A systematic investigation of oxidation on a superconductive Fe Te_（0.5）Se_（0.5）thin film,which was grown on Nb-doped SrTiO_3（001） by pulsed laser deposition,has been carried out.The sample was exposed to ambien...A systematic investigation of oxidation on a superconductive Fe Te_（0.5）Se_（0.5）thin film,which was grown on Nb-doped SrTiO_3（001） by pulsed laser deposition,has been carried out.The sample was exposed to ambient air for one month for oxidation.Macroscopically,the exposed specimen lost its superconductivity due to oxidation.The specimen was subjected to in situ synchrotron radiation photoelectron spectroscopy（PES） and x-ray absorption spectroscopy（XAS） measurements following cycles of annealing and argon ion etching treatments to unravel what happened in the electronic structure and composition after exposure to air.By the spectroscopic measurements,we found that the as-grown FeTe_（0.5）Se_（0.5）superconductive thin film experienced an element selective substitution reaction.The oxidation preferentially proceeds through pumping out the Te and forming Fe–O bonds by O substitution of Te.In addition,our results certify that in situ vacuum annealing and low-energy argon ion etching methods combined with spectroscopy are suitable for depth element and valence analysis of layered structure superconductor materials.展开更多
Synchrotron radiation sources, whose number is steadily increasing, are undoubtedly the most powerful and brilliant sources in the X-ray range. Although the synchrotron emission covers with high brilliance also the in...Synchrotron radiation sources, whose number is steadily increasing, are undoubtedly the most powerful and brilliant sources in the X-ray range. Although the synchrotron emission covers with high brilliance also the infrared region, its use in this energy range has developed at a much slower rate. Nowadays, after a couple of decades of attempts, the aim of extending the unique performances of the synchrotron source to the infrared domain is achieved by several dedicated beamlines in different countries. With their high-brilliance, polarized and broad-band radiation one may perform experiments that are out of the range of conventional sources from the near-IR up to the far-IR range.展开更多
The band lineups at Ge/ZnS(111) interfaces have been studied by synchrotron radiation photoemission spectroscopy. Surface sensitive core level spectra show that Ge and S atoms react with each other at the interface. U...The band lineups at Ge/ZnS(111) interfaces have been studied by synchrotron radiation photoemission spectroscopy. Surface sensitive core level spectra show that Ge and S atoms react with each other at the interface. Using both the techniques of core level and valence band spectra, the valence band offsets of such a kind of heterojunctions have been measured. The values are (1.94+0.1)eV and (2.23+0.1)eV for the heterojunctions grown at the substrate temperature of 200C and room temperature, respectively. The experimental results are in good agreement with some theoretical predictions.展开更多
A comprehensive understanding of the microscopic reaction mechanisms at the gas-solid-liquid electrochemical interfaces is urgently required for the development of advanced electrocatalysts applied in burgeoning susta...A comprehensive understanding of the microscopic reaction mechanisms at the gas-solid-liquid electrochemical interfaces is urgently required for the development of advanced electrocatalysts applied in burgeoning sustainable energy conversion systems. In-situ synchrotron radiation Fourier transform infrared(SR-FTIR) spectroscopy is one of the most powerful techniques for investigating the evolving dynamics of reactive intermediates during electrocatalytic reactions. In this review, we methodically summarize the recent progress in the research of dynamic mechanisms for valuable electrocatalytic reactions based on in-situ SR-FTIR methodology. Moreover, the merits and drawbacks of SRFTIR spectroscopy, the design principles of infrared beam setups and in-situ cells, as well as the in-situ measurement criteria are also discussed in detail. Lastly, the potential challenges and opportunities in this field are prudently stated. This review is expected to stimulate a broad interest in the material science and electrochemistry communities for exploring the dynamic mechanisms of prominent catalysis at the atomic/molecular level by using SR-based spectroscopy.展开更多
