The ground and the lowest-lying triplet excited state geometries, electronic structures, and spectroscopic properties of three mixed-ligand Ru(II) complexes [Ru(terpy)(phen)X]+ (terpy=2,2',6',2″-terpyridine...The ground and the lowest-lying triplet excited state geometries, electronic structures, and spectroscopic properties of three mixed-ligand Ru(II) complexes [Ru(terpy)(phen)X]+ (terpy=2,2',6',2″-terpyridine, phen=l,10-phenanthroline, and X=-C-=CH (1), X=Cl (2), X-CN (3)) were investigated theoretically using the density functional theory method. The ground and excited state geometries have been fully optimized at the B3LYP/LanL2DZ and UB3LYP/LanL2DZ levels, respectively. The absorption and emission spectra of the com- plexes in CHaCN solutions were calculated by time-dependent density functional theory with the PCM solvent model. The calculated bond lengths of Ru-C, Ru-N, and Ru-Cl in the ground state agree well with the corresponding experimental results. The highest occupied molecular orbital were dominantly localized on the Ru atom and monodentate X ligand for 1 and 2, Ru atom and terpy ligand for a, while the lowest unoccupied molecular orbital were π*(terpy) type orbital. Therefore, the lowest-energy absorptions of 1 and 2 at 688 and 631 nln are attributed to a dyz (Ru)+Tr/p(X)--π* (terpy) transition with MLCT/XLCT (metal-to-ligand charge transfer/X ligand to terpy ligand charge transfer) character, whereas that of 3 at 529 nm is related to a dyz (Ru)+π(terpy)-π* (terpy) transition with MLCT and ILCT transition character. The calculated phosphorescence of three complexes at 1011 nm (1), 913 nm (2), and 838 nm (3) have similar transition properties to that of the lowest-lying absorption. It is shown that the lowest lying absorptions and emissions transition character of these Ru(II) complexes can be tuned by changing the electron-withdrawing ability of the monodentate ligand.展开更多
Texture and grain boundary character distribution of Cu interconnects with different line width for as-deposited and annealed conditions were measured by EBSD. All specimens appear mixed texture and (111) texture is...Texture and grain boundary character distribution of Cu interconnects with different line width for as-deposited and annealed conditions were measured by EBSD. All specimens appear mixed texture and (111) texture is the dominate component.As-deposited interconnects undergo the phenomenon of self-annealing at RT,in which some abnormally large grains are found. Lower aspect ratio of lines and anneal treatment procured larger grains and stronger (111) texture. Meanwhile, the intensity proportion of other textures with lower strain energy to (111) texture is decreased. As-deposited specimens reveal (111)(112? and (111) (231) components, (111) (110) component appeared and (111) (112? and (111) (231) components were developed during the annealing process. High angle boundaries are dominant in all specimens, boundaries with a misorientation of 55°-60° and ∑3 ones in higher proportion, followed by lower boundaries with a misorientation of 35°-40° and 29 boundaries. As the aspect ratio of lines and anneal treatment increase,there is a gradual in- crement in ∑3 boundaries and a decrease in ∑9 boundaries.展开更多
Small RNAs are non-coding RNA molecules with 20-30 nucleotides (nt) in length that mainly play regulatory roles in gene expression at the post-transcription level by directly cutting target mRNA or inhibiting its tr...Small RNAs are non-coding RNA molecules with 20-30 nucleotides (nt) in length that mainly play regulatory roles in gene expression at the post-transcription level by directly cutting target mRNA or inhibiting its translation. Small RNAs play regulatory roles in the growth and development process of plants at the core of gene regulatory networks, which has been widely studied and confirmed in sporophyte generation of plants. However, few researches have been conducted on small RNAs and gametophyte generation. It is reported that small RNAs play important roles in floral organ development, gametogenesis, fertilization, and early zygotic development of plants. In addition, various small RNAs also play roles in controlling genetic integrity, cell differentiation and functions during the sexual reproduction process of plants. However, most of the specific functions of small RNAs in the sexual reproduction process are unknown yet. This study mainly aimed to introduce small RNAs in plants, summarize the latest advances in researches of small RNAs and plant sexual reproduction, and make prospect on its future.展开更多
The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu(bipy)]4[Mo15O47].2H2O (1) and [Cu1(bix)][(Cu1bix) (δ-MoVl8O26)0....The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu(bipy)]4[Mo15O47].2H2O (1) and [Cu1(bix)][(Cu1bix) (δ-MoVl8O26)0.5] (2) (bipy = 4,4'-bipyridine, bix = 1,4-bis(imidazole-1-ylmethyl)benzene). Both compounds were catalytically active and stable for the epoxidation of cyclooctene, 1-octene, and styrene with tert-butyl hydroperoxide (t-BuOOH) as oxidant. The excellent catalytic performance was attributed to the presence of stable coordination bonds between the molybdenum oxide and copper complex, which resulted in the formation of easily accessible Mo species with high electropositivity. In addition, the copper complex also acted as an active site for the activation of t-BuOOH, thus im- proving these copper complex-modified polyoxometalates.展开更多
