高度单分散聚乙烯基倍半硅氧烷球形纳米粒子的制备及性能

在水溶液中, 以乙烯基三乙氧基硅烷(VTES)为前驱体, 氨水(NH₃ · H₂O)为催化剂, 在表面活性剂十二烷基苯磺酸钠(SDBS)存在下, 通过溶胶-凝胶法成功合成了具有不同粒径、 高度单分散的聚乙烯基倍半硅氧烷(PVSQ)球形纳米粒子. 研究结果表明, 催化剂NH₃ · H₂O与表面活性剂SDBS的用量对PVSQ的粒径和粒径分布影响很大, 而前驱体VTES的用量对PVSQ的粒径无明显影响. 通过场发射扫描电子显微镜(FESEM)、 傅里叶变换红外光谱(FTIR)、 X射线光电子能谱(XPS)及热重(TG)分析对产物的形貌、 粒径和粒径分布、 结构及热性能进行了表征.     

CuO-WO3-ZrO2的结构和性质对苯甲醛加氢反应催化性能的影响

采用共沉淀法制备了不同CuO和WO₃含量的CuO-WO₃-ZrO₂催化剂. 利用X射线衍射(XRD)、 扫描电子显微镜(SEM)、 X射线荧光光谱(XRF)、 N₂气物理吸附、 氢气程序升温还原(H₂-TPR)、 X射线光电子能谱(XPS)及程序升温脱附(TPD)等手段对催化剂的结构和表面性质进行了表征. 结果表明, WO₃的引入可以调变ZrO₂的晶型, 从而使催化剂的比表面积和孔径发生变化, 促进CuO在催化剂表面的分散, 并影响催化剂的酸碱性. 在苯甲醛加氢制备苯甲醇反应中, 以CuO质量分数为18%, WO₃质量分数为10%的CuO-WO₃-ZrO₂为催化剂时苯甲醛单程转化率达到92.03%, 产物苯甲醇的选择性为94.76%.     

负载型AgBr/CaWO4催化剂的制备及其可见光催化活性

采用化学取代的方式将AgBr负载到Ca WO₄载体上形成新型的AgBr/Ca WO₄复合结构光催化剂.利用XRD、SEM和UV-Vis对AgBr/Ca WO₄催化剂进行了表征.在可见光条件下(500 W、λ>420 nm)研究了AgBr的负载量、催化剂用量对甲基橙(MO)溶液的催化降解性能.结果表明,AgBr/Ca WO₄在可见光下表现出良好的催化活性,甲基橙溶液的降解遵从假一级动力学方程.AgBr的负载量和催化剂用量分别增加时,AgBr/Ca WO₄催化剂对甲基橙的催化活性增强,均趋向于最大值.     

集成二维层状CdS/WO3S型异质结及金属化Ti3C2MXene基欧姆结高效光催化产氢

开发低成本的半导体光催化剂以实现可见光下高效、持久的光催化分解水产氢是一个非常具有挑战性的课题.近年来,具有高产氢活性的CdS光催化剂引起了人们的研究兴趣.但是光生电子-空穴对快速复合、反应活性位点不足以及严重的光腐蚀等问题,严重地制约了CdS在光催化领域的实际应用.构建S型异质结和负载助催化剂被认为是促进光生电子空穴分离和加速产氢动力学的有效策略.本文通过在低成本的WO₃和Ti₃C₂MXene(MX)纳米片上生长CdS纳米片,设计并构建了具有二维耦合界面的2D/2D/2D层状异质结光催化剂,以实现高效的可见光光催化分解水产氢.首先通过水热煅烧和刻蚀的方法分别制备了WO₃和MX纳米片,然后以乙酸镉和硫脲为原料在乙二胺溶剂中通过水热法合成了MX-CdS/WO₃层状异质结光催化剂.在可见光下,以乳酸为牺牲剂测试了光催化剂的产氢活性且经过4次连续的循环反应,MX-CdS/WO₃体系展现出良好的活性及稳定性.在可见光的照射下,MX-CdS/WO₃层状异质结光催化剂最高的可见光光催化分解水产氢速率达到了27.5 mmol/g/h,是纯CdS纳米片的11倍.与此同时,在450 nm的光照下,表观量子效率达到了12.0%.为了深入探讨其高效产氢机理,通过X射线衍射、X射线光电子能谱、原子力显微镜、透射电镜、高分辨电子显微镜等对MX-CdS/WO₃体系的组成和结构进行分析.结果表明,实验成功地合成了CdS,WO₃和MX三种纳米片及其复合材料.通过紫外-可见漫反射光谱研究了样品材料的光吸收能力.通过表面光电压、稳态及瞬态荧光光谱等研究了材料的电荷载流子复合和转移行为,发现MX-CdS/WO₃的光生电子空穴对相比与纯CdS或者二元复合材料具有更高的分离效率.UPS和ESR等表征结果说明,材料内部电场的方向和在光照条件下光生载流子的迁移方向,从而证实了S型异质结和欧姆结的成功构建.综上,在MX-CdS/WO₃光催化剂体系中,S型异质结形成较强的界面电场能够有效促进CdS纳米片与WO₃纳米片之间光生电子-空穴对的分离.同时,二维Ti₃C₂MXene纳米片作为辅助催化剂,通过与CdS/WO₃纳米片构建欧姆结,进而提供大量的电子转移途径和更多的析氢反应活性位点,使得CdS光催化剂的光催化活性和稳定性得到了很大的提升.通过构建S型内建电场、欧姆结和2D/2D界面可以协同提高CdS纳米片的光催化性能,从而加速光生电子在异质结中的分离和利用.本文所采用基于S型异质结与欧姆结基助催化剂之间的耦合策略可以作为一种通用策略扩展到其它传统半导体光催化剂的改性中,从而推进高效光催化产氢材料的有效合成.     

