Enhancement of Photocatalytic Activity for Hydrogen Production of Nano-TiO2 Using Ru(II)-Phenantroline Derivatives

IF 16.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Hui-Qin Zheng, Jun Wang, Ming-Cai Yin, Yao-Ting Fan
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引用次数: 0

Abstract

Two novel Ru(II)-phenanthroline derivatives complexes, Ru-1 and Ru-2, were synthesized and characterized. The key distinction between Ru-1 and Ru-2 lies in their ligands: L1 (2-hydroxy-5-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl) benzoic acid) and L2 (2-hydroxy-3-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)benzoic acid). In L1, the –OH group is located in the para-position, while in L2, it resides in the ortho-position. Subsequently, Pt/TiO2 and Ru-1/Pt/TiO2 (and Ru-2/Pt/TiO2) composites were prepared using photo-deposition and impregnation methods, respectively. The Ru-1/Pt/TiO2 and Ru-2/Pt/TiO2 composites were thoroughly characterized using various techniques, including ultraviolet-visible spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), fluorescence spectroscopy (FL), cyclic voltammetry (CV) experiments, and other relevant techniques. Photocatalytic hydrogen production systems were established by employing Ru-1/Pt-TiO2 and Ru-2/Pt-TiO2 as photocatalysts and ascorbic acid (H2A) as a sacrificial reagent. The results demonstrated that the maximum hydrogen production reached 1461 μmol (Ru-1/Pt/TiO2) and 843 μmol (Ru-2/Pt/TiO2) under optimized conditions with 20 mg of composite photocatalyst, 0.3 mol L–1 of H2A, and pH 4, within 4 h of irradiation (λ > 420 nm). Correspondingly, the photocatalytic hydrogen production rates were 18 267 and 10 523 μmol g–1 h–1, respectively. Mechanism studies revealed that electrons flow from the highest occupied molecular orbital (HOMO) of Ru-1 to the conduction band (CB) of TiO2, subsequently combining with H+ on the surface of the Pt metal nanoparticles to generate hydrogen gas. The holes on the lowest unoccupied molecular orbital (LUMO) of the photosensitizer are oxidized by H2A, thereby regenerating the activity of the composite catalyst by restoring the photosensitizer.

Abstract Image

Abstract Image

利用 Ru(II)-Phenantroline 衍生物提高纳米二氧化钛制氢的光催化活性
摘要 合成并鉴定了两种新型 Ru(II)-菲罗啉衍生物配合物 Ru-1 和 Ru-2。Ru-1 和 Ru-2 的主要区别在于它们的配体:L1(2-羟基-5-(1H-咪唑并[4,5-f][1,10]菲罗啉-2-基)苯甲酸)和 L2(2-羟基-3-(1H-咪唑并[4,5-f][1,10]菲罗啉-2-基)苯甲酸)。在 L1 中,-OH 基位于对位,而在 L2 中,它位于正位。随后,分别采用光沉积法和浸渍法制备了 Pt/TiO2 和 Ru-1/Pt/TiO2(以及 Ru-2/Pt/TiO2)复合材料。利用紫外可见光谱、X 射线衍射(XRD)、透射电子显微镜(TEM)、荧光光谱(FL)、循环伏安法(CV)实验等多种技术对 Ru-1/Pt/TiO2 和 Ru-2/Pt/TiO2 复合材料进行了全面的表征。以 Ru-1/Pt-TiO2 和 Ru-2/Pt-TiO2 为光催化剂,抗坏血酸(H2A)为牺牲试剂,建立了光催化制氢系统。结果表明,在 20 mg 复合光催化剂、0.3 mol L-1 H2A 和 pH 值为 4 的优化条件下,辐照(λ > 420 nm)4 h 内,最大产氢量达到 1461 μmol(Ru-1/Pt/TiO2)和 843 μmol(Ru-2/Pt/TiO2)。相应地,光催化产氢率分别为 18 267 和 10 523 μmol g-1 h-1。机理研究表明,电子从 Ru-1 的最高占位分子轨道(HOMO)流向 TiO2 的导带(CB),随后与铂金属纳米粒子表面的 H+ 结合生成氢气。光敏剂最低未占据分子轨道(LUMO)上的空穴被 H2A 氧化,从而通过恢复光敏剂来再生复合催化剂的活性。
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来源期刊
Accounts of Chemical Research
Accounts of Chemical Research 化学-化学综合
CiteScore
31.40
自引率
1.10%
发文量
312
审稿时长
2 months
期刊介绍: Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance. Accounts of Chemical Research replaces the traditional article abstract with an article "Conspectus." These entries synopsize the research affording the reader a closer look at the content and significance of an article. Through this provision of a more detailed description of the article contents, the Conspectus enhances the article's discoverability by search engines and the exposure for the research.
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