A new calculation formula of THM coupling stress intensity factor was derived by the boundary collocation method, in which an additional constant stress function was successfully introduced for the cracked specimen wi...A new calculation formula of THM coupling stress intensity factor was derived by the boundary collocation method, in which an additional constant stress function was successfully introduced for the cracked specimen with hydraulic pressure applied on its crack surface. Based on the newly derived formula, THM coupling fracture modes (including tensile, shear and mixed fracture mode) can be predicted by a new fracture criterion of stress intensity factor ratio, where the maximum axial load was measured by self-designed THM coupling fracture test. SEM analyses of THM coupling fractured surface indicate that the higher the temperature and hydraulic pressure are and the lower the confining pressure is, the more easily the intergranular (tension) fracture occurs. The transgranular (shear) fracture occurs in the opposite case while the mixed-mode fracture occurs in the middle case. The tested THM coupling fracture mechanisms are in good agreement with the predicted THM coupling fracture modes, which can verify correction of the newly-derived THM coupling stress intensity factor formula.展开更多
A formula was proposed to calculate the distribution of metal ions quantitatively in chemical reaction system forming hydroxide where precipitation and complex are formed together. The effects of some factors on forma...A formula was proposed to calculate the distribution of metal ions quantitatively in chemical reaction system forming hydroxide where precipitation and complex are formed together. The effects of some factors on formation of precipitation and complex were investigated, and the corresponding precipitation rates of zinc, iron (III), aluminum, copper and magnesium were calculated. As a result, it shows that the proposed formula is reliable. By the proposed formula, the existence state of metal ions in hydroxides reaction system with any metal ions can be well described and the effects of some factors on the distribution of metal ions were determined.展开更多
The neutral palladium(Ⅱ) complex bis-[1-(5'-diphenylphosphinothiazol-2'-yl)-imidazolyl]dichloropalladium(Ⅱ)(1A) ligated by thiazolylimidazolyl-based phosphine(L1) in which thiazolylimidazolyl acted as an...The neutral palladium(Ⅱ) complex bis-[1-(5'-diphenylphosphinothiazol-2'-yl)-imidazolyl]dichloropalladium(Ⅱ)(1A) ligated by thiazolylimidazolyl-based phosphine(L1) in which thiazolylimidazolyl acted as an S- and N-donor provider with weak coordinating nature,and the ionic complex bis-[1-(5'-diphenylphosphinothiazol-2'-yl)-3-methylimidazolium]dichloropalladium(Ⅱ) trifluoromethanesulfonate(2A) ligated by thiazolylimidazolium-based phosphine(L2) after quaternization of L1 using methyl trifluoromethanesulphonate were synthesized.It was found that the introduced positive charges and strong electron-withdrawing effect in 2A not only led to changes in the configuration and structural stability of the complex,but also lowered its catalytic performance in carbonylative Sonogashira reactions.These effects reveal the important role of the N-donor in 1A.In addition,as an ionic palladium complex,2A combined with the room-temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate could be recycled eight times as the catalyst in carbonylative Sonogashira reactions without detectable metal leaching.展开更多
Water oxidation is one of the most important reactions in natural and artificial energy conversion schemes.In nature,solar energy is converted to chemical energy via water oxidation at the oxygen-evolving center of ph...Water oxidation is one of the most important reactions in natural and artificial energy conversion schemes.In nature,solar energy is converted to chemical energy via water oxidation at the oxygen-evolving center of photosystem II to generate dioxygen,protons,and electrons.In artificial energy schemes,water oxidation is one of the half reactions of water splitting,which is an appealing strategy for energy conversion via photocatalytic,electrocatalytic,or photoelectrocatalytic processes.Because it is thermodynamically unfavorable and kinetically slow,water oxidation is the bottleneck for achieving large-scale water splitting.Thus,developing highly efficient water oxidation catalysts has attracted the interests of researchers in the past decades.The formation of O-O bonds is typically the rate-determining step of the water oxidation catalytic cycle.Therefore,better understanding this key step is critical for the rational design of more efficient catalysts.This review focuses on elucidating the evolution of metal-oxygen species during transition metal-catalyzed water oxidation,and more importantly,on discussing the feasible O-O bond formation mechanisms during the oxygen evolution reaction over synthetic molecular catalysts.展开更多
