Supercritical fluids play a crucial role in material transport within Earth's deep interior.Investigating the pressure-dependent atomic structures and transport properties of such fluids is essential for understan...Supercritical fluids play a crucial role in material transport within Earth's deep interior.Investigating the pressure-dependent atomic structures and transport properties of such fluids is essential for understanding their petrological,chemical,and geophysical behaviors.In this study,we employed first-principles molecular dynamics simulations to explore the structures,self-diffusion coefficients(D),and viscosities(η)of supercritical NaAlSi_(3)O_(8)-H_(2)O fluids under conditions of 2000 K and 3-10 GPa,with water contents of 30 wt% and 50 wt%.Our calculations indicate that at a water content of 30 wt%,Q^(2) and Q^(3) exhibit a certain degree of positive and negative pressure dependence,respectively,while other Q^(n) species(n represents the number of bridging oxygens connected to Si/Al)show minimal changes.At a water content of 50 wt%,Q^(2) and Q^(0) exhibit a certain degree of positive and negative pressure dependence,respectively,while other Q^(n) species show minimal changes.At both water contents,Si-O-H and molecular water in the system exhibit negative pressure dependence,suggesting that the migration of supercritical fluids from deep to shallow regions is accompanied by the release of water.The self-diffusion coefficients in the supercritical NaAlSi_(3)O_(8)-H_(2)O fluid follow the order D_(Na)≈D_(H)>D_(O)>D_(Al)≈D_(Si),with an overall weak negative pressure dependence.By comparing the viscosities of anhydrous and hydrous silicate melts from previous studies,we found that the addition of water caused a transition from negative to positive pressure dependence of viscosity,corresponding to a structural change from polymerization to depolymerization.Additionally,we calculated the fluid mobility Δp/η of supercritical NaAlSi_(3)O_(8)-H_(2)O fluids and found that their mobility is several orders of magnitude higher than that of basalt melt and is also significantly greater than that of carbonate melt.As supercritical fluids ascend from deeper to shallower regions,their mobility is further enhanced,significantly contributing to the transport of elements from subducting slabs to the overlying mantle wedge.展开更多
P2型层状过渡金属氧化物(P2-Na_(x)TMO_(2))因其优异的循环稳定性和倍率性能,成为钠离子电池正极材料的有力候选者。然而,其在高电压下的不可逆相变和固有低理论容量问题,阻碍了实际应用。本研究工作提出高熵策略与双相结构的协同设计...P2型层状过渡金属氧化物(P2-Na_(x)TMO_(2))因其优异的循环稳定性和倍率性能,成为钠离子电池正极材料的有力候选者。然而,其在高电压下的不可逆相变和固有低理论容量问题,阻碍了实际应用。本研究工作提出高熵策略与双相结构的协同设计来克服这些挑战。通过在P2相高熵基体中引入O3相,构建新型P2/O3双相高熵层状氧化物Na_(0.70)Ni_(0.25)Mn_(0.35)Co_(0.15)Fe_(0.05)Ti_(0.20)O_(2)(简称Na_(0.70)NMCFT)。其中,高熵设计通过构型熵稳定效应有效抑制P2相的不可逆相变,而O3相则通过协同作用弥补容量不足并提升循环稳定性。此外,双相组分之间的相互作用进一步促进P2-O3与P2-P3相变的高度可逆性。Na_(0.70)NMCFT在1C倍率下的初始放电容量为102.08 mAhg^(-1),200次循环后容量保持率达88.15%,表明具有优异的循环稳定性。更重要的是,即使在10C的高倍率下,Na_(0.70)NMCFT仍能提供85.67 mAh g^(-1)的初始放电比容量,并在1000次循环后容量保持率达70%。本工作证实双相高熵设计在提升钠离子电池正极性能中的关键作用,为开发先进钠离子电池正极材料提供了新思路。展开更多
The formation characteristics of calcium aluminates in the CaO-Al2O3-SiO2 system with sodium oxide was investigated by XRD, SEM-EDS and DSC-TG technologies. The main phases in the clinker after sintering at 1350 °...The formation characteristics of calcium aluminates in the CaO-Al2O3-SiO2 system with sodium oxide was investigated by XRD, SEM-EDS and DSC-TG technologies. The main phases in the clinker after sintering at 1350 °C are 12CaO?7Al2O3, 2CaO?Al2O3?SiO2 and 2CaO?SiO2 when the mass ratio of Al2O3 to SiO2 is 3.0 and the molar ratio of CaO to Al2O3 is 1.0. The proportion of 12CaO?7Al2O3 increases with the increase of Na2O addition when the molar ratio of Na2O to Al2O3 is from 0 to 0.4, while the proportion of 2CaO?Al2O3?SiO2 decreases with the increase of Na2O addition. Na2O forms solid solution in 12CaO?7Al2O3, which increases the volume of elementary cell of 12CaO?7Al2O3. The formation temperature of 12CaO?7Al2O3 is decreased by 30 °C when the molar ratio of Na2O to Al2O3 increases from 0 to 0.4 determined by DSC. The alumina leaching property of clinker increases obviously with the increase of Na2O addition.展开更多
