Novel counter electrode catalysts of niobium oxides supersede Pt for dye-sensitized solar cells

Synthesized niobium oxides (Nb(2)O(5) and NbO(2)) were applied for the first time as counter electrodes (CEs) in dye-sensitized solar cells (DSCs). The DSC using NbO(2) CE showed a higher power conversion efficiency of 7.88%, compared with that of the DSC using Pt CE (7.65%).     

Economical Pt-free catalysts for counter electrodes of dye-sensitized solar cells

Three classes (carbides, nitrides and oxides) of nanoscaled early-transition-metal catalysts have been proposed to replace the expensive Pt catalyst as counter electrodes (CEs) in dye-sensitized solar cells (DSCs). Of these catalysts, Cr(3)C(2), CrN, VC(N), VN, TiC, TiC(N), TiN, and V(2)O(3) all showed excellent catalytic activity for the reduction of I(3)(-) to I(-) in the electrolyte. Further, VC embedded in mesoporous carbon (VC-MC) was prepared through in situ synthesis. The I(3)(-)/I(-) DSC based on the VC-MC CE reached a high power conversion efficiency (PCE) of 7.63%, comparable to the photovoltaic performance of the DSC using a Pt CE (7.50%). In addition, the carbide catalysts demonstrated catalytic activity higher than that of Pt for the regeneration of a new organic redox couple of T(2)/T(-). The T(2)/T(-) DSCs using TiC and VC-MC CEs showed PCEs of 4.96 and 5.15%, much higher than that of the DSC using a Pt CE (3.66%). This work expands the list of potential CE catalysts, which can help reduce the cost of DSCs and thereby encourage their fundamental research and commercial application.     

Curing of dicyanate ester/epoxy copolymers modified with polysiloxane and butadiene-acrylonitrile rubbers

The cyanate ester (CE) and epoxy (EP) resins were cured together at various mass compositions. The curing behavior of CE and CE/EP systems was studied by means of differential scanning calorimetry (DSC) in non-isothermal conditions. The DSC measurements indicated that the curing reactions were dependent on the stoichiometric ratio of the mixtures and showed the dilution effect of the EP resin in the cyclotrimerization of the catalyzed CE resin. The CE and CE/EP (70/30) systems were modified using reactive liquid butadiene-acrylonitrile copolymer (ETBN) and polysiloxane core?Cshell (PS) elastomer. The influence of ETBN and PS on the curing process and glass transition temperature (T _g) of CE/EP systems was determined. The impact resistance characteristics of the completely cured systems indicated the influence of the modifiers and the EP content in the mixtures on its impact resistance.     

物理老化无规聚苯乙烯屈服机理的研究

利用机械拉伸、示差扫描量热(DSC)以及溶剂溶胀等方法研究了物理老化后的无规聚苯乙烯(α-PS)的应力屈服行为,并从凝聚缠结的观点对实验结果进行了解释.实验结果表明,经物理老化后的α-PS在拉伸过程中出现应力屈服峰实质上是逐步打开凝聚缠结的过程.凝聚缠结是聚合物非晶相在物理老化过程中相邻的两三条链的局部链段由于范德华吸引力的作用形成的一种有序结构,其作用能很弱,升温至T_g附近,机械拉伸至屈服点以及溶胀剂都可将其完全破坏.     

Determination of oxoanions in river water by capillary electrophoresis

A new capillary electrophoresis (CE) procedure was developed for simultaneous determination of ten oxoanions (CrO4(2-), SeO4(2-), MoO4(2-), WO4(2-), VO4(3-), SeO3(2-), As04(3-), TeO3(2-), TeO4(2-), and AsO3(3-)) which were baseline-separated from each other and from the interfering UV absorbing anions (NO3- and NO2-) commonly found in environmental water samples. The new background electrolyte system developed contained 5 mM potassium phosphate and 0.007 mM octadecyltrimethylammonium hydroxide, pH 11.2. The optimized working conditions were electrokinetic sampling at -5 kV for 10 s, running voltage at -15 kV with 5 microA current, and detection wavelength at 205 nm. No interference was observed for non-UV-absorbing anions and UV-absorbing anions up to 20 and 10 times higher concentrations respectively. The speed of analysis was fast, with a complete CE run within 6 min. Wide linear ranges (1-2,000 microg/L), good repeatability in migration time (relative standard deviation RSD 0.55-2.8%), satisfactory precision in peak area (RSD 3.8-5.6%) and peak height (RSD 3.9-5.3%) measurement, and detection limits (1-25 microg/L) sufficiently sensitive to detect oxoanions found in environmental water samples were obtained. The reliability of the CE procedure developed had been established by recovery test and parallel method determination using atomic absoprtion spectrophotometry for real river water sample.     

