SnO2纳米微晶的合成及气敏性分析

采用溶剂热技术分别在油酸体系及无水乙醇体系中成功地合成了球形和菱形的 Sn O2 纳米微晶。通过X-射线粉末衍射、选区电子衍射、透射电镜和比表面积测定等手段对合成产物的结构进行了表征 ,并对合成产物的气敏性进行了分析。结果表明 :含有精细结构的球形 Sn O2 纳米微晶的比表面积为 1 4 6 m2· g-1,灵敏温度为 1 6 0℃左右 ,适合于作气敏元件材料     

三维有序In2O3纳米线阵列的合成及纳米结构有序度对气敏性能的影响

采用SBA-15硬模板复制技术合成出三维有序纳米线阵列结构的In₂O₃, 通过离心分离获得了2个尺寸不同的块状颗粒样品. 利用XRD、 SEM和紫外-可见光谱对样品的晶体结构、 晶粒尺寸、 形貌及带隙宽度进行了分析. 结果表明, 2个样品具有相同的纳米微结构, 均为由晶粒尺寸约12 nm的近球形In₂O₃晶粒规则有序排列生长而成的三维纳米线阵列结构, 纳米线的直径约为12 nm, 间距约为2 nm, 且块状尺寸较大样品的带隙宽度略大. In₂O₃样品对乙醇气体的气敏性能测试结果显示, 当乙醇气体在空气中的体积分数为100×10^-6, 温度为320 ℃时, A样品的灵敏度达到50. 6, 优于尺寸较小的B样品. 通过对比研究发现该纳米结构样品的气敏性能明显优于同级别纳米颗粒和介孔结构材料, 纳米材料的气敏性能随纳米结构形态有序度的增加而提高.     

氢化石墨纳米结构的合成及尺寸相关的荧光性质

在溶剂热反应条件下(180℃),利用还原剂金属钾对卤代苯(溴苯和二溴苯)中的C—Br键进行选择性裂解,而含氢的碳六元环仍稳定且之间可以发生聚合成键,成功合成了2种不同的氢化石墨纳米结构,获得的产物分别呈黄褐色和黑色.拉曼和红外光谱分析结果表明,黑色产物为尺寸约2 nm的氢化石墨纳米片,而黄褐色样品为尺寸更小的氢化碳纳米结构;X射线衍射分析结果表明,2种产物都具有菱方结构但结晶性较低.对合成的氢化石墨纳米结构的荧光性质分析发现,样品具有尺寸相关的荧光现象,同等激发条件下,尺寸较小的黄褐色样品的发光强度约为黑色样品的15倍.     

热处理温度对溶剂热合成Co3O4纳米片气敏和吸附性能之影响

以Co（Ac）₂·4H₂O和六次甲基四胺（HMTA）为起始反应物,聚氧乙烯-聚氧丙烯-聚氧乙烯（P123）为表面活性剂,在乙二醇（EG）和水混合溶剂中用溶剂热法得到中间产物,通过煅烧热处理制备了Co₃O₄纳米片。利用XRD、SEM和N₂吸附-脱附等方法进行了样品表征,研究了不同热处理温度对产物形貌和结晶度的影响,以及所制备纳米片的气敏性能。根据气敏测试和吸附性能结果,分析了气敏机理和吸附动力学。结果表明：热处理温度是影响产物形貌的关键因素,350℃是最佳的热处理温度,此时得到的纳米片最薄也最均匀。由于产物形貌变化改变了材料的比表面积,进而影响到产物的气敏性能和吸附性能。总体而言,纳米片厚度越小,比表面面积越大,材料的气敏灵敏度和吸附效率越高。     

热处理温度对溶剂热合成Co3O4纳米片气敏和吸附性能之影响

以Co(Ac)2·4H_2O和六次甲基四胺(HMTA)为起始反应物,聚氧乙烯-聚氧丙烯-聚氧乙烯(P123)为表面活性剂,在乙二醇(EG)和水混合溶剂中用溶剂热法得到中间产物,通过煅烧热处理制备了Co_3O_4纳米片。利用XRD、SEM和N_2吸附-脱附等方法进行了样品表征,研究了不同热处理温度对产物形貌和结晶度的影响,以及所制备纳米片的气敏性能。根据气敏测试和吸附性能结果,分析了气敏机理和吸附动力学。结果表明:热处理温度是影响产物形貌的关键因素,350℃是最佳的热处理温度,此时得到的纳米片最薄也最均匀。由于产物形貌变化改变了材料的比表面积,进而影响到产物的气敏性能和吸附性能。总体而言,纳米片厚度越小,比表面积越大,材料的气敏灵敏度和吸附效率越高。     

