负载金属磷化物的多孔碳材料的制备及在催化产氢方面的应用

发布时间：2018-02-05 04:03

  本文关键词： 有机多孔聚合物 过渡金属磷化物 电解水产氢 BODIPY　出处：《上海应用技术学院》2015年硕士论文　论文类型：学位论文

【摘要】：有机多孔聚合物因其优异的性能和特点,引起材料研究领域的广泛关注,因此有机多孔聚合物在单体的构建、聚合物的制备方法、以及聚合物的性能应用都得到极大的发展。氢气作为非常有开发前景的新能源,传统的制氢工艺仍然消耗化石燃料且增加了碳排放。电解水制氢是一种节能、可持续性的实行氢气量产的方法。过渡金属磷化物因其优异的电解水催化产氢性能成为了研究热点。鉴于传统的过渡金属磷化物材料比表面积不高,稳定性还需提高的缺点,本课题将有机多孔聚合物的优点与过渡金属磷化物优异的催化产氢性能相结合,将含磷多孔聚合物分别作为磷源和电子受体,把金属磷化物以及具有光电效应的功能分子引入到聚合物母体当中,不仅保留了母体比表面积高,化学稳定性好的有点,又赋予了新多孔材料在电催化产氢方面优异的性能。具体研究内容如下：(1)首先合成了具有乙烯基官能团的单体三苯乙烯基膦(TVP),然后以1,3,5-三乙烯基苯为结构单元,在AIBN的引发下发生自由基聚合,制备了新的超高交联有机骨架HC-T P。并HC-TVP的结构,多孔性,热稳定性等进行了研究。将HC-TVP用氢碘酸离子化为了HT-Ⅰ,然后利用HT-Ⅰ中的碘离子与含有金属阴离子基团经行离子交换,或其自身的孔结构对金属阴离子进行吸附,从而将金属Mo或Fe引入到多孔骨架中,制备了负载有金属的超交联多孔框架HT-Mo和HT-Fe。并研究了它们的多孔性、热稳定性等相关物理化学性质。然后通过将HT-Mo和HT-Fe在氢气的氛围中,热裂解制备了含有金属磷化物的多孔碳材料MoP@PC 和 FeP@PC。MoP@PC和FeP@PC不仅拥有较高的比表面积,且含有电解水产氢活性高的磷化钼和磷化铁颗粒,因此材料有较高的催化活性。(2)与上一章离子交换法制备负载有金属的多孔聚合物的方法不同,我们利用磷与过渡金属的配位作用,直接制备配位有金属的多孔聚合物,并对其电解水产氢性能进行了研究。(3)以含有乙烯键的含磷化合物为母体,利用乙烯基和卤族元素在钯(0)的催化下发生的Mizoroki-Heck偶联反应,将BODIPY引入到聚合物框架中,成功制备了多孔聚合物B-TVP线性聚合物B-BVP。并对BODIPY和类三苯基膦单元组成了donor-acceptor结构进行了研究。
[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，

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