不同钨基催化剂上葡萄糖和纤维二糖催化转化制备乙二醇

以葡萄糖和纤维二糖为模型化合物研究了逆羟醛缩合速率与加氢速率之间的匹配对纤维素转化产物分布的影响。葡萄糖和纤维二糖在共浸渍的Ni-WO₃/SBA-15催化剂和物理混合的Ni/SBA-15、WO₃/SBA-15催化剂上具有不同的产物分布。葡萄糖和纤维二糖在不同钨基催化剂上具有不同的乙二醇收率,其顺序为WO₃ < WO₃/SBA-15 < (NH₄)₆W₇O₂₄·6H₂O (偏钨酸铵),这与它们的颗粒粒径成反比。在相同钨基催化剂用量条件下,葡萄糖转化中乙二醇收率小于纤维二糖。     

三氧化钨基催化剂在纤维素选择性转化合成二元醇反应中的活性相态（英文）

纤维素是自然界最丰富的生物质资源,大量来源于农林废弃物.近年来,人们相继发展了以纤维素为原料合成高附加值化学品的多条路径,它们有望替代目前相应的化石资源路径.其中,以碳化钨(W₂C)、三氧化钨(WO₃)和钨酸(H₂WO₄)为代表的钨基催化剂表现出选择性断裂糖分子C-C键的独特催化性质,结合不同种类的共催化剂,可以将纤维素直接解聚转化为乙二醇、1,2-丙二醇、乙醇和乳酸等多种重要的C_2,3产物.然而,钨基催化剂在纤维素反应中的真实状态和活性相结构尚不确定.W₂C最早被报道可以高效催化纤维素直接转化为乙二醇.随后,我们发现晶态WO₃也具有相似的催化性能,W₂C在反应后其表面被WO₃所覆盖.在纤维素反应中,氢气可以将H₂WO₄还原为钨青铜(H_xWO₃)物种.本文以WO₃和H₂     

Ag3PO4量子点/石墨相氮化碳纳米片复合光催化剂的制备及其对苯甲醇选择性氧化活性

以热氧化剥离法得到的超薄石墨相氮化碳(g-C₃N₄)纳米片为载体,首次在室温条件下,制备了系列Ag₃PO₄量子点/g-C₃N₄纳米片复合光催化剂;通过透射电子显微镜(TEM)、高分辨透射电子显微镜(HRTEM)、X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、紫外-可见漫反射光谱(UV-Vis DRS)、荧光光谱(PL),对复合光催化剂的形貌、结构和光学性质进行了表征,考察了系列光催化剂对苯甲醇的光催化选择性氧化性能。 结果表明,粒径为3~5 nm Ag₃PO₄颗粒均匀分散g-C₃N₄纳米片上,结晶度良好。 以乙腈为溶剂时,当m(Ag₃PO₄)/m(g-C₃N₄)=0.6时,苯甲醇具有32.1%的最大转化率,对产物苯甲醛具有90%的最高选择性;活性物种捕捉实验结果表明,该催化氧化反应的主要活性物是光生空穴的氧化作用,能带计算结果表明,该复合催化剂结构具有合适的苯甲醇的氧化电位而选择性生成苯甲醛。     

