WO3纳米花的热处理晶格调控及WO3/CdS/α-S异质结的构筑

为研究热处理过程与异质结构筑对WO₃的光电化学效应的影响机制, 采用低温溶剂热法制备纳米花状WO₃, 通过热处理精确调控WO₃纳米花的活性晶面、晶粒尺寸及结晶度。进一步借助循环化学浴法, 构筑WO₃/CdS/α-S异质结, 并研究其光电化学性能与浓度效应。结果表明, (200)晶面是WO₃纳米花的主要暴露晶面, 且比例随热处理温度升高而增大。350 ℃热处理的WO₃纳米花表现出最高的光响应电流。通过构筑WO₃/CdS/α-S梯形异质结, 增强材料在可见光区的吸收, 以牺牲少部分载流子的方式提高整体光生载流子的分离效率, 促进WO₃的宏观光电化学效应的提升。     

双铁电复合材料的制备及其光电化学性能研究

通过模板法制备钒酸铋(BiVO₄)薄膜, 用溶胶-凝胶法制备铁电材料铁酸铋(BiFeO₃)并对BiVO₄进行修饰, 以半导体复合的方式提高BiVO₄的光电化学性能。电化学测试结果表明, 经BiFeO₃修饰后, BiVO₄薄膜的光电化学性能有所提高, 其中经BiFeO₃旋涂5次后的BiVO₄薄膜具有最优的光电化学性能, 光电流密度达到0.72 mA·cm^-2, 较未修饰样品提高了67.4%。利用外场极化调节能带弯曲可以显著地提高BiVO₄/nBiFeO₃铁电复合物的光电化学性能, 复合物经正极化20 V电压处理后的光电流密度最高为0.91 mA·cm^-2, 比BiVO₄薄膜提升了1倍以上, 具有良好的光电化学性能。BiFeO₃与BiVO₄复合后有利于形成异质结, 促进光生电子、光生空穴的产生与分离, 并且外场极化调节能带弯曲使光生电荷加速转移, 是铁电复合物光电化学性能提高的主要原因。     

Characterization of Electrodeposited CuInSe2 Thin Films for Photovoltaic and Photoelectrochemical Applications

CuInSe₂ (CIS) thin films were deposited galvanostatically as well as potentiostatically by an aqueous method. The films were characterized with respect to their structural, opto-electronic and photoelectrochemical properties for application in photovoltaic and photoelectrochemical cells. The film properties depend on parameters like electrode potential, current density, deposition temperature and post-deposition heat treatment. The photoelectrochemical characterization of the film showed that electrodeposited CIS films may be used as photodiodes for hydrogen production by a photocatalytic method. The carrier concentration and flatband potential were determined from C-V measurement, and conductivity type was determined from photoelectrochemical characterization. The annealed films showed N_A = 6×l0¹⁸ cm^× and flat band potential V^B = 0.15 eV.     

Modification on crystallization of poly(vinylidene fluoride) (PVDF) by solvent extraction of poly(methyl methacrylate) (PMMA) in PVDF/PMMA blends

The crystallization modification of poly(vinylidene fluoride) (PVDF) was investigated for the blend films of PVDF and poly(methyl methacrylate) (PMMA). The mass crystallinity (χ_c) and further, the β-phase content (F_(β)) of PVDF, were studied for the as-prepared blend films with different mass ratios. In addition, the variations of χ_c and F_(β) were systematically probed once the PMMA component was removed from the related blend systems. DSC, FTIR and XRD measurements all indicated that 1) χ_c, F_(β) and even the content of α-phase (F_(α)) decreased with the addition of PMMA; 2) with the extraction of PMMA, both χ_c and F_(β) increased while F_(α) decreased. It is worth noting that the increase of χ_c and F_(β) depended on the relative amount of extracted PMMA (E_PMMA), i.e., the more PMMA was removed, the more χ_c and F_(β) increased. These results reveal the hindrance effect from the PMMA constituent to the crystallization of PVDF, and consequently, this restriction would be released when the PMMA was extracted.     