CdS和CdSe新型纳米结构的高效溶剂热合成

采用快速高效的溶剂热法合成了海星形CdS纳米结构和一维CdSe纳米结构。用XRD、SEM和UV-Vis等表征手段对产物进行了表征，结果表明产物为单一的CdS和CdSe纳米结构，且CdS纳米结构具有良好的分散性，其形成极大地受到pH值影响，而CdSe先形成层状的二维结构、再形成一维纳米结构。     

溶剂热法制备纳米氧化镍及其表征

以乙酰丙酮镍、油酸、油胺为原料，十八烯为溶剂，聚乙烯吡咯烷酮为表面活性剂，采用溶剂热法，在不同反应条件制备了纳米级氧化镍材料.通过X射线衍射（X-ray diffraction，XRD）、透射电子显微镜（Transmission electron microscope，TEM）、紫外-可见光吸收光谱（Ultraviolet-visible spectroscopy，UV-Vis）光谱分析以及塔菲尔（Tafel）测试考察了反应物比例、保温时间、表面活性剂（PVP）、油胺的量对产物微结构、粒径、形貌、光学以及电化学活性性能的影响.实验结果表明：在反应物n[Ni（acac）₂]∶n（OA）=1∶2、添加剂PVP质量分数为1.66%、油胺物质的量为30 mmol、200℃下保温8 h时，可获得粒径约为30～40 nm纯相氧化镍，具有最佳电化学活性，交换电流密度为J₀=1.23×10^-2 mA·cm^-2.     

钛酸钠纳米带的合成、表征与气敏性能

通过钛酸丁酯与氢氧化钠浓溶液的两步水热反应合成出宽度为20～240 nm、厚度为10～40 nm、长度达几十微米的单一物相的Na₂Ti₃O₇纳米带。用X-射线衍射和电子显微镜分别表征了它们的结构和形貌。这些纳米带被加工成化学电阻型传感器以测量气敏特性。测试表明在350～400 ℃之间对丙酮、乙醇和二硫化碳具有明显感应,而对一氧化碳、苯、氨气和30%的甲醛水溶液几乎不敏感。用化学吸附模型解释其气敏机理。     

两种一维纳米结构钒氧化物的合成与表征

在水热条件下，分别利用十六胺和十六烷基三甲基溴化铵为模板，合成了两种一维纳米结构的钒氧化物：纳米管和纳米棒，采用XRD、TEM、HRTEM、FT-IR、TG/DTA对产物的形貌和结构进行了表征。研究表明，纳米管的长度主要分布在1～10 μm，外径50～100 nm，内径10～30 nm；纳米棒长1～2 μm，径向尺寸50～200 nm。     

一步法溶剂热催化合成纳米碳纤维

利用四氢呋喃为溶剂和碳源,通过溶剂热催化方法在500 ℃一步合成了纳米碳纤维,X-射线衍射（XRD）分析显示此法合成的碳纤维晶型为碳的六方石墨相,场发射电镜(FESEM)和透射电镜(TEM)照片进一步表明碳纤维平均直径为100 nm,长度达几百纳米至几微米,高分辨电镜照片揭示产品中碳的晶间距为0.34 nm;产品纯度通过热重法（TGA）分析;同时,拉曼光谱图显示在1 347和1 584 cm^-1处有2个强峰,这与石墨相碳的典型拉曼光谱图是一致的。     

Synthesis and Characterization of Macroporous Tungsten Oxide Films for Electrochromic Application

Macroporous tungsten oxide films have been prepared by combining a nonhydrolytic sol-gel method with a molecular assembly templating strategy. The material has been prepared by hydrolysis of an ethanolic solution of tungsten ethoxide in the presence of polyethylene glycol (PEG), followed by calcination of the dip-coated films. AFM images indicated that an important morphological diversity can be obtained by simply varying the amount of PEG in the coating solution and the conditions of the heat-treatment. The formation of nanostructures of controlled shapes and patterns (fibrils or striped phases) with relatively uniform channel spacings is accounted for by strong hydrogen bonding interactions between the PEG and the partially hydrolyzed tungsten oxide oligomers. XRD and FTIR data showed that PEG delays the crystallization of WO₃. When compared to sol-gel prepared tungsten oxide fims prepared without PEG, the coloration efficiency of the macroporous films appears to be significantly improved especially in the near-infrared region.     

