本文選題：雜多酸 + 離子液體��； 參考：《浙江大學》2017年博士論文

【摘要】：雜多酸或多金屬含氧酸鹽是一類重要的含有氧橋的多核配合物,具有特殊的結(jié)構(gòu)和獨特的物理化學性質(zhì)。針對它們的性質(zhì)研究與應用已涉及到許多領域,如催化、光化學、電化學、生物醫(yī)學和材料科學等。新型雜多酸及雜多酸衍生物的設計合成與性能研究是多酸化學領域的前沿和熱點之一。本文合成了五種多元雜多酸H_4[In(H_2O)PW11039]·11H_20(PW11In)、H5PW10V2O40·14H_2O(PW10V2)、H8P2W16V2O62·20H_2O(P2W16V2)、H6P2W16Mo2O40·29H_2O(P2W16Mo2)和 H_4[In(H_2O)PW9Mo2039]·11H_20(PW9Mo2In),確定了合成反應的適宜條件。通過一系列手段如元素分析、紅外光譜(FT/IR)、紫外光譜(UV)、X-射線粉末衍射(XRD)和熱重差熱分析(TG-DTA)對它們的結(jié)構(gòu)和熱穩(wěn)定性進行了表征。在此基礎上,測定了這些雜多酸在室溫(18 ℃C)環(huán)境下的質(zhì)子電導率,并通過測定其不同溫度下的質(zhì)子電導率,研究了它們的質(zhì)子導電機理。實驗結(jié)果表明這些雜多酸在室溫下電導率均達到10-4 S·cm-1以上,為新型固體高質(zhì)子導體,它們的質(zhì)子導電機理均為Vehicle機理。除此之外,以含磺酸基的咪唑類(MIMPS)、吡啶類(PyPS)、季胺類(TEAPS)離子液體陽離子以及三丁基十四烷基氯化擕(TBTPC1),季銨類離子液體((C4H9)3N(C10H_21)Br(TBDABr)、(C4H9)3N(C14H_29)Br(TBTABr)、(C8H17)3NCH3Cl(TOAMeCl))為原料,分別與多元雜多酸PW11In、PW10V、P2W16V2、P2W16Mo2和其它磷系多元雜多酸(H7[In(H_2O)P2W17O61](P2W17In)、H7P2W17VO62(P2W17V)、H9P2W15V3O62(P2W15V3)和 H_4PW11VO40(PW11V))化合,合成了—系列新型雜多化合物離子液體:[MIMPS]8P2W16V2O62、[MIMPS]6H_2P2W16V2O62、[MIMPS]4H_4P2W16V2O62、[MIMPS]5PW10V2O40、[MIMPS]3H_2PW10V2O40、[PyPS]8P2W16V2O62、[PyPS]5PW10V2O40、[TEAPS]5PW10V2O40、[TEAPS]7P2W17VO62、[TEAPS]8P2W16V2O62、[TEAPS]9P2W15V3O62、[TBTP]5PW10V2O40、[TBTP]8P2W16V2O62、[TOAMe]4[In(H_2O)PW11O39]、[TOAMe]7[In(H_2O)P2W17O61]、[TOAMe]4PW11VO40、[TBDA]8P2W16V2O62 和[TBTA]8P2W16V2O62。在此基礎上,以特定的分類方式對它們分別加以討論。通過IR、UV、XRD、TG-DTA和TEM等一系列分析手段對這些離子液體的結(jié)構(gòu)和熱穩(wěn)定性進行了表征,同時也研究了它們的電化學性能。TG-DTA曲線表明所有離子液體在100℃C以下均能發(fā)生可逆相轉(zhuǎn)變過程,是新型溫度控制型離子液體。實驗結(jié)果顯示產(chǎn)物的陰陽離子種類與其物理化學性質(zhì)之間有密切關系:酸式鹽比相應的正鹽在熱穩(wěn)定性和電導率上更高,并且隨著氫離子數(shù)目的增加而增加;對于同種陽離子,比如三丁基十四烷基擕和三辛基甲基銨來說,Dawson結(jié)構(gòu)多酸離子液體中比Keggin結(jié)構(gòu)具有更高的電導率;但當陽離子不同時,碳鏈較短的陽離子(TBDA)往往比碳鏈較長的陽離子(TBTA)具有更高的電導率。相變過程將顯著提高其電導率,高溫下所有離子液體的電導率均達到10-4 S·cm-1以上,而且它們可以在100℃以下經(jīng)歷相變,同時電導率大幅度提高,證明它們是新型相變多酸離子液體。
[Abstract]:Heteropoly or polyoxometalates are one of the most important Polyoxometalates Containing Oxygen bridges, with special structures and unique physical and chemical properties. The study and application of their properties have been involved in many fields, such as catalysis, photochemistry, electrochemistry, biomedicine and material science. Synthesis and performance research are one of the frontiers and hot spots in the field of polyacid chemistry. This paper syntheses five kinds of Heteropoly heteropoly acids H_4[In (H_2O) PW11039] / 11H_20 (PW11In), H5PW10V2O40 14H_2O (PW10V2), H8P2W16V2O62 20H_2O (P2W16V2), H6P2W16Mo2O40. By means of a series of means such as elemental analysis, infrared spectroscopy (FT/IR), ultraviolet spectroscopy (UV), X- ray powder diffraction (XRD) and thermogravimetric analysis (TG-DTA), their structure and thermal stability were characterized. On this basis, the proton conductivity of these heteropoly acids at room temperature (18 C C) was measured and measured by them. The conduction mechanism of proton conductivities at