Zsolt Pap

Immobilization of crystallized photocatalysts on ceramic paper by titanium(IV) ethoxide and photocatalytic decomposition of phenol

A simple method of persistent immobilization was developed for the fixing of highly efficient precrystallized (or even doped) titania (TiO2) based photocatalysts. TiO2 nanoparticles (Aeroxide P25 and VLP7000) were immobilized on the surface of Al2O3-based ceramic paper. For the immobilization, a titanium alkoxide (Ti(OEt)4) was applied as a fixing agent. This type of immobilization resulted in a photocatalytically active surface, which was used in fixed-bed flow reactors through the application of different forms of artificial or solar irradiation to activate the TiO2. To verify the stability, the decomposition of phenol was repeatedly measured on the same TiO2-covered ceramic paper; the photocatalytic performance proved to remain constant throughout five 2-h cycles. The potential for application on an industrial scale was demonstrated by a pilot-plant-scale flow reactor. The developed immobilization method is a simple technique that can be used to investigate the long-term efficiency of novel TiO2 samples, or can be applied in real air/water treatments.

Synthesis of Shape-Tailored WO3 Micro-/Nanocrystals and the Photocatalytic Activity of WO3/TiO2 Composites

A traditional semiconductor (WO3) was synthesized from different precursors via hydrothermal crystallization targeting the achievement of three different crystal shapes (nanoplates, nanorods and nanostars). The obtained WO3 microcrystals were analyzed by the means of X-ray diffraction (XRD), scanning electron microscopy (SEM) and diffuse reflectance spectroscopy (DRS). These methods contributed to the detailed analysis of the crystal morphology and structural features. The synthesized bare WO3 photocatalysts were totally inactive, while the P25/WO3 composites were efficient under UV light radiation. Furthermore, the maximum achieved activity was even higher than the bare P25’s photocatalytic performance. A correlation was established between the shape of the WO3 crystallites and the observed photocatalytic activity registered during the degradation of different substrates by using P25/WO3 composites.

Visible light driven photocatalytic elimination of organic- and microbial pollution by rutile-phase titanium dioxides: new insights on the dynamic relationship between morpho-structural parameters and photocatalytic performance

The characteristic properties and the resulted photocatalytic efficiencies of rutile-phase titanium dioxides were investigated in the present study. A series of rutile with different primary particle sizes (5.2–290 nm) were produced by a sol–gel method followed by calcination and were characterized by XRD, DRS, TEM, XPS, EPR, IR and N2 adsorption. Their photocatalytic efficiencies were determined in the decomposition of phenol, and in the inactivation of E. coli bacteria under visible light irradiation. The results were compared with the photocatalytic performance of commercial Aldrich rutile and Aeroxide P25 powders. Of the non-commercial products, the TiO2 with the smallest particle size displayed the highest efficiency, while the surface-normalized photocatalytic performance was significantly higher for the larger rutile particles. This can be explained by the red shift of light absorption at higher calcination temperatures. Although Aldrich rutile and the corresponding laboratory-made photocatalyst exhibited similar structural features (e.g. particle size, specific surface area, morphology and light absorption), the latter proved to be less efficient despite its Ti3+ content (while Aldrich rutile contains only Ti4+). The main reason for the much higher photocatalytic performance was the presence of Ti–O–O– entities on the surface of Aldrich rutile. On the basis of these results, in the case of rutile-phase titanium dioxide, the presence of Ti–O–O– entities was more beneficial, than the presence of Ti3+ and low-binding-energy oxygen (which indicates defects) in relation with the photocatalytic performance under visible light irradiation.

Photocatalytic, Morphological and Structural Properties of the TiO2-SiO2-Ag Porous Structures Based System

TiO2-SiO2-based nanocomposites with highly porous structures are gaining ever increasing attention due to their specific properties and large variability of synthesis pathways together with wide information on the impact of the synthesis on the activity of the catalyst. This thereby offers an alternative approach to traditional/commercially available photocatalysts. In our work TiO2-SiO2 based aerogels were obtained and modified with various amount of Ag nanoparticles, using different synthesis pathways. In the first instance their photocatalytic activity was examined in detail, by observing major differences toward salicylic acid and correlating them with their morphological and structural properties (investigating their mesoporous character, band-gap values, crystallinity grade etc.). Applying different techniques such as diffuse reflectance spectroscopy (DRS), X-ray diffraction measurements (XRD), transmission electron microscopy (TEM), Raman- and X-ray photoelectron spectroscopy (XPS) the nanoparticles and their composite morphological and structural details were successfully evaluated. Major differences were observed in the activity towards salicylic acid.

Differently Shaped Au Nanoparticles: A Case Study on the Enhancement of the Photocatalytic Activity of Commercial TiO2

In the present work, the influence of a gold nanoparticle’s shape was investigated on the commercially available Evonik Aeroxide P25. By the variation of specific synthesis parameters, three differently shaped Au nanoparticles were synthetized and deposited on the surface of the chosen commercial titania. The nanoparticles and their composites’ morphological and structural details were evaluated, applying different techniques such as Diffuse Reflectance Spectroscopy (DRS), X-ray Diffraction (XRD), and Transmission Electron Microscopy (TEM). The influence of the Au nanoparticles’ shape was discussed by evaluating their photocatalytic efficiency on phenol and oxalic acid degradation and by investigating the H2 production efficacy of the selected composites. Major differences in their photocatalytic performance depending on the shape of the deposited noble metal were evidenced.

