基于钴配合物分子催化剂的染料敏化半导体光致产氢研究

发布时间：2018-05-14 18:50

本文选题：光催化产氢 + 钴配合物　；参考：《郑州大学》2015年硕士论文

【摘要】：本文基于非贵金属钴,设计合成了四个钴配合物,并将其作为光催化产氢反应中的析氢催化剂,以半导体材料作为主催化剂,以有机染料作为光敏剂,三乙胺作为电子给体牺牲剂,构建了完全不含贵金属的非均相光催化产氢体系。具体研究内容如下:1.以Co Cl2·6H2O、水杨酸和1,10-邻菲Up琳为起始原料,设计并制备了4个具有析氢活性的分子催化剂,即[Co(phen)2(L)](用Co L1-Co L4表示),并通过元素分析、红外光谱和核磁共振氢谱(1H NMR)等手段对其进行了表征。2.将上述四个钴配合物负载于Ti O2上得到Co L/Ti O2并以其作为催化剂,以有机氧杂蒽醌类染料作为光敏剂,三乙胺为电子给体构建了非均相光催化产氢体系。产氢测定结果表明,4个配合物中,Co L2具有最高析氢活性;且在最佳条件下(4μmol EY2-(醇溶),5%(v/v)TEA,p H为11),催化剂2wt%Co L2/Ti O2(50 mg)6h内产氢量达到了91μmol。此外,体系失活的主要原因为光敏剂的降解和Co L从Ti O2表面的脱附。3.将上述四种钴配合物负载于g-C3N4表面作为析氢催化剂,类似地,以EY2-(醇溶)作为光敏剂,三乙胺作为电子给体构建了产氢体系,并对各析氢条件进行了优化。结果表明:Co L3具有最佳析氢活性。在最佳条件下(50 mg催化剂,6μmol EY2-,7.5%(v/v)TEA,p H=11),2wt%Co L3/g-C3N4 2.5h内的产氢量达到72μmol。此外,同样地,该体系光照2.5h失活的主要原因源自敏化剂的光解和Co L的部分脱附。
[Abstract]:In this paper, four cobalt complexes were designed and synthesized based on non-noble metal cobalt, and they were used as catalysts for hydrogen evolution in photocatalytic hydrogen production reactions. Semiconductor materials were used as main catalysts and organic dyes as Guang Min agents. A heterogeneous photocatalytic hydrogen production system without noble metals was constructed by triethylamine as an electron donor sacrificial agent. The specific contents of the study are as follows: 1. Using Co Cl2 6H _ 2O, salicylic acid and 1-10-phenanthroline as starting materials, four molecular catalysts with hydrogen evolution activity, namely [Cochlein 2L] (expressed by Co L1-Co L4), were designed and prepared by elemental analysis. It was characterized by IR and 1H NMRs. Co L/Ti O 2 was prepared by loading the above four cobalt complexes on TIO 2. The heterogeneous photocatalytic hydrogen production system was constructed using organic oxygen heteranthracene quinone dyes as Guang Min agent and triethylamine as electron donor. The results of hydrogen production showed that L2 had the highest hydrogen evolution activity in the four complexes, and under the optimum conditions, 4 渭 mol EY2-H was obtained, and the hydrogen production of the catalyst 2wt%Co L2/Ti O _ 2O _ (50) mg)6h was 91 渭 mol / h. In addition, the main reasons for the deactivation of the system are the degradation of Guang Min and the desorption of Co L from the surface of TIO 2. 3. The above four cobalt complexes were loaded on the surface of g-C3N4 as catalyst for hydrogen evolution. Similarly, EY2-( alcohol-soluble) was used as Guang Min agent, triethylamine as electron donor to construct the hydrogen production system, and the conditions of hydrogen evolution were optimized. The results show that: (1) Co L _ 3 has the best hydrogen evolution activity. Under the optimum conditions, the hydrogen production of 6 渭 mol EY2-5 / v / v / Similarly, the main reason for the inactivation of the system at 2.5 h is the photolysis of the sensitizer and the partial desorption of Co L.
【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：O643.36;TQ116.2

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