Background: Nickel-induced allergic contact dermatitis (Ni-ACD) is a global health problem. More detailed knowledge on the skin uptake of haptens is required. This study aimed to investigate the penetration process an...Background: Nickel-induced allergic contact dermatitis (Ni-ACD) is a global health problem. More detailed knowledge on the skin uptake of haptens is required. This study aimed to investigate the penetration process and distribution of nickel in skin tissues with late phase and early phase of Ni-ACD to understand the mechanisms of metal allergy. Methods: Forty Hartley guinea pigs were divided into four groups according to the NiSO4 sensitizing concentration and the NiSO4 challenged concentration: the 5% NiSO4-group, 5% to 10%(sensitization-challenge;late phase group);10% NiSO4-group, 10% to 10%(sensitization-challenge;early-phase group);and the positive and negative controls. Pathological biopsies were performed on each group. The depth profile of nickel element concentration in the skin of guinea pigs was detected by synchrotron radiation micro X-ray fluorescence spectroscopy (SR-μ-XRF) and micro X-ray absorption near-edge spectroscopy (μ-XANES). Results: In each section, the nickel element concentration in both the 5% NiSO4-group and 10% NiSO4-group was significantly higher than that in the negative control group. In the upper 300-μm section of skin for the early phase group, the nickel element concentration was significantly higher than that in the lower section of skin. In deeper sections (>200 μm) of skin, the concentration of nickel in the early phase group was approximately equal to that in the late phase group. The curve of the late phase group was flat, which means that the nickel element concentration was distributed uniformly by SR-μ-XRF. According to the XANES data for the 10% NiSO4 metal salt solution, structural changes occurred in the skin model sample, indicating that nickel was not present in the Ni^2+ aqueous ionic state but in the nickel-binding protein. Conclusions: This study showed that the distribution of the nickel element concentration in ACD skin tissue was different between the early phase and late phase groups. The nickel element was not present in the Ni^2+ aqueous ionic state but bound with certain proteins to form a complex in the stratum corneum in ACD model tissue.展开更多
Molecular frame photoemission is a very sensitive probe of the photoionization （PI） dynamics of molecules. This paper reports a comparative study of non-resonant and resonant photoionization of D2 induced by VUV cir...Molecular frame photoemission is a very sensitive probe of the photoionization （PI） dynamics of molecules. This paper reports a comparative study of non-resonant and resonant photoionization of D2 induced by VUV circularly polarized synchrotron radiation at SOLEIL at the level of the molecular frame photoelectron angular distributions （MFPADs）. We use the vector correlation method which combines imaging and time-of-flight resolved electron-ion coincidence techniques, and a generalized formalism for the expression of the Ⅰ（χ, θe, Фe） MFPADs, where χ is the orientation of the molecular axis with respect to the light quantization axis and （θe, Фe） the electron emission direction in the molecular frame. Selected MFPADs for a molecule aligned parallel or perpendicular to linearly polarized light, or perpendicular to the propagation axis of circularly polarized light, are presented for dissociative photoionization （DPI） of D2 at two photon excitation energies, hv=19 eV, where direct PI is the only channel opened, and hv=32.5 eV, i.e. in the region involving resonant excitation of Q1 and Q2 doubly excited state series. We discuss in particular the properties of the circular dichroism characterizing photoemission in the molecular frame for direct and resonant PI. In the latter case, a remarkable behavior is observed which may be attributed to the interference occurring between undistinguishable autoionization decay channels.展开更多
The effect of temperature on the electronic structure of Nb-doped SrTiO3（100） surface is investigated by highresolution synchrotron radiation photoemission spectroscopy.According to the x-ray photoemission spectrosc...The effect of temperature on the electronic structure of Nb-doped SrTiO3（100） surface is investigated by highresolution synchrotron radiation photoemission spectroscopy.According to the x-ray photoemission spectroscopy（XPS）results,at an annealing temperature of less than 700 ℃,the adsorbed carbon and hydroxyl on the STO surface could be removed,to expose the fresh intrinsic surface with a constant ratio of Ti/O.It is obvious that the STO would be doped by Ca^＋ impurities of bulks and O vacancies in the surface after annealing at 920 ℃ for one hour.展开更多
