The extraction conditions of aluminum by the disproportionation process of A1C1 in vacuum were investigated using alumina and graphite as raw materials, including reaction temperature, pre-reaction and condenser struc...The extraction conditions of aluminum by the disproportionation process of A1C1 in vacuum were investigated using alumina and graphite as raw materials, including reaction temperature, pre-reaction and condenser structure. The results show that the extent of the reaction between alumina and carbon increases with increasing reaction temperature at 1643-1843 K; however, the extraction rate of aluminum increases firstly, and reaches the highest at 1743 K, and then decreases with rise in reaction temperature. The pre-reaction of alumina and carbon increases the extraction rate of aluminum. The impurities C, AlaC3 and A1203 in the aluminum product are reduced with reducing the contact surface of the aluminum with CO and with decreasing the condensation temperature, depending on the structure of the condenser.展开更多
The formation conditions of C, Al4C3 and Al2O3 in the Al Cl disproportionation process in vacuum to produce aluminum was investigated by thermodynamics analysis. It is demonstrated that the required temperatures for t...The formation conditions of C, Al4C3 and Al2O3 in the Al Cl disproportionation process in vacuum to produce aluminum was investigated by thermodynamics analysis. It is demonstrated that the required temperatures for the reactions to form these impurities, the disproportionation of CO and the reactions of metallic aluminum with CO, decrease with decreasing pressure. The lg pCO-1/T diagram of metallic aluminum-CO system agrees with the experimental results, indicating that the reaction rate is very high and this system in vacuum is approximately in equilibrium; therefore, the equilibrium diagram can be used to predict the possible reactions in this system in vacuum.展开更多
Shape-selective catalysts for the disproportionation of toluene were prepared by the modification of the cylinder-shaped ZSM-5 zeolite extrudates with chemical liquid deposition with TEOS (tetraethyl orthosilicate)....Shape-selective catalysts for the disproportionation of toluene were prepared by the modification of the cylinder-shaped ZSM-5 zeolite extrudates with chemical liquid deposition with TEOS (tetraethyl orthosilicate).Various parameters for preparing catalysts were changed to investigate the suitable conditions.The resulting cata-lysts were tested in a pressured fixed bed reactor and characterized by SEM (scanning electron microscopy).The conversion of toluene and para-xylene selectivity were influenced remarkably by the n(SiO2)/n(Al2O3) ratio of ZSM-5 zeolite,the type and amount of deposition agent,acid and solvent used,and the time and cycle of deposition treatment.TEOS was proved to be a more efficient agent than the conventional polysiloxanes when the deposition amount was low.The catalyst prepared at the suitable conditions exhibited a high para-xylene selectivity of 91.1% with considerable high conversion of 25.6%.SEM analyses confirmed the formation of a layer of amorphous silica on the external surface of ZSM-5 zeolie crystals,which was responsible for the highly enhanced shape-selectivity.展开更多
The carbothermal reduction-chlorination-disproportionation of alumina in vacuum was investigated by XRD and thermodynamic analysis. The experiments on alumina and graphite at 1643-1843 K in vacuum were carried out. Th...The carbothermal reduction-chlorination-disproportionation of alumina in vacuum was investigated by XRD and thermodynamic analysis. The experiments on alumina and graphite at 1643-1843 K in vacuum were carried out. The results demonstrate that AlCl3(g) reacts with Al2O(g) or Al(g) generated from the carbothermal reduction of alumina to form AlCl(g), and the AlCl(g) disproportionates to aluminum and AlCl3(g) at a lower temperature and the reaction rate of AlCl(g) reaches 90% at 980 K and 100 Pa. The aluminum can absorb CO to catalyze its disproportionation to C and CO2, and react backward with CO to form Al4C3, Al2O3, C and CO2, resulting in the aluminum product containing C, Al4C3 and Al2O3. The impurities in the aluminum product decrease as the AlCl(g) disproportionation temperature decreases. AlCl3 condenses at a temperature approximated to the room temperature.展开更多
A new kinetic model for commercial unit of toluene disproportionation and C9-armatiocs transalkylation is developed based on the reported reaction scheme.A time based catalyst deactivation function taking weight hourl...A new kinetic model for commercial unit of toluene disproportionation and C9-armatiocs transalkylation is developed based on the reported reaction scheme.A time based catalyst deactivation function taking weight hourly space velocity(WHSV)into account is incorporated into the model,which reasonably accounts for the loss in activity because of coke deposition on the surface of catalyst during long-term operation.The kinetic parameters are benchmarked with several sets of balanced plant data and estimated by the differential variable metric optimiza- tion method.Sets of plant data at different operating conditions are applied to make sure validation of the model and the results show a good agreement between the model predictions and plant observations.The simulation analysis of key variables such as temperature and WHSV affecting process performance is discussed in detail,giv- ing the guidance to select suitable operating conditions.展开更多
