The photocatalytic mechanism of TiO2 (P25) nanoparticles coated with SiO2 (SiO2:TiO2) by atomic layer deposition was investigated. The deposition of SiO2 on TiO2 not only gives a photocatalytic improvement for the degradation of both Rhodamine B (3.6–fold) and Acid Blue 9 (3–fold). SiO2 deposition also changes the mechanism from direct oxidation of the pollutant at the surface of TiO2 to a predominantly OH⁎ radical based degradation of the pollutants originating from SiO2:TiO2. Low SiO2 loadings on TiO2, where the coating is incomplete, improve the OH⁎ radicals generation due to the higher number of acidic Si–OH groups combined with the facilitated charge separation at the TiO2–SiO2 interface. As a consequence of incomplete coverage, the TiO2 surface remains accessible, which allows both the oxidation and reduction reactions at the SiO2:TiO2 surface. On the other hand, high loading of SiO2 (>3 wt.% Si) results in photocatalytic suppression due to the coverage of TiO2 surface by SiO2. The degradation of differently charged dyes on the SiO2:TiO2 surface demonstrates the independence of the adsorption properties on the photocatalytic improvement. Simultaneous degradation of two dyes demonstrated the advantage of SiO2:TiO2 being less selective and, therefore, better suited for general water purification.@en

Photocatalysts for water purification typically lack efficiency for practical applications. Here we present a multi-component (Pt:SiO2:TiO2 (P25)) material that was designed using knowledge of reaction mechanisms of mono-modified catalysts (SiO2:TiO2, and Pt:TiO2 ) combined with the potential of atomic layer deposition (ALD). The deposition of ultrathin SiO2 layers on TiO2 nanoparticles, applying ALD in a fluidized bed reactor, demonstrated in earlier studies their beneficial effects for the photocatalytic degradation of organic pollutants due to more acidic surface Si–OH groups which benefit the generation of hydroxyl radicals. Furthermore, our investigation on the role of Pt on TiO2 (P25), as an improved photocatalyst, demonstrated that suppression of charge recombination by oxygen adsorbed on the Pt particles, reacting with the separated electrons to superoxide radicals, acts as an important factor for the catalytic improvement. Combining both materials into the resulting Pt:SiO2:TiO2 (P25) nanopowder exceeded the dye degradation performance of both the individual SiO2:TiO2 (P25) (1.5 fold) and Pt:TiO2 (P25) (4-fold) catalysts by 6-fold as compared to TiO2 (P25). This approach thus shows that by understanding the individual materials’ behavior and using ALD as an appropriate deposition technique enabling control on the nano-scale, new materials can be designed and developed, further improving the photocatalytic activity. Our research demonstrates that ALD is an attractive technology to synthesize multicomponent catalysts in a precise and scalable way.@en

This work presents a gas-phase approach for the synthesis of Cu2O/TiO2 powder-based photocatalysts using atomic layer deposition (ALD). The process is carried out in a fluidized bed reactor working at atmospheric pressure using (trimethylvinylsilyl)-hexafluoroacetulacetonate copper(I) as the Cu-precursor and H2O vapor as the oxidizer. The saturating regime of the chemical reactions and the linear growth of ALD are achieved. In combination with the unsaturated regime, the ALD approach enables the deposition of ultrasmall Cu2O clusters with average diameters in the range of 1.3-2.0 nm, narrow particle size distributions and tunable Cu2O loadings on P25 TiO2 nanoparticles. The photocatalytic performance of Cu2O/TiO2 photocatalysts is investigated by the degradation of organic dyes, including Rhodamine B (RhB), methyl orange, and methylene blue; the results demonstrate that the surface modification of TiO2 nanoparticles by Cu2O nanoclusters significantly enhances the photocatalytic activity of TiO2. This is attributed to the efficient charge transfer between Cu2O and TiO2 that reduces the charge recombination. The photocatalytic reaction mechanism is further investigated for the degradation of RhB, revealing the dominating role of holes, which contribute to both direct hole oxidation and indirect oxidation (i.e. via the formation of hydroxyl radicals). Our approach provides a fast, scalable and efficient process to deposit ultrasmall Cu2O clusters in a controllable fashion for surface engineering and modification.@en

