In sub nanometer carbon nanotubes,water exhibits unique dynamic characteristics,and in the high-frequency region of the infrared spectrum,where the stretching vibrations of the internal oxygen-hydrogen(O-H)bonds are c...In sub nanometer carbon nanotubes,water exhibits unique dynamic characteristics,and in the high-frequency region of the infrared spectrum,where the stretching vibrations of the internal oxygen-hydrogen(O-H)bonds are closely related to the hydrogen bonds(H-bonds)network between water molecules.Therefore,it is crucial to analyze the relationship between these two aspects.In this paper,the infrared spectrum and motion characteristics of the stretching vibrations of the O-H bonds in one-dimensional confined water(1DCW)and bulk water(BW)in(6,6)single-walled carbon nanotubes(SWNT)are studied by molecular dynamics simulations.The results show that the stretching vibrations of the two O-H bonds in 1DCW exhibit different frequencies in the infrared spectrum,while the O-H bonds in BW display two identical main frequency peaks.Further analysis using the spring oscillator model reveals that the difference in the stretching amplitude of the O-H bonds is the main factor causing the change in vibration frequency,where an increase in stretching amplitude leads to a decrease in spring stiffness and,consequently,a lower vibration frequency.A more in-depth study found that the interaction of H-bonds between water molecules is the fundamental cause of the increased stretching amplitude and decreased vibration frequency of the O-H bonds.Finally,by analyzing the motion trajectory of the H atoms,the dynamic differences between 1DCW and BW are clearly revealed.These findings provide a new perspective for understanding the behavior of water molecules at the nanoscale and are of significant importance in advancing the development of infrared spectroscopy detection technology.展开更多
The finite difference method such as alternating group iterative methods is useful in numerical method for evolutionary equations and this is the standard approach taken in this paper. Alternating group explicit (AGE)...The finite difference method such as alternating group iterative methods is useful in numerical method for evolutionary equations and this is the standard approach taken in this paper. Alternating group explicit (AGE) iterative methods for one-dimensional convection diffusion equations problems are given. The stability and convergence are analyzed by the linear method. Numerical results of the model problem are taken. Known test problems have been studied to demonstrate the accuracy of the method. Numerical results show that the behavior of the method with emphasis on treatment of boundary conditions is valuable.展开更多
SnO_(2)is used as electrode material with excellent properties,but it has some disadvantages such as slow reaction kinetics,low inherent conductivity and complex preparation process.Here,SnO_(2)@carbon nanotubes(SnO_(...SnO_(2)is used as electrode material with excellent properties,but it has some disadvantages such as slow reaction kinetics,low inherent conductivity and complex preparation process.Here,SnO_(2)@carbon nanotubes(SnO_(2)@CNTs)is synthesized through an efficient method of one-pot alternating current electrochemical dispersion.By using heat treatment at 400℃,the SnO_(2)@CNTs-400 composite material with abundant mesoporous structure is obtained,while the crystal particles are grown,and a strong bonding effect is formed with CNTs via powerful Sn-O-C bond.Benefiting from the introduction of high electrical conductivity CNTs and outstanding structural characteristics,as prepared composite material(SnO_(2)@CNTs-400)exhibit enhanced diffusion dynamics,lithium-ion transmission rate and structural steadiness.The specific capacity of SnO_(2)@CNTs and SnO_(2)@CNTs-400 as anodes for lithium-ion batteries can reach 690.2 mA·h/g and 836.5 mA·h/g,respectively,after 100 cycles at 0.5 A/g.The abundant chemical bonds and porous structure can be formed in composite via alternating current synthesis method,which takes significant in improving electrochemical properties.展开更多
Rotational isomerism effects on the optical spectra of a push-pull nonlinear optical chro-mophore 2-dicyanomethylen-3-cyano-4-f2-[E-（4-N,N-di（2-acetoxyethyl）-amino）-phenylene-（3,4-dibutyl）-thien-5]-E-vinylg-5,5-...Rotational isomerism effects on the optical spectra of a push-pull nonlinear optical chro-mophore 2-dicyanomethylen-3-cyano-4-f2-[E-（4-N,N-di（2-acetoxyethyl）-amino）-phenylene-（3,4-dibutyl）-thien-5]-E-vinylg-5,5-dimethyl-2,5-dihydrofuran （FTC） in a few solvents have been studied using the time-dependent density functional theory in combination with the polarizable continuum model. It is shown that the maximum absorption peaks of the ro-tamers have difference of nearly 30 nm both in vacuum and in solutions. The population of the rotamers changes a lot in different solvents. Based on the geometries optimized by Hartree-Fock method, the Maxwell-Boltzmann averaged absorption has been calculated and the maximum absorption peak is in good agreement with experiment. It indicates that the bond length alternation can have an important effect on the optical spectra.展开更多