CeO2表面分散态WO3的氨选择性催化还原性能

铈基材料在氨选择性催化还原氮氧化物(NH3-SCR)的研究中备受关注,亦被认为是潜在的新型环境友好型催化剂.CeO2具有独特的氧化还原性能和优良的储释氧性能,易与其它金属氧化物发生协同催化而有利于提高催化剂的催化反应性能,而WO3可以改善催化剂的表面酸性.研究亦报道了WO3可以改善CeO2的NH3-SCR反应的高温活性和N2选择性,其原因在于WO3增加了铈基催化剂NH3的吸附性能且抑制了NH3非选择性氧化成NOx.我们采用浸渍法制备了一系列负载型WO3/CeO2催化剂,并利用XRD,Raman,XPS,H2-TPR,NH3-TPD和in situ DRIFT对其理化性质进行了表征,系统研究了WO3负载量对WO3/CeO2催化剂NH3-SCR催化性能的影响,主要研究的内容包括:(1)WO3/CeO2催化剂中WO3的状态与催化性能之间的关系;(2)WO3负载量对WO3/CeO2催化剂的NH3和NO吸附行为的影响.NH3-SCR反应测试表明WO3负载量对WO3/CeO2催化剂有显著影响,优化的WO3/CeO2催化剂在200–450℃具有良好的脱硝性能,且在300℃通入SO2+H2O条件下依然保持优异的催化活性.XPS和H2-TPR结果表明,WO3分散在CeO2表面抑制了CeO2表面活性氧和表面晶格氧的氧化能力,这导致催化剂对NO的氧化以及对硝酸盐的吸附性能相比于纯CeO2显著降低,同时,in situ DRIFT也证实,随着WO3负载量的增加,WO3/CeO2催化剂表面吸附硝酸盐能力下降.因此,我们认为,由于低活性的晶相WO3覆盖在催化剂表面,阻碍了催化剂的表面活性位,降低了催化剂的氧化还原能力和表面酸量,从而晶相WO3抑制了WO3/CeO2催化剂的催化活性.同时,我们发现在70℃下采用氨水可以洗掉WO3/CeO2催化剂中的晶相WO3,且洗涤后的样品催化活性有所提升,这进一步验证了晶相WO3对催化活性的抑制作用.In situ DRIFT结果表明WO3/CeO2催化剂上NH3-SCR反应是通过Eley-Rideal机理进行,即吸附NH3物种与气相NO之间发生反应.随着WO3负载量的增加,WO3/CeO2催化剂中NH3的吸附能力先增强后减弱,而NO吸附能力持续减弱,这有利于表面酸位在反应过程中不被硝酸盐阻碍,当WO3负载量在分散容量附近时,这种吸附特性的效果发挥到最大,从而最大限度地促进NH3-SCR反应按照Eley-Rideal机理顺利进行.     

