可溶性共轭聚合物作为氧还原催化剂的研究

发布时间：2018-03-26 03:23

本文选题：燃料电池　切入点：氧还原反应　出处：《聊城大学》2017年硕士论文

【摘要】：由于燃料电池具有能量转换效率高、稳定性高及无污染等特点,使其成为替代使用常规化石燃料为能源的能量转换装置。但是,用于燃料电池的阴极氧还原催化剂资源短缺、价格昂贵阻碍了燃料电池的市场化。因此,制备新型、高效、价格便宜的氧还原催化剂是目前燃料电池研究的主要内容。基于对碳载体、含氮催化剂前体和金属在催化剂催化活性中作用的研究,本文主要介绍了三种由碳(vulcan XC-72)负载的含氮非贵金属聚合物(M-N_x/C)作为氧还原催化剂的研究。通过电子扫描电镜(SEM)、X-射线光电子能谱(XPS)、紫外可见吸收光谱(UV)、红外光谱(IR)、热重分析(TGA)等手段对催化剂的物理特性进行了分析。采用循环伏安法(CV)、线性扫描伏安法(LSV)、旋转环盘电极测试法(RRDE)对催化剂的电催化特性进行了测试。由数据计算得到H_2O_2的产量和电子转移数,了解各种催化剂的催化活性,进一步通过动力学分析明确在各种催化剂的作用下氧气被还原时电子转移途径。(1)通过化学聚合法合成可溶性共轭聚合物标记为PBBDP,并成功制备PBBDP/C和Cu-PBBDP/C催化剂。通过物理表征、电化学测试和动力学分析表明:Cu-PBBDP/C的催化活性高于PBBDP/C。进一步将Cu-PBBDP/C与商业Pt/C(20%)比较得出Cu-PBBDP/C在电子转移数(ETN)和H_2O_2产量方面与Pt/C(20%)相近,并且催化活性高于文献中相同类型的催化剂,是一种高效的催化剂。(2)通过化学聚合方法合成含1,10-菲咯啉单元的单体OCBP。通过引入铜离子形成超分子聚合物Cu-OCBP,并采用碳粉为载体制备Cu-OCBP/C催化剂。研究表明:Cu-OCBP/C的催化活性虽然低于Pt/C(20%),但是与文献中同种类型的催化剂相比在电子转移数及H_2O_2产量方面仍具有较大的优势。(3)采用聚酰胺-胺型树枝状高分子(G4-NH_2)与1,10-菲咯啉-5-羧酸反应合成催化剂前体,标记为PAMAMPhen。采用简单方法制备PAMAMPhen/C、PAMAMPhen-Cu/C催化剂。通过物理表征、电化学表征、动力学分析表明PAMAMPhen-Cu/C的催化活性高于PAMAMPhen/C且与Pt/C相当。
[Abstract]:Because the fuel cell has high energy conversion efficiency, high stability and no pollution, make it become an alternative to the use of conventional fossil fuel energy conversion device for energy. However, for the cathode oxygen reduction catalyst shortage, expensive market hindered the fuel cell. Therefore, the preparation of a new type, high price. Cheap oxygen reduction catalyst is the main content of the fuel cell research. Based on the study of effect of nitrogen containing carbon carrier, catalyst precursors and metal catalyst in catalytic activity, this paper mainly introduces three kinds of carbon (Vulcan XC-72) load of nitrogen containing non noble metal polymer (M-N_x/C) as catalyst for oxygen reduction research by scanning electron microscopy (SEM), X- ray photoelectron spectroscopy (XPS), ultraviolet visible absorption spectroscopy (UV), infrared spectroscopy (IR), thermogravimetric analysis (TGA) on the physical properties of catalyst and other means The analysis using cyclic voltammetry (CV), linear sweep voltammetry (LSV), a rotating ring disk electrode testing method (RRDE) on the electrocatalytic properties of the catalysts were tested. The number and yield of electron transfer by H_2O_2 data, understand the catalytic activity of various catalysts, further clear in all through the dynamic analysis the effect of catalyst under oxygen is reduced when the electron transfer pathway. (1) by chemical polymerization of soluble conjugated polymers labeled PBBDP, and successfully prepared PBBDP/C and Cu-PBBDP/C catalysts. The physical characterization, electrochemical testing and analysis of kinetics showed that the catalytic activity of Cu-PBBDP/C was higher than that of PBBDP/C. and Cu-PBBDP/C will be further compared with commercial Pt/C (20%) Cu-PBBDP/C in the number of electron transfer (ETN) and H_2O_2 yield and Pt/C (20%) are similar, and higher catalytic activity than that of the same type of catalyst in the literature, is a kind of high efficient The catalyst. (2) by chemical polymerization of OCBP. monomer containing 1,10- phenanthroline unit by introducing copper ions to form supramolecular polymer Cu-OCBP as the carrier, and Cu-OCBP/C catalysts were prepared by carbon powder. The study shows that the catalytic activity of Cu-OCBP/C was lower than Pt/C (20%), but compared with the literature in the same type of catalyst electron transfer number and the yield of H_2O_2 is still a big advantage. (3) using polyamidoamine dendrimer (G4-NH_2) and synthesis catalyst 1,10- phenanthroline -5- carboxylic acid precursors, labeled as PAMAMPhen. prepared to adopt PAMAMPhen/C, prepared by a simple method of PAMAMPhen-Cu/C catalyst. The physical characterization, electrochemical characterization, kinetic analysis showed that the catalytic activity of PAMAMPhen-Cu/C is higher than that of PAMAMPhen/C and Pt/C.

【学位授予单位】：聊城大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36

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