The temperature-induced molecular chain motions of styrenic triblock copolymers （SBC）, i.e. polysty- rene-block-polybutadiene-block-polystyrene （SBS） and polystyrene-block-poly（ethylene-co-l-butene）-block-poly- ...The temperature-induced molecular chain motions of styrenic triblock copolymers （SBC）, i.e. polysty- rene-block-polybutadiene-block-polystyrene （SBS） and polystyrene-block-poly（ethylene-co-l-butene）-block-poly- styrene （SEBS）, were studied by intrinsic fluorescence method. For SBS, the glass transition temperatures （Tgs） of B block and S block obtained by intrinsic fluorescence method were in good agreement with differential scanning calorimetry measurements （DSC）. In the case of SEBS, an isoemission point was observed at about 310 nm at ele- vated temperatures, suggesting the slight conversion between the monomer and excimer emission. On this basis, the molecular chain motion of SEBS was monitored by both fluorescence intensity and excimer/monomer fluorescence ratio. Besides the Tgs of S block and EB blocks, a melting point （Tin） of weak crystalline in EB block was unambiguously determined by intrinsic fluorescence. Furthermore, it was found that the melting process directly led to the slight loosening of PS segments in interface and consequently the reduction of the amount of excimer. A reasonable mechanism was proposed to describe the molecular chain movements and phase transitions of SEBS upon heating. Moreover, the influence of temperature on the apparent activation energy of non-radiative process （ E^T ） around Tg of S block was much stronger than that around Tg of B or EB blocks.展开更多
The efficient separation of styrene(ST)and ethylbenzene(EB)remains a significant challenge in the petrochemical industry due to their similar physical properties and kinetic molecular sizes.In this study,we cleverly u...The efficient separation of styrene(ST)and ethylbenzene(EB)remains a significant challenge in the petrochemical industry due to their similar physical properties and kinetic molecular sizes.In this study,we cleverly utilized the voids of a fluorescent flexible hydrogen-bonded organic framework(X-HOF-10)constructed from a pure organic phenothiazine derivative with three cyano groups(PTTCN)to selectively adsorb and separate ST and EB based on their slight size difference.Single crystal structure analysis and fluorescence spectra reveal that the adsorption process of ST involves a gate-opening mechanism accompanied by a fluorescent color switch behavior.Upon simple heating,ST can be released from the voids through a gate-closing process.Conversely,exposure to EB vapor does not promote X-HOF-10a to adsorb EB due to its slightly larger size in comparison with ST,facilitating a single crystal to single crystal transition,leading to the formation of a new non-porous crystal without EB.Under equimolar vapor condition,X-HOF-10a transforms into X-HOF-10 rather than X-HOF-11 owing to the superior stability of X-HOF-10over X-HOF-11,accompanied by selective adsorption of ST.The purity of ST can reach 92%after release from the framework,which further increases to over 98%when exposed to the mixed vapor containing 90%ST.Additionally,this HOF material exhibits recyclability without any discernible loss in performance.展开更多
The sulfonated poly(α-methyl styrene-b-isobutylene-b-α-methyl styrene)copolymers(S-ASIBS)with the average molar percentage of sulfonic acid(-SO_(3)H)groups(SP)ranging from 3.6 mol%to 14.3 mol%could be synthesized by...The sulfonated poly(α-methyl styrene-b-isobutylene-b-α-methyl styrene)copolymers(S-ASIBS)with the average molar percentage of sulfonic acid(-SO_(3)H)groups(SP)ranging from 3.6 mol%to 14.3 mol%could be synthesized by sulfonation of ASIBS with acetyl sulfate.The hydrophilic ionic channels were generated for proton exchange membranes(PEMs)by ion aggregation of-SO_(3)H groups and microphase separation between hydrophobic polyisobutylene and hydrophilic sulfonated poly(α-methyl styrene)segments in S-ASIBS.The proton transport ability was improved while oxidative stability was decreased by increasing SP in S-ASIBS.The appropriate SP of about 12.7 mol%in S-ASIBS provides the available PEMs with high proton transport ability,low methanol permeability and good oxidative stability.The absence of active tertiary hydrogen atoms along S-ASIBS copolymer chains avoids their attack by peroxy radicals.The residual rates of weight(RW)and proton conductivity(Rσ)of S-ASIBS-12.7 membrane after oxidation treatment for 916 h were 84.3%and 88.1%respectively,near to those of commercial Nafion 117(RW=87.9%,Rσ=90.3%).The membrane electrode assembly(MEA)could be prepared by using various S-ASIBS as PEMs for direct methanol fuel cell.The single cell with S-ASIBS-12.7 MEA behaves high performance of open circuit voltage(OCV)of 548 mV and peak power density(Pmax)of 36.1 mW·cm^(-2),which is similar to those of Nafion 117(OCV=506 mV,P_(max)=35.6 mW·cm^(-2)).To the best of our knowledge,this is the first example of advanced S-ASIBS membrane with high proton conductivity,excellent fuel barrier property and remarkable oxidative stability for promising PEMs.展开更多