This work presents a gas-phase approach for the synthesis of Cu2O/TiO2 powder-based photocatalysts using atomic layer deposition (ALD). The process is carried out in a fluidized bed reactor working at atmospheric pressure using (trimethylvinylsilyl)-hexafluoroacetulacetonate copper(I) as the Cu-precursor and H2O vapor as the oxidizer. The saturating regime of the chemical reactions and the linear growth of ALD are achieved. In combination with the unsaturated regime, the ALD approach enables the deposition of ultrasmall Cu2O clusters with average diameters in the range of 1.3-2.0 nm, narrow particle size distributions and tunable Cu2O loadings on P25 TiO2 nanoparticles. The photocatalytic performance of Cu2O/TiO2 photocatalysts is investigated by the degradation of organic dyes, including Rhodamine B (RhB), methyl orange, and methylene blue; the results demonstrate that the surface modification of TiO2 nanoparticles by Cu2O nanoclusters significantly enhances the photocatalytic activity of TiO2. This is attributed to the efficient charge transfer between Cu2O and TiO2 that reduces the charge recombination. The photocatalytic reaction mechanism is further investigated for the degradation of RhB, revealing the dominating role of holes, which contribute to both direct hole oxidation and indirect oxidation (i.e. via the formation of hydroxyl radicals). Our approach provides a fast, scalable and efficient process to deposit ultrasmall Cu2O clusters in a controllable fashion for surface engineering and modification.@en

We employed atomic layer deposition (ALD) to deposit ultrathin SiO2 layers on P25 TiO2 nanoparticles to fabricate TiO2/SiO2 core/shell nanostructures. The ALD process was carried out in a fluidized bed reactor working at atmospheric pressure using SiCl4 and H2O as precursors, enabling the deposition of SiO2 at 100 °C with the ability to control the thickness at the sub-nanometer level. By controlling the thickness of the SiO2 in a very narrow range, i.e., below 2 nm, the photocatalytic activity of TiO2 can be tuned. In particular, an enhancement was obtained for the SiO2 layers with a thickness below 1.4 nm, in which the layer with a thickness of about 0.7 nm exhibited the highest photocatalytic activity; for SiO2 layers thicker than 1.4 nm, the photocatalytic activity was strongly suppressed. The photocatalytic activity enhancement and the degradation mechanism of RhB by the TiO2/SiO2 photocatalysts were investigated by combining X-ray photoelectron spectroscopy, UV–Vis absorption spectroscopy, photoluminescence spectroscopy and the aid of charge carrier and radical scavengers. Our findings have revealed an improvement of photogenerated charge separation due to the SiO2 coating and the dominating role of hydroxyl radicals in the degradation of RhB.@en

We employed atomic layer deposition (ALD) to deposit ultrathin SiO2 layers on P25 TiO2 nanoparticles to fabricate TiO2/SiO2 core/shell nanostructures. The ALD process was carried out in a fluidized bed reactor working at atmospheric pressure using SiCl4 and H2O as precursors, enabling the deposition of SiO2 at 100 °C with the ability to control the thickness at the sub-nanometer level. By controlling the thickness of the SiO2 in a very narrow range, i.e., below 2 nm, the photocatalytic activity of TiO2 can be tuned. In particular, an enhancement was obtained for the SiO2 layers with a thickness below 1.4 nm, in which the layer with a thickness of about 0.7 nm exhibited the highest photocatalytic activity; for SiO2 layers thicker than 1.4 nm, the photocatalytic activity was strongly suppressed. The photocatalytic activity enhancement and the degradation mechanism of RhB by the TiO2/SiO2 photocatalysts were investigated by combining X-ray photoelectron spectroscopy, UV–Vis absorption spectroscopy, photoluminescence spectroscopy and the aid of charge carrier and radical scavengers. Our findings have revealed an improvement of photogenerated charge separation due to the SiO2 coating and the dominating role of hydroxyl radicals in the degradation of RhB.@en

We employed atomic layer deposition (ALD) to deposit ultrathin SiO2 layers on P25 TiO2 nanoparticles to fabricate TiO2/SiO2 core/shell nanostructures. The ALD process was carried out in a fluidized bed reactor working at atmospheric pressure using SiCl4 and H2O as precursors, enabling the deposition of SiO2 at 100 °C with the ability to control the thickness at the sub-nanometer level. By controlling the thickness of the SiO2 in a very narrow range, i.e., below 2 nm, the photocatalytic activity of TiO2 can be tuned. In particular, an enhancement was obtained for the SiO2 layers with a thickness below 1.4 nm, in which the layer with a thickness of about 0.7 nm exhibited the highest photocatalytic activity; for SiO2 layers thicker than 1.4 nm, the photocatalytic activity was strongly suppressed. The photocatalytic activity enhancement and the degradation mechanism of RhB by the TiO2/SiO2 photocatalysts were investigated by combining X-ray photoelectron spectroscopy, UV–Vis absorption spectroscopy, photoluminescence spectroscopy and the aid of charge carrier and radical scavengers. Our findings have revealed an improvement of photogenerated charge separation due to the SiO2 coating and the dominating role of hydroxyl radicals in the degradation of RhB.@en

