介孔氧化镍的合成、表征和在电化学电容器中的应用

以十二烷基硫酸钠为模板剂, 采用尿素为沉淀剂, 用均匀沉淀法, 适当控制尿素的水解速度, 制备具有介孔结构的氢氧化镍胶体, 在不同温度下焙烧处理得到孔分布集中的氧化镍介孔分子筛. 结果表明, 在523 K下焙烧得到的氧化镍BET比表面达到477.7 m²•g^－1. 结构表征还显示, 介孔氧化镍的孔壁为多晶结构, 其孔结构形成机理应为准反胶束模板机理. 循环伏安法表明用NiO介孔分子筛制备的电极有很好的电容性能. 与浸渍法和阴极沉淀法制得的NiO相比, 这种介孔结构的NiO能够大量用来制作电化学电容器电极, 并且保持较高的比电容量和良好的电容性能.     

电沉积三维多孔Pt/SnO2薄膜及其对甲醇的电催化氧化

在高电流密度下以阴极析出的氢气泡为“模板”电沉积三维多孔Sn薄膜, 经在200 ℃ 2 h和400 ℃ 2 h热处理氧化后电沉积金属Pt, 制得三维多孔的Pt/SnO₂ (3D-Pt/SnO₂)薄膜. 通过扫描电镜(SEM)和X射线衍射(XRD)分析了薄膜的形貌和结构. 结果显示Pt主要沉积在SnO₂枝晶上, 形成Pt_shell/SnO_2core结构的枝晶. 在0.5 mol•dm^－3 H₂SO₄＋1.0 mol•dm^－3 CH₃OH溶液中的循环伏安结果表明, 3D-Pt/SnO₂薄膜电极在酸性溶液中电催化氧化甲醇的性能优于电沉积的纯铂电极, 而且具有较高的稳定性.     

电沉积三维多孔Pt/SnO2薄膜及其对甲醇的电催化氧化

在高电流密度下以阴极析出的氢气泡为“模板”电沉积三维多孔Sn薄膜, 经在200 ℃ 2 h和400 ℃ 2 h热处理氧化后电沉积金属Pt, 制得三维多孔的Pt/SnO₂ (3D-Pt/SnO₂)薄膜. 通过扫描电镜(SEM)和X射线衍射(XRD)分析了薄膜的形貌和结构. 结果显示Pt主要沉积在SnO₂枝晶上, 形成Pt_shell/SnO_2core结构的枝晶. 在0.5 mol•dm^－3 H₂SO₄＋1.0 mol•dm^－3 CH₃OH溶液中的循环伏安结果表明, 3D-Pt/SnO₂薄膜电极在酸性溶液中电催化氧化甲醇的性能优于电沉积的纯铂电极, 而且具有较高的稳定性.     

污泥活性炭的结构特征及表面分形分析

以城市污水厂污泥为主要原料添加适量添加剂, 采用ZnCl₂化学活化法制备的污泥活性炭, 借助XRD, BET法, FT-IR, SEM等现代分析测试方法结合液相吸附法, 表征结构特征和分析表面分形维数. 结果表明: 在适宜的活化温度、活化时间、ZnCl₂浓度、原料粒度等工艺条件下, 加入少量添加剂制备的污泥活性炭, 最可几孔径分布在4.16 nm左右,平均孔容0.4484～0.5122 mL•g^－1, 比表面积为634.8～748 m²•g^－1, IR峰中出现C—OH, C—H, N＝O, C＝C功能组, 孔结构是具有平行壁的狭缝状介孔结构. 由液相吸附法得到的污泥活性炭分维近似为2, 属于低分维二维表面.     

聚苯胺/活性碳复合型超电容器的电化学特性

电化学电容器作为一种新型储能器件具有广泛的应用.采用(NH₄)₂S₂O₈化学氧化聚合苯胺法制备了聚苯胺电极材料，采用化学物理二次催化活化法制备了高比表面积活性碳材料.并用循环伏安、恒流充放电以及交流阻抗等方法对上述电极材料的电化学特性进行了研究.实验结果表明,所制备的聚苯胺电极材料具有高于420 F•g^－1的法拉第赝电容和良好的电化学特性，所制备的活性碳电极材料则具有160 F•g^－1的双电层电容量.分别采用聚苯胺作为正极，活性碳作为负极，38％硫酸作为电解液制备了复合型电化学电容器.复合型电容器工作电压达到1.4 V, 电容器单体比电容达到57 F•g^－1，最大比能量和最大真实比功率分别达到15.5 W•h•kg^－1和2.4 W•g^－1, 峰值比功率达到20.4 W•g^－1,电容器循环工作寿命超过500次. 与活性碳双电层电容器相比，复合型电容器还具有较低的自放电率.     