Effects of spacer-chain length on the photoelectrochemical responses of monolayer assemblies with ruthenium tris(2,2′-bipyridine) - viologen linked disulfides

Photochemical and photoelectrochemical properties of ruthenium tris(2,2′-bipyridine) (Ru²⁺)-viologen (V²⁺) linked disulfides [RuCnVC₆S]₂ (n (number of methylene groups)=3, 7) with different spacer-chain lengths and Ru²⁺ disulfides [RuC_mS]₂ (m=13, 17) were compared. The luminescence intensity in CH₃CN was in the order of [RuC₁₃S]₂≈[RuC₁₇S]₂>[RuC₇VC₆S]₂[RuC₃VC₆S]₂, implying efficient photoinduced electron-transfer between Ru²⁺ and V²⁺ moieties in the linked compounds. The monolayer assembly of the compound was fabricated on a gold surface. In the presence of triethanolamine, the anodic photocurrent was clearly observed from the RuC_nVC₆S/Au (n=3, 7) electrode (gold electrode modified with [RuCnVC₆S]₂), and its intensity was substantially larger for n=7 than for n=3. Photocurrent action spectra for the RuC_nVC₆S/Au (n=3, 7) electrodes were well correlated with the corresponding electronic absorption spectra in solution. The photocurrent from the RuC₇VC₆S/Au electrode was reduced more effectively by the coexistence of a water-soluble viologen as compared with the RuC₃VC₆S/Au electrode. The photocurrent from the RuC_mS/Au (m=13, 17) electrode was very small. The results suggest that the spacer-chain length between the Ru²⁺ and the V²⁺ moieties profoundly affects the Ru²⁺-sensitized photocurrent.     

The (SmZr)Co$_3$Phase in Sm(CoFeCuZr)$_rm z$Magnets

Detailed microstructural characterization of magnets and homogenized as-cast alloys, which included X-ray diffraction Rietveld analysis, has indicated that the so-called platelet or lamellae phase is (SmZr)₁(CoFeCu)₃ with the PuNi₃ structure and lattice parameters a~0.5 nm and c~2.4 nm. The structural and magnetic properties of the (SmZr)Co₃ phase were investigated. The microstructure shows two phases differing in their Zr/Sm ratio. Magnetization curves for the samples (Sm_0.33Zr _0.67)Co₃, (Sm_0.33Zr_0.67)Co _2.97Fe_0.03, and (Sm_0.67Zr_0.33)Co₃ are consistent with the two-phase microstructure observed. Room temperature coercivity values of these samples are low (ap1 kOe.)     

高性能CeO2/片状CdS复合光电极材料的制备及在光阴极保护中应用

通过逐步合成法制备了具有储存电子和物理阻隔功能的CeO₂/CdS纳米复合材料, 并用于光电阴极保护。通过XRD, TEM, UV-Vis和PL等手段对制备的纳米复合材料进行表征。在模拟白光照射下研究不同质量比的CeO₂/CdS复合材料的光电化学性质。在黑暗条件下, 涂有CeO₂/CdS(质量比0.2 : 1)的304不锈钢涂层的电位比 CeO₂/CdS(质量比0.2 : 1)粒子涂层更正。在白光照射下, CeO₂/CdS(质量比0.2 : 1)复合材料的最大光电流密度为 700 μA·cm ^-2, 涂有CeO₂/CdS(质量比0.2 : 1)的304不锈钢涂层的电位为-650 mV(vs. SCE), 明显低于304不锈钢腐蚀电位(-200 mV vs. SCE), 表明片状CdS具有物理阻隔性能及CeO₂/CdS复合材料具有显著的光电化学性能。这主要是由于CeO₂纳米颗粒和CdS纳米片之间形成了异质结, 促进了光致电子和空穴的有效分离, 从而提高了光电转换效率。此外, 由于CeO₂具有储存电子的功能, 在黑暗条件下可以继续释放电子, 能够提供12 h的阴极保护性能。     

ISOLATION AND CHARACTERISATION OF C60(CF3)2

From the products of reactions of [60]fullerene with either K₂PtF₆ at 470 °C or AgF at 520 °C, we have isolated C₆₀(CF₃)₂, the simplest trifluoromethylfullerene, which gives a single ¹⁹F NMR line at -69.5 ppm. The HPLC retention time is less than that of C₆₀F₂ confirming the trend observed for other fluoro- vs. trifluoromethylfullerenes namely that the latter elute more rapidly. Other trifluoromethyl- containing species, C₆₀(CF₃)₄O, C₆₀F₅CF₃, C₆₀(CF₃)₄H₂, C₆₀(CF₃)₆H₂, and C₆₀(CF₃H)₃ were detected in the product mixture.     

