N-电子参与对反应速度的影响

有机化合物的分子是一个统一整体,分子内的原子或原子团总是相互影响的和相互制约的.本文对含氧原子的n—电子参与作用,含卤素的n—电子参与作用,含氮原子团的n—电子参与作用等邻基参与作对反应速度的影响进行了讨论.

HR-ICP-MS测定电子级N-甲基吡咯烷酮中痕量金属杂质

文章采用高分辨电感耦合等离子体质谱仪(HR-ICP-MS)检测电子级N-甲基吡咯烷酮(NMP)中金属杂质元素,采用标准加入法进行定量测试,回收率为92.40%~110.25%,重复性相对标准偏差为0.19%~3.78%,检测限满足电子级NMP中金属杂质含量在0.1~1μg/kg级别测试需求。

微波法合成磷掺杂石墨相氮化碳催化剂及n-π^(*)电子跃迁对其光催化固氮性能的影响

通过微波处理制备了具有优异光催化固氮性能的磷掺杂石墨相氮化碳(g-C_(3)N_(4))催化剂.采用XRD、N_(2)吸附、UV-Vis、SEM、XPS、ESR、PL等测试手段对制备的催化剂进行了表征.结果表明,P掺杂与微波处理工艺相结合能破坏g-C_(3)N_(4)中平面对称性的结构单元,激发了n-π^(*)电子跃迁过程.制备催化剂的吸收边界从465移动至600 nm处,明显促进了对可见光的吸收.P掺杂和微波处理的协同效应也提高了催化剂的比表面积和电子空穴对的分离效率.制备的催化剂的NH_(4)^(+)产率最高达到6.5 mg·L^(-1)·g_(cat)^(-1),是纯g-C_(3)N_(4)的13.5倍以上,且具有良好的光催化稳定性,为拓宽催化剂的光响应范围提供了新的途径.

Sulfur promoted n-π^(*)electron transitions in thiophene-doped g-C_(3)N_(4)for enhanced photocatalytic activity

Expanding the optical absorption range of photocatalysts is still a key endeavor in graphitic carbon nitride(g-C_(3)N_(4))studies.Here,we report on a novel thiophene group extending the optical property,which is assigned to n-π^(*)electronic transitions involving the two lone pairs on sulfur(TLPS).The as-prepared samples,denoted as CN-ThAx(where x indicates the amount of ThA added,mg),showed an additional absorption above 500 nm as compared to pristine g-C_(3)N_(4).Further,the thiophene group enhanced charge carrier separation to suppress e‒/h+pair recombination.The experimental results suggest that the thiophene group can obstruct the polymerization of melem to generate a large plane,thus exposing the lone electron pairs on the sulfur.The photocatalytic activity was evaluated in the decomposition of bisphenol A and H2 evolution.Compared with g-C_(3)N_(4),the optimized CN-ThA_(30) sample led to a 6.6-and 2-fold enhancement of the degradation and H2 generation rates,respectively.The CN-ThA_(30) sample allowed for synchronous H2 production and BPA decomposition.

Influence of oxygen partial pressure on properties of N-doped ZnO films deposited by magnetron sputtering

N-doped ZnO films were radio frequency(RF)sputtered on glass substrates and studied as a function of oxygen partial pressure(OPP)ranging from 3.0×10-4 to 9.5×10-3 Pa.X-ray diffraction patters confirmed the polycrystalline nature of the deposited films.The crystalline structure is influenced by the variation of OPP.Atomic force microscopy analysis confirmed the agglomeration of the neighboring spherical grains with a sharp increase of root mean square(RMS)roughness when the OPP is increased above 1.4×10-3 Pa.X-ray photoelectron spectroscopy analysis revealed that the incorporation of N content into the film is decreased with the increase of OPP,noticeably N 1s XPS peaks are hardly identified at 9.5×10-3 Pa.The average visible transmittance(380-700 nm) is increased with the increase of OPP(from～17%to 70%),and the optical absorption edge shifts towards the shorter wavelength.The films deposited with low OPP(≤3.0×10-4 Pa)show n-type conductivity and those deposited with high OPP(≥9.0×10-4 Pa)are highly resistive(>105Ω·cm)

