金属纳米颗粒在促进TiO2光催化中的作用

IF 7.1 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Topics in Current Chemistry Pub Date : 2022-03-03 DOI:10.1007/s41061-022-00373-x
Michael Bowker, Christopher O’Rourke, Andrew Mills
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引用次数: 10

摘要

在这篇综述中,我们重点介绍了金属纳米颗粒(NPs)在二氧化钛作为载体的光催化氧化中的作用。这分为两部分,即部分光氧化,其中有机牺牲剂在厌氧条件下氧化产生氢气(光重整),以及在有氧条件下有机物的光氧化矿化。我们提出了这类反应的一些规则,这些规则规定了哪些有机分子容易反应,哪些金属可能对这类反应有用。一般来说,金属NPs的存在极大地增强了二氧化钛光重整产氢的能力,并且可以使用广泛的分子,包括生物质。最常用的金属NPs是那些容易被还原的,即贵金属。在氧化反应中,金属产氢速率的大幅提高并不是那么极端,但仍然很重要。在所有这些催化中,一个重要的因素是金属NPs与光活性载体之间相互作用的性质,NPs可以发挥多种化学和电子作用。速率与金属的载荷有很大的关系,根据所用金属的不同,最大速率为~0.5 - 2% wt%的载荷。这种依赖的来源是系统的双功能性质,其中两种材料的亲密性对性能至关重要。这种速率变化与两者之间的界面有关,而界面又与金属NPs的大小有关。事实上,速率与金属颗粒附近的面积成正比,我们称之为扩展光催化区域和重叠(EPAO)动力学模型。该模型很好地描述了依赖性。随着颗粒覆盖率的增加,速率的增加与总面积的增加有关,但是,在最大值时,这些区域重叠,在更高的负载下,可用的活动面积减少,很好地再现了所观察到的行为。
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The Role of Metal Nanoparticles in Promoting Photocatalysis by TiO2

In this review, we highlight the role played by metal nanoparticles (NPs) in photocatalytic oxidation with titania as a support. This is presented in two parts, namely, partial photo-oxidation in which an organic sacrificial agent is oxidised in anaerobic conditions to produce hydrogen (photo-reforming), and photo-oxidative mineralisation of organics in aerobic conditions. We present some rules for such reactions that dictate which organic molecules can react readily, and which metals are likely to be useful for such reactions. Generally, the presence of metal NPs enhances enormously the ability of titania to yield hydrogen from photo-reforming, and a wide range of molecules can be used, including biomass. The metal NPs most used are those that are easily reduced, that is, the precious metals. The large enhancement in rate seen with metal for hydrogen production is not so extreme for the oxidation reactions, but is still significant. An important factor in all of this catalysis is the nature of the interaction between the metal NPs, which can play a multiplicity of chemical and electronic roles, and the photoactive support. A sharp dependency of rate on loading of metal is found, with maximum rates at ~0.5–2 wt% loading, depending on the metal used. The source of this dependency is the bifunctional nature of the system, in which the intimacy of both materials is crucial to performance. This rate variation is linked to the interface between the two, which is then linked to the size of the metal NPs. In fact, the rate is proportional to an area adjacent to the metal particles that we call the expanding photocatalytic area and overlap (EPAO) kinetic model. This model describes the dependence well. Rising rates with increasing coverage of particles is associated with increase in this total area but, at the maximum, these areas overlap and at higher loadings the available active area diminishes, reproducing the observed behaviour well.

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来源期刊
Topics in Current Chemistry
Topics in Current Chemistry Chemistry-General Chemistry
CiteScore
13.70
自引率
1.20%
发文量
48
期刊介绍: Topics in Current Chemistry is a journal that presents critical reviews of present and future trends in modern chemical research. It covers all areas of chemical science, including interactions with related disciplines like biology, medicine, physics, and materials science. The articles in this journal are organized into thematic collections, offering a comprehensive perspective on emerging research to non-specialist readers in academia or industry. Each review article focuses on one aspect of the topic and provides a critical survey, placing it in the context of the collection. Selected examples highlight significant developments from the past 5 to 10 years. Instead of providing an exhaustive summary or extensive data, the articles concentrate on methodological thinking. This approach allows non-specialist readers to understand the information fully and presents the potential prospects for future developments.
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