二硫代钨酸铵晶体的合成、表征与热分解机理的研究

本工作用偏钨酸铵和硫化铵为原料，在水溶液中合成二硫代钨酸铵晶体[(NH₄)₂WO₂S₂]。用紫外-可见光谱(UV-Vis)的方法研究了二硫代钨酸铵晶体的形成机理。采用元素分析、X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、激光拉曼光谱(LRS)等对化合物进行了表征。结果表明采用该方法制备出的二硫代钨酸铵晶体，晶型良好。热重-差热分析(TG-DTA)、原位X射线衍射(in situ XRD)和FTIR等结果表明二硫代钨酸铵晶体在氢气气氛下的热分解主要发生在160～450 ℃之间，分两步进行，首先分解为{WOS₂}，随后转化为二硫化钨。     

碳化钨纳米晶合成及其电化学性能

用Mg作还原剂,无水乙醇和WO3分别作为C源和W源,采用简单的溶剂热法合成了碳化钨(WC)纳米晶,并讨论了温度和时间对合成WC的影响,以及其形成的机理.通过X射线衍射、透射电子显微镜、能量色散谱和电化学方法表征了WC的物相结构、表面形貌、化学组成和电化学性能.结果表明,合成温度低至500℃时也能合成六方WC相.生成C的量超过W的量,说明纯化后的产物由C和WC组成.WC的粒径大约在40~70nm,分布于膜状碳上.将溶剂热法制备出的WC加入Pt/C中,其协同催化氧还原效果非常明显,起峰电势比Pt/C催化剂正移了173mV.     

介稳态氧化钨超微粉体的水热合成与光致变色性质研究

Under hydrothermal conditions, the superfine powders of cubic pyrochlore-type of tungsten oxide and hexagonal tungsten bronze were obtained by using Na₂WO₄·2H₂O as the starting material. The products were characterized by XRD, TG, IR, UV and EPMA, respectively. The effects of the pH value, the acid concentration, reaction temperature and time on the structure and particle size of products were investigated in detail. The conditions for the preparation of superfine powders of tungsten oxide were optimized. The pH 2.5～4.5 of the reaction system led to the formation of a pyrochlore phase and pH 0.5～2.0 gave the hexagonal tungsten bronze structure. The photochromism property of the hexagonal tungsten bronze was studied. The results show that pyrochlore and bronze phases are decomposed at 300 ℃ and 450 ℃, respectively. With the increasing of temperature, the structure of the two oxides changes. The pyrochlore-type powder changes completely into triclinic Na₂W₄O₁₃ around 500 ℃, while the bronze phase into a mixture of Na₂W₆O₁₉ and triclinic WO₃ at 550 ℃. The powder of the hexagonal tungsten bronze showed better photochromism property.     

水热合成二硫化钨/石墨烯复合材料及其氧还原性能

以六氯化钨、硫代乙酰胺、氧化石墨烯为原料,采用一步水热法合成了二维的二硫化钨/石墨烯(WS_2/RGO)复合材料。水热合成的WS_2/RGO具有薄层的二维结构,且由于石墨烯的存在,WS_2以较少的层数形成薄片状生长在石墨烯的表面。尝试将这种非Pt类材料用于电催化氧化原反应,测试结果表明,WS_2在碱性条件下氧还原活性非常低,但是复合RGO形成WS_2/RGO复合材料后,电催化氧化原性能有了极大的提高,其起始电位为-0.17 V(vs SCE),转移电子数为3.7,极限电流密度为2.5 m A·cm-2,同时其具有较好的抗甲醇性能和循环稳定性。这是因为WS_2/RGO复合材料的二维结构具有更高的电子传输速率,同时硫化钨和石墨烯可以发挥协同催化作用。这种新型的二硫化钨/石墨烯(WS_2/RGO)复合材料作为非贵金属催化剂表现出良好的氧还原性能,在燃料电池上具有较好的应用前景。     

水热合成二硫化钨/石墨烯复合材料及其氧还原性能

以六氯化钨、硫代乙酰胺、氧化石墨烯为原料,采用一步水热法合成了二维的二硫化钨/石墨烯(WS₂/RGO)复合材料。水热合成的WS₂/RGO具有薄层的二维结构,且由于石墨烯的存在,WS₂以较少的层数形成薄片状生长在石墨烯的表面。尝试将这种非Pt类材料用于电催化氧化原反应,测试结果表明,WS₂在碱性条件下氧还原活性非常低,但是复合RGO形成WS₂/RGO复合材料后,电催化氧化原性能有了极大的提高,其起始电位为-0.17 V(vs SCE),转移电子数为3.7,极限电流密度为2.5 mA·cm^-2,同时其具有较好的抗甲醇性能和循环稳定性。这是因为WS₂/RGO复合材料的二维结构具有更高的电子传输速率,同时硫化钨和石墨烯可以发挥协同催化作用。这种新型的二硫化钨/石墨烯(WS₂/RGO)复合材料作为非贵金属催化剂表现出良好的氧还原性能,在燃料电池上具有较好的应用前景。     