The surface disproportionation reaction mechanism of aluminum subchloride on the aluminum (100) surfaces has been investigated by the plane-wave density functional theory (DFT). Three kinds of possible reaction me...The surface disproportionation reaction mechanism of aluminum subchloride on the aluminum (100) surfaces has been investigated by the plane-wave density functional theory (DFT). Three kinds of possible reaction mechanism of AlCl disproportionation reaction on the aluminum (100) surfaces have been taken into account. The structures of reactants and products have been optimized, transition states have been confirmed and activation energies have been calculated. The adsorption energy of reactants and desorption energy of products have been determined. All of these have been employed to confirm the reaction mechanism and the rate determining step ofAlCl disproportionation reaction on the aluminum (100) surfaces.展开更多
The selective synthesis of p-diethylbenzene (p-DEB) by disproportionation of ethylbenzene (EB) in the presence of aromatics like m- and p- xylene isomers has been studied over a pore size regulated HZSM-5 catalyst...The selective synthesis of p-diethylbenzene (p-DEB) by disproportionation of ethylbenzene (EB) in the presence of aromatics like m- and p- xylene isomers has been studied over a pore size regulated HZSM-5 catalyst. The industrial feed having different compositions of ethylbenzene and xylene isomers was used for the experimentation. Hence, they were expected to hinder the movement of reactant molecules both on the external surface and within the zeolite channels. It was observed that irrespective of the different feed compositions the concentration of the xylene isomers was intact in the product. There is no other byproducts formation like para-ethylmethyl benzene. The effects of varying the concentration of aromatic compounds in the feed on ethylbenzene conversion and product distribution over the parent and modified H-ZSM-5 catalyst have been discussed. Ethylbenzene disproportionation reaction follows the pseudo first order reaction with an activation energy of 8.6 kcal/mol.展开更多
A new method of synthesizing single-component molecular conductor [Ni(dmit)2] by the reaction 2(Me4N)[Ni(dmit)2]2 [Ni(dmit)2] + (Me4N)[Ni(dmit)2] is reported. [Ni(dmit)2] exhibits a semiconductive behavior above 167...A new method of synthesizing single-component molecular conductor [Ni(dmit)2] by the reaction 2(Me4N)[Ni(dmit)2]2 [Ni(dmit)2] + (Me4N)[Ni(dmit)2] is reported. [Ni(dmit)2] exhibits a semiconductive behavior above 167 K, while from 167 K down to the measuring limit of 60 K, it exhibits metallic conductivity.展开更多
The paper refers to disproportionation of HIO and NaIO in aqueous media, in static and dynamic systems. The results of calculations, realized according to GATES/GEB principles, with use of an iterative computer progra...The paper refers to disproportionation of HIO and NaIO in aqueous media, in static and dynamic systems. The results of calculations, realized according to GATES/GEB principles, with use of an iterative computer program, are presented graphically. An example of the computer program with all physicochemical knowledge involved in the related algorithm is attached herewith.展开更多
Metal-to-insulator transitions (MITs),which are achieved in 3d-band correlated transitional metal oxides,trigger abrupt variations in electrical,optical,and/or magnetic properties beyond those of conventional semicond...Metal-to-insulator transitions (MITs),which are achieved in 3d-band correlated transitional metal oxides,trigger abrupt variations in electrical,optical,and/or magnetic properties beyond those of conventional semiconductors.Among such material families,iron(Fe:3d^(6)4s^(2))-containing oxides pique interest owing to their widely tunable MIT properties,which are associated with the various valence states of Fe.Their potential electronic applications also show promise,given the large abundance of Fe on Earth.Representative MIT properties triggered by critical temperature (TMIT) were reported for ReFe_(2)O_(4)(Fe^(2.5+)),ReBaFe_(2)O_(5)(Fe^(2.5+)),Fe_(3)O_(4)(Fe^(2.67+)),Re_(1/3)Sr_(2/3)FeO_(3)(Fe^(3.67+)),Re Cu_(3)Fe_(4)O_(12)(Fe^(3.75+)),and Ca_(1-x)Sr_(x)FeO_(3)(Fe^(4+))(where Re represents rare-earth elements).The common feature of MITs of these Fe-containing oxides is that they are usually accompanied by charge ordering transitions or disproportionation associated with the valence states of Fe.Herein,we review the material family of Fe-containing MIT oxides,their MIT functionalities,and their respective mechanisms.From the perspective of potentially correlated electronic applications,the tunability of the TMITand its resultant resistive change in Fe-containing oxides are summarized and further compared with those of other materials exhibiting MIT functionality.In particular,we highlight the abrupt MIT and wide tunability of TMITof Fe-containing quadruple perovskites,such as Re Cu3Fe4O12.However,their effective material synthesis still needs to be further explored to cater to potential applications.展开更多
A high-efficiency method is developed to in-situ synthesize nanocrystalline TiC powders,nanorods,and nanosheets by using equimolar ratio of Ti powder and acetylene black,multiwalled carbon nanotubes(MWCNTs),and graphe...A high-efficiency method is developed to in-situ synthesize nanocrystalline TiC powders,nanorods,and nanosheets by using equimolar ratio of Ti powder and acetylene black,multiwalled carbon nanotubes(MWCNTs),and graphene,respectively,as precursor in eutectic Na Cl-KCl molten salt at 800–900℃for 2–3 h.Higher temperature and longer duration are more beneficial for TiC preparation.In addition,mechanism of TiC formation was investigated by linear scan voltammetry.Results indicate that nanocrystalline TiC is in-situ synthesized by reaction between Ti atoms,which come from disproportionation reaction of Ti(Ⅱ)species in the molten salt,and C atoms on the surface of carbon sources.展开更多
