聚丙烯酰胺凝胶法合成TbFeO3 纳米颗粒及其可见光催化活性

采用聚丙烯酰胺凝胶法制备了TbFeO3纳米颗粒, 研究了不同络合剂对样品的纯度、 颗粒尺寸及形貌的影响. XRD分析结果表明, 以酒石酸、 柠檬酸或乙二胺四乙酸(EDTA)为络合剂, 在650 ℃下烧结均可制备出单相TbFeO3纳米颗粒, 但产物的平均粒径不同; 而采用乙酸或草酸为络合剂则难以制得纯相样品. SEM观测结果表明, 以酒石酸为络合剂制备的颗粒细小, 均匀、 形貌规整、 呈球状, 平均粒径约为50 nm; 以柠檬酸为络合剂制备的颗粒主要以近球形为主, 颗粒的尺寸分布相对较宽, 平均粒径约为100 nm; 以EDTA为络合剂制备的颗粒主要呈椭球状, 颗粒尺寸较均匀, 但颗粒间存在不同程度的黏连现象, 平均粒径约为110 nm. 这3种样品的BET比表面积分别为15.4, 8.3和6.8 m2/g. 紫外-可见漫反射吸收光谱研究表明, TbFeO3纳米颗粒的带隙为1.95~1.98 eV. 分别以甲基橙(MO)、 罗丹明B(RhB)、 亚甲基蓝(MB)、 酸性品红(AF)和刚果红(CR)5种有机染料为目标降解物, 考察了TbFeO3颗粒的光催化活性. 结果表明, 在可见光辐照下颗粒表现出良好的光催化活性, 其中, 以酒石酸为络合剂制备的样品光催化效果最好.     

原位沉积法制备掺杂柠檬酸PI/ZnO复合薄膜及性能研究

以4,4-二氨基二苯醚(ODA)、均苯四甲酸酐(PMDA)、硝酸锌和柠檬酸(CA)为原料,采用原位沉积法制备PI/ZnO复合薄膜,通过络合剂柠檬酸的加入改善纳米ZnO在聚酰亚胺(PI)表面的分散情况。利用X射线衍射仪(XRD)、扫面电子显微镜(SEM)、能谱(EDS)和红外(FTIR)等对样品的结构和形貌进行了表征。通过亚甲基蓝的降解率来评价复合薄膜的光催化活性。研究结果表明:添加络合剂可使ZnO颗粒更均匀地分散在PI薄膜中,掺杂柠檬酸的复合薄膜比不掺杂柠檬酸的复合薄膜具有更高的光催化活性。当柠檬酸与硝酸锌摩尔比为2∶1,煅烧至350℃,并保温2h制得的复合薄膜对亚甲基蓝降解2h时降解率达97.7%。     

单质铁纳米颗粒的液相还原制备

采用水合肼作还原剂, 在有柠檬酸存在的情况下, 以FeCl2为铁源, 通过液相化学还原制备粒径为15~50 nm的单质铁纳米颗粒. 采用X射线衍射(XRD)、X射线能谱仪(EDS)和场发射扫描电镜(FESEM)对制备的Fe纳米粒子的结构、组成和形貌进行了表征, 并使用超导量子干涉仪(SQUID)对制备的Fe纳米粒子的磁学性能进行了表征. 研究结果表明, 在柠檬酸存在下, 可以用肼在常温常压下液相还原亚铁离子制备出单质铁纳米颗粒, 改变络合剂后还原无法进行, 并对可能的反应机理进行了讨论.     

