Z型InN/SnS2范德华异质结增强光催化水分解

寻找高效的光催化剂分解水制氢是解决能源危机和环境问题的有效途径之一.基于第一性原理,对InN/SnS₂异质结的几何结构、电子结构和光催化水分解性能进行研究.结果表明InN/SnS₂异质结是具有的Ⅱ型能带排列半导体材料可以有效地分离电子空穴对.在光激发下,较小的带隙以及合适的内建电场使得光生载流子迁移路径成“Z”字型,这保留了InN/SnS₂异质结强氧化还原能力.光生电子在InN的导带底累积并发生析氢反应,而积累在SnS₂上的光生空穴使析氧反应自发发生.它们的带边位置都跨越了水的氧化还原电位,证明能够实现水的完全分解.因此,InN/SnS₂异质结有希望成为高效光解水催化剂.     

卟啉基非金属纳米片用于可见光光催化制氢

本文基于密度泛函理论预测了一种用于可见光范围光催化制氢的新型二维非金属纳米材料，该材料可以由HTAP分子脱氢聚合得到，具有良好的结构稳定性，且带隙为2.12 eV，可以实现可见光区域的光捕获. 材料的带边能级位置恰好包裹水的氧化还原电位，有利于实现全光解水. 电子的迁移率略高于空穴的迁移率，有利于光生载流子的分离. 光生电子可以提供足够的驱动力使得析氢反应自发进行.     

卟啉基非金属纳米片用于可见光光催化制氢（英文）

本文基于密度泛函理论预测了一种用于可见光范围光催化制氢的新型二维非金属纳米材料,该材料可以由HTAP分子脱氢聚合得到,具有良好的结构稳定性,且带隙为2.12 eV,可以实现可见光区域的光捕获.材料的带边能级位置恰好包裹水的氧化还原电位,有利于实现全光解水.电子的迁移率略高于空穴的迁移率,有利于光生载流子的分离.光生电子可以提供足够的驱动力使得析氢反应自发进行.     

时间分辨红外光谱研究Pt/TiO2上甲醇光催化反应中光生电子衰减动力学

采用时间分辨红外光谱直接观测了甲醇在Pt/TiO2上光催化反应制氢过程中光生电子还原氢离子生成氢气的反应过程．结果表明Pt的担载量存在一最佳值，使得该催化剂中光生电子的反应速度最快．当Pt担载量相同时，Pt/TiO2催化剂中光生电子参与产氢反应的速度随样品还原温度的不同而明显变化．可能的原因是较高温度下氢气还原的Pt/TiO2催化剂中Pt粒子占据了TiO2表面的一些能够解离吸附甲醇的活性位置，而对于较低温度下氢气还原的Pt/TiO2催化剂，这种占据作用很不明显．实验中还发现瞬态动力学研究中光生电子衰减较快     

TiO2膜光催化剂的改进及表征

提出用粉末一溶胶法制备TiO2薄膜型光催化剂,介绍了粉溶法的制备工艺及改变pH值对催化活性的影响。研究结果表明,利用粉溶法或添加浓HNO3后制备的TiO2薄膜光催化剂表现出了较高的光催化活性,结合结构表征详细分析了其中的原因,认为粉溶法制备的催化剂表面更粗糙,比表面积增大,膜厚度减小,这些都可能是其催化活性提高的原因,而加酸后膜催化活性提高主要是因为酸性条件下表面几乎没有Ti^3+表面态,利于光生电子与光生穴穴的分离。     