Supported single-atom catalysts(SACs)possess high catalytic activity,selectivity,and atom utilizations.However,the atom coordination environments of SACs are difficult to accurately regulate due to the high complexity...Supported single-atom catalysts(SACs)possess high catalytic activity,selectivity,and atom utilizations.However,the atom coordination environments of SACs are difficult to accurately regulate due to the high complexity of coordination site and local environment of support.Herein,we develop an in-situ electrochemical cation-exchange method to fill the cation vacancies in MnO_(2)with Ru single atoms(SAs).This obtained catalyst exhibits high mass activity,which is~44 times higher than commercial RuO2 catalyst and excellent stability,superior to the most state-of-the-art oxygen evolution reaction(OER)catalysts.The experimental and theoretical results confirm that the doped Ru can induce charge density redistribution,resulting in the optimized binding of oxygen species,and the strong covalent interaction between Ru and MnO2 for resisting oxidation and corrosion.This work will provide a new concept in the synthesis of well-defined local environments of supported SAs.展开更多
Mesoporous TiO2 was synthesized via nonhydrolytic template-mediated sol-gel route.Catalytic degradation performance upon dichloromethane over as-prepared mesoporous TiO2,pure anatase and rutile were investigated respe...Mesoporous TiO2 was synthesized via nonhydrolytic template-mediated sol-gel route.Catalytic degradation performance upon dichloromethane over as-prepared mesoporous TiO2,pure anatase and rutile were investigated respectively.Disproportionation took place over as-made mesoporous TiO2 and pure anatase under the presence of water.The mechanism of disproportionation was studied by in situ FTIR.The interaction between chloromethoxy species and bridge coordinated methylenes was the key step of disproportionation.Formate species and methoxy groups would be formed and further turned into carbon monoxide and methyl chloride.Anatase(001)played an important role for disproportionation in that water could be dissociated into surface hydroxyl groups on such structure.As a result,the consumed hydroxyl groups would be replenished.In addition,there was another competitive oxidation route governed by free hydroxyl radicals.In this route,chloromethoxy groups would be oxidized into formate species by hydroxyl radicals transfering from the surface of TiO2.The latter route would be more favorable at higher temperature.展开更多
We observed an exchange bias effect in La0.5Ca0.5FeO3 perovskite compound.The exchange bias is associated with the charge disproportionation transition from Fe4+ions to Fe3+and Fe5+ions below 175 K.The competition bet...We observed an exchange bias effect in La0.5Ca0.5FeO3 perovskite compound.The exchange bias is associated with the charge disproportionation transition from Fe4+ions to Fe3+and Fe5+ions below 175 K.The competition between the ferromagnetic interaction of Fe3+and Fe5+ions and the antiferromagnetic one of Fe3+and Fe3+ions results in a unidirectional anisotropy in the cluster-glass system.An antiferromagnetically interfacial exchange coupling constant Ji1.95 meV at the cluster-glass region was yielded by fitting the cooling field-dependence of the exchange bias field.展开更多
Compressed CO~ could promote the disproportionation reactions of aryl alcohols in water medium significantly. The control experiments indicated that the effect of CO2 on the properties of the reactant/water emulsions ...Compressed CO~ could promote the disproportionation reactions of aryl alcohols in water medium significantly. The control experiments indicated that the effect of CO2 on the properties of the reactant/water emulsions was the main reason for the ac- celeration of the reactions rate.展开更多
Symmetry breaking of metal cluster-based strongly correlated systems can give rise to collective phenomena.Here,the twodimensional Nb_(3) cluster compound Nb_(3)Cl_(8) is shown to suffer dramatic symmetry breaking and...Symmetry breaking of metal cluster-based strongly correlated systems can give rise to collective phenomena.Here,the twodimensional Nb_(3) cluster compound Nb_(3)Cl_(8) is shown to suffer dramatic symmetry breaking and electron disproportionation under compression.A structural phase transition from trigonal P–3m1 to monoclinic C2/m is observed near 8 GPa with the three-fold symmetry breaking.Electron disproportionation occurs on Nb_(3) clusters from delocalized Nb^(8/3+)Nb^(8/3+)Nb^(8/3+)to localized Nb^(3+)Nb^(3+)Nb^(2+),which results in a subtle bandgap discontinuity,as evidenced by electrical transport and UV-Vis absorption measurements.展开更多
Transformation-temperature-hydrogen pressure phase diagram was constructed for a Nd15Fe79B6 alloy in order to estimate appropriate conditions for hydrogenation, disproportionation, desorption and recombination reacti...Transformation-temperature-hydrogen pressure phase diagram was constructed for a Nd15Fe79B6 alloy in order to estimate appropriate conditions for hydrogenation, disproportionation, desorption and recombination reaction (the HDDR). Optimised recom- bination time (the highest coercivity) was found to be 10 rain. for 5 g samples processed at 740 ℃. Several HDDR processes were carried out at 30 kPa of hydrogen pressure at various temperatures. No correlation between magnetic propertiec and a direction of measurement was observed for the samples processed at 740 ℃. Remanence anisotropy was induced along an alignment direction when the temperature of the HDDR process was increased up to 800 ℃ and 850℃ for 〈100 gm and 100-160 p.m particles, respec- tively. Simultaneously, a small drop in coercivity was observed in the direction of alignment for 〈100 pm particles, but no for 100-160 grn particles. Furthermore, probably an ordered phase was found by TEM microstructure analysis in the bulk sample dis- proportionated at 850 ℃ under 150 kPa of hydrogen. Grains with antiphase domains were observed and corresponding electron dif- fraction patterns were resolved, likely indicating superlattice structures.展开更多