Photoelectrochemical Investigation of Fullerenes

Fullerene solar cells are demonstrated. Illuminated, C₆₀ drives oxidation of redox couples in solution. a photoelectrochemical solid/liquid, rather than a solid state, junction, improves photocurrent, and a C₆₀ single crystal, and not polycrystalline film, decreases dark current, and thereby light driven charge transfer dominates.     

Production and Characterization of (Al, Fe)-C (Graphite or Fullerene) Composites Prepared by Mechanical Alloying

(Al, Fe)-C_graphite and (Al, Fe)-C_fullerene composites have been prepared by mechanical alloying using ball milling of powders. Consolidation has been achieved by a spark plasma sintering technique (SPS). Results of XRD and TEM indicate that pure fullerene withstands milling. SEM results show homogeneous powders after milling but with different morphologies depending on the specific system. Milling produces a fine mixture of Al or Fe and graphite or fullerene. SPS produces a dense material with a nanocrystalline structure. The sintered samples have a metallic matrix (Al or Fe) with a fine dispersion of AI₄C₃ in the case of Al-C_{( graphiteorfullerene)}, Fe₃,C in the case of Fe-C_(graphite), and fullerene in the case of Fe-C _(fullerene), Hardness measurements show that higher values are obtained in the Al-C_(fullerene), and Fe-C_{(graphite )} specimens.     

First principles total energy studies of the adsorption of germane on Ge(001)-c(2 × 4)

We perform first principles total energy calculations to study the energetics, and the atomic structure of the adsorption of germane (GeH₄) molecules on the Ge(001)-c(2 × 4) surface. The adsorption of a GeH₄ unit occurs after its dissociation into a germanium trihydride (GeH₃) and a hydrogen atom and a subsequent decomposition into a germanium dihydride (GeH₂) subunit and H atoms. Consequently, we first consider the adsorption of GeH₂ in two different configurations; the on-dimer and the intra-row geometries. Similar to the adsorption of SiH₂ and GeH₂ on Si(001), it is found that the on-dimer site is more stable than the intra-row geometry by 0.13 eV. However, in the adsorption of a GeH₂ fragment together with two H atoms we find that the intra-row geometry is energetically more favorable, again, similar to the adsorption of SiH₂ and GeH₂ (plus two H atoms) on the Si(001) surface.     

Energy Transfer from Photoexcited State of Water Soluble Hexa(Sulfobutyl)fullerene (C60((CH2)4SO3Na)6)

Photophysical properties and reactivities of water-soluble micelle-like C₆₀ derivative, C₆₀((CH₂)₄SO₃Na)₆ (abbreviated as FC₄S), at the excited triplet state were investigated using laser flash photolysis. A new transient absorption band appearing at ca. 700 nm was attributed to the triplet-triplet (T-T) absorption band of FC₄S. This absorption was quenched by O₂ via energy transfer forming singlet oxygen, which was confirmed by its luminescence emission band; the quantum yield was evaluated to be 0.36.     

Mn掺杂Ni(OH)2的合成及电化学性能研究

本工作采用缓冲溶液法制备Mn掺杂Ni(OH)₂(Ni_1-xMn_x(OH)₂, x=0.1, 0.2, 0.3, 0.4), X射线衍射测试表明样品主要是β相, 有少量Mn₃O₄杂相; 循环伏安测试表明, x=0.2的材料还原峰积分面积最大、还原分支的峰电流最高; 恒流充放电测试表明, 在100 mA/g电流密度下, Ni_0.8Mn_0.2(OH)₂放电比容量最高, 其第20次循环放电比容量为271.8 mAh/g, 同等条件测试的商用β-Ni(OH)₂放电比容量为253.6 mAh/g; 在300、500 mA/g电流密度下, Ni_0.8Mn_0.2(OH)₂放电比容量仍保持最高, 分别为294.7、291.5 mAh/g, 而且Mn掺杂Ni(OH)₂的循环稳定性也优于商用β-Ni(OH)₂。Mn掺杂可改善镍电极的循环稳定性、降低镍电极成本, 具有广阔的应用前景。     

