Electron donors(EDs)are widely used to improve the H 2 production performance of Schottky junction photocatalysts,but the functions of EDs are still unknown from the perspective of electron transfer dy-namics.Herein,P...Electron donors(EDs)are widely used to improve the H 2 production performance of Schottky junction photocatalysts,but the functions of EDs are still unknown from the perspective of electron transfer dy-namics.Herein,Pt nanocluster-decorated CdS nanorod is successfully prepared to construct a typical CdS/Pt Schottky junction.Pt nanoclusters with a diameter of∼2 nm are deposited on the surface of CdS nanorods by in situ photoreduction at sub-zero temperature.The CdS/Pt photocatalyst using lactic acid shows a higher H_(2)production rate of 4762μmol g^(-1)h^(-1)compared to that using methanol,tri-ethanolamine,and glycerol.To understand the cause,the dynamics of photogenerated carriers in CdS/Pt photocatalysts during ED-assisted H_(2)production are revealed by femtosecond transient absorption spec-troscopy.Among the four organic EDs,lactic acid enables the fastest electron transfer rate of 1.8×10^(9)s^(-1)and the highest electron transfer efficiency of 76%at the CdS/Pt interface due to the most efficient hole consumption.This work sheds light on the importance of efficient interfacial electron transfer for im-proving the photocatalytic performance of Schottky junction photocatalysts.展开更多
The metal transfer mode of electron beam welding （EBW） with filler wire was studied experimentally. The spatial position between the electron beam and the filler wire was defined. Basing on the charge coupled device...The metal transfer mode of electron beam welding （EBW） with filler wire was studied experimentally. The spatial position between the electron beam and the filler wire was defined. Basing on the charge coupled device （CCD） visual sensing system, the metal transfer mode of filler wire was investigated. The results showed that there were five transfer modes during EBW process due to different wire feed rates and spatial positions between beam and filler wire, such as short-circuiting mode, molten metal bridge mode, small droplet mode, big droplet mode and mixed mode. By comparing the weld appearance of different transfer modes, the molten metal bridge transfer was proved to be the best transfer mode.展开更多
The changes of chlorophyll_protein complexes and photosynthetic activities of chloroplast isolated from lotus ( Nelumbo nucifera Gaertn.) seeds germinating under illumination were studied. SDS PAGE analysis of c...The changes of chlorophyll_protein complexes and photosynthetic activities of chloroplast isolated from lotus ( Nelumbo nucifera Gaertn.) seeds germinating under illumination were studied. SDS PAGE analysis of chlorophyll_protein complexes showed that there was only the light harvesting chlorophyll a/b protein complex from PSⅡ (LHCⅡ) precursor in chloroplast from lotus seeds germinated for 2 to 6 days, while LHC Ⅱ 1, and the chlorophyll_protein complex of PSⅠ (CPⅠ) appeared on the 8th day of germination and PSⅡ reaction center complex appeared later. Studies on the polypeptides composition of the chloroplast revealed the following results: 1) Small amount of the 27 kD polypeptide was synthesized in invisible light; 2) The 30 kD polypeptide existed previously in the plumules of the dry seeds; 3) The amount of the 30 kD polypeptide was more than any other polypeptides before germination and decreased gradually throughout germination, while the 27 kD polypeptide changed in the opposite way; 4) In the process of germination, measurement of the electron transport rate and the fluorescence induction kinetics at room temperature showed that PSⅡ activities and efficiency of primary light energy transformation were only experimentally measurable after 7 days of germination and gradually increased afterwards. At the same time, the chl a/b ratio rose from the lower value to normal; 5) The changes of chloroplast membrane components and its functions are concomitant in concert with that of the ultrastructure of chloroplast membranes during germination, as shown in our earlier work . The results have proved again that a different developmental pathway of chloroplast is likely to exist in the lotus plumules, which might provide an important clue for N. nucifera in having an unique position in the phylogeny of the angiosperm.展开更多
Electron transfer reaction between a simplified model molecule of α amino carbon centered radical and O 2 has been studied with ab initio calculations at the MP2/6 31++G ** //UHF/6 31++G ** leve...Electron transfer reaction between a simplified model molecule of α amino carbon centered radical and O 2 has been studied with ab initio calculations at the MP2/6 31++G ** //UHF/6 31++G ** level. The reactant complex and the ion pair complex have been optimized and employed to perform calculations of the reaction heat and the reorganization energy. Solvent effects have been considered by applying the conductor like screening model. Theoretical results show that the highly endothermic charge separation process, in which one electron transfers from the α amino carbon centered radical to O 2, so as to form an ion pair complex, is difficult to occur in gas phase. By applying an external electronic field to prepare the charge localized molecular orbitals, the charge separated state has been obtained using the initial guess induced self consistent field technique. The theoretical investigations indicate that the solvent effect in the process of the oxidation of α amino carbon centered radical by O 2 is remarkable. From the rate constant estimation, it can be predicted that the oxidation of the model donor molecule by O 2 can proceed, but not very fast. A peroxyl radical compound has been found to be a competitive intermediate in the oxidation process.展开更多