Relativistic Treatment of Massive Klein-Gordon Particle by Modified Generalized Hulthen Potential

Approximate bound state solutions of spinless particles with a special case of equal scalar and vector modified generalized Hulthen potential has been obtained under the massive Klein-Gordon equation. The energy eigenvalues and the corresponding wave functions expressed in terms of a Jacobi polynomial are also obtained using the parametric generalization of the Nikiforov-Uvarov （NU） method. Under limiting cases our result are in agreement with the existing literature. Our results could be used to study the interactions and binding energies of the central potential for diatomic molecules in the relativistic framework which have many applications in physics and some others related disciplines.

Organic Light-Emitting Diodes by Doping Liq into an Electron Transport Layer

Organic light emitting diodes （OLEDs） incorporating an n-doping transport layer comprised of 8-hydroxy-quin- olinato lithium （Liq） doped into 4＇ 7- diphyenyl-1,10-phenanthroline （BPhen） as ETL and a p-doping transport layer that includes tetrafluro-tetracyano-quinodimethane （F4- TCNQ） doped into 4,4′, 4″-tris （3-methylphenylphenylamono） triphe- nylamine （m-MTDATA） are demonstrated. In order to examine the improvement in the conductivity of transport layers, hole-only and electron-only devices are fabricated. The current and power efficiency Of organic light-emitting diodes are improved significantly after introducing an n-doping （BPhen：33wt% Liq） layer as an electron transport layer （ETL） and a p-doping layer composed of m-MTDATA and F4- TCNQ as a hole transport layer （HTL）. Compared with the control device （without doping） , the current efficiency and power efficiency of the most efficient device （device C） are enhanced by approximately 51% and 89% ,respectively, while driving voltage is reduced by 29%. This improvement is attributed to the improved conductivity of the transport layers that leads to efficient charge balance in the emission zone.

Theoretical Studies on Structures and Spectroscopic Properties of Highly Efficient Phosphorescent [Ru（terpy）（phen）X]＋ Complexes

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.

Micro-heterogeneity of Storage Glutelin in Rice Seed

The storage glutelin in rice ( Oryza sativa L.) seeds could be separated at least into more than 13 acidic and 19 basic polypeptides by two dimensional electrophoresis. Rice glutelin might be mainly controlled by about six major genes according to the expression of glutelin polypeptides. The acidic polypeptide of glutelin could be clearly separated into two groups by peptide mapping and N-terminal amino acid sequence analysis. These two groups were just in accord with the GluA and GluB subfamilies exactly.

The Influence of Rapid Thermal Annealing on SiGe/Si Multiple-Quantum Wells p_-i_-n Photodiodes

The influence of thermal treatment on Si 1-x Ge x/Si multiple-quantum wells (MQW) p-i-n photodiodes has been investigated by photocurrent spectroscopy combined with X-ray double crystal diffraction.The cutoff wavelength is significantly reduced due to the Si-Ge interdiffusion and partial relaxation of the strained SiGe alloy.The values of the blue shift increase slowly with the annealing temperatures in the range of 750℃ to 850℃.However,the nonlinear changes in photocurrent intensities of the samples annealed at different temperatures have been observed,which is mainly dominated by the generation of misfit dislocations and the reduction of the point defects in the heating process.

Computation of Diffusion Activation Energies of C, N in γFe

A structure relaxation model based on the empirical electron theory of solids and molecules is developed to compute the diffusion active energies of C, N in γFe. First, adding a restriction, the lattice maintains rigidity when solute atom migrates to the saddle point. In this step, the hybridization classes of every atom do not change. Then, the restriction is loosed and the atoms are relaxed under the coulomb repulsive forces. It is supposed that the energy needed in the first step would be compensated partly by the second step. In this way, the diffusion active energies of C, N in γFe are computed. Compared with the experiment data, the relative errors are less than 5%, which are good results in the computation of activation energy of diffusion.