Nanoparticles self-assembly plays a pivotal role in designing new functional structural materials.The manipulation of interactions among nanoparticle building blocks is crucial for achieving assemblies with desired st...Nanoparticles self-assembly plays a pivotal role in designing new functional structural materials.The manipulation of interactions among nanoparticle building blocks is crucial for achieving assemblies with desired structures and properties.In this work,we assemble binary inorganic nanoparticles into alternating copolymer-like nanostructures by independently regulating hydrogen bonding and electrostatic interactions.The block copolymers grafted on nanoparticles feature oppositely charged groups,where electrostatic attraction drives the linear assembly of nanoparticles into alternate chain configurations.The hydrogen bonding interaction originates from the direct introduction of polyethylene glycol into the systems,serving as hydrogen bond acceptors with the grafted polymer and facilitating the side-by-side assembly of the chain structures.These two forces were observed to compete with each other during the assembly process,and could be precisely controlled by adjusting the quantities of acetic acid and polyethylene glycol,thus regulating the nanoparticle assembly behavior.This work provides a practical framework for the design of muti-force interactions in hierarchical colloid nanomaterials.展开更多
We use the Schwinger-boson approach to study the anisotropy ferrimagnetic spin-（1/2,1） chain with bond alternation.Based on the effect of bond alternation δ,we obtain energy gap,free energy,and specific heat,respec...We use the Schwinger-boson approach to study the anisotropy ferrimagnetic spin-（1/2,1） chain with bond alternation.Based on the effect of bond alternation δ,we obtain energy gap,free energy,and specific heat,respectively.The specific heat with larger bond alternation（δ 〉 0.7） displays a peak at low temperature.Based on the effect of XXZ anisotropy parameter Δ,we present excited spectrums,free energy,and specific heat,respectively.展开更多
We present a quantum-chemical analysis of the relationship between the bond length alteration （BLA） and the static first hyperpolarizability of a series of one-dimensional （1D） chromophores with donor-bridge-accep...We present a quantum-chemical analysis of the relationship between the bond length alteration （BLA） and the static first hyperpolarizability of a series of one-dimensional （1D） chromophores with donor-bridge-acceptor （D-B-A） structures. The calculated results show that the parameter BLA can be considered as an indicator to evaluate the molecular first hyper- polarizability. Along the direction of molecular ground-state dipole moments, the evolutions of BLA can be classified into three categories： the first is a non-monotonic line, which represents most chromophores; the second is monotonic increasing; and the third, contrarily, is monotonic decreasing. On the whole, the first hyperpolarizabilities of these studied chromophores are the monotonic functions of BLA along the direction of dipole moments. Therefore, the first hyperpolarizability of these 1D chromophores can be preliminarily evaluated in terms of the development of BLA without a rigorous computation. In other words, one can roughly estimate the relative magnitude of the first hyperpolarizability according to the optimized geometry.展开更多
The preparation and crystal structure of complex Co（Hsae）2·2H2O （1, H2sae = N-salicylidene-2-iminoethanol） are reported. X- ray analysis revealed that every six Co（Hsae）2 forms a cyclic chip and every 12 wa...The preparation and crystal structure of complex Co（Hsae）2·2H2O （1, H2sae = N-salicylidene-2-iminoethanol） are reported. X- ray analysis revealed that every six Co（Hsae）2 forms a cyclic chip and every 12 water forms a novel gear-like cluster. Acting as building blocks, the gear-like water cluster and complex chip are connected in A-B fashion and extend into one-dimensional supramolecular chain. Hydrogen bond is the primary bridging force in the formation of supramolecular framework.展开更多