Electron transfer (ET) reactions are of great importance to nearly every subdiscipline of chemistry. Marcus classical model, quantum model treating the nuclei as a quantum system, and the semiclassical model neglectin...Electron transfer (ET) reactions are of great importance to nearly every subdiscipline of chemistry. Marcus classical model, quantum model treating the nuclei as a quantum system, and the semiclassical model neglecting the nuclear tunneling effects but taking the nonadiabatic transition between two electronic states into account, have been widely used in the kinetic research of ET reactions. For the symmetric double-well potential vs. the nuclear configuration Q along the reaction path (fig.1(a)), a semiclassical kinetic model展开更多
The fluorescence spectra of three different dyes adsorbed on the tabular and cubic AgBr microcrystals are obtained by the picosecond time-resolved streak camera technique. The dependence of the ultrafast electron tran...The fluorescence spectra of three different dyes adsorbed on the tabular and cubic AgBr microcrystals are obtained by the picosecond time-resolved streak camera technique. The dependence of the ultrafast electron transferring from dye-aggre-gates to the conduction band of AgBr and the efficiency of spectral sensitization on different kinds of dyes with different concentrations is analyzed. Further more,the microcosmic mechanism of the sensitization process is discussed. It is found that the fluorescence decay curves are fitted very well by the double exponential func-tion,consisting of a slow component and a fast one with large amplitude. We con-sider this fast one mainly attributable to the electron transfer from dye J-aggre-gates to the conduction band of AgBr.展开更多
he electrochemistry of cytochrome C was investigated at a spectrographicgraphite electrode. In phosphate buffer solution (pH= 7. 0) , cytochrome C showedstable and quasi-reversible response. The formal potential E￣(o...he electrochemistry of cytochrome C was investigated at a spectrographicgraphite electrode. In phosphate buffer solution (pH= 7. 0) , cytochrome C showedstable and quasi-reversible response. The formal potential E￣(o') was 0. 015 V (at25℃ , vs. SCE) and the heterogeneous electron transfer rate constant k_s obtainedvaried form 1. 10×10￣(-3) cm · s￣(-1) to 1. 80k×10￣(-3) cm · s￣(-1). The thermodynamic pa-rameters of the electron transfer reaction of cvtochrome C was also estimated. Fur-thermore, the effect of the various electrode surface states on the electrochemistryof cytochrome C was discussed.展开更多
基金the National Key Research and Development Program of China(Nos.2022YFB3803600 and 2018YFB1502001)National Natural Science Foundation of China(Nos.22238009,51932007,U1905215,52073223,52173065,and 52202375)+2 种基金the Natural Science Foundation of Hubei Province of China(No.2022CFA001)China Postdoctoral Science Foundation(Nos.2021TQ0311 and 2021M702990)International Postdoc-toral Exchange Fellowship Program(No.PC2022051).
文摘Electron donors(EDs)are widely used to improve the H 2 production performance of Schottky junction photocatalysts,but the functions of EDs are still unknown from the perspective of electron transfer dy-namics.Herein,Pt nanocluster-decorated CdS nanorod is successfully prepared to construct a typical CdS/Pt Schottky junction.Pt nanoclusters with a diameter of∼2 nm are deposited on the surface of CdS nanorods by in situ photoreduction at sub-zero temperature.The CdS/Pt photocatalyst using lactic acid shows a higher H_(2)production rate of 4762μmol g^(-1)h^(-1)compared to that using methanol,tri-ethanolamine,and glycerol.To understand the cause,the dynamics of photogenerated carriers in CdS/Pt photocatalysts during ED-assisted H_(2)production are revealed by femtosecond transient absorption spec-troscopy.Among the four organic EDs,lactic acid enables the fastest electron transfer rate of 1.8×10^(9)s^(-1)and the highest electron transfer efficiency of 76%at the CdS/Pt interface due to the most efficient hole consumption.This work sheds light on the importance of efficient interfacial electron transfer for im-proving the photocatalytic performance of Schottky junction photocatalysts.
文摘The metal transfer mode of electron beam welding （EBW） with filler wire was studied experimentally. The spatial position between the electron beam and the filler wire was defined. Basing on the charge coupled device （CCD） visual sensing system, the metal transfer mode of filler wire was investigated. The results showed that there were five transfer modes during EBW process due to different wire feed rates and spatial positions between beam and filler wire, such as short-circuiting mode, molten metal bridge mode, small droplet mode, big droplet mode and mixed mode. By comparing the weld appearance of different transfer modes, the molten metal bridge transfer was proved to be the best transfer mode.