Diphenyl carbonate(DPC)is one of the versatile carbonates,and is often used for the production of polycarbonates.In recent years,the catalytic synthesis of DPC has become an important topic but the development of a hi...Diphenyl carbonate(DPC)is one of the versatile carbonates,and is often used for the production of polycarbonates.In recent years,the catalytic synthesis of DPC has become an important topic but the development of a highly active metal-free catalyst is a great challenge.Herein,a series of ionic liquids-SBA-15 hybrid catalysts with different functional groups have been developed for the synthesis of DPC under solventfree condition,which are effective and clean instead of the metal-containing catalysts.It is found that in the presence of[SBA-15-IL-OH]Br catalyst,methyl phenyl carbonate(MPC)conversion of 80.5%along with 99.6%DPC selectivity is achieved,the TOF value is thrice higher than the best value reported by using transition metal-based catalysts.Moreover,the catalyst displays remarkable stability and recyclability.This work provides a new idea to design and prepare eco-friendly catalysts in a broad range of applications for the green synthesis of carbonates.展开更多
Caesarean section (CS) is a surgical procedure performed to remove a fetus from the mother’s uterus through an incision on the abdominal wall, then on the uterine wall. The indications of CS vary not only between cou...Caesarean section (CS) is a surgical procedure performed to remove a fetus from the mother’s uterus through an incision on the abdominal wall, then on the uterine wall. The indications of CS vary not only between countries, but also from one hospital to another and from one team to another within the same hospital. Despite advances in asepsis and anesthesia/resuscitation technics, there are still complications of varying severity inherent to the gravid-puerperal state on one hand and the technics used on the other, irrespective of the operative indication. Thus, the present study was carried out with the objectives of determining the prevalence, identifying the indications, and evaluating the morbidity linked to caesarean sections in our environment. Cameroon has also set up a health voucher program in its northern region, aimed at reducing maternal and fetus morbidity and mortality. The program aims to improve financial access in antenatal care and deliveries, including caesarean sections, in this low-income region of the country. We conducted a descriptive cross-sectional study with retrospective data collection, from February 1, 2022, to May 31, 2022. We included all women who gave birth by caesarean section. In our study series, out of 905 parturient admissions into the Department of Obstetrics and Gynecology, 226 were caesarian cases. The overall frequency of CS during our study period was 25%. Fetal indications were dominated by cephalopelvic disproportion and non-reassuring fetal heart in 17.3% and 13.7% of cases respectively. Intraoperative complications were dominated by hemorrhage (15.5%). In our study, we noted an 11.1% of prevalence perinatal mortality. Cameroon is a low-income country with limited financial resources, especially in the Northern region. The health voucher program has improved financial access to caesarean sections for parturient in northern Cameroon, and consequently to emergency obstetric and neonatal care.展开更多
The thermal dissolved sulfuration technology is brought forward and performed based on the characteristic of low grade lead-zinc oxide ore in lanpin. Using sulfur as the sulphidizing agent in the experiment, the oxide...The thermal dissolved sulfuration technology is brought forward and performed based on the characteristic of low grade lead-zinc oxide ore in lanpin. Using sulfur as the sulphidizing agent in the experiment, the oxides in the sandstone and ignimbrite are changed into sulfides. The disproportionation reaction of sulfur in a solution is confirmed as 4S+3H2O=2S^2-+S2O3^2--+6H^+. The dynamics process is studied and the first-order reaction rate equation -1n(1-a)=ktt is obtained. The effects of the reactive products, stirring speed, dosage of sulfuration agent, value of pH and sulphidizing temperature on the sulfuration of oxide ore are investigated. The results indicate that the reactive apparent activation energy is 100.8 kJ/mol and the sulfuration ratio of lead-zinc oxide ore reaches 60% under the conditions of pH 5.9-7.5, the sulfuration temperature of 130 ℃, sulfuration time of 180 min and the stirring speed of 800 r/min.展开更多
基金Project(51264023)supported by the National Natural Science Foundation of ChinaProject(KKSY201207016)supported by Yunnan Provincial Science and Technology Department,China
文摘The extraction conditions of aluminum by the disproportionation process of A1C1 in vacuum were investigated using alumina and graphite as raw materials, including reaction temperature, pre-reaction and condenser structure. The results show that the extent of the reaction between alumina and carbon increases with increasing reaction temperature at 1643-1843 K; however, the extraction rate of aluminum increases firstly, and reaches the highest at 1743 K, and then decreases with rise in reaction temperature. The pre-reaction of alumina and carbon increases the extraction rate of aluminum. The impurities C, AlaC3 and A1203 in the aluminum product are reduced with reducing the contact surface of the aluminum with CO and with decreasing the condensation temperature, depending on the structure of the condenser.