We employed atomic layer deposition (ALD) to deposit ultrathin SiO2 layers on P25 TiO2 nanoparticles to fabricate TiO2/SiO2 core/shell nanostructures. The ALD process was carried out in a fluidized bed reactor working at atmospheric pressure using SiCl4 and H2O as precursors, enabling the deposition of SiO2 at 100 °C with the ability to control the thickness at the sub-nanometer level. By controlling the thickness of the SiO2 in a very narrow range, i.e., below 2 nm, the photocatalytic activity of TiO2 can be tuned. In particular, an enhancement was obtained for the SiO2 layers with a thickness below 1.4 nm, in which the layer with a thickness of about 0.7 nm exhibited the highest photocatalytic activity; for SiO2 layers thicker than 1.4 nm, the photocatalytic activity was strongly suppressed. The photocatalytic activity enhancement and the degradation mechanism of RhB by the TiO2/SiO2 photocatalysts were investigated by combining X-ray photoelectron spectroscopy, UV–Vis absorption spectroscopy, photoluminescence spectroscopy and the aid of charge carrier and radical scavengers. Our findings have revealed an improvement of photogenerated charge separation due to the SiO2 coating and the dominating role of hydroxyl radicals in the degradation of RhB.@en

We employed atomic layer deposition (ALD) to deposit ultrathin SiO2 layers on P25 TiO2 nanoparticles to fabricate TiO2/SiO2 core/shell nanostructures. The ALD process was carried out in a fluidized bed reactor working at atmospheric pressure using SiCl4 and H2O as precursors, enabling the deposition of SiO2 at 100 °C with the ability to control the thickness at the sub-nanometer level. By controlling the thickness of the SiO2 in a very narrow range, i.e., below 2 nm, the photocatalytic activity of TiO2 can be tuned. In particular, an enhancement was obtained for the SiO2 layers with a thickness below 1.4 nm, in which the layer with a thickness of about 0.7 nm exhibited the highest photocatalytic activity; for SiO2 layers thicker than 1.4 nm, the photocatalytic activity was strongly suppressed. The photocatalytic activity enhancement and the degradation mechanism of RhB by the TiO2/SiO2 photocatalysts were investigated by combining X-ray photoelectron spectroscopy, UV–Vis absorption spectroscopy, photoluminescence spectroscopy and the aid of charge carrier and radical scavengers. Our findings have revealed an improvement of photogenerated charge separation due to the SiO2 coating and the dominating role of hydroxyl radicals in the degradation of RhB.@en

We employed atomic layer deposition (ALD) to deposit ultrathin SiO2 layers on P25 TiO2 nanoparticles to fabricate TiO2/SiO2 core/shell nanostructures. The ALD process was carried out in a fluidized bed reactor working at atmospheric pressure using SiCl4 and H2O as precursors, enabling the deposition of SiO2 at 100 °C with the ability to control the thickness at the sub-nanometer level. By controlling the thickness of the SiO2 in a very narrow range, i.e., below 2 nm, the photocatalytic activity of TiO2 can be tuned. In particular, an enhancement was obtained for the SiO2 layers with a thickness below 1.4 nm, in which the layer with a thickness of about 0.7 nm exhibited the highest photocatalytic activity; for SiO2 layers thicker than 1.4 nm, the photocatalytic activity was strongly suppressed. The photocatalytic activity enhancement and the degradation mechanism of RhB by the TiO2/SiO2 photocatalysts were investigated by combining X-ray photoelectron spectroscopy, UV–Vis absorption spectroscopy, photoluminescence spectroscopy and the aid of charge carrier and radical scavengers. Our findings have revealed an improvement of photogenerated charge separation due to the SiO2 coating and the dominating role of hydroxyl radicals in the degradation of RhB.@en

We employed atomic layer deposition (ALD) to deposit ultrathin SiO2 layers on P25 TiO2 nanoparticles to fabricate TiO2/SiO2 core/shell nanostructures. The ALD process was carried out in a fluidized bed reactor working at atmospheric pressure using SiCl4 and H2O as precursors, enabling the deposition of SiO2 at 100 °C with the ability to control the thickness at the sub-nanometer level. By controlling the thickness of the SiO2 in a very narrow range, i.e., below 2 nm, the photocatalytic activity of TiO2 can be tuned. In particular, an enhancement was obtained for the SiO2 layers with a thickness below 1.4 nm, in which the layer with a thickness of about 0.7 nm exhibited the highest photocatalytic activity; for SiO2 layers thicker than 1.4 nm, the photocatalytic activity was strongly suppressed. The photocatalytic activity enhancement and the degradation mechanism of RhB by the TiO2/SiO2 photocatalysts were investigated by combining X-ray photoelectron spectroscopy, UV–Vis absorption spectroscopy, photoluminescence spectroscopy and the aid of charge carrier and radical scavengers. Our findings have revealed an improvement of photogenerated charge separation due to the SiO2 coating and the dominating role of hydroxyl radicals in the degradation of RhB.@en

