NiCo2O4/氧化石墨烯复合材料制备与电化学性能研究

为了研究NiCo₂O₄/氧化石墨烯(NiCo₂O₄/GO)复合材料的电化学性能,本文通过先水热合成前驱体再煅烧的方法制备了一系列NiCo₂O₄/GO复合材料.利用X射线衍射(XRD)、扫描电子显微镜(SEM)和电化学方法对其进行物理表征,其中以GO质量浓度为1 mg/mL悬浊液制备出的NiCo₂O₄ /GO-3复合材料呈类海胆状结构.在1 M KOH水溶液中使用循环伏安法、恒电流充/放电法和交流阻抗法研究了NiCo₂O₄/GO复合材料电化学性能.研究表明,与纯NiCo₂O₄相比,制备的NiCo₂O₄ /GO复合材料的比容量和赝电容性能均有明显提高,这主要是由于NiCo₂O₄ /GO复合材料中NiCo₂O₄与GO纳米片的相互作用形成的高孔隙率复合结构;NiCo₂O₄ /GO-3复合材料在电流密度为0.5~3.0 A/g时,比电容超过650 F/g,具有良好的倍率性能和高比容量.采用本文方法合成的NiCo₂O₄/GO复合材料,既提高了其倍率性能又保证了高比容量,是一种良好的超级电容器电极材料.     

二维材料CrPS4电子自旋密度的研究

为探究二维磁性材料CrPS₄的电子性质,依据拓扑学原理,运用密度泛函理论,对该团簇的电子性质进行了具体研究分析,从团簇的原子电荷量、构型布居数及电子自旋密度3个方面出发,经分析后得到如下结论:团簇CrPS₄ 3种原子中,S原子为团簇电子受体,Cr、P原子为电子供体,且Cr原子向外提供的电荷量要多于P原子,构型2^{(4)电子流动性最大;从原子轨道角度来看,电子主要由S原子的3s轨道、Cr原子的4s和3d轨道、P原子的3s和3p轨道流向S原子的3p、3d和4f轨道、Cr原子的4p和4f轨道及P原子的3d和4f轨道;相较于非金属原子来说,金属原子电子自旋密度更大,外层电子的流动性更强,活泼性更好,构型8(4)与构型1(4)}的Cr原子活泼性最强;另外,通过对其原子间自旋密度值进行细致观察,发现其值与稳定性有一定关系。     

团簇Mo3S4异构转化热力学与动力学研究

为研究团簇Mo₃S₄的稳定性和异构化转化机理,本文以密度泛函理论和过渡态理论为基础,在B3LYP/Lanl2dz水平下对初始构型进行优化计算,得到8种优化构型,从热力学和动力学两种角度对团簇Mo₃S₄的异构化反应进行分析与讨论。结果表明:团簇Mo₃S₄各异构化反应中的反应3(3)→2(3)和3(1)→2(1)的反应限度较小;反应4(3)→1(3)的正反应活化能最低,说明在常温下4(3)→1(3)的正反应最易发生。同理,对于反应3(3)→2(3)、3(1)→4(3)而言,构型3(3)、3(1)通过正反应3(3)→2(3)、3(1)→4(3)能够转化为更稳定的构型2(3)、4(3),而反应3(1)→3(3)、3(1)→2(1)、2(1)→4(3)、4(1)→3(3)、4(1)→1(1)很难发生。因此,构型1(3)、2(3)、2(1)、4(1)均能够稳定存在,所以在实际开发中,应首先考虑对其进行实验。除TS3(3)→2(3)、TS2(1)→4(3)外,其余6种异构转化过程均趋向于向正反应方向转化。     

