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。     

超重力下燃烧合成ZrO2(4Y)/Al2O3的成分、显微组织与力学性能

采用超重力下燃烧合成技术,通过调整ZrO₂体积分数,制备出不同成分与显微组织形态的ZrO₂(4Y)/Al₂O₃复合陶瓷,研究了材料成分、显微组织与力学性能之间的关系。XRD、SEM和EDS结果表明：当ZrO₂体积分数低于37%,陶瓷熔体生成为生长取向各异且以ZrO₂四方相亚微米纤维镶嵌于α-Al₂O₃上的棒状共晶团为基体的复合陶瓷;当ZrO₂体积分数高于40%,复合陶瓷基体则生长为略呈球形的ZrO₂四方相微米晶粒。性能测试结果显示,随着ZrO₂体积分数增加 , 陶瓷相对密度逐渐降低,陶瓷硬度与断裂韧性均在ZrO₂体积分数为33%时出现最高值,而陶瓷弯曲强度则在ZrO₂体积分数为29%达到最大值。     

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。     

共沉淀法合成近零膨胀ZrW2O8/ZrO2复合陶瓷的致密化

采用化学共沉淀法合成前驱体,经1150℃ 烧结3.5 h得到近零膨胀26 wt% ZrW₂O₈/ZrO₂复合陶瓷,并利用X射线衍射仪、扫描电镜和热膨胀仪研究了原料中加入Al(NO₃)₃·9H₂O对26 wt% ZrW₂O₈/ZrO₂复合陶瓷的相组成、致密度和热膨胀性能的影响。研究结果表明,少量添加Al(NO₃)₃·9H₂O可有效提高复合材料致密度,所得复合陶瓷的组分仍为立方结构的α-ZrW₂O₈和单斜的m-ZrO₂,其中添加2.21 wt% Al(NO₃)₃·9H₂O的复合材料的致密度达到理论密度的98.67%,且对复合陶瓷的热膨胀性能影响不大。其促进致密化机制为晶界处低熔点液相物质Al₂(WO₄)₃提高了复合材料的烧结性能,消除气孔促进致密化。     

Photoluminescence spectra of MnIn2S4

MnIn₂S₄ single crystals grown by the directional crystallization method were investigated by using the temperature and excitation power dependencies of photoluminescence (PL) spectra. PL spectra consist of one broad band resulting from donor-acceptor pair recombination. The analysis of the temperature quenching of the PL intensity yields one defect donor level with a thermal ionization energy of about 0.17 eV. The broad band of PL spectra indicates that radiative recombination is related to multiphonon optical processes. The energy of the involved phonon was found to be around 0.025 eV and the energy of the acceptor level is about 0.86 eV.     

Growth of crystalline HgCr2S4 thin films at mild reaction conditions

Thin films of crystalline HgCr₂S₄ have been deposited on glass substrates at low temperature as low as 65 °C using a chemical bath deposition method. Typical thickness of the deposited HgCr₂S₄ thin films was 264 nm.The films were composed of closely packed irregular grains of 165-175 nm in diameter. The X-ray diffraction analysis and the selected area electron diffraction analysis revealed the deposited thin films were polycrystalline with highly (2 2 0) preferential orientation. The films exhibit a pure faint black. Their direct band gap energy was 2.39 eV with room temperature electrical resistivity of the order of 10⁻³ Ω cm.     

Preparation of rod-like Sb2S3 dendrites processed in conventional hydrothermal

Large-scale rod-like antimony sulfide (Sb₂S₃) dendrites have been prepared by hydrothermal method using antimony chloride (SbCl₃), citric acid and thioacetamide as raw materials at 160 °C for 12 h. The powder X-ray diffraction pattern shows the Sb₂S₃ crystals belong to the orthorhombic phase with calculated lattice parameters a = 1.120 nm, b = 1.128 nm and c = 0.3830 nm. The quantification of energy dispersive X-ray spectrometry analysis peaks gives an atomic ratio of 2:3 for Sb:S. Transmission electron microscopy micrograph studies reveal the appearance of the as-prepared Sb₂S₃ is dendrites-like which is composed of nanorods with the typical width of 300-500 nm and length of 5-20 µm. Finally the influences of the reaction conditions are discussed and a possible mechanism for the formation of rod-like Sb₂S₃ dendrites is proposed.     

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.     

Preparation and properties of NiFe2O4 nanowires

Polycrystalline NiFe₂O₄ nanowires have been synthesized by PEG assisted co-precipitation method. The formation mechanism of the nanowires proposed is by means of the orientational aggregation of individual nanoparticles. X-ray diffraction, high resolution scanning electron microscopy, transmission electron microscopy, microRaman and vibrating sample magnetometry studies were carried out. The results show that NiFe₂O₄ nanowires were in polycrystalline form with diameter of 58 nm. The synthesized nanowires show room temperature ferromagnetic property with high coercivity. This method is expected to be useful for large scale synthesis of NiFe₂O₄ nanowires for the application of magnetic recording.     

Influence of sodium compounds at the Cu(In,Ga)Se2/(PVD)In2S3 interface on solar cell properties

The present contribution deals with indium sulfide buffer layers grown by thermal co-evaporation of elemental indium and sulfur. It has been found necessary to deposit these buffer layers at low substrate temperatures in order to reach V_oc values similar to those with (CBD)CdS. However, such deposition conditions lead to the formation of a highly recombinative Cu(In,Ga)Se₂/indium sulfide interface. This behaviour may be associated to the presence of sodium carbonates/oxides at the interface even though the Cu(In,Ga)Se₂ surface was cleaned in NH₃ (1 M, room temperature) prior to the indium sulfide deposition. An explanation is that, despite the chemical etch, sodium carbonates/oxides remain in the air exposed Cu(In,Ga)Se₂ grain boundaries and can migrate towards the surface when the Cu(In,Ga)Se₂ is heated under vacuum. These polluted interface areas act as recombination zones and thus inferior devices. A possibility to improve the device performance (i.e. improve the interface quality) is to sulfurize the remaining sodium carbonates/oxides. The resulting Na₂S can then leave the interface by formation of a solid solution with the indium sulfide. By adapting the buffer layer deposition process, 13.3% efficiency devices with co-evaporated indium sulfide are realized, performance which is close to that reached with (CBD)CdS.     

Preparation and visible-light photocatalytic activity of In2S3/TiO2 composite

A novel In₂S₃/TiO₂ composite with visible-light photocatalytic activity was prepared by a chemical precipitation method and characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope and UV–vis diffuse reflectance spectroscopy. Under both UV- and visible-light irradiation, the In₂S₃/TiO₂ composite shows good photocatalytic activity to degrade methyl orange, ascribed to the absorption of visible light by In₂S₃ sensitizer and enhanced separation of photoinduced electron–hole pairs in the composite semiconductors.