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The main objective of the present study is to synthesize iron oxide catalysts with engineered crystal defects and to clarify their crucial impact on the final catalytic activity in the CO2 hydrogenation process. The method used to engineer the desired crystal defects is based on changing the precipitation reaction conditions, such as the addition rate and the order of the precipitant during the primary phase of the synthesis of iron oxide catalysts. The catalyst synthesis process is based on the formation of iron oxalates in the first step, followed by thermal decomposition into iron oxides in the second step, which were subsequently tested as catalysts in CO2 hydrogenation. The reversed double-beam photoacoustic spectroscopy used for advanced characterization of the prepared catalysts demonstrated that the observed change in catalytic activity is related to the energy and density of electron traps connected with the defects in the crystal lattice of the catalysts. These defects occur during the precipitation of oxalates, and their formation is significantly affected by changes in the precipitation conditions, i.e., the course of nucleation and growth of iron oxalate crystals. The results of the presented study thus affirmed the cardinal importance of defect engineering in heterogeneous catalysis.

Abstract Photoabsorption properties of cellulose fibres under continuous and modulated irradiation were investigated in situ by the use of reversed double-beam photoacoustic spectroscopy (RDB-PAS). This photoacoustic (PA) measurement enabled observation of ultraviolet- and visible light-induced, electron trap filling, and reductive change on the surface of the fibres. Energy-resolved measurements and analysis of the kinetics of photoinduced de-excitation suggested that electrons that accumulated in the different cellulose crystalline phases had moderate reactivity toward molecular oxygen. Saturation limits of the intensities of the PA and RDB-PAS signals under de-aerated conditions in the presence of surface-adsorbed methanol were estimated for softwood and hardwood cellulose samples. The results suggest that the RDB-PAS technique is a feasible method for the estimation of the electron trap distribution, which is a potential measure of the density of crystalline cellulose defects.

Metal-doped graphitic carbon nitride (MCN) materials have shown great promise as effective photocatalysts for the conversion of acetic acid to carbon dioxide under UV–visible irradiation and are superior to pristine carbon nitride (g-C3N4, CN). In this study, the effects of metal dopants on the physicochemical properties of metal-doped CN samples (Fe-, Cu-, Zn-, FeCu-, FeZn-, and CuZn-doped CN) and their catalytic activity in the photooxidation of acetic acid were investigated and discussed for their correlation, especially on their surface and bulk structures. The materials in the order of highest to lowest photocatalytic activity are FeZn_CN, FeCu_CN, Fe_CN, and Cu_CN (rates of CO2 evolution higher than for CN), followed by Zn_CN, CuZn_CN, and CN (rates of CO2 evolution lower than CN). Although Fe doping resulted in the extension of the light absorption range, incorporation of metals did not significantly alter the crystalline phase, morphology, and specific surface area of the CN materials. However, the extension of light absorption into the visible region on Fe doping did not provide a suitable explanation for the increase in photocatalytic efficiency. To further understand this issue, the materials were analyzed using two complementary techniques, reversed double-beam photoacoustic spectroscopy (RDB-PAS) and electron spin resonance spectroscopy (ESR). The FeZn_CN, with the highest electron trap density between 2.95 and 3.00 eV, afforded the highest rate of CO2 evolution from acetic acid photodecomposition. All Fe-incorporated CN materials and Cu-CN reported herein can be categorized as high activity catalysts according to the rates of CO2 evolution obtained, higher than 0.15 μmol/min−1, or >1.5 times higher than that of pristine CN. Results from this research are suggestive of a correlation between the rate of CO2 evolution via photocatalytic oxidation of acetic acid with the threshold number of free unpaired electrons in CN-based materials and high electron trap density (between 2.95 and 3.00 eV).

