Pyrite （FeS2） bulk and （100） surface properties and the oxygen adsorption on the surface were studied by using density functional theory methods. The results show that in the formation of FeS2 （100） surface, the...Pyrite （FeS2） bulk and （100） surface properties and the oxygen adsorption on the surface were studied by using density functional theory methods. The results show that in the formation of FeS2 （100） surface, there exists a process of electron transfer from Fe dangling bond to S dangling bond. In this situation, surface Fe and S atoms have more ionic properties. Both Fe2+ and S2- have high electrochemistry reduction activity, which is the base for oxygen adsorption. From the viewpoint of adsorption energy, the parallel form oxygen adsorption is in preference. The result also shows that the state of oxygen absorbed on FeS2 surface acts as peroxides rather than O2.展开更多
Titanium cenosphere syntactic foam of varying relative densities with coarse cenospheres was developed through powder metallurgy route at lower compaction loads. The cold compaction load was varied in the range of 60 ...Titanium cenosphere syntactic foam of varying relative densities with coarse cenospheres was developed through powder metallurgy route at lower compaction loads. The cold compaction load was varied in the range of 60 to 75 MPa to obtain the foams of different relative densities. A function of cold compaction load between crushing tendency of cenosphere and relative density was investigated. The compressive deformation behavior of these foams was studied, and empirical relationships among plateau stress, elastic modulus, densification strains and energy absorption are formulated considering their practical significance. The performance indices of the developed foam in comparison with dense titanium were studied and it was found that the foam is superior alternative to titanium for engineering applications.展开更多
A styryl phosphonate ester(SPE) collector was used to improve the flotation performance of ilmenite, and the adsorption mechanism and model were revealed and established, respectively. Microflotation tests showed that...A styryl phosphonate ester(SPE) collector was used to improve the flotation performance of ilmenite, and the adsorption mechanism and model were revealed and established, respectively. Microflotation tests showed that SPE exhibited a stronger collecting ability for ilmenite than the traditional collector styrene phosphonic acid(SPA). Zeta potential measurements revealed that both SPE and SPA could negatively shift the zeta potential of ilmenite, while SPE had more effects than SPA, suggesting the stronger adsorption of SPE. The analysis of X-ray photoelectron spectroscopy confirmed the chemisorption of SPA and SPE onto the Fe/Ti sites of ilmenite. According to frontier orbital theory, the chemical activities of SPE are greater than those of SPA. The partial densities of states analysis indicated that the PO—H groups of the collectors could interact with the Ti/Fe atoms of the ilmenite surface to generate a stable four-membered ring. The bonding model of the collector and(104) ilmenite surface showed that the adsorption energy of SPE was higher than that of SPA. Overall, SPE presented a better collecting ability and interaction effect for ilmenite flotation than SPA, and had the potential to replace SPA in the industry.展开更多
Interlayer Pd for the Li/Pd/Cu neutron target for BNCT （boron neutron capture therapy） was characterized after 0.1-5 keV H2^＋ irradiation by XAFS （X-ray absorption fine structure） technique, and following conclus...Interlayer Pd for the Li/Pd/Cu neutron target for BNCT （boron neutron capture therapy） was characterized after 0.1-5 keV H2^＋ irradiation by XAFS （X-ray absorption fine structure） technique, and following conclusions were derived： （1） from the XAFS observation of white line of Pd, remarkable Pd L3 edge jump was found in 1.1-3 times higher than before irradiation in low irradiation fluence; （2） this fact indicates increase of hole density in Pd 4d-band, whereas, no change was observed for XASF spectra of Ag sample under the same irradiation conditions; （3） remarkable Pd L3 edge shift of 0.12-0.66 eV was also found with increase of H2＋ irradiation energy in low fluence, and drastically decreased after peak in high irradiation energy and fluence; （4） implanted protons deposited in Pd as negative under the balance of electron population enhanced by proton irradiation and charge transfer.展开更多
Platinum(Pt)-based noble metal catalysts(PGMs)are the most widely used commercial catalysts,but they have the problems of high cost,low reserves,and susceptibility to small-molecule toxicity.Transition metal oxides(TM...Platinum(Pt)-based noble metal catalysts(PGMs)are the most widely used commercial catalysts,but they have the problems of high cost,low reserves,and susceptibility to small-molecule toxicity.Transition metal oxides(TMOs)are regarded as potential substitutes for PGMs because of their stability in oxidizing environments and excellent catalytic performance.In this study,comprehensive investigation into the influence of elastic strains on the adsorption energies of carbon(C),hydrogen(H)and oxygen(O)on TMOs was conducted.Based on density functional theory(DFT)calculations,these effects in both tetragonal structures(PtO_(2),PdO_(2))and hexagonal structures(ZnO,CdO),along with their respective transition metals were systematically explored.It was identified that the optimal adsorption sites on metal oxides pinpointed the top of oxygen or the top of metal atom,while face-centered cubic(FCC)and hexagonal close-packed(HCP)holes were preferred for the transition metals.Furthermore,under the influence of elastic strains,the results demonstrated significant disparities in the adsorption energies of H and O between oxides and transition metals.Despite these differences,the effect of elastic strains on the adsorption energies of C,H and O on TMOs mirrored those on transition metals:adsorption energies increased under compressive strains,indicating weaker adsorption,and decreased under tension strains,indicating stronger adsorption.This behavior was rationalized based on the d-band model for adsorption atop a metallic atom or the p-band model for adsorption atop an oxygen atom.Consequently,elastic strains present a promising avenue for tailoring the catalytic properties of TMOs.展开更多