基金Project(51364020)supported by the National Natural Science Foundation of China
文摘The formation conditions of C, Al4C3 and Al2O3 in the Al Cl disproportionation process in vacuum to produce aluminum was investigated by thermodynamics analysis. It is demonstrated that the required temperatures for the reactions to form these impurities, the disproportionation of CO and the reactions of metallic aluminum with CO, decrease with decreasing pressure. The lg pCO-1/T diagram of metallic aluminum-CO system agrees with the experimental results, indicating that the reaction rate is very high and this system in vacuum is approximately in equilibrium; therefore, the equilibrium diagram can be used to predict the possible reactions in this system in vacuum.
基金Supported by the Key Natural Science Foundation for Universities of Jiangsu Province(06KJA53012) the National Natural Science Foundation of China(20776069 20976084)
文摘Shape-selective catalysts for the disproportionation of toluene were prepared by the modification of the cylinder-shaped ZSM-5 zeolite extrudates with chemical liquid deposition with TEOS (tetraethyl orthosilicate).Various parameters for preparing catalysts were changed to investigate the suitable conditions.The resulting cata-lysts were tested in a pressured fixed bed reactor and characterized by SEM (scanning electron microscopy).The conversion of toluene and para-xylene selectivity were influenced remarkably by the n(SiO2)/n(Al2O3) ratio of ZSM-5 zeolite,the type and amount of deposition agent,acid and solvent used,and the time and cycle of deposition treatment.TEOS was proved to be a more efficient agent than the conventional polysiloxanes when the deposition amount was low.The catalyst prepared at the suitable conditions exhibited a high para-xylene selectivity of 91.1% with considerable high conversion of 25.6%.SEM analyses confirmed the formation of a layer of amorphous silica on the external surface of ZSM-5 zeolie crystals,which was responsible for the highly enhanced shape-selectivity.
基金Project (u0837604) supported by the Joint Funds of the National Natural Science Foundation of China and Yunnan Province
文摘The carbothermal reduction-chlorination-disproportionation of alumina in vacuum was investigated by XRD and thermodynamic analysis. The experiments on alumina and graphite at 1643-1843 K in vacuum were carried out. The results demonstrate that AlCl3(g) reacts with Al2O(g) or Al(g) generated from the carbothermal reduction of alumina to form AlCl(g), and the AlCl(g) disproportionates to aluminum and AlCl3(g) at a lower temperature and the reaction rate of AlCl(g) reaches 90% at 980 K and 100 Pa. The aluminum can absorb CO to catalyze its disproportionation to C and CO2, and react backward with CO to form Al4C3, Al2O3, C and CO2, resulting in the aluminum product containing C, Al4C3 and Al2O3. The impurities in the aluminum product decrease as the AlCl(g) disproportionation temperature decreases. AlCl3 condenses at a temperature approximated to the room temperature.
基金Supported by the National'Creative Research Groups Science Foundation of China (No.60421002) and priority supported financially by "the New Century 151 Talent Project" of Zhejiang Province.
文摘A new kinetic model for commercial unit of toluene disproportionation and C9-armatiocs transalkylation is developed based on the reported reaction scheme.A time based catalyst deactivation function taking weight hourly space velocity(WHSV)into account is incorporated into the model,which reasonably accounts for the loss in activity because of coke deposition on the surface of catalyst during long-term operation.The kinetic parameters are benchmarked with several sets of balanced plant data and estimated by the differential variable metric optimiza- tion method.Sets of plant data at different operating conditions are applied to make sure validation of the model and the results show a good agreement between the model predictions and plant observations.The simulation analysis of key variables such as temperature and WHSV affecting process performance is discussed in detail,giv- ing the guidance to select suitable operating conditions.
