Magneli phase titanium sub-oxide conductive ceramic Tin O2n-1 was used as the support for Pt due to its excellent resistance to electrochemical oxidation, and Pt/Tin O2n-1 composites were prepared by the impregnation-...Magneli phase titanium sub-oxide conductive ceramic Tin O2n-1 was used as the support for Pt due to its excellent resistance to electrochemical oxidation, and Pt/Tin O2n-1 composites were prepared by the impregnation-reduction method. The electrochemical stability of Tin O2n-1 was investigated and the results show almost no change in the redox region after oxidation for 20 h at 1.2 V(vs NHE) in 0.5 mol/L H2SO4 aqueous solution. The catalytic activity and stability of the Pt/Tin O2n-1 toward the oxygen reduction reaction(ORR) in 0.5 mol/L H2SO4 solution were investigated through the accelerated aging tests(AAT), and the morphology of the catalysts before and after the AAT was observed by transmission electron microscopy. At the potential of 0.55 V(vs SCE), the specific kinetic current density of the ORR on the Pt/Tin O2n-1 is about 1.5 times that of the Pt/C. The LSV curves for the Pt/C shift negatively obviously with the half-wave potential shifting about 0.02 V after 8000 cycles AAT, while no obvious change takes place for the LSV curves for the Pt/Tin O2n-1. The Pt particles supported on the carbon aggregate obviously, while the morphology of the Pt supported on Tin O2n-1 remains almost unchanged, which contributes to the electrochemical surface area loss of Pt/C being about 2times that of the Pt/Tin O2n-1. The superior catalytic stability of Pt/Tin O2n-1 toward the ORR could be attributed to the excellent stability of the Tin O2n-1 and the electronic interaction between the metals and the support.展开更多
In this paper .the change of the crystalline phases in hardened magnesium oxychloride cement (MOC) paste in mater was analyzed by XRD. It was developed that the reaction products 5 phase or 3 phase of MOC are instable...In this paper .the change of the crystalline phases in hardened magnesium oxychloride cement (MOC) paste in mater was analyzed by XRD. It was developed that the reaction products 5 phase or 3 phase of MOC are instable in water and can be changed into Mg(OH)2 by the action of water, which causes the content of 5 phase or 3 phase to be less and less,the content of Mg(OH)2 to be more and more and the strength to be the lower the lower,after hardended MOC paste was immersed in water. The change of 5 pliase and 3 phase into Mg(OH)2 is not a dissolve process, but a hydrolysis process. The hydrolysis products of 5 phase and 3 phase are Mg(OH)2 precipitation and soluble Cl-,AIg+ ions and H2O. The hydrolysis is sponta-neous thermodynamically and its chemical kinatic equation is C = C,,e-k Thus .it is suggested that only by enhancing the stability of 5 phase or 3 phase in water and preventing 5 phase or 3 phase from the hydrolyzing can the water resistance of MOC be improved well.展开更多
In this paper we are interested in the large time behavior of the nonlinear diffusion equationWe consider functions which allow the equation to possess traveling wave solutions. We first present an existence and uniqu...In this paper we are interested in the large time behavior of the nonlinear diffusion equationWe consider functions which allow the equation to possess traveling wave solutions. We first present an existence and uniqueness as well as some comparison principle result of generalized solutions to the Cauchy problem. Then we give for some threshold results, from which we can see that u=a is stable, while u= 0 or u=1 is unstable under some assumptions, etc.展开更多
