煤液化残渣可溶有机质中杂原子结构片段的赋存特征

煤液化残渣(CLR)是一种典型的煤化工固废。但煤液化残渣中的可溶有机质含量高,且富含缩合芳环结构,又可视为一种宝贵的重质炭资源。基于CLR在有机溶剂中的优良溶解性,选择等体积甲醇/甲苯混合溶剂为萃取剂,采用超声-索氏协同萃取法,实现CLR可溶有机质(CLR-SO)的温和提取,并通过逐级钌离子催化氧化,结合气相色谱/质谱联用分析,揭示CLR-SO中的杂原子结构单元特征,为其清洁转化和高值化利用提供支撑。结果表明,在CLR-SO的氧化产物中,含杂原子的酸类化合物中杂原子主要是氧、氮、硫,所构成的官能团有甲氧基、羰基、醚桥键、硝基、氨基、乙腈、吲哚、吩嗪、硫羰基等。此外,还检测到含氮、硫、氟等杂原子的酯类化合物。除了含氧化合物以外,其他杂原子化合物基本从第3级氧化产物中出现。杂原子结构存在于CLR-SO的大分子骨架内部,在氧化过程中,受到周围芳环的电子云保护,优先氧化CLR-SO分子骨架外围的芳环结构。除了酸和酯类化合物,在CLR-SO氧化产物中还检测到其他含杂原子的化合物,主要分布在第3,4级氧化产物中,且在第4级氧化产物中的种类最多。此外还检测到氯、氟等杂原子,以共价键的形式存在于CLR-SO有机质的分子骨架结构中。通过逐级选择性氧化,实现了有机质分子结构的“层层剥离”,获取了更多的结构单元片段,丰富了CLR中的杂原子结构信息。

First-Principle Calculation of the Electronic Structure of Sb-Doped SrTiO_3

The electronic structure,including band structure,density of states （DOS）, and partial density of states of SrTi1-xSbxO3 with x = 0,0. 125,0.25,and 0.33 is calculated from the first principles of plane wave ultra-soft pseudo-potential technology based on density function theory. The calculated results reveal that due to the electron doping,the Fermi level moves into the conduction bands for SrTi1-xSbxO3 with x = 0. 125 and the system shows metallic behavior. In addition, the DOS moves towards low energy and the optical band gap is broadened. The wide band gap and the low density of the states in the conduction band result in the transparency of the films.

Electronic and optical properties of anion-doped c-ZrO_2 from first-principles calculations

Using the first-principles calculations based on density functional theory(DFT),the structure stability,electronic and some optical properties of C and N doped cubic ZrO2(c-ZrO2) in 24-atom systems were investigated.It is found from the formation energies calculations that N ions are easier to be doped into c-ZrO2 than C ions.The electronic structure results show that Zr8O15C and Zr8O15N systems are semiconductors with the band gap of 2.3 eV and 2.8 eV,respectively,which are lower than that of the pure ZrO2(3.349 eV).And optical properties results depict that anion doping,especially C adding,can enhance the static dielectric function,visible and ultraviolet light absorption and reflecting ability of c-ZrO2 crystal.

Electronic Structure and Optical Properties of Antimony-Doped SnO_2 from First-Principle Study

A first-principles study has been performed to calculate the electronic and optical properties of the SbxSn1xO system.The simulations are based upon the method of generalized gradient approximations with the Perdew-Burke-Ernzerhof form in the framework of density functional theory.The supercell structure shows a trend from expanding to shrinking with the increasing Sb concentration.The increasing Sb concentration induces the band gap narrowing.Optical transition has shifted to the low energy range with increasing Sb concentration.Other important optical constants such as the dielectric function,reflectivity,refractive index,and electron energy loss function for Sb-doped SnO2 are discussed.The optical absorption edge of SnO2 doped with Sb also shows a redshift.

First-principles study on electronic structure, magnetic and dielectric properties of Cr-doped Fe_3C

The first-principles calculations were performed to investigate the electronic structure, magnetic and dielectric properties of Cr-doped Fe_3C, in comparison to those of pure Fe_3C and Cr_3C. The obtained results show that the thermodynamic stability of Crdoped Fe_3C becomes weaker in terms of the larger formation enthalpy, on the contrary, the metallicity and covalency are found to strengthen to some extent. The magnetic moments of Fe_3C, Fe_(11)CrC_4(g), and Fe_(11)CrC_4(s) are respectively 21.36 μB/cell, 16.92 μB/cell, and 17.62 μB/cell, and in Fe_(11)CrC4(g) and Fe_(11)CrC_4(s), the Fe of Wyckoff positions of 8d and 4c is substituted by Cr. The local magnetic moment of Cr at 8d site is larger than that at 4c site in the doped structure, which is opposite to that of Fe. In low frequency band, the permittivity follows the ranking of Fe_(11)Cr C_4(s)>Cr_3C>Fe_(11)Cr C_4(g)>Fe_3C. Once exceeding a certain frequency, the sequence will be broken. Besides the electron transition, the polarization of atoms also makes a contribution to the dielectric properties.

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.

Two-dimensional photovoltaic copolymers with spatial D-A-D structures: synthesis, characterization and hetero-atom effect

A series of two-dimensional （2D） conjugated copolymers with spatial D-A-D structures （PTNBTB, PTCBTB, and PTSBTB） consisting of hetero-atom-bridged dithiophene and phenylvinyl-substituted benzothiadiazole blocks in the main chain have been designed, synthesized, and characterized. The structure-property relationships of the resulting copolymers were systematically investigated. The effects of the bridging atoms （N, C, and Si） on their thermal, optical, electrochemical and charge- transporting properties were also studied. PTNBTB exhibits a smaller band gap with red-shifted absorption, whereas PTSBTB possesses deeper HOMO level and higher hole mobility than PTCBTB or PTSBTB. Bulk heterojunction （BHJ） solar cells were fabricated and characterized with the conventional configuration of ITO/PEDOT：PSS/copolymer：PCT^BM （I：I）/Ca/A1. As ex- pected, PTSBTB devices showed the highest PCE, up to 4.01%, which was due to the lower HOMO level, higher carrier mobility, and stronger optical response as well as the finer nanoscale phase separation of the pristine polymer and/or the corresponding blending active layer with PC71BM. The primary results offer useful insights in designing 2D copolymers with spatial D-A-D backbone and different hetero-atom bridged donor units to finely tune the absorptions, electronic energy levels, carrier mobilities and the photovoltaic properties.