The rapid recombination of photogenerated carriers poses a significant limitation on the use of CdS quantum dots(QDs)in photocatalysis.Herein,the construction of a novel S-scheme heterojunction between cubic-phase CdS...The rapid recombination of photogenerated carriers poses a significant limitation on the use of CdS quantum dots(QDs)in photocatalysis.Herein,the construction of a novel S-scheme heterojunction between cubic-phase CdS QDs and hollow nanotube In_(2)O_(3)is successfully achieved using an electrostatic self-assembly method.Under visible light irradiation,all CdS-In_(2)O_(3)composites exhibit higher hydrogen evolution efficiency compared to pure CdS QDs.Notably,the photocatalytic H_(2)evolution rate of the optimal CdS-7%In_(2)O_(3)composite is determined to be 2258.59μmol g^(−1)h^(−1),approximately 12.3 times higher than that of pure CdS.The cyclic test indicates that the CdS-In_(2)O_(3)composite maintains considerable activity even after 5 cycles,indicating its excellent stability.In situ X-ray photoelectron spectroscopy and density functional theory calculations confirm that carrier migration in CdS-In_(2)O_(3)composites adheres to a typical S-scheme heterojunction mechanism.Additionally,a series of characterizations demonstrate that the formation of S-scheme heterojunctions between In_(2)O_(3)and CdS inhibits charge recombination and accelerates the separation and migration of photogenerated carriers in the CdS QDs,thus achieving enhanced photocatalytic performance.This work elucidates the pivotal role of S-scheme heterojunctions in photocatalytic H_(2)production and offers novel insights into the construction of effective composite photocatalysts.展开更多
A method to extract inclusion particles from solid steel by electrolysis with organic electrolyte solution was introduced; meanwhile, thermodynamics of inclusion formation was calculated using FaetSage software. The r...A method to extract inclusion particles from solid steel by electrolysis with organic electrolyte solution was introduced; meanwhile, thermodynamics of inclusion formation was calculated using FaetSage software. The results showed that there were two kinds of inclusions in the billet, i.e. Al2O3-MnO-SiO2-MnS （AMS-MnS） and Al2O3- MnO-SiO2 （AMS）. Most of AMS-MnS inclusion particles, with diameter of 10--30 μm, showed three-layer structures： SiO2-rich core with a small quantity of Mn, intermediate AMS layer, and MnS outer layer containing small quanti- ties of A1 and O. Most AMS inclusion particles were 50--90 μm and exhibited homogeneous composition. Thermo- dynamic results indicated that SiO2-rich core could form firstly by Si reacting with O in molten steel at temperatures above 1 923 K during Si-Fe alloy addition, and then, the SiO2-rich core could react with Mn and Al to form liquid AMS enveloping the SiO2 rich core at 1823- 1873 K. MnS began to precipitate from AMS when temperature reached 1 728 K. Liquid AMS could form by coupled reaction among Si, Mn, Al and O in molten steel.展开更多
Fluorite is widely employed as fluxing agent in metallurgy flux , which inevitably leads to serious fluorine pollution.B2O3 is employed as fluxing agent of CaO-SiO2-Fe2O3steelmaking fluxes to substitute for CaF2.The e...Fluorite is widely employed as fluxing agent in metallurgy flux , which inevitably leads to serious fluorine pollution.B2O3 is employed as fluxing agent of CaO-SiO2-Fe2O3steelmaking fluxes to substitute for CaF2.The effects of B2O3 and CaF2 on the melting properties of this system were investigated.The melting temperatures of fluxes including softening temperature （Ts）, hemispherical temperature （Th）, and flow temperature （Tf） were measured using the hemisphere method.The results indicate that the fluxing effect of B2O3is more significant than that of CaF2 .When the addition amount of B2O3 （mass percent） exceeds 6% , the melting temperatures of fluxes including Ts , Th and Tf are decreased lower than 1 300℃.The basicity of fluxes has a significant effect on the melting temperature , and the melting temperatures of the fluxes increase with the increase of fluxes basicity.However , when B2O3 is used as fluxing agent , the melting temperature changes little with the basicity increasing from 2.5 to 5.0. These characteristics are suitable for steelmaking process.Moreover , Fe2O3 has an important fluxing effect on this CaO-based steelmaking fluxes.This indicates that the fluxes system is suitable for steelmaking process.展开更多