Herein,we report an excellent,supported Ru(III)‐ChCl/AC catalyst with lower Ru content,where the ionic complex ChRuCl4 serves as the active component for acetylene hydrochlorination.The prepared heterogeneous Ru‐10%...Herein,we report an excellent,supported Ru(III)‐ChCl/AC catalyst with lower Ru content,where the ionic complex ChRuCl4 serves as the active component for acetylene hydrochlorination.The prepared heterogeneous Ru‐10%ChCl/AC catalyst shows excellent activity and long‐term stability.In this system,ChCl provides an environment for the ChRuCl4 to be stabilized as Ru(III),thus suppressing the reduction of the active species and the aggregation of ruthenium species during the reaction.The interaction between reactants and catalyst species was investigated by catalyst characterizations in combination with DFT calculations to disclose the effect of the ChRuCl4 complex and ChCl on the catalytic performance.This inexpensive,efficient,and long‐term catalyst is a competitive candidate for application in the hydrochlorination industry.展开更多
The structure, spectroscopic properties and chemical stability of [VS4-(CuPPh3)3 (CuCl)Br2] in CDCl3 solution have been studied by multinuclear NMR tech-nique. Two peaks with relative intensity of 1: 4 are found in th...The structure, spectroscopic properties and chemical stability of [VS4-(CuPPh3)3 (CuCl)Br2] in CDCl3 solution have been studied by multinuclear NMR tech-nique. Two peaks with relative intensity of 1: 4 are found in the31P-{1H} spectra.Some 13C-{1H} and 1H NMR peaks have the same integral intensity ratio. These com-plemented the results of 31P-{1H} NMR. The experimental results demonstrates that the PPh3 ligand bound to Cu(6) is not equivalent with the four PPh3 ligands bound toCu(2) ~Cu (5 )- It affords an evidence that the title compound in the solution keepssimilar structure to solid state.展开更多
A multi-objective particle swarm optimization (MOPSO) approach for multi-objective economic load dispatch problem in power system is presented in this paper. The economic load dispatch problem is a non-linear constrai...A multi-objective particle swarm optimization (MOPSO) approach for multi-objective economic load dispatch problem in power system is presented in this paper. The economic load dispatch problem is a non-linear constrained multi-objective optimization problem. The proposed MOPSO approach handles the problem as a multi-objective problem with competing and non-commensurable fuel cost, emission and system loss objectives and has a diversity-preserving mechanism using an external memory (call “repository”) and a geographically-based approach to find widely different Pareto-optimal solutions. In addition, fuzzy set theory is employed to extract the best compromise solution. Several optimization runs of the proposed MOPSO approach were carried out on the standard IEEE 30-bus test system. The results revealed the capabilities of the proposed MOPSO approach to generate well-distributed Pareto-optimal non-dominated solutions of multi-objective economic load dispatch. Com- parison with Multi-objective Evolutionary Algorithm (MOEA) showed the superiority of the proposed MOPSO approach and confirmed its potential for solving multi-objective economic load dispatch.展开更多
The AgOCH3- and Ag-(CH3OH)x(x=l, 2) anions are studied by photoelectron imaging as well as ab initio calculations. The adiabatic and vertical detachment energies (ADE and VDE) of AgOCH3- are determined as 1.29(...The AgOCH3- and Ag-(CH3OH)x(x=l, 2) anions are studied by photoelectron imaging as well as ab initio calculations. The adiabatic and vertical detachment energies (ADE and VDE) of AgOCH3- are determined as 1.29(2) and 1.34(2) eV, respectively, from the vibrational resolved photoelectron spectrum. The Ag-(CH3OH)l,2 anionic complexes are characterized as metal atomic anion solvated by the CH3OH molecules with the electron mainly localized on the metal. The photoelectron spectra of Ag-(CH3OH)x (x=O, 1, 2) show a gradual increase in VDE with increasing x, due to the solvent stabilization. Evidence for the methanol-methanol hydrogen bonding interactions appears when the Ag- is solvated by two methanol molecules.展开更多
Morphology and life history of a brown alga Scytosiphon lomentaria (Lyngbye) Link (Scytosiphonaceae, Phaeophyceae) were investigated from 2005 to 2009 in the coastal waters of Dalian, China. The erect thalli collected...Morphology and life history of a brown alga Scytosiphon lomentaria (Lyngbye) Link (Scytosiphonaceae, Phaeophyceae) were investigated from 2005 to 2009 in the coastal waters of Dalian, China. The erect thalli collected in the field were tubular, hollow, and commonly constricted at intervals. Ascocysts were presented. Plurilocular gametangia, which were positioned in continuous sori on the erect thallus surface, produced biflagellar gametes. Gametophytes were dioecious and gametes were nearly isogamous. Gametes fusion occurred in three types. Type one, female and male gametes fused directly while swimming; type two, female gamete settled first, with which a male one contacted and fused rapidly; type three, while settling adjacently, a male gamete's entire protoplast moved slowly into the previously settled female one, with only an empty cell membrane left. In culture zygotes developed into crustose sporophytes that formed unilocular sporangia. Biflagellar zoospores developed into erect thalli that formed plurilocular gametangia. The results indicated that a periodical heteromorphic alternation history with haploid gametophyte generation and diploid sporophyte generation exists in S. lomentaria of the Dalian populations.展开更多
