Photocatalytic solar fuel generation is currently a hot topic because of its potential for solving the energy crisis owing to its low cost and zero-carbon emissions.However,the rapid bulk recombination of photoexcited...Photocatalytic solar fuel generation is currently a hot topic because of its potential for solving the energy crisis owing to its low cost and zero-carbon emissions.However,the rapid bulk recombination of photoexcited carrier pairs is a fundamental disadvantage.To resolve this problem,we synthesized a dual cocatalysts system of cobalt phosphide(Co P)and molybdenum carbide(Mo_(2)C)embedded on strontium titanate(Sr TiO_(3))nanofibers.Compared with those of pristine SrTiO_(3) and binary samples,the dual cocatalysts system(denoted SCM)showed a significant improvement in the hydrogen evolution and CO_(2) reduction performance.Further,the structure of SCM effectively promoted spatial charge separation and enhanced the photocatalytic performance.In addition,the Schottky junction formed between the SrTiO_(3) and cocatalysts enabled the rapid transfer of photoexcited electrons from SrTiO_(3) to the cocatalysts,resulting in effective separation and prolonged photoexcited electron lifetimes.The electron migration route between SrTiO_(3) and the cocatalysts was determined by in situ irradiation X-ray spectroscopy,and band structures of Sr TiO_(3) and the cocatalysts are proposed based on results obtained from UV-vis diffraction reflection spectroscopy and ultraviolet photoelectron spectroscopy measurements.On the basis of our results,the dual cocatalysts unambiguously boosts charge separation and enhances photocatalytic performance.In summary,we have investigated the flux of photoexcited electrons in a dual cocatalysts system and provided a theoretical basis and ideas for subsequent research.展开更多
Spectral and photophysical investigations of 4＇-（p-aminophenyl）-2,2＇：6＇,2″-terpyridine （APT） have been performed in various solvents with different polarity and hydrogen-bonding ability. The emission spectra ...Spectral and photophysical investigations of 4＇-（p-aminophenyl）-2,2＇：6＇,2″-terpyridine （APT） have been performed in various solvents with different polarity and hydrogen-bonding ability. The emission spectra of APT are found to exhibit dual fluorescence in polar solvents, which attributes to the local excited and intramolecular charge transfer states, respectively. The two-state model is proven out for APT in polar solvent by the time-correlated single photon counting emission decay measurement. Interestingly, the linear relationships of different emission maxima and solvent polarity parameter are found for APT in protic and aprotic solvents, because of the hydrogen bond formation between APT and alcohols at the amino nitrogen N25. Furthermore, the effects of the complexation of the metal ion with tpy group of APT and the hydrogen bond formation between APT with methanol at the terpyridine nitrogen N4-NS-N14 are also presented. The appearance of new long-wave absorption and fluorescence bands indicates that a new ground state of the complexes is formed.展开更多
The developed visualization methods of two dimensional （2D） site and three dimensional （3D） cube representations have been performed to show the orientation of transition dipole, charge transfer, and electron-hole...The developed visualization methods of two dimensional （2D） site and three dimensional （3D） cube representations have been performed to show the orientation of transition dipole, charge transfer, and electron-hole coherence in two-photon absorption （TPA）. The 3D cube representations of transition density can reveal visually the orientation and strength of transition dipole moment, and charge different density show the orientation of charge transfer in TPA. The 2D site representation can reveal visually the electron-hole coherence in TPA. The combination of 2D site and 3D cube representations provide clearly inspect into the charge transfer process and the contribution of excited molecular segments for TPA.展开更多
The present work concerns the study of solvent effects on the geometrical structures, as well as one- and two-photon absorption （TPA） processes, for two series of alkyne and alkene π-bridging molecules, within the ...The present work concerns the study of solvent effects on the geometrical structures, as well as one- and two-photon absorption （TPA） processes, for two series of alkyne and alkene π-bridging molecules, within the framework of the polarization continuum model. Particular emphasis was put on the characterization of solvent effects on the molecular geometrical structures and geometric distortion, which were measured by the bond-length-alternation parameter. The π centres in the compounds are seen to play a decisive role in increasing the TPA cross section and nonlinear optical properties. All studied molecules have relatively strong TPA characteristics, while the alkyne π-bridging ones yield larger TPA cross sections.展开更多