基金Supported by the Joint Funds of the National Natural Science Foundation of China(No.u0837604) the Funds for Applied Basic Researches of Yunnan Province(No.2010CD022)
文摘The surface disproportionation reaction mechanism of aluminum subchloride on the aluminum (100) surfaces has been investigated by the plane-wave density functional theory (DFT). Three kinds of possible reaction mechanism of AlCl disproportionation reaction on the aluminum (100) surfaces have been taken into account. The structures of reactants and products have been optimized, transition states have been confirmed and activation energies have been calculated. The adsorption energy of reactants and desorption energy of products have been determined. All of these have been employed to confirm the reaction mechanism and the rate determining step ofAlCl disproportionation reaction on the aluminum (100) surfaces.
文摘The selective synthesis of p-diethylbenzene (p-DEB) by disproportionation of ethylbenzene (EB) in the presence of aromatics like m- and p- xylene isomers has been studied over a pore size regulated HZSM-5 catalyst. The industrial feed having different compositions of ethylbenzene and xylene isomers was used for the experimentation. Hence, they were expected to hinder the movement of reactant molecules both on the external surface and within the zeolite channels. It was observed that irrespective of the different feed compositions the concentration of the xylene isomers was intact in the product. There is no other byproducts formation like para-ethylmethyl benzene. The effects of varying the concentration of aromatic compounds in the feed on ethylbenzene conversion and product distribution over the parent and modified H-ZSM-5 catalyst have been discussed. Ethylbenzene disproportionation reaction follows the pseudo first order reaction with an activation energy of 8.6 kcal/mol.
基金supported by the National Natural Science Foundation of China(No.20172034)Foundation for Univemity Key Teacher by Ministry of Educationthe grant for the State Key Program of China.
文摘A new method of synthesizing single-component molecular conductor [Ni(dmit)2] by the reaction 2(Me4N)[Ni(dmit)2]2 [Ni(dmit)2] + (Me4N)[Ni(dmit)2] is reported. [Ni(dmit)2] exhibits a semiconductive behavior above 167 K, while from 167 K down to the measuring limit of 60 K, it exhibits metallic conductivity.
文摘The paper refers to disproportionation of HIO and NaIO in aqueous media, in static and dynamic systems. The results of calculations, realized according to GATES/GEB principles, with use of an iterative computer program, are presented graphically. An example of the computer program with all physicochemical knowledge involved in the related algorithm is attached herewith.
基金financially supported by the National Key Research and Development Program of China (No.2021YFA0718900)the National Natural Science Foundation of China (No.62074014)the Xiaomi Scholar project。
文摘Metal-to-insulator transitions (MITs),which are achieved in 3d-band correlated transitional metal oxides,trigger abrupt variations in electrical,optical,and/or magnetic properties beyond those of conventional semiconductors.Among such material families,iron(Fe:3d^(6)4s^(2))-containing oxides pique interest owing to their widely tunable MIT properties,which are associated with the various valence states of Fe.Their potential electronic applications also show promise,given the large abundance of Fe on Earth.Representative MIT properties triggered by critical temperature (TMIT) were reported for ReFe_(2)O_(4)(Fe^(2.5+)),ReBaFe_(2)O_(5)(Fe^(2.5+)),Fe_(3)O_(4)(Fe^(2.67+)),Re_(1/3)Sr_(2/3)FeO_(3)(Fe^(3.67+)),Re Cu_(3)Fe_(4)O_(12)(Fe^(3.75+)),and Ca_(1-x)Sr_(x)FeO_(3)(Fe^(4+))(where Re represents rare-earth elements).The common feature of MITs of these Fe-containing oxides is that they are usually accompanied by charge ordering transitions or disproportionation associated with the valence states of Fe.Herein,we review the material family of Fe-containing MIT oxides,their MIT functionalities,and their respective mechanisms.From the perspective of potentially correlated electronic applications,the tunability of the TMITand its resultant resistive change in Fe-containing oxides are summarized and further compared with those of other materials exhibiting MIT functionality.In particular,we highlight the abrupt MIT and wide tunability of TMITof Fe-containing quadruple perovskites,such as Re Cu3Fe4O12.However,their effective material synthesis still needs to be further explored to cater to potential applications.
基金supported financially by the National Natural Science Foundation of China(Nos.51671204 and 51501205).
文摘A high-efficiency method is developed to in-situ synthesize nanocrystalline TiC powders,nanorods,and nanosheets by using equimolar ratio of Ti powder and acetylene black,multiwalled carbon nanotubes(MWCNTs),and graphene,respectively,as precursor in eutectic Na Cl-KCl molten salt at 800–900℃for 2–3 h.Higher temperature and longer duration are more beneficial for TiC preparation.In addition,mechanism of TiC formation was investigated by linear scan voltammetry.Results indicate that nanocrystalline TiC is in-situ synthesized by reaction between Ti atoms,which come from disproportionation reaction of Ti(Ⅱ)species in the molten salt,and C atoms on the surface of carbon sources.