Chiral 3-aryl alkanoic acids and their derivatives present a class of highly valued framework in natural products and pharmaceuticals.Among multifarious synthetic strategies,asymmetric intermolecular hydrocarbonylatio...Chiral 3-aryl alkanoic acids and their derivatives present a class of highly valued framework in natural products and pharmaceuticals.Among multifarious synthetic strategies,asymmetric intermolecular hydrocarbonylation ofα-alkyl styrenes exhibit high atom-economy and straightforwardness,nonetheless facing problems in simultaneously addressing the activity,chemoselectivity,regioselectivity and stereoselectivity of the strategy,which remain unresolved to date.Herein,we disclosed an enantioselective Pd-catalyzed exclusive anti-Markovnikov hydroesterification ofα-alkyl styrenes with thiols(hydrothiocarbonylation).The catalytic system,consisting of Pd source,chiral sulfoxide phosphine ligand(SOP),pTs OH·H_(2)O and Li Cl,efficiently achieved the correspondingα-chiral 3-aryl alkanoic thioesters in excellent results(68 examples,up to 99%yield,generally 90%-98%ee).The chloride anion from lithium chloride(Li Cl)acts as a coordinating ligand for palladium,promoting the activity while simultaneously enhancing stereochemical control.Moreover,the potential of the method was demonstrated by the late-stage functionalization of natural products,formal synthesis of biologically active molecules intermediates(RC-33,AM-6226)as well as intermediate analogue of R-106578.展开更多
This study investigates the potential of metal additives in acrylonitrile butadiene styrene(ABS)polymer fuel to enhance hybrid rocket motor(HRM)performance through computational analysis,Chemical Equilibrium with Appl...This study investigates the potential of metal additives in acrylonitrile butadiene styrene(ABS)polymer fuel to enhance hybrid rocket motor(HRM)performance through computational analysis,Chemical Equilibrium with Applications(CEA),software.ABS was selected as the base fuel due to its thermoplastic nature,which allows for the creation of complex fuel geometries through 3D printing,offering significant flexibility in fuel design.Hybrid rockets,which combine a solid fuel with a liquid oxidiser,offer advantages in terms of operational simplicity and safety.However,conventional polymer fuels often exhibit low regression rates and suboptimal combustion efficiencies.In this research,we evaluated a range of metal additives-aluminium(Al),boron(B),nickel(Ni),copper(Cu),and iron(Fe)-at chamber pressures ranging from 1 to 30 bar and oxidiser-to-fuel(O/F)ratios between 1.1 and 12,resulting in 1800 unique test conditions.The main performance parameters used to assess each formulation were characteristic velocity(C^(*))and adiabatic flame temperature.The results revealed that each test produced a different optimum O/F ratio,with most ratios falling between 4 and 6.The highest performance was achieved at a chamber pressure of 30 bar across all formulations.Among the additives,Al and B demonstrated significant potential for improved combustion performance with increasing metal loadings.In contrast,Fe,Cu,and Ni reached optimal performance at a minimum loading of 1%.Future work includes investigating B-Al metal composites as additives into the ABS base polymer fuel,and doing experimental validation tests where the metallised ABS polymer fuel is 3D printed.展开更多
The heterogeneously copper-catalyzed oxidative cleavage of styrene was studied using copper-doped mesoporous KIT-6（CU-KIT-6_x） prepared via pH adjustment（where x is the pH：1.43,2.27,3.78,3.97,4.24 or 6.62）.Variat...The heterogeneously copper-catalyzed oxidative cleavage of styrene was studied using copper-doped mesoporous KIT-6（CU-KIT-6_x） prepared via pH adjustment（where x is the pH：1.43,2.27,3.78,3.97,4.24 or 6.62）.Variations in the catalyst structure and morphology with pH values were characterized by X-ray power diffraction,nitrogen adsorption-desorption analysis,transmission electron microscopy and X-ray photoelectron spectroscopy.As the pH value applied during the initial synthesis,the resulting Cu-KIT-6_x exhibited different structural,textural and surface characteristics,especially in terms of specific copper species and copper content At a pH value of 3.78,approximately 4.6 wt%copper（Ⅱ） was successfully incorporated into the framework of the initial KIT-6,in the form of-Cu-O-Si- groups.The catalytic performance of each catalyst was evaluated by following the epoxidation of styrene,employing tert-butyl hydroperoxide as the oxidant and CH_3CN as the solvent.A significant styrene conversion of 43.5%with 86.6%selectivity for the desired styrene epoxide was obtained over the Cu-KIT-63.78.A higher Cu content,an ordered cubic laid mesoporous architecture and various specific textural characteristics all combined to endow the Cu-KIT-63.78 with high catalytic activity and good stability.展开更多
The polymerization of styrene is monitored by pyrene excimer formation. The ratio of monomer to excimer intensities ( I m/ I e) of pyrene increases as polymerization proceeds. The increase of I m/ I e...The polymerization of styrene is monitored by pyrene excimer formation. The ratio of monomer to excimer intensities ( I m/ I e) of pyrene increases as polymerization proceeds. The increase of I m/ I e is ascribed to the increase of microviscosity surrounding the probes forming excimer during polymerization. The linear relationship between the changing rate of I m/ I e and the polymerization rate of styrene is obtained. Therefore, I m/ I e may be used to monitor the progress of the polymerization of styrene.展开更多
The products of thermal desorption were generated under the temperature of 280 ℃ and were analyzed by gas chromatography-mass spectrometry with capillary column,the residual monomer styrene was no detected.The produc...The products of thermal desorption were generated under the temperature of 280 ℃ and were analyzed by gas chromatography-mass spectrometry with capillary column,the residual monomer styrene was no detected.The products of pyrolysis were generated under the temperature of 550 ℃ and were analyzed by chromatography-mass spectrometry,14 compounds were detected.展开更多