Ti+(CO2)2Ar and Ti+(CO2)n (n=3-7) complexes are produced by laser vaporization in a pulsed supersonic expansion. The ion complexes of interest are each mass-selected in a time- of-flight spectrometer, and stud...Ti+(CO2)2Ar and Ti+(CO2)n (n=3-7) complexes are produced by laser vaporization in a pulsed supersonic expansion. The ion complexes of interest are each mass-selected in a time- of-flight spectrometer, and studied with infrared photodissociation spectroscopy. For each complex, a sharp band in the CO stretching frequency region is observed, which confirms the formation of the OTi+CO(CO2)~_l oxide-carbonyl species. Small OTi+CO(CO2)~_1 complexes (n_〈5) exhibit CO stretching and antisymmetric CO2 stretching vibrational bands that are blue-shifted from those of free CO and CO2. The experimental observations indicate that the coordination number of CO and CO2 molecules around TiO+ is five. Evidence is also observed for the presence of another electrostatic bonding Ti+(CO2)2 structural isomer for the Ti+(CO2)2Ar complex, which is characterized to have a bent OCO-Ti+-OCO structure stabilized by argon coordination.展开更多
A[H3AgI(H2O)PW11O39]3?‐TiO2/ITO electrode was fabricated by immobilizing a molecular polyoxometalate‐based water oxidation catalyst,[H3AgI(H2O)PW11O39]3?(AgPW11),on a TiO2electrode.The resulting electrode was charac...A[H3AgI(H2O)PW11O39]3?‐TiO2/ITO electrode was fabricated by immobilizing a molecular polyoxometalate‐based water oxidation catalyst,[H3AgI(H2O)PW11O39]3?(AgPW11),on a TiO2electrode.The resulting electrode was characterized by X‐ray powder diffraction,scanning electron microscopy,and energy dispersive X‐ray spectroscopy.Linear sweep voltammetry,chronoamperometry,and electrochemical impedance measurements were performed in aqueous Na2SO4solution(0.1molL?1).We found that a higher applied voltage led to better catalytic performance by AgPW11.The AgPW11‐TiO2/ITO electrode gave currents respectively10and2.5times as high as those of the TiO2/ITO and AgNO3‐TiO2/ITO electrodes at an applied voltage of1.5V vs Ag/AgCl.This result was attributed to the lower charge transfer resistance at the electrode‐electrolyte interface for the AgPW11‐TiO2/ITO electrode.Under illumination,the photocurrent was not obviously enhanced although the total anode current increased.The AgPW11‐TiO2/ITO electrode was relatively stable.Cyclic voltammetry of AgPW11was performed in phosphate buffer solution(0.1mol L?1).We found that oxidation of AgPW11was a quasi‐reversible process related to one‐electron and one‐proton transfer.We deduced that disproportionation of the oxidized[H2AgII(H2O)PW11O39]3?might have occurred and the resulting[H3AgIIIOPW11O39]3?oxidized water to O2.展开更多
The theoretical calculation and spectroscopic experiments indicate a kind of triangular three bonding supramolecular complexes CBr4…X^-…-H-C, which consist of carbon tetrabromide, halide, and protic solvent molecule...The theoretical calculation and spectroscopic experiments indicate a kind of triangular three bonding supramolecular complexes CBr4…X^-…-H-C, which consist of carbon tetrabromide, halide, and protic solvent molecule (referring to dichloromethane, chloroform and acetonitrile), can be formed in solution. The strength of halogen and hydrogen bonds in the triangular complexes using halide as common acceptor obeys the order of iodide〉bromide〉chloride. The halogen and hydrogen bonds work weak-cooperatively. Charge transfer bands of halogen bonding complexes between CBra and halide are observed in UV-Vis absorption spectroscopy in three solvents, and then the stoichiometry of 1:1, formation constants K and molar extinction coefficients ε of the halogen bonding complexes are obtained by Benesi-Hildebrand method. The K and ε show a dependence on the solvent dielectric constant and, on the whole, obey an order of iodide〉bromide〉chloride in the same solvents. Furthermore, the C-H vibrational frequencies of solvent molecules vary obviously with the addition of halide, which indicates the C-H…X- interaction. The experimental data indicate that the halogen bond and hydrogen bond coexist by sharing a common halide acceptor as predicted by calculation.展开更多
