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•Interparticle electron transfer between different and same phases of titania.•Sample annealing results in formation of titania aggregates.•Platinum is deposited preferably on rutile ...phase.•Platinized rutile is the most active photocatalyst for methanol dehydrogenation.•Formation of titania aggregates lowers necessary amount of deposited platinum.
Commercial titania sample (P25) was homogenized first (HomoP25), and then crystalline phases (anatase and rutile) were isolated from it by chemical dissolution methods followed by samples’ purification by washing and annealing. The photocatalytic activities were tested for anaerobic methanol dehydrogenation in two reaction systems: (1) under UV/vis polychromatic irradiation with in situ platinum (Pt) deposition, and (2) under UV/vis monochromatic irradiation (action spectra) for ex situ platinum deposition. The properties of bare and modified titania samples were investigated by XRD, DRS, STEM, BET and zeta potential measurements. It was found that platinized rutile was more active than platinized anatase and platinized HomoP25, due to ability of photoabsorption of more photons (narrower band gap). Moreover, in HomoP25 sample, rutile was platinized first, probably due to positively charged surface allowing favorable adsorption of chloroplatinate ions. More than 10 times lower content of Pt (<0.1wt%) deposited on annealed samples (forming aggregates with an increased interface between titania NPs) than that on HomoP25 (2wt%) resulted in similar level of photocatalytic activity, suggesting an interparticle electron transfer (IPET) between titania NPs inside one aggregates (one Pt NP was sufficient for one aggregate).
A simple, low-cost method was applied to prepare hybrid photocatalysts of copper (I) oxide/titania. Five different TiO₂ powders were used to perform the study of the effect of titania matrix on the ...photocatalytic and antimicrobial properties of prepared nanocomposites. The photocatalytic efficiency of such a dual heterojunction system was tested in three reaction systems: ultraviolet-visible (UV-Vis)-induced methanol dehydrogenation and oxidation of acetic acid, and 2-propanol oxidation under visible light irradiation. In all the reaction systems considered, the crucial enhancement of photocatalytic activity in relation to corresponding bare titania was observed. The reaction mechanism for a specific reaction and the influence of titania matrix were discussed. Furthermore, antimicrobial (bactericidal and fungicidal) properties of Cu₂O/TiO₂ materials were analyzed. The antimicrobial activity was found under UV, visible and solar irradiation, and even for dark conditions. The origin of antimicrobial properties with emphasis on the role of titania matrix was also discussed.
Titania is probably the most widely investigated semiconductor photocatalyst because of various advantages, such as high activity, thermal and chemical stability, low price, abundance, and negligible ...toxicity. However, pristine titania is also characterized by charge carriers’ recombination, and thus lower quantum yields of photocatalytic reactions than theoretical 100%. Moreover, its wide bandgap, despite being recommended for excellent redox properties, means also inactivity under visible part of solar radiation. Accordingly, titania has been surface modified, doped and coupled with various elements/compounds. For example, platinum deposited on the surface of titania has shown to improve both UV activity and the performance under vis. Although the studies on titania modification with platinum started almost half a century ago, and huge number of papers have been published up to now, it is unclear which properties are the most crucial and recommended to obtain highly efficient photocatalyst. In the literature, the opposite findings could be found on the property-governed activities that could result from huge differences in the reaction systems, and also examined photocatalysts. Considering the platinum properties, its content, the size of nanoparticles and the oxidation state, must be examined. Obviously, the characteristics of titania also influence the resultant properties of deposited platinum, and thus the overall photocatalytic performance. Although so many reports on Pt/TiO
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have been published, it is hardly possible to give indispensable advice on the recommended properties. However, it might be concluded that usually fine platinum NPs uniformly deposited on the titania surface result in high photocatalytic activity, and thus in the low optimal content of necessary platinum. Moreover, the aggregation of titania particles might also help in the lowering the necessary platinum amount (even to 0.2 wt%) due to the interparticle electron transfer mechanism between titania particles in one aggregate. In respect of platinum state, it is thought that it is highly substrate-specific case, and thus either positively charged or zero valent platinum is the most recommended. It might be concluded that despite huge number of papers published on platinum-modified titania, there is still a lack of comprehensive study showing the direct correlation between only one property and the resultant photocatalytic activity.