The sintering characteristics at 1350℃ and leaching property at 80℃ of calcium aluminate clinkers in the CaO-Al2O3-SiO2 （C-A-S） system with different additions of FeO and Fe2O3 were investigated. FeO inhibits the ...The sintering characteristics at 1350℃ and leaching property at 80℃ of calcium aluminate clinkers in the CaO-Al2O3-SiO2 （C-A-S） system with different additions of FeO and Fe2O3 were investigated. FeO inhibits the conversion of β-Ca2SiO4 to γ-Ca2SiO4 and makes the clinker not pulverizable. FeO and Fe2O3 inhibit the formation of CaAl2O4, but promote the formation of Ca12Al14O33. The interplanar spacing at （2 1 1） crystal face of Ca12 Al14O33 in the clinker increases with the increase of FeO addition, which indicates that FeO forms solid solutions in Ca12Al14O33. The clinkers with Fe2O3 addition form a new phase Ca2Fe2O5, and the amount of Ca2Fe2o5 increases with the in crease of Fe2O3 addition. Both FeO and Fe2O3 do not affect the Al2O3 leaching rate of calcium aluminate clinker in sodium carbonate solution, but they increase the molar ratio of caustic Na2O to Al2O3 in the leached liquor.展开更多
A near infrared to visible blue, green, and red upconversion luminescence in a Tb^3＋-doped CaO-Al2O3-SiO2 glass was studied, which was excited using 800 nm femtosecond laser irradiation. The upconversion luminescence...A near infrared to visible blue, green, and red upconversion luminescence in a Tb^3＋-doped CaO-Al2O3-SiO2 glass was studied, which was excited using 800 nm femtosecond laser irradiation. The upconversion luminescence was attributed to ^5D3→^7F5, ^5D3→^7F4, ^5D3→^7F3, ^5D4→^7F6, ^5D4→^7F5, ^5D4→^7F4, and ^5D4→^7F3 transitions of Tb^3＋. The relationship between upconversion luminescence intensity and the pump power indicated that a three-photon simultaneous absorption process was dominant in this upconversion luminescence. The intense red, green, and blue upconversion luminescence of Tb^3＋-doped CaO-Al2O3-SiO2 glass may be potentially useful in developing three-dimensional display applications.展开更多
基金funded by National Natural Science Foundation of China(42373033,Yicheng Sun)Fundamental Research Funds for the Central Universities(B240201111,Yicheng Sun)。
文摘Supercritical fluids play a crucial role in material transport within Earth's deep interior.Investigating the pressure-dependent atomic structures and transport properties of such fluids is essential for understanding their petrological,chemical,and geophysical behaviors.In this study,we employed first-principles molecular dynamics simulations to explore the structures,self-diffusion coefficients(D),and viscosities(η)of supercritical NaAlSi_(3)O_(8)-H_(2)O fluids under conditions of 2000 K and 3-10 GPa,with water contents of 30 wt% and 50 wt%.Our calculations indicate that at a water content of 30 wt%,Q^(2) and Q^(3) exhibit a certain degree of positive and negative pressure dependence,respectively,while other Q^(n) species(n represents the number of bridging oxygens connected to Si/Al)show minimal changes.At a water content of 50 wt%,Q^(2) and Q^(0) exhibit a certain degree of positive and negative pressure dependence,respectively,while other Q^(n) species show minimal changes.At both water contents,Si-O-H and molecular water in the system exhibit negative pressure dependence,suggesting that the migration of supercritical fluids from deep to shallow regions is accompanied by the release of water.The self-diffusion coefficients in the supercritical NaAlSi_(3)O_(8)-H_(2)O fluid follow the order D_(Na)≈D_(H)>D_(O)>D_(Al)≈D_(Si),with an overall weak negative pressure dependence.By comparing the viscosities of anhydrous and hydrous silicate melts from previous studies,we found that the addition of water caused a transition from negative to positive pressure dependence of viscosity,corresponding to a structural change from polymerization to depolymerization.Additionally,we calculated the fluid mobility Δp/η of supercritical NaAlSi_(3)O_(8)-H_(2)O fluids and found that their mobility is several orders of magnitude higher than that of basalt melt and is also significantly greater than that of carbonate melt.As supercritical fluids ascend from deeper to shallower regions,their mobility is further enhanced,significantly contributing to the transport of elements from subducting slabs to the overlying mantle wedge.