基金supported by the National Natural Science Foundation of China(Nos.21805051 and 21875048)Outstanding Youth Project of Guangdong Natural Science Foundation(No.2020B1515020028)+4 种基金Science and Technology Research Project of Guangzhou(No.202002010007)the Research Fund Program of Key Laboratory of Fuel Cell Technology of Guangdong Province,Australian Research Council(ARC)Future Fellowship(No.FT210100298)Discovery Project(No.DP220100603)CSIRO Energy Centre and Kick-Start ProjectThe Study Melbourne Research Partnerships program has been made possible by funding from the Victorian Government through Study Melbourne.
文摘Supported single-atom catalysts(SACs)possess high catalytic activity,selectivity,and atom utilizations.However,the atom coordination environments of SACs are difficult to accurately regulate due to the high complexity of coordination site and local environment of support.Herein,we develop an in-situ electrochemical cation-exchange method to fill the cation vacancies in MnO_(2)with Ru single atoms(SAs).This obtained catalyst exhibits high mass activity,which is~44 times higher than commercial RuO2 catalyst and excellent stability,superior to the most state-of-the-art oxygen evolution reaction(OER)catalysts.The experimental and theoretical results confirm that the doped Ru can induce charge density redistribution,resulting in the optimized binding of oxygen species,and the strong covalent interaction between Ru and MnO2 for resisting oxidation and corrosion.This work will provide a new concept in the synthesis of well-defined local environments of supported SAs.
文摘Mesoporous TiO2 was synthesized via nonhydrolytic template-mediated sol-gel route.Catalytic degradation performance upon dichloromethane over as-prepared mesoporous TiO2,pure anatase and rutile were investigated respectively.Disproportionation took place over as-made mesoporous TiO2 and pure anatase under the presence of water.The mechanism of disproportionation was studied by in situ FTIR.The interaction between chloromethoxy species and bridge coordinated methylenes was the key step of disproportionation.Formate species and methoxy groups would be formed and further turned into carbon monoxide and methyl chloride.Anatase(001)played an important role for disproportionation in that water could be dissociated into surface hydroxyl groups on such structure.As a result,the consumed hydroxyl groups would be replenished.In addition,there was another competitive oxidation route governed by free hydroxyl radicals.In this route,chloromethoxy groups would be oxidized into formate species by hydroxyl radicals transfering from the surface of TiO2.The latter route would be more favorable at higher temperature.
基金supported by the National Basic Research Program of Chinathe National Natural Sciences Foundation of China(Grant No.11205015)+1 种基金the Natural Sciences Foundation of Beijing(Grant No.1113017)Beijing Area Logistics System&Technology Major Laboratory and the Logistics Management and Engineering Innovation Platform of Beijing Wuzi University
文摘We observed an exchange bias effect in La0.5Ca0.5FeO3 perovskite compound.The exchange bias is associated with the charge disproportionation transition from Fe4+ions to Fe3+and Fe5+ions below 175 K.The competition between the ferromagnetic interaction of Fe3+and Fe5+ions and the antiferromagnetic one of Fe3+and Fe3+ions results in a unidirectional anisotropy in the cluster-glass system.An antiferromagnetically interfacial exchange coupling constant Ji1.95 meV at the cluster-glass region was yielded by fitting the cooling field-dependence of the exchange bias field.
基金National Natural Science Foundation of China(21003133,20932002,21021003)Chinese Academy of Sciences(KJCX2.YW.H30)
文摘Compressed CO~ could promote the disproportionation reactions of aryl alcohols in water medium significantly. The control experiments indicated that the effect of CO2 on the properties of the reactant/water emulsions was the main reason for the ac- celeration of the reactions rate.
基金supported by the National Natural Science Foundation of China(Grant No.52073003)the Major Program of National Natural Science Foundation of China(Grant No.22090041)+1 种基金the National Key R&D Program of China(Grant No.2018YFA0305900)the Shanghai Sailing Program(Grant No.21YF1454400)。
文摘Symmetry breaking of metal cluster-based strongly correlated systems can give rise to collective phenomena.Here,the twodimensional Nb_(3) cluster compound Nb_(3)Cl_(8) is shown to suffer dramatic symmetry breaking and electron disproportionation under compression.A structural phase transition from trigonal P–3m1 to monoclinic C2/m is observed near 8 GPa with the three-fold symmetry breaking.Electron disproportionation occurs on Nb_(3) clusters from delocalized Nb^(8/3+)Nb^(8/3+)Nb^(8/3+)to localized Nb^(3+)Nb^(3+)Nb^(2+),which results in a subtle bandgap discontinuity,as evidenced by electrical transport and UV-Vis absorption measurements.
