Methyl methoxyacetate(MMAc)and methyl formate(MF)can be produced directly by heterogeneous zeolite-catalyzed carbonylation and disproportionation of dimethoxymethane(DMM),with near 100%selectivity for each process.Des...Methyl methoxyacetate(MMAc)and methyl formate(MF)can be produced directly by heterogeneous zeolite-catalyzed carbonylation and disproportionation of dimethoxymethane(DMM),with near 100%selectivity for each process.Despite continuous research efforts,the insight into the reaction mechanism and kinetics theory are still in their nascent stage.In this study,ZEO-1 material,a zeolite with up to now the largest cages comprising 16×16-MRs,16×12-MRs,and 12×12-MRs,was explored for DMM carbonylation and disproportionation reactions.The rate of MMAc formation based on accessible Brönsted acid sites is 2.5 times higher for ZEO-1(Si/Al=21)relative to the previously investigated FAU(Si/Al=15),indicating the positive effect of spatial separation of active sites in ZEO-1 on catalytic activity.A higher MF formation rate is also observed over ZEO-1 with lower activation energy(79.94 vs.95.19 kJ/mol)compared with FAU(Si/Al=30).Two types of active sites are proposed within ZEO-1 zeolite:Site 1 located in large cages formed by 16×16-MRs and 16×12-MRs,which is active predominantly for MMAc formation,and Site 2 located in smaller cages for methyl formate/dimethyl ether formation.Kinetics investigation of DMM carbonylation over ZEO-1 exhibit a first-order dependence on CO partial pressure and a slightly inverse-order dependence on DMM partial pressure.The DMM disproportionation is nearly first-order dependence on DMM partial pressure,while it reveals a strongly inverse dependence with increasing CO partial pressure.Furthermore,ZEO-1 exhibits good catalytic stability,and almost no deactivation is observed during the more than 70 h test with high carbonylation selectivity of above 89%,due to the well-enhanced diffusion property demonstrated by intelligent-gravimetric analysis.展开更多
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
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
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
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
This paper evaluates the thermodynamic possibility of coalbed methane formation as a result of direct reaction of coal and water during the process of hydrolytic disproportionation of carbon(HDC).Some examples of expe...This paper evaluates the thermodynamic possibility of coalbed methane formation as a result of direct reaction of coal and water during the process of hydrolytic disproportionation of carbon(HDC).Some examples of experimental and natural evidences of HDC are discussed.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
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
Tacrolimus(Tac)is a cornerstone immunosuppressant in the treatment regimens for organ transplant recipients.However,its extensive clinical use has brought attention to its associated drug safety concerns.Recent case r...Tacrolimus(Tac)is a cornerstone immunosuppressant in the treatment regimens for organ transplant recipients.However,its extensive clinical use has brought attention to its associated drug safety concerns.Recent case reports highlighting Tac-induced gastrointestinal ulcers have prompted further investigation.In the present study,we analyzed Tac-associated adverse events using data from the U.S.Food and Drug Administration Adverse Event Reporting System(FAERS)to identify potential adverse event signals.Adverse event reports were collected up to the third quarter(Q3)of 2023,revealing 339 cases of Tac-related gastrointestinal ulcers.A disproportionality analysis was conducted utilizing the Bayesian confidence propagation neural network of information component(IC)and reporting odds ratio(ROR)methods.All statistical analyses were performed using R version 3.6.1.The findings demonstrated a significant signal for gastrointestinal ulcers associated with Tac use,with a ROR1 of 1.87(95%CI:1.68-2.08)and an IC1 of 0.89(95%CI:0.73-1.05)when compared to all other drugs.When compared specifically to cyclosporine,Tac also showed a significant signal(ROR2=1.55,95%CI:1.28-1.86;IC2=0.24,95%CI:0.04-0.44).Further analysis identified age,male gender,and European descent as risk factors for mortality outcomes in patients with Tac-associated gastrointestinal ulcers.These findings highlighted the critical need for clinicians to strengthen the monitoring and early detection of gastrointestinal ulcers in patients undergoing Tac therapy.Enhanced vigilance in this regard is essential to optimize the management and care of transplant patients.展开更多
Maintaining a residual disinfectant/oxidant(e.g., chlorine and chlorine dioxide), is a generally used strategy to control microbial contaminants and bacterial regrowth in distribution systems. Secondarily oxidant, suc...Maintaining a residual disinfectant/oxidant(e.g., chlorine and chlorine dioxide), is a generally used strategy to control microbial contaminants and bacterial regrowth in distribution systems. Secondarily oxidant, such as hypobromous acid(HOBr), can be formed during chlorination of bromide-containing waters. The decay of oxidants and formation of disinfection byproducts(DBPs) due to the interaction between oxidants and selected metal oxides were studied. Selected metal oxides generally enhanced the decay of these halogencontaining oxidants via three pathways:(1) catalytic disproportionation to yield an oxidized form of halogen(i.e., halate) and reduced form(halide for chlorine and bromine or chlorite for chlorine dioxide),(2) oxygen formation, and(3) oxidation of a metal in a reduced form(e.g., cuprous oxide) to a higher oxidation state. Cupric oxide(Cu O) and nickel oxide(Ni O)showed significantly strong abilities for the first pathway, and oxygen formation was a side reaction. Cuprous oxide can react with oxidants via the third pathway, while goethite was not involved in these reactions. The ability of Cu O on catalytic disproportionation of HOBr remained stable up to four cycles. In chlorination process, bromate formation tends to be important(exceeding 10 μg/L) when initial bromide concentration is above 400 μg/L in the presence of dissolved organic matter. Increasing initial bromide concentrations increased the formation of DBPs and calculated cytotoxicity, and the maximum was observed at p H8.6 during chlorination process. Therefore, the possible disinfectant loss and DBP formation should be carefully considered in drinking water distribution systems.展开更多