基于电子顺磁共振的锌卟啉敏化TiO2光催化性机理的研究

为了研究锌卟啉/TiO₂复合光催化剂的光催化效率及电子转移问题, 本文采用溶胶凝胶法制备了锌卟啉/TiO₂的混合光催化材料, 并利用紫外可见光谱、电子顺磁共振谱对锌卟啉/TiO₂复合光催化剂进行了表征与分析. 采用溶胶凝胶法制备了锌卟啉-TiO₂的混合光催化材料, 通过比较纯P25型TiO₂和掺入质量比分别为0.2%, 0.5%, 0.9%锌卟啉敏化剂的锌卟啉/TiO₂混合光催化材料的紫外可见光谱图可知, 加入适量锌卟啉敏化剂可提高TiO₂对甲基橙溶液的降解效率, 过多的掺入锌卟啉敏化剂会导致TiO₂表面被敏化剂覆盖, 从而影响了其对光子的吸收, 降低TiO₂的光催化效率, 降低TiO₂的光降解率, 甚至低于纯TiO₂的光降解率. 应用电子顺磁共振技术对锌卟啉敏化TiO₂光催化剂的光催化机理进行了合理的解释, 当使用紫外可见光源对粉末样品进行辐照时, 锌卟啉受光辐照产生的激发态电子促进具有强氧化性的Ti³⁺和超氧根自由基的生成, 从而有效的促进了光生空穴-电子对的分离, 提高了TiO₂的光催化性能.     

铁电材料光催化活性的研究进展

光催化技术被认为是最有前景的环境污染处理技术,这就使得光催化剂材料备受瞩目.近年来,铁电材料作为新型光催化剂材料受到人们越来越多的关注,其原因在于铁电材料特有的自发极化有望解决催化反应过程中的电子-空穴对复合问题,进而提高光催化活性.本文从两个方面对铁电极化如何影响光催化进行综述:一方面,从铁电极化入手归纳总结其对电子-空穴对分离的影响,进而更深入地从极化引发的退极化场和能带弯曲两个部分来阐述具体的影响机理;另一方面,为了消除静电屏蔽,分别从温度、应力(应变)、电场三个外场因素调控极化入手,归纳总结外场调控极化对电子-空穴对分离的影响,进而影响光催化活性.最后对该领域今后的发展前景进行了展望.     

二硫化钼/石墨烯异质结的界面结合作用及其对带边电位影响的理论研究

采用基于色散修正的平面波超软赝势方法研究了二硫化钼/石墨烯异质结的界面结合作用及其对电荷分布和带边电位的影响.研究表明二硫化钼与石墨烯之间可以形成范德瓦耳斯力结合的稳定堆叠结构.通过能带结构计算,发现二硫化钼与石墨烯的耦合导致二硫化钼成为n型半导体,石墨烯转变成小带隙的p型体系.并通过电子密度差分图证实了界面内二硫化钼附近聚集负电荷,石墨烯附近聚集正电荷,界面内形成的内建电场可以抑制光生电子-空穴对的复合.石墨烯的引入可以调制二硫化钼的能带,使其导带底上移至-0.31 eV,提高了光生电子还原能力,有利于光催化还原反应.     

二维光催化材料的电子结构调控与应用研究进展(特邀)

首先综述了基于二维光催化剂的电子结构调控方式,包括厚度调节、元素掺杂、缺陷工程和异质结的设计等.其次,由于半导体异质结在减少光生电子空穴复合速度方面具有独特的优势,着重介绍了由二维材料与其它不同维数的半导体界面组成的异质结的研究进展.最后介绍了新型二维光催化材料在析氢、CO2还原、固氮和污染物降解等方面的应用.总结文献...     

卤氧化铋与半导体光催化剂偶合研究新进展

两种半导体耦合能够形成异质结而使系统的电荷分离效率得到提高,扩展对光谱吸收范围,以便提高其光催化性能。半导体耦合在制备过程中容易受到制备方法、反应温度等影响,引起耦合半导体晶体结构和表面性质发生变化,从而使得其光催化量子效率增大。主要从以下三个方面进行了论述,(1) 卤氧化铋-氧化物偶合体系, 将半导体材料与BiOX进行复合,能够形成高效异质结型结构能提高光催化降解污染物光催化性能; (2)AgX-BiOX偶合体系, 与纯净的AgI或BiOI相比,复合光催化材料AgI/BiOI在可见光下具有更高的光催化反应活性。(3)卤氧化铋与其它化合物偶合体系,Bi₂S₃与BiOX进行偶合后,光生电子在两种催化剂中进行迁移,提高了电子与空穴分离效率,因而偶合物的光催化性能得到提高。另外,本文综述了近年来国内外半导体耦合制备方法、影响其光催化性能的因素、提高可见光利用效率的最新研究进展,并提出在半导体耦合研究中所要解决的主要问题及今后努力方向。     