稀土催化制备窄分子量分布高顺式聚异戊二烯及聚合反应动力学

由稀土羧酸钕盐(Nd)、三异丁基铝(Al)、含氯活化剂(CE)及醇(OH)组成的均相稀土羧酸盐催化体系,用于异戊二烯(Ip)定向聚合,其中含氯活化剂(CE)为氯代烃(CE1)或氯代羧酸酯(CE2).研究了CE和OH的化学结构及Al用量对Ip聚合及聚异戊二烯(PIp)微观结构、分子量及分子量分布的影响,将原位全反射傅立叶红外光谱(in situ ATR-FTIR)技术应用于研究稀土催化Ip配位聚合反应过程及聚合反应动力学,采用FTIR、GPC、NMR及DSC等测试手段表征PIp的微观结构、分子量及其分布、序列分布及热性能.实验结果表明,在稀土催化异戊二烯聚合反应中,少量的CE2和OH有助于提高催化活性、降低分子量分布和提高顺式含量.聚合速率对单体浓度呈现一级动力学关系,表观增长活化能(Ea)为69.5 kJ/mol.通过调节催化剂组分配比及聚合工艺条件,可制备出顺-1,4结构含量可达98%以上、窄分子量分布(Mw/Mn=1.6～2.4)的高顺式聚异戊二烯.     

Facile in situ synthesis of the bismuth oxychloride/bismuth niobate/TiO(2) composite as a high efficient and stable visible light driven photocatalyst

Fe-ions modified mesoporous Bi(2)WO(6) nanosheets (Fe-Bi(2)WO(6)) were successfully synthesized via a simple two-step method, which involved a template-free hydrothermal process and a following impregnation treatment. The resultant products were characterized by XRD, TEM, XPS, EDX, ESR, UV-Vis, PL, and visible light photocatalytic measurements. Experimental results indicated that the addition of a small amount Fe-ions (optimized content at 0.1 wt.%) could evidently improve the activity of Bi(2)WO(6). The apparent reaction rate of Fe-Bi(2)WO(6)-0.1% (k, 0.099 min(-1)) was 3.2 times higher than that of Fe-Bi(2)WO(6)-0% (k, 0.031 min(-1)). The Fe-ions mainly existed as Fe(3+) and Fe(2+) ions, which were uniformly distributed on the surface of Bi(2)WO(6) nanosheets and some Fe(3+)-ions substituted Bi(3+)-ions in Bi(2)O(2) layers. Both of the concentration and state of Fe-ions played vital factors for the improved visible light photocatalytic activities.     

Li-Mn/WO_(3)/TiO_(2)固体酸催化剂的制备及其甲烷氧化偶联催化性能研究北大核心CSCD

Li-Mn/WO_(3)/TiO_(2)催化剂具有良好的低温OCM催化性能,采用浸渍法制备Li-Mn/WO_(3)/TiO_(2)催化剂,并详细考察WO_(3)对催化剂物理化学性质及催化性能的影响.利用X射线衍射(XRD)、CO_(2)程序升温脱附(CO_(2)-TPD)、O_(2)程序升温脱附(O_(2)-TPD)、H_(2)程序升温还原(H_(2)-TPR)、拉曼光谱(Raman)和X射线光电子能谱(XPS)等表征技术对催化剂进行了研究,发现WO_(3)的添加提高了C_(2)选择性,并有效抑制了深度氧化.XRD与CO_(2)-TPD结果表明,WO_(3)的添加不仅有利于金红石型TiO_(2)的形成而且能够中和催化剂表面的强碱位,从而抑制了深度氧化反应.O_(2)-TPD和H_(2)-TPR结果表明,WO_(3)的添加降低了晶格氧(O^(2-))移动性,进而提高了反应的C_(2)选择性.此外,WO_(3)的添加促使了低温氧化偶联活性物种MnTiO_(3)的形成并提高了活性物种的分散性,因此提高了催化剂甲烷氧化偶联的反应活性和选择性.所有Li-Mn/x%WO_(3)/TiO_(2)催化剂中,Li-Mn/5%WO_(3)/TiO_(2)催化剂显示出最佳的OCM反应性能.在750℃,CH_(4)∶O_(2)∶N_(2)=10∶4∶5,GHSV=2280 mL·g^(-1)·h^(-1)条件下,最高的C_(2)产物收率可达16.3%.     