[Objective] The paper was to study the structure and performance of starch and styrene graft copolymer. [Method] The microscopic structure of corn starch and styrene graft copolymer was analyzed by using infrared spec...[Objective] The paper was to study the structure and performance of starch and styrene graft copolymer. [Method] The microscopic structure of corn starch and styrene graft copolymer was analyzed by using infrared spectrum and scanning electron microscope, and the property of starch and styrene graft copoly- mer was confirmed through grinding experiment, tensile strength, water absorption rate, hot water resistance properties and enzymatic properties analysis. [Result] The starch and styrene graft copolymer had the properties of thermoplastic and microbial degradation. IConclusion] The starch and styrene graft copolymer is expected to be developed as a biodegradable material.展开更多
Bottled water may not be safer, or healthier, than tap water. The present studies have proved that styrene and some other aromatic compounds leach continuously from polystyrene （PS） bottles used locally for packagin...Bottled water may not be safer, or healthier, than tap water. The present studies have proved that styrene and some other aromatic compounds leach continuously from polystyrene （PS） bottles used locally for packaging. Water sapmles in contact with PS were extracted by a preconcentration technique called as ＂purge and trap＂ and analysed by gas chromatograph-mass spectrometer （GC/MS）. Eleven aromatic compounds were identified in these studies. Maximum concentration of styrene in PS bottles was 29.5 μg/L. Apart from styrene, ethyl benzene, toluene and benzene were also quantified but their concentrations were much less than WHO guide line values. All other compounds were in traces. Quality of plastic and storage time were the major factor in leaching of styrene. Concentration of styrene was increased to 69.53 μg/L after one-year storage. In Styrofoam and PS cups studies, hot water was found to be contaminated with styrene and other aromatic compounds. It was observed that temperature played a major role in the leaching of styrene monomer from Styrofoam cups. Paper cups were found to be safe for hot drinks.展开更多
Using cetyl-trimethyl-ammonium bromide （CTMAB） as the template agent and tetraethylorthosilicate （TEOS） as the silica source, the MCM-41 mesoporous materials were synthesized with La or Ce incorporated in the fram...Using cetyl-trimethyl-ammonium bromide （CTMAB） as the template agent and tetraethylorthosilicate （TEOS） as the silica source, the MCM-41 mesoporous materials were synthesized with La or Ce incorporated in the framework under hydrothermal conditions. The structure and the state of La or Ce were investigated through the analyses of XRD, nitrogen adsorption-desorption, FT-IR, and UV-Vis. XRD and N2 adsorption-desorption results showed that Ln-MCM-41 exhibited the loss of the lattice ordering of the MCM-41 construct, and larger unit cell parameter and pore diameter than pure silica MCM-41. The FT-IR and UV-Vis results indicated the presence of isolated tetra-coordinated La or Ce ions in the framework and other Ln species dispersed highly on the Ln-MCM-41 surface simultaneously. Furthermore, their catalytic behaviors in the oxidation of styrene were studied using H2O2 as the oxidant. The La-MCM-41 catalysts exhibited high reactivity and the reactivity increased with the increase of the La content in the La-MCM-41 samples. On the contrary, Ce-MCM-41 catalysts showed low reactivity in the oxidation of styrene and the conversion of styrene decreased with the increase of the Ce content in the Ce-MCM-41 samples.展开更多
La-doped and La-B-doped KIT-6 mesoporous materials were prepared by direct hydrothermal synthesis with pH-adjusting method and characterized by X-ray diffractometer(XRD),nitrogen sorption,FT-IR,UV-Vis,X-ray photoelect...La-doped and La-B-doped KIT-6 mesoporous materials were prepared by direct hydrothermal synthesis with pH-adjusting method and characterized by X-ray diffractometer(XRD),nitrogen sorption,FT-IR,UV-Vis,X-ray photoelectron spectroscopy(XPS) and ICP-AES.The catalytic performance for the oxidation of styrene by hydrogen peroxide,tert-butyl hydroperoxide or oxygen was investigated.The results showed that the introduction of heteroatoms did not destroy the mesostructure of KIT-6 with cubic Ia3d space group.La or ...展开更多
A series of calcined HTLcs catalysts were prepared and modified with potassium phosphate by impregnation method to clarify the influence of catalyst alkalinity on the side chain alkylation of toluene with methanol for...A series of calcined HTLcs catalysts were prepared and modified with potassium phosphate by impregnation method to clarify the influence of catalyst alkalinity on the side chain alkylation of toluene with methanol for synthesis of ethylbenzene and styrene.The catalysts were characterized by X-ray diffraction(XRD),N_(2)physical adsorption-desorption,Fourier-transform infrared spectroscopy(FT-IR),Scanning electron microscopy(SEM),X-ray photoelectron spectrometry(XPS),NH_(3)temperature-programmed desorption(NH_(3)-TPD)and CO_(2)temperature-programmed desorption(CO_(2)-TPD).It was found that the selectivity of styrene was highest(39.25%)when the K_(3)PO_(4)loading was 7.5 wt%.And the total yield of styrene and ethylbenzene could reach 65.08%with 10 wt%K_(3)PO_(4)loading.This might due to the fact that the addition of K_(3)PO_(4)could adjust the acid and basic sites of catalysts.In addition,appropriate strength and amount of basic sites were favorable to producing more styrene.展开更多
The adsorption behavior and description behavior of benzene , ethylene and ethylbenzene over HZSM-5 and Co/HZSM-5 catalysts were studied by means of TPSR (Temperature programmed surface reaction) technique. TPSR resul...The adsorption behavior and description behavior of benzene , ethylene and ethylbenzene over HZSM-5 and Co/HZSM-5 catalysts were studied by means of TPSR (Temperature programmed surface reaction) technique. TPSR results of ben- zene and ethylene co-adsorption show that the maian products are styrene , ethylben- zene, toluene, propane, and butane. In a separate experiment of ethylbenzene ad- sorption, styrene . toluene and benzene are formed due to cracking and dehydro- genation. The mechanism of styrene formation was proposed , i. e. , the reaction was carried out via. the dehydrogenation of mediate species ethylbenzene according to the results of TPSR-MS , activity testing and thermodynamic analysis.展开更多
