Synthesis of a Novel Solid Acid with both Sulfonic and Carbonyl Acid Groups and Its Catalytic Activities in Acetalization

The novel solid acid with both sulfonic and carbonyl acid groups has been synthesized from 3-((2-sulfoethoxy) carbonyl)acrylic acid and tetraethyl orthosilicate(TEOS). The catalytic activities were investigated through the acetalization. The results showed that the novel solid acid was very efficient for the reactions with the high yields. The high acidity, high stability and reusability were the key feature of the novel solid acid. Moreover, the sulfonic and carbonyl acid groups could cooperate during the catalytic process, which improved its catalytic activities. The catalyst shows recyclability, and hold great potential for replacement of homogeneous catalysts.

Octa-membered Water Ring Chain Based on Sulfonic Group in Ni(II) Complex with 2-[(E)-(2-Oxidophenyl)methyleneamino] Ethanesulfonato and 2,2′-Bipyridinyl

The title compound, [Ni（tssb）（2,2-bipy）2].5（H2O） 1 （tssbH2 =2-[（E）-（2-oxido- phenyl）methyleneamino]ethanesulfonato, 2,2-bipy = 2,2＇-bipyridinyl）, belongs to orthorhombic, space group Pbcn with a = 20.3983（18）, b = 17.6929（15）, c = 17.0897（15） nm, V= 6167.8（9） nm^3, Mr= 688.38, Z = 8, De = 1.481 g.cm^-3, F（000） = 2880,μ = 0.758 mm-1 and S =1.099. Each NiIr atom is six-coordinated by one N and one O atoms from one tssb^2- anion and four N atoms from two 2,2-bipy ligands to give a distorted octahedral geometry. Noticeably, there exists a rare octa-mem- bered water ring which presents a 1D chain by sulfonic group.

Modification of Interfacial Interaction of PBT/PP Blends by Adding Main-chain Liquid Crystalline Ionomer with Sulfonic Group

A main-chain liquid crystalline ionomer（MLCI） containing sulfonic group was synthesized by an interfacial condensation reaction.The MLCI was blended with polybutylene terephthalate（PBT） and polypropylene（PP）.MLCI interacted with both the dispersed（PP） phase and the matrix（PBT） phase to modify the interfacial interaction of PBT and PP.Differential scanning calorimetry（DSC）,scanning electron microscopy（SEM） and FTIR imaging system analysis demonstrated the significance of interfacial interaction in the polymer blends.MLCI brought about good adhesion at the interfacial,which reduced the disperse phase size and enabled a fine PP phase at matrix.The mechanical properties of the ternary blends were improved when a proper amount of MLCI was added.This was attributed to enhanced adhesion at the interface,which invoked better mechanical properties in the blends.

Regulating interfacial behavior of zinc metal anode via metal-organic framework functionalized separator

Aqueous zinc ion batteries(AZIBs)are one of the promising energy storage devices.However,uncontrolled dendrite and side reactions have seriously hindered its further application.In this study,the metal-organic framework(MOF)functionalized glass fiber separator(GF-PFC-31)was used to regulate interfacial behavior of zinc metal anode,enabling the development of high-performance AZIBs.In PFC-31,there areπ-πinteractions between two adjacent benzene rings with a spacing of 3.199 A.This spacing can block the passage of[Zn(H_(2)O)_6]^(2+)(8.6 A in diameter)through the GF-PFC-31 separator to a certain extent,which promotes the deposition process of Zn ions.In addition,the sulfonic acid group(-S03H)contained in GF-PFC-31 can form a hydrogen bonding network with H_(2)O,which can provide a desolvation effect and reduce the side reaction.Consequently,GF-PFC-31 separator achieves uniform deposition of Zn ions.The Zn‖GF-PFC-31‖Zn symmetric cell exhibits stable cycle life(3000 h at 1.2 mA cm^(-2),2000 h at 0.3 mA cm^(-2),and 2000 h at 5.0 mA cm^(-2)),and Zn‖GF-PFC-31‖MnO_(2) full cell with GF-PFC-31 separator can cycle for 1000 cycles at 1.2 A g^(-1)with capacity retention rate of 82.5%.This work provides a promising method to achieve high-performance AZIBs.