Vacuum ultraviolet photon-induced ionization and dissociation of isoleucine are investi- gated with synchrotron radiation photoionization mass spectroscopy and theoretical cal- culations. The main fragment ions at m/z...Vacuum ultraviolet photon-induced ionization and dissociation of isoleucine are investi- gated with synchrotron radiation photoionization mass spectroscopy and theoretical cal- culations. The main fragment ions at m/z=86, 75, 74, 69, 57, 46, 45, 44, 41, 30, 28, and 18 from isoleucine are observed in the mass spectrum at the photon energy of 13 eV. From the photoionization efficiency curves, appearance energies for the principal fragment ions CsH12N＋ （rn/z=86）, C2H5NO2＋ （m/z=75）, C5H9＋ （rn/z=-69）, C4H9＋ （m/z=57）, and CH4N＋ （m/z=30） are determined to be 8.844-0.07, 9.254-0.06, 10.20-4-0.12, 9.254-0.10, and 11.05＋0.07 eV, respectively, and possible formation pathways are established in detail by the calculations at the B3LYP/6-31＋＋G（d, p） levels. These proposed channels include simple bond cleavage reactions as well as reactions involving intermediates and transition structures. The experimental and computational appearance energies or barriers are in good agreement.展开更多
基金Project supported by the Chinese Academy of Sciences(Grant No.1G2009312311750101)the National Natural Science Foundation of China(Grant Nos.11375228,11204303,and U1332105)
文摘A systematic investigation of oxidation on a superconductive Fe Te_（0.5）Se_（0.5）thin film,which was grown on Nb-doped SrTiO_3（001） by pulsed laser deposition,has been carried out.The sample was exposed to ambient air for one month for oxidation.Macroscopically,the exposed specimen lost its superconductivity due to oxidation.The specimen was subjected to in situ synchrotron radiation photoelectron spectroscopy（PES） and x-ray absorption spectroscopy（XAS） measurements following cycles of annealing and argon ion etching treatments to unravel what happened in the electronic structure and composition after exposure to air.By the spectroscopic measurements,we found that the as-grown FeTe_（0.5）Se_（0.5）superconductive thin film experienced an element selective substitution reaction.The oxidation preferentially proceeds through pumping out the Te and forming Fe–O bonds by O substitution of Te.In addition,our results certify that in situ vacuum annealing and low-energy argon ion etching methods combined with spectroscopy are suitable for depth element and valence analysis of layered structure superconductor materials.
文摘Synchrotron radiation sources, whose number is steadily increasing, are undoubtedly the most powerful and brilliant sources in the X-ray range. Although the synchrotron emission covers with high brilliance also the infrared region, its use in this energy range has developed at a much slower rate. Nowadays, after a couple of decades of attempts, the aim of extending the unique performances of the synchrotron source to the infrared domain is achieved by several dedicated beamlines in different countries. With their high-brilliance, polarized and broad-band radiation one may perform experiments that are out of the range of conventional sources from the near-IR up to the far-IR range.
基金supported by the National Natural Science Foundation of China.
文摘The band lineups at Ge/ZnS(111) interfaces have been studied by synchrotron radiation photoemission spectroscopy. Surface sensitive core level spectra show that Ge and S atoms react with each other at the interface. Using both the techniques of core level and valence band spectra, the valence band offsets of such a kind of heterojunctions have been measured. The values are (1.94+0.1)eV and (2.23+0.1)eV for the heterojunctions grown at the substrate temperature of 200C and room temperature, respectively. The experimental results are in good agreement with some theoretical predictions.
基金supported by the National Natural Science Foundation of China (Nos. 1932212, U1932109, 11875257)。
文摘A comprehensive understanding of the microscopic reaction mechanisms at the gas-solid-liquid electrochemical interfaces is urgently required for the development of advanced electrocatalysts applied in burgeoning sustainable energy conversion systems. In-situ synchrotron radiation Fourier transform infrared(SR-FTIR) spectroscopy is one of the most powerful techniques for investigating the evolving dynamics of reactive intermediates during electrocatalytic reactions. In this review, we methodically summarize the recent progress in the research of dynamic mechanisms for valuable electrocatalytic reactions based on in-situ SR-FTIR methodology. Moreover, the merits and drawbacks of SRFTIR spectroscopy, the design principles of infrared beam setups and in-situ cells, as well as the in-situ measurement criteria are also discussed in detail. Lastly, the potential challenges and opportunities in this field are prudently stated. This review is expected to stimulate a broad interest in the material science and electrochemistry communities for exploring the dynamic mechanisms of prominent catalysis at the atomic/molecular level by using SR-based spectroscopy.
基金the grants from National Natural Science Foundation of China (No.81373175)CAMS Innovation Fund for Medical Sciences (No.2016-I2M-1003).
