In this study,hierarchical Ag/La2 O2 CO3 micro/nanostructures(MNSs)were synthesized by in situ loading Ag nanoparticles(NPs)on the surface of the La2 O2 CO3 MNSs.The prepared La2 O2 CO3 MNSs present flower-like shape ...In this study,hierarchical Ag/La2 O2 CO3 micro/nanostructures(MNSs)were synthesized by in situ loading Ag nanoparticles(NPs)on the surface of the La2 O2 CO3 MNSs.The prepared La2 O2 CO3 MNSs present flower-like shape and can be tuned by the molar ratio of La(NO3)3 and CO(NH2)2.In the molar ratio of 1:2 to 1:55,the La2 O2 CO3 MNSs mainly consist of polyhedral rods,irregular rods and irregular spindles and their size is about 10,8 and 7μm,respectively.After loading Ag NPs,the spindle-like Ag/La2 O2 CO3 MNSs were used for phosphate removal and antibacterial activity.At the initial phosphate concentration of20 mg/L,the removal rate is 59.6%.The Ag/La2 O2 CO3 MNSs have significant antibacterial activity and their MIC values for S.aureus and E.coli are 31.3 and 15.6μg/mL,respectively.The results indicate that Ag/La2 O2 CO3 MNSs may have good application prospects in open water to inhibit bacterial growth.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
Devising S-scheme heterostructure is considered as a cutting-edge strategy for advanced photocatalysts with effectively segregated photo-carriers and prominent redox potential for emerging organic pollutants control.H...Devising S-scheme heterostructure is considered as a cutting-edge strategy for advanced photocatalysts with effectively segregated photo-carriers and prominent redox potential for emerging organic pollutants control.Herein,an S-scheme Ag_(2)CO_(3)/C_(3)N_(5) heterojunction photocatalyst was developed via a simple in situ chemical deposition procedure,and further photoreduction operation made metallic Ag(size:3.5–12.5 nm)being in situ formed on Ag_(2)CO_(3)/C_(3)N_(5) for a plasmonic S-scheme Ag/Ag_(2)CO_(3)/C_(3)N_(5) heterojunction photocatalyst.Consequently,Ag/Ag_(2)CO_(3)/C_(3)N_(5) manifests pronouncedly upgraded photocatalytic performance toward oxytetracycline degradation with a superior photoreaction rate constant of 0.0475 min‒1,which is 13.2,3.9 and 2.2 folds that of C_(3)N_(5),Ag_(2)CO_(3),and Ag_(2)CO_(3)/C_(3)N_(5),respectively.As evidenced by comprehensive characterizations and density functional theory calculations,the localized surface plasmon resonance effect of metallic Ag and the unique S-scheme charge transfer mechanism in 0D/0D/2D Ag/Ag_(2)CO_(3)/C_(3)N_(5) collaboratively strengthen the visible-light absorption,and facilitate the effective separation of powerful charge carriers,thereby significantly promoting the generation of reactive species like·OH^(-),h^(+)and·O_(2)^(-)for efficient oxytetracycline destruction.Moreover,four consecutive cycles demonstrate the reusability of Ag/Ag_(2)CO_(3)/C_(3)N_(5).Furthermore,the authentic water purification tests affirm its practical application potential.This work not only provides a candidate strategy for advancing S-scheme heterojunction photocatalysts but also makes a certain contribution to water decontamination.展开更多