中空树枝状三氧化钨载铂催化剂对甲醇的电催化氧化性能研究

采用水热法和牺牲模板法相结合制备具有中空树枝结构的三氧化钨载体(d-WO₃),在其表面进一步负载活性成分Pt,得到纳米Pt/d-WO₃复合催化剂。采用X射线粉末衍射(XRD)、透射电镜(TEM)和比表面积和孔结构分析(BET)等对催化剂的形貌和结构进行了表征。结果表明,三氧化钨具有长6 μm和宽2 μm的中空树枝状结构,孔径分布主要集中在20~120 nm,比表面积为24 m²/g,平均粒径为7.2 nm的Pt纳米粒子均匀分布在其表面。采用循环伏安和计时电流法研究了Pt/d-WO₃催化剂在酸性溶液中对甲醇的电催化氧化性能。结果表明,Pt/d-WO₃催化剂比Pt/C和Pt/WO₃催化剂对甲醇有更高的电催化氧化活性和稳定性。d-WO₃所具有的中空介孔结构和双功能作用机理有利于甲醇在铂表面的直接脱氢氧化过程。     

二维/一维BiOBr0.5Cl0.5/WO3 S型异质结助力光催化CO2还原

S型异质结不但可以提高载流子的分离效率,还可以维持较强的氧化还原能力。因此,构建S型异质是提高光催化二氧化碳还原反应的有效途径。本研究通过静电自组装法构建了具有近红外光响应(> 780 nm)的二维BiOBr_0.5Cl_0.5纳米片和一维WO₃纳米棒S型异质结光催化剂,并用于高效还原二氧化碳。能带位置和界面电子相互作用的综合分析表明：在光催化二氧化碳还原反应过程中,BiOBr_0.5Cl_0.5/WO₃遵循S型电子转移路径;不仅提高了载流子的高效分离,还维持了两相(BiOBr_0.5Cl_0.5和WO₃)较高的氧化还原能力。此外,二维纳米片/一维纳米棒的结构使得半导体之间具备良好的界面接触,有利于载流子的分离,且暴露更多的活性位点,最终提高催化效率。结果显示,BiOBr_0.5Cl_0.5/WO₃异质结催化剂表现出较高的CO₂还原能力和CO选择性,CO的产率高达16.68 μmol∙g^-1∙h^-1,分别是BiOBr_0.5Cl_0.5的1.7倍和WO₃的9.8倍。本工作为构建S型二维/一维异质结光催化剂高效还原二氧化碳提供了新的思路。     

FeOOH明胶复合纳米粒子的制备与表征

采用两步法制备具有弱磁性的FeOOH纳米粒子和FeOOH明胶复合纳米粒子. 透射电镜、扫描电镜、红外光谱、X射线衍射和磁滞回线等测量结果表明: 在一定FeCl₃/Fe₂(SO₄)₃/H₂O摩尔比条件下, 加入十二烷基苯磺酸钠(ABS)溶液, 可制备粒径为30～150 nm弱磁性FeOOH纳米粒子, 其磁性可达6.5×10^－6 emu/g. 弱磁性FeOOH纳米粒子可被明胶包裹. 随着FeCl₃/Fe₂(SO₄)₃摩尔比减小或明胶浓度增加, 纳米球粒径增大, 磁性降低. 随着固化时间增加, FeOOH明胶复合纳米粒子的粒径先增大后减小.     

纳米WO3粉体的制备与光催化活性研究

报道了以钨酸钠和盐酸为主要原料,通过气液反应制备纳米WO3粉体光催化剂的新方法．在XPS,XRD,TEM等手段对催化剂进行了表征的基础上,又讨论了焙烧温度和乙醇加入量对催化剂粒度大小以及光催化活性的影响．同时对纳米WO3粉体催化剂的光催化重整乙醇制氢反应活性进行了研究,观察了产氢效率和光电化学行为．研究结果表明,气液反应法是一种简单有效的制备纳米WO3粉体催化剂的方法,并显示出较好的光催化活性;该方法所得的三氧化钨粉末粒子平均直径在100nm以下;钨酸钠溶液中乙醇加入量对三氧化钨粉末粒子的尺寸和分散性都有影响,随着乙醇量的增加,粒子尺寸减小,且分散性较好．焙烧温度引起的WO3粒子晶体结构的变化会导致光氧化还原电位变化,是引起光催化活性差异的主要原因．     