Gaseous phases of carbon-containing and metastable oxides will be resulted from the carbonization of phenolic resin binders and the reduced reactions between C and oxides at high temperatures in carbon-containing refr...Gaseous phases of carbon-containing and metastable oxides will be resulted from the carbonization of phenolic resin binders and the reduced reactions between C and oxides at high temperatures in carbon-containing refractories. With the in-situ catalysis technique, these gaseous phases can be transformed to one-or two-dimensional bonding phases by deposition,which is favorable for the improvement on strength and toughness of carboncontaining refractories,especially low carbon refractories. The research results reveal that：（ 1） the amorphous carbon resulted from phenolic resin can be transformed to carbon nanotubes,thus,the oxidation peak temperature is raised from 506 to 664. 6 ℃;（ 2） onedimensional whiskers of MgO or Mg Al2 O4 can be in-situ formed in MgO-C refractories, and their CMOR,CCS,rupture displacement and residual CCS（ two water quenching cycles,1 100 ℃） are increased by 66%,47%,13% and 26%,respectively;（ 3） two-dimensional array structure of flake β-SiAlON can be in-situ formed in Al2 O3-C refractories,which improves the material strength by 60% and decreases the residual strength after thermal shock by only 4. 5 MPa. It is believed that the in-situ formation of one-or two-dimensional bonding phases at high temperatures can improvethe comprehensive thermal physical properties of carboncontaining refractories,and will be the developing trend of the strengthening and toughening of low carbon-containing refractories.展开更多
Four dithiooxalato (Dto) bridged one-dimensional Ni(ll) and Ni(ll)Cu(ll) complexes (Me6[14]dieneN4)Ni2(Dto)2) (1), (Me6[14]dieneN4)CuNi(Dto)2 (2), (Me6[14]aneN4)Ni2(Dto)2 (3), and (Me6[14]aneN4)CuNi(Dto)2(4), were syn...Four dithiooxalato (Dto) bridged one-dimensional Ni(ll) and Ni(ll)Cu(ll) complexes (Me6[14]dieneN4)Ni2(Dto)2) (1), (Me6[14]dieneN4)CuNi(Dto)2 (2), (Me6[14]aneN4)Ni2(Dto)2 (3), and (Me6[14]aneN4)CuNi(Dto)2(4), were synthesized. These complexes have been characterized by elemental analysis, IR, UV and ESR spectra. The crystal structure of complex 3 was determined. It crystallizes in the monoclinic system, space group C2/c with a = 2.2425(4) nm, b = 1.0088(2) nm, c=1.4665(3) nm, β= 125.32(3)° ;Z=4; R = 0.076, Rw = 0.079. In the complex, Ni(1) coordinates four sulphur atoms of two Dto ligands in plane square environment. Ni(2) lies in the center of mac-rocyclic ligand. For Dto ligand, two sulphur atoms coordinate Ni(1), and O(1) coordinates Ni(2) and forms weak coordination bond. O(2) is linked to N(2) of macrocyclic ligand through hydrogen bond.展开更多
Alternating current(AC)electrolysis is a promising,yet challenging,and under-developed protocol in organic synthesis.To achieve as high an atomefficiency as possible and avoid the use of external oxidant,electrochemis...Alternating current(AC)electrolysis is a promising,yet challenging,and under-developed protocol in organic synthesis.To achieve as high an atomefficiency as possible and avoid the use of external oxidant,electrochemistry has become a standard organic synthesis tool.Herein,an AC-basedprotocol is a superior option than its counterpart,direct current(DC),especially for those reactions that cannot be accomplished by DC.展开更多
基金Supported by the Natural Science Foundation of China(51705326,52075339)。
文摘In sub nanometer carbon nanotubes,water exhibits unique dynamic characteristics,and in the high-frequency region of the infrared spectrum,where the stretching vibrations of the internal oxygen-hydrogen(O-H)bonds are closely related to the hydrogen bonds(H-bonds)network between water molecules.Therefore,it is crucial to analyze the relationship between these two aspects.In this paper,the infrared spectrum and motion characteristics of the stretching vibrations of the O-H bonds in one-dimensional confined water(1DCW)and bulk water(BW)in(6,6)single-walled carbon nanotubes(SWNT)are studied by molecular dynamics simulations.The results show that the stretching vibrations of the two O-H bonds in 1DCW exhibit different frequencies in the infrared spectrum,while the O-H bonds in BW display two identical main frequency peaks.Further analysis using the spring oscillator model reveals that the difference in the stretching amplitude of the O-H bonds is the main factor causing the change in vibration frequency,where an increase in stretching amplitude leads to a decrease in spring stiffness and,consequently,a lower vibration frequency.A more in-depth study found that the interaction of H-bonds between water molecules is the fundamental cause of the increased stretching amplitude and decreased vibration frequency of the O-H bonds.Finally,by analyzing the motion trajectory of the H atoms,the dynamic differences between 1DCW and BW are clearly revealed.These findings provide a new perspective for understanding the behavior of water molecules at the nanoscale and are of significant importance in advancing the development of infrared spectroscopy detection technology.
文摘The finite difference method such as alternating group iterative methods is useful in numerical method for evolutionary equations and this is the standard approach taken in this paper. Alternating group explicit (AGE) iterative methods for one-dimensional convection diffusion equations problems are given. The stability and convergence are analyzed by the linear method. Numerical results of the model problem are taken. Known test problems have been studied to demonstrate the accuracy of the method. Numerical results show that the behavior of the method with emphasis on treatment of boundary conditions is valuable.