介孔炭的孔结构对其负载的Ru基氨合成催化剂性能的影响

采用模板法合成了介孔炭(MC),研究了其孔结构对其负载的Ru基氨合成催化剂Ba-Ru-K/MC性能的影响,采用N₂吸附脱附、扫描电镜和透射电镜等手段对介孔炭的孔结构进行了表征.研究发现,介孔炭载体的孔结构取决于模板剂的用量,当SiO₂/C质量比为1.0时,所制介孔炭比表面积最大.介孔炭负载的Ba-Ru-K催化剂活性与其介孔比表面积相关.在425℃,10MPa和10000h^-1条件下,合成氨的反应速率为139mmol/(g_cat·h).     

纳米TiO2介孔薄膜的模板组装制备研究

以TiCl₄为无机前驱体、三嵌段高分子共聚物EO₂₀PO₇₀EO₂₀为模板剂，在非水条件下制备了有序的锐钛矿TiO₂纳米晶介孔薄膜。通过热重-差热（TG-DTA）分析、X射线衍射（XRD）分析、原子力显微观察（AFM）及N₂吸附-脱附等测试对样品进行了表征。结果表明，薄膜具有均一的大介孔孔径（～10 nm），其BET比表面积为150 m²·g^-1，薄膜较宽的无机壁厚显著提高了介孔结构的热稳定性。通过红外（IR）光谱分析考察了溶胶-凝胶过程中发生的物理化学变化。在对薄膜表面形貌进行AFM观察的基础上初步探讨了嵌段共聚物EO₂₀PO₇₀EO₂₀对薄膜孔结构形成的导向机理。     

266 nm光照下水溶液中氯苯与H2O2的反应机理研究

利用瞬态吸收光谱技术研究了不同条件下C₆H₅Cl与H₂O₂水溶液的激光闪光光解情况, 初步考察了其瞬态物种的生长和衰减等行为. 研究表明, •OH自由基和C₆H₅Cl反应生成C₆H₅Cl-OH adduct, 其反应速率常数在近中性、酸性条件下约为(5.89±0.65)×10⁹和(7.07±0.61)×10⁹ L•mol^－1•s^－1; 其衰减则符合双分子二级反应, 速率常数2k/εl＝1.1×10⁶ s^－1, 而在碱性时则为(4.34±0.51)×10⁹ L•mol^－1•s^－1, 衰减呈准一级反应, 速率常数为2.11×10⁵ s^－1. 在有氧条件下, O₂与C₆H₅Cl-OH adduct反应生成C₆H₅Cl-OHO₂ adduct, 其反应速率常数为6.8×10⁸ L•mol^－1•s^－1.     

[Me3NC2H4OH]Zn2Cl5水溶液的激光光解研究

利用时间分辨激光光解技术研究了季铵盐型离子液体[Me₃NC₂H₄OH]Zn₂Cl₅(简写R-Zn₂Cl₅)的光解行为, 研究发现离子液体能被266 nm激光单光子电离, 生成阳离子自由基、[Zn₂Cl₅]^•中性自由基和水合电子, 观察到胆碱激发三线态的存在, 并测定了离子液体光电离的量子产额为0.04. 利用266 nm激光对离子液体、胆碱、氯化锌、氯化钠的光解行为比较, 发现胆碱阳离子的贡献很小, [Zn₂Cl₅]^－阴离子起主要作用. 采用氧化性自由基SO₄^•－引发离子自由基, 揭示其光电离机理, 测定离子液体的动力学反应速率常数, SO₄^•－ 460 nm的衰减速率常数为1.3×10⁹ L•mol^－1•s^－1, 320 nm离子自由基瞬态产物的生成速率常数为1.5×10⁹ L•mol^－1•s^－1, 两者很接近, 说明SO₄^•－自由基的衰减与瞬态自由基的生成是同步的.     