用于电化学水氧化的铁、镍、钴金属及其二元金属纳米颗粒比较研究

从环境兼容角度来设计应用于氧析出反应的电催化剂是否有效、耐用和廉价对能源转化过程至关重要. 本文报告了一种快速制备低成本、原料丰富的金属催化剂制备方法。通过一步电化学沉积法在钛金属基材上制备了铁、镍、钴金属及其钴镍、钴铁二元金属纳米颗粒. 采用场发射电子显微镜 (FE-SEM), 能量散射X-射线能谱 (EDX), X-射线衍射光谱 (XRD), X-射线光电子能谱 (XPS)和电化学技术对制备的不同纳米颗粒进行了表征. 电化学结果显示,在合成的五种钛基金属纳米催化剂中, 钛基上沉积钴金属纳米颗粒(Ti/Co)电极在0.l mol·L^-1氢氧化钾溶液中氧析出反应的电催化活性最好,0.70 V(相对于银/氯化银电极)的电流密度为10.0 mA·cm^-2. 经优化后Ti/Co电极的过电位(η)很小,当电流密度为10.0 mA·cm^-2时η为0.43 V,质量活性高达105.7 A·g^-1,逆转频率(TOF)值为1.63×10^-3 s^-1, 这些与当前最好的碳载铂(Pt/C)和氧化钌(RuO₂)电催化剂的性能相当. 此外,通过计时电位技术对优化后Ti/Co电极的耐久性进行了测试, 发现该电极在碱性溶液中氧析出反应的稳定性良好. 本工作制备的钛金属基材上电化学沉积金属钴纳米颗粒具有高催化活性、高稳定性、原料来源丰富、廉价且易于大规模生产,在工业化水分解领域具有潜在的应用前景.     

无机盐溶液源溶胶-凝胶法制备锶铋钽铁电陶瓷薄膜过程研究

采用可溶性无机盐Sr(NO₃)₂,Bi(NO₃)₃及HTaF6为原料,以柠檬酸、乙二醇及乙二胺四乙酸(EDTA)为络合剂,利用溶胶-凝胶旋转涂覆工艺,分别在Al₂O₃和Pt/Ti/SiO₂/Si的衬底上制备了SrBi₂Ta₂O₉(SBT)铁电陶瓷薄膜.采用SEM,XRD及FTIR等微观分析手段,对制备的SBT溶胶与薄膜过程机理进行了实验研究.结果表明,由无机盐溶液原料络合合成SBT溶胶是此方法制膜的关键,其中络合剂的种类、用量和pH值的控制等是重要的影响因素.制备了相组成均一、薄膜表面致密、均匀、无开裂、晶粒尺寸为150nm的多晶膜,获得了剩余极化(2P_r)与矫顽电场强度(2E_c)分别为9.6μC/cm²与76kV/cm铁电性能较好的薄膜材料.     

掺杂Mo6+对纳米TiO2薄膜亲水性的影响

用溶胶 凝胶法制备了一系列掺杂钼量不同的TiO₂纳米薄膜.用XRD,SEM和CAS(ContactAngleSystem)对TiO₂薄膜的结构和性能进行了表征.结果表明,Mo⁶⁺掺杂浓度对薄膜的热致亲水性和光致亲水性均有影响,当掺Mo⁶⁺质量分数为0.75%,热处理温度为400℃时,掺钼TiO₂薄膜在黑暗中放置72h后仍能表现超亲水性.     

ITO和ZnO基底对电化学沉积氧化亚铜薄膜的形貌、结构的影响及作用机制

采用电化学恒电位沉积方法在ITO导电玻璃上和在ZnO薄膜上沉积氧化亚铜(Cu₂O),并通过X射线衍射(XRD)和扫描电镜(SEM)对晶体的微观结构和表面形貌进行了分析.在ZnO基底上沉积得到了纳米级的Cu₂O粒子并且具有明显择优取向,而在ITO导电玻璃上仅得到粒径为2—5μm的Cu₂O粒子,没有明显的择优取向.对薄膜的生长机理进行了讨论.     