Structural analogues of bicyclic peroxides belonging to the G factors family have been synthesised under Mannieh type conditions, followed by an autoxidation step furnishing exclusively the peroxide. As electron trans...Structural analogues of bicyclic peroxides belonging to the G factors family have been synthesised under Mannieh type conditions, followed by an autoxidation step furnishing exclusively the peroxide. As electron transfer from heine or free iron to peroxide is the first step in the mode of action ofartemisinin -like compound, Fe（fl） induced reduction was studied and the reactivity of the intermediate C-centered radical formed was correlated to the antimalarial activity. Dissociative electron transfer was studied by electrochemistry and allowed the evaluation of the standard reduction potentials and other pertinent thermochemical information. These bicyclic peroxides were evaluated in vitro against Plasmodium falciparum and revealed moderate to good activity.展开更多
A non-sulfur chemosensor based on an easy to prepare double naphthalene Schiff base is reported for the colorimetric and fluorometric dual-channel sensing of Hg2+ ions by taking advantage of the twisted intramolecular...A non-sulfur chemosensor based on an easy to prepare double naphthalene Schiff base is reported for the colorimetric and fluorometric dual-channel sensing of Hg2+ ions by taking advantage of the twisted intramolecular charge transfer (TICT) mechanism. This work provides a novel approach for the selective recognition of mercury ions. Moreover, this sensor serves as a potential recyclable component in sensing materials and the complex L-Hg2+ (L = 1-[(2-naphthalenylimino)methyl]-2-naphthalenol) can therefore be used as a fluorescent sensor for iodine anions. Notably, the color changes are very significant and all the recognition and recycling processes can be observed by the naked eye.展开更多
In this work,we demonstrated the enhanced oxygen evolution reaction（OER） activity of flower-shaped cobalt-nickel oxide（NiCo_2O_4） decorated with iridium-nickel bimetal as an electrode material.The samples were pre...In this work,we demonstrated the enhanced oxygen evolution reaction（OER） activity of flower-shaped cobalt-nickel oxide（NiCo_2O_4） decorated with iridium-nickel bimetal as an electrode material.The samples were prepared by carefully depositing pre-synthesized IrNi nanopartides on the surfaces of the NiCo_2O_4 nano-flowers.Compared with bare NiCo_2O_4,IrNi,and IrNi/Co_3O_4,the IrNi/NiCo_2O_4 exhibited significantly enhanced electrocatalytic activity in the OER,including a lower overpotential of 210 mV and a higher current density at an overpotential of 540 mV.We found that the IrNi/NiCo_2O_4 showed more efficient electron transport behavior and reduced polarization because of its bimetal IrNi modification by analyzing its Tafel slope and turnover frequency.Furthermore,the electrocatalytic mechanism of IrNi/NiCo_2O_4 in the OER was studied,and it was found that the combined active sites of the composite effectively improved the rate determining step.The synergic effect of the bimetal and metal oxide plays an important role in this reaction,enhancing the transmission efficiency of electrons and providing more active sites for the OER.The results reveal that IrNi/NiCo_2O_4 is an excellent electrocatalyst for OER.展开更多
文摘Photocatalytic solar fuel generation is currently a hot topic because of its potential for solving the energy crisis owing to its low cost and zero-carbon emissions.However,the rapid bulk recombination of photoexcited carrier pairs is a fundamental disadvantage.To resolve this problem,we synthesized a dual cocatalysts system of cobalt phosphide(Co P)and molybdenum carbide(Mo_(2)C)embedded on strontium titanate(Sr TiO_(3))nanofibers.Compared with those of pristine SrTiO_(3) and binary samples,the dual cocatalysts system(denoted SCM)showed a significant improvement in the hydrogen evolution and CO_(2) reduction performance.Further,the structure of SCM effectively promoted spatial charge separation and enhanced the photocatalytic performance.In addition,the Schottky junction formed between the SrTiO_(3) and cocatalysts enabled the rapid transfer of photoexcited electrons from SrTiO_(3) to the cocatalysts,resulting in effective separation and prolonged photoexcited electron lifetimes.The electron migration route between SrTiO_(3) and the cocatalysts was determined by in situ irradiation X-ray spectroscopy,and band structures of Sr TiO_(3) and the cocatalysts are proposed based on results obtained from UV-vis diffraction reflection spectroscopy and ultraviolet photoelectron spectroscopy measurements.On the basis of our results,the dual cocatalysts unambiguously boosts charge separation and enhances photocatalytic performance.In summary,we have investigated the flux of photoexcited electrons in a dual cocatalysts system and provided a theoretical basis and ideas for subsequent research.