文摘Background: Nickel-induced allergic contact dermatitis (Ni-ACD) is a global health problem. More detailed knowledge on the skin uptake of haptens is required. This study aimed to investigate the penetration process and distribution of nickel in skin tissues with late phase and early phase of Ni-ACD to understand the mechanisms of metal allergy. Methods: Forty Hartley guinea pigs were divided into four groups according to the NiSO4 sensitizing concentration and the NiSO4 challenged concentration: the 5% NiSO4-group, 5% to 10%(sensitization-challenge;late phase group);10% NiSO4-group, 10% to 10%(sensitization-challenge;early-phase group);and the positive and negative controls. Pathological biopsies were performed on each group. The depth profile of nickel element concentration in the skin of guinea pigs was detected by synchrotron radiation micro X-ray fluorescence spectroscopy (SR-μ-XRF) and micro X-ray absorption near-edge spectroscopy (μ-XANES). Results: In each section, the nickel element concentration in both the 5% NiSO4-group and 10% NiSO4-group was significantly higher than that in the negative control group. In the upper 300-μm section of skin for the early phase group, the nickel element concentration was significantly higher than that in the lower section of skin. In deeper sections (>200 μm) of skin, the concentration of nickel in the early phase group was approximately equal to that in the late phase group. The curve of the late phase group was flat, which means that the nickel element concentration was distributed uniformly by SR-μ-XRF. According to the XANES data for the 10% NiSO4 metal salt solution, structural changes occurred in the skin model sample, indicating that nickel was not present in the Ni^2+ aqueous ionic state but in the nickel-binding protein. Conclusions: This study showed that the distribution of the nickel element concentration in ACD skin tissue was different between the early phase and late phase groups. The nickel element was not present in the Ni^2+ aqueous ionic state but bound with certain proteins to form a complex in the stratum corneum in ACD model tissue.
文摘Molecular frame photoemission is a very sensitive probe of the photoionization （PI） dynamics of molecules. This paper reports a comparative study of non-resonant and resonant photoionization of D2 induced by VUV circularly polarized synchrotron radiation at SOLEIL at the level of the molecular frame photoelectron angular distributions （MFPADs）. We use the vector correlation method which combines imaging and time-of-flight resolved electron-ion coincidence techniques, and a generalized formalism for the expression of the Ⅰ（χ, θe, Фe） MFPADs, where χ is the orientation of the molecular axis with respect to the light quantization axis and （θe, Фe） the electron emission direction in the molecular frame. Selected MFPADs for a molecule aligned parallel or perpendicular to linearly polarized light, or perpendicular to the propagation axis of circularly polarized light, are presented for dissociative photoionization （DPI） of D2 at two photon excitation energies, hv=19 eV, where direct PI is the only channel opened, and hv=32.5 eV, i.e. in the region involving resonant excitation of Q1 and Q2 doubly excited state series. We discuss in particular the properties of the circular dichroism characterizing photoemission in the molecular frame for direct and resonant PI. In the latter case, a remarkable behavior is observed which may be attributed to the interference occurring between undistinguishable autoionization decay channels.
基金supported by the Funds from the Chinese Academy of Sciences(Grant No.1G2009312311750101)the National Natural Science Foundation of China(Grant No.11375228)
文摘The effect of temperature on the electronic structure of Nb-doped SrTiO3（100） surface is investigated by highresolution synchrotron radiation photoemission spectroscopy.According to the x-ray photoemission spectroscopy（XPS）results,at an annealing temperature of less than 700 ℃,the adsorbed carbon and hydroxyl on the STO surface could be removed,to expose the fresh intrinsic surface with a constant ratio of Ti/O.It is obvious that the STO would be doped by Ca^＋ impurities of bulks and O vacancies in the surface after annealing at 920 ℃ for one hour.
基金V. ACKNOWLEDGMENTS This work is supported by the National Natural Science Foundation of China （No.10875126 and No.10979048） and the Specialized Research Fund for the Doctoral Program of Higher Education, SRF for ROCS, SEM.
文摘Vacuum ultraviolet photon-induced ionization and dissociation of isoleucine are investi- gated with synchrotron radiation photoionization mass spectroscopy and theoretical cal- culations. The main fragment ions at m/z=86, 75, 74, 69, 57, 46, 45, 44, 41, 30, 28, and 18 from isoleucine are observed in the mass spectrum at the photon energy of 13 eV. From the photoionization efficiency curves, appearance energies for the principal fragment ions CsH12N＋ （rn/z=86）, C2H5NO2＋ （m/z=75）, C5H9＋ （rn/z=-69）, C4H9＋ （m/z=57）, and CH4N＋ （m/z=30） are determined to be 8.844-0.07, 9.254-0.06, 10.20-4-0.12, 9.254-0.10, and 11.05＋0.07 eV, respectively, and possible formation pathways are established in detail by the calculations at the B3LYP/6-31＋＋G（d, p） levels. These proposed channels include simple bond cleavage reactions as well as reactions involving intermediates and transition structures. The experimental and computational appearance energies or barriers are in good agreement.