可见光响应Bi2WO6薄膜的制备与光电化学性能

采用非晶态配合物-提拉法在ITO导电玻璃基底上制备得到Bi2WO6薄膜. 采用FE-SEM、XRD、Raman、DRS、光电流响应谱、IPCE等手段, 研究了Bi2WO6薄膜的形貌、结构、光电性能以及薄膜结构与光电性能的关系. 结果表明, 450 ℃以上煅烧可以得到Bi2WO6结晶薄膜, 薄膜由沿(131)晶面趋向生长的Bi2WO6纳米颗粒组成, 颗粒的粒度随煅烧温度的升高而增大, 同时颗粒之间的间距也相应增大. ITO/Bi2WO6薄膜电极在可见光(λ>400 nm)照射下可以产生光电流, 光电流强度与光强度线性相关; 光电流强度和光电转换量子效率受Bi2WO6薄膜结构的影响, 通过控制薄膜的煅烧温度等制备条件, 可以提高薄膜光电极的光电转换量子效率.     

离子交换法制备AgBr/Ag2WO4复合催化剂及其可见光催化性能

以Ag₂WO₄为载体,采用离子交换法合成了新型的AgBr/Ag₂WO₄复合光催化剂.利用XRD、SEM和UV-Vis对AgBr/Ag₂WO₄催化剂进行了表征,在可见光条件下(500 W、λ>420 nm)、以甲基橙(MO)为染料模型研究了AgBr/Ag₂WO₄的光催化活性.结果表明,AgBr/Ag₂WO₄具有比单独的AgBr和Ag₂WO₄更佳的催化活性,其中30%-AgBr/Ag₂WO₄复合催化剂具有最大光催化活性.机理研究表明,在MO的降解过程中,·O₂^-起主要作用,h⁺次之而·OH可以忽略.AgBr和Ag₂WO₄之间构成的异质结有效分离了光生电子和空穴,提高了催化剂的活性.     

Improved photocatalytic activity of WO3 through clustered Fe2O3 for organic degradation in the presence of H2O2

Photocatalytic degradation of organic substrates over WO(3) in an aerated aqueous suspension is very slow due to the difficulty of O(2) reduction by the conduction band electron on WO(3). In this work, we report on H(2)O(2) as an electron scavenger significantly accelerating the photodegradation of phenol and azo-dye X3B in water under UV or visible light. More importantly, an iron-containing WO(3) (FeW) synthesized through thermal decomposition of a ferrotungstenic acid displayed a much higher activity than pure WO(3) (HW) prepared in parallel. As the sintering temperature increased, both FeW and HW showed an exponential increase in activity. The maximum rate constant of phenol degradation obtained with FeW at 400 °C was about 2 times larger than that with HW at 600 °C. Sample characterization with electron paramagnetic resonance (EPR) spectroscopy and other techniques revealed that ferric species (0.3 wt % Fe(2)O(3)) were mainly present as clusters on the oxide surface at 120 °C and then they diffused toward the lattice sites of WO(3) at high temperature, which was detrimental to the photocatalytic reaction. 5,5-Dimethyl-1-pyrroline N-oxide spin-trapping EPR showed that the production of hydroxyl radicals was greatly enhanced upon the addition of H(2)O(2), the trend of which among different catalysts was the same as that of the rate of phenol degradation. The catalysts after excitation at 350 nm displayed a blue emission centered at 469 nm, the intensity of which varied with the catalyst activity nearly as expected. A possible mechanism for the improved photoactivity of WO(3) is proposed involving the electron transfer from WO(3) to Fe(2)O(3) and the reaction of the reduced oxide with H(2)O(2) to generate hydroxyl radicals.     

Effect of alkali-metal ions on the local structure and luminescence for double tungstate compounds AEu(WO4)2 (A = Li, Na, K)

The effect of alkali-metal ions on the local structure and luminescence properties for alkali-metal europium double tungstate compounds AEu(WO(4))(2) (A = Li, Na, K) has been investigated by a dual-space structural technique, atomic pair distribution function (PDF) analysis, and the Rietveld method of powder X-ray diffraction. The compounds AEu(WO(4))(2) (A = Li, Na) crystallize in the isostructure with the tetragonal space group I41/a (No. 88) and show the same luminescence properties in spite of the different doped alkali metals. However, KEu(WO(4))(2) crystallizes in monoclinic symmetry with the space group C2/c (No. 15). Compared with the two other counterparts, KEu(WO(4))(2) exhibits a more effective charge-transfer excitation, a larger Stokes shift, and a broader 612 nm emission band. This phenomenon is ascribed to the lower crystal symmetry in KEu(WO(4))(2), which influences bond distances and the coordination number of Eu(3+). Two complementary methods, the Rietveld method and PDF analysis, reveal that both LiEu(WO(4))(2) and NaEu(WO(4))(2) afford the same local surroundings of Eu(3+). The local structure determined by the Rietveld and PDF methods well account for the observed luminescent properties.     