超临界流体干燥法制备TiO2/ Fe2O3 和TiO2/ Fe2O3/ SiO2 复合纳米粒子及光催化性能

以TiCl₄ 、Fe (NO₃ )₃·9H₂O 和Na₂SiO₃19H₂O 为原料, 采用溶胶凝胶法结合超临界流体干燥法(SCFD)制备了纳米级TiO₂/ Fe₂O₃ 和TiO₂/ Fe₂O₃/ SiO₂ 复合光催化剂。以光催化降解苯酚对所得催化剂的催化活性进行了评价。结果表明, 纳米TiO₂/ Fe₂O₃ 复合粒子与单组分TiO₂ 比较, 复合粒子光催化活性高于单组分的TiO₂, 6h 苯酚降解率高达95.9 %。SiO₂ 的加入可以抑制纳米粒子粒径的长大和晶相的转变, 增强TiO₂ 纳米粒子的热稳定性。复合光催化剂中Fe₂O₃ 最佳掺入量为0.06 %, SiO₂ 最佳掺入量为10 %(摩尔分数) 。并用XRD、TEM 和FTIR 等手段进行了表征。TiO₂ 以锐钛矿型形式存在, SiO₂ 以无定性形式存在。比较了不同制备方法制得的TiO₂/ Fe₂O₃ 复合光催化剂, 得出超临界干燥法制备的光催化剂具有粒径小、比表面积大、分散性好、光催化活性高等特点。采用超临界流体干燥可直接得锐钛型纳米复合光催化剂。     

水热法制备γ-Ce2S3@ZrO2包裹型大红色料

以γ-Ce_2S_3和Zr(SO4)2·4H2O为原料,采用水热法合成了核壳结构的ZrO_2包裹的γ-Ce_2S_3大红色料(记为γ-Ce_2S_3@ZrO_2),研究了水热体系的p H值、水热助剂、水热时间、水热温度以及水热次数对色料结构和形貌的影响。采用X射线衍射(XRD)、扫描电镜(SEM)、透射电子显微镜(TEM)和色度计对样品进行了表征。研究结果表明:调节溶液的p H值为13.0,以C2H3Na O2为助剂,180℃下水热反应18 h,重复水热3次,可获得抗酸腐蚀性能良好、色泽鲜艳的γ-Ce_2S_3@ZrO_2包裹型大红色料。     

团簇Co3FeP的成键方式与磁性

为研究非晶态合金Co-Fe-P体系的成键方式及磁性,在较高的量子化学水平下,利用密度泛函理论,以团簇Co₃FeP为局域模型展开研究,结果发现：团簇的自旋多重度和几何形态均会影响其成键杂化方式和磁性;团簇Co₃FeP中存在pd²、s²p²d³、p²d、p³d、p³、pd³杂化,其中Co-Fe键主要由Co3d和Fe3d、Co4p和Fe4p形成的d²和p²杂化组成;Co-P键主要是Co3d和P3p形成的pd杂化;Fe-P键主要是Fe3d和P3p形成的pd杂化。Co原子和Fe原子在提供磁性时,相互制衡。综合来看,d轨道对团簇Co₃FeP的成键方式和磁性有着重要影响。     

ZrO2在β\"─Al2O3复合陶瓷中的作用

本文研究了四方和立方ZrO₂在与Na-β\"-Al₂O₃的复合陶瓷中作为第二相所起的各种作用。结果说明ZrO₂对复合陶瓷具有细化晶粒、改善显微结构、提高强度和断裂韧性的作用,与此同时也在一定程度上降低离子电导率。在提高力学性能方面,四方ZrO₂除了具有与立方ZrO₂相同的弥散颗粒的作用外,相变所起的作用也是很显着的。ZrO₂-Na-β\"-Al₂O₃复合陶瓷是一种有应用价值的固体电解质材料。     

分子氧在Con小团簇吸附的密度泛函研究

采用基于密度泛函理论（DFT）的Dmol3程序广义梯度近似PBE泛函,系统研究了Con（n =1~5）团簇及其对分子氧（O2）（垂直和平行）吸附后的ConO2团簇几何结构、稳定性和电子性质。结果表明：Con团簇的结合能随团簇数目的增加而增大,变化趋势趋于平缓,稳定性增强;分子氧在Con团簇顶位、桥位、空位的吸附稳定性、Co—O键长、O—O键长、分子氧的电荷转移都随团簇数目增大呈现规律性变化,说明分子氧被活化;Con团簇和分子氧之间的电荷转移越多,相互作用越强,吸附能和结合能也越大;分子氧垂直吸附型Co2O2 B团簇的吸附能和结合能最强,分别是-6.744 eV和4.611 eV,分子氧所得电荷最强为 -1.130 e。     

短纤维增强透气性莫来石/铁(A3S2/Fe)复合材料烧结特性的研究

本文研究了A₃S₂/Fe复合材料的烧结特性、透气性和纤维增强效果,分析了烧结过程中材料宏观结构和微观组织的形成机理.实验结果表明:纤维增强A₃S₂/Fe复合材料在900～1000℃具有良好的烧结性能,烧成后表层存在一定厚度的硬化层;纤维增强效果显着.材料抗压强度达17～23MPa,相对透气系数为4.30～9.69cm3/(cm2·s·atm).已能满足实际应用的需要.     