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•Two-faceted (DAP) ― more favorable configuration than single-faceted (OAP) under UV irradiation.•Bare and modified DAP ― efficient charge carriers’ separation under UV ...irradiation.•Noble metal-modified OAP ― higher activity than respective DAP under vis irradiation.•“Hot” (plasmonic) electron transfer via shallow electron traps in OAP.•Localization of noble metal on DAP – key factor of vis activity.
Octahedral anatase particles (OAP, with eight equivalent {101} facets) and decahedral anatase particles (DAP, with two additional {001} facets) were modified with nanoparticles of noble metals (Au, Ag, Cu). The titania morphology, expressed by the presence of different arrangements of exposed crystal facets, played a key role in the photocatalytic properties of metal-modified faceted titania. In the UV/vis systems, two-faceted configuration of DAP was more favorable for the reaction efficiency than single-faceted OAP because of an efficient charge separation described by the transfer of electrons to {101} facets and holes to {001} facets. Time-resolved microwave conductivity (TRMC) and reversed double-beam photoacoustic spectroscopy (RDB-PAS) confirmed that distribution of electron traps (ET) and mobility of electrons were key-factors of photocatalytic activity. In contrast, metal-modified OAP samples had higher photocatalytic activity than metal-modified DAP and metal-modified commercial titania samples under visible light irradiation. This indicates that the presence of single type of facets ({101}) is favorable for efficient electron transfer via shallow ET, whereas intrinsic properties of DAP result in fast charge carriers’ recombination when gold is deposited on {101} facets (migration of “hot” electrons: Au→{101}→Au).
Plasmonic photocatalysts have gained more and more attention because of possible applications for solar energy conversion, environmental decontamination, and water treatment. However, the activity ...under visible light is usually very low, and the property-governed activity as well as the mechanisms are not fully understood yet. Accordingly, this study examines four different titania photocatalysts (anatase and rutile with fine and large crystallites) modified with gold by photodeposition. Three kinds of samples were prepared, as follows: (i) gold-modified titania (Au/TiO2), (ii) physically mixed Au/TiO2 samples (Au/TiO2(1) + Au/TiO2(2)), and (iii) Au/(TiO2(1) + Au/TiO2(2)) samples, prepared by subsequent deposition of gold on the mixture of bare and gold-modified titania. In total, twelve samples were prepared and well characterized, including diffuse reflectance spectroscopy (DRS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and scanning transmission electron microscopy (STEM). The photocatalytic activity was examined in three reaction systems: (i) methanol dehydrogenation during gold photodeposition under UV/vis irradiation, (ii) oxidative decomposition of acetic acid (UV/vis), and (iii) oxidation of 2-propanol to acetone under visible light irradiation (λ > 450 nm). It was found that during subsequent deposition, gold is mainly formed on the surface of pre-deposited Au nanoparticles (NPs), localized on fine titania NPs, through the electrostatic attractions (negatively charged gold resulting from photogenerated electrons’ accumulation). This gold aggregation, though detrimental for UV activity (many “naked” large titania with low activity), is highly beneficial for vis activity because of efficient light harvesting and increased interface between gold and titania (gold deposits surrounded by fine titania NPs). Moreover, it was found that rutile is more active than anatase for plasmonic photocatalysis, probably due to easier electron transfer from gold via titania to adsorbed oxygen (more negative conduction band), which might hinder the back reaction (electron transfer: Au→TiO2→Au).
Plasmonic photocatalysts have been extensively studied for the past decade as a possible solution to energy crisis and environmental problems. Although various reports on plasmonic photocatalysts ...have been published, including synthesis methods, applications, and mechanism clarifications, the quantum yields of photochemical reactions are usually too low for commercialization. Accordingly, it has been proposed that preparation of plasmonic photocatalysts with efficient light harvesting and inhibition of charge carriers’ recombination might result in improvement of photocatalytic activity. Among various strategies, nano-architecture of plasmonic photocatalysts seems to be one of the best strategies, including the design of properties for both semiconductor and noble-metal-deposits, as well as the interactions between them. For example, faceted nanoparticles, nanotubes, aerogels, and super-nano structures of semiconductors have shown the improvement of photocatalytic activity and stability. Moreover, the selective deposition of noble metals on some parts of semiconductor nanostructures (e.g., specific facets, basal or lateral surfaces) results in an activity increase. Additionally, mono-, bi-, and ternary-metal-modifications have been proposed as the other ways of performance improvement. However, in some cases, the interactions between different noble metals might cause unwanted charge carriers’ recombination. Accordingly, this review discusses the recent strategies on the improvements of the photocatalytic performance of plasmonic photocatalysts.
