联吡啶钌配合物光催化产氢的研究与1,8-萘啶衍生物催化加氢体系

发布时间：2018-04-24 00:16

本文选题：稠环芳烃 + 三联吡啶钌配合物　；参考：《云南师范大学》2017年硕士论文

【摘要】：联吡啶钌配合物在许多光催化反应中都有着重要的应用,这些反应包括光催化还原水生成氢气、光催化氧化水生成氧气、光催化有机合成和光催化还原二氧化碳生成甲醇等含碳化合物。在这些光催化反应中,联吡啶钌配合物可作为光敏剂,也可以作为催化剂。在此篇论文中,我们采用商业购买的Ru(bpy)_2Cl_2,β-环糊精作为反应底物,设计合成两个钌吡啶配合物,研究它们作为光敏剂的产氢性能。此外,在有机合成中,稠环芳烃的选择性催化加氢是一类很重要的反应,并且稠环芳烃具有一定的致癌性,将其部分饱和后会降低其毒性,稠环芳烃还原后的产物被广泛用在医药、燃料等领域。到目前为止,用来选择性催化加氢的催化剂主要是Ni、Pd、Ru、Pt、Rh、Os等贵金属及其配合物,H_2作为氢源,在高温、高压下进行反应,从而导致这类反应存在成本高,技术难度大等缺点。因此,探索能高效、有选择性的催化杂环化合物氢化的先进材料依旧是个挑战。本论文使用Ni_2P/NH_3BH_3体系,在室温、常压下还原5个1,8-萘啶衍生物,为在温和条件下还原杂环化合物提供了新的研究方向。主要内容有:1、合成2个三联吡啶钌配合物C1、C2,在DMF作为溶剂的条件下测定了它们的光谱性质及其电化学性质,并分别以它们作为光敏剂,FeCl_3以及以FeCl_3为底物得到的配合物Fe(TEOA)_2Cl_3作为光催化产氢的催化剂前体,研究了在不同条件下的光催化产氢情况。2、结合Ni_2P的Ni周围电子云密度大,有利于H_2解离和底物吸附以及在常压下,简便、易得且稳定的过渡金属磷化物(Ni_2P)能够有效地催化氨硼烷分解释放氢气的优势,制备磷化镍纳米粒子,选取具有刚性结构的1,8-萘啶衍生物作为底物,利用Ni_2P/NH_3BH_3体系在常温常压下将其选择性还原,并通过核磁氢谱、碳谱和质谱分别对还原主产物结构进行表征,确定了产物的结构。通过对5种主要还原产物对比得出给电子基团和吸电子基团对催化还原反应的影响。
[Abstract]:Bipyridine ruthenium complexes have important applications in many photocatalytic reactions including photocatalytic reduction of water to hydrogen and photocatalytic oxidation of water to oxygen. Photocatalytic organic synthesis and photocatalytic reduction of carbon dioxide to methanol and other carbon compounds. In these photocatalytic reactions, bipyridine ruthenium complex can be used as Guang Min or catalyst. In this paper, we design and synthesize two ruthenium pyridine complexes using Rubpyridine as the substrate, and study their hydrogen production properties as Guang Min. In addition, selective catalytic hydrogenation of polycyclic aromatic hydrocarbons is a very important reaction in organic synthesis. The products after the reduction of polycyclic aromatic hydrocarbons are widely used in medicine, fuel and other fields. Up to now, the main catalysts used for selective hydrogenation are noble metals such as NiOPdN, Ru-PtRh, RhOOs and their complexes, such as H _ (2), which are used as hydrogen sources to react at high temperature and high pressure, resulting in the high cost and high technical difficulty of these reactions. Therefore, it remains a challenge to explore advanced materials that can efficiently and selectively catalyze the hydrogenation of heterocyclic compounds. In this paper, Ni_2P/NH_3BH_3 system was used to reduce 5 1H 8 naphthalene derivatives at room temperature and atmospheric pressure, which provided a new research direction for the reduction of heterocyclic compounds under mild conditions. Two tripyridine ruthenium complexes C _ 1 C _ 2 were synthesized. Their spectral properties and electrochemical properties were determined under the condition of DMF as solvent. The photocatalytic hydrogen production under different conditions was studied by using them as Guang Min and Fe(TEOA)_2Cl_3 as precursors of photocatalytic hydrogen production respectively. The electron cloud density around Ni combined with Ni_2P was high. It is beneficial to the dissociation and substrate adsorption of H2 and the simple, easy and stable transition metal phosphates, Ni2P), which can effectively catalyze the decomposition and release of hydrogen from ammonioborane and prepare nickel phosphide nanoparticles. The structure of the main product was determined by Ni_2P/NH_3BH_3 system, which was characterized by NMR, carbon spectrum and mass spectrometry, and the structure of the main product was characterized by nuclear magnetic resonance spectroscopy, carbon spectrum and mass spectrometry, respectively, using the Ni_2P/NH_3BH_3 system to reduce the product selectively at room temperature and atmospheric pressure. The effects of electron group and electron group on the catalytic reduction reaction were obtained by comparing the five main reduction products.
【学位授予单位】：云南师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4;TQ116.2

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