Increasing interest has been paid to the development of earth‐abundant metal complexes as promising surrogates of platinum for the electrocatalytically and photocatalytically driven hydrogen evolution reaction.In thi...Increasing interest has been paid to the development of earth‐abundant metal complexes as promising surrogates of platinum for the electrocatalytically and photocatalytically driven hydrogen evolution reaction.In this work,we report on molecular H2‐evolving catalysts based on two octahedral complexes of cobalt thiosemicarbazide,fac‐[Co(Htsc)3]Cl3·3H2O(C1,Htsc=thiosemicarbazide)and mer‐[Co(Htsc)3]Cl3·4H2O(C2),which have facial(fac)and meridional(mer)geometry,respectively.Electrochemical studies confirmed that both C1and C2are active electrocatalysts in MeOH solution using acetic acid as the proton source,with the same overpotential of^640mV and TOF of^210s–1.The complex C1also exhibits electrocatalytic activity for hydrogen evolution reaction in aqueous media free of organic solvent with a moderate overpotential(560mV).Visible light‐driven hydrogen evolution experiments were carried out in combination with fluorescein as photosensitizer and triethylamine as sacrificial reductant in homogeneous environments.Our studies showed that both C1and C2can be used as efficient proton‐reduction catalysts in purely aqueous solution and have the same photocatalytic activities.A TOF of125h–1with a TON of900for photocatalytic H2generation using C1and C2in water were achieved for the noble‐metal‐free homogeneous system.It should be noted that this is the first reported study investigating the effect on the catalytic hydrogen production performance of using fac‐and mer‐isomers of molecular catalysts.展开更多
文摘The ground and the lowest-lying triplet excited state geometries, electronic structures, and spectroscopic properties of three mixed-ligand Ru(II) complexes [Ru(terpy)(phen)X]+ (terpy=2,2',6',2″-terpyridine, phen=l,10-phenanthroline, and X=-C-=CH (1), X=Cl (2), X-CN (3)) were investigated theoretically using the density functional theory method. The ground and excited state geometries have been fully optimized at the B3LYP/LanL2DZ and UB3LYP/LanL2DZ levels, respectively. The absorption and emission spectra of the com- plexes in CHaCN solutions were calculated by time-dependent density functional theory with the PCM solvent model. The calculated bond lengths of Ru-C, Ru-N, and Ru-Cl in the ground state agree well with the corresponding experimental results. The highest occupied molecular orbital were dominantly localized on the Ru atom and monodentate X ligand for 1 and 2, Ru atom and terpy ligand for a, while the lowest unoccupied molecular orbital were π*(terpy) type orbital. Therefore, the lowest-energy absorptions of 1 and 2 at 688 and 631 nln are attributed to a dyz (Ru)+Tr/p(X)--π* (terpy) transition with MLCT/XLCT (metal-to-ligand charge transfer/X ligand to terpy ligand charge transfer) character, whereas that of 3 at 529 nm is related to a dyz (Ru)+π(terpy)-π* (terpy) transition with MLCT and ILCT transition character. The calculated phosphorescence of three complexes at 1011 nm (1), 913 nm (2), and 838 nm (3) have similar transition properties to that of the lowest-lying absorption. It is shown that the lowest lying absorptions and emissions transition character of these Ru(II) complexes can be tuned by changing the electron-withdrawing ability of the monodentate ligand.
文摘Texture and grain boundary character distribution of Cu interconnects with different line width for as-deposited and annealed conditions were measured by EBSD. All specimens appear mixed texture and (111) texture is the dominate component.As-deposited interconnects undergo the phenomenon of self-annealing at RT,in which some abnormally large grains are found. Lower aspect ratio of lines and anneal treatment procured larger grains and stronger (111) texture. Meanwhile, the intensity proportion of other textures with lower strain energy to (111) texture is decreased. As-deposited specimens reveal (111)(112? and (111) (231) components, (111) (110) component appeared and (111) (112? and (111) (231) components were developed during the annealing process. High angle boundaries are dominant in all specimens, boundaries with a misorientation of 55°-60° and ∑3 ones in higher proportion, followed by lower boundaries with a misorientation of 35°-40° and 29 boundaries. As the aspect ratio of lines and anneal treatment increase,there is a gradual in- crement in ∑3 boundaries and a decrease in ∑9 boundaries.
基金Supported by National Natural Science Foundation of China(30971986)Specialized Research Fund for the Doctoral Program of Higher Education of China(20110182110013)Doctoral Fund of Southwestern University(SWU111016)~~
文摘Small RNAs are non-coding RNA molecules with 20-30 nucleotides (nt) in length that mainly play regulatory roles in gene expression at the post-transcription level by directly cutting target mRNA or inhibiting its translation. Small RNAs play regulatory roles in the growth and development process of plants at the core of gene regulatory networks, which has been widely studied and confirmed in sporophyte generation of plants. However, few researches have been conducted on small RNAs and gametophyte generation. It is reported that small RNAs play important roles in floral organ development, gametogenesis, fertilization, and early zygotic development of plants. In addition, various small RNAs also play roles in controlling genetic integrity, cell differentiation and functions during the sexual reproduction process of plants. However, most of the specific functions of small RNAs in the sexual reproduction process are unknown yet. This study mainly aimed to introduce small RNAs in plants, summarize the latest advances in researches of small RNAs and plant sexual reproduction, and make prospect on its future.
