【摘要】：多酸(POMs)是由前過渡金屬與氧負離子縮聚而成的多金屬氧簇陰離子,具有獨特的結構和豐富的性質。對多酸進行有機修飾改性,是調控和改善其性能,實現其材料化及實際應用的重要手段。多釩酸是一類重要的多酸,在催化、醫(yī)藥、磁性材料等領域有著廣泛的應用。但目前多釩酸的有機修飾研究進展緩慢,已報道的多釩酸有機衍生物存在著結構、價態(tài)單一等缺點,特別是混合價態(tài)多釩酸的有機修飾更是鮮有報道,影響了多釩酸化合物的性能研究及實際應用。本論文通過對文獻的總結和實驗探索,開發(fā)了一條以偏釩酸鹽為原料,水合肼為還原劑,通過水熱法制備混合價態(tài)多釩酸的新方法,并合成了四種混合價態(tài)或全還原態(tài)的六釩酸三羥甲基三取代衍生物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。該方法不但產率高,產物分離提純容易,而且原料廉價無毒,適合大量合成,為混合價態(tài)多釩酸的深入研究打下了重要的基礎。產物利用單晶X射線衍射、紅外、電噴霧質譜等手段對其結構進行了表征,通過紫外光譜、循環(huán)伏安法等技術對產物的光、電化學等性質進行了研究。在進一步工作中,本論文利用酰胺化反應對帶有氨基基團的化合物H_2[VIV_3VV_3O10{NH_2C(CH_2O)_3}_3]·10H_2O進行后修飾,合成了十一個全新的混合價態(tài)六釩酸衍生物,表明化合物H_2[VIV_3VV_3O10{NH_2C(CH_2O)_3}_3]·10H_2O是一類優(yōu)異的后修飾平臺,并開創(chuàng)了通過后修飾法設計與可控合成混合價態(tài)多釩酸衍生物的新途徑。產物利用單晶X射線及電噴霧質譜等手段確定了結構。對修飾產物的循環(huán)伏安法研究發(fā)現,這類化合物具有豐富的電化學性質,在催化及光電領域有著潛在的應用價值。
[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.
【學位授予單位】：湖北工業(yè)大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O641.4

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