【作者】 杨敬贺；

【导师】 陆安慧；

【作者基本信息】 大连理工大学 ， 工业催化， 2013， 博士

【摘要】 石墨烯基材料导电性较好,比表面积较大且表面易被官能化,具有良好的耐酸碱和耐高温特性。石墨烯基材料本身可以作为非金属催化剂,同时它还可以作为载体用于担载多种类型的传统催化剂。本论文设计合成了一系列石墨烯基复合催化剂,将其用于氧化反应、还原反应以及电催化氧化反应,表现出了优异的催化活性。主要研究结果如下：(1)石墨烯作为催化剂用于苯一步氧化制备苯酚的反应,苯的转化率达到18%,苯酚的选择性为97%。催化剂重复应用7次以后,活性仍然没有明显的降低。研究结果表明,石墨烯对双氧水适中的活化能力及对芳环较强的吸附平衡,是此反应获得高选择性和活性的关键。(2)通过溶剂蒸发法,合成了钴酞菁/氧化石墨和钴酞菁/石墨烯复合物。由于酞菁钴和氧化石墨之间有着复杂的电子相互作用,石墨烯骨架上的部分电子会转移给钴酞菁,酞菁钴上的电子又会通过类似反馈配位键的方式,转移到氧化石墨上的含氧基团上面。这种复合材料可用于阿司匹林的电化学药物检测。钴酞菁/石墨烯在超大剂量的抗坏血酸干扰下,仍然获得了比较理想的多巴胺的电化学检测效果。(3)以氧化石墨烯担载的磷酸银为前体,以载体为还原剂,合成了石墨烯担载的银粒子。并将此材料用于葡萄糖电化学氧化,在较低的氧化电压下获得了较高的催化活性。微波辅助合成了石墨烯担载的钯纳米粒子,其在微波辅助条件下,催化异佛尔酮加氢生成3,3,5-三甲基环己酮,获得了较高的转化率和选择性。(4)合成了具有特定形貌的磷酸镍/氧化石墨和磷酸镍/石墨烯复合材料,考察了石墨烯骨架上的含氧基团对材料自组装的影响。进一步合成了磷化镍/石墨烯纳米复合材料。结果表明,具有特定结构的磷化镍/石墨烯,具有较高的电化学氧化甲醇的催化性能。采用类似的方法合成了磷化铁/石墨烯复合材料,并将其用于催化F-T合成反应,获得了较高的活性。更多还原

【Abstract】 Graphene has good electrical conductivity, large specific surface area, whose surface is easily functionalized with acid and alkali. The graphene based materials are considered to be as a kind of very good nonmetallic catalysts and substrate. In this thesis, we design and synthesize a series of graphene-based materials for the oxidation, reduction reactions and electrochemical catalytic field. They showed higher catalytic activity and. the results are summarized as follow:(1) We report an efficient, highly selective, and low temperature graphene-catalyzed reaction process for one-step oxidation of benzene to phenol with hydrogen peroxide as the oxidant. The conversion of benzene reaches18%, with phenol being the sole product. The catalyst was reusable. It was concluded that the moderate H2O2activation rate and good benzene adsorption ability over the oxidation reaction are responsible for the outstanding catalytic performance.(2) Cobalt phthalocyanine/graphene oxide (CoPc-GO) and cobalt phthalocyanine/graphene (CoPc-G) layers were prepared via a simple solvent evaporation method driven by the electronic interaction between cobalt phthalocyanine and graphene oxide. The interaction between cobalt phthalocyanine and graphene oxide has been studied in detail by various methods. The result suggests that the interaction is complicated two-way process including the transfer of electron from the graphitic domain to the adsorbed cobalt phthalocyanine, and a feedback from the Co ions through the ligand-like attacking to oxygen functional groups of graphene oxide. The obtained structural hybrid materials have potential in the electrochemical detection of the compounded medicine. The CoPc-G modified glassy electrode showed excellent response to the electro-oxidation of dopamine.(3) Graphene nanosheets decorated with gourd-shaped Ag nanoparticles (GAg) were prepared from the precursor silver phosphate-graphene oxide nanocomposite (GOAgPO) by original substrate self-generated reduction methods. The material was studied for electrochemical oxidation of glucose in alkaline solution. GAg showed excellent activity at low peak potential. Graphene-supported Pd nanoparticles were prepared by a microwave-assisted reduction approach. The obtained Pd/G can be very effectively coupled to the microwave field, making it a high-performance catalyst for microwave-assisted selective hydrogenation of isophorone at low temperatures. (4) The nickel phosphide graphene nanomaterial (NiPG) was obtained by H2calcination the specific morphology nickel phosphates on graphene oxide (NiPOGO) and graphene (NiPOG) substrate, respectively which were synthesized by one-pot hydrothermal synthesis method. The obtained different structure of nickel phosphates in the same way depended on the influence of different kinds of oxygen-containing groups on graphene substrate. The substrate can also affect the particle size and distribution of nickel phosphates nanoparticles. These materials were employed to be as catalysts for electrochemical oxidation of methanol and the NiPG exhibited high activity. The iron phosphide graphene nanomaterial (FePG) was also obtained by the same method. The Fischer Tropsch Synthesis (FTS) reaction has been selected as model reaction for evaluating FePG.更多还原