Li＋, Na＋//SO42－, CO32－-H2O交互四元体系288 K介稳相平衡研究

采用等温蒸发法研究了四元体系Li^＋, Na^＋// SO₄^2－, CO₃^2－-H₂O 288 K介稳相平衡及平衡液相的密度、电导率、折光率、粘度和pH值, 测定了该四元体系288 K条件下介稳平衡溶液溶解度及物化性质. 根据实验数据绘制了相应的介稳相图. 研究发现: 该体系介稳平衡中有复盐Na₃Li(SO₄)₂•6H₂O形成. 其介稳相图中有3个共饱点, 7条单变量曲线, 平衡固相为: Li₂SO₄•H₂O, Na₂SO₄, Na₃Li(SO₄)₂•6H₂O, Li₂CO₃, Na₂CO₃•10H₂O. 复盐Na₃Li(SO₄)₂•6H₂O和一水硫酸锂(Li₂SO₄•H₂O)的结晶区较小, 而Li₂CO₃的结晶区最大; 该四元体系介稳平衡条件下未发现Na₂SO₄•10H₂O的结晶区.     

Thick porous tungsten trioxide films by anodization of tungsten in fluoride containing phosphoric acid electrolyte

In the present work, we report on the formation of mesoporous thick tungsten trioxide films grown on tungsten foil by anodization in fluoride containing concentrated phosphoric acid (85%) electrolyte. Under optimized experimental conditions, mesoporous WO₃ films with a thickness up to approximately 2 μm are formed. SEM shows the films to consist of a connected network with a typical pore and feature diameter of ca 50 nm. These films as formed are amorphous and can be annealed to orthorhombic WO₃ structure. These thick porous films can show significant enhanced electrochromic and improved photocatalytic properties.     

Sol–gel synthesis of mesoporous WO3–TiO2 composite thin films for photochromic devices

Mesoporous WO₃–TiO₂ composite films were prepared by a sol gel based two stage dip coating method and subsequent annealing at 450, 500 and 600 °C. An organically modified silicate based templating strategy was adopted in order to obtain a mesoporous structure. The composite films were prepared on ITO coated glass substrates. The porosity, morphology, and microstructures of the resultant products were characterized by scanning electron microscopy, N₂ adsorption–desorption measurements, μ-Raman spectroscopy and X-ray diffraction. Calcination of the films at 450, and 500 °C resulted in mixed hexagonal (h) plus monoclinic phases, and pure monoclinic (m) phase of WO₃, respectively. The degree of crystallization of TiO₂ present in these composite films was not evident. The composite films annealed at 600 °C, however, consist of orthorhombic (o) WO₃ and anatase TiO₂. It was found that the o-WO₃ phase was stabilized by nanocrystalline anatase TiO₂. The thus obtained mesoporous WO₃–TiO₂ composite films were dye sensitized and applied for the construction of photochromic devices. The device constructed using dye sensitized WO₃–TiO₂ composite layer heat treated at 600 °C showed an optical modulation of 51 % in the NIR region, whereas the devices based on the composite layers heat treated at 450, and 500 °C showed only a moderate optical modulation of 24.9, and 38 %, respectively. This remarkable difference in the transmittance response is attributed to nanocrystalline anatase TiO₂ embedded in the orthorhombic WO₃ matrix of the WO₃–TiO₂ composite layer annealed at 600 °C.     

Erratum to: Sol–gel synthesis of mesoporous WO3–TiO2 composite thin films for photochromic devices

Mesoporous WO₃–TiO₂ composite films were prepared by a sol gel based two stage dip coating method and subsequent annealing at 450, 500 and 600 °C. An organically modified silicate based templating strategy was adopted in order to obtain a mesoporous structure. The composite films were prepared on ITO coated glass substrates. The porosity, morphology, and microstructures of the resultant products were characterized by scanning electron microscopy, N₂ adsorption–desorption measurements, μ-Raman spectroscopy and X-ray diffraction. Calcination of the films at 450, and 500 °C resulted in mixed hexagonal (h) plus monoclinic phases, and pure monoclinic (m) phase of WO₃, respectively. The degree of crystallization of TiO₂ present in these composite films was not evident. The composite films annealed at 600 °C, however, consist of orthorhombic (o) WO₃ and anatase TiO₂. It was found that the o-WO₃ phase was stabilized by nanocrystalline anatase TiO₂. The thus obtained mesoporous WO₃–TiO₂ composite films were dye sensitized and applied for the construction of photochromic devices. The device constructed using dye sensitized WO₃–TiO₂ composite layer heat treated at 600 °C showed an optical modulation of 51 % in the NIR region, whereas the devices based on the composite layers heat treated at 450, and 500 °C showed only a moderate optical modulation of 24.9, and 38 %, respectively. This remarkable difference in the transmittance response is attributed to nanocrystalline anatase TiO₂ embedded in the orthorhombic WO₃ matrix of the WO₃–TiO₂ composite layer annealed at 600 °C.     