Fabrication of supported acid catalytic composite fibers by a simple and low-cost method and their application on the synthesis of liquid biofuel 5-ethoxymethylfurfural

In this paper,sulfonic groups functionalized annealed bio-based carbon microspheres loaded polytetrafluoroethylene(A-BCMSs-SO_(3)H@PTFE)fibers with high activity,high stability,and easy regeneration were successfully fabricated by a simple method using low-cost raw materials.The characterization results showed that the annealed biomass carbon microspheres derived from waste Camellia oleifera shells were evenly distributed on the polytetrafluoroethylene fibers and the sulfonic groups can be successfully loaded on the surface of annealed biomass carbon microspheres by room temperature sulfonation.Subsequently,the as-prepared A-BCMSs-SO_(3)H@PTFE fibers were applied to the acidcatalyzed synthesis of liquid biofuel 5-ethoxymethylfurfural.The catalytic experiment results indicated that the annealing temperature and time during catalyst preparation have a significant effect on the activity and selectivity of A-BCMSs-SO_(3)H@PTFE fibers.The results of catalytic reaction kinetics showed that the yield of 5-ethoxymethylfurfural can reach more than 60%after 72 h of acid-catalyzed reaction.The stability test showed that the as-prepared A-BCMSs-SO_(3)H@PTFE fibers still maintained a stable acid catalytic activity after four recycles.

Modified graphene‐based materials as effective catalysts for transesterification of rapeseed oil to biodiesel fuel

Production of biodiesel by the transesterification process using different modified graphene‐based materials as catalysts was studied.Solid acid graphene‐based samples were prepared by grafting sulfonic or phosphate groups on the surface of thermally reduced graphene oxide.The obtained materials were thoroughly characterized using scanning electron microscopy,X‐ray diffraction,thermogravimetric analysis,X‐ray photoelectron spectroscopy,N2 adsorption‐desorption measurements,potentiometric titration,elemental analysis,and Fourier transform infrared spectroscopy.The prepared catalysts were tested in the transesterification of rapeseed oil with methanol at 130°C under pressure,and their activities were compared to the performance of a commercially available heterogeneous acidic catalyst,Amberlyst‐15.All modified samples were active in the transesterification process;however,significant differences were observed in the yield of biodiesel,depending on the method of catalyst preparation and strength of the acidic sites.The highest yield of fatty acid methyl esters of 70%was obtained for thermally reduced graphene oxide functionalized with 4‐benzenediazonium sulfonate after 6 h of processing,and this result was much higher than that obtained for the commercial catalyst Amberlyst‐15.The results of the reusability test were also promising.

Synthesis, Structure and Physical Properties of a Barium(II) Complex with 5-Sulfoisophthalic Acid Sodium

An alkaline earth metal-organic framework [Ba（Hsip）（H2O）4]n （1, NaH2sip = 5-sulfoisophthalic acid sodium） has been constructed, and characterized by single-crystal X-ray diffraction. In complex 1, each Ba（II） atom coordinates to one ligand Hsip3- and four water molecules with a distorted nine-coordinated monocapped tetragonal antiprism geometry. Each Hsip2- anion acts as a μ3-bridging ligand, in which two carboxylate groups adopt the same bidentate chelating coordinating model and the sulfonate group takes a monodentate coordinating model, resulting in a wave-like two-dimensional network with a （6, 3） topological structure. The two-dimensional networks are further linked by O–H···O to form a three-dimensional structure. Luminescent property and thermal stability of complex 1 are investigated. 1 belongs to the orthorhombic system, space group Pna21 with a = 7.3333（2）, b = 16.7044（3）, c = 10.4817（2）, Z = 4, V = 1283.99（5）3, Mr = 453.58, Dc = 2.346 g/cm3, F（000） = 880, μ = 3.314 mm–1, the final R = 0.0261 and wR = 0.0592 for 2425 observed reflections with I 2σ（I）.

Effective and irreversible removal of radioactive barium ions in MOF-808 framework functionalized sulfonic acid groups

The simultaneous high-capacity and fast removal of radioactive barium ion(Ba^(2+))from nuclear wastewater is necessary but still faces large challenge.In this study,a novel adsorbent containing sulfonic group,MOF-808-SO_(3)H,was prepared based on the oxidation of-SH group.Characterizations confirm the successful introduction of-SO_(3)H,good porosity,and stability of the material.The adsorbent exhibits excellent capture ability for Ba^(2+)due to strong hard acid-base and electrostatic interactions,with the adsorption capacity of 152.0 mg g^(-1)and fast equilibrium adsorption time,superior to other reported materials.Optimal pH was found to be almost neutral and temperature cannot affect the adsorption largely.Besides,the irreversible adsorption was demonstrated and thereby the secondary pollution may be avoided.Therefore,our work provides an efficient adsorbent for capturing Ba^(2+)irreversibly,and proposes a feasible strategy for constructing adsorbents with simultaneous high adsorption capacity and fast kinetics.