The performance of the two newly developed bimetallic catalysts based on the precursor, Mo/Al_2O_3, was compared for reverse water gas shift(RWGS) reaction. The structures of the precursor and the catalysts were studi...The performance of the two newly developed bimetallic catalysts based on the precursor, Mo/Al_2O_3, was compared for reverse water gas shift(RWGS) reaction. The structures of the precursor and the catalysts were studied using X-ray diffraction(XRD), Brunauer–Emmett–Teller(BET) analysis, inductively coupled plasma-atomic emission spectrometry(ICP-AES), CO chemisorption, temperature programmed reduction of hydrogen(H_2-TPR) and scanning electron microscopy(SEM) techniques. The activity of Fe-Mo and Co-Mo catalysts was compared in a fixed bed reactor at different temperatures. It is shown that the Co-Mo catalyst has higher CO_2 conversion at all temperature level. The time-on-stream(TOS) analysis of the activity of catalysts for the RWGS reaction was carried out over a continuous period of 60h for both catalysts. The Fe-Mo/Al_2O_3 catalyst exhibits good stability within a period of 60h, however, the Co-Mo/Al_2O_3 is gradually deactivated after 50h of reaction time. Existence of(Fe_2(MoO4_))_3 phase in Fe-Mo/Al_2O_3 catalyst makes this catalyst more stable for RWGS reaction.展开更多
The catalytic performance of co mmonly used heteropolyacids (H3PW12O40, H4SiW12O40 and H3PMO12O40 synthesis of 4,4'-methylenedianiline (4,4'-MDA) from aniline and formaldehyde was evaluated and the result showed ...The catalytic performance of co mmonly used heteropolyacids (H3PW12O40, H4SiW12O40 and H3PMO12O40 synthesis of 4,4'-methylenedianiline (4,4'-MDA) from aniline and formaldehyde was evaluated and the result showed that H4SiW12O40 with moderate acid strength exhibited the best catalytic performance. Then HaSiW12O40@MIL-100(Fe) was prepared by encapsulating H4SiW12O40 within the pores of MIL-100(Fe) to facilitate its recovery and reuse. The prepared H4SiW12O40@MIL-100(Fe) was characterized by means of FT-IR, N2 adsorption-desorption, XRD, TG and then the catalytic performance was evaluated. The result showed that H4SiW12O40 was highly dispersed in the pores of MIL-100(Fe), and both the Keggin structure of HaSiW12O40 and the crystal skeleton structure of MIL-100(Fe) could be effectively/preserved. Furthermore, H4SiW12O40@ MIL-100(Fe) showed excellent catalytic performance under the following reaction conditions: a molar ratio of aniline to formaldehyde = 5, a mass ratio of catalyst to formaldehyde = 1.2, a reaction temperature of 120 ℃ and a reaction time of 6 h. Under the above reaction conditions, the conversion of aniline was 41.1%, and the yield and selectivity of 4,4'-MDA were 81,6% and 79.2%, respectively. Unfortunately, an appreciable loss in the catalytic activity of the recovered H4SiW12O40@MIL-100(Fe) was observed because of the blocking of the pores and the change of the acidity resulted from the adsorption of alkaline organics such as aniline and 4,4'-MDA. The adsorbed alkaline organics could be cleaned up when the recovered catalyst was washed by methanol and DMF. Then the catalyst was effectively reused up to three cycles without much loss in its activity.展开更多
The accelerating rate calorimeter was applied to study the thermal hazard of two kinds of organic peroxides, i.e. methyl ethyl ketone peroxide (MEKPO) and benzoyl peroxide (BPO). And their thermal decomposition charac...The accelerating rate calorimeter was applied to study the thermal hazard of two kinds of organic peroxides, i.e. methyl ethyl ketone peroxide (MEKPO) and benzoyl peroxide (BPO). And their thermal decomposition characteristics were discussed. Meanwhile, thermal decomposition characteristics of MEKPO and BPO vvere compared. The result indicated that MEKPO is more sensitive to thermal effect than BPO. While once the thermal decomposition takes place. BPO will be more hazardous than MEKPO due to its serious pressure effect. Thermal kinetic analysis of these two kinds of organic peroxides was also taken, and the kinetic parameters for them were calculated. The study of thermal decomposition of MEKPO solution with different initial concentrations indicated that, the lower concentration MEKPO solution is, the higher onset temperature will be. And with the addition of organic solvent, it becomes more difficult for MEKPO to reach a thermal decomposition. Therefore, its thermal hazard is reduced.展开更多