This study fabricated tantalum (Ta)-doped titanium dioxide with a unique nanorod-assembled actinomorphic-flower-like microsphere structured film. The Ta-doped TiO2 actinomorphic-flower-like microsphere (TAFM) was fabricated via the solution immersion method in a Schott bottle with a home-made improvised clamp. The samples were characterised using FESEM, HRTEM, XRD, Raman, XPS, and Hall effect measurements for their structural and electrical properties. Compared to the undoped sample, the rutile-phased TAFM sample had finer nanorods with an average 42 nm diameter assembled to form microsphere-like structures. It also had higher oxygen vacancy sites, electron concentration, and mobility. In addition, a reversed double-beam photoacoustic spectroscopy measurement was performed for TAFM, revealing that the sample had a high electron trap density of up to 2.5 μmolg−1. The TAFM showed promising results when employed as the resistive-type sensing film for a humidity sensor, with the highest sensor response of 53,909% obtained at 3 at.% Ta doping. Adding rGO to 3 at.% TAFM further improved the sensor response to 232,152%.

Developing eco-friendly strategies to produce green fuel has attracted continuous and extensive attention. In this study, a novel gas-templating method was developed to prepare 2D porous S-doped g-C3N4 photocatalyst through simultaneous pyrolysis of urea (main g-C3N4 precursor) and ammonium sulfate (sulfur source and structure promoter). Different content of ammonium sulfate was examined to find the optimal synthesis conditions and to investigate the property-governed activity. The physicochemical properties of the obtained photocatalysts were analyzed by X-ray diffraction (XRD), field emission-scanning electron microscopy (FE-SEM), scanning transmission electron microscopy (STEM), specific surface area (BET) measurement, ultraviolet-visible light diffuse reflectance spectroscopy (UV/vis DRS), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) spectroscopy and reversed double-beam photo-acoustic spectroscopy (RDB-PAS). The as-prepared S-doped g-C3N4 photocatalysts were applied for photocatalytic H2 evolution under vis irradiation. The condition-dependent activity was probed to achieve the best photocatalytic performance. It was demonstrated that ammonium sulfate played a crucial role to achieve concurrently 2D morphology, controlled nanostructure, and S-doping of g-C3N4 in a one-pot process. The 2D nanoporous S-doped g-C3N4 of crumpled lamellar-like structure with large specific surface area (73.8 m2 g−1) and improved electron−hole separation showed a remarkable H2 generation rate, which was almost one order in magnitude higher than that of pristine g-C3N4. It has been found that though all properties are crucial for the overall photocatalytic performance, efficient doping is probably a key factor for high photocatalytic activity. Moreover, the photocatalysts exhibit significant stability during recycling. Accordingly, a significant potential of S-doped g-C3N4 has been revealed for practical use under natural solar radiation.

Five different (commercial and self-synthesized) titania samples were mixed with NaBH4 and then heated to obtain black titania samples. The change in synthesis conditions resulted in the preparation of nine different photocatalysts, most of which were black in color. The photocatalysts were characterized by various methods, including X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), photoacoustic and reverse-double beam photoacoustic spectroscopy (PAS/RDB-PAS). The photocatalytic activity was tested for oxidative decomposition of acetic acid, methanol dehydrogenation, phenol degradation and bacteria inactivation (Escherichia coli) under different conditions, i.e., irradiation with UV, vis, and NIR, and in the dark. It was found that the properties of the obtained samples depended on the features of the original titania materials. A shift in XRD peaks was observed only in the case of the commercial titania samples, indicating self-doping, whereas faceted anatase samples (self-synthesized) showed high resistance towards bulk modification. Independent of the type and degree of modification, all modified samples exhibited much worse activity under UV irradiation than original titania photocatalysts both under aerobic and anaerobic conditions. It is proposed that the strong reduction conditions during the samples’ preparation resulted in the partial destruction of the titania surface, as evidenced by both microscopic observation and crystallographic data (an increase in amorphous content), and thus the formation of deep electron traps (bulk defects as oxygen vacancies) increasing the charge carriers’ recombination. Under vis irradiation, a slight increase in photocatalytic performance (phenol degradation) was obtained for only four samples, while two samples also exhibited slight activity under NIR. In the case of bacteria inactivation, some modified samples exhibited higher activity under both vis and NIR than respective pristine titania, which could be useful for disinfection, cancer treatment and other purposes. However, considering the overall performance of the black titania samples in this study, it is difficult to recommend them for broad environmental applications.