Facile Green Synthesis of BiOBr Nanostructures with Superior Visible-Light-Driven Photocatalytic Activity

Novel green bismuth oxybromide (BiOBr-G) nanoflowers were successfully synthesized via facile hydrolysis route using an Azadirachta indica (Neem plant) leaf extract and concurrently, without the leaf extract (BiOBr-C). The Azadirachta indica leaf extract was employed as a sensitizer and stabilizer for BiOBr-G, which significantly expanded the optical window and boosted the formation of photogenerated charge carriers and transfer over the BiOBr-G surface. The photocatalytic performance of both samples was investigated for the degradation of methyl orange (MO) and phenol (Ph) under the irradiation of visible light. The leaf extract mediated BiOBr-G photocatalyst displayed significantly higher photocatalytic activity when compared to BiOBr-C for the degradation of both pollutants. The degradation rate of MO and Ph by BiOBr-G was found to be nearly 23% and 16% more when compared to BiOBr-C under visible light irradiation, respectively. The substantial increase in the photocatalytic performance of BiOBr-G was ascribed to the multiple synergistic effects between the efficient solar energy harvesting, narrower band gap, high specific surface area, porosity, and effective charge separation. Furthermore, BiOBr-G displayed high stability for five cycles of photocatalytic activity, which endows its practical application as a green photocatalyst in the long run.

Biofabricated BiOI with enhanced photocatalytic activity under visible light irradiation

In the recent past, there has been a large-scale utilization of plant extracts for the synthesis of various photocatalysts. The biofabrication technology eliminates the usage of harmful chemicals and serves as an eco-friendly approach for environmental remediation. Herein, a comparative analysis between bismuth oxyiodide synthesized via Azadirachta indica (neem) leaf extract (BiOI-G) and without leaf extract (BiOI-C) has been envisaged. The BiOI-G and BiOI-C samples were characterized by spectral and microscopic techniques, which revealed that the Azadirachta indica assisted BiOI-G attained enhanced features over BiOI-C such as narrower band gap, large surface area, porosity, increased absorption range of visible light and effectual splitting of the photogenerated e−–h+ pairs. Benefiting from these enhanced features, BiOI-G degraded methyl orange (MO), rhodamine B (RhB), and benzotriazole (BT) at a significantly higher rate in comparison to BiOI-C. The degradation rate of MO, RhB and BT by BiOI-G was observed to be 1.3, 1.25 and 1.29 times higher in comparison to BiOI-C. Moreover, BiOI-G displayed high stability upto five cycles of the photocatalytic activity, which endow its effectiveness as a highly-efficient green photocatalyst.

Surface Plasmon Resonance or Biocompatibility—Key Properties for Determining the Applicability of Noble Metal Nanoparticles

Metal and in particular noble metal nanoparticles represent a very special class of materials which can be applied as prepared or as composite materials. In most of the cases, two main properties are exploited in a vast number of publications: biocompatibility and surface plasmon resonance (SPR). For instance, these two important properties are exploitable in plasmonic diagnostics, bioactive glasses/glass ceramics and catalysis. The most frequently applied noble metal nanoparticle that is universally applicable in all the previously mentioned research areas is gold, although in the case of bioactive glasses/glass ceramics, silver and copper nanoparticles are more frequently applied. The composite partners/supports/matrix/scaffolds for these nanoparticles can vary depending on the chosen application (biopolymers, semiconductor-based composites: TiO2, WO3, Bi2WO6, biomaterials: SiO2 or P2O5-based glasses and glass ceramics, polymers: polyvinyl alcohol (PVA), Gelatin, polyethylene glycol (PEG), polylactic acid (PLA), etc.). The scientific works on these materials’ applicability and the development of new approaches will be targeted in the present review, focusing in several cases on the functioning mechanism and on the role of the noble metal.

The Comparison of the Photocatalytic Performance Shown by TiO2 and TiO2/WO3 Composites— A Parametric and Kinetic Study

Kinetic and mechanistic related approaches for mostly titania were intensively studied in the literature. However, combined modelling and kinetic studies are few. Therefore, the present work focuses on modelling the dependence of the degradation kinetics of two model compounds (salicylic acid-SA and methyl orange-MO) on Evonik Aeroxide P25, hydrothermally prepared hierarchical TiO₂ and P25/WO₃ nanostars, obtained also by hydrothermal crystallization. The obtained individual semiconductors and the composites were characterized using XRD, DRS, SEM, while the photocatalytic degradation of the model pollutants were carried out varying the catalyst load, the initial pollutant concentration and incident light intensity. It was found that the degradation kinetics were independent from the hierarchical nature of the material, while significant dependencies of the degradation efficiency was found from the previously mentioned investigation parameters. All these parametric interdependences were successfully studied and a kinetic model was proposed for both bare TiO₂ and TiO₂/WO₃ composite systems.

Detailed Spectroscopic and Structural Analysis of TiO2/WO3 Composite Semiconductors

WO3-TiO2 composite materials were obtained using commercial titania (Evonik Aeroxide P25) and hydrothermally crystallized WO3. Different ratios of TiO2/WO3 were investigated, starting at 1 wt.% of WO3 to 50 wt.%. The morphology of WO3 was of the star-like type, and its structure is basically composed of monoclinic crystalline phase. All spectroscopic characteristics of the composites and their derived data (band-gap energy value, light absorption threshold, and IR specific bands) directly varied with the increase of the WO3 content. However, the oxalic acid photodegradation achieved under UV light reached the highest yield for 24 wt.% WO3 content, a result that was attributed to the charge separation efficiency and the surface hydrophilicity. The latter mentioned reason points out the crucial importance of the surface quality of the investigated structure in photocatalytic tests.