MoS2/g-C3N4复合催化剂的制备及CdSe量子点敏化产氢性能研究

太阳能光催化分解水制氢被认为是从根本上解决能源与环境问题较为理想的途径之一。在以尿素为原料制得石墨相氮化碳(g-C_3N_4)的基础之上,采用简单的低温溶液反应法将二硫化钼(MoS_2)与石墨相氮化碳(g-C_3N_4)复合得到复合催化剂MoS_2/g-C_3N_4,并利用透射电子显微镜(TEM)、X射线衍射(XRD)、紫外-可见漫反射(DRS)、傅里叶变换红外光谱(FT-IR)和荧光光谱等对该复合光催化剂的组成、形貌和光物理性能进行了表征;进而以CdSe量子点为光敏剂,三乙醇胺(TEOA)为牺牲剂,构建了不含贵金属的三组分光催化产氢体系,并对体系pH值、CdSe量子点浓度等对产氢性能的影响进行了研究。结果表明:将MoS_2纳米颗粒负载到g-C_3N_4上可使g-C_3N_4的光催化产氢性能得到显著提高。当MoS_2负载量为7%(质量比)时,在最佳的条件下(pH=9.0,CdSe量子点的体积为25mL),最大产氢速率达到了141.74μmol·h-1,6h的产氢总量达到了212.61μmol。最后,结合荧光猝灭实验,推测了该体系的产氢机理。     

Infrared optical properties of calcium lanthanum sulfide

The fundamental infrared optical properties of CaLa₂S₄ were determined by specular reflectance measurements from theoretically dense, optically transparent, polycrystalline ceramics. Kramers-Kronig transformation of the reflectance spectra permitted the extraction of refractive index, and transverse and longitudinal optic modes. Five transverse modes predicted by factor group analysis were observed with the intense high wavenumber mode occurring at 142 and 205 cm^− 1. The other three modes are weak and occur at 37, 59, and 86 cm^− 1. The two high wavenumber intense modes have identifiable longitudinal modes at l51 and 318 cm^− 1.     

Effect of complexing agent on growth process and properties of nanostructured Bi2S3 thin films deposited by chemical bath deposition method

Nanostructured Bi₂S₃ thin films have been prepared onto amorphous glass substrates by chemical bath deposition method at room temperature using bismuth nitrate and sodium thiosulphate as cationic and anionic precursors with EDTA as complexing agent in aqueous medium. The X-ray diffraction study reveals that the films deposited without the complexing agent are amorphous in nature and becomes nanocrystalline in the presence of EDTA. The resistivity for the films prepared from EDTA complexed bath is decreased due to the improvement in grain structure. The decrease in optical bandgap and activation energy is observed as the thickness of the film varies from 45 to 211 nm on account of the variation of the volume of complexing agent in reaction bath. Studies reveal that the growth mechanism of Bi₂S₃ gets affected in the presence of complexing agent EDTA and shows impact on structural, electrical and optical properties.     

Structural,optical, and magnetic properties of polycrystalline Co-doped TiO2 synthesized by solid-state method

We have used a solid-state method to synthesize polycrystalline Co-doped TiO₂ diluted magnetic semiconductors (DMSs) with Co concentrations of 0, and 0.5 at.%. X-ray diffraction patterns reveal that Co doped TiO₂ crystallizes in the rutile tetragonal structure with no additional peaks. Transmission electron microscopy (TEM) did not indicate the presence of magnetic parasitic phases and confirmed that Co ions are uniformly distributed inside the samples. Optical absorbance measurements showed an energy band gap which decreases after doping with the Co atoms into the TiO₂ matrix. Magnetization measurements revealed a paramagnetic behavior for the as-prepared Co-doped TiO₂ and a ferromagnetic behavior for the same samples after annealed under a mixture of H₂/N₂ atmosphere.     