聚天冬氨酸与钨酸钠复配对白铜B10的缓蚀作用

应用光电化学的方法研究了两种环境友好型缓蚀剂聚冬天氨酸(PASP)和钨酸钠(Na2WO4)的单一配方及其复配对白铜B10在硼砂-硼酸缓冲溶液中的缓蚀作用援研究表明, 在光电流循环伏安测试中, 单一的PASP与Na2WO4均能够使B10表面Cu2O膜引起的p型光电流响应增大, 这说明缓蚀剂增大了Cu2O膜的厚度, 使B10的腐蚀速率减小. 单一的PASP与Na2WO4的最佳添加浓度分别为3和5 mg·L-1, 单一的Na2WO4比单一的PASP使p型光电流响应增大趋势更大. 若以总浓度为5 mg·L-1时对两者进行复配, 当PASP与Na2WO4的质量浓度比为1:1和1:3时, 两者复配比单一使用时的p型电流光响应都更大, B10的腐蚀更小, 即缓蚀剂的效果更好. 交流阻抗测试结果与光电化学测试相一致.     

离子交换法制备高光催化活性Bi2WO6@Bi2S3异质结纳米片

社会经济快速发展的同时, 也带来了日益严峻的环境污染问题. 半导体光催化氧化技术因节能环保而在环境领域有广阔的应用前景. 作为最具有代表性的半导体光催化材料, TiO2因为其禁带宽度(3.2 eV)比较大, 只能被紫外光激发, 因而对太阳能的利用率较低. 作为一种最简单的含铋层状氧化物, Bi2WO6的禁带宽度(2.7 eV)相对较小, 可以部分利用太阳光中的可见光, 因而受到广大研究者的青睐. 但是, Bi2WO6光催化材料的可见光响应范围较窄, 仅能被波长小于450 nm的光激发, 且激发后的光生载流子容易复合, 导致光催化效率不高. 因此, 迫切需要对Bi2WO6光催化材料进行结构修饰与改性,采用拓展其光响应范围和抑制载流子复合, 来提高其光催化活性.本文采用离子交换法原位合成了具有核-壳结构的Bi2S3@Bi2WO6纳米片, 充分利用Bi2S3优良的可见光响应性能和半导体异质结光催化剂的构建, 来提高Bi2WO6的光催化活性. 结果表明, 随着Na2S·9H2O用量从0增加到1.5 g, 所得催化剂的光活性不断提高, X3B的降解速率常数由0.40×10-3min-1增加到6.6×10-3min-1, 催化剂活性提高了16.5倍. 当进一步增加Na2S·9H2O的用量时(1.5-3.0 g), 复合催化剂的光活性下降. 这是由于过多Na2S·9H2O的引入导致在催化剂表面生成了没有光活性的NaBiS2层(Bi2S3+ Na2S = 2NaBiS2), 占据了催化剂的活性位点, 阻碍了染料分子与催化剂的直接接触. Bi2WO6@Bi2S3异质结纳米片光活性的提高, 可归因于Bi2S3的敏化作用极大拓展了复合催化剂的光响应范围; 另一方面, Bi2WO6和Bi2S3两者之间的半导体异质结效应有效促进了光生载流子在空间的有效分离, 抑制了光生电子-空穴的复合, 从而提高了复合催化剂的催化效率. 本研究为其他半导体复合材料的原位生长制备提供了新的思路.     