Ag/Al_(2)O_(3) powders are highly effective catalytic materials utilized in the epoxidation of ethylene to produce ethylene oxide.One of the critical challenges in this catalytic process is the stability of nano-sized...Ag/Al_(2)O_(3) powders are highly effective catalytic materials utilized in the epoxidation of ethylene to produce ethylene oxide.One of the critical challenges in this catalytic process is the stability of nano-sized Ag particles,especially during high-temperature catalysis.However,this issue can be effectively addressed through in-situ reaction synthesis.To gain a deeper understanding of the underlying mechanisms,the phase transformation process and the thermodynamic mechanism of the oxidation reaction in the Ag/Al_(2)O_(3) system have been investigated using firstprinciples thermodynamic calculations in conjunction with traditional thermodynamic data.These calculations,whose accuracy has been verified,provide valuable insights into the behavior of Ag and Al under different conditions.The results indicate that,during AgAl solid-solution oxidation,Ag-containing Al preferentially forms the stable intermediate phase Ag_(2)Al instead of undergoing direct oxidation;this pathway becomes thermodynamically more favorable at higher Ag concentrations.With increasing temperature,Ag2Al is further oxidized to yield Ag and Al_(2)O_(3).It is also found that above 237℃,Ag_(2)O and AgAlO_(2) become unstable.The overall reaction pathway is solid solution→Ag_(2)Al→Ag+Al_(2)O_(3).This comprehensive study provides a robust theoretical calculation basis for the development and optimization of in-situ reaction-synthesized Ag/Al_(2)O_(3) powder composite materials,which have significant potential for practical applications in catalysis.展开更多
Piezoelectric effect,plasma effect and semiconductor heterostructure are important strategies for enhanced photocatalytic performance.Herein,we developed a novel heterostructure piezoelectric photocatalyst,Ag/Ag_(2)S/...Piezoelectric effect,plasma effect and semiconductor heterostructure are important strategies for enhanced photocatalytic performance.Herein,we developed a novel heterostructure piezoelectric photocatalyst,Ag/Ag_(2)S/BiFeO_(3)(AAS/BFO),for photocatalytic degradation of ciprofloxacin from water.Experimental results verified the enhancement of combining heterostructure piezoelectric polarization effect,which promotes efficient migration and separation of photogenerated carriers due to the localized surface plasmon resonance effect of Ag nanoparticles.Additionally,the introduction of Ag_(2)S constructs a new heterostructure,that enhances the electron transport rate and improves the separation efficiency on electron-hole pairs.Under ultrasonic stimulation and visible light irradiation,the degradation efficiencies of 15%-AAS/BFO towards ciprofloxacin,methyl orange and methylene blue are significantly enhanced compared to pure BFO fibers.The demonstrated AAS/BFO material based on the synergistic piezoelectric effect and plasmon heterostructure shows potential in efficient organic pollutants water treatment and transforming mechanical energy into chemical energy.展开更多
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
基金Project supported by the National Natural Science Foundation of China(21271062)。
文摘In this study,hierarchical Ag/La2 O2 CO3 micro/nanostructures(MNSs)were synthesized by in situ loading Ag nanoparticles(NPs)on the surface of the La2 O2 CO3 MNSs.The prepared La2 O2 CO3 MNSs present flower-like shape and can be tuned by the molar ratio of La(NO3)3 and CO(NH2)2.In the molar ratio of 1:2 to 1:55,the La2 O2 CO3 MNSs mainly consist of polyhedral rods,irregular rods and irregular spindles and their size is about 10,8 and 7μm,respectively.After loading Ag NPs,the spindle-like Ag/La2 O2 CO3 MNSs were used for phosphate removal and antibacterial activity.At the initial phosphate concentration of20 mg/L,the removal rate is 59.6%.The Ag/La2 O2 CO3 MNSs have significant antibacterial activity and their MIC values for S.aureus and E.coli are 31.3 and 15.6μg/mL,respectively.The results indicate that Ag/La2 O2 CO3 MNSs may have good application prospects in open water to inhibit bacterial growth.
