Does Symmetry Control Photocatalytic Activity of Titania-Based Photocatalysts?

Janczarek, Marcin; Wei, Zhishun; Mogan, Tharishinny R.; Wang, Lei; Wang, Kunlei; Nitta, Akio; Ohtani, Bunsho; Kowalska, Ewa

doi:10.3390/sym13091682

Cited by 3 publications

(2 citation statements)

References 61 publications

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“…According to the anatase symmetry, the two square and eight trapezoid surfaces should be {001} and {101} facets, respectively, as presented in the inset of Figure 1f [13,[30][31][32]. It should be mentioned that simple calcination of the S pm precursor despite obvious conversion of amorphous titania to the crystalline forms (anatase first and then anatase/rutile mixture) does not result in the formation of faceted-based microballs [28].…”

Section: Resultsmentioning

confidence: 99%

Development of Monodisperse Mesoporous Microballs Composed of Decahedral Anatase Nanocrystals

et al. 2022

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Mesoporous monodisperse microballs of amorphous titania were prepared from solution of absolute ethanol, tetrabutyl titanate (TBOT) and potassium chloride via a sub-zero sol–gel route. The as-obtained microballs were used as the precursor in an alcohothermal (ethanol with a small amount of water) process to synthesize monodisperse mesoporous microballs built of decahedral anatase nanocrystals. FE-SEM observation and XRD analysis have confirmed that the formed decahedral anatase-rich powder retained the original spherical morphology of the precursor. Importantly, a hierarchical structure composed of faceted anatase has been achieved under “green” conditions, i.e., fluorine-free. Additionally, the hysteresis loops (BET results) have confirmed the existence of mesopores. Interestingly, faceted microballs show noticeable photocatalytic activity under UV/vis irradiation for hydrogen generation without any co-catalyst use, reaching almost forty times higher activity than that by famous commercial titania photocatalyst—P25. It has been proposed that enhanced photocatalytic performance is caused by mesoporous structure and co-existence of two kinds of facets, i.e., {001} and {101}, and thus hindered charge carriers’ recombination.

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Section: Resultsmentioning

confidence: 99%

Development of Monodisperse Mesoporous Microballs Composed of Decahedral Anatase Nanocrystals

et al. 2022

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“…However, due to the fast recombination of electrons and holes and limited active catalytic sites on surface, the solar energy conversion efficiency is suppressed to a quite low level (even <1%), which dramatically hinders the practical applications of photocatalysis [12]. Another reason comes from the common use of photocatalytic materials with wide bandgaps such as TiO 2 and ZnO (~3.2 eV), which only respond to UV light consisting of a small part (5%) of solar energy [13][14][15][16]. Consequently, visible and near-infrared (NIR) light, which accounts for 46% and 49% of solar energy respectively, is hugely wasted [17].…”

Section: Introductionmentioning

confidence: 99%

Recent Developments in Heterogeneous Photocatalysts with Near-Infrared Response

Chen

Xi²,

Li³

et al. 2022

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Photocatalytic technology has been considered as an efficient protocol to drive chemical reactions in a sustainable and green way. With the assistance of semiconductor-based materials, heterogeneous photocatalysis converts solar energy directly into chemical energy that can be readily stored. It has been employed in several fields including CO2 reduction, H2O splitting, and organic synthesis. Given that near-infrared (NIR) light occupies 47% of sunlight, photocatalytic systems with a NIR response are gaining more and more attention. To enhance the solar-to-chemical conversion efficiency, precise regulation of the symmetric/asymmetric nanostructures and band structures of NIR-response photocatalysts is indispensable. Under the irradiation of NIR light, the symmetric nano-morphologies (e.g., rod-like core-shell shape), asymmetric electronic structures (e.g., defect levels in band gap) and asymmetric heterojunctions (e.g., PN junctions, semiconductor-metal or semiconductor-dye composites) of designed photocatalytic systems play key roles in promoting the light absorption, the separation of electron/hole pairs, the transport of charge carriers to the surface, or the rate of surface photocatalytic reactions. This review will comprehensively analyze the four main synthesis protocols for the fabrication of NIR-response photocatalysts with improved reaction performance. The design methods involve bandgap engineering for the direct utilization of NIR photoenergy, the up-conversion of NIR light into ultraviolet/visible light, and the photothermal effect by converting NIR photons into local heat. Additionally, challenges and perspectives for the further development of heterogeneous photocatalysts with NIR response are also discussed based on their potential applications.

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Fabrication and Characterization of Inverse-Opal Titania Films for Enhancement of Photocatalytic Activity

et al. 2022

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Novel materials with a periodic structure have recently been intensively studied for various photonic and photocatalytic applications due to an efficient light harvesting ability. Here, inverse opal titania (IOT) has been investigated for possible enhancement of photocatalytic activity. The IOT films were prepared on a glass support from silica and polystyrene (PS) opals by sandwich-vacuum-assisted infiltration and co-assembly methods, respectively. The reference sample was prepared by the same method (the latter) but with PS particles of different sizes, and thus without photonic feature. The modification of preparation conditions was performed to prepare the films with a high quality and different photonic properties, i.e., photonic bandgap (PBG) and slow photons’ wavelengths. The morphology and optical properties were characterized by scanning electron microscopy (SEM) and UV/vis spectroscopy, respectively. The photocatalytic activity was evaluated (also in dependence on the irradiation angle) for oxidative decomposition of acetaldehyde gas under irradiation with blue LED by measuring the rate of evolved carbon dioxide (CO2). It has been found that PBG wavelength depends on the size of particles forming opal, the void diameter of IOT, and irradiation angle, as expected from Bragg’s law. The highest activity (more than two-fold enhancement in the comparison to the reference) has been achieved for the IOT sample of 226-nm void diameter and PBG wavelengths at 403 nm, prepared from almost monodisperse PS particles of 252-nm diameter. Interestingly, significant decrease in activity (five times lower than reference) has been obtained for the IOT sample of also high quality but with 195-nm voids, and thus PBG at 375 nm (prohibited light). Accordingly, it has been proposed that the perfect tunning of photonic properties (here the blue-edge slow-photon effect) with bandgap energy of photocatalyst (e.g., absorption of anatase) results in the improved photocatalytic performance.

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Does Symmetry Control Photocatalytic Activity of Titania-Based Photocatalysts?

Cited by 3 publications

References 61 publications

Development of Monodisperse Mesoporous Microballs Composed of Decahedral Anatase Nanocrystals

Development of Monodisperse Mesoporous Microballs Composed of Decahedral Anatase Nanocrystals

Recent Developments in Heterogeneous Photocatalysts with Near-Infrared Response

Fabrication and Characterization of Inverse-Opal Titania Films for Enhancement of Photocatalytic Activity

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