Excellent visible light photocatalytic properties of novel graphene based CdLa2S4/TiO2 heterojunction nanocomposite

This paper introduced one pot method for the synthesis of hybrid CdLa₂S₄-graphene/TiO₂ nanocomposite. The surface properties seen by SEM present a characterization of the texture on CdLa₂S₄-graphene/TiO₂ composites and showed a homogenous composition in the particles. The EDX spectra for the elemental identification showed the presence of C, O and Ti with strong Cd, La and S peaks for the CdLa₂S₄-graphene/TiO₂ nanocomposite. The generation of reactive oxygen species were detected through the oxidation reaction from 1,5-diphenyl carbazide (DPCI) to 1,5-diphenyl carbazone (DPCO). It is found that the photocurrent density and the photocatalytic effect increase in the case with the modified CdLa₂S₄.From the photocatalytic results, the excellent activity of CdLa₂S₄-graphene/TiO₂ nanocompositefor degradation of methylene blue (MB) and Texbrite BA-L (TBA) undervisible irradiation could be attributed to both the effects between photocatalysis of the supported TiO₂ and charge transfer of the grapheme nanosheet, and the introduction of CdLa₂S₄ to enhance the photogenerated electrons.     

Effect of copper-deficiency on multi-stage co-evaporated Cu(In,Ga)S2 absorber layers and solar cells

Solar cell absorber films of Cu(In,Ga)S₂ have been fabricated by multi-stage co-evaporation resulting in compositional ratios [Cu]/([In] + [Ga]) = 0.93-0.99 and [Ga]/([In] + [Ga]) = 0.15. Intentional doping is provided by sodium supplied from NaF precursor layers of different thicknesses. Phases, structure and morphology of the resulting films are investigated by X-ray diffraction (XRD) and scanning electron microscopy. The XRD patterns show CuIn₅S₈ thiospinel formation predominantly at the surface in order to accommodate decreasing Cu content. Correlated with the CuIn₅S₈ formation, a Ga-enrichment of the chalcopyrite phase is seen at the surface. Since no CuS layer is present on the as-deposited films, functioning solar cells with CdS buffer and ZnO window layers were fabricated without KCN etch. The open-circuit voltage of solar cells correlates with the copper content and with the amount of sodium supplied. The highest efficiency cell (open-circuit voltage 738 mV, short-circuit current 19.3 mA/cm², fill factor 65%, efficiency 9.3%) is based on the absorber with the least Cu deficiency, [Cu]/([In] + [Ga]) = 0.99. The activation energy of the diode saturation current density of such a cell is extracted from temperature- and illumination-dependent current-voltage measurements. A value of 1.04 eV, less than the band gap, suggests the heterojunction interface as the dominant recombination zone, just as in cells based on Cu-rich grown Cu(In,Ga)S₂.     

磷酸银稳定性能与热力学性质的第一性原理研究

磷酸银差的稳定性能是限制其发展的主要瓶颈,与之相关的理论研究依然匮乏;同时,通过实验手段难以获得描述Ag_3PO_4熵、焓、自由能等热力学性质的相关信息.基于上述问题,本文从理论上探讨了磷酸银稳定性能与热力学性质.基于密度泛函理论的第一性原理,应用规范-守恒赝势平面波方法,对Ag_3PO_4Mulliken布居、能带结构、态密度以及声子谱、声子态密度进行了计算分析.研究结果表明:P—O、O—O间共价健的存在导致Ag_3PO_4原胞中易形成稳定PO4四面体结构,该结构能够弱化Ag—O健合力,使Ag+处于亚稳态;当Ag_3PO_4接触光生电子时,Ag+易摆脱O2-束缚获得电子形成单质银而表现出光不稳定性;Ag_3PO_4具有动力学稳定性特征;300~3 000 K范围内,Ag_3PO_4晶体体系熵、焓随温度增加呈非线性增加,自由能下降,等容热容CV在1 200 K时达到恒定,约为93 cal/cell·K.上述计算结果与实验结果吻合.