Nanocrystalline electrodes based on nanoporous-walled WO3 nanotubes for organic-dye-sensitized solar cells

Nanoporous-walled tungsten oxide (WO(3)) nanotubes (NTs), which had a more positive conduction band edge level compared to that of TiO(2), were applied to various organic dyes for dye-sensitized solar cells (DSSCs). The dye-sensitized WO(3) NTs displayed photosensitization for the organic dyes whose lowest unoccupied molecular orbital (LUMO) level was relatively positive to the conventional TiO(2) electrode and, thus, not applicable for electron injection to the TiO(2) electrode. Electron transport time and electron lifetime for the WO(3) electrode in the DSSCs were investigated. In comparison to the DSSCs based on TiO(2), SnO(2), and In(2)O(3), the WO(3) DSSCs displayed the longest lifetime. On the other hand, non-diffusion-like electron transport may be an issue to apply WO(3) for the DSSCs.     

Development of a high-performance anode for lithium ion batteries using novel ordered mesoporous tungsten oxide materials with high electrical conductivity

An ordered mesoporous WO(3-X) with high electrical conductivity (m-WO(3-X)) was prepared and evaluated as an anode material for lithium ion batteries (LIBs). Ordered mesoporous tungsten trioxide (m-WO(3)) with an identical pore structure to that of m-WO(3-X) and bulk WO(3-X) (b-WO(3-X)) was prepared for the comparison purpose. An m-WO(3-X) electrode exhibited a high reversible capacity (748 mAh g(-1), 6.5 Li/W) and a high volumetric capacity (～1500 mAh cm(-3)), which is comparable to the Li metal itself (ca. 2000 mAh cm(-3)). Also, an improved rate capability and a good cyclability were observed in the m-WO(3-X) electrode when compared with m-WO(3) and b-WO(3-X) electrodes. From electrochemical impedance spectroscopy (EIS) analysis, the advanced anode performance of the m-WO(3-X) electrode was probably attributed to large ordered mesopores and a high electrical conductivity. Differential scanning calorimetry (DSC) result displayed that the safety of m-WO(3-X) was more improved than those of graphite and Si anode materials.     

Elucidating the structure-dependent photocatalytic properties of Bi2WO6: a synthesis guided investigation

Polycrystalline microspheres and single-crystalline microplates of Bi(2)WO(6) have been synthesized by ultrasonic spray pyrolysis. Herein, these materials are evaluated as photocatalysts for the visible light mediated degradation of rhodamine B, a model pollutant, and the results compared to those obtained with Bi(2)WO(6) prepared by traditional methods. The microplates, which displayed the best crystallinity and highest surface area, were anticipated to facilitate the greatest rate of dye photodegradation. However, the polycrystalline microspheres outperformed both the Bi(2)WO(6) microplates and traditional samples. To understand the origin of this result, the local and macroscale structures of the Bi(2)WO(6) samples were comprehensively characterized by spectroscopy techniques (diffuse reflectance, fluorescence, Raman, and X-ray photoelectron spectroscopy) as well as electron microscopy and diffraction. This analysis found that the enhanced performance of the Bi(2)WO(6) microspheres results from the expression of a hydrophilic surface, a low concentration of point defects, and a moderate surface area. This finding highlights the significant role synthesis plays in imparting structure and functionality to solid materials.     

Free volume hole size of Cyanate ester resin/Epoxy resin interpenetrating networks and its correlations with physical properties

Cyanate ester (CE) resin was blended with epoxy resin (EP) at different mass ratios (CE/EP: 100/0, 90/10, 70/30, 50/50, 30/70, 10/90, and 0/100). The curing process of the blend system was characterized by Fourier transform infrared spectrometry (FTIR) and differential scanning calorimetry (DSC). Examination of the mechanical properties, thermal stability, and morphology of the blend systems showed that addition of epoxy resin resulted in improved toughness but a little sacrifice in thermal stability when compared with neat CE. The free volume size of the blend system determined by positron annihilation lifetime spectroscopy (PALS) decreased with the epoxy resin content, which is consistent with the chemical structure changes for the copolymerization between CE and EP. The crosslinking units of curing products (oxazoline, oxazolidinone, and polyether network) of the blends are all smaller in size than those of triazine ring structure from neat CE. Therefore, the free volume size of the blends decreases with increase of EP content. The correlations between the free volume properties and other physical properties (thermal stability and mechanical properties) have also been discussed.