本文關(guān)鍵詞： 有機(jī)多孔聚合物 過渡金屬磷化物 電解水產(chǎn)氫 BODIPY　出處：《上海應(yīng)用技術(shù)學(xué)院》2015年碩士論文　論文類型：學(xué)位論文

【摘要】：有機(jī)多孔聚合物因其優(yōu)異的性能和特點,引起材料研究領(lǐng)域的廣泛關(guān)注,因此有機(jī)多孔聚合物在單體的構(gòu)建、聚合物的制備方法、以及聚合物的性能應(yīng)用都得到極大的發(fā)展。氫氣作為非常有開發(fā)前景的新能源,傳統(tǒng)的制氫工藝仍然消耗化石燃料且增加了碳排放。電解水制氫是一種節(jié)能、可持續(xù)性的實行氫氣量產(chǎn)的方法。過渡金屬磷化物因其優(yōu)異的電解水催化產(chǎn)氫性能成為了研究熱點。鑒于傳統(tǒng)的過渡金屬磷化物材料比表面積不高,穩(wěn)定性還需提高的缺點,本課題將有機(jī)多孔聚合物的優(yōu)點與過渡金屬磷化物優(yōu)異的催化產(chǎn)氫性能相結(jié)合,將含磷多孔聚合物分別作為磷源和電子受體,把金屬磷化物以及具有光電效應(yīng)的功能分子引入到聚合物母體當(dāng)中,不僅保留了母體比表面積高,化學(xué)穩(wěn)定性好的有點,又賦予了新多孔材料在電催化產(chǎn)氫方面優(yōu)異的性能。具體研究內(nèi)容如下：(1)首先合成了具有乙烯基官能團(tuán)的單體三苯乙烯基膦(TVP),然后以1,3,5-三乙烯基苯為結(jié)構(gòu)單元,在AIBN的引發(fā)下發(fā)生自由基聚合,制備了新的超高交聯(lián)有機(jī)骨架HC-T P。并HC-TVP的結(jié)構(gòu),多孔性,熱穩(wěn)定性等進(jìn)行了研究。將HC-TVP用氫碘酸離子化為了HT-Ⅰ,然后利用HT-Ⅰ中的碘離子與含有金屬陰離子基團(tuán)經(jīng)行離子交換,或其自身的孔結(jié)構(gòu)對金屬陰離子進(jìn)行吸附,從而將金屬Mo或Fe引入到多孔骨架中,制備了負(fù)載有金屬的超交聯(lián)多孔框架HT-Mo和HT-Fe。并研究了它們的多孔性、熱穩(wěn)定性等相關(guān)物理化學(xué)性質(zhì)。然后通過將HT-Mo和HT-Fe在氫氣的氛圍中,熱裂解制備了含有金屬磷化物的多孔碳材料MoP@PC 和 FeP@PC。MoP@PC和FeP@PC不僅擁有較高的比表面積,且含有電解水產(chǎn)氫活性高的磷化鉬和磷化鐵顆粒,因此材料有較高的催化活性。(2)與上一章離子交換法制備負(fù)載有金屬的多孔聚合物的方法不同,我們利用磷與過渡金屬的配位作用,直接制備配位有金屬的多孔聚合物,并對其電解水產(chǎn)氫性能進(jìn)行了研究。(3)以含有乙烯鍵的含磷化合物為母體,利用乙烯基和鹵族元素在鈀(0)的催化下發(fā)生的Mizoroki-Heck偶聯(lián)反應(yīng),將BODIPY引入到聚合物框架中,成功制備了多孔聚合物B-TVP線性聚合物B-BVP。并對BODIPY和類三苯基膦單元組成了donor-acceptor結(jié)構(gòu)進(jìn)行了研究。
[Abstract]:Due to its excellent properties and characteristics, organic porous polymers have attracted extensive attention in the field of material research. Therefore, the construction of organic porous polymers in monomer, polymer preparation methods. Hydrogen is a promising new energy source. Traditional hydrogen production process still consumes fossil fuels and increases carbon emissions. Hydrogen production from electrolytic water is a kind of energy saving. Transition metal phosphates have become a research hotspot for their excellent catalytic performance in hydrogen production by electrolytic water. Because the specific surface area of traditional transition metal phosphates is not high. The advantages of organic porous polymers are combined with the excellent catalytic hydrogen production performance of transition metal phosphates, and phosphorus-containing porous polymers are used as phosphorus sources and electron receptors, respectively. The introduction of metal phosphates and functional molecules with photoelectric effect into the polymer matrix not only retains the high specific surface area of the matrix, but also has a little good chemical stability. The new porous materials were also endowed with excellent performance in electrocatalytic hydrogen production. Firstly, the monomer triphenylvinylphosphine (TVB) with vinyl functional group was synthesized, and then the monomer TVB _ (3) was synthesized. A novel ultrahigh crosslinked organic skeleton, HC-T P. and HC-TVP, was prepared by radical polymerization of 5-trivinylbenzene under the initiation of AIBN. The thermal stability of HC-TVP was studied. The HC-TVP was transformed into HT- 鈪，

本文編號：1492066