混合价态六钒酸衍生物的合成及其后修饰
发布时间：2019-03-29 21:28
【摘要】：多酸(POMs)是由前过渡金属与氧负离子缩聚而成的多金属氧簇阴离子,具有独特的结构和丰富的性质。对多酸进行有机修饰改性,是调控和改善其性能,实现其材料化及实际应用的重要手段。多钒酸是一类重要的多酸,在催化、医药、磁性材料等领域有着广泛的应用。但目前多钒酸的有机修饰研究进展缓慢,已报道的多钒酸有机衍生物存在着结构、价态单一等缺点,特别是混合价态多钒酸的有机修饰更是鲜有报道,影响了多钒酸化合物的性能研究及实际应用。本论文通过对文献的总结和实验探索,开发了一条以偏钒酸盐为原料,水合肼为还原剂,通过水热法制备混合价态多钒酸的新方法,并合成了四种混合价态或全还原态的六钒酸三羟甲基三取代衍生物H_2[VIV_3VV_3O_(10){NH_2C(CH_2O)_3}_3]·10H_2O;Na_2[VIV_6O_7(OH)_3{(OCH_2)_3CCH_2OH}_3]·9H_2O;(NH_4)_3[VIV_6O_8(OH)2{(OCH_2)_3CCH_3}_3];(NH_4)_3[VIV_6O_8(OH)2{(OCH_2)_3CC_2H_5}_3]·3H_2O。该方法不但产率高,产物分离提纯容易,而且原料廉价无毒,适合大量合成,为混合价态多钒酸的深入研究打下了重要的基础。产物利用单晶X射线衍射、红外、电喷雾质谱等手段对其结构进行了表征,通过紫外光谱、循环伏安法等技术对产物的光、电化学等性质进行了研究。在进一步工作中,本论文利用酰胺化反应对带有氨基基团的化合物H_2[VIV_3VV_3O10{NH_2C(CH_2O)_3}_3]·10H_2O进行后修饰,合成了十一个全新的混合价态六钒酸衍生物,表明化合物H_2[VIV_3VV_3O10{NH_2C(CH_2O)_3}_3]·10H_2O是一类优异的后修饰平台,并开创了通过后修饰法设计与可控合成混合价态多钒酸衍生物的新途径。产物利用单晶X射线及电喷雾质谱等手段确定了结构。对修饰产物的循环伏安法研究发现,这类化合物具有丰富的电化学性质,在催化及光电领域有着潜在的应用价值。
[Abstract]:Polyacid (POMs) is a polymetallic oxygen cluster anion formed by condensation of pre-transition metal and oxygen anion. It has a unique structure and rich properties. Organic modification of polyacids is an important means to control and improve their properties and realize their materialization and practical application. Polyvanadate is an important polyacid, which is widely used in catalysis, medicine, magnetic materials and so on. However, the progress of organic modification of polyvanadate is slow at present. The reported organic derivatives of polyvanadate have some disadvantages, such as structure, single valence and so on, especially the organic modification of mixed valence polyvanadate is rarely reported. The properties of polyvanadate compounds and their practical application were affected. In this paper, a new method for the preparation of mixed valence polyvanadate by hydrothermal method using metavanadate as raw material and hydrazine hydrate as reducing agent was developed through the summary of literature and experimental exploration. Four trimethylol hexavanadanadate trisubstituted derivatives H _ (2) [VIV_3VV_3O_ (10) {NH_2C (CH_2O) _ 3} _ 3] 10 H ~ (2 +) O _ 2O were synthesized. Na_2 [VIV_6O_7 (OH) _ 3 {(OCH_2) _ 3CCH_2OH} _ 3] 9H _ 2O; (NH_4) _ 3 [VIV_6O_8 (OH) 2 {(OCH_2) _ 3CCH_3} _ 3]; (NH_4) _ 3 [VIV_6O_8 (OH) 2 {(OCH_2) _ 3CC_2H_5} _ 3] This method not only has the advantages of high yield, easy separation and purification of products, but also cheap and non-toxic raw materials, which is suitable for a large number of synthesis, and lays an important foundation for the further study of mixed valence polyvanadate. The structure of the product was characterized by single crystal X-ray diffraction, infrared spectroscopy and electrospray mass spectrometry. The optical and electrochemical properties of the product were studied by UV spectroscopy and cyclic voltammetry. In the further work, the amino group compound H\ [VIV_3VV_3O10 {NH_2C (CH_2O) _ 3} _ 3] 10H_2O was modified by amidation reaction. Eleven novel mixed valence hexa vanadate derivatives have been synthesized. The results show that compound H _ (2) [VIV_3VV_3O10 {NH_2C (CH_2O) _ 3} _ 3] 10H_2O is a kind of excellent post-modification platform. A new method for the design and controllable synthesis of mixed valence polyvanadate derivatives by post-modification method was also developed. The structure of the product was determined by single crystal X-ray and electrospray mass spectrometry. The cyclic voltammetry of the modified products shows that these compounds have rich electrochemical properties and have potential applications in the field of catalysis and photoelectricity.