Oxygen evolution reaction(OER) is one of the most important reactions in the energy storage devices such as metal–air batteries and unitized regenerative fuel cells(URFCs). However, the kinetically sluggishness o...Oxygen evolution reaction(OER) is one of the most important reactions in the energy storage devices such as metal–air batteries and unitized regenerative fuel cells(URFCs). However, the kinetically sluggishness of OER and the high prices as well as the scarcity of the most active precious metal electrocatalysts are the major bottleneck in these devices. Developing low-cost non-precious metal catalysts with high activity and stability for OER is highly desirable. A facile, in situ template method combining the dodecyl benzene sulfuric acid sodium(SDBS) assisted hydrothermal process with subsequent high-temperature treatment was developed to prepare porous Co3O4 with improved surface area and hierarchical porous structure as precious catalysts alternative for oxygen evolution reaction(OER). Due to the unique structure, the as-prepared catalyst shows higher electrocatalytic activity than Co3O4 prepared by traditional thermal-decomposition method(noted as Co3O4-T) and commercial IrO2 catalyst for OER in 0.1M KOH aqueous solution. Moreover, it displays improved stability than Co3O4-T. The results demonstrate a highly efficient, scalable, and low cost method for developing highly active and stable OER electrocatalysts in alkaline solutions.展开更多
In the present contribution,we demonstrate that the sluggish kinetics of oxygen evolution reaction(OER)over the bismuth sulfide(Bi_(2)S_(3))photoanode,which severely restricts its photoelectrochemical activity,is mark...In the present contribution,we demonstrate that the sluggish kinetics of oxygen evolution reaction(OER)over the bismuth sulfide(Bi_(2)S_(3))photoanode,which severely restricts its photoelectrochemical activity,is markedly accelerated by employing a sulfatecontaining electrolyte.First-principle calculation points to the spontaneous adsorption of sulfate(SO_(4)^(2−))on Bi_(2)S_(3)and its capacity of stabilizing the OER intermediates through hydrogen bonding,which is further reinforced by increasing the local density of states near the Fermi level of Bi_(2)S_(3).Meanwhile,the electron transfer is also promoted to synergistically render the ratedetermining step(from O*to OOH*)of OER over Bi_(2)S_(3)kinetically facile.Last but not least,benefitting from such enhanced OER activity and efficient charge separation resulted from depositing Bi_(2)S_(3)on the zinc oxide nanorods(ZnO NRs),forming a core–shell heterojunction,its photocurrent density achieves 8.61 mA·cm^(−2)at 1.23 VRHE,far surpassing those reported for additional Bi_(2)S_(3)-based and several state-of-the-art photoanodes in the literature and further exceeding their theoretical limit.The great promise of the Bi_(2)S_(3)/ZnO NRs is in view of such outperformance,the superior Faradaic yield of oxygen of more than~80%and the outstanding half-cell applied bias photon-to-current efficiency of~1%well corroborated.展开更多
基金Project(21406273)supported by the National Natural Science Foundation of China
文摘Magneli phase titanium sub-oxide conductive ceramic Tin O2n-1 was used as the support for Pt due to its excellent resistance to electrochemical oxidation, and Pt/Tin O2n-1 composites were prepared by the impregnation-reduction method. The electrochemical stability of Tin O2n-1 was investigated and the results show almost no change in the redox region after oxidation for 20 h at 1.2 V(vs NHE) in 0.5 mol/L H2SO4 aqueous solution. The catalytic activity and stability of the Pt/Tin O2n-1 toward the oxygen reduction reaction(ORR) in 0.5 mol/L H2SO4 solution were investigated through the accelerated aging tests(AAT), and the morphology of the catalysts before and after the AAT was observed by transmission electron microscopy. At the potential of 0.55 V(vs SCE), the specific kinetic current density of the ORR on the Pt/Tin O2n-1 is about 1.5 times that of the Pt/C. The LSV curves for the Pt/C shift negatively obviously with the half-wave potential shifting about 0.02 V after 8000 cycles AAT, while no obvious change takes place for the LSV curves for the Pt/Tin O2n-1. The Pt particles supported on the carbon aggregate obviously, while the morphology of the Pt supported on Tin O2n-1 remains almost unchanged, which contributes to the electrochemical surface area loss of Pt/C being about 2times that of the Pt/Tin O2n-1. The superior catalytic stability of Pt/Tin O2n-1 toward the ORR could be attributed to the excellent stability of the Tin O2n-1 and the electronic interaction between the metals and the support.
