摘要
过渡金属—N4大环化合物(如钴卟啉、铁卟啉、铁酞菁等)因其特殊的共轭结构是当前研究较多且极具应用前景的一类非贵金属氧还原催化剂。催化剂一般都要经过高温热处理提高活性,催化活性中心的结构特征一直是有机大环化合物催化剂研究中倍受关注的课题,实验证明在高温条件下大环化合物本身已经分解。所以,大环结构可能并非该类催化剂具备氧还原催化活性的必备条件。本文制备了新型的M-N3结构的环状化合物,进行表征;并首次将其负载到碳黑上,制备成氧还原电催化剂,采用电化学和物理测试手段对催化剂氧还原性能进行了分析,并对电池性能进行初试。
合成了双亚胺基苯基吡啶化合物以及Fe,Co系列的金属配合物,利用了晶体XRD、UV-vis、IR进行表征;并测试了该类配合物在DMSO溶液中的循环伏安,结果表明,受配体取代基和中心金属离子的影响,Co系列的金属配合物的电化学性质效果最好。
将金属亚胺基吡啶配合物负载到经过预处理的炭黑上,对其采取不同温度的热处理,制备了了电催化剂。利用循环伏安测试研究了催化剂结构、负载方法对催化剂性能影。结果表明,重结晶方法制备的CoBPML/BP催化剂的活性最好。与商业Pt/C催化剂相比,CoBPML/BP催化剂虽然电位值略低,但是电流值却能与之媲美,具有很好的模拟抗甲醇性能,说明新型催化剂还是一种很有希望的氧还原催化剂。
研究了热处理对催化剂电化学性能的影响。利用循环伏安法研究了200~900℃热处理温度对催化性能的影响。研究表明热处理提高了CoBPML/BP的催化活性,低温热处理对催化剂的性能影响不大,高温热处理可提高催化剂稳定性;利用TG、TEM、BET、XRD、XPS等手段对催化剂表面进行分析,结果表明,热处理增大了催化剂N和C原子的表面浓度,Co3C(101)和Co(111)晶型的形成以及组分N1、O1s、CoⅢ和CoⅡ的结合能的降低,都有利于Co-Nx-C催化活性位.的形成。
并利用旋转圆盘RDE和旋转环盘RRDE测试了新型催化剂的电子转移数和产生双氧水的百分比。发现催化剂的电子转移数3.0-4.0之间,试验还发现电极催化剂的厚度对试验产生H_2O_2%的检测有影响,催化剂层越薄,实验数据越准确。计算得催化反应产生的H_2O_2%为19%。以CoBPML/BP30%H_2O_2作为阴极催化剂的PEMFC测试结果表明,催化剂有较好的氧催化活性。
Transition metal-N4 macrocyclic compounds (such as cobalt-porphyrins, iron porphyrins, iron phthalocyanines, etc.) have been investigated widely as a class of effectively non-noble metal catalysts for electrocatalysts for ORR(oxygen reduction reaction). In general, the capability of the catalysts was improved with different temperature heat-treatment. The structural features of macro-cyclic compounds catalytic active site has been well-focused topic all the years. Lots of researches have investigated that macro-cyclic compounds were decomposed after pyrolysis. So the macro-cyclic structure of catalyst may not be the essential conditions for ORR. In this paper, we have synthesized and characterized a new type M-N3 compounds metal-2,6-bis(imino) pyridines, and prepared the carbon black supported M-N3 catalysts as novel kind of non-noble catalysts for ORR.
We have prepared and characterized the bis(imino)pyridine compounds and metal-bis(imino)pyridine compounds. The Cyclic Voltammetry (CV) of metal-2,6-bis(imino)pyridyl in DMSO have been investigated. Catalysts with different substituted groups and different metals irons have been investigated. It is found that the most efficient catalyst is consist of Co and–OCH3 substituted groups, and the CoBPML Co-bis(imino)pyridines compound is most efficient.
We prepared carbon Black supported metal bis(imino)pyridines compounds electrocatalysts. The effect of structures and different cabon supported methods on the electrocatalytic activities for oxygen reduction of CoBPML/BP were investigated by CV. Results reveal that CoBPML/BP catalyst prepared by re-crystallization is better efficient for ORR. And the potential value of CoBPML catalyst is lower than Pt/C catalyst, but the current value is higher. CoBPML/BP catalyst can work in menthol solution with a good performance.
The effect of various heated-treating temperature from 200℃to 900℃on the electro catalytic activities for oxygen reduction of CoBPML/BP were investigated by CV. Studies have shown that heat treatment improved the CoBPML / BP catalytic activity and the stability, low-temperature heat treatment have little effect on the catalytic performance. The surface information of catalysts after pretreatment of BP support were investigated by TG、TEM、BET、XRD、XPS. It can be seen that heat-treatment lead to formation of Co3C(101) and Co(111) crystal type, and the binding energy reduction of N1, O1s, CoⅢand CoⅡcomponents. Above all these factors are in favor of the formation of Co-Nx-C active site.
The catalytic activity for oxygen reduction was evaluated by ring disk electrode (RDE) and rotating ring disk electrode (RRDE) techniques. The number of electrons exchanged during ORR and the percentage of peroxide (H_2O_2%) produced by the reaction were evaluated for catalysts by RRDE measurements. It was found that the number of electron transfer between the number of 3.0-4.0 for ORR. It also showed that the thickness of catalyst on electrode influenced the experiment result, and the H_2O_2% was 19%. The zinc-air battery performance of single cell using CoBPML/BP as cathodic oxygen reduction catalyst was examined; the results show that the novel catalysts have excellent prospect.
引文
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