本文關(guān)鍵詞： 金屬有機(jī)框架(metal-organic-framework) 普魯士藍(lán)類似物 熱致變色 析氧反應(yīng)(OER)　出處：《山東大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：金屬一有機(jī)框架材料(MOF)是近幾十年來(lái)發(fā)展起來(lái)的一類配位聚合物,在催化、儲(chǔ)能和分離中都有著廣泛的應(yīng)用。本文中,我們通過(guò)鈷基化合物與不同的有機(jī)配體進(jìn)行反應(yīng),形成不同的鈷基MOF配位化合物,然后對(duì)其進(jìn)行性質(zhì)測(cè)試,主要研究了鈷基MOF材料在變色響應(yīng)及電催化產(chǎn)氧方面的性能。主要工作如下:1、鈷基普魯士藍(lán)類似物(PBA)的制備及其熱致變色和溶劑致變色性能研究以醋酸鈷和鈷氰化鉀為原料,通過(guò)簡(jiǎn)單的溶液法在水中合成了鈷基PBA,通過(guò)調(diào)節(jié)體系中檸檬酸鈉的加入量,合成了形貌和尺寸大小都有差異的鈷基普魯士藍(lán)類似物(Co3[Co(CN)6]2)。通過(guò)實(shí)驗(yàn)和理論計(jì)算對(duì)PBA的形成機(jī)理進(jìn)行了研究,結(jié)果表明合成的PBAs中與二價(jià)鈷配位的水分子會(huì)部分被加入的檸檬酸根所取代,同時(shí)檸檬酸根與相鄰的配位水之間形成氫鍵,從而抑制了加熱過(guò)程中PBA中配位水分子的脫除,最終實(shí)現(xiàn)了對(duì)PBA熱致變色溫度(40-80℃)的可調(diào)控制。除具有可調(diào)的熱致變色溫度外,所合成的PBAs還表現(xiàn)出非�？斓臒嶂伦兩俾屎透叩难h(huán)穩(wěn)定性等特征。另外這種PBAs還具有溶劑致變色性能。以PBA-0為例,在水、各種醇類及乙睛等溶液中可以顯示出不同的顏色,這主要是由于產(chǎn)物中的配位水與溶劑具有較強(qiáng)的結(jié)合能力,使配位水脫離骨架,使得產(chǎn)物Co(Ⅱ)從6配位轉(zhuǎn)變成4配位,顏色也發(fā)生變化;但是PBA-300在不同溶劑中依然保持粉紅色不變,主要是由于檸檬酸根的存在對(duì)配位水的脫除具有阻礙作用,使產(chǎn)物失去溶劑致變色效應(yīng)。2、3D納米花狀鈷基MOF材料的制備及其電化學(xué)性能研究以乙酸鈷、乙酸鎳和對(duì)苯二甲酸為原料,采用了簡(jiǎn)單的液相方法合成了鎳摻雜的鈷基MOF—Co10-xNix-BDC(0-3),此類MOF呈現(xiàn)均勻的花狀,由薄的片層相互交叉而成。通過(guò)XRD、TEM、SEM、FTIR、XPS等手段對(duì)MOF產(chǎn)物進(jìn)行了表征,并且通過(guò)調(diào)整體系中不同CoNi比例的合成方法和不同時(shí)間的跟蹤實(shí)驗(yàn)過(guò)程研究了其形成機(jī)理。將所得的一系列MOF材料作為電催化劑用于電化學(xué)產(chǎn)氧(OER)測(cè)試,對(duì)其催化性能進(jìn)行了對(duì)比,發(fā)現(xiàn)不同CoNi比例的MOFs產(chǎn)物均有較好的OER性能,其中MOF Co7Ni3-BDC性質(zhì)最好,在1M的KOH溶液中的起始電勢(shì)僅有1.44V,當(dāng)電流密度為10mA cm-1時(shí),其過(guò)電勢(shì)只有334mV,塔菲爾斜率為72mV/dec。而且MOF材料的穩(wěn)定性也不錯(cuò),循環(huán)1000圈后性能仍然保持很好,在350mV的過(guò)電勢(shì)下,電流密度能一直保持平穩(wěn)不變。
[Abstract]:Metal-organic frame material (MOF) is a kind of coordination polymer developed in recent decades, which has been widely used in catalysis, energy storage and separation. We react with different organic ligands to form different cobalt-based MOF coordination compounds, and then test their properties. The performance of cobalt-based MOF in chromotropic response and electrocatalytic oxygen production was studied. The main work is as follows: 1. Preparation of Cobalt Prussian Blue analogue (PBA) and its Thermochromic and Solvent-Chromotropic Properties; Cobalt based PBA was synthesized in water by a simple solution method using cobalt acetate and potassium cobalt cyanide as raw materials. By adjusting the amount of sodium citrate in the system, the cobalt based Prussian blue analogue, CoCo3, which has different morphology and size, has been synthesized. [The formation mechanism of PBA was studied by means of experiments and theoretical calculations. The results show that the water molecules coordinated with cobalt in the synthesized PBAs will be partially replaced by the addition of citrate, and the hydrogen bond between the citrate and the adjacent coordination water will be formed. Thus, the removal of coordination water molecules in PBA during heating is restrained, and the adjustable control of thermochromic temperature of PBA (40-80 鈩，

本文編號(hào)：1493578