水热法制备微纳结构氧化钨

氧化钨(WOx)无机半导体材料因其独特的物理化学性质及在气敏、光催化、电致变色、光致变色和场发射等领域的广泛应用,得到人们的普遍关注。近年来,研究者采用水热法制备出多种不同尺寸和形貌的氧化钨半导体材料。本文结合本课题组在水热法制备WOx粉体方面的最新工作,综述了近十年水热法制备微米及纳米级氧化钨粉体的研究进展,探讨了原料、辅助试剂、表面活性剂、反应时间、反应温度等条件对水热法制备氧化钨粉体材料的影响。最后,对水热法制备氧化钨粉体的发展趋势进行了展望。     

纳米空腔堆积的一维碳纳米结构的合成与表征

Quasi-periodically intermittent hollow-cavity-stacked one-dimensional carbon nanostructures were obtained by microwave plasma chemical vapor deposition from the mixture of CH₄ and N₂ on Fe/γ-Al₂O₃ catalyst. This structure was characterized by transmission electron microscope (TEM), high-resolution TEM and X-ray energy dispersive spectral analysis. The results indicate that the trace impurity of nitrogen might account mainly for the formation of these novel nanostructures. The structural units in these one-dimensional carbon nanostructures are full of nanocavities, which may be of potential importance in hydrogen storage.     

桥连氧化钨纳米线的可控合成及气敏性质

The rapid development of industrialization has resulted in severe environmental problems. A comprehensive assessment of air quality is urgently required all around the world. Among various technologies used in gas molecule detection, including Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, mass spectroscopy (MS), electrochemical sensors, and metal oxide semiconductor (MOS) gas sensors, MOS gas sensors possess the advantages of small dimension, low power consumption, high sensitivity, low production cost, and excellent silicon chip compatibility. MOS sensors hold great promise for future Internet of Things (IoT) sensors, which will have a profound impact on indoor and outdoor air quality monitoring. The development of nanotechnology has significantly enhanced the development of MOS gas sensors. Among various nanostructures like nanoparticles, nanosheets and nanowires, the emergence of quasi-one-dimensional (q1D) nanowires/nanorods/nanofibers, with unique q1D geometry (facilitating fast carrier transport) and large surface-to-volume ratio, potentially act as ideal sensing channels for MOS sensors with extremely small dimension, and good stability and sensitivity. These structures have thus been the focus of extensive research. Among the various MOS nanomaterials available, tungsten oxide (WO_3-x, 0 ≤ x < 1) nanowires feature the characteristic properties (multiple oxidation states, rich substoichiometric oxides with distinct properties, photo/electrochromism, (photo)catalytic properties, etc.), and unique q1D geometry (single-crystalline pathway for fast carrier transport, large surface-to-volume ratio, etc.). WO_3-x nanowires have broad applications in smart windows, energy conversation & storage, and gas sensing devices, and have thus become a focus of attention. In this paper, the fundamental properties of tungsten oxide, synthesis methods and growth mechanism of tungsten oxide nanowires are reviewed. Among various (vapor-liquid-solid (VLS), vapor-solid (VS) and thermal oxidation) growth methods, the thermal oxidation method enables an in situ integration of WO_3-x nanowires on predefined electrodes (so-called bridged nanowire devices) via the oxidation of lithographically patterned W film at relatively low growth temperature (~500 ℃) because of interfacial strain, defects and oxygen on the surface of the W film. The novel bridged nanowire-based sensor devices outperform traditional lateral nanowire devices in terms of larger exposure area, low power consumption via self-heating, and greater convenience in device processing. Recent progress in bridged WO_3-x nanowire devices and sensitive NO_x molecule detection under low power consumption have also been reviewed. Power consumption of as low as a few milliwatts was achieved, and the detection limit of NO₂ was reduced to 0.3 ppb (1 ppb = 1 × 10^-9, volume fraction). In situ formed bridged WO_3-x nanowire devices potentially satisfy the strict requirements of IoT sensors (small dimension, low power consumption, high integration, low cost, high sensitivity, and selectivity), and hold great promises for future IoT sensors.