基金supported by the National Natural Science Foundation of China(21173100 and 21320102001)~~
文摘The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu(bipy)]4[Mo15O47].2H2O (1) and [Cu1(bix)][(Cu1bix) (δ-MoVl8O26)0.5] (2) (bipy = 4,4'-bipyridine, bix = 1,4-bis(imidazole-1-ylmethyl)benzene). Both compounds were catalytically active and stable for the epoxidation of cyclooctene, 1-octene, and styrene with tert-butyl hydroperoxide (t-BuOOH) as oxidant. The excellent catalytic performance was attributed to the presence of stable coordination bonds between the molybdenum oxide and copper complex, which resulted in the formation of easily accessible Mo species with high electropositivity. In addition, the copper complex also acted as an active site for the activation of t-BuOOH, thus im- proving these copper complex-modified polyoxometalates.
基金Project(11072269)supported by the National Natural Science Foundation of ChinaProject(20090162110066)supported by the Research Fund for the Doctoral Program of Higher Education of China
文摘A new calculation formula of THM coupling stress intensity factor was derived by the boundary collocation method, in which an additional constant stress function was successfully introduced for the cracked specimen with hydraulic pressure applied on its crack surface. Based on the newly derived formula, THM coupling fracture modes (including tensile, shear and mixed fracture mode) can be predicted by a new fracture criterion of stress intensity factor ratio, where the maximum axial load was measured by self-designed THM coupling fracture test. SEM analyses of THM coupling fractured surface indicate that the higher the temperature and hydraulic pressure are and the lower the confining pressure is, the more easily the intergranular (tension) fracture occurs. The transgranular (shear) fracture occurs in the opposite case while the mixed-mode fracture occurs in the middle case. The tested THM coupling fracture mechanisms are in good agreement with the predicted THM coupling fracture modes, which can verify correction of the newly-derived THM coupling stress intensity factor formula.
基金Project (51304047) supported by the National Natural Science Foundation of ChinaProject (20131037) supported by Science and Technology Foundation of Liaoning Province,China
文摘A formula was proposed to calculate the distribution of metal ions quantitatively in chemical reaction system forming hydroxide where precipitation and complex are formed together. The effects of some factors on formation of precipitation and complex were investigated, and the corresponding precipitation rates of zinc, iron (III), aluminum, copper and magnesium were calculated. As a result, it shows that the proposed formula is reliable. By the proposed formula, the existence state of metal ions in hydroxides reaction system with any metal ions can be well described and the effects of some factors on the distribution of metal ions were determined.
基金supported by the National Natural Science Foundation of China(21473058,21273077)~~
文摘The neutral palladium(Ⅱ) complex bis-[1-(5'-diphenylphosphinothiazol-2'-yl)-imidazolyl]dichloropalladium(Ⅱ)(1A) ligated by thiazolylimidazolyl-based phosphine(L1) in which thiazolylimidazolyl acted as an S- and N-donor provider with weak coordinating nature,and the ionic complex bis-[1-(5'-diphenylphosphinothiazol-2'-yl)-3-methylimidazolium]dichloropalladium(Ⅱ) trifluoromethanesulfonate(2A) ligated by thiazolylimidazolium-based phosphine(L2) after quaternization of L1 using methyl trifluoromethanesulphonate were synthesized.It was found that the introduced positive charges and strong electron-withdrawing effect in 2A not only led to changes in the configuration and structural stability of the complex,but also lowered its catalytic performance in carbonylative Sonogashira reactions.These effects reveal the important role of the N-donor in 1A.In addition,as an ionic palladium complex,2A combined with the room-temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate could be recycled eight times as the catalyst in carbonylative Sonogashira reactions without detectable metal leaching.
文摘Water oxidation is one of the most important reactions in natural and artificial energy conversion schemes.In nature,solar energy is converted to chemical energy via water oxidation at the oxygen-evolving center of photosystem II to generate dioxygen,protons,and electrons.In artificial energy schemes,water oxidation is one of the half reactions of water splitting,which is an appealing strategy for energy conversion via photocatalytic,electrocatalytic,or photoelectrocatalytic processes.Because it is thermodynamically unfavorable and kinetically slow,water oxidation is the bottleneck for achieving large-scale water splitting.Thus,developing highly efficient water oxidation catalysts has attracted the interests of researchers in the past decades.The formation of O-O bonds is typically the rate-determining step of the water oxidation catalytic cycle.Therefore,better understanding this key step is critical for the rational design of more efficient catalysts.This review focuses on elucidating the evolution of metal-oxygen species during transition metal-catalyzed water oxidation,and more importantly,on discussing the feasible O-O bond formation mechanisms during the oxygen evolution reaction over synthetic molecular catalysts.
文摘Herein,we report an excellent,supported Ru(III)‐ChCl/AC catalyst with lower Ru content,where the ionic complex ChRuCl4 serves as the active component for acetylene hydrochlorination.The prepared heterogeneous Ru‐10%ChCl/AC catalyst shows excellent activity and long‐term stability.In this system,ChCl provides an environment for the ChRuCl4 to be stabilized as Ru(III),thus suppressing the reduction of the active species and the aggregation of ruthenium species during the reaction.The interaction between reactants and catalyst species was investigated by catalyst characterizations in combination with DFT calculations to disclose the effect of the ChRuCl4 complex and ChCl on the catalytic performance.This inexpensive,efficient,and long‐term catalyst is a competitive candidate for application in the hydrochlorination industry.