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.

Surface modification of titania with noble and semi-noble metals resulted in significant enhancement of photocatalytic activity. Presented data, showing the photocatalytic properties of TiO2-M (where M is Pt and/or Cu) photocatalysts were further used as Fe3O4@SiO2/TiO2-M magnetic nanocomposites shells in ''Mono- and bimetallic (Pt/Cu) titanium(IV) oxide core-shell photocatalysts with Vis light activity and magnetic separability'' [1]. Platinum and copper were photodeposited on four different titania matrices (commercial and self-obtained ones). The prepared photocatalysts were characterized by X-ray diffraction (XRD) analysis, specific surface area measurements using the Brunauer-Emmet-Teller (BET) isotherm, diffuse reflectance spectroscopy (DR-UV/Vis) analysis as well as scanning transmission electron microscopy (STEM) analysis. Photocatalytic properties were investigated in three different reactions: H2 generation, acetic acid oxidation to CO2, and phenol degradation.

Abstract Colored wide‐bandgap semiconductor oxides with abundant mid‐gap states have long been regarded as promising visible light responsive photocatalysts. However, their catalytic activities are hampered by charge recombination at deep level defects, which constitutes the critical challenge to practical applications of these oxide photocatalysts. To address the challenge, a strategy is proposed here that includes creating shallow‐level defects above the deep‐level defects and thermal activating the migration of trapped electrons out of the deep‐level defects via these shallow defects. A simple and scalable solution plasma processing (SPP) technique is developed to process the presynthesized yellow TiO2 with numerous oxygen vacancies (Ov), which incorporates hydrogen dopants into the TiO2 lattice and creates shallow‐level defects above deep level of Ov, meanwhile retaining the original visible absorption of the colored TiO2. At elevated temperature, the SPP‐treated TiO2 exhibits a 300 times higher conversion rate for CO2 reduction under solar light irradiation and a 7.5 times higher removal rate of acetaldehyde under UV light irradiation, suggesting the effectiveness of the proposed strategy to enhance the photoactivity of colored wide‐bandgap oxides for energy and environmental applications.

Commercial titania photocatalysts were modified with silver and gold by photodeposition, and characterized by diffuse reflectance spectroscopy (DRS), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning transmission electron microscopy (STEM). It was found that silver co-existed in zero valent (core) and oxidized (shell) forms, whereas gold was mainly zero valent. The obtained noble metal-modified samples were examined with regard to antibacterial (Escherichia coli (E. coli)) and antifungal (Aspergillus niger (A. niger), Aspergillus melleus (A. melleus), Penicillium chrysogenum (P. chrysogenum), Candida albicans (C. albicans)) activity under visible-light irradiation and in the dark using disk diffusion, suspension, colony growth (“poisoned food”) and sporulation methods. It was found that silver-modified titania, besides remarkably high antibacterial activity (inhibition of bacterial proliferation), could also decompose bacterial cells under visible-light irradiation, possibly due to an enhanced generation of reactive oxygen species and the intrinsic properties of silver. Gold-modified samples were almost inactive against bacteria in the dark, whereas significant bactericidal effect under visible-light irradiation suggested that the mechanism of bacteria inactivation was initiated by plasmonic excitation of titania by localized surface plasmon resonance of gold. The antifungal activity tests showed efficient suppression of mycelium growth by bare titania, and suppression of mycotoxin generation and sporulation by gold-modified titania. Although, the growth of fungi was hardly inhibited through disc diffusion (inhibition zones around discs), it indicates that gold does not penetrate into the media, and thus, a good stability of plasmonic photocatalysts has been confirmed. In summary, it was found that silver-modified titania showed superior antibacterial activity, whereas gold-modified samples were very active against fungi, suggesting that bimetallic photocatalysts containing both gold and silver should exhibit excellent antimicrobial properties.