Different mole ratio Al-B catalysts (Al-10B to Al-35B) were synthesized by using sol-gel (SG) method. Ethyl benzene (EB) dehydrogenation in the presence of oxygen and water steam was carried out on these catalysts at ...Different mole ratio Al-B catalysts (Al-10B to Al-35B) were synthesized by using sol-gel (SG) method. Ethyl benzene (EB) dehydrogenation in the presence of oxygen and water steam was carried out on these catalysts at 450–500℃ with EB contact time of 0.54 gcat.s.cm^–3. Acidity of Al-B catalysts was estimated by using NH3-TPD-mass spectral analysis studies. SEM-mapping images revealed fine distribution of boron up to 15% of its loading in alumina (Al-15B), whereas, boron aggregation was observed in higher boron content (Al-25B and Al-35B) catalysts. Essentially, acid sites of very weak strength (Tmax ≤ 125℃) were observed for Al and Al-10B catalysts and resulted in low EB conversion and styrene yield. On the other hand, acid sites of weak strength (Tmax ≤ 180℃) were observed for Al-25B and Al-35B catalysts and resulted in high EB conversion. However, greater styrene yield (43.2%) with reasonable EB conversion (46%) was obtained on acid sites of weak moderate strength in Al-15B catalyst. Further, Al-15B catalyst was synthesized by using co-precipitation (COP) and impregnation (IMP) methods. Acid sites related to NOx formation during the NH3-TPD-mass analysis on IMP and COP catalyst essentially improved the EB conversion to 66% and 63% respectively at 500℃. However, these acid sites were diminished in Al-B SG catalyst and resulted in 50% of EB conversion at 500 ℃. At 50% of EB conversion level, styrene selectivity of 73%, 82.5% and 84% were observed on Al-B IMP, Al-B COP and Al-SG catalysts, respectively. Hence, different method of preparation of Al-B catalyst generated acid sites of different strength and density and thereby influenced the styrene formation.展开更多
Dehydrogenation of ethylbenzene （EB） to styrene （ST） in the presence of CO2, in which EB dehydrogenation is coupled with the reverse water-gas shift （RWGS）, was investigated extensively through both theoretical ...Dehydrogenation of ethylbenzene （EB） to styrene （ST） in the presence of CO2, in which EB dehydrogenation is coupled with the reverse water-gas shift （RWGS）, was investigated extensively through both theoretical analysis and experimental characterization. The reaction coupling proved to be superior to the single dehydrogenation in several respects. Thermodynamic analysis suggests that equilibrium conversion of EB can be improved greatly by reaction coupling due to the simultaneous elimination of the hydrogen produced from dehydrogenation. Catalytic tests proved that iron and vanadium supported on activated carbon or Al2O3 with certain promoters are potential catalysts for this coupling process. The catalysts of iron and vanadium are different in the reaction mechanism, although ST yield is always associated with CO2 conversion over various catalysts. The two-step pathway plays an important role in the coupling process over Fe/Al2O3, while the one-step pathway dominates the reaction over V/Al2O3. Coke deposition and deep reduction of active components are the major causes of catalyst deactivation. CO2 can alleviate the catalyst deactivation effectively through preserving the active species at high valence in the coupling process, though it can not suppress the coke deposition.展开更多
The flotation performances of styrene phosphonic acid（SPA） to synthetic（Ce,La）2O3（REO）, calcium fluorite（CaF2） and fluorapatite（Ca5F（PO4）3） were investigated by flotation tests, flotation of synthetic mixe...The flotation performances of styrene phosphonic acid（SPA） to synthetic（Ce,La）2O3（REO）, calcium fluorite（CaF2） and fluorapatite（Ca5F（PO4）3） were investigated by flotation tests, flotation of synthetic mixed mineral, the surface adsorption capacity and the polarizing microscopy to solve the flotation separation problem of rare earth oxides from roasted concentrate. The flotation test results indicated that compared with CaF2 and Ca5F（PO4）3, SPA exhibited superior collecting performance to direct flotation recovery of REO and floated out above 90% REO at pH 3–6. However, the collecting ability of SPA to CaF2 and Ca5F（PO4）3 was extremely weak and the highest recovery was only 20% at pH 2–11. The flotation of synthetic mixed mineral showed that SPA was a good collector reagent for flotation of synthetic REO at pH 5, so REO, CaF2 and Ca5F（PO4）3 could be separated from roasted concentrate by using SPA as a collector. The surface adsorption capacity tests and polarizing microscopy results confirmed that SPA was adsorbed on REO surface, while CaF2 and Ca5F（PO4）3 were not. The adsorption mechanism of SPA to synthetic REO was studied by solution chemistry analysis of collector, the ζ-potential tests, infrared spectroscopy and X-ray photoelectron spectroscopy（XPS） analyses. The results indicated that SPA was physically adsorbed onto REO surface, which exhibited excellent flotation selectivity to REO against CaF2 and Ca5F（PO4）3.展开更多