基于纳米多孔钛酸锂结构的染料敏化太阳电池复合光阳极研究

本研究探索了具有良好导电性能的多孔钛酸锂结构对传统氧化钛纳米晶光阳极的增强效果。以钛酸四丁酯、氢氧化锂为源, 采用溶胶-凝胶结合溶剂热反应和高温烧结方法, 制备了具有多孔结构的尖晶石型Li₄Ti₅O₁₂纳米粉体; 在表征其结晶性、微观形貌及孔结构的基础上, 将其与TiO₂纳米晶浆料复合, 制备复合光阳极, 并详细考察了钛酸锂掺量、结晶性和孔结构等对电池光电转换性能的影响规律。结果表明: 随热处理温度升高, Li₄Ti₅O₁₂结晶性增强, 晶粒尺寸明显增大, 比表面积下降。掺入Li₄Ti₅O₁₂粉体可以有效提高光阳极膜的染料负载量, 降低TiO₂/染料分子/电解液界面的电子传输阻抗, 从而明显提高复合光阳极的光电流密度(J_sc=13.91 mA/cm²)和开路电压(V_oc =0.8 V)。Li₄Ti₅O₁₂含量为1wt%的复合光阳极电池光电转化效率最好, 达到7.011%, 比纯TiO₂电池(效率: 5.384%)提高30%。     

GROUP TRANSFER AND DIMERIZATION PROCESSES OF C60(CN)2 UNDER ATMOSPHERIC PRESSURE IONIZATION CONDITIONS

Neutral and anionic C₆₀(CN)₂ were investigated with electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) mass spectrometry. It was observed that its anions underwent cyano- group and oxygen transfer, and dimerization processes in ESI conditions to form C₆₀(CN)₃H^-, C₆₀(CN)₂(OH₂)^-, [C₆₀(CN)₃H]^-₂, [C₆₀(CN)₂(OH₂)]^-₂ and [(C₆₀)₂(CN)₂(OH)]^-. Meanwhile, neutral C₆₀(CN)₂, for which no signal was observed in ESIMS, showed a base peak corresponding to C₆₀(CN)₂Cl^- in APCIMS spectra with CHCl₃ used as solvent, while only a molecular ion peak corresponding to C₆₀(CN)^-₂ was observed for the toluene solution of neutral C₆₀(CN)₂ in the same conditions. Possible mechanisms for group transfer and dimerization were proposed based on these observations.     

TiO2(B)表面修饰富锂层状氧化物Li(Li0.17Ni0.2Mn0.58Co0.05)O2正极材料

采用喷雾干燥法和沉淀法, 制备了表面修饰TiO₂(B) (2wt%、4wt%、6wt%和8wt%)的富锂层状氧化物Li(Li_0.17Ni_0.2Mn_0.58Co_0.05)O₂正极材料。X射线衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)结构测试分析结果表明, 修饰TiO₂(B)后样品的体相结构仍然保持初始样品的层状结构, 仅氧化物颗粒表面附着有少量TiO₂(B)纳米晶。示差扫描量热测试(DSC)表明, 与初始样品比较, 修饰TiO₂(B)后样品的热稳定性得到明显改善。在2.0~4.8 V范围内进行恒流电化学性能测试。研究显示, 在0.1C(1C=300 mA/g)倍率下, 修饰4wt%TiO₂(B)样品的首次放电比容量可达296.4 mAh/g, 首次库伦效率则由初始样品的77.7%提升到修饰TiO₂(B)后样品的84.3%, 100周循环后电极容量保持率由初始样品的69.5%提升到修饰TiO₂(B)后样品的80.2%。即使在阶梯倍率的2C倍率下, 修饰4wt%TiO₂(B)的样品仍具有较高的电化学容量(166.5 mAh/g)。以上研究结果表明, 表面修饰TiO₂(B)纳米晶可以显著改善富锂层状氧化物Li(Li_0.17Ni_0.2Mn_0.58Co_0.05)O₂的热稳定性和电化学性能。     

Adsorption of Dinitrogen Tetroxide (N2O4) on Multi-walled Carbon Nanotubes (MWCNTs)

The adsorption of dinitrogen tetroxide (N₂O₄) on multi-walled carbon nanotubes (MWCNTs) has been studied by FT-IR, Raman and X-ray photoelectron spectroscopy (XPS). The N₂O₄ adsorption is fully reversible, and after the desorption there is no evidences of MWCNTs nitration. Instead, the MWCNTs have been found oxidized by the action of N₂O₄. By thermogravimetric analysis (TGA) about 5% by weight of oxygenated groups have been found. Thermal analysis has revealed that MWCNTs having a surface area of 275 m²/g are able to reversibly adsorb about 25% by weight of N₂O₄, a value comparable to that observed for certain active carbons.     