Owing to the worldwide abundance and low-cost of Na, room-temperature Na-ion batteries are emerging as attractive energy storage systems for large- scale grids. Increasing the Na content in cathode materials is one of...Owing to the worldwide abundance and low-cost of Na, room-temperature Na-ion batteries are emerging as attractive energy storage systems for large- scale grids. Increasing the Na content in cathode materials is one of the effective ways to achieve high energy density. Prussian blue and its analogues （PBAs） are promising Na-rich cathode materials since they can theoretically store two Na＋ ions per formula unit. However, increasing the Na content in PBAs cathode materials remains a major challenge. Here we show that sodium iron hexacyanoferrate with high Na content can be obtained by simply controlling the reducing agent and reaction atmosphere during synthesis. The Na content can reach as high as 1.63 per formula, which is the highest value for sodium iron hexacyanoferrate. This Na-rich sodium iron hexacyanoferrate demonstrates a high specific capacity of 150 mAh·g^-1 and remarkable cycling performance with 90% capacity retention after 200 cycles. Furthermore, the Na intercalation/ de-intercalation mechanism has been systematically studied by in situ Raman spectroscopy, X-ray diffraction and X-ray absorption spectroscopy analysis for the first time. The Na-rich sodium iron hexacyanoferrate can function as a plenteous Na reservoir and has great potential as a cathode material for practical Na-ion batteries.展开更多
Bromine-based flow batteries(Br-FBs)are well suitable for stationary energy storage owing to their high energy density and low cost.However,their power density and lifespan are limited by relatively low reaction kinet...Bromine-based flow batteries(Br-FBs)are well suitable for stationary energy storage owing to their high energy density and low cost.However,their power density and lifespan are limited by relatively low reaction kinetics of Br_(2)/Br-couple and serious self-discharge caused by bromine migration.Herein,lamella-like porous carbon nitride nanosheets(PCNS)with adsorption and spatial confinement effects are used to modify cathodes for Br-FBs.The large specific surface area and plentiful N-containing groups enable PCNS with excellent adsorption capacity,which captures bromine species into the pores on PCNS layers.The captured bromine species is subsequently confined in PCNS interlayers due to the strong interaction between bromine species and N-containing groups,thus effectively depressing bromine diffusion/migration.Moreover,the strong bromine adsorption capacity significantly improves the electrochemical activity of PCNS.Consequently,a zinc-bromine flow battery(ZBFB)employing PCNS-modified cathode achieves a high current density of 180 m A cm^(-2),with an ultra-high coulombic efficiency of 99.22%.It also exhibits better self-discharge performance and a long cycle life of 500 cycles.Furthermore,a complexing agent-free ZBFB is successfully realized based on the superior bromineentrapping/retaining capacity of the PCNS-modified cathode.Consequently,this work provides a promising strategy toward electrode modifications for high-performance and long-lifespan Br-FBs.展开更多
Polaron induced double electron in a quantum dot is investigated using the exact diagonalization techniques and the compact density-matrix approach. The dependence of nonlinear optical processes on the incident photon...Polaron induced double electron in a quantum dot is investigated using the exact diagonalization techniques and the compact density-matrix approach. The dependence of nonlinear optical processes on the incident photon energies and the polaronic effect are brought out. The linear, third order non-linear optical absorption coefficients and the refractive index changes of singlet and triplet states as a function of photon energy are obtained with and without the inclusion of polaronic effect. It is found that the geometrical confinement and the effect of polaron have great influence on the optical properties of dots.展开更多
文摘Pyrite （FeS2） bulk and （100） surface properties and the oxygen adsorption on the surface were studied by using density functional theory methods. The results show that in the formation of FeS2 （100） surface, there exists a process of electron transfer from Fe dangling bond to S dangling bond. In this situation, surface Fe and S atoms have more ionic properties. Both Fe2+ and S2- have high electrochemistry reduction activity, which is the base for oxygen adsorption. From the viewpoint of adsorption energy, the parallel form oxygen adsorption is in preference. The result also shows that the state of oxygen absorbed on FeS2 surface acts as peroxides rather than O2.