NaGd（WO4）2:Yb3+,Tm3+纳米粉的制备与上转换发光性能

以聚乙二醇为络合剂,采用水热法成功制备了NaGd(WO4)2:Yb3+,Tm3+纳米粉。运用X射线粉末衍射、扫描电镜和光谱分析对制备的样品结构和发光性能进行了表征。结果表明,NaGd(WO4)2:Yb3+,Tm3+为四方晶系,晶粒尺寸约为50 nm。在980 nm半导体激光器激发下获得了发射光谱,有3个发射峰,发光中心位于455,476和650 nm,分别对应1D2→3F4,1G4→3H6,1G4→3F4的跃迁。讨论了Yb3+,Tm3+能量转换过程和机制。泵浦功率与发光强度关系表明,455,476和650 nm的3个发射均属于三光子过程。     

Crystallographically oriented mesoporous WO3 films: synthesis, characterization, and applications.

Mesoporous semiconducting films consisting of preferentially orientated monoclinic-phase nanocrystals of tungsten trioxide have been prepared using a novel version of the sol-gel method. Transformations undergone by a colloidal solution of tungstic acid, stabilized by an organic additive such as poly(ethylene glycol) (PEG) 300, as a function of the annealing temperature have been followed by means of a confocal Raman microscope. The shape and size of WO3 nanoparticles, the porosity, and the properties of the films depend critically on preparation parameters, such as the tungstic acid/PEG ratio, the PEG chain length, and the annealing conditions. Well-crystallized WO3 films combine excellent photoresponse to the blue region of the solar spectrum, up to 500 nm, with good transparency at wavelengths larger than 550 nm. Particular applications of these nanocrystalline WO3 films include photoelectrochemical and electrochromic devices.     

表面活性剂对制备MoS2纳米微粉的影响

Mo0_2纳米微粉在催化l‘l、敏感元件［‘·’］及磁记录材料［‘］等方面具有特殊用途,其传统制备方法是通过在高温下用氢还原l’,‘l,利用这种方法制备M。0。纳米微粉、所得产品粒子尺寸较大,比表面积小,且反应在条件苛刻,从而限制了M00。纳米微粉的使用范围．文献曾报导用y一辐照法制备了一系列金属、合金和氧化物的纳米粒子”－‘Q’,这种方法利用水辐解产生的水合电子（efo）作为还原剂,具有在常温常压下进行操作的显著优点,因而受到普遍关注．本实验室l‘’1曾报导通过v一辐照法可制备Moo。纳米非晶,其颗粒尺寸为8－30urn…     

表面活性剂对制备MoO2纳米微粉的影响

Using polyvinyl alcohol(PVA)and sodium dodecyl sulfate(SDS)as the surfactants respectively,nano-size amorphous molybdenum dioxide powders were prepared by γ-radiation method at ambient pressure and room temperature,and the products were characterized by use of laser Raman spectra(LRS)、 X-ray powder diffraction(XRD)and transmisson electron micrograph(TEM).The experimental results reveal that the relative pure samples can be obtained using PVA as surfactant,and the average particle size is about 10nm,but using SDS as surfactant,the samples with the average particle size 30nm are a mixture of MoO2 and MoO3.This suggestes PVA is prior to SDS in the preparation of nano-sized amorphous molybdenum dioxide powders by γ-radiation method.     

Synthesis and characterization of ultrathin WO3 nanodisks utilizing long-chain poly(ethylene glycol)

Metal oxide nanostructures hold great potential for photovoltaic (PV), photoelectrochemical (PEC), and photocatalytic applications. Whereas thin films of various materials of both nanoparticle and nanorod morphologies have been widely investigated, there have been few inquiries into nanodisk structures. Here, we report the synthesis of ultrathin WO3 nanodisks using a wet chemical route with poly(ethylene glycol) (PEG) as a surface modulator. The reported nanodisk structure is based on the interaction of the nonionic 10000 g/mol PEG molecules with tungsten oxoanion precursors. The WO3 nanostructures formed are dominated by very thin disks with dimensions on the nanometer to micrometer scale. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images reveal the structures to have dimensions on the order of 350-1000 nm in length, 200-750 nm in width, and 7-18 nm in thickness and possessing textured single-crystalline features. A number of analytical techniques were used to characterize the WO3 nanodisks, including selected-area electron diffraction (SAED), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), atomic force microscopy (AFM), Raman scattering spectroscopy, UV-visible spectrophotometry, and cyclic voltammetry (CV). The growth of the WO3 nanodisks was inhibited in the [010] crystal direction, leading to ultrathin morphologies in the monoclinic crystal phase. The large flat surface area and high aspect ratio of the WO3 nanodisks are potentially useful in PEC cells for hydrogen production via direct water splitting, as has been demonstrated in a preliminary experiment with external bias.     