Nd-modified TiO2 photocatalysts have been obtained via hydrothermal (HT) and sol–hydrothermal (SHT) methods. The as-prepared samples were characterized by X-ray diffraction (XRD), BET surface area measurements, scanning electron microscopy (SEM), diffuse reflectance spectroscopy (DRS), luminescence spectroscopy and X-ray photoelectron spectroscopy (XPS). The photocatalytic activity of the synthesized samples was evaluated by the degradation of phenol in aqueous solution under irradiation with UV–vis (λ > 350 nm) and vis (λ > 420 nm) light, as well as by the degradation of gaseous toluene under irradiation with vis (λmax = 415 nm) light. It was found that Nd-modified TiO2 is an efficient photocatalyst for the degradation of phenol and toluene under visible light. XPS analysis revealed that the photocatalyst prepared via HT method contains a three-times higher amount of hydroxy groups at the surface layer and a two-times higher amount of surface defects than that obtained by the SHT method. The photocatalytic efficiency of phenol and toluene degradation under vis irradiation in the presence of 0.25% Nd-TiO2(HT) reached 0.62 and 3.36 μmol·dm−1·min−1, respectively. Photocatalytic activity tests in the presence of Nd-TiO2 and scavenger confirm that superoxide radicals were responsible for the visible light-induced degradation of the model pollutant in aqueous solution.

The Fe(III)-doped montmorillonite (Mt)/TiO2 composites were fabricated by adding Fe(III) during or after the aging of TiO2/Ti(OH)4 sol–gel in Mt, named as xFe-Mt/(1 − x)Fe-TiO2 and Fe/Mt/TiO2, respectively. In the xFe-Mt/(1 − x)Fe-TiO2, Fe(III) cations were expected to be located in the structure of TiO2, in the Mt, and in the interface between them, while Fe(III) ions are physically adsorbed on the surfaces of the composites in the Fe/Mt/TiO2. The narrower energy bandgap (Eg) lower photo-luminescence intensity were observed for the composites compared with TiO2. Better photocatalytic performance for phenol degradation was observed in the Fe/Mt/TiO2. The 94.6% phenol degradation was due to greater charge generation and migration capacity, which was confirmed by photocurrent measurements and electrochemical impedance spectroscopy (EIS). The results of the energy-resolved distribution of electron traps (ERDT) suggested that the Fe/Mt/TiO2 possessed a larger amorphous rutile phase content in direct contact with crystal anatase than that of the xFe-Mt/(1 − x)Fe-TiO2. This component is the fraction that is mainly responsible for the photocatalytic phenol degradation by the composites. As for the xFe-Mt/(1 − x)Fe-TiO2, the active rutile phase was followed by isolated amorphous phases which had larger (Eg) and which did not act as a photocatalyst. Thus, the physically adsorbed Fe(III) enhanced light adsorption and avoided charge recombination, resulting in improved photocatalytic performance. The mechanism of the photocatalytic reaction with the Fe(III)-doped Mt/TiO2 composite was proposed.

The effect of ion doping and the incorporation of additives on photocatalysts’ textural properties have been reviewed. Generally, it can be summarised that ion doping and additives have beneficial effects on photocatalytic efficiency and not all have an increase in the surface area. The excessive amount of dopants and additives will produce larger aggregated particles and also cover the mesoporous structures, thereby increasing the pore size (Pd) and pore volume (Pv). An excessive amount of dopants also leads to visible light shielding effects, thus influence photocatalytic performance. Ion doping also shows some increment in the surface areas, but it has been identified that synergistic effects of the surface area, porosity, and dopant amount contribute to the photocatalytic performance. It is therefore important to understand the effect of doping and the application of additives on the textural properties of photocatalysts, thus, their performance. This review will provide an insight into the development of photocatalyst with better performance for wastewater treatment applications.