Sulfonation of （1 →6）-β-D-Glucan （Lasiodiplodan） and Its Antioxidant and Antimicrobial Potential

The objective of this study was to investigate the sulfonation of （1→6）-β-D-glucan （lasiodiplodan） as a potentiating mechanism for biological functionalities. Lasiodiplodan was sulfonated by the chlorosulfonic acid-pyridine method. The modified exopolysaccharide was characterized by FT-IR and 13C NMR spectroscopy, X-ray diffraction and SEM. Antioxidant activity was assessed by the methods of H2O2 and OH radical removal and reducing power. Antimicrobial potential was evaluated by the broth-microdilution method. Sulfonation resulted in a derivative with DS of 0.24. FT-IR analysis indicated the introduction of sulfonyl groups in the macromolecule structure through specific bands in the regions of 1,240 cm-1 and 810 cm-1. 13C NMR analysis suggested that sulfonation occurred at carbon 2 of the glucose residue. Sulfonation led to morphological changes in the structure of the biopolymer resulting in a heterogeneous structure with the presence of fibrils. Derivatization promoted an increase in the antioxidant ability of the macromolecule, with a high OH removal potential （74.32%）. Bacteriostatic activity against E. coli （Escherichia coli） and S. enterica （Salmonella enterica） typhimurium and fungicidal activity against C. albicans （Candida albicans） and C. tropicalis （Candida tropicalis） were found in the sulfonated sample. Sulfonation potentiated the antioxidant and antimicrobial activities of the biomacromolecule, suggesting that it is a potentiating mechanism of biological functions.

Syntheses, Structure and Properties of a Strontium(Ⅱ) Complex with 5-Sulfoisophthalic Acid Monosodium

A new Sr（Ⅱ） complex, [Sr（Hsip）（H2O）] （1, NaH2sip = 5-sulfoisophthalic acid monosodium）, has been synthesized by solvothermal reaction of SrCO3 and NaH2sip at 120 ℃, and characterized by single-crystal X-ray diffraction studies, elemental analysis and FT-IR. Single- crystal X-ray diffraction reveals that compound 1 has a 3D architecture, and there is only one crystallographically independent Sr（Ⅱ） ion in 1. The coordination geometry of Sr（Ⅱ） is a distorted tetragonai anti-prism. The whole Hsip2- ligand performs aμ6-coordination model. In the solid state, complex 1 shows luminescence with the maximum emission intensity at 417 nm upon excitation at 320 nm. Thermal stability of complex 1 was also investigated.

Radiation-Induced Graft Polymerization of Sodium 4-Styrene Sulfonate onto Multiwalled Carbon Nanotubes and Their Application as Electrogenerated Chemiluminescence Biosensors

Sulfonate groups were introduced to the surfaces of multiwalled carbon nanotubes by the radiation-induced graft polymerization of sodium 4-styrene sulfonate for the use as biosensor supports. Alcohol dehydrogenase was immobilized onto a sulfonated nanotube-supporting electrode with tris（2,2＇-bipyridyl） ruthenium（II） complex to form an electrogenerated chemilluminesce sensor of alcohol. When it was used to detect alcohol in cyclic voltammetric measurements, the sensor showed the linearity over the range of 1.0 × 10^-4 M-5.0 ×10^-2 M, with a correlation coefficient of 0.992 and a detection limit of 1.9 ×10^-6 M. In electrogenerated chemilluminesce detection, it showed linearity over 5.0 × 10^-4 M-1.0 × 10^-2 M, with a correlation coefficient of 0.986 and a detection limit of 1.0 × 10^-6 M. The sensor was demonstrated to be able to detect ethanol in commercial drinks.

An unusual substitution reaction of an aromatic sulfonic group based on 3-carbonyl-4-phenolsulfonic acid

An unusual substitution reaction of an aromatic sulfonic group based on 3-carbonyl-4-phenolsulfonic acid was discovered in a diazo-coupling process. The reaction occurred under mild reaction conditions （pH 8.0-9.0, 0-5 ℃, solvent： water） within a short reaction time （1 h）. A plausible substitution reaction mechanism by phenol-ketone resonance was proposed.