文摘P2型层状过渡金属氧化物(P2-Na_(x)TMO_(2))因其优异的循环稳定性和倍率性能,成为钠离子电池正极材料的有力候选者。然而,其在高电压下的不可逆相变和固有低理论容量问题,阻碍了实际应用。本研究工作提出高熵策略与双相结构的协同设计来克服这些挑战。通过在P2相高熵基体中引入O3相,构建新型P2/O3双相高熵层状氧化物Na_(0.70)Ni_(0.25)Mn_(0.35)Co_(0.15)Fe_(0.05)Ti_(0.20)O_(2)(简称Na_(0.70)NMCFT)。其中,高熵设计通过构型熵稳定效应有效抑制P2相的不可逆相变,而O3相则通过协同作用弥补容量不足并提升循环稳定性。此外,双相组分之间的相互作用进一步促进P2-O3与P2-P3相变的高度可逆性。Na_(0.70)NMCFT在1C倍率下的初始放电容量为102.08 mAhg^(-1),200次循环后容量保持率达88.15%,表明具有优异的循环稳定性。更重要的是,即使在10C的高倍率下,Na_(0.70)NMCFT仍能提供85.67 mAh g^(-1)的初始放电比容量,并在1000次循环后容量保持率达70%。本工作证实双相高熵设计在提升钠离子电池正极性能中的关键作用,为开发先进钠离子电池正极材料提供了新思路。
基金Projects(51174054,51104041)supported by the National Natural Science Foundation of China
文摘The formation characteristics of calcium aluminates in the CaO-Al2O3-SiO2 system with sodium oxide was investigated by XRD, SEM-EDS and DSC-TG technologies. The main phases in the clinker after sintering at 1350 °C are 12CaO?7Al2O3, 2CaO?Al2O3?SiO2 and 2CaO?SiO2 when the mass ratio of Al2O3 to SiO2 is 3.0 and the molar ratio of CaO to Al2O3 is 1.0. The proportion of 12CaO?7Al2O3 increases with the increase of Na2O addition when the molar ratio of Na2O to Al2O3 is from 0 to 0.4, while the proportion of 2CaO?Al2O3?SiO2 decreases with the increase of Na2O addition. Na2O forms solid solution in 12CaO?7Al2O3, which increases the volume of elementary cell of 12CaO?7Al2O3. The formation temperature of 12CaO?7Al2O3 is decreased by 30 °C when the molar ratio of Na2O to Al2O3 increases from 0 to 0.4 determined by DSC. The alumina leaching property of clinker increases obviously with the increase of Na2O addition.
文摘The rapid recombination of photogenerated carriers poses a significant limitation on the use of CdS quantum dots(QDs)in photocatalysis.Herein,the construction of a novel S-scheme heterojunction between cubic-phase CdS QDs and hollow nanotube In_(2)O_(3)is successfully achieved using an electrostatic self-assembly method.Under visible light irradiation,all CdS-In_(2)O_(3)composites exhibit higher hydrogen evolution efficiency compared to pure CdS QDs.Notably,the photocatalytic H_(2)evolution rate of the optimal CdS-7%In_(2)O_(3)composite is determined to be 2258.59μmol g^(−1)h^(−1),approximately 12.3 times higher than that of pure CdS.The cyclic test indicates that the CdS-In_(2)O_(3)composite maintains considerable activity even after 5 cycles,indicating its excellent stability.In situ X-ray photoelectron spectroscopy and density functional theory calculations confirm that carrier migration in CdS-In_(2)O_(3)composites adheres to a typical S-scheme heterojunction mechanism.Additionally,a series of characterizations demonstrate that the formation of S-scheme heterojunctions between In_(2)O_(3)and CdS inhibits charge recombination and accelerates the separation and migration of photogenerated carriers in the CdS QDs,thus achieving enhanced photocatalytic performance.This work elucidates the pivotal role of S-scheme heterojunctions in photocatalytic H_(2)production and offers novel insights into the construction of effective composite photocatalysts.