基于光诱导单电子转移反应历程合成醚-聚N-苄基甘氨酸肽环化物

研究了以邻苯二甲酰亚胺为电子受体,以末端三甲基硅烷基的醚-聚N-苄基甘氨酸肽链为电子给体的化合物5a^5f的光反应,发展了新的合成环肽类化合物的方法.末端三甲基硅烷基的醚-聚N-苄基甘氨酸肽链——邻苯二甲酰亚胺5a^5f在甲醇溶剂中进行光反应,经连续的单电子转移(SET)历程有效地合成了环肽类化合物6a^6f.所合成的环肽类化合物的结构经核磁共振谱、高分辨质谱、X光晶体衍射所确定.

An Analytical Model of Electron Mobility for Strained-Si Channel nMOSFETs

An analytical model of electron mobility for strained-silicon channel nMOSFETs is proposed in this paper. The model deals directly with the strain tensor,and thus is independent of the manufacturing process. It is suitable for （100〉/ 〈110） channel nMOSFETs under biaxial or （100〉/〈 110 ） uniaxial stress and can be implemented in conventional device simulation tools .

Strong Current-Polarization and Negative Differential Resistance in FeN3-Embedded Armchair Graphene Nanoribbons

Motivated by the recent advances of transition-metal-nitrogen-carbon (TM-N-C) materials in catalysis, we investigate the electronic structure and transport properties of FeN3-embedded armchair and zigzag graphene nanoribbons (FeN3@AGNRs, FeN3@ZGNRs) with different widths. The first-principles results indicate that the FeN3 induces significant changes on the band structures of both ZGNRs and AGNRs, making the resultant systems quite different from the pristine ones and own room-temperature stable ferromagnetic (FM) ground states. While only FeN3@AGNRs possess a significant spin-dependent negative differential resistance (NDR) and a striking current polarization (nearly 100%) behaviors, due to that FeN3 introduces two isolated spin-down states, which contribute current with different performances when they couple with different frontier orbits. It is suggested that by embedding FeN3 complexes, AGNRs can be used to build spin devices in spintronics.

Thermal decomposition kinetics of basic carbonate cobalt nanosheets obtained from spent Li-ion batteries:Deconvolution of overlapping complex reactions

A new non-isothermal method of kinetic analysis was employed to investigate the thermal decomposition kinetic modeling of the basic carbonate cobalt nanosheets（n-BCoC） synthesized from spent lithium-ion batteries（LIBs）. Fraser–Suzuki function was applied to deconvoluting overlapping complex processes from the overall differential thermal curves obtained under the linear heating rate conditions, followed by the kinetic analysis of the discrete processes using a new kinetic analysis method. Results showed that the decomposition of n-BCo C in air occurred through two consecutive reactions in the 136-270 ℃ temperature intervals. Decomposition started by hydroxide component（Co（OH）2） decomposition until to 65% and simultaneously carbonate phase decarbonation began. The process was continued by CO2 evolution and finally carbonate cobalt nanosheets have been produced. The reaction mechanism of the whole process can be kinetically characterized by two successive reactions： a phase boundary contracting reaction followed by an Avrami-Erofeev equation. Mechanistic information obtained by the kinetic study was in good agreement with FT-IR（Fourier transform infrared spectroscopy） and SEM（scanning electron microscopy） results.

DFT-Study on Antioxydant of 3-Alkyl-4-P henylacetylam i no-1H-1,2,4-Triazol-5-O nes and Its Derivatives

In this article, we have performed B3LYP/6-31＋G（d） calculations of geometrical and reaction enthalpies of antioxidant mechanisms for ADPHT 1-4 （3-alkyl-4-phenylacetylamino-lH-1,2,4-triazol-5-ones） and its derivatives： HAT （hydrogen atom transfer）, SET-PT （single electron transfer-proton transfer） and SPLET （sequential proton-loss electron transfer） were investigated in gas and solution-phases. Solvent contribution to enthalpies was computed employing integral equation formalism IEF-PCM （integral equation formalism method） method. It turned out that the lowest BDEs （bond dissociation energies） is obtained for C-H bonds due to captodative effect in various media. Results indicate that HAT mechanism represents the most anticipated process in gas-phase from thermodynamic point of view. But, the SPLET represents the thermodynamically preferred reaction pathway in solvents （2-propanol, acetonitrile, DMF （N,N-dimethylformamide） and water）. The authors showed that bond dissociation energies, IP （ionization potential） and PA （proton affinity） are sufficient to evaluate the thermodynamically preferred mechanism.