纳米TiO2薄膜的制备方法*

本文对纳米TiO₂薄膜的各种制备方法,包括基于溶胶－凝胶的涂层方法、电沉积、化学气相沉积、物理气相沉积、自组装制膜,以及喷雾热分解等方法的研究进展进行了综述,对不同方法的优缺点进行了比较和评述,对今后TiO₂薄膜制备的研究方法提出了一些建议。     

Sb2S3纳米粒子修饰ZnO纳米片微纳分级结构的光电化学性能

采用恒电位方法,选择氯化钾和乙二胺(EDA)为添加剂,在氧化铟锡(ITO)导电玻璃上制备了高度有序的ZnO纳米片阵列,通过二次电沉积得到了ZnO纳米片上生长纳米棒的微纳分级结构.利用化学浴沉积法在ZnO基底上沉积Sb₂S₃纳米粒子制备出了Sb₂S₃/ZnO纳米片壳核结构和Sb₂S₃/ZnO微纳分级壳核结构.利用扫描电子显微镜(SEM)、X射线衍射(XRD)、紫外-可见(UV-Vis)吸收光谱、瞬态光电流等对其形貌、结构组成和光电化学性能进行了表征和分析.结果表明, Sb₂S₃/ZnO纳米片上生长纳米棒分级壳核结构的光电流明显高于Sb₂S₃/ZnO纳米片壳核结构.在Sb₂S₃/ZnO纳米片壳核结构和Sb₂S₃/ZnO微纳分级壳核结构的基础上旋涂一层P3HT薄膜形成P3HT/Sb₂S₃/ZnO复合结构,以上述复合结构薄膜为光活性层组装成杂化太阳电池,其中, P3HT/Sb₂S₃/ZnO分级壳核结构杂化太阳电池的能量转换效率最高,达到了0.81%.     

BiVO4/CuBi2O4薄膜光电极的制备及光电性能

通过金属有机物分解法(MOD)协同光电化学沉积法, 将p型氧化物半导体CuBi₂O₄沉积在BiVO₄纳米薄膜上, 形成包覆性异质结结构, 制备了一种新型p-n异质结光阳极n-BiVO₄/p-CuBi₂O₄, 用于太阳能光电化学(Photoelectrochemical, PEC)水分解. 研究结果表明, 在1.23 V(vs. RHE)电势下, BiVO₄/CuBi₂O₄ 异质结光阳极表现出优良的PEC水氧化性能, 光电流密度达到2.8 mA/cm², 负载磷酸钴(Co-Pi)的BiVO₄/CuBi₂O₄/Co-Pi光电极, 光电流密度达到4.45 mA/cm², 分别为BiVO₄电极光电流密度的3.1倍和4.9倍. X射线衍射(XRD)、 紫外-可见吸收光谱(UV-Vis)、 电化学阻抗谱(EIS)和能级结构图等结果也证实, BiVO₄/CuBi₂O₄和BiVO₄/CuBi₂O₄/Co-Pi复合电极材料在内建电场和能带弯曲作用下, 光吸收特性增强, 载流子界面转移电阻减小, 具有良好的光电化学性能与稳定性.     

CuInSe_2薄膜的电化学沉积及其形成机理

采用电化学沉积法制备了太阳电池用CuInSe2薄膜.利用循环伏安法(CV)、X射线能谱(EDS)和X射线衍射技术(XRD)研究了电沉积过程中CuInSe2的形成机理,并研究了制备工艺对膜层成分、形貌和物相结构的影响.研究结果表明,铟进入固相是通过In3+受Cu3Se2诱导作用欠电势还原或者In3+与H2Se反应这两种途径实现;先沉积的Cu3Se2与新生成的铟或铟硒化合物反应最后生成CuInSe2.在阴极电位为-0.58~-0.9 V(vs.SCE)时出现了不随电位变化的极限还原电流,在该电位范围内进行电沉积获得了化学计量组成稳定可控且相对致密平整的CuInSe2薄膜.电沉积的CuInSe2薄膜经真空退火处理后结晶质量得到明显改善.     

Study of Anatase to Rutile Phase Transition in Nanocrystalline Titania Films

Nanocrystalline titania films were prepared by a complexing agent-assisted sol-gel dip-coating process. The effect of acetylacetone, diethanolamine and polyethylene glycol on the structure of the heat-treated titania films was examined by Raman and FTIR spectroscopy and X-ray diffraction. The effect the complexing agents have on the anatase to rutile phase transition during the heat treatment process is studied. The understanding of this effect is expected to enhance our capacity to tailor the composition and morphology of films and thus their properties. The Raman and the infrared spectra of nanocrystalline titania films and the changes induced by the heat treatment were also investigated. We have also studied the size of the crystallites in TiO₂ films and its dependence on the type of complexing agent used.     