文摘Methyl methoxyacetate(MMAc)and methyl formate(MF)can be produced directly by heterogeneous zeolite-catalyzed carbonylation and disproportionation of dimethoxymethane(DMM),with near 100%selectivity for each process.Despite continuous research efforts,the insight into the reaction mechanism and kinetics theory are still in their nascent stage.In this study,ZEO-1 material,a zeolite with up to now the largest cages comprising 16×16-MRs,16×12-MRs,and 12×12-MRs,was explored for DMM carbonylation and disproportionation reactions.The rate of MMAc formation based on accessible Brönsted acid sites is 2.5 times higher for ZEO-1(Si/Al=21)relative to the previously investigated FAU(Si/Al=15),indicating the positive effect of spatial separation of active sites in ZEO-1 on catalytic activity.A higher MF formation rate is also observed over ZEO-1 with lower activation energy(79.94 vs.95.19 kJ/mol)compared with FAU(Si/Al=30).Two types of active sites are proposed within ZEO-1 zeolite:Site 1 located in large cages formed by 16×16-MRs and 16×12-MRs,which is active predominantly for MMAc formation,and Site 2 located in smaller cages for methyl formate/dimethyl ether formation.Kinetics investigation of DMM carbonylation over ZEO-1 exhibit a first-order dependence on CO partial pressure and a slightly inverse-order dependence on DMM partial pressure.The DMM disproportionation is nearly first-order dependence on DMM partial pressure,while it reveals a strongly inverse dependence with increasing CO partial pressure.Furthermore,ZEO-1 exhibits good catalytic stability,and almost no deactivation is observed during the more than 70 h test with high carbonylation selectivity of above 89%,due to the well-enhanced diffusion property demonstrated by intelligent-gravimetric analysis.
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.
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.
文摘This paper evaluates the thermodynamic possibility of coalbed methane formation as a result of direct reaction of coal and water during the process of hydrolytic disproportionation of carbon(HDC).Some examples of experimental and natural evidences of HDC are discussed.
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.
文摘Tacrolimus(Tac)is a cornerstone immunosuppressant in the treatment regimens for organ transplant recipients.However,its extensive clinical use has brought attention to its associated drug safety concerns.Recent case reports highlighting Tac-induced gastrointestinal ulcers have prompted further investigation.In the present study,we analyzed Tac-associated adverse events using data from the U.S.Food and Drug Administration Adverse Event Reporting System(FAERS)to identify potential adverse event signals.Adverse event reports were collected up to the third quarter(Q3)of 2023,revealing 339 cases of Tac-related gastrointestinal ulcers.A disproportionality analysis was conducted utilizing the Bayesian confidence propagation neural network of information component(IC)and reporting odds ratio(ROR)methods.All statistical analyses were performed using R version 3.6.1.The findings demonstrated a significant signal for gastrointestinal ulcers associated with Tac use,with a ROR1 of 1.87(95%CI:1.68-2.08)and an IC1 of 0.89(95%CI:0.73-1.05)when compared to all other drugs.When compared specifically to cyclosporine,Tac also showed a significant signal(ROR2=1.55,95%CI:1.28-1.86;IC2=0.24,95%CI:0.04-0.44).Further analysis identified age,male gender,and European descent as risk factors for mortality outcomes in patients with Tac-associated gastrointestinal ulcers.These findings highlighted the critical need for clinicians to strengthen the monitoring and early detection of gastrointestinal ulcers in patients undergoing Tac therapy.Enhanced vigilance in this regard is essential to optimize the management and care of transplant patients.
基金supported by the Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences (Project No. 20Z01KLDWST)。
文摘Maintaining a residual disinfectant/oxidant(e.g., chlorine and chlorine dioxide), is a generally used strategy to control microbial contaminants and bacterial regrowth in distribution systems. Secondarily oxidant, such as hypobromous acid(HOBr), can be formed during chlorination of bromide-containing waters. The decay of oxidants and formation of disinfection byproducts(DBPs) due to the interaction between oxidants and selected metal oxides were studied. Selected metal oxides generally enhanced the decay of these halogencontaining oxidants via three pathways:(1) catalytic disproportionation to yield an oxidized form of halogen(i.e., halate) and reduced form(halide for chlorine and bromine or chlorite for chlorine dioxide),(2) oxygen formation, and(3) oxidation of a metal in a reduced form(e.g., cuprous oxide) to a higher oxidation state. Cupric oxide(Cu O) and nickel oxide(Ni O)showed significantly strong abilities for the first pathway, and oxygen formation was a side reaction. Cuprous oxide can react with oxidants via the third pathway, while goethite was not involved in these reactions. The ability of Cu O on catalytic disproportionation of HOBr remained stable up to four cycles. In chlorination process, bromate formation tends to be important(exceeding 10 μg/L) when initial bromide concentration is above 400 μg/L in the presence of dissolved organic matter. Increasing initial bromide concentrations increased the formation of DBPs and calculated cytotoxicity, and the maximum was observed at p H8.6 during chlorination process. Therefore, the possible disinfectant loss and DBP formation should be carefully considered in drinking water distribution systems.