Pre-dispersed carbon black as conductive agent for LiFePO_4 cathodes

High dispersed carbon black was applied for LiFePO4 cathodes as conductive agent.Nano-conductive carbon agent was pre-dispersed with poly acrylic acid(PAA) as dispersant in organic N-methyl-pyrrolidone(NMP) solvent system.The dispersion property of nano-conductive carbon agent was evaluated using particle size distribution measurements,scanning electron microscopy(SEM) and transmission electron microscope(TEM).LiFePO4 cathode with as-received nano-conductive carbon agent(SP) and LiFePO4 cathode with pre-dispersed nano-conductive carbon agent(SP-PAA) were examined by scanning electron microscopy(SEM),cyclic voltammetry(CV),electrochemical impendence spectroscopy(EIS) and charge/discharge cycling performance.Results show that the dispersion property of carbon black is improved by using PAA as the dispersant.The LiFePO4 cathodes with SP-PAA exhibit improved rate behaviors(4C,135.1 mAh/g) and cycle performance(95%,200 cycles) compared to LiFePO4 cathodes with SP(4C,103.9 mAh/g and 83%,200 cycles).Because pre-dispersed carbon black(SP-PAA) is dispersed homogeneously in the dried composite electrode to form a more uniform conductive network between the active material particles,electrochemical performances of the LiFePO4 cathodes are improved.

Charicteristic of a novel optoelectronic polymer and related device fabrication

In this paper a preliminary investigation of a novel optoelectronic polymer, poly (p-phenylene N-4-n-butylphenyl-N,N-bis- 4-vinylenephenylamine) (PNB), is reported. A single layer structure of ITO/PNB/Al was prepared via spin-coating of PNB solution as a thin film on the top of an ITO substrate, while aluminum top electrode was vacuum evaporated. Dark current- voltage characteristics of this device showed a typical rectifying behaviour. Photovoltaic response under a monochromatic illumination at 420 nm was observed, with an open circuit voltage of 0.3 V and fill factor of 0.21. Spectral response and optical absorption were found to be matched well. It was also discovered that the device showed a green electroluminescent emission at a forward bias. Turn-on voltage of the device was about 6 V and light output about 22.6 nW at a forward bias of 10 V. The work demonstrated that the PNB material might possess dual exciton sites resulting in a competition for excitons to be either separated or recombined. Both effects were associated with each other, which limited the photovoltaic or electroluminescence to some degrees.

非富勒烯小分子有机太阳能电池电子受体材料的研究进展

富勒烯及其衍生物是一类重要的n-型电子受体材料,在有机太阳能电池器件中发挥了至关重要的作用.但由于富勒烯材料吸光波长较窄、亲和能高、溶解性差等,严重限制了富勒烯作为有机太阳能电池n-型电子受体材料的更广泛应用和器件性能的进一步提升.非富勒烯n-型电子受体材料具有能级可调、合成简便、加工成本低、溶解性能优异等特点,更重要的是,此类材料在可见太阳光光谱中比富勒烯及其衍生物材料有更加宽广的吸收范围;近年来,受到越来越多的关注和研究.本文较为系统地阐述了非富勒烯小分子材料作为有机太阳能电池n-型电子受体材料的研究进展,并对其发展前景作了展望.

First-principles study on electronic structure and optical properties of N-doped P-type β-Ga_2O_3

The band structure, density of states, electron density difference and optical properties of intrinsic β-Ga2O3 and N-doped β-Ga2O3 were calculated using first-principles based on density functional theory. After N doping, the band gap decreases, shallow acceptor impurity levels are introduced over the top of the valence band and the absorption band edge is slightly red-shifted compared to that of the intrinsic one. The anisotropic optical properties are investigated by means of the complex dielectric function, which are explained by the selection rule of the band-to-band transitions. All calculation results indicate that N-doping is a very promising method to get P-type β-Ga2O3.