基金Item Sponsored by National Natural Science Foundation of China(51004054)Foundation from Liaoning Province Education Department of China(L2013127)
文摘A method to extract inclusion particles from solid steel by electrolysis with organic electrolyte solution was introduced; meanwhile, thermodynamics of inclusion formation was calculated using FaetSage software. The results showed that there were two kinds of inclusions in the billet, i.e. Al2O3-MnO-SiO2-MnS （AMS-MnS） and Al2O3- MnO-SiO2 （AMS）. Most of AMS-MnS inclusion particles, with diameter of 10--30 μm, showed three-layer structures： SiO2-rich core with a small quantity of Mn, intermediate AMS layer, and MnS outer layer containing small quanti- ties of A1 and O. Most AMS inclusion particles were 50--90 μm and exhibited homogeneous composition. Thermo- dynamic results indicated that SiO2-rich core could form firstly by Si reacting with O in molten steel at temperatures above 1 923 K during Si-Fe alloy addition, and then, the SiO2-rich core could react with Mn and Al to form liquid AMS enveloping the SiO2 rich core at 1823- 1873 K. MnS began to precipitate from AMS when temperature reached 1 728 K. Liquid AMS could form by coupled reaction among Si, Mn, Al and O in molten steel.
基金Item Sponsored by National Natural Science Foundation of China ( 51174099 )Natural Science Foundation of Jiangsu Province of China ( BK2010355 )National Science Foundation for Post-Doctoral Scientists of China ( 20100471382 )
文摘Fluorite is widely employed as fluxing agent in metallurgy flux , which inevitably leads to serious fluorine pollution.B2O3 is employed as fluxing agent of CaO-SiO2-Fe2O3steelmaking fluxes to substitute for CaF2.The effects of B2O3 and CaF2 on the melting properties of this system were investigated.The melting temperatures of fluxes including softening temperature （Ts）, hemispherical temperature （Th）, and flow temperature （Tf） were measured using the hemisphere method.The results indicate that the fluxing effect of B2O3is more significant than that of CaF2 .When the addition amount of B2O3 （mass percent） exceeds 6% , the melting temperatures of fluxes including Ts , Th and Tf are decreased lower than 1 300℃.The basicity of fluxes has a significant effect on the melting temperature , and the melting temperatures of the fluxes increase with the increase of fluxes basicity.However , when B2O3 is used as fluxing agent , the melting temperature changes little with the basicity increasing from 2.5 to 5.0. These characteristics are suitable for steelmaking process.Moreover , Fe2O3 has an important fluxing effect on this CaO-based steelmaking fluxes.This indicates that the fluxes system is suitable for steelmaking process.
基金Item Sponsored by National Natural Science Foundation of China(51174054,51104041,51374065)
文摘The sintering characteristics at 1350℃ and leaching property at 80℃ of calcium aluminate clinkers in the CaO-Al2O3-SiO2 （C-A-S） system with different additions of FeO and Fe2O3 were investigated. FeO inhibits the conversion of β-Ca2SiO4 to γ-Ca2SiO4 and makes the clinker not pulverizable. FeO and Fe2O3 inhibit the formation of CaAl2O4, but promote the formation of Ca12Al14O33. The interplanar spacing at （2 1 1） crystal face of Ca12 Al14O33 in the clinker increases with the increase of FeO addition, which indicates that FeO forms solid solutions in Ca12Al14O33. The clinkers with Fe2O3 addition form a new phase Ca2Fe2O5, and the amount of Ca2Fe2o5 increases with the in crease of Fe2O3 addition. Both FeO and Fe2O3 do not affect the Al2O3 leaching rate of calcium aluminate clinker in sodium carbonate solution, but they increase the molar ratio of caustic Na2O to Al2O3 in the leached liquor.
基金supported by the Education Department of Zhejiang Province (20050359)
文摘A near infrared to visible blue, green, and red upconversion luminescence in a Tb^3＋-doped CaO-Al2O3-SiO2 glass was studied, which was excited using 800 nm femtosecond laser irradiation. The upconversion luminescence was attributed to ^5D3→^7F5, ^5D3→^7F4, ^5D3→^7F3, ^5D4→^7F6, ^5D4→^7F5, ^5D4→^7F4, and ^5D4→^7F3 transitions of Tb^3＋. The relationship between upconversion luminescence intensity and the pump power indicated that a three-photon simultaneous absorption process was dominant in this upconversion luminescence. The intense red, green, and blue upconversion luminescence of Tb^3＋-doped CaO-Al2O3-SiO2 glass may be potentially useful in developing three-dimensional display applications.