【学位授予单位】：湖北工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4
本文编号：2449902
[Abstract]:Polyacid (POMs) is a polymetallic oxygen cluster anion formed by condensation of pre-transition metal and oxygen anion. It has a unique structure and rich properties. Organic modification of polyacids is an important means to control and improve their properties and realize their materialization and practical application. Polyvanadate is an important polyacid, which is widely used in catalysis, medicine, magnetic materials and so on. However, the progress of organic modification of polyvanadate is slow at present. The reported organic derivatives of polyvanadate have some disadvantages, such as structure, single valence and so on, especially the organic modification of mixed valence polyvanadate is rarely reported. The properties of polyvanadate compounds and their practical application were affected. In this paper, a new method for the preparation of mixed valence polyvanadate by hydrothermal method using metavanadate as raw material and hydrazine hydrate as reducing agent was developed through the summary of literature and experimental exploration. Four trimethylol hexavanadanadate trisubstituted derivatives H _ (2) [VIV_3VV_3O_ (10) {NH_2C (CH_2O) _ 3} _ 3] 10 H ~ (2 +) O _ 2O were synthesized. Na_2 [VIV_6O_7 (OH) _ 3 {(OCH_2) _ 3CCH_2OH} _ 3] 9H _ 2O; (NH_4) _ 3 [VIV_6O_8 (OH) 2 {(OCH_2) _ 3CCH_3} _ 3]; (NH_4) _ 3 [VIV_6O_8 (OH) 2 {(OCH_2) _ 3CC_2H_5} _ 3] This method not only has the advantages of high yield, easy separation and purification of products, but also cheap and non-toxic raw materials, which is suitable for a large number of synthesis, and lays an important foundation for the further study of mixed valence polyvanadate. The structure of the product was characterized by single crystal X-ray diffraction, infrared spectroscopy and electrospray mass spectrometry. The optical and electrochemical properties of the product were studied by UV spectroscopy and cyclic voltammetry. In the further work, the amino group compound H\ [VIV_3VV_3O10 {NH_2C (CH_2O) _ 3} _ 3] 10H_2O was modified by amidation reaction. Eleven novel mixed valence hexa vanadate derivatives have been synthesized. The results show that compound H _ (2) [VIV_3VV_3O10 {NH_2C (CH_2O) _ 3} _ 3] 10H_2O is a kind of excellent post-modification platform. A new method for the design and controllable synthesis of mixed valence polyvanadate derivatives by post-modification method was also developed. The structure of the product was determined by single crystal X-ray and electrospray mass spectrometry. The cyclic voltammetry of the modified products shows that these compounds have rich electrochemical properties and have potential applications in the field of catalysis and photoelectricity.
【学位授予单位】：湖北工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4
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