基金Project(2023JЛ10041)supported by the Distinguished Young Scholar Fund Project of Hunan Province Natural Science Foundation,ChinaProject(22A0114)supported by the Hunan Provincial Education Office Foundation of China+2 种基金Projects(GX-ZD20211004,GX-ZD20221007)supported by the Science and Technology Program of Xiangtan,ChinaProject(R24-5979269037)supported by the RSC Research Fund Grout,EnglandProject(S202310530037X)supported by the National College Students Innovative Experimental Program Funding Project,China。
文摘SnO_(2)is used as electrode material with excellent properties,but it has some disadvantages such as slow reaction kinetics,low inherent conductivity and complex preparation process.Here,SnO_(2)@carbon nanotubes(SnO_(2)@CNTs)is synthesized through an efficient method of one-pot alternating current electrochemical dispersion.By using heat treatment at 400℃,the SnO_(2)@CNTs-400 composite material with abundant mesoporous structure is obtained,while the crystal particles are grown,and a strong bonding effect is formed with CNTs via powerful Sn-O-C bond.Benefiting from the introduction of high electrical conductivity CNTs and outstanding structural characteristics,as prepared composite material(SnO_(2)@CNTs-400)exhibit enhanced diffusion dynamics,lithium-ion transmission rate and structural steadiness.The specific capacity of SnO_(2)@CNTs and SnO_(2)@CNTs-400 as anodes for lithium-ion batteries can reach 690.2 mA·h/g and 836.5 mA·h/g,respectively,after 100 cycles at 0.5 A/g.The abundant chemical bonds and porous structure can be formed in composite via alternating current synthesis method,which takes significant in improving electrochemical properties.
基金ACKNOWLEDGMENTS This work was supported by Young Scientists Fund of the National Natural Science Foundation of China （No.10904085）.
文摘Rotational isomerism effects on the optical spectra of a push-pull nonlinear optical chro-mophore 2-dicyanomethylen-3-cyano-4-f2-[E-（4-N,N-di（2-acetoxyethyl）-amino）-phenylene-（3,4-dibutyl）-thien-5]-E-vinylg-5,5-dimethyl-2,5-dihydrofuran （FTC） in a few solvents have been studied using the time-dependent density functional theory in combination with the polarizable continuum model. It is shown that the maximum absorption peaks of the ro-tamers have difference of nearly 30 nm both in vacuum and in solutions. The population of the rotamers changes a lot in different solvents. Based on the geometries optimized by Hartree-Fock method, the Maxwell-Boltzmann averaged absorption has been calculated and the maximum absorption peak is in good agreement with experiment. It indicates that the bond length alternation can have an important effect on the optical spectra.
基金This work is financially supported by the Innovation Program of Shanghai Municipal Education Commission(No.2021-01-07-0007-E00073)the National Natural Science Foundation of China(Nos.52125308 and 52293473)+3 种基金the Shanghai Municipal Science and Technology Project(No.23JC1400100)the National Key Research&Development Program of China(No.2022YFA1404700)the Shanghai Pujiang Program(No.23PJ1401000)China Postdoctoral Science Foundation(No.2022M720754).
文摘Nanoparticles self-assembly plays a pivotal role in designing new functional structural materials.The manipulation of interactions among nanoparticle building blocks is crucial for achieving assemblies with desired structures and properties.In this work,we assemble binary inorganic nanoparticles into alternating copolymer-like nanostructures by independently regulating hydrogen bonding and electrostatic interactions.The block copolymers grafted on nanoparticles feature oppositely charged groups,where electrostatic attraction drives the linear assembly of nanoparticles into alternate chain configurations.The hydrogen bonding interaction originates from the direct introduction of polyethylene glycol into the systems,serving as hydrogen bond acceptors with the grafted polymer and facilitating the side-by-side assembly of the chain structures.These two forces were observed to compete with each other during the assembly process,and could be precisely controlled by adjusting the quantities of acetic acid and polyethylene glycol,thus regulating the nanoparticle assembly behavior.This work provides a practical framework for the design of muti-force interactions in hierarchical colloid nanomaterials.
基金supported by the National Natural Science Foundation of China(Grant No.10774035)the Qianjiang RenCai Program of Zhejiang Province,China(Grant No.2007R0010)
文摘We use the Schwinger-boson approach to study the anisotropy ferrimagnetic spin-（1/2,1） chain with bond alternation.Based on the effect of bond alternation δ,we obtain energy gap,free energy,and specific heat,respectively.The specific heat with larger bond alternation（δ 〉 0.7） displays a peak at low temperature.Based on the effect of XXZ anisotropy parameter Δ,we present excited spectrums,free energy,and specific heat,respectively.