The morphology effect of Zr-doped CeOwas studied in terms of their activities in the selective oxidation of styrene to styrene oxide using tert-butyl hydroperoxide as the oxidant. In the present work, Zrdoped CeOnanor...The morphology effect of Zr-doped CeOwas studied in terms of their activities in the selective oxidation of styrene to styrene oxide using tert-butyl hydroperoxide as the oxidant. In the present work, Zrdoped CeOnanorods exhibited the highest catalytic performance（yield of styrene oxide and TOF value）followed by nanoparticles and nanocubes. For the Zr-doped CeOnanorods, the apparent activation energy is 56.3 k J/mol, which is much lower than the values of catalysts supported on nanoparticles and nanocubes（73.3 and 93.4 k J/mol）. The high resolution transmission electron microscopy results indicated that（100） and（110） crystal planes are predominantly exposed for Zr-doped CeOnanorods while（100）and（111） for nanocubes,（111） for nanoparticles. The remarkably increased catalytic activity of the Zrdoped CeOnanorods is mainly attributed to the higher percentage of Cespecies and more oxygen vacancies, which are associated with their exposed（100） and（110） crystal planes. Furthermore, recycling studies proved that the heterogeneous Zr-doped CeOnanorods did not lose its initial high catalytic activity after five successive recycles.展开更多
文摘The temperature-induced molecular chain motions of styrenic triblock copolymers （SBC）, i.e. polysty- rene-block-polybutadiene-block-polystyrene （SBS） and polystyrene-block-poly（ethylene-co-l-butene）-block-poly- styrene （SEBS）, were studied by intrinsic fluorescence method. For SBS, the glass transition temperatures （Tgs） of B block and S block obtained by intrinsic fluorescence method were in good agreement with differential scanning calorimetry measurements （DSC）. In the case of SEBS, an isoemission point was observed at about 310 nm at ele- vated temperatures, suggesting the slight conversion between the monomer and excimer emission. On this basis, the molecular chain motion of SEBS was monitored by both fluorescence intensity and excimer/monomer fluorescence ratio. Besides the Tgs of S block and EB blocks, a melting point （Tin） of weak crystalline in EB block was unambiguously determined by intrinsic fluorescence. Furthermore, it was found that the melting process directly led to the slight loosening of PS segments in interface and consequently the reduction of the amount of excimer. A reasonable mechanism was proposed to describe the molecular chain movements and phase transitions of SEBS upon heating. Moreover, the influence of temperature on the apparent activation energy of non-radiative process （ E^T ） around Tg of S block was much stronger than that around Tg of B or EB blocks.
基金supported by the Scientific Research Foundation of Tianjin Normal University(No.5RL151)the Tianjin Research Innovation Project for Postgraduate Students(No.2022SKY252)+1 种基金the National Natural Science Foundation of China(NSFC,Nos.22265026,22002108)the Project of Qinghai Science&Technology Department(No.2024-ZJ-935)。
文摘The efficient separation of styrene(ST)and ethylbenzene(EB)remains a significant challenge in the petrochemical industry due to their similar physical properties and kinetic molecular sizes.In this study,we cleverly utilized the voids of a fluorescent flexible hydrogen-bonded organic framework(X-HOF-10)constructed from a pure organic phenothiazine derivative with three cyano groups(PTTCN)to selectively adsorb and separate ST and EB based on their slight size difference.Single crystal structure analysis and fluorescence spectra reveal that the adsorption process of ST involves a gate-opening mechanism accompanied by a fluorescent color switch behavior.Upon simple heating,ST can be released from the voids through a gate-closing process.Conversely,exposure to EB vapor does not promote X-HOF-10a to adsorb EB due to its slightly larger size in comparison with ST,facilitating a single crystal to single crystal transition,leading to the formation of a new non-porous crystal without EB.Under equimolar vapor condition,X-HOF-10a transforms into X-HOF-10 rather than X-HOF-11 owing to the superior stability of X-HOF-10over X-HOF-11,accompanied by selective adsorption of ST.The purity of ST can reach 92%after release from the framework,which further increases to over 98%when exposed to the mixed vapor containing 90%ST.Additionally,this HOF material exhibits recyclability without any discernible loss in performance.
基金financially supported by the National Natural Science Foundation of China (No. 21774006)
文摘The sulfonated poly(α-methyl styrene-b-isobutylene-b-α-methyl styrene)copolymers(S-ASIBS)with the average molar percentage of sulfonic acid(-SO_(3)H)groups(SP)ranging from 3.6 mol%to 14.3 mol%could be synthesized by sulfonation of ASIBS with acetyl sulfate.The hydrophilic ionic channels were generated for proton exchange membranes(PEMs)by ion aggregation of-SO_(3)H groups and microphase separation between hydrophobic polyisobutylene and hydrophilic sulfonated poly(α-methyl styrene)segments in S-ASIBS.The proton transport ability was improved while oxidative stability was decreased by increasing SP in S-ASIBS.The appropriate SP of about 12.7 mol%in S-ASIBS provides the available PEMs with high proton transport ability,low methanol permeability and good oxidative stability.The absence of active tertiary hydrogen atoms along S-ASIBS copolymer chains avoids their attack by peroxy radicals.The residual rates of weight(RW)and proton conductivity(Rσ)of S-ASIBS-12.7 membrane after oxidation treatment for 916 h were 84.3%and 88.1%respectively,near to those of commercial Nafion 117(RW=87.9%,Rσ=90.3%).The membrane electrode assembly(MEA)could be prepared by using various S-ASIBS as PEMs for direct methanol fuel cell.The single cell with S-ASIBS-12.7 MEA behaves high performance of open circuit voltage(OCV)of 548 mV and peak power density(Pmax)of 36.1 mW·cm^(-2),which is similar to those of Nafion 117(OCV=506 mV,P_(max)=35.6 mW·cm^(-2)).To the best of our knowledge,this is the first example of advanced S-ASIBS membrane with high proton conductivity,excellent fuel barrier property and remarkable oxidative stability for promising PEMs.