文摘The structure, spectroscopic properties and chemical stability of [VS4-(CuPPh3)3 (CuCl)Br2] in CDCl3 solution have been studied by multinuclear NMR tech-nique. Two peaks with relative intensity of 1: 4 are found in the31P-{1H} spectra.Some 13C-{1H} and 1H NMR peaks have the same integral intensity ratio. These com-plemented the results of 31P-{1H} NMR. The experimental results demonstrates that the PPh3 ligand bound to Cu(6) is not equivalent with the four PPh3 ligands bound toCu(2) ~Cu (5 )- It affords an evidence that the title compound in the solution keepssimilar structure to solid state.
基金Project (Nos. 60074040 and 6022506) supported by the NationalNatural Science Foundation of China
文摘A multi-objective particle swarm optimization (MOPSO) approach for multi-objective economic load dispatch problem in power system is presented in this paper. The economic load dispatch problem is a non-linear constrained multi-objective optimization problem. The proposed MOPSO approach handles the problem as a multi-objective problem with competing and non-commensurable fuel cost, emission and system loss objectives and has a diversity-preserving mechanism using an external memory (call “repository”) and a geographically-based approach to find widely different Pareto-optimal solutions. In addition, fuzzy set theory is employed to extract the best compromise solution. Several optimization runs of the proposed MOPSO approach were carried out on the standard IEEE 30-bus test system. The results revealed the capabilities of the proposed MOPSO approach to generate well-distributed Pareto-optimal non-dominated solutions of multi-objective economic load dispatch. Com- parison with Multi-objective Evolutionary Algorithm (MOEA) showed the superiority of the proposed MOPSO approach and confirmed its potential for solving multi-objective economic load dispatch.
基金This work was supported by the National Natural Science Foundation of China (No.20933003 and No.21073186) and the National Basic Research Program of China (No.2007CBSI5203, No.2010CB732306, and No.2007CBSI5201).
文摘The AgOCH3- and Ag-(CH3OH)x(x=l, 2) anions are studied by photoelectron imaging as well as ab initio calculations. The adiabatic and vertical detachment energies (ADE and VDE) of AgOCH3- are determined as 1.29(2) and 1.34(2) eV, respectively, from the vibrational resolved photoelectron spectrum. The Ag-(CH3OH)l,2 anionic complexes are characterized as metal atomic anion solvated by the CH3OH molecules with the electron mainly localized on the metal. The photoelectron spectra of Ag-(CH3OH)x (x=O, 1, 2) show a gradual increase in VDE with increasing x, due to the solvent stabilization. Evidence for the methanol-methanol hydrogen bonding interactions appears when the Ag- is solvated by two methanol molecules.
基金supported by National Key Project of Scientific and Technical Supporting Programs Funded by Ministry of Science and Technology of China (No. 2006B AD09A01)
文摘Morphology and life history of a brown alga Scytosiphon lomentaria (Lyngbye) Link (Scytosiphonaceae, Phaeophyceae) were investigated from 2005 to 2009 in the coastal waters of Dalian, China. The erect thalli collected in the field were tubular, hollow, and commonly constricted at intervals. Ascocysts were presented. Plurilocular gametangia, which were positioned in continuous sori on the erect thallus surface, produced biflagellar gametes. Gametophytes were dioecious and gametes were nearly isogamous. Gametes fusion occurred in three types. Type one, female and male gametes fused directly while swimming; type two, female gamete settled first, with which a male one contacted and fused rapidly; type three, while settling adjacently, a male gamete's entire protoplast moved slowly into the previously settled female one, with only an empty cell membrane left. In culture zygotes developed into crustose sporophytes that formed unilocular sporangia. Biflagellar zoospores developed into erect thalli that formed plurilocular gametangia. The results indicated that a periodical heteromorphic alternation history with haploid gametophyte generation and diploid sporophyte generation exists in S. lomentaria of the Dalian populations.
文摘Ti+(CO2)2Ar and Ti+(CO2)n (n=3-7) complexes are produced by laser vaporization in a pulsed supersonic expansion. The ion complexes of interest are each mass-selected in a time- of-flight spectrometer, and studied with infrared photodissociation spectroscopy. For each complex, a sharp band in the CO stretching frequency region is observed, which confirms the formation of the OTi+CO(CO2)~_l oxide-carbonyl species. Small OTi+CO(CO2)~_1 complexes (n_〈5) exhibit CO stretching and antisymmetric CO2 stretching vibrational bands that are blue-shifted from those of free CO and CO2. The experimental observations indicate that the coordination number of CO and CO2 molecules around TiO+ is five. Evidence is also observed for the presence of another electrostatic bonding Ti+(CO2)2 structural isomer for the Ti+(CO2)2Ar complex, which is characterized to have a bent OCO-Ti+-OCO structure stabilized by argon coordination.