基金Project supported by the National Centre for Research and Development(INNOTECH-K2/IN2/18/181960/NCBR/13)
文摘Transformation-temperature-hydrogen pressure phase diagram was constructed for a Nd15Fe79B6 alloy in order to estimate appropriate conditions for hydrogenation, disproportionation, desorption and recombination reaction (the HDDR). Optimised recom- bination time (the highest coercivity) was found to be 10 rain. for 5 g samples processed at 740 ℃. Several HDDR processes were carried out at 30 kPa of hydrogen pressure at various temperatures. No correlation between magnetic propertiec and a direction of measurement was observed for the samples processed at 740 ℃. Remanence anisotropy was induced along an alignment direction when the temperature of the HDDR process was increased up to 800 ℃ and 850℃ for 〈100 gm and 100-160 p.m particles, respec- tively. Simultaneously, a small drop in coercivity was observed in the direction of alignment for 〈100 pm particles, but no for 100-160 grn particles. Furthermore, probably an ordered phase was found by TEM microstructure analysis in the bulk sample dis- proportionated at 850 ℃ under 150 kPa of hydrogen. Grains with antiphase domains were observed and corresponding electron dif- fraction patterns were resolved, likely indicating superlattice structures.
基金support from the National Natural Science Foundation of China(No.21808048 and U1704251)Training Plan for University's Young Backbone Teachers of Henan Province(2021GGJS121)+5 种基金Program for Science&Technology Innovation Talents in Universities of Henan Province(23HASTIT014)Postgraduate Education Reform and Quality Improvement Project of Henan Province(YJS2022KC22)Project funded by China Postdoctoral Science Foundation(No.2018M632782)Project funded by Postdoctoral Research Grant in Henan Province(No.001802030)Key Project of Science and Technology Program of Henan Province(No.222102230109,212102310330 and 182102210050)the Science Research Start-up Fund of Henan Institute of Science and Technology(No.2015031).
文摘Diphenyl carbonate(DPC)is one of the versatile carbonates,and is often used for the production of polycarbonates.In recent years,the catalytic synthesis of DPC has become an important topic but the development of a highly active metal-free catalyst is a great challenge.Herein,a series of ionic liquids-SBA-15 hybrid catalysts with different functional groups have been developed for the synthesis of DPC under solventfree condition,which are effective and clean instead of the metal-containing catalysts.It is found that in the presence of[SBA-15-IL-OH]Br catalyst,methyl phenyl carbonate(MPC)conversion of 80.5%along with 99.6%DPC selectivity is achieved,the TOF value is thrice higher than the best value reported by using transition metal-based catalysts.Moreover,the catalyst displays remarkable stability and recyclability.This work provides a new idea to design and prepare eco-friendly catalysts in a broad range of applications for the green synthesis of carbonates.
文摘Caesarean section (CS) is a surgical procedure performed to remove a fetus from the mother’s uterus through an incision on the abdominal wall, then on the uterine wall. The indications of CS vary not only between countries, but also from one hospital to another and from one team to another within the same hospital. Despite advances in asepsis and anesthesia/resuscitation technics, there are still complications of varying severity inherent to the gravid-puerperal state on one hand and the technics used on the other, irrespective of the operative indication. Thus, the present study was carried out with the objectives of determining the prevalence, identifying the indications, and evaluating the morbidity linked to caesarean sections in our environment. Cameroon has also set up a health voucher program in its northern region, aimed at reducing maternal and fetus morbidity and mortality. The program aims to improve financial access in antenatal care and deliveries, including caesarean sections, in this low-income region of the country. We conducted a descriptive cross-sectional study with retrospective data collection, from February 1, 2022, to May 31, 2022. We included all women who gave birth by caesarean section. In our study series, out of 905 parturient admissions into the Department of Obstetrics and Gynecology, 226 were caesarian cases. The overall frequency of CS during our study period was 25%. Fetal indications were dominated by cephalopelvic disproportion and non-reassuring fetal heart in 17.3% and 13.7% of cases respectively. Intraoperative complications were dominated by hemorrhage (15.5%). In our study, we noted an 11.1% of prevalence perinatal mortality. Cameroon is a low-income country with limited financial resources, especially in the Northern region. The health voucher program has improved financial access to caesarean sections for parturient in northern Cameroon, and consequently to emergency obstetric and neonatal care.
基金supported by Cooperated Project of Academy and College Yunnan province(2003CBALA02P023)
文摘The thermal dissolved sulfuration technology is brought forward and performed based on the characteristic of low grade lead-zinc oxide ore in lanpin. Using sulfur as the sulphidizing agent in the experiment, the oxides in the sandstone and ignimbrite are changed into sulfides. The disproportionation reaction of sulfur in a solution is confirmed as 4S+3H2O=2S^2-+S2O3^2--+6H^+. The dynamics process is studied and the first-order reaction rate equation -1n(1-a)=ktt is obtained. The effects of the reactive products, stirring speed, dosage of sulfuration agent, value of pH and sulphidizing temperature on the sulfuration of oxide ore are investigated. The results indicate that the reactive apparent activation energy is 100.8 kJ/mol and the sulfuration ratio of lead-zinc oxide ore reaches 60% under the conditions of pH 5.9-7.5, the sulfuration temperature of 130 ℃, sulfuration time of 180 min and the stirring speed of 800 r/min.