新型钌和钴配合物的制备及其光解水制氢的研究

发布时间：2018-04-29 03:12

本文选题：钌配合物 + 染料敏化TiO2　；参考：《郑州大学》2015年硕士论文

【摘要】：光催化分解水制氢作为一种清洁、可持续的产氢方法,备受科学家的关注。本文构建了两种光分解水催化产氢体系:基于联吡啶钌配合物敏化二氧化钛的非均相光催化产氢体系和基于钴催化剂的均相光催化产氢体系。合成了两种联吡啶钌类光敏配合物(PS1、PS2),并通过质谱、元素分析、红外、核磁、紫外-可见光谱以及循环伏安图谱等进行表征。然后,将两种联吡啶钌类光敏配合物敏化到Pt-Ti O2的固体表面得到相应的复合光敏催化剂,以抗坏血酸为电子给体,在纯水溶剂里构建非均相光催化产氢体系。研究表明,优化的反应条件下,以20mg PS1敏化的Pt负载Ti O2作为复合光敏催化剂,牺牲剂为抗坏血酸(1.0g),反应液p H值为5.3,可见光照射5h下,在水体系中获得了375.8μmol的最大累积产氢量,3h内产氢速率为11903.3μmol/g/h。循环实验表明复合光敏催化剂具有较好的稳定性,对反应体系失活原因的初步研究表明钌配合物光敏染料从Ti O2表面的脱附是主要原因。合成了三种基于钴的光催化剂(C1、C2、C3),并通过红外、核磁、单晶衍射、紫外-可见光谱和循环伏安图谱等进行了表征。以三种钴配合物为光催化剂,曙红Y为光敏剂,TEA或TEOA为电子给体,在乙腈/水混合溶剂里构建均相产氢体系,并对反应条件进行了优化。研究表明,催化剂C1浓度为2×10-5M,曙红Y浓度为1×10-4M,TEA体积分数为10%,p H=10.0,乙腈/水(v/v)=1:1,可见光照射3h后,体系相对于催化剂的TON最高,可以达到352。
[Abstract]:Photocatalytic decomposition of water for hydrogen production as a clean and sustainable method of hydrogen production has attracted the attention of scientists. In this paper, two kinds of photocatalytic hydrogen production systems were constructed: heterogeneous photocatalytic hydrogen production system based on bipyridine ruthenium complex sensitized titanium dioxide and homogeneous photocatalytic hydrogen production system based on cobalt catalyst. Two kinds of bipyridine ruthenium Guang Min complexes were synthesized and characterized by mass spectrometry, elemental analysis, IR, NMR, UV-Vis spectra and cyclic voltammetry. Then, two kinds of bipyridine ruthenium Guang Min complexes were sensitized to the solid surface of Pt-Ti O 2 to obtain the corresponding composite Guang Min catalyst. Using ascorbic acid as the electron donor, the heterogeneous photocatalytic hydrogen production system was constructed in pure water solvent. The results showed that under the optimized reaction conditions, the Pt / TIO _ 2 supported on 20mg PS1 was used as the composite Guang Min catalyst, the sacrificial agent was ascorbic acid (1.0 g), the pH value of the reaction solution was 5.3, and the visible light irradiation was 5 h. The maximum cumulative hydrogen production rate of 375.8 渭 mol is 11903.3 渭 mol / g / h within 3 h. The cycling experiment showed that the composite Guang Min catalyst had good stability, and the primary study on the deactivation of the reaction system showed that the desorption of the ruthenium complex Guang Min dye from the surface of TIO 2 was the main reason. Three kinds of cobalt based photocatalysts were synthesized and characterized by IR, NMR, single crystal diffraction, UV-Vis spectra and cyclic voltammetry. Using three cobalt complexes as photocatalyst, eosin Y as Guang Min agent tea or TEOA as electron donor, homogeneous hydrogen production system was constructed in acetonitrile / water mixed solvent, and the reaction conditions were optimized. The results show that the catalyst C1 concentration is 2 脳 10 ~ (-5) M, eosin Y concentration is 1 脳 10 ~ (-4) M ~ (-1) tea volume fraction is 10 脳 10 ~ (-4) M ~ (-1), acetonitrile / water v / v ~ (-1) 1: 1, and visible light irradiation for 3 h, the TON of the catalyst is the highest, which can reach 352.
【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】：TQ116.2;O643.36

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