m L and the coefficient of friction was only 0.105 under certain condition. Then the stable chemical properties and good anti-corrosion properties of the metal-graphene layer were further confirmed using salt spray corrosion test. In summary, sulfonated graphene can be used as a new kind of self repairing additive, and it has excellent wear-resistant and self-repairing performances.

PREPARATION OF Au/SULFONATED POLYSTYRENE CATALYSTS FOR LOW-TEMPERATURE CO OXIDATION

Supported Au catalysts for low-temperature CO oxidation were prepared by solvated metal atom impregnation (SMAI) and conventional impregnation (Cl). X-ray photoelectron spectroscopy (XPS) investigations indicated that the elemental gold in all the samples was in the metallic state, XRD measurements showed that the mean diameters of Au particles prepared by SMAI were smaller than those prepared by Cl with the same gold content. Catalytic tests showed that the SMAI catalyst had higher CO oxidation activity than the CI catalyst with the same compositions. Both SMAI and Cl catalysts exhibited high activity in low temperature CO oxidation. Full CO conversion was obtained at 323-383K.

Harvesting Microalgae Biomass Using Sulfonated Polyethersulfone(SPES)/PES Porous Membranes in Forward Osmosis Processes

This study was performed to investigate the availability of forward osmosis(FO)for microalgae harvesting using sulfonated polyethersulfone(SPES)/PES porous membranes.In FO process,porous membranes(<25.0 L m^−2 h^−1)exhibited more superior water flux than TFC FO membranes(<2.6 L m^−2 h^−1).Furthermore,the incorporation of SPES has been demonstrated to enhance membrane performance.The effects of SPES content on pore structure and separation performance were investigated.Compared with pure PES porous membranes,porous membranes with 40%SPES yielded an improved hydrophilicity and greater porosity.It exhibited two times higher water fluxes than the pure PES porous membrane.For microalgae harvesting,AL-FS mode(active layer facing the feed solution)was more favourable than AL-DS mode(active layer facing the draw solution)because less deposited microalgae on the active layer mitigate the membrane biofouling.FO operation combined with SPES/PES porous membranes is conducive to preserving microalgae cell integrity under the mild condition.In addition,FO membrane can be cleaned by a simple water rinse.Potential implications were highlighted as a sustainable method for microalgae harvesting because of no pressure input and less chemical cleaning demand.