Formation of water-in-oil (W/O) nano-emulsions in a water/mixed non-ionic surfactant/oil systems prepared by a low-energy emulsification method

W/O nano-emulsion formation by a low-energy emulsification method is described for the first time. The nano-emulsions have been formed in water/mixed Cremophor EL:Cremophor WO7 surfactant/isopropyl myristate systems at Cremophor EL:Cremophor WO7 ratios between 1:2 and 1:9, by slow addition of isopropyl myristate to surfactant/water mixtures. Phase behaviour studies have showed that the compositions giving rise to W/O nano-emulsions belong to multiphase regions, one of the phases being a lamellar liquid crystalline phase. The droplet size of the nano-emulsions at a fixed oil concentration of 85% and mixed surfactants/water ratio of 70/30 ranged from 60 to 160 nm as Cremophor EL:Cremophor WO7 ratio increased from 1:8 to 1:2. These nano-emulsions showed high kinetic stability. No phase separation was observed during 5 months in nano-emulsions of the water/Cremophor EL:Cremophor WO7 1:8/isopropyl myristate system with 85% oil concentration, although droplet size experienced an increase with time.     

Ultrasonically induced Au nanoprisms and their size manipulation based on aging

A simple sonochemical approach was developed for the synthesis of single-crystal Au nanoprisms with triangular or hexagonal shape, 30-40 nm planar dimension, and 6-10 nm thickness in an ethylene glycol solution. It has been shown that ethylene glycol, the surfactant poly(vinylpyrrolidone), and ultrasonic irradiation play important roles in the formation of Au nanoprisms. The subsequent aging induces the growth of Au nanoprisms, which is attributed to the existence of residual reduced Au degrees atoms and Au clusters in the solution. Further growth of Au nanoprisms could be realized by adding a given amount of HAuCl4 to the irradiated and aged Au nanodisk colloidal solution, which provides a simple and an effective method to synthesize Au nanoprisms with different sizes. Au nanoprisms with planar sizes from 70 to 400 nm have been successfully synthesized based on this strategy.     

Yb3+/Tm3+掺杂的NaY(WO4)2纳米晶的制备及发光特性

以聚乙二醇为配位剂,用水热法制备出纳米级上转换发光粉Yb3+和Tm3+共掺杂的NaY(WO4)2。研究了不同cYb/cTm对上转换发光强度的影响,实验表明当cYb/cTm=5∶1时,上转换发光强度最强。用XRD,SEM确定了Yb3+和Tm3+共掺杂的NaY(WO4)2是四方晶系,其粒径在25~35 nm范围,且分散均匀。用980 nm半导体激光器(LD)对其进行激发,在室温下观察到了365 nm附近紫外发射峰、456 nm,476 nm附近的蓝光发射峰和648 nm附近的红光发射峰,分别对应于Tm3+离子的1D2→3H6,1D2→3F4,1G4→3H6和1G4→3F4的跃迁。根据泵浦功率与发光强度的关系得出紫外发射峰、蓝光和红光发射均为双光子过程。     

Structural stability and phase transitions in WO3 thin films

Tungsten oxide (WO3) thin films have been produced by KrF excimer laser (lambda = 248 nm) ablation of bulk ceramic WO3 targets. The crystal structure, surface morphology, chemical composition, and structural stability of the WO3 thin films have been studied in detail. Characterization of freshly grown WO3 thin films has been performed using X-ray diffraction (XRD), atomic force microscopy (AFM), energy-dispersive X-ray spectroscopy (EDX), Raman spectroscopy (RS), transmission electron microscopy (TEM), and selected area electron diffraction (SAED) measurements. The results indicate that the freshly grown WO3 thin films are nearly stoichiometric and well crystallized as monoclinic WO3. The surface morphology of the resulting WO3 thin film has grains of approximately 60 nm in size with a root-mean-square (rms) surface roughness of 10 nm. The phase transformations in the WO3 thin films were investigated by annealing in the TEM column at 30-500 degrees C. The phase transitions in the WO3 thin films occur in sequence as the temperature is increased: monoclinic --> orthorhombic --> hexagonal. Distortion and tilting of the WO6 octahedra occurs with the phase transitions and significantly affects the electronic properties and, hence, the electrochemical device applications of WO3.