文摘Spectral and photophysical investigations of 4＇-（p-aminophenyl）-2,2＇：6＇,2″-terpyridine （APT） have been performed in various solvents with different polarity and hydrogen-bonding ability. The emission spectra of APT are found to exhibit dual fluorescence in polar solvents, which attributes to the local excited and intramolecular charge transfer states, respectively. The two-state model is proven out for APT in polar solvent by the time-correlated single photon counting emission decay measurement. Interestingly, the linear relationships of different emission maxima and solvent polarity parameter are found for APT in protic and aprotic solvents, because of the hydrogen bond formation between APT and alcohols at the amino nitrogen N25. Furthermore, the effects of the complexation of the metal ion with tpy group of APT and the hydrogen bond formation between APT with methanol at the terpyridine nitrogen N4-NS-N14 are also presented. The appearance of new long-wave absorption and fluorescence bands indicates that a new ground state of the complexes is formed.
基金This work was supported by the National Natural Science Foundation of China （No.10874234, No.20703064, and No.10604012）. Authors thank Prof. Chuan-kui Wang for his valuable suggestions.
文摘The developed visualization methods of two dimensional （2D） site and three dimensional （3D） cube representations have been performed to show the orientation of transition dipole, charge transfer, and electron-hole coherence in two-photon absorption （TPA）. The 3D cube representations of transition density can reveal visually the orientation and strength of transition dipole moment, and charge different density show the orientation of charge transfer in TPA. The 2D site representation can reveal visually the electron-hole coherence in TPA. The combination of 2D site and 3D cube representations provide clearly inspect into the charge transfer process and the contribution of excited molecular segments for TPA.
文摘The present work concerns the study of solvent effects on the geometrical structures, as well as one- and two-photon absorption （TPA） processes, for two series of alkyne and alkene π-bridging molecules, within the framework of the polarization continuum model. Particular emphasis was put on the characterization of solvent effects on the molecular geometrical structures and geometric distortion, which were measured by the bond-length-alternation parameter. The π centres in the compounds are seen to play a decisive role in increasing the TPA cross section and nonlinear optical properties. All studied molecules have relatively strong TPA characteristics, while the alkyne π-bridging ones yield larger TPA cross sections.
文摘Structural analogues of bicyclic peroxides belonging to the G factors family have been synthesised under Mannieh type conditions, followed by an autoxidation step furnishing exclusively the peroxide. As electron transfer from heine or free iron to peroxide is the first step in the mode of action ofartemisinin -like compound, Fe（fl） induced reduction was studied and the reactivity of the intermediate C-centered radical formed was correlated to the antimalarial activity. Dissociative electron transfer was studied by electrochemistry and allowed the evaluation of the standard reduction potentials and other pertinent thermochemical information. These bicyclic peroxides were evaluated in vitro against Plasmodium falciparum and revealed moderate to good activity.
基金supported by the National Natural Science Foundation of China (21064006, 21161018)the Natural Science Foundation of Gansu Province (1010RJZA018)the Program for Changjiang Scholars and Innovative Research Teams in Universities of the Ministry of Education of China (IRT1177)
文摘A non-sulfur chemosensor based on an easy to prepare double naphthalene Schiff base is reported for the colorimetric and fluorometric dual-channel sensing of Hg2+ ions by taking advantage of the twisted intramolecular charge transfer (TICT) mechanism. This work provides a novel approach for the selective recognition of mercury ions. Moreover, this sensor serves as a potential recyclable component in sensing materials and the complex L-Hg2+ (L = 1-[(2-naphthalenylimino)methyl]-2-naphthalenol) can therefore be used as a fluorescent sensor for iodine anions. Notably, the color changes are very significant and all the recognition and recycling processes can be observed by the naked eye.
基金supported by the National Natural Science Foundation of China(61371021 and 61671284)the support of Shanghai Education Commission(Peak Discipline Construction)
文摘In this work,we demonstrated the enhanced oxygen evolution reaction（OER） activity of flower-shaped cobalt-nickel oxide（NiCo_2O_4） decorated with iridium-nickel bimetal as an electrode material.The samples were prepared by carefully depositing pre-synthesized IrNi nanopartides on the surfaces of the NiCo_2O_4 nano-flowers.Compared with bare NiCo_2O_4,IrNi,and IrNi/Co_3O_4,the IrNi/NiCo_2O_4 exhibited significantly enhanced electrocatalytic activity in the OER,including a lower overpotential of 210 mV and a higher current density at an overpotential of 540 mV.We found that the IrNi/NiCo_2O_4 showed more efficient electron transport behavior and reduced polarization because of its bimetal IrNi modification by analyzing its Tafel slope and turnover frequency.Furthermore,the electrocatalytic mechanism of IrNi/NiCo_2O_4 in the OER was studied,and it was found that the combined active sites of the composite effectively improved the rate determining step.The synergic effect of the bimetal and metal oxide plays an important role in this reaction,enhancing the transmission efficiency of electrons and providing more active sites for the OER.The results reveal that IrNi/NiCo_2O_4 is an excellent electrocatalyst for OER.