基金supported financially by National Nature Science Foundation of China(No.22171258)the Youth Innovation Promotion Association CAS(No.2022375)+1 种基金the Biological Resources Programme,Chinese Academy of Sciences(No.KFJ-BRP-008)the Sichuan Science and Technology Program(No.2022ZYD0038)。
文摘Chiral 3-aryl alkanoic acids and their derivatives present a class of highly valued framework in natural products and pharmaceuticals.Among multifarious synthetic strategies,asymmetric intermolecular hydrocarbonylation ofα-alkyl styrenes exhibit high atom-economy and straightforwardness,nonetheless facing problems in simultaneously addressing the activity,chemoselectivity,regioselectivity and stereoselectivity of the strategy,which remain unresolved to date.Herein,we disclosed an enantioselective Pd-catalyzed exclusive anti-Markovnikov hydroesterification ofα-alkyl styrenes with thiols(hydrothiocarbonylation).The catalytic system,consisting of Pd source,chiral sulfoxide phosphine ligand(SOP),pTs OH·H_(2)O and Li Cl,efficiently achieved the correspondingα-chiral 3-aryl alkanoic thioesters in excellent results(68 examples,up to 99%yield,generally 90%-98%ee).The chloride anion from lithium chloride(Li Cl)acts as a coordinating ligand for palladium,promoting the activity while simultaneously enhancing stereochemical control.Moreover,the potential of the method was demonstrated by the late-stage functionalization of natural products,formal synthesis of biologically active molecules intermediates(RC-33,AM-6226)as well as intermediate analogue of R-106578.
文摘This study investigates the potential of metal additives in acrylonitrile butadiene styrene(ABS)polymer fuel to enhance hybrid rocket motor(HRM)performance through computational analysis,Chemical Equilibrium with Applications(CEA),software.ABS was selected as the base fuel due to its thermoplastic nature,which allows for the creation of complex fuel geometries through 3D printing,offering significant flexibility in fuel design.Hybrid rockets,which combine a solid fuel with a liquid oxidiser,offer advantages in terms of operational simplicity and safety.However,conventional polymer fuels often exhibit low regression rates and suboptimal combustion efficiencies.In this research,we evaluated a range of metal additives-aluminium(Al),boron(B),nickel(Ni),copper(Cu),and iron(Fe)-at chamber pressures ranging from 1 to 30 bar and oxidiser-to-fuel(O/F)ratios between 1.1 and 12,resulting in 1800 unique test conditions.The main performance parameters used to assess each formulation were characteristic velocity(C^(*))and adiabatic flame temperature.The results revealed that each test produced a different optimum O/F ratio,with most ratios falling between 4 and 6.The highest performance was achieved at a chamber pressure of 30 bar across all formulations.Among the additives,Al and B demonstrated significant potential for improved combustion performance with increasing metal loadings.In contrast,Fe,Cu,and Ni reached optimal performance at a minimum loading of 1%.Future work includes investigating B-Al metal composites as additives into the ABS base polymer fuel,and doing experimental validation tests where the metallised ABS polymer fuel is 3D printed.
基金supported by Guangdong Science and Technology Planning Project(2015A020216002)Guangdong Natural Science Foundation(2014A030313259)the National Natural Science Foundation of China(21543014,21173086,U1301245)~~
文摘The heterogeneously copper-catalyzed oxidative cleavage of styrene was studied using copper-doped mesoporous KIT-6（CU-KIT-6_x） prepared via pH adjustment（where x is the pH：1.43,2.27,3.78,3.97,4.24 or 6.62）.Variations in the catalyst structure and morphology with pH values were characterized by X-ray power diffraction,nitrogen adsorption-desorption analysis,transmission electron microscopy and X-ray photoelectron spectroscopy.As the pH value applied during the initial synthesis,the resulting Cu-KIT-6_x exhibited different structural,textural and surface characteristics,especially in terms of specific copper species and copper content At a pH value of 3.78,approximately 4.6 wt%copper（Ⅱ） was successfully incorporated into the framework of the initial KIT-6,in the form of-Cu-O-Si- groups.The catalytic performance of each catalyst was evaluated by following the epoxidation of styrene,employing tert-butyl hydroperoxide as the oxidant and CH_3CN as the solvent.A significant styrene conversion of 43.5%with 86.6%selectivity for the desired styrene epoxide was obtained over the Cu-KIT-63.78.A higher Cu content,an ordered cubic laid mesoporous architecture and various specific textural characteristics all combined to endow the Cu-KIT-63.78 with high catalytic activity and good stability.
文摘The polymerization of styrene is monitored by pyrene excimer formation. The ratio of monomer to excimer intensities ( I m/ I e) of pyrene increases as polymerization proceeds. The increase of I m/ I e is ascribed to the increase of microviscosity surrounding the probes forming excimer during polymerization. The linear relationship between the changing rate of I m/ I e and the polymerization rate of styrene is obtained. Therefore, I m/ I e may be used to monitor the progress of the polymerization of styrene.
文摘The products of thermal desorption were generated under the temperature of 280 ℃ and were analyzed by gas chromatography-mass spectrometry with capillary column,the residual monomer styrene was no detected.The products of pyrolysis were generated under the temperature of 550 ℃ and were analyzed by chromatography-mass spectrometry,14 compounds were detected.