Decahedral anatase particles (DAPs) have been prepared by the gas-phase method, characterized, and analyzed for property-governed photocatalytic activity. It has been found that depending on the reaction systems, different properties control the photocatalytic activity, that is, the particle aspect ratio, the density of electron traps and the morphology seem to be responsible for the efficiency of water oxidation, methanol dehydrogenation and oxidative decomposition of acetic acid, respectively. For the discussion on the dependence of the photocatalytic activity on the morphology and/or the symmetry other titania-based photocatalysts have also been analyzed, that is, octahedral anatase particles (OAP), commercial titania P25, inverse opal titania with and without incorporated gold NPs in void spaces and plasmonic photocatalysts (titania with deposits of gold). It has been concluded that though the morphology governs photocatalytic activity, the symmetry (despite its importance in many cases) rather does not control the photocatalytic performance.

Seven commercial titania (titanium(IV) oxide; TiO2) powders with different structural properties and crystalline compositions (anatase/rutile) were modified with copper by two variants of a photodeposition method, i.e., methanol dehydrogenation and water oxidation. The samples were characterized by diffuse reflectance spectroscopy (DRS), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). Although zero-valent copper was deposited on the surface of titania, oxidized forms of copper, post-formed in ambient conditions, were also detected in dried samples. All samples could absorb visible light (vis), due to localized surface plasmon resonance (LSPR) of zero-valent copper and by other copper species, including Cu2O, CuO and CuxO (x:1-2). The photocatalytic activities of samples were investigated under both ultraviolet (UV) and visible light irradiation (>450 nm) for oxidative decomposition of acetic acid. It was found that titania modification with copper significantly enhanced the photocatalytic activity, especially for anatase samples. The prolonged irradiation (from 1 to 5 h) during samples’ preparation resulted in aggregation of copper deposits, thus being detrimental for vis activity. It is proposed that oxidized forms of copper are more active under vis irradiation than plasmonic one. Antimicrobial properties against bacteria (Escherichia coli) and fungi (Aspergillus niger) under vis irradiation and in the dark confirmed that Cu/TiO2 exhibits a high antibacterial effect, mainly due to the intrinsic activity of copper species.

In order to clarify the reason of often reported low photocatalytic activity of rutile titania compared to that of anatase titania and the sluggish kinetics for oxygen reduction of rutile titania, in this study, faceted copper(I) oxide (Cu2O) particles (FCPs), i.e., cube, cuboctahedron and octahedron, were deposited onto rutile particles by an in-situ wet chemical method, and the co-catalytic action of FCPs was studied in the oxidative decomposition of acetic acid. The oxygen reduction reaction kinetics of bare and FCP-loaded titania samples in photodecomposition of organic compounds were investigated by light-intensity dependence measurement. FCPs serve as the specific sites (sink) which accumulate excited electrons to drive multielectron oxygen reduction reactions, as the counter reaction in photodecomposition of organic compounds by positive holes, which significantly improves the photocatalytic activity of rutile titania particles.

Noble metal (NM)-modified wide-bandgap semiconductors with activity under visible light (Vis) irradiation, due to localized surface plasmon resonance (LSPR), known as plasmonic photocatalysts, have been intensively studied over the last few years. Despite the novelty of the topic, a large number of reports have already been published, discussing the optimal properties, synthesis methods and mechanism clarification. It has been proposed that both efficient light harvesting and charge carriers’ migration are detrimental for high and stable activity under Vis irradiation. Accordingly, photonic crystals (PCs) with photonic bandgap (PBG) and slow photon effects seem to be highly attractive for efficient use of incident photons. Therefore, the study on PCs-based plasmonic photocatalysts has been conducted, mainly on titania inverse opal (IO) modified with nanoparticles (NPs) of NM. Although, the research is quite new and only several reports have been published, it might be concluded that the matching between LSPR and PBG (especially at red edge) by tuning of NMNPs size and IO-void diameter, respectively, is the most crucial for the photocatalytic activity.