different temperatures was studied. The experimental results showed that the conductivity of these heteropoly acids reached 10-4 S. Cm-1 at room temperature. It was a new solid high proton conductor, and their proton conduction mechanism was Vehicle mechanism. In addition, the sulfonic acid imidazole (MIMPS), pyridine (PyPS), and the quaternary system were used. Ammonium (TEAPS) ionic liquid cations and three butyl fourteen alkyl chloride (TBTPC1), quaternary ammonium ionic liquids (C4H9) 3N (C10H_21) Br (TBDABr) and 3N (C14H_29) Br (TBTABr) are used as raw materials. 17In), H7P2W17VO62 (P2W17V), H9P2W15V3O62 (P2W15V3) and H_4PW11VO40 (PW11V) combine to synthesize a series of new heteropoly compound ionic liquids: [MIMPS]8P2W16V2O62, [MIMPS]6H_2P2W16V2O62, [MIMPS]4H_4P2W16V2O62, [MIMPS]5PW10V2O40, [MIMPS]. 62, [TEAPS]8P2W16V2O62, [TEAPS]9P2W15V3O62, [TBTP]5PW10V2O40, [TBTP]8P2W16V2O62, [TOAMe]4[In (H_2O) PW11O39], [TOAMe]7[In (H_2O) P2W17O61], [TOAMe]4PW11VO40, [TBDA]8P2W16V2O62, and, on this basis, discuss them in a specific way. The structure and thermal stability of these ionic liquids were characterized, and their electrochemical performance.TG-DTA curves showed that all ionic liquids could have reversible phase transition process under 100 centigrade C. It was a new type of temperature controlled ionic liquid. The experimental results showed that the types of ions and yang ions of the products and their physical and chemical properties were found. There is a close relationship between the quality: the acid salt is higher in the thermal stability and the conductivity than the corresponding positive salt, and increases with the increase of the number of hydrogen ions; for the homologous cations, such as three butyl fourteen alkyl groups and three octyl ammonium, the conductivity of the Dawson structure polyacid ionic liquid is higher than that of the Keggin structure; but Dangyang is the same. When ions are different, the shorter cations (TBDA) tend to have higher electrical conductivity than the longer cations (TBTA). The phase transition process will significantly increase the conductivity. The conductivity of all ionic liquids at high temperatures is up to 10-4 S. Cm-1, and they can undergo phase transitions below 100 C, and the conductivity is greatly improved. It is clear that they are new phase change polyacid ionic liquids.
【學位授予單位】：浙江大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：O641.4

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相關期刊論文 前3條

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2 ;Synthesis and conductivity of substituted heteropoly acid with Dawson structure H_7[Ga(H_2O)P_2W_(17)O_(61)].18H_2O[J];Chinese Science Bulletin;2011年22期

3 ;Preparation and Conductivity of Triheteropoly Tungstozincoaluminic Acid[J];Rare Metals;2001年04期

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本文編號：1934701