In the past few decades, extensive studies have been performed to utilize the solar energy for photocatalytic water splitting; however, up to the present, the overall efficiencies reported in the ...literature are still unsatisfactory for commercialization. The crucial element of this challenging concept is the proper selection and design of photocatalytic material to enable significant extension of practical application perspectives. One of the important features in describing photocatalysts, although underestimated, is particle morphology. Accordingly, this review presents the advances achieved in the design of photocatalysts that are dedicated to hydrogen generation, with an emphasis on the particle morphology and its potential correlation with the overall reaction performance. The novel concept of this work—with the content presented in a clear and logical way—is based on the division into five parts according to dimensional arrangement groups of 0D, 1D, 2D, 3D, and combined systems. In this regard, it has been shown that the consideration of the discussed aspects, focusing on different types of particle morphology and their correlation with the system’s efficiency, could be a promising route for accelerating the development of photocatalytic materials oriented for solar-driven hydrogen generation. Finally, concluding remarks (additionally including the problems connected with experiments) and potential future directions of particle morphology-based design of photocatalysts for hydrogen production systems have been presented.
Serum deprivation-response protein (SDPR), a phosphatidylserine-binding protein, which is known to have a promising role in caveolar biogenesis and morphology. However, its function in hepatocellular ...carcinoma (HCC) was still largely unknown. In this study, we discussed the characterization and identification of SDPR, and to present it as a novel apoptosis candidate in the incidence of HCC. We identified 81 HCC cases with lower SDPR expression in the tumor tissues with the help of qRT-PCR assay, and lower SDPR expression was potentially associated with poor prognostication. The phenotypic assays revealed that cell proliferation, invasion, and migration were profoundly connected with SDPR, both in vivo and in vitro. The data obtained from the gene set enrichment analysis (GSEA) carried out on the liver hepatocellular carcinoma (LIHC), and also The Cancer Genome Atlas (TCGA) findings indicated that SDPR was involved in apoptosis and flow cytometry experiments further confirmed this. Furthermore, we identified the interaction between SDPR and apoptosis signal-regulating kinase 1 (ASK1), which facilitated the ASK1 N-terminus-mediated dimerization and increased ASK1-mediated signaling, thereby activating the JNK/p38 mitogen-activated protein kinases (MAPKs) and finally enhanced cell apoptosis. Overall, this work identified SDPR as a tumor suppressor, because it promoted apoptosis by activating ASK1-JNK/p38 MAPK pathways in HCC.
Visible-responsive photocatalysts for environmental purification and fuel generation are, currently, highly sought after. Among the possible candidates, Bi2WO6 (BWO) has been considered due to its ...efficient light harvesting, stability, and promising activities. Here, hierarchical BWO microballs have been prepared using a hydrothermal method, and additionally modified with deposits of noble metals (gold, silver, copper, palladium and platinum) by the photodeposition method. The structure, morphology, photoabsorption properties, and surface composition of bare and metal-modified BWO samples were investigated by XRD, SEM, DRS and XPS analyses. The photocatalytic activity was evaluated by the oxidative degradation of model dye (methyl orange (MO)) under UV/vis, and hydrogen generation under vis and/or UV irradiation. It was found that hierarchical morphology is detrimental for high photocatalytic activity in both tested systems, resulting in the improved degradation of MO (ca. 65% during 90 min of UV/vis irradiation), and hydrogen evolution (0.1 and 0.4 μmol h−1 under vis and UV/vis irradiation, respectively). Moreover, the type of noble metal and its properties influence the overall photocatalytic performance. It was found that, under UV/vis irradiation, only platinum accelerates hydrogen evolution, whereas under vis irradiation the activity follows the order: BWO < BWO/Cu < BWO/Ag < BWO/Pt < BWO/Pd < BWO/Au. It was concluded that zero-valent metal is recommended for high vis response, probably due to plasmonic photocatalysis, efficient light harvesting ability, and co-catalytic role.
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