The influence of changes in structural and physical properties on the photocatalytic activity of octahedral anatase particles (OAPs), exposing eight equivalent {101} facets, caused by calcination (2 h) in air or grinding (1 h) in an agate mortar was studied with samples prepared by ultrasonication (US; 1 h)–hydrothermal reaction (HT; 24 h, 433 K). Calcination in air at temperatures up to 1173 K induced particle shape changes, evaluated by aspect ratio (AR; d001/d101 = depth vertical to anatase {001} and {101} facets estimated by the Scherrer equation with data obtained from X-ray diffraction (XRD) patterns) and content of OAP and semi-OAP particles, without transformation into rutile. AR and OAP content, as well as specific surface area (SSA), were almost unchanged by calcination at temperatures up to 673 K and were then decreased by elevating the calcination temperature, suggesting that calcination at a higher temperature caused dull-edging and particle sintering, the latter also being supported by the analysis of particle size using XRD patterns and scanning electron microscopic (SEM) images. Time-resolved microwave conductivity (TRMC) showed that the maximum signal intensity (Imax), corresponding to a product of charge-carrier density and mobility, and signal-decay rate, presumably corresponding to reactivity of charge carriers, were increased with increase in AR, suggesting higher photocatalytic activity of OAPs than that of dull-edged particles. Grinding also decreased the AR, indicating the formation of dull-edged particles. The original non-treated samples showed activities in the oxidative decomposition of acetic acid (CO2 system) and dehydrogenation of methanol (H2 system) comparable to and lower than those of a commercial anatase titania (Showa Denko Ceramics FP-6), respectively. The activities of calcined and ground samples for the CO2 system and H2 system showed almost linear relations with AR and Imax, respectively, suggesting that those activities may depend on different properties.

This short review paper shows the significance of recombination of a photoexcited electron and a hole in conduction and valence bands, respectively, of a titania photocatalyst, since recombination has not yet been fully understood and has not been evaluated adequately during the past several decades of research on heterogeneous photocatalysis.

The bromination of hydrocarbons with CBr4 as a bromine source, induced by light-emitting diode (LED) irradiation, has been developed. Monobromides were synthesized with high efficiency without the need for any additives, catalysts, heating, or inert conditions. Action and absorption spectra suggest that CBr4 absorbs light to give active species for the bromination. The generation of CHBr3 was confirmed by NMR spectroscopy and GC–MS spectrometry analysis, indicating that the present bromination involves the homolytic cleavage of a C–Br bond in CBr4 followed by radical abstraction of a hydrogen atom from a hydrocarbon.

Facet-selective gold or platinum-nanoparticle deposition on decahedral-shaped anatase titania particles (DAPs) exposing {001} and {101} facets via photodeposition (PD) from metal-complex sources was reexamined using DAPs prepared with gas-phase reaction of titanium (IV) chloride and oxygen by quantitatively evaluating the area deposition density on {001} and {101} and comparing with the results of deposition from colloidal metal particles in the dark (CDD) or under photoirradiation (CDL). The observed facet selectivity, more or less {101} preferable, depended mainly on pH of the reaction suspensions and was almost non-selective at low pH regardless of the deposition method, PD or CDL, and the metal-source materials. Based on the results, the present authors propose that facet selectivity is attributable to surface charges (zeta potential) depending on the kind of facets, {001} and {101}, and pH of the reaction mixture and that this concept can explain the observed facet selectivity and possibly the reported facet selectivity without taking into account facet-selective reaction of photoexcited electrons and positive holes on {101} and {001} facets, respectively.

The electronic structure of N-TiO2 samples prepared by a sol-gel method was investigated by EPR (Electronic Paramagnetic Resonance) measurements and the energy-resolved distribution of electron traps. In EPR spectra, some of the resonance lines assigned to paramagnetic species of nitrogen and Ti3+ were detected. Sample prepared at 300 °C revealed the highest intensity line of the nitrogen paramagnetic centers, whereas that prepared at 400 °C showed a paramagnetic line for Ti3+. Measurements of the electron trap distribution showed higher density of electron traps for sample prepared at 400 °C than that at 300 °C. Sample prepared at 300 °C, which revealed the highest amount of nitrogen built in the titania in the interstitial position was the most active under visible light. It was evidenced that photocatalytic decomposition of acetaldehyde was dependent strongly on the BET surface area and electrokinetic potential of the photocatalyst surface. The UV content in the fluorescent lamp affected the yield of acetaldehyde decomposition.