文摘[Objective] The paper was to study the structure and performance of starch and styrene graft copolymer. [Method] The microscopic structure of corn starch and styrene graft copolymer was analyzed by using infrared spectrum and scanning electron microscope, and the property of starch and styrene graft copoly- mer was confirmed through grinding experiment, tensile strength, water absorption rate, hot water resistance properties and enzymatic properties analysis. [Result] The starch and styrene graft copolymer had the properties of thermoplastic and microbial degradation. IConclusion] The starch and styrene graft copolymer is expected to be developed as a biodegradable material.
文摘Bottled water may not be safer, or healthier, than tap water. The present studies have proved that styrene and some other aromatic compounds leach continuously from polystyrene （PS） bottles used locally for packaging. Water sapmles in contact with PS were extracted by a preconcentration technique called as ＂purge and trap＂ and analysed by gas chromatograph-mass spectrometer （GC/MS）. Eleven aromatic compounds were identified in these studies. Maximum concentration of styrene in PS bottles was 29.5 μg/L. Apart from styrene, ethyl benzene, toluene and benzene were also quantified but their concentrations were much less than WHO guide line values. All other compounds were in traces. Quality of plastic and storage time were the major factor in leaching of styrene. Concentration of styrene was increased to 69.53 μg/L after one-year storage. In Styrofoam and PS cups studies, hot water was found to be contaminated with styrene and other aromatic compounds. It was observed that temperature played a major role in the leaching of styrene monomer from Styrofoam cups. Paper cups were found to be safe for hot drinks.
基金Project supported by the National Basic Research Program of China (2004CB719500)the Commission of Science and Technology of Shanghai Municipality (03DJ14006)
文摘Using cetyl-trimethyl-ammonium bromide （CTMAB） as the template agent and tetraethylorthosilicate （TEOS） as the silica source, the MCM-41 mesoporous materials were synthesized with La or Ce incorporated in the framework under hydrothermal conditions. The structure and the state of La or Ce were investigated through the analyses of XRD, nitrogen adsorption-desorption, FT-IR, and UV-Vis. XRD and N2 adsorption-desorption results showed that Ln-MCM-41 exhibited the loss of the lattice ordering of the MCM-41 construct, and larger unit cell parameter and pore diameter than pure silica MCM-41. The FT-IR and UV-Vis results indicated the presence of isolated tetra-coordinated La or Ce ions in the framework and other Ln species dispersed highly on the Ln-MCM-41 surface simultaneously. Furthermore, their catalytic behaviors in the oxidation of styrene were studied using H2O2 as the oxidant. The La-MCM-41 catalysts exhibited high reactivity and the reactivity increased with the increase of the La content in the La-MCM-41 samples. On the contrary, Ce-MCM-41 catalysts showed low reactivity in the oxidation of styrene and the conversion of styrene decreased with the increase of the Ce content in the Ce-MCM-41 samples.
基金supported by the National Basic Research Program of China (2010CB732300)Education Commission of Shanghai Municipality (2008CG35)Science and Technology Commission of Shanghai Municipality (09ZR1408200)
文摘La-doped and La-B-doped KIT-6 mesoporous materials were prepared by direct hydrothermal synthesis with pH-adjusting method and characterized by X-ray diffractometer(XRD),nitrogen sorption,FT-IR,UV-Vis,X-ray photoelectron spectroscopy(XPS) and ICP-AES.The catalytic performance for the oxidation of styrene by hydrogen peroxide,tert-butyl hydroperoxide or oxygen was investigated.The results showed that the introduction of heteroatoms did not destroy the mesostructure of KIT-6 with cubic Ia3d space group.La or ...
基金financial support from the National Key Technology Research&Development Program(Grant No.2013BAC14B04)the National Natural Science Foundation of China(Grant No.21336006)+1 种基金the Shanxi Province Key Research&Development Program(international cooperation,Grant No.201803D421099)Supported by Shanxi Scholarship Council of China(Grant No.2017-035)。
文摘A series of calcined HTLcs catalysts were prepared and modified with potassium phosphate by impregnation method to clarify the influence of catalyst alkalinity on the side chain alkylation of toluene with methanol for synthesis of ethylbenzene and styrene.The catalysts were characterized by X-ray diffraction(XRD),N_(2)physical adsorption-desorption,Fourier-transform infrared spectroscopy(FT-IR),Scanning electron microscopy(SEM),X-ray photoelectron spectrometry(XPS),NH_(3)temperature-programmed desorption(NH_(3)-TPD)and CO_(2)temperature-programmed desorption(CO_(2)-TPD).It was found that the selectivity of styrene was highest(39.25%)when the K_(3)PO_(4)loading was 7.5 wt%.And the total yield of styrene and ethylbenzene could reach 65.08%with 10 wt%K_(3)PO_(4)loading.This might due to the fact that the addition of K_(3)PO_(4)could adjust the acid and basic sites of catalysts.In addition,appropriate strength and amount of basic sites were favorable to producing more styrene.
文摘The adsorption behavior and description behavior of benzene , ethylene and ethylbenzene over HZSM-5 and Co/HZSM-5 catalysts were studied by means of TPSR (Temperature programmed surface reaction) technique. TPSR results of ben- zene and ethylene co-adsorption show that the maian products are styrene , ethylben- zene, toluene, propane, and butane. In a separate experiment of ethylbenzene ad- sorption, styrene . toluene and benzene are formed due to cracking and dehydro- genation. The mechanism of styrene formation was proposed , i. e. , the reaction was carried out via. the dehydrogenation of mediate species ethylbenzene according to the results of TPSR-MS , activity testing and thermodynamic analysis.