(1-x)K0.48Na0.52NbO3-xBi0.45Nd0.05(Na0.92Li0.08)0.5ZrO3无铅压电陶瓷相结构及压电性能

为了在获得较高压电性能的同时又不大大降低陶瓷的居里温度(T_C), 设计和制备了Bi_0.45Nd_0.05(Na_0.92Li_0.08)_0.5ZrO₃改性的K_0.48Na_0.52NbO₃系无铅压电陶瓷((1-x)KNN-xBNNLZ), 研究了BNNLZ含量对KNN基无铅压电陶瓷相结构和电学性能的影响。研究结果表明, 所有陶瓷样品均具有较高的居里温度T_C(>300℃)。随着BNNLZ含量的增加, 陶瓷的正交-四方相变温度(T_O-T)不断向低温方向移动, 而三方-正交相变温度(T_R-O)不断向高温方向移动, 最终在陶瓷中形成了三方-四方(R-T)共存相, R-T共存相处于0.05<x<0.07范围。BNNLZ的加入引起陶瓷相结构的演化改变导致压电常数(d₃₃ )、介电常数(ε_r )、剩余极化强度 (P_r )和机电耦合系数(k_p )都先增大后减小, 当x=0.06时陶瓷具有最佳压电性能: d₃₃=313 pC/N, k_p=42%, P_r=25.48 μC/cm², ε_r=1353, tanδ=2.5%, T_C=327℃。     

Selective Supercritical Fluid Extraction of Uranium(VI) using N-Phenyl-(1,2-Methano-Fullerene C60)61-Formohydroxamic acid and Simultaneous On-line Determination by Inductively-Coupled Plasma-Mass Spectrometry (ICP-MS)

Uranium(VI) is extracted with N-phenyl-(1,2-methano-fullerene C₆₀)61-formohydroxamic acid, PMFFHA, in dichloromethane by supercritical carbon dioxide (SF-CO₂)-dichloromethane (modifier) medium. A 2.0 µL aqueous uranium is extracted accurately and also preconcentrated in an especially designed extraction vessel of 80 µL capacity. The extracted microdrop orange-red colored uranium(VI)-PMFFHA complex in dichloromethane was online measured by fiber optics spectrometry and ICP-MS. The distribution ratio (D_UO2²⁺) of U(VI) was determined. The slopes of log D_UO2²⁺ versus PMFFHA concentration plot, the extracted species both in SF-CO₂ extraction (SFE) and the solvent extraction (SE) were determined to be 2.0 as UO₂(PMFFHA)₂ complex. The uranium is determined as low as 0.10 ng mL^-1 in presence of several cations and anions. The effect of diluents, modifier concentration, temperature and pressure on the extraction and separation of uranium was studied. The uranium is determined in human blood serum, natural water, seawater, standard samples and also in monazite sand. The PMFFHA has been successfully used as carrier for the selective and efficient transport of uranium(VI). The feed comprised of a solution of uranium(VI) and aqueous solution of diverse cations and anions in pH 4.5, while 1M HNO₃ was used as a stripping agent in the receiving compartment of permeated cell. Maximum transportation was observed for 12 minutes with t_1/2 equal to 6.3 min. The uranium(VI) was determined in presence of uranium(IV).     

CdS/TiO2纳米晶薄膜的原位法制备及光电化学性能研究

CdS/TiO₂异质结薄膜因其优异的可见光催化性能, 在光催化领域引起了广泛关注。然而, 目前传统方法制备的CdS/TiO₂薄膜可能存在交界面结合不紧密的问题, 不利于光生载流子在交界面处的传输。因此, 本研究基于原位转换的原理(TiO₂→CdTiO₃→CdS), 将TiO₂纳米晶表层原位转换成CdS, 制备了CdS/TiO₂纳米晶薄膜。采用X射线衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)手段对样品薄膜的形貌和结构进行了表征。由表征结果可知, 在TiO₂纳米晶表面形成了CdS, 构成了交界面结合紧密的CdS/TiO₂异质结薄膜。光电化学性能研究表明, 与传统的连续离子层吸附反应法(SILAR)制备的薄膜相比, 原位法制备的CdS/TiO₂薄膜的光电流密度更高, 达到9.8 mA·cm^-2(V=0.4 V (vs. RHE)); 交流阻抗谱(EIS)结果表明, 原位法制备的CdS/TiO₂薄膜具有更小的电荷传输电阻, 说明原位法形成的CdS/TiO₂异质结结合更紧密, 能减小光生载流子在CdS/TiO₂界面处的传输阻力, 降低光生载流子在传输过程中的复合几率, 进而提高CdS/TiO₂薄膜的光电化学性能。