文摘Titanium cenosphere syntactic foam of varying relative densities with coarse cenospheres was developed through powder metallurgy route at lower compaction loads. The cold compaction load was varied in the range of 60 to 75 MPa to obtain the foams of different relative densities. A function of cold compaction load between crushing tendency of cenosphere and relative density was investigated. The compressive deformation behavior of these foams was studied, and empirical relationships among plateau stress, elastic modulus, densification strains and energy absorption are formulated considering their practical significance. The performance indices of the developed foam in comparison with dense titanium were studied and it was found that the foam is superior alternative to titanium for engineering applications.
基金the support from the National Natural Science Foundation of China(Nos.51904214 and 51804238)the Young Elite Scientists Sponsorship Program by CAST(No.YESS20200276)+3 种基金the Natural Science Foundation of Hubei Province,China(No.ZRMS2021000085)the Fundamental Research Funds for the Central Universities,China(No.2021IVA039)the Open Foundation of State Key Laboratory of Mineral Processing,BGRIMM Technology,China(Nos.BGRIMM-KJSKL-202122 and BGRIMM-KJSKL-2022-02)the Open Project of Engineering Research Center of Phosphorus Resources Development and Utilization of Ministry of Education,China(No.201904)。
文摘A styryl phosphonate ester(SPE) collector was used to improve the flotation performance of ilmenite, and the adsorption mechanism and model were revealed and established, respectively. Microflotation tests showed that SPE exhibited a stronger collecting ability for ilmenite than the traditional collector styrene phosphonic acid(SPA). Zeta potential measurements revealed that both SPE and SPA could negatively shift the zeta potential of ilmenite, while SPE had more effects than SPA, suggesting the stronger adsorption of SPE. The analysis of X-ray photoelectron spectroscopy confirmed the chemisorption of SPA and SPE onto the Fe/Ti sites of ilmenite. According to frontier orbital theory, the chemical activities of SPE are greater than those of SPA. The partial densities of states analysis indicated that the PO—H groups of the collectors could interact with the Ti/Fe atoms of the ilmenite surface to generate a stable four-membered ring. The bonding model of the collector and(104) ilmenite surface showed that the adsorption energy of SPE was higher than that of SPA. Overall, SPE presented a better collecting ability and interaction effect for ilmenite flotation than SPA, and had the potential to replace SPA in the industry.
文摘Interlayer Pd for the Li/Pd/Cu neutron target for BNCT （boron neutron capture therapy） was characterized after 0.1-5 keV H2^＋ irradiation by XAFS （X-ray absorption fine structure） technique, and following conclusions were derived： （1） from the XAFS observation of white line of Pd, remarkable Pd L3 edge jump was found in 1.1-3 times higher than before irradiation in low irradiation fluence; （2） this fact indicates increase of hole density in Pd 4d-band, whereas, no change was observed for XASF spectra of Ag sample under the same irradiation conditions; （3） remarkable Pd L3 edge shift of 0.12-0.66 eV was also found with increase of H2＋ irradiation energy in low fluence, and drastically decreased after peak in high irradiation energy and fluence; （4） implanted protons deposited in Pd as negative under the balance of electron population enhanced by proton irradiation and charge transfer.