基金funded by the Deanship of Scientific Research(DSR)at King Abdulaziz University,Jeddah,under grant no.(G-1281-135-1440)DSR for technical and financial support
文摘Different mole ratio Al-B catalysts (Al-10B to Al-35B) were synthesized by using sol-gel (SG) method. Ethyl benzene (EB) dehydrogenation in the presence of oxygen and water steam was carried out on these catalysts at 450–500℃ with EB contact time of 0.54 gcat.s.cm^–3. Acidity of Al-B catalysts was estimated by using NH3-TPD-mass spectral analysis studies. SEM-mapping images revealed fine distribution of boron up to 15% of its loading in alumina (Al-15B), whereas, boron aggregation was observed in higher boron content (Al-25B and Al-35B) catalysts. Essentially, acid sites of very weak strength (Tmax ≤ 125℃) were observed for Al and Al-10B catalysts and resulted in low EB conversion and styrene yield. On the other hand, acid sites of weak strength (Tmax ≤ 180℃) were observed for Al-25B and Al-35B catalysts and resulted in high EB conversion. However, greater styrene yield (43.2%) with reasonable EB conversion (46%) was obtained on acid sites of weak moderate strength in Al-15B catalyst. Further, Al-15B catalyst was synthesized by using co-precipitation (COP) and impregnation (IMP) methods. Acid sites related to NOx formation during the NH3-TPD-mass analysis on IMP and COP catalyst essentially improved the EB conversion to 66% and 63% respectively at 500℃. However, these acid sites were diminished in Al-B SG catalyst and resulted in 50% of EB conversion at 500 ℃. At 50% of EB conversion level, styrene selectivity of 73%, 82.5% and 84% were observed on Al-B IMP, Al-B COP and Al-SG catalysts, respectively. Hence, different method of preparation of Al-B catalyst generated acid sites of different strength and density and thereby influenced the styrene formation.
基金The authors are grateful for the financial support of The Sate Key Fundamental Research Project and the Natural Science Foundation of China.
文摘Dehydrogenation of ethylbenzene （EB） to styrene （ST） in the presence of CO2, in which EB dehydrogenation is coupled with the reverse water-gas shift （RWGS）, was investigated extensively through both theoretical analysis and experimental characterization. The reaction coupling proved to be superior to the single dehydrogenation in several respects. Thermodynamic analysis suggests that equilibrium conversion of EB can be improved greatly by reaction coupling due to the simultaneous elimination of the hydrogen produced from dehydrogenation. Catalytic tests proved that iron and vanadium supported on activated carbon or Al2O3 with certain promoters are potential catalysts for this coupling process. The catalysts of iron and vanadium are different in the reaction mechanism, although ST yield is always associated with CO2 conversion over various catalysts. The two-step pathway plays an important role in the coupling process over Fe/Al2O3, while the one-step pathway dominates the reaction over V/Al2O3. Coke deposition and deep reduction of active components are the major causes of catalyst deactivation. CO2 can alleviate the catalyst deactivation effectively through preserving the active species at high valence in the coupling process, though it can not suppress the coke deposition.
基金Project supported by National Basic Research Program of China(973 Program)(2012CBA01205)
文摘The flotation performances of styrene phosphonic acid（SPA） to synthetic（Ce,La）2O3（REO）, calcium fluorite（CaF2） and fluorapatite（Ca5F（PO4）3） were investigated by flotation tests, flotation of synthetic mixed mineral, the surface adsorption capacity and the polarizing microscopy to solve the flotation separation problem of rare earth oxides from roasted concentrate. The flotation test results indicated that compared with CaF2 and Ca5F（PO4）3, SPA exhibited superior collecting performance to direct flotation recovery of REO and floated out above 90% REO at pH 3–6. However, the collecting ability of SPA to CaF2 and Ca5F（PO4）3 was extremely weak and the highest recovery was only 20% at pH 2–11. The flotation of synthetic mixed mineral showed that SPA was a good collector reagent for flotation of synthetic REO at pH 5, so REO, CaF2 and Ca5F（PO4）3 could be separated from roasted concentrate by using SPA as a collector. The surface adsorption capacity tests and polarizing microscopy results confirmed that SPA was adsorbed on REO surface, while CaF2 and Ca5F（PO4）3 were not. The adsorption mechanism of SPA to synthetic REO was studied by solution chemistry analysis of collector, the ζ-potential tests, infrared spectroscopy and X-ray photoelectron spectroscopy（XPS） analyses. The results indicated that SPA was physically adsorbed onto REO surface, which exhibited excellent flotation selectivity to REO against CaF2 and Ca5F（PO4）3.
基金the financial support from NNSFC(Project 21373054,21303023,21173052)the Natural Science Foundation of Shanghai Science and Technology Committee(08DZ2270500)
文摘The morphology effect of Zr-doped CeOwas studied in terms of their activities in the selective oxidation of styrene to styrene oxide using tert-butyl hydroperoxide as the oxidant. In the present work, Zrdoped CeOnanorods exhibited the highest catalytic performance（yield of styrene oxide and TOF value）followed by nanoparticles and nanocubes. For the Zr-doped CeOnanorods, the apparent activation energy is 56.3 k J/mol, which is much lower than the values of catalysts supported on nanoparticles and nanocubes（73.3 and 93.4 k J/mol）. The high resolution transmission electron microscopy results indicated that（100） and（110） crystal planes are predominantly exposed for Zr-doped CeOnanorods while（100）and（111） for nanocubes,（111） for nanoparticles. The remarkably increased catalytic activity of the Zrdoped CeOnanorods is mainly attributed to the higher percentage of Cespecies and more oxygen vacancies, which are associated with their exposed（100） and（110） crystal planes. Furthermore, recycling studies proved that the heterogeneous Zr-doped CeOnanorods did not lose its initial high catalytic activity after five successive recycles.