文摘In this paper .the change of the crystalline phases in hardened magnesium oxychloride cement (MOC) paste in mater was analyzed by XRD. It was developed that the reaction products 5 phase or 3 phase of MOC are instable in water and can be changed into Mg(OH)2 by the action of water, which causes the content of 5 phase or 3 phase to be less and less,the content of Mg(OH)2 to be more and more and the strength to be the lower the lower,after hardended MOC paste was immersed in water. The change of 5 pliase and 3 phase into Mg(OH)2 is not a dissolve process, but a hydrolysis process. The hydrolysis products of 5 phase and 3 phase are Mg(OH)2 precipitation and soluble Cl-,AIg+ ions and H2O. The hydrolysis is sponta-neous thermodynamically and its chemical kinatic equation is C = C,,e-k Thus .it is suggested that only by enhancing the stability of 5 phase or 3 phase in water and preventing 5 phase or 3 phase from the hydrolyzing can the water resistance of MOC be improved well.
文摘In this paper we are interested in the large time behavior of the nonlinear diffusion equationWe consider functions which allow the equation to possess traveling wave solutions. We first present an existence and uniqueness as well as some comparison principle result of generalized solutions to the Cauchy problem. Then we give for some threshold results, from which we can see that u=a is stable, while u= 0 or u=1 is unstable under some assumptions, etc.
基金the Iranian Nano Technology Initiative Council and the Petroleum University of Technology for financial support
文摘The performance of the two newly developed bimetallic catalysts based on the precursor, Mo/Al_2O_3, was compared for reverse water gas shift(RWGS) reaction. The structures of the precursor and the catalysts were studied using X-ray diffraction(XRD), Brunauer–Emmett–Teller(BET) analysis, inductively coupled plasma-atomic emission spectrometry(ICP-AES), CO chemisorption, temperature programmed reduction of hydrogen(H_2-TPR) and scanning electron microscopy(SEM) techniques. The activity of Fe-Mo and Co-Mo catalysts was compared in a fixed bed reactor at different temperatures. It is shown that the Co-Mo catalyst has higher CO_2 conversion at all temperature level. The time-on-stream(TOS) analysis of the activity of catalysts for the RWGS reaction was carried out over a continuous period of 60h for both catalysts. The Fe-Mo/Al_2O_3 catalyst exhibits good stability within a period of 60h, however, the Co-Mo/Al_2O_3 is gradually deactivated after 50h of reaction time. Existence of(Fe_2(MoO4_))_3 phase in Fe-Mo/Al_2O_3 catalyst makes this catalyst more stable for RWGS reaction.
基金Supported by the National Natural Science Foundation of China(21236001,21476058,21506046)
文摘The catalytic performance of co mmonly used heteropolyacids (H3PW12O40, H4SiW12O40 and H3PMO12O40 synthesis of 4,4'-methylenedianiline (4,4'-MDA) from aniline and formaldehyde was evaluated and the result showed that H4SiW12O40 with moderate acid strength exhibited the best catalytic performance. Then HaSiW12O40@MIL-100(Fe) was prepared by encapsulating H4SiW12O40 within the pores of MIL-100(Fe) to facilitate its recovery and reuse. The prepared H4SiW12O40@MIL-100(Fe) was characterized by means of FT-IR, N2 adsorption-desorption, XRD, TG and then the catalytic performance was evaluated. The result showed that H4SiW12O40 was highly dispersed in the pores of MIL-100(Fe), and both the Keggin structure of HaSiW12O40 and the crystal skeleton structure of MIL-100(Fe) could be effectively/preserved. Furthermore, H4SiW12O40@ MIL-100(Fe) showed excellent catalytic performance under the following reaction conditions: a molar ratio of aniline to formaldehyde = 5, a mass ratio of catalyst to formaldehyde = 1.2, a reaction temperature of 120 ℃ and a reaction time of 6 h. Under the above reaction conditions, the conversion of aniline was 41.1%, and the yield and selectivity of 4,4'-MDA were 81,6% and 79.2%, respectively. Unfortunately, an appreciable loss in the catalytic activity of the recovered H4SiW12O40@MIL-100(Fe) was observed because of the blocking of the pores and the change of the acidity resulted from the adsorption of alkaline organics such as aniline and 4,4'-MDA. The adsorbed alkaline organics could be cleaned up when the recovered catalyst was washed by methanol and DMF. Then the catalyst was effectively reused up to three cycles without much loss in its activity.
