【摘要】：多酸(POMs)是由前過渡金屬與氧負(fù)離子縮聚而成的多金屬氧簇陰離子,具有獨(dú)特的結(jié)構(gòu)和豐富的性質(zhì)。對(duì)多酸進(jìn)行有機(jī)修飾改性,是調(diào)控和改善其性能,實(shí)現(xiàn)其材料化及實(shí)際應(yīng)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(lǐng)域有著廣泛的應(yīng)用。但目前多釩酸的有機(jī)修飾研究進(jìn)展緩慢,已報(bào)道的多釩酸有機(jī)衍生物存在著結(jié)構(gòu)、價(jià)態(tài)單一等缺點(diǎn),特別是混合價(jià)態(tài)多釩酸的有機(jī)修飾更是鮮有報(bào)道,影響了多釩酸化合物的性能研究及實(shí)際應(yīng)用。本論文通過對(duì)文獻(xiàn)的總結(jié)和實(shí)驗(yàn)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(jià)態(tài)多釩酸的新方法,并合成了四種混合價(jià)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(chǎn)率高,產(chǎn)物分離提純?nèi)菀?而且原料廉價(jià)無毒,適合大量合成,為混合價(jià)態(tài)多釩酸的深入研究打下了重要的基礎(chǔ)。產(chǎn)物利用單晶X射線衍射、紅外、電噴霧質(zhì)譜等手段對(duì)其結(jié)構(gòu)進(jìn)行了表征,通過紫外光譜、循環(huán)伏安法等技術(shù)對(duì)產(chǎn)物的光、電化學(xué)等性質(zhì)進(jìn)行了研究。在進(jìn)一步工作中,本論文利用酰胺化反應(yīng)對(duì)帶有氨基基團(tuán)的化合物H_2[VIV_3VV_3O10{NH_2C(CH_2O)_3}_3]·10H_2O進(jìn)行后修飾,合成了十一個(gè)全新的混合價(jià)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(tái),并開創(chuàng)了通過后修飾法設(shè)計(jì)與可控合成混合價(jià)態(tài)多釩酸衍生物的新途徑。產(chǎn)物利用單晶X射線及電噴霧質(zhì)譜等手段確定了結(jié)構(gòu)。對(duì)修飾產(chǎn)物的循環(huán)伏安法研究發(fā)現(xiàn),這類化合物具有豐富的電化學(xué)性質(zhì),在催化及光電領(lǐng)域有著潛在的應(yīng)用價(jià)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(xué)位授予單位】：湖北工業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O641.4

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本文編號(hào)：2449902