本文選題：鋯/鉿氧簇合物 + 堿金屬鹵化物簇　； 參考：《山東大學(xué)》2017年碩士論文

【摘要】：二氧化鋯和二氧化鉿具有硬度大、耐高溫、良好的化學(xué)穩(wěn)定性等優(yōu)點,被廣泛用于隔熱、電子信息、燃料電池及仿生材料等領(lǐng)域。鋯/鉿氧簇合物不僅可以作為二氧化鋯/二氧化鉿的分子模型和形成的中間體,還是構(gòu)筑功能化金屬有機框架Zr/Hf-MOFs材料的基本結(jié)構(gòu)單元。溶膠凝膠法是合成二氧化鋯/二氧化鉿最常用方法,鋯/鉿氧簇合物作為預(yù)成核階段的納米簇合物,存在于二氧化鋯/二氧化鉿形成過程中,因而捕獲并解析其晶體結(jié)構(gòu),對于研究二氧化鋯/二氧化鉿形成的分子機制具有重要意義。其次,堿金屬鹵化物廣泛存在于自然界中,堿金屬鹵化物納米簇合物同樣作為預(yù)成核階段的納米簇合物,是連接微觀分子世界和宏觀固體材料世界的橋梁,它的研究對于理解溶液成核過程及其成核階段微觀團簇結(jié)構(gòu)具有重要價值。鑒于此,本論文采用溶膠凝膠法,成功獲得了二氧化鋯/二氧化鉿形成中間體—被羧酸基團和硫酸根基團共同穩(wěn)定的鋯/鉿氧簇合物;并通過溶液中靜電吸引和分子識別相互作用,利用鋯/鉿氧簇合物成功捕獲到預(yù)成核階段能夠代表體相晶體結(jié)構(gòu)的堿金屬鹵化物納米簇合物。對這些化合物的結(jié)構(gòu)和光譜性質(zhì)做了充分表征,對形成條件做了詳細研究,最后對這些簇合物的超離子導(dǎo)電性和溶液化學(xué)做了進一步探索。論文內(nèi)容分為以下三個部分:第一部分:綜述了二氧化鋯/鉿以及金屬氧簇合物的研究進展、種7類及合成方法;總結(jié)了文獻報道的鋯/鉿氧簇合物的結(jié)構(gòu)及性質(zhì)以及堿金屬鹵化物簇合物研究進展;最后,闡述了本論文選題的科學(xué)意義。第二部分:以ZrOC12/HfOC12為前驅(qū)體,采用溶膠凝膠法,獲得了一個具有風(fēng)車狀結(jié)構(gòu)的新穎的十七核鋯/鉿氧簇合物;對合成條件做了詳細篩選,并在改變條件后獲得了一個六核鋯/鉿氧簇;圍繞ZrⅣ離子水解縮聚為Zr02納米晶的過程,對上述化合物的角色做了詳細分析;進一步表征了化合物的結(jié)構(gòu)和光譜性質(zhì),并探究了它們的超離子導(dǎo)電性。第三部分:以ZrC14/HfC14為前驅(qū)體,通過溶液中靜電吸引和分子識別相互作用,采用四核的鋯/鉿氧簇合物成功從鹵化銫(CsCl和CsBr)溶液中捕獲到預(yù)成核階段的堿金屬鹵化物納米簇合物[Cs8X27]19-(X = Cl,Br),該離子簇跟CsCl晶體的體相結(jié)構(gòu)相同,非常接近于后者的四個晶胞;并對它們進行了詳細的結(jié)構(gòu)和光譜表征;最后對它們的超離子導(dǎo)電性和溶液化學(xué)做了研究。
[Abstract]:Zirconium dioxide and hafnium oxide have many advantages such as high hardness, high temperature resistance and good chemical stability. They are widely used in thermal insulation, electronic information, fuel cells and bionic materials. Zirconium / hafnium oxide cluster can be used not only as molecular model and intermediate of zirconium dioxide / hafnium dioxide, but also as the basic structure unit of functionalized organometallic frame Zr/Hf-MOFs material. The sol-gel method is the most commonly used method to synthesize zirconium dioxide / hafnium oxide. The zirconium / hafnium oxide cluster, as a nano-cluster in the pre-nucleation stage, exists in the formation of zirconium dioxide / hafnium oxide, so its crystal structure is captured and analyzed. It is of great significance to study the molecular mechanism of zirconium dioxide / hafnium dioxide formation. Secondly, alkali metal halide widely exists in nature, and alkali metal halide nanoclusters are also used as nanoclusters in pre-nucleation stage, which is a bridge between micromolecular world and macroscopic solid material world. Its research is of great value in understanding the microstructure of the solution nucleation process and its nucleation stage. In view of this, zirconium dioxide / hafnium oxide has been successfully obtained by sol-gel method to form zirconium dioxide / hafnium oxide cluster, which is stabilized by carboxylic acid group and sulfate group. Through the interaction of electrostatic attraction and molecular recognition in solution, zirconium / hafnium oxide cluster was used to capture the alkali-metal halide nanoclusters which can represent the bulk crystal structure in the pre-nucleation stage. The structure and spectral properties of these compounds were fully characterized, and the formation conditions were studied in detail. Finally, the superionic conductivity and solution chemistry of these clusters were further explored. The content of this paper is divided into three parts as follows: in the first part, the progress of research on zirconium dioxide / hafnium and metal oxygen cluster, 7 kinds of zirconium dioxide / hafnium and their synthesis methods are reviewed. The structure and properties of zirconium / hafnium oxide cluster and the research progress of alkali metal halide cluster were summarized. Part two: using ZrOC12/HfOC12 as precursor, a novel cluster of zirconium / hafnium with windmill structure was obtained by sol-gel method. A hexanuclear zirconium / hafnium oxide cluster was obtained after changing the conditions, the roles of the compounds were analyzed in detail around the process of hydrolysis and condensation of Zr 鈪，

本文編號：1968263