Sulfonate group modified Ni catalyst for highly efficient liquid-phase selective hydrogenation of bio-derived furfural

The liquid-phase furfural （FAL） hydrogenation to furfuryl alcohol （FOL） and tetrahydrofurfuryl alcohol （THFOL） was investigated using sulfonate group （-SO3H） grafted activated carbon （AC） supported Ni catalyst, which was prepared and activated simultaneously by liquid phase reduction method. This functionalized nickel catalyst demonstrated an enhanced catalytic performance for selective hydrogenation of FAL, in which almost 100% FOL （〈80℃） and THFOL （〉100℃） selectivity with complete conversion was obtained, respectively. More importantly, the conversion of transfer hydrogenation of FAL to FOL also can reach almost 100% under optimal conditions （140℃, 4.0h）. The effect of -SO3H was evaluated and systematically analyzed by the combination of reaction performance and physico-chemical characterizations. Cycling test proved the prepared catalyst could be recycled and reused for several times without noticeably reducing catalytic activity of hvdrogenation.

Promotion of the oxygen evolution performance of Ni–Fe layered hydroxides via the introduction of a proton-transfer mediator anion

Developing efficient catalysts with high durability and activity for the oxygen evolution reaction(OER)is imperative for sustainable energy conversion technologies,including hydrogen generation and CO_(2) reduction,as well as other electrochemical energy storage systems.To this end,a comprehensive understanding of the mechanism for the water oxidation reaction is vital.Herein,a surfactant,nonafluoro-1-butanesulfonate(FBS),was introduced into Ni-Fe layered double hydroxide(Ni Fe-FBS/CFP)via electrochemical deposition on the surface of a carbon fiber paper(CFP)substrate.The as-prepared Ni Fe-FBS/CFP electrode exhibited excellent catalytic activities for OER compared to the Ni-Fe layered double hydroxide based electrode(Ni Fe-LDH/CFP),an excellent stability of 15 h,and an ultralow Tafel slope of 25.8 m V dec-1.Furthermore,by combining the results of p H-dependent kinetics investigations,chemical probing,proton inventory studies,and isotopic and atom-protontransfer measurements,it was observed that a proton-transfer process controls the reaction rates of both the Ni Fe-LDH and Ni Fe-FBS catalysts,and the residual sulfonate groups serve as proton transfer mediator to accelerate the proton transfer rate.

Increased Hydrogen-bonding of Poly(m-phenylene isophthalamide) (PMIA) with Sulfonate Moiety for High-performance Easily Dyeable Fiber

The demand for high thermal stability and high strength agents is growing steadily as a result of their increasing application in advanced materials.A series of sulfonated poly(m-phenyleneisophthalamide)(SPMIA)copolymers with superior thermal stability and good mechanical properties have been prepared via low temperature polycondensation method.Then the structures of 5PMA copolymers with different content quantities of 2,4-diaminobenzenesulfonic acid(2,4-DABSA)were confimed by Fourier transform infrared(FTiR).Besides,their superior thermal properties were systematically investigated by differential canning calorimetry DSC),thermalgravimetreic analysis(TGA),and dynamic mechanical analysis(DMA).SPMA fbers were obtained by wet spinning using the resultant SPMIAsolutions.n addition,the obtained SPMIA fibers were proved to combine enhanced mechanical properties and unprecedented dyeability.Significantly,the SPMlA iber with great mechanical property,thermal stability,and dyeability shows great potential in easily dyeing high-performance protective fibers.

A Sulfonate-based Metal-organic Framework for the Transformation of CO and Epoxides into Cyclic Carbonates

An interesting metal-organic framework(MOF) PFC-31 was synthesized by a simple solvothermal reaction. X-ray crystallography reveals that PFC-31 crystallizes in monoclinic system, space group P21/c with a = 6.8410(17), b = 20.123(5), c = 7.689(2) ?, β = 104.239(7)°, V = 1026.0(5) ?3, Z = 2, C16 H22 CuN4 O8 S2, Mr = 526.03, μ = 1.322 mm-1, Dc = 1.703 g/cm3, F(000) = 542, GOOF = 1.214, R = 0.0975 and w R = 0.2324. According to X-ray analysis, PFC-31 shows one-dimensional chain constructed by Cu(Ⅱ) centers coordinating with two pyridine groups, two sulfonate groups and two DMF molecules. Owing to the orderly functionalized sulfonate group and Lewis metal sites, PFC-31 exhibits good catalytic capability for CO2 cycloaddition of epoxide under normal pressure and temperature.