Soluble precursors for CuInSe2, CuIn(1-x)Ga(x)Se2, and Cu2ZnSn(S,Se)4 based on colloidal nanocrystals and molecular metal chalcogenide surface ligands

We report a new platform for design of soluble precursors for CuInSe(2) (CIS), Cu(In(1-x)Ga(x))Se(2) (CIGS), and Cu(2)ZnSn(S,Se)(4) (CZTS) phases for thin-film potovoltaics. To form these complex phases, we used colloidal nanocrystals (NCs) with metal chalcogenide complexes (MCCs) as surface ligands. The MCC ligands both provided colloidal stability and represented essential components of target phase. To obtain soluble precursors for CuInSe(2), we used Cu(2-x)Se NCs capped with In(2)Se(4)(2-) MCC surface ligands or CuInSe(2) NCs capped with {In(2)Cu(2)Se(4)S(3)}(3-) MCCs. A mixture of Cu(2-x)Se and ZnS NCs, both capped with Sn(2)S(6)(4-) or Sn(2)Se(6)(4-) ligands was used for solution deposition of CZTS films. Upon thermal annealing, the inorganic ligands reacted with NC cores forming well-crystallized pure ternary and quaternary phases. Solution-processed CIS and CZTS films featured large grain size and high phase purity, confirming the prospects of this approach for practical applications.     

Solvothermal preparation and spectroscopic characterization of copper indium diselenide nanorods

Single-crystalline chalcopyrite CuInSe(2) nanorods (CuInSe(2)NRs) of 50-100 nm in diameter and up to a few micrometers in length have been synthesized solvothermally. High-resolution transmission electron microscopic images of the CuInSe(2)NRs reveal the d-spacing of 0.335 nm for the (112) crystalline planes and a growth direction along [331]. The near-infrared absorption spectrum of the chalcopyrite CuInSe(2)NRs shows a peak maximum at 1162 nm and an onset at 1262 nm, indicating no apparent blue-shift compared with those of Cu-rich CuInSe(2) thin films. An intense peak at 175.1 cm(-1) in the room-temperature Raman scattering spectrum of CuInSe(2)NRs corresponds to the A(1) phonon mode of tetragonal CuInSe(2) chalcopyrite. The narrower full width at half-maximum (fwhm) of 9.5 cm(-1) for CuInSe(2)NRs, in comparison with fwhm approximately 12 cm(-1) for CuInSe(2) films, indicates a uniform size distribution and single crystallization in the nanorods. Analysis of the photoluminescence from the single-crystalline CuInSe(2)NRs measured at 10 K has categorized the emission into seven groups of transitions as characterized by free excitons, bound excitons, conduction band to acceptor levels, and bound excitons at different defects.     

pH值对电沉积CuInSe2薄膜的组份、结构及光电性能的影响

本文采用一步恒电位沉积法在铟锡氧化物(ITO)基底上制备CuInSe2薄膜,研究了沉积过程中不同的离子浓度配比及pH值对CuInSe2膜结构性能的影响。利用扫描电子显微镜(SEM)、X射线能谱仪(EDS)及X射线衍射仪(XRD)研究了薄膜材料的结构性能,结果发现pH值对薄膜的化学成份、表面形貌、晶格结构都有显著影响,通过控制合适的浓度及酸度分别制备了高质量富铟与富铜薄膜。利用表面光电压(SPS)技术分别对富铟与富铜薄膜的光电分离特性进行了研究,结果发现富铟薄膜具有很强的光电响应;而富铜薄膜由于Cu-Se相的存在,在薄膜中形成了新的界面,电子-空穴对在其界面处因捕获而发生复合,从而导致其光电响应的强烈降低。所得到的结果为提高铜铟硒薄膜的光电效率提供了有价值的新思路。     