One of the methods used to produce buffer layers for thin film solar cells is the Spray ion layer gas reaction (SPRAY-ILGAR). This method has exhibited astonishing efficiencies in the fabrication of homogenous compact metal chalcogenide films. The same approach can be applied in the preparation of photocatalyst on a substrate, in order to acquire a homogeneous and durable layer. In this work, the Spray-ILGAR technique has been utilized in the preparation of titania photocatalysts on stainless steel, which was carried out at Helmholtz-Zentrum Berlin for Materials and Energy, in Berlin, Germany. The characterizations and photocatalytic testing of the synthesized materials were then done at the Institute of Catalysis, Hokkaido University. The scanning electron microscopy (SEM) analysis showed that the titania was dispersed uniformly on top of the stainless steel, with a very durable and strong attachment. It was also found that the concentration of the titania on stainless steel can be easily varied by changing the concentration of the titania-precursor solution. Higher concentrations will result in a more compact and dense layer, while lowering the concentration of the precursor solution produces a less dense layer of TiO2. Apart from that, different temperatures did not change the distribution of the samples much. The photocatalytic activity of the synthesized materials was determined in terms of the photocatalytic decomposition of acetaldehyde under ultra violet (UV) light irradiation. The photocatalytic testing results proved that the samples can completely degrade acetaldehyde under UV irradiation. The heating temperature played a crucial role, as the sample prepared by with heating temperature of 550 °C, concentration of titania-precursor of 6.83 mM and a spraying time of 12 min showed the best results, requiring only 35 min to fully degrade 500 ppm of acetaldehyde.

This short review paper shows some misconceptions hidden in the discussion on the mechanism of heterogeneous photocatalysis, which may lead to fatal errors in conclusions. Topics described in this review are semiconductor photocatalysis, control experiments for proof of photocatalysis, and converse-proposition pitfalls in discussion.

Zeolite loaded with alkylsilane-covered titanium oxide was found to be more effective than its nonporous silica counterpart as phase-boundary catalyst (PBC) to promote epoxidation of alkenes with aqueous hydrogen peroxide. It was demonstrated that the phase-boundary catalyst system required neither stirring to make an emulsion, nor addition of a cosolvent to make a homogeneous solution to drive the reaction. However, some basic facts about them remain unclear, such as the question as to where an effective location of the active sites of PBC resides: is it on the external surface of the catalysts, or in their pores? In order to elucidate this problem, TS-1, HZSM-5 and zeolite loaded with alkylsilane"“covered sulfonic acid in which the location of the active sites is mainly inside the pore system, were chosen as model catalysts. Catalytic activities of the catalysts TS-1 and HZSM-5 were examined after modification with n-octadecyltrichlorosilane (ODS). Their activities were compared with zeolite loaded with alkysilane-covered titanium oxide particles, in which the active sites are on the external surface in reactions of 1-octene with aqueous H2O2 and cyclohexene with water as model reactions. The study suggests that the location of the active sites on the external surface plays an important role in the phenomenon of phase-boundary catalysis.

Plasmonic titania photocatalysts were prepared by titania modification with gold by photodeposition. It was found that for smaller amount of deposited gold (≤0.1 wt%), anatase presence and large surface area were beneficial for efficient hydrogen evolution during methanol dehydrogenation. After testing twelve amounts of deposited gold on large rutile titania, the existence of three optima for 0.5, 2 and >6 wt% of gold was found during acetic acid degradation. Under visible light irradiation, in the case of small gold NPs deposited on fine anatase titania, the dependence of photoactivity on gold amount was parabolic, and large gold amount (2 wt%), observable as an intensively coloured powder, caused photoactivity decrease. While for large gold NPs deposited on large rutile titania, the dependence represented cascade increase, due to change of size and shape of deposited gold with its amount increase. It has been thought that spherical/hemispherical shape of gold NPs, in comparison with rod-like ones, is beneficial for higher level of photoactivity under visible light irradiation. For all tested systems and regardless of deposited amount of gold, each rutile Au/TiO2 photocatalyst of large gold and titania NPs exhibited much higher photoactivity than anatase Au/TiO2 of small gold and titania NPs.