Prediction study of the structural,elastic, electronic and optical properties of the antiperovskite BiNBa3

We use an ab initio full-potential linear muffin-tin orbital method within the local density approximation (LDA) to study the structural, elastic, electronic and optical properties of the antiperovskite BiNBa₃. The calculated lattice parameter is in good agreement with previous calculations. The elastic constants and their pressure dependence are calculated; we found a linear dependence of elastic stiffness on the pressure. We estimated the Debye temperature of this compound from the average sound velocity. We also present results of the effective masses for the electrons in the conduction band (CB) and the holes in the valence band (VB). To complete the fundamental characteristics of this compound we have analyzed the optical properties.     

Photocatalytic Oxidation of Hydrosulfide Ions by Molecular Oxygen Over Cadmium Sulfide Nanoparticles

Photocatalytic activity of CdS nanoparticles in hydrosulfide-ions air oxidation was revealed and thoroughly investigated. HS⁻ photooxidation in the presence of CdS nanoparticles results predominantly in the formation of SO₃ ²⁻ and SO₄ ²⁻ ions. Photocatalytic activity of ultrasmall CdS crystallites in HS^– photooxidation is much more prononced as compared to bulk CdS crystals due to high surface area of nanoparticles, their negligible light scattering, improved separation of photogenerated charge carriers etc. It was shown that hydrosulfide ions can be oxidized in two ways. The first is HS⁻ oxidation by the CdS valence band holes. This process rate depends on the rate of comparatively slow reaction between molecular oxygen and CdS conduction band electrons. The second reaction route is the chain-radical HS⁻ oxidation induced by photoexcited CdS nanoparticles and propagating in the bulk of a solution. In conditions favourable to chain-radical oxidation of HS⁻(i.e. at low light intensities and CdS concentration and high oxygen and Na₂S concentrations) quantum yields of the photoreaction reach 2.5.     

非均相电子转移的探讨

本文用ESR方法研究了六种新的双吡啶盐(PQ⁺⁺)与CdS的水及非水悬浮体系间的非均相光诱导单电子转移过程。结果表明,在λ<520nm的光照射下,CdS价带中的电子被激发至导带,再转移至PQ⁺⁺使之还原为PQ⁺⁺自由基,呈现明显的ESR信号。当体系中有电子给体EDTA存在时,有电子从EDTA转移至CdS价带的正空穴,价带中的电子吸收光子跃迁至导带再转移至PQ⁺⁺,以生成更多的PQ⁺⁺,从而使ESR信号大大增强。     

Observation of quadratic magnetoresistance in twisted double bilayer graphene

Magnetoresistance ({MR}) provides rich information about Fermi surface, carrier scatterings, and exotic phases for a given electronic system. Here, we report a study of the magnetoresistance for the metallic states in twisted double bilayer graphene (TDBG). We observe quadratic magnetoresistance in both Moiré valence band (VB) and Moiré conduction band (CB). The scaling analysis shows validity of Kohler's rule in the Moiré valence band. On the other hand, the quadratic magnetoresistance appears near the halo structure in the Moiré conduction band, and it violates Kohler's rule, demonstrating the {MR} scaling related to band structure in TDBG. We also propose an alternative scaling near the halo structure. Further analysis implies that the observed quadratic magnetoresistance and alternative scaling in conduction band are related to the halo boundary. Our results may inspire investigation on {MR} in twisted 2D materials and provide new knowledge for {MR} study in condensed matter physics.     