电沉积CuInSe2薄膜的热处理研究

报道了热处理对电沉积ＣｕＩｎＳｅ２薄膜的表观形貌、结构及光电性质的影响。     

Formation pathway of CuInSe2 nanocrystals for solar cells

Copper, indium, and gallium chalcogenide nanocrystals (binary, ternary, and quaternary) have been used to fabricate high-efficiency thin-film solar cells. These solution-based methods are being scaled-up and may serve as the basis for the next generation of low-cost solar cells. However, the formation pathway to reach stoichiometric ternary CuInSe(2) or any chalcopyrite phase ternary or quaternary nanocrystal in the system has not been investigated but may be of significant importance to improving nanocrystal growth and discovering new methods of synthesis. Here, we present the results of X-ray diffraction, electron microscopy, compositional analysis, IR absorption, and mass spectrometry that reveal insights into the formation pathway of CuInSe(2) nanocrystals. Starting with CuCl, InCl(3), and elemental Se all dissolved in oleylamine, the overall reaction that yields CuInSe(2) involves the chlorination of the hydrocarbon groups of the solvent. Further, we show that the amine and alkene functional groups in oleylamine are not necessary for the formation of CuInSe(2) nanocrystals by conducting successful syntheses in 1-octadecene and octadecane. Hence, the role of oleylamine is not limited to nanocrystal size and morphology control; it also acts as a reactant in the formation pathway. Typically, the formation of copper selenide (CuSe) and indium selenide (InSe) nanocrystals precedes the formation of CuInSe(2) nanocrystals in oleylamine. But it was also found that Cu(2-x)Se (0 < x < 0.5) and In(2)Se(3) were the primary intermediates involved in the formation of CISe in a purely non-coordinating solvent such as 1-octadecene, which points to the surface-stabilization effect of the coordinating solvent on the less thermodynamically stable indium selenide (InSe) nanocrystals. We also show that the yield of the chalcopyrite phase of CuInSe(2) (as opposed to the sphalerite phase) can be increased by reacting CuSe nanocrystals with InCl(3).     

Shape-controlled synthesis of ternary chalcogenide ZnIn2S4 and CuIn(S,Se)2 nano-/microstructures via facile solution route

We demonstrated in this paper the shape-controlled synthesis of ZnIn2S4, CuInS2, and CuInSe2 nano- and microstructures through a facile solution-based route. One-dimensional ZnIn2S4 nanotubes and nanoribbons were synthesized by a solvothermal method with pyridine as the solvent, while ZnIn2S4 solid or hollow microspheres were hydrothermally prepared in the presence of a surfactant such as cetyltrimethylammonium bromide (CTAB) or poly(ethylene glycol) (PEG). The mechanisms related to the phase formation and morphology control of ZnIn2S4 are proposed and discussed. The UV-vis absorption spectra show that the as-prepared nano- and micromaterials have strong absorption in a wide range from UV to visible light and that their band gaps are somewhat relevant to the size and morphology. The photoluminescence measurements of the ZnIn2S4 microspheres at room temperature reveal intense excitation at approximately 575 nm and red emission at approximately 784 nm. Furthermore, CuInS2 and CuInSe2 with different morphologies such as spheres, platelets, rods, and fishbone-like shapes were also obtained by similar hydrothermal and solvothermal synthesis.     

三种络合剂对LaFeO3晶体形成的影响

稀土钙钛矿型复合氧化物LaFeo。由于其独特的晶体结构和优良的吸附性能,近年来在催化及气敏领域都显示出了较好的应用前景”,’‘．然而有关LaFe03的合成方法及形成过程的研究,特别是各种络合剂对LaFeo。形成的影响,目前文献报导尚不多．本文将采用直接硝酸盐分解法和加入络合剂的硝酸盐分解法,研究和比较柠檬酸、醋酸,EDTA三种络合剂对LaFe03晶相形成的影响．1实验部分1．五样品制备样品制备分别采用混合硝酸盐分解法和络合分解法,混合硝酸盐分解法是用分析纯试剂La（＊0。）。·6认O,似＊O小·9o0,按La：Fe＝1：1的比例配…     

宽带隙Cu(In,Al)Se2薄膜的制备及表征

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