基金supported by the National Natural Science Foundation of China (21573099, 21601077, 21573100)~~
文摘A[H3AgI(H2O)PW11O39]3?‐TiO2/ITO electrode was fabricated by immobilizing a molecular polyoxometalate‐based water oxidation catalyst,[H3AgI(H2O)PW11O39]3?(AgPW11),on a TiO2electrode.The resulting electrode was characterized by X‐ray powder diffraction,scanning electron microscopy,and energy dispersive X‐ray spectroscopy.Linear sweep voltammetry,chronoamperometry,and electrochemical impedance measurements were performed in aqueous Na2SO4solution(0.1molL?1).We found that a higher applied voltage led to better catalytic performance by AgPW11.The AgPW11‐TiO2/ITO electrode gave currents respectively10and2.5times as high as those of the TiO2/ITO and AgNO3‐TiO2/ITO electrodes at an applied voltage of1.5V vs Ag/AgCl.This result was attributed to the lower charge transfer resistance at the electrode‐electrolyte interface for the AgPW11‐TiO2/ITO electrode.Under illumination,the photocurrent was not obviously enhanced although the total anode current increased.The AgPW11‐TiO2/ITO electrode was relatively stable.Cyclic voltammetry of AgPW11was performed in phosphate buffer solution(0.1mol L?1).We found that oxidation of AgPW11was a quasi‐reversible process related to one‐electron and one‐proton transfer.We deduced that disproportionation of the oxidized[H2AgII(H2O)PW11O39]3?might have occurred and the resulting[H3AgIIIOPW11O39]3?oxidized water to O2.
基金ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (No.20675009 and No. 90922023). The basis set aug-cc-pVDZ-PP for iodine atom is downloaded at the website http://bse.pnl.gov/ bse/portal.
文摘The theoretical calculation and spectroscopic experiments indicate a kind of triangular three bonding supramolecular complexes CBr4…X^-…-H-C, which consist of carbon tetrabromide, halide, and protic solvent molecule (referring to dichloromethane, chloroform and acetonitrile), can be formed in solution. The strength of halogen and hydrogen bonds in the triangular complexes using halide as common acceptor obeys the order of iodide〉bromide〉chloride. The halogen and hydrogen bonds work weak-cooperatively. Charge transfer bands of halogen bonding complexes between CBra and halide are observed in UV-Vis absorption spectroscopy in three solvents, and then the stoichiometry of 1:1, formation constants K and molar extinction coefficients ε of the halogen bonding complexes are obtained by Benesi-Hildebrand method. The K and ε show a dependence on the solvent dielectric constant and, on the whole, obey an order of iodide〉bromide〉chloride in the same solvents. Furthermore, the C-H vibrational frequencies of solvent molecules vary obviously with the addition of halide, which indicates the C-H…X- interaction. The experimental data indicate that the halogen bond and hydrogen bond coexist by sharing a common halide acceptor as predicted by calculation.
基金supported by the National Natural Science Foundation of China (21641011, 21773313)the Natural Science Foundation of Fujian Province (2015J01053, 2016J01060)+1 种基金Program for New Century Excellent Talents in Fujian Province UniversityPromotion Program for Young and Middle-aged Teacher in Science, Technology Research of Huaqiao University (ZQN-PY104)~~
文摘Increasing interest has been paid to the development of earth‐abundant metal complexes as promising surrogates of platinum for the electrocatalytically and photocatalytically driven hydrogen evolution reaction.In this work,we report on molecular H2‐evolving catalysts based on two octahedral complexes of cobalt thiosemicarbazide,fac‐[Co(Htsc)3]Cl3·3H2O(C1,Htsc=thiosemicarbazide)and mer‐[Co(Htsc)3]Cl3·4H2O(C2),which have facial(fac)and meridional(mer)geometry,respectively.Electrochemical studies confirmed that both C1and C2are active electrocatalysts in MeOH solution using acetic acid as the proton source,with the same overpotential of^640mV and TOF of^210s–1.The complex C1also exhibits electrocatalytic activity for hydrogen evolution reaction in aqueous media free of organic solvent with a moderate overpotential(560mV).Visible light‐driven hydrogen evolution experiments were carried out in combination with fluorescein as photosensitizer and triethylamine as sacrificial reductant in homogeneous environments.Our studies showed that both C1and C2can be used as efficient proton‐reduction catalysts in purely aqueous solution and have the same photocatalytic activities.A TOF of125h–1with a TON of900for photocatalytic H2generation using C1and C2in water were achieved for the noble‐metal‐free homogeneous system.It should be noted that this is the first reported study investigating the effect on the catalytic hydrogen production performance of using fac‐and mer‐isomers of molecular catalysts.