基金Science and Technology Commission of Shanghai Municipality(21ZR1472900,22ZR1471600)。
文摘Platinum(Pt)-based noble metal catalysts(PGMs)are the most widely used commercial catalysts,but they have the problems of high cost,low reserves,and susceptibility to small-molecule toxicity.Transition metal oxides(TMOs)are regarded as potential substitutes for PGMs because of their stability in oxidizing environments and excellent catalytic performance.In this study,comprehensive investigation into the influence of elastic strains on the adsorption energies of carbon(C),hydrogen(H)and oxygen(O)on TMOs was conducted.Based on density functional theory(DFT)calculations,these effects in both tetragonal structures(PtO_(2),PdO_(2))and hexagonal structures(ZnO,CdO),along with their respective transition metals were systematically explored.It was identified that the optimal adsorption sites on metal oxides pinpointed the top of oxygen or the top of metal atom,while face-centered cubic(FCC)and hexagonal close-packed(HCP)holes were preferred for the transition metals.Furthermore,under the influence of elastic strains,the results demonstrated significant disparities in the adsorption energies of H and O between oxides and transition metals.Despite these differences,the effect of elastic strains on the adsorption energies of C,H and O on TMOs mirrored those on transition metals:adsorption energies increased under compressive strains,indicating weaker adsorption,and decreased under tension strains,indicating stronger adsorption.This behavior was rationalized based on the d-band model for adsorption atop a metallic atom or the p-band model for adsorption atop an oxygen atom.Consequently,elastic strains present a promising avenue for tailoring the catalytic properties of TMOs.
文摘Owing to the worldwide abundance and low-cost of Na, room-temperature Na-ion batteries are emerging as attractive energy storage systems for large- scale grids. Increasing the Na content in cathode materials is one of the effective ways to achieve high energy density. Prussian blue and its analogues （PBAs） are promising Na-rich cathode materials since they can theoretically store two Na＋ ions per formula unit. However, increasing the Na content in PBAs cathode materials remains a major challenge. Here we show that sodium iron hexacyanoferrate with high Na content can be obtained by simply controlling the reducing agent and reaction atmosphere during synthesis. The Na content can reach as high as 1.63 per formula, which is the highest value for sodium iron hexacyanoferrate. This Na-rich sodium iron hexacyanoferrate demonstrates a high specific capacity of 150 mAh·g^-1 and remarkable cycling performance with 90% capacity retention after 200 cycles. Furthermore, the Na intercalation/ de-intercalation mechanism has been systematically studied by in situ Raman spectroscopy, X-ray diffraction and X-ray absorption spectroscopy analysis for the first time. The Na-rich sodium iron hexacyanoferrate can function as a plenteous Na reservoir and has great potential as a cathode material for practical Na-ion batteries.
基金supported by CAS Strategic Leading Science&Technology Program(A)(XDA21070100)CAS Engineering Laboratory for Electrochemical Energy Storage(KFJ-PTXM-027)+1 种基金DICP funding(DICP I202026 DICP I201928)Liaoning Natural Science Foundation(2021-MS-024)。
文摘Bromine-based flow batteries(Br-FBs)are well suitable for stationary energy storage owing to their high energy density and low cost.However,their power density and lifespan are limited by relatively low reaction kinetics of Br_(2)/Br-couple and serious self-discharge caused by bromine migration.Herein,lamella-like porous carbon nitride nanosheets(PCNS)with adsorption and spatial confinement effects are used to modify cathodes for Br-FBs.The large specific surface area and plentiful N-containing groups enable PCNS with excellent adsorption capacity,which captures bromine species into the pores on PCNS layers.The captured bromine species is subsequently confined in PCNS interlayers due to the strong interaction between bromine species and N-containing groups,thus effectively depressing bromine diffusion/migration.Moreover,the strong bromine adsorption capacity significantly improves the electrochemical activity of PCNS.Consequently,a zinc-bromine flow battery(ZBFB)employing PCNS-modified cathode achieves a high current density of 180 m A cm^(-2),with an ultra-high coulombic efficiency of 99.22%.It also exhibits better self-discharge performance and a long cycle life of 500 cycles.Furthermore,a complexing agent-free ZBFB is successfully realized based on the superior bromineentrapping/retaining capacity of the PCNS-modified cathode.Consequently,this work provides a promising strategy toward electrode modifications for high-performance and long-lifespan Br-FBs.
文摘Polaron induced double electron in a quantum dot is investigated using the exact diagonalization techniques and the compact density-matrix approach. The dependence of nonlinear optical processes on the incident photon energies and the polaronic effect are brought out. The linear, third order non-linear optical absorption coefficients and the refractive index changes of singlet and triplet states as a function of photon energy are obtained with and without the inclusion of polaronic effect. It is found that the geometrical confinement and the effect of polaron have great influence on the optical properties of dots.