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。
文摘Devising S-scheme heterostructure is considered as a cutting-edge strategy for advanced photocatalysts with effectively segregated photo-carriers and prominent redox potential for emerging organic pollutants control.Herein,an S-scheme Ag_(2)CO_(3)/C_(3)N_(5) heterojunction photocatalyst was developed via a simple in situ chemical deposition procedure,and further photoreduction operation made metallic Ag(size:3.5–12.5 nm)being in situ formed on Ag_(2)CO_(3)/C_(3)N_(5) for a plasmonic S-scheme Ag/Ag_(2)CO_(3)/C_(3)N_(5) heterojunction photocatalyst.Consequently,Ag/Ag_(2)CO_(3)/C_(3)N_(5) manifests pronouncedly upgraded photocatalytic performance toward oxytetracycline degradation with a superior photoreaction rate constant of 0.0475 min‒1,which is 13.2,3.9 and 2.2 folds that of C_(3)N_(5),Ag_(2)CO_(3),and Ag_(2)CO_(3)/C_(3)N_(5),respectively.As evidenced by comprehensive characterizations and density functional theory calculations,the localized surface plasmon resonance effect of metallic Ag and the unique S-scheme charge transfer mechanism in 0D/0D/2D Ag/Ag_(2)CO_(3)/C_(3)N_(5) collaboratively strengthen the visible-light absorption,and facilitate the effective separation of powerful charge carriers,thereby significantly promoting the generation of reactive species like·OH^(-),h^(+)and·O_(2)^(-)for efficient oxytetracycline destruction.Moreover,four consecutive cycles demonstrate the reusability of Ag/Ag_(2)CO_(3)/C_(3)N_(5).Furthermore,the authentic water purification tests affirm its practical application potential.This work not only provides a candidate strategy for advancing S-scheme heterojunction photocatalysts but also makes a certain contribution to water decontamination.
基金sponsored by Major Science and Technology Project of the Yunnan Provincial Department of Science and Technology(202502AB080011)Yunnan Province Industrial High-Tech Project(202403AA080015)Special Science and Technology Research Project of Yunnan Province for the South Asia and Southeast Asia Innovation Center(202403AP140006).
文摘Ag/Al_(2)O_(3) powders are highly effective catalytic materials utilized in the epoxidation of ethylene to produce ethylene oxide.One of the critical challenges in this catalytic process is the stability of nano-sized Ag particles,especially during high-temperature catalysis.However,this issue can be effectively addressed through in-situ reaction synthesis.To gain a deeper understanding of the underlying mechanisms,the phase transformation process and the thermodynamic mechanism of the oxidation reaction in the Ag/Al_(2)O_(3) system have been investigated using firstprinciples thermodynamic calculations in conjunction with traditional thermodynamic data.These calculations,whose accuracy has been verified,provide valuable insights into the behavior of Ag and Al under different conditions.The results indicate that,during AgAl solid-solution oxidation,Ag-containing Al preferentially forms the stable intermediate phase Ag_(2)Al instead of undergoing direct oxidation;this pathway becomes thermodynamically more favorable at higher Ag concentrations.With increasing temperature,Ag2Al is further oxidized to yield Ag and Al_(2)O_(3).It is also found that above 237℃,Ag_(2)O and AgAlO_(2) become unstable.The overall reaction pathway is solid solution→Ag_(2)Al→Ag+Al_(2)O_(3).This comprehensive study provides a robust theoretical calculation basis for the development and optimization of in-situ reaction-synthesized Ag/Al_(2)O_(3) powder composite materials,which have significant potential for practical applications in catalysis.
基金supported by the National Natural Science Foundation of China(Nos.52372090 and 52073177)the National Natural Science Foundation of Guangdong,China(No.2023A1515010947)Shenzhen Basic Research Program(No.JCYJ20220531102207017).
文摘Piezoelectric effect,plasma effect and semiconductor heterostructure are important strategies for enhanced photocatalytic performance.Herein,we developed a novel heterostructure piezoelectric photocatalyst,Ag/Ag_(2)S/BiFeO_(3)(AAS/BFO),for photocatalytic degradation of ciprofloxacin from water.Experimental results verified the enhancement of combining heterostructure piezoelectric polarization effect,which promotes efficient migration and separation of photogenerated carriers due to the localized surface plasmon resonance effect of Ag nanoparticles.Additionally,the introduction of Ag_(2)S constructs a new heterostructure,that enhances the electron transport rate and improves the separation efficiency on electron-hole pairs.Under ultrasonic stimulation and visible light irradiation,the degradation efficiencies of 15%-AAS/BFO towards ciprofloxacin,methyl orange and methylene blue are significantly enhanced compared to pure BFO fibers.The demonstrated AAS/BFO material based on the synergistic piezoelectric effect and plasmon heterostructure shows potential in efficient organic pollutants water treatment and transforming mechanical energy into chemical energy.
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.
