Zhishun Wei , Limeng Wu , Xin Yue , Haoran Mu , Zhenhao Li , Ying Chang , Marcin Janczarek , Saulius Juodkazis , Ewa Kowalska
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引用次数: 0
Abstract
Preparation of porous micro-sized materials with solar response is urgent for fast commercialization of green technologies based on semiconductor photocatalysis. Here, mesoporous titania microballs composed of nanocrystalline anatase with exposed facets were prepared by a sub-zero sol-gel method followed by hydrothermal/alcohothermal crystallization. The mechanism of microballs formation and the influence of preparation conditions on the properties, and thus resultant photocatalytic activity, were investigated in detail. The photocatalytic performance was examined in four reaction systems under UV/vis irradiation, i.e., oxidative decomposition of methyl orange (MO) dye, hydrogen evolution, degradation of tetracycline (TC) antibiotic, and carbon dioxide reduction. Moreover, hydrogen generation was also examined under visible-light (vis) irradiation. Amorphous and faceted (octahedral- and decahedral-based) microballs were additionally modified with nanoparticles (NPs) of noble metals (Pt, Au, Ag, Pt/Au, Pt/Ag) for both UV-activity enhancement and vis response (i.e., plasmonic photocatalysis). It has been found that nano-architecture of microballs might be controlled by the ratio of alcohol to water used during hydrothermal/alcohothermal treatment. Accordingly, highly active microballs composed of pure octahedral- or decahedral-shaped anatase crystals, i.e., with {101} facets only (bipyramids) or eight {101} and two {001} facets, respectively, could be synthesized by a facile and environmental-friendly method. The versatility and high activity of faceted microballs have been confirmed in both oxidation and reduction reactions under UV and/or vis irradiation (comparable performance to that by famous P25). Decahedral-based samples exhibit usually higher photocatalytic activity than octahedral ones, despite worse photoelectronic properties (charge carriers’ separation, electron transport capacity and photocurrent density), due to higher hydrophilicity. However, single type {101} facet photocatalyst (octahedral shape) is preferable for efficient CO2 adsorption and reduction into CO and CH4. Among noble metals, though platinum shows much higher positive effect on UV activity, gold is responsible for the highest activity under vis, which corresponds to the strongest plasmonic filed enhancement, as proven by finite difference time domain (FDTD) simulations. Concluding, micro-sized balls composed of faceted anatase are undoubtedly prospective photocatalyst for diverse environmental applications.
要使基于半导体光催化的绿色技术快速商业化，迫切需要制备具有太阳能响应的多孔微尺寸材料。本文采用零度以下溶胶-凝胶法和水热/等温结晶法制备了由具有裸露切面的纳米锐钛矿组成的介孔二氧化钛微球。详细研究了微球的形成机理和制备条件对其特性的影响，以及由此产生的光催化活性。在紫外线/可见光照射下的四个反应体系中考察了光催化性能，即甲基橙（MO）染料的氧化分解、氢气进化、四环素（TC）抗生素降解和二氧化碳还原。此外，还考察了在可见光（vis）照射下的氢气生成情况。此外，还用贵金属（铂、金、银、铂/金、铂/银）的纳米颗粒（NPs）对无定形和刻面（八面体和十面体基）微球进行了修饰，以增强其紫外线活性和可见光响应（即等离子光催化）。研究发现，微球的纳米结构可能受水热/铝热处理过程中使用的酒精与水的比例控制。因此，高活性微球由纯粹的八面体或十面体锐钛矿晶体组成，即分别具有{101}面（双锥体）或八个{101}面和两个{001}面，可通过简便、环保的方法合成。在紫外和/或可见光照射下，切面微球在氧化和还原反应中的多功能性和高活性已得到证实（与著名的 P25 性能相当）。尽管十面体样品的光电子特性（电荷载流子分离、电子传输能力和光电流密度）比八面体样品差，但由于亲水性较高，十面体样品通常比八面体样品表现出更高的光催化活性。然而，单一类型的{101}面光催化剂（八面体形状）更适于高效吸附 CO2 并将其还原为 CO 和 CH4。在贵金属中，虽然铂对紫外线活性的积极影响更大，但金在可见光下的活性最高，这与有限差分时域（FDTD）模拟证明的最强等离子体增强效果相对应。总之，由切面锐钛矿组成的微球无疑是一种具有多种环境应用前景的光催化剂。
期刊介绍：
Applied Catalysis B: Environment and Energy (formerly Applied Catalysis B: Environmental) is a journal that focuses on the transition towards cleaner and more sustainable energy sources. The journal's publications cover a wide range of topics, including:
1.Catalytic elimination of environmental pollutants such as nitrogen oxides, carbon monoxide, sulfur compounds, chlorinated and other organic compounds, and soot emitted from stationary or mobile sources.
2.Basic understanding of catalysts used in environmental pollution abatement, particularly in industrial processes.
3.All aspects of preparation, characterization, activation, deactivation, and regeneration of novel and commercially applicable environmental catalysts.
4.New catalytic routes and processes for the production of clean energy, such as hydrogen generation via catalytic fuel processing, and new catalysts and electrocatalysts for fuel cells.
5.Catalytic reactions that convert wastes into useful products.
6.Clean manufacturing techniques that replace toxic chemicals with environmentally friendly catalysts.
7.Scientific aspects of photocatalytic processes and a basic understanding of photocatalysts as applied to environmental problems.
8.New catalytic combustion technologies and catalysts.
9.New catalytic non-enzymatic transformations of biomass components.
The journal is abstracted and indexed in API Abstracts, Research Alert, Chemical Abstracts, Web of Science, Theoretical Chemical Engineering Abstracts, Engineering, Technology & Applied Sciences, and others.
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