Highly Ordered Mesoporous Tungsten Oxides with a Large Pore Size and Crystalline Framework for H2S Sensing

An ordered mesoporous WO₃ material with a highly crystalline framework was synthesized by using amphiphilic poly(ethylene oxide)‐b‐polystyrene (PEO‐b‐PS) diblock copolymers as a structure‐directing agent through a solvent‐evaporation‐induced self‐assembly method combined with a simple template‐carbonization strategy. The obtained mesoporous WO₃ materials have a large uniform mesopore size (ca. 10.9 nm) and a high surface area (ca. 121 m² g^?1). The mesoporous WO₃‐based H₂S gas sensor shows an excellent performance for H₂S sensing at low concentration (0.25 ppm) with fast response (2 s) and recovery (38 s). The high mesoporosity and continuous crystalline framework are responsible for the excellent performance in H₂S sensing.     

Sol–gel derived mesoporous Pt and Cr-doped WO<Subscript>3</Subscript> thin films: the role played by mesoporosity and metal doping in enhancing the gas sensing properties

Mesoporous Cr or Pt-doped WO₃ thin films to be employed as ammonia gas sensors were prepared by a fast one-step sol–gel procedure, based on the use of triblock copolymer as templating agent. The obtained films were constituted by aggregates of interconnected WO₃ nanocrystals (20–50 nm) separated by mesopores with dimensions ranging between 2 and 15 nm. The doping metals, Pt and Cr, resulted differently hosted in the WO₃ mesoporous matrix. Chromium is homogeneously dispersed in the oxide matrix, mainly as Cr(III) and Cr(V) centers, as revealed by EPR spectroscopy; instead platinum segregated as Pt (0) nanoparticles (4 nm) mainly included inside the WO₃ nanocrystals. The semiconductor layers containing Pt nanoclusters revealed, upon exposure to NH₃, remarkable electrical responses, much higher than Cr-doped and undoped layers, particularly at low ammonia concentration (6.2 ppm). This behavior was attributed to the presence of Pt nanoparticles segregated inside the semiconductor matrix, which act as catalysts of the N–H bond cleavage, decreasing the activation barrier in the ammonia dissociation. The role of the mesoporous structure in influencing the chemisorption and the gas diffusion in the WO₃ matrix appeared less decisive than the electronic differences between the two examined doping metals. The overall results suggest that a careful combination between mesoporous architecture and metal doping can really promote the electrical response of WO₃ toward ammonia.     

Electrochromic and structural characteristics of mesoporous WO<Subscript>3</Subscript> films prepared by a sol-gel method

The preparation of electrochromic films of mesoporous tungsten trioxide from tungstic acid and tungstic hexaethoxide precursors with the addition of an organic stabiliser via a sol-gel method is reported. These films have been structurally characterised and both the film morphology and crystalline composition of the films were found to be significantly dependent on the temperature at which the films were annealed and upon the choice of precursor. Films annealed at lower temperatures consisted of amorphous and hexagonal tungsten trioxide, whereas films annealed above 500 °C comprised solely of monoclinic WO₃. The electrochromic activity of the films was found to be equally dependent on method of preparation, and both the composition and the structure of the WO₃ films were shown to clearly influence the colouration efficiency of the films.Dedicated to Zbigniew Galus on the occasion of his 70^th birthday.     

Facile synthesis of mesoporous WO3@graphene aerogel nanocomposites for low-temperature acetone sensing

Nanocomposites constructed by combining mesoporous metal oxides and graphene have received tremendous attention in wide fields of catalysis,energy storage and conversion,gas sensing and so on.Herein,we present a facile interface-induced co-assembly process to synthesize the mesoporous W03@graphene aerogel nanocomposites(denoted as mW03@GA),in which graphene aerogel(GA) was used as a macroporous substrate,mesoporous W03 was uniformly coated on both sides of graphene sheets through a solvent evaporation-induced self-assembly(EISA) strategy using diblock copolymer poly(ethylene oxide)-b-polystyrene(PEO-b-PS) as a template.The resultant mW03@GA nanocomposites possess well-interconnected macroporous graphene networks covered by mesoporous W03 layer with a uniform pore size of 19 nm,high surface area of 167 m~2/g and large pore volume of 0.26 cm~3/g.The gas sensing performance of mW03@GA nanocomposites toward acetone and other gases was studied,showing a high selectivity and great response to acetone at low temperature of 150℃,which could be developed as a promising candidate as novel sensors for VOCs detection.     