文摘The changes of chlorophyll_protein complexes and photosynthetic activities of chloroplast isolated from lotus ( Nelumbo nucifera Gaertn.) seeds germinating under illumination were studied. SDS PAGE analysis of chlorophyll_protein complexes showed that there was only the light harvesting chlorophyll a/b protein complex from PSⅡ (LHCⅡ) precursor in chloroplast from lotus seeds germinated for 2 to 6 days, while LHC Ⅱ 1, and the chlorophyll_protein complex of PSⅠ (CPⅠ) appeared on the 8th day of germination and PSⅡ reaction center complex appeared later. Studies on the polypeptides composition of the chloroplast revealed the following results: 1) Small amount of the 27 kD polypeptide was synthesized in invisible light; 2) The 30 kD polypeptide existed previously in the plumules of the dry seeds; 3) The amount of the 30 kD polypeptide was more than any other polypeptides before germination and decreased gradually throughout germination, while the 27 kD polypeptide changed in the opposite way; 4) In the process of germination, measurement of the electron transport rate and the fluorescence induction kinetics at room temperature showed that PSⅡ activities and efficiency of primary light energy transformation were only experimentally measurable after 7 days of germination and gradually increased afterwards. At the same time, the chl a/b ratio rose from the lower value to normal; 5) The changes of chloroplast membrane components and its functions are concomitant in concert with that of the ultrastructure of chloroplast membranes during germination, as shown in our earlier work . The results have proved again that a different developmental pathway of chloroplast is likely to exist in the lotus plumules, which might provide an important clue for N. nucifera in having an unique position in the phylogeny of the angiosperm.
文摘Electron transfer reaction between a simplified model molecule of α amino carbon centered radical and O 2 has been studied with ab initio calculations at the MP2/6 31++G ** //UHF/6 31++G ** level. The reactant complex and the ion pair complex have been optimized and employed to perform calculations of the reaction heat and the reorganization energy. Solvent effects have been considered by applying the conductor like screening model. Theoretical results show that the highly endothermic charge separation process, in which one electron transfers from the α amino carbon centered radical to O 2, so as to form an ion pair complex, is difficult to occur in gas phase. By applying an external electronic field to prepare the charge localized molecular orbitals, the charge separated state has been obtained using the initial guess induced self consistent field technique. The theoretical investigations indicate that the solvent effect in the process of the oxidation of α amino carbon centered radical by O 2 is remarkable. From the rate constant estimation, it can be predicted that the oxidation of the model donor molecule by O 2 can proceed, but not very fast. A peroxyl radical compound has been found to be a competitive intermediate in the oxidation process.
基金Project supported by the National Natural Science Foundation of China.
文摘Electron transfer (ET) reactions are of great importance to nearly every subdiscipline of chemistry. Marcus classical model, quantum model treating the nuclei as a quantum system, and the semiclassical model neglecting the nuclear tunneling effects but taking the nonadiabatic transition between two electronic states into account, have been widely used in the kinetic research of ET reactions. For the symmetric double-well potential vs. the nuclear configuration Q along the reaction path (fig.1(a)), a semiclassical kinetic model
基金the National Natural Science Foundation of China (Grant No. 60478033)the Doctoral Foundation of Hebei Province of China (Grant No. B2003119)the Science and Technology Project of Hebei Province of China (Grant No. 05215102)
文摘The fluorescence spectra of three different dyes adsorbed on the tabular and cubic AgBr microcrystals are obtained by the picosecond time-resolved streak camera technique. The dependence of the ultrafast electron transferring from dye-aggre-gates to the conduction band of AgBr and the efficiency of spectral sensitization on different kinds of dyes with different concentrations is analyzed. Further more,the microcosmic mechanism of the sensitization process is discussed. It is found that the fluorescence decay curves are fitted very well by the double exponential func-tion,consisting of a slow component and a fast one with large amplitude. We con-sider this fast one mainly attributable to the electron transfer from dye J-aggre-gates to the conduction band of AgBr.
文摘he electrochemistry of cytochrome C was investigated at a spectrographicgraphite electrode. In phosphate buffer solution (pH= 7. 0) , cytochrome C showedstable and quasi-reversible response. The formal potential E￣(o') was 0. 015 V (at25℃ , vs. SCE) and the heterogeneous electron transfer rate constant k_s obtainedvaried form 1. 10×10￣(-3) cm · s￣(-1) to 1. 80k×10￣(-3) cm · s￣(-1). The thermodynamic pa-rameters of the electron transfer reaction of cvtochrome C was also estimated. Fur-thermore, the effect of the various electrode surface states on the electrochemistryof cytochrome C was discussed.