文摘The accelerating rate calorimeter was applied to study the thermal hazard of two kinds of organic peroxides, i.e. methyl ethyl ketone peroxide (MEKPO) and benzoyl peroxide (BPO). And their thermal decomposition characteristics were discussed. Meanwhile, thermal decomposition characteristics of MEKPO and BPO vvere compared. The result indicated that MEKPO is more sensitive to thermal effect than BPO. While once the thermal decomposition takes place. BPO will be more hazardous than MEKPO due to its serious pressure effect. Thermal kinetic analysis of these two kinds of organic peroxides was also taken, and the kinetic parameters for them were calculated. The study of thermal decomposition of MEKPO solution with different initial concentrations indicated that, the lower concentration MEKPO solution is, the higher onset temperature will be. And with the addition of organic solvent, it becomes more difficult for MEKPO to reach a thermal decomposition. Therefore, its thermal hazard is reduced.
基金supported by the Youth Innovation Promotion Association(no.2015147)CAS and National Program on Key Basic Research Project(973 Program,2012CB215500)+1 种基金the Outstanding Youngest Scientist FoundationChinese Academy of Sciences(CAS)
文摘Oxygen evolution reaction(OER) is one of the most important reactions in the energy storage devices such as metal–air batteries and unitized regenerative fuel cells(URFCs). However, the kinetically sluggishness of OER and the high prices as well as the scarcity of the most active precious metal electrocatalysts are the major bottleneck in these devices. Developing low-cost non-precious metal catalysts with high activity and stability for OER is highly desirable. A facile, in situ template method combining the dodecyl benzene sulfuric acid sodium(SDBS) assisted hydrothermal process with subsequent high-temperature treatment was developed to prepare porous Co3O4 with improved surface area and hierarchical porous structure as precious catalysts alternative for oxygen evolution reaction(OER). Due to the unique structure, the as-prepared catalyst shows higher electrocatalytic activity than Co3O4 prepared by traditional thermal-decomposition method(noted as Co3O4-T) and commercial IrO2 catalyst for OER in 0.1M KOH aqueous solution. Moreover, it displays improved stability than Co3O4-T. The results demonstrate a highly efficient, scalable, and low cost method for developing highly active and stable OER electrocatalysts in alkaline solutions.
基金supported by the National Natural Science Foundation of China and Shanghai Jiao Tong University(Nos.22109096,WF220528005 and ZXDF280001/024).
文摘In the present contribution,we demonstrate that the sluggish kinetics of oxygen evolution reaction(OER)over the bismuth sulfide(Bi_(2)S_(3))photoanode,which severely restricts its photoelectrochemical activity,is markedly accelerated by employing a sulfatecontaining electrolyte.First-principle calculation points to the spontaneous adsorption of sulfate(SO_(4)^(2−))on Bi_(2)S_(3)and its capacity of stabilizing the OER intermediates through hydrogen bonding,which is further reinforced by increasing the local density of states near the Fermi level of Bi_(2)S_(3).Meanwhile,the electron transfer is also promoted to synergistically render the ratedetermining step(from O*to OOH*)of OER over Bi_(2)S_(3)kinetically facile.Last but not least,benefitting from such enhanced OER activity and efficient charge separation resulted from depositing Bi_(2)S_(3)on the zinc oxide nanorods(ZnO NRs),forming a core–shell heterojunction,its photocurrent density achieves 8.61 mA·cm^(−2)at 1.23 VRHE,far surpassing those reported for additional Bi_(2)S_(3)-based and several state-of-the-art photoanodes in the literature and further exceeding their theoretical limit.The great promise of the Bi_(2)S_(3)/ZnO NRs is in view of such outperformance,the superior Faradaic yield of oxygen of more than~80%and the outstanding half-cell applied bias photon-to-current efficiency of~1%well corroborated.