Solution Processing of Topochemically Converted Layered WO3 for Multifunctional Applications

Solution processing of nanomaterials is a promising technique for use in various applications owing to its simplicity and scalability. However, the studies on liquid-phase exfoliation (LPE) of tungsten oxide (WO₃) are limited, unlike others, by a lack of commercial availability of bulk WO₃ with layered structures. Herein, a one-step topochemical synthesis approach to obtain bulk layered WO₃ from commercially available layered tungsten disulfide (WS₂) by optimizing various parameters like reaction time and temperature is reported. Detailed microscopic and spectroscopic techniques confirmed the conversion process. Further, LPE was carried out on topochemically converted bulk layered WO₃ in 22 different solvents; among the solvents studied, the propan-2-ol/water (1 : 1) co-solvent system appeared to be the best. This indicates that the possible values of surface tension and Hansen solubility parameters for bulk WO₃ could be close to that of the co-solvent system. The obtained WO₃ dispersions in a low-boiling-point solvent enable thin films of various thickness to be fabricated by using spray coating. The obtained thin films were used as active materials in supercapacitors without any conductive additives/binders and exhibited an areal capacitance of 31.7 mF cm⁻² at 5 mV s⁻¹. Photo-electrochemical measurements revealed that these thin films can also be used as photoanodes for photo-electrochemical water oxidation.     

An investigation on the assembling of WO3 particles on the matrix of silica solution

A facile way to prepare modified WO₃ structure by silica support through sol–gel method is reported. The WO₃/SiO₂ complex film was synthesized from a two steps process and dip-coating method. The films were characterized with laser particle analyzer, IR, Raman. The studies of gelation time and particle size distribution of WO₃/SiO₂ sol indicate that the silica addition could largely reduce the polycondensation of WO₃ clusters. The reaction between WO₃ and SiO₂ were further systematically investigated using IR spectra, and an insight of this reaction was illuminated. Results reveal that Si–OH in SiO₂ sols tended to crosslink with WO₃ at the corner-sharing W–O sites, by which only edge-sharing WO_x clusters could be detected. This modified the WO₃ structure was also approved by the Raman spectra, TEM and AFM images. Moreover, gas sensing properties of the WO₃/SiO₂ films were tested. The assembled WO₃ films exhibited more stable gas sensing stability than pure WO₃ films.     

Highly Efficient Mesoporous V<Subscript>2</Subscript>O<Subscript>5</Subscript>/WO<Subscript>3</Subscript>–TiO<Subscript>2</Subscript> Catalyst for Selective Catalytic Reduction of NO<Subscript>x</Subscript>: Effect of the Valence of V on the Catalytic Performance

Mesoporous WO₃–TiO₂ support was synthesized by hydrothermal method, mesoporous V₂O₅/WO₃–TiO₂ catalyst was synthesized by impregnation method and used for selective catalytic reduction (SCR) of NO_x with a excellent NO_x conversion at a wider operating temperature ranging from 200 to 460?°C. In the range of 260–440?°C, NO_x conversion reached to 98.6%, and nearly a complete conversion. Even with the existence of 300 ppm SO₂, NO_x conversion was only a little decline. The catalyst was characterized by a series of techniques, such as XRD, BET, XPS, TEM, Raman and H₂-TPR. It was concluded that V₂O₅/WO₃–TiO₂ catalyst was ascribe to antase TiO₂, and also the high crystallinity of anatase TiO₂ could improve the SCR performance. More interested, V₂O₅/WO₃–TiO₂ catalyst exhibited the typical mesoporous structure according to the BET results. In addition, the TEM results indicated that the active components of V and W were well-dispersed on the surface of TiO₂, while the enhancement of dispersion could improve the activity of catalysts. More importantly, the concentration ratio of V⁴⁺/(V⁵⁺?+?V⁴⁺?+?V³⁺) performed the key role in improving the activity of V₂O₅/WO₃–TiO₂ catalyst.