Fowler–Nordheim plot characteristics for ZnO virtual field emitter array

Linear and nonlinear Fowler–Nordheim (FN) plots from semiconductors emitters arrays were equally reported by researchers with occasionally inexplicit justification of either behaviour. Interpretation of experimental field emission data depends on explaining the FN plot behaviour from these arrays. The FN plot behaviour was investigated for virtual arrays of ZnO emitters with defined geometries based on fundamental electron tunnelling from semiconductors. The effects of emitters’ size distribution, saturation of conduction band (CB) current and contribution of valence band (VB) current on FN plot behaviour were investigated and discussed in detail. Comparison with some experimental results was introduced in support of the discussion. Results showed that saturation of CB current and contribution of VB electrons may not always be manifested as a well-observed deviation from linear characteristic of the FN plot. In addition, the dependence of the CB current on the emitters’ geometries was found to affect the FN plot behaviour. The present investigation is thought to be of great importance to field emission community and help for better interpretation of experimental field emission data.     

On the origin of photoluminescence in heavily-doped silicon

The origin of the photoluminescence in heavily-doped silicon is examined. Transient photoluminescence data for Si(P) are presented and used to identify the “Low Level” emission bands in terms of recombination of impurity band electrons with holes bound to acceptor sites. The “High Level” bands are attributed to recombination of impurity band electrons with free holes. The energies of the band gap and optical band gap in heavily-doped silicon are determined from the photoluminescence measurements.     

Zener tunneling in one-dimensional organic semiconductors

Tunneling effect in one-dimensional organic semiconductors in the presence of an external electric field is studied within the framework of a tight-binding model and a nonadiabatic dynamical method. It is found that under a high electric field, electrons can transit from the valence band (VB) to the conduction band (CB), which is demonstrated to be Zener tunneling in organic semiconductors. The results also indicate a field-induced insulator-metal transition accompanied by the vanishing of the energy gap. It is found that, after the field is turned off, the Peierls phase cannot be recovered.     

Structural, electronic and optical properties of AgI under pressure

We report results of first-principles total-energy calculations for structural properties of the group I-VII silver iodide (AgI) semiconductor compound under pressure for B1 (rocksalt), B2 (cesium chloride), B3 (zinc-blende) and B4 (wurtzite) structures. Calculations have been performed using all-electron full-potential linearized augmented plane wave plus local orbitals FP-LAPW + lo method based on density-functional theory (DFT) and using generalised gradient approximation (GGA) for the purpose of exchange correlation energy functional. In agreement with experimental and earlier ab initio calculations, we find that the B3 phase is slightly lower in energy than the B4 phase, and it transforms to B1 structure at 4.19 GPa. Moreover, we found AgI has direct gap in B3 structure with a band gap of 1.378 eV and indirect band gap in B1 phase with a bandgap around 0.710 eV. We also present results of the effective masses for the electrons in the conduction band (CB) and the holes in the valence band (VB). To complete the fundamental characteristics of this compound we have analyzed their linear optical properties such as the dynamic dielectric function and energy loss function for a wide range of 0-25 eV.     

绿色长余辉材料MgAl_2O_4∶Mn~(2+)的合成及其发光特性

采用高温固相法在1350℃下合成了Mn2+掺杂的MgAl2O4发光材料,利用X射线衍射对所合成样品的结构进行了表征。用209nm的紫外灯照射样品后,观察到来自Mn2+的4T1-6A1跃迁的绿色长余辉发光。发光的激发光谱表明:Mn2+-3d组态内存在一系列强的激发峰,分别在279,361,386,427,451nm,同时还有209nm处的Mn-O电荷迁移带,激发该吸收带会产生很强的绿色余辉。测量了余辉的衰减曲线及热释光谱,分析了Mn2+掺杂浓度对样品余辉性质的影响,给出了余辉产生的可能模型。