多金属氧酸盐纳米晶功能材料开发及光伏性质研究

发布时间：2018-01-05 20:10

本文关键词：多金属氧酸盐纳米晶功能材料开发及光伏性质研究　出处：《东北师范大学》2015年博士论文　论文类型：学位论文

【摘要】：多金属氧酸盐(Polyoxometalates),简称多酸(POMs),因组成结构的多样性,多功能性和稳定性,使其在光学,电学和催化等领域备受关注,并成为人们解决近年来日渐凸显的能源和环境问题的新方向之一。本文中我们主要致力于构筑多酸基多功能纳米晶光伏材料,通过依次与Zn O,表面活性剂和金属有机骨架相结合构筑各种多酸基纳米功能材料。将成功制备的各种多酸基纳米功能材料应用于制备染料敏化太阳能电池和量子点太阳能电池中,最终获得了电池光伏性能的显著提升。1.通过简单的溶剂热路线首次成功合成了多酸(H3PW12O40)基Zn O纳米粒子并将其制备成光阳极薄膜用于组装染料敏化太阳能电池(DSSCs),测试其整体光电转换效率达2.7%,这比不含有多酸的纯Zn O膜效率高出49.2%。此外我们还对其他Keggin型多酸包括W系,Mo系及其钾盐(K3PW12O40)的DSSCs性能进行了研究。结果证明含W系多酸HXMW12O40(M=P,x=3;M=Si,Ge,x=4)的引入显著提高DSSCs的性能,这是由于W系多酸增加了DSSCs的电子寿命和减小了暗电流。选择适当的H3PW12O40的浓度对获取优越的DSSCs性能十分关键。这为多酸复合半导体纳米材料的光伏应用打开了一扇窗。2.我们首次开发了Keggin型无机-有机杂化多酸[(CH3)4N]5[PW11O39Rh CH2COOH]?6H2O(PW11Rh-COOH)光敏剂用于组装多酸敏化太阳能电池(PSSCs)。通过电化学测试,固体紫外漫反射光谱,表面光电压谱和X-射线光电子能谱等证实PW11Rh-COOH具有十分优异的光伏响应,这是因为其具有更好的可见光敏感性,与Ti O2相匹配的能级和更高的电荷分离效率。该工作为筛选合适带隙和能级的多酸纳米晶光伏材料提供了指导。3.我们成功制备了首例DODA+包裹的光敏性多酸[PW11O39Rh CH2CO2H]5-液晶纳米材料。采用理论计算方法模拟了多酸阴离子周围DODA+的电荷分布。表面光电压谱(SPS)测试证明复合物在光照下具有光伏效应并展示出类似P型半导体材料的特征,这为开发基于表面活性剂包裹多酸的液晶纳米材料的光电应用铺设了一条新路。4.在能源和材料领域,获得高分散小尺寸纳米晶材料对于改善材料的光电和催化性能至关重要。这里,我们发展了一种新策略用于在Ti O2表面负载高分散小尺寸~1nm的K6Co W12O40(Co W12)纳米晶材料,采用金属有机骨架MIL-101封装合适尺寸的多酸,防止多酸聚集,随后烧结破坏MOF骨架,将多酸均匀分散到纳米Ti O2支撑膜中制备光阳极组装量子点敏化太阳能电池(QDSCs),能够显著提升QDSCs性能。这一策略具有普适性,不仅为MOF材料这个庞大家族的应用研究提供了一条新的途径,并且有望在制备各种量子点尺寸金属氧化物和其它多酸纳米晶功能材料领域有所贡献。
[Abstract]:Polyoxometalates (Polyoxometalates), referred to as multi acid (POMs), because the diversity of structure, function and stability, so that in the optical, electrical and catalytic fields has attracted much attention, and has become one of the new direction of the people to solve the energy and environmental problems become increasingly prominent in recent years. In this paper we mainly. Committed to build a multi acid based multifunctional nanocrystalline photovoltaic materials, followed by Zn and O, surface active agent and metal organic framework combined to build a variety of polyoxometalate based functional nanomaterials. Polyoxometalate based nano functional materials used in the preparation of dye-sensitized solar cell and quantum dot solar cells will be successfully prepared, finally obtained the first successful synthesis of Polyoxometalates significantly enhance.1. cell photovoltaic performance through simple solvothermal route (H3PW12O40) based Zn O nanoparticles and prepared a photoanode for dye-sensitized assembly The solar cell (DSSCs), test the overall photoelectric conversion efficiency of 2.7%, the pure Zn O film does not contain more efficiency than acid 49.2%. higher than that in addition we have on the other Keggin type polyoxometalates including W, Mo and potassium (K3PW12O40) DSSCs were studied. The results showed that W containing acid system HXMW12O40 (M=P, x=3; M=Si, Ge, x=4) was introduced to improve the performance of DSSCs, this is because the W system increases the electron lifetime of DSSCs acid and reduced the dark current. Choose a proper concentration of H3PW12O40 is the key to obtain the excellent performance of DSSCs. The photovoltaic application as much acid compound semiconductor nano materials open a window for the first time.2. we developed Keggin type inorganic organic hybrid poly [(CH3) 4N]5[PW11O39Rh CH2COOH]? 6H2O (PW11Rh-COOH) photosensitizer for assembled acid sensitized solar cell (PSSCs). The electrochemical test, UV visible diffuse reflectance spectroscopy, table Surface photovoltage spectroscopy and X- ray photoelectron spectroscopy confirmed that PW11Rh-COOH has very excellent photovoltaic response, this is because it has better visible light sensitivity, energy level matching with Ti O2 and higher charge separation efficiency. This work is selected with acid nanocrystalline photovoltaic materials and energy gap provides we successfully prepared the first guide.3. DODA+ coated photosensitive acid [PW11O39Rh CH2CO2H]5- liquid crystal nano materials were prepared. By theoretical calculation method to simulate the charge distribution around DODA+ polyoxoanions. Surface photovoltage spectroscopy (SPS) test proved that the compound has the photovoltaic effect under illumination and display characteristics similar to the P type semiconductor material this, for the development of optoelectronic applications of liquid crystal nano material coated surfactants polyoxometalate based on laying a new path of.4. in the energy and material field, high dispersion small size nanocrystalline material To improve the photoelectric and catalytic properties of essential materials. Here, we developed a new strategy for the high dispersion of small size ~1nm K6Co W12O40 Ti O2 (Co load on the surface of W12) nanocrystalline materials, the acid metal organic framework MIL-101 package size, prevent acid accumulation, then sintered to destroy MOF skeleton. The acid is uniformly dispersed into nano Ti O2 support membrane prepared in light anode assembling quantum dot sensitized solar cell (QDSCs), can significantly improve the performance of QDSCs. This method is universal, not only provides a new way for the application of MOF material in this huge family, and is expected in the field of preparation all the size of quantum dots and other multi metal oxide nanocrystalline materials contribute to acid function.

【学位授予单位】：东北师范大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：TB34;TM914.4

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