基金the National Natural Science Foundation of China (20573114)the MOST projects of 2004CB720605and 2006DFA403020
文摘We present a quantum-chemical analysis of the relationship between the bond length alteration （BLA） and the static first hyperpolarizability of a series of one-dimensional （1D） chromophores with donor-bridge-acceptor （D-B-A） structures. The calculated results show that the parameter BLA can be considered as an indicator to evaluate the molecular first hyper- polarizability. Along the direction of molecular ground-state dipole moments, the evolutions of BLA can be classified into three categories： the first is a non-monotonic line, which represents most chromophores; the second is monotonic increasing; and the third, contrarily, is monotonic decreasing. On the whole, the first hyperpolarizabilities of these studied chromophores are the monotonic functions of BLA along the direction of dipole moments. Therefore, the first hyperpolarizability of these 1D chromophores can be preliminarily evaluated in terms of the development of BLA without a rigorous computation. In other words, one can roughly estimate the relative magnitude of the first hyperpolarizability according to the optimized geometry.
基金supported by the Natural Science Foundation of Education Bureau of Liaoning Province,China(No.05L159).
文摘The preparation and crystal structure of complex Co（Hsae）2·2H2O （1, H2sae = N-salicylidene-2-iminoethanol） are reported. X- ray analysis revealed that every six Co（Hsae）2 forms a cyclic chip and every 12 water forms a novel gear-like cluster. Acting as building blocks, the gear-like water cluster and complex chip are connected in A-B fashion and extend into one-dimensional supramolecular chain. Hydrogen bond is the primary bridging force in the formation of supramolecular framework.
文摘Gaseous phases of carbon-containing and metastable oxides will be resulted from the carbonization of phenolic resin binders and the reduced reactions between C and oxides at high temperatures in carbon-containing refractories. With the in-situ catalysis technique, these gaseous phases can be transformed to one-or two-dimensional bonding phases by deposition,which is favorable for the improvement on strength and toughness of carboncontaining refractories,especially low carbon refractories. The research results reveal that：（ 1） the amorphous carbon resulted from phenolic resin can be transformed to carbon nanotubes,thus,the oxidation peak temperature is raised from 506 to 664. 6 ℃;（ 2） onedimensional whiskers of MgO or Mg Al2 O4 can be in-situ formed in MgO-C refractories, and their CMOR,CCS,rupture displacement and residual CCS（ two water quenching cycles,1 100 ℃） are increased by 66%,47%,13% and 26%,respectively;（ 3） two-dimensional array structure of flake β-SiAlON can be in-situ formed in Al2 O3-C refractories,which improves the material strength by 60% and decreases the residual strength after thermal shock by only 4. 5 MPa. It is believed that the in-situ formation of one-or two-dimensional bonding phases at high temperatures can improvethe comprehensive thermal physical properties of carboncontaining refractories,and will be the developing trend of the strengthening and toughening of low carbon-containing refractories.
文摘Four dithiooxalato (Dto) bridged one-dimensional Ni(ll) and Ni(ll)Cu(ll) complexes (Me6[14]dieneN4)Ni2(Dto)2) (1), (Me6[14]dieneN4)CuNi(Dto)2 (2), (Me6[14]aneN4)Ni2(Dto)2 (3), and (Me6[14]aneN4)CuNi(Dto)2(4), were synthesized. These complexes have been characterized by elemental analysis, IR, UV and ESR spectra. The crystal structure of complex 3 was determined. It crystallizes in the monoclinic system, space group C2/c with a = 2.2425(4) nm, b = 1.0088(2) nm, c=1.4665(3) nm, β= 125.32(3)° ;Z=4; R = 0.076, Rw = 0.079. In the complex, Ni(1) coordinates four sulphur atoms of two Dto ligands in plane square environment. Ni(2) lies in the center of mac-rocyclic ligand. For Dto ligand, two sulphur atoms coordinate Ni(1), and O(1) coordinates Ni(2) and forms weak coordination bond. O(2) is linked to N(2) of macrocyclic ligand through hydrogen bond.
基金supported by the National Natural Science Foundation of China(no.22031008)and the Science Foundation of Wuhan(no.2020010601012192).
文摘Alternating current(AC)electrolysis is a promising,yet challenging,and under-developed protocol in organic synthesis.To achieve as high an atomefficiency as possible and avoid the use of external oxidant,electrochemistry has become a standard organic synthesis tool.Herein,an AC-basedprotocol is a superior option than its counterpart,direct current(DC),especially for those reactions that cannot be accomplished by DC.