We employed atomic layer deposition (ALD) to deposit ultrathin SiO2 layers on P25 TiO2 nanoparticles to fabricate TiO2/SiO2 core/shell nanostructures. The ALD process was carried out in a fluidized bed reactor working at atmospheric pressure using SiCl4 and H2O as precursors, enabling the deposition of SiO2 at 100 °C with the ability to control the thickness at the sub-nanometer level. By controlling the thickness of the SiO2 in a very narrow range, i.e., below 2 nm, the photocatalytic activity of TiO2 can be tuned. In particular, an enhancement was obtained for the SiO2 layers with a thickness below 1.4 nm, in which the layer with a thickness of about 0.7 nm exhibited the highest photocatalytic activity; for SiO2 layers thicker than 1.4 nm, the photocatalytic activity was strongly suppressed. The photocatalytic activity enhancement and the degradation mechanism of RhB by the TiO2/SiO2 photocatalysts were investigated by combining X-ray photoelectron spectroscopy, UV–Vis absorption spectroscopy, photoluminescence spectroscopy and the aid of charge carrier and radical scavengers. Our findings have revealed an improvement of photogenerated charge separation due to the SiO2 coating and the dominating role of hydroxyl radicals in the degradation of RhB.@en

We employed atomic layer deposition (ALD) to deposit ultrathin SiO2 layers on P25 TiO2 nanoparticles to fabricate TiO2/SiO2 core/shell nanostructures. The ALD process was carried out in a fluidized bed reactor working at atmospheric pressure using SiCl4 and H2O as precursors, enabling the deposition of SiO2 at 100 °C with the ability to control the thickness at the sub-nanometer level. By controlling the thickness of the SiO2 in a very narrow range, i.e., below 2 nm, the photocatalytic activity of TiO2 can be tuned. In particular, an enhancement was obtained for the SiO2 layers with a thickness below 1.4 nm, in which the layer with a thickness of about 0.7 nm exhibited the highest photocatalytic activity; for SiO2 layers thicker than 1.4 nm, the photocatalytic activity was strongly suppressed. The photocatalytic activity enhancement and the degradation mechanism of RhB by the TiO2/SiO2 photocatalysts were investigated by combining X-ray photoelectron spectroscopy, UV–Vis absorption spectroscopy, photoluminescence spectroscopy and the aid of charge carrier and radical scavengers. Our findings have revealed an improvement of photogenerated charge separation due to the SiO2 coating and the dominating role of hydroxyl radicals in the degradation of RhB.@en

The promotional effects on photocatalytic hydrogen production of CuxO clusters deposited using atomic layer deposition (ALD) on P25 TiO2 are presented. The structural and surface chemistry study of CuxO/TiO2 samples, along with first principles density functional theory simulations, reveal the strong interaction of ALD deposited CuxO with TiO2, leading to the stabilization of CuxO clusters on the surface; it also demonstrated substantial reduction of Ti4+ to Ti3+ on the surface of CuxO/TiO2 samples after CuxO ALD. The CuxO/TiO2 photocatalysts showed remarkable improvement in hydrogen productivity, with 11 times greater hydrogen production for the optimum sample compared to unmodified P25. With the combination of the hydrogen production data and characterization of CuxO/TiO2 photocatalysts, we inferred that ALD deposited CuxO clusters have a dual promotional effect: increased charge carrier separation and improved light absorption, consistent with known copper promoted TiO2 photocatalysts and generation of a substantial amount of surface Ti3+ which results in self-doping of TiO2 and improves its photo-activity for hydrogen production. The obtained data were also employed to modify the previously proposed expanding photocatalytic area and overlap model to describe the effect of cocatalyst size and weight loading on photocatalyst activity. Comparing the trend of surface Ti3+ content increase and the photocatalytically promoted area, calculated with our model, suggests that the depletion zone formed around the heterojunction of CuxO-TiO2 is the main active area for hydrogen production, and the hydrogen productivity of the photocatalyst depends on the surface coverage by this active area. However, the overlap of these areas suppresses the activity of the photocatalyst.@en

This work presents a novel chemical vapor deposition (CVD) approach that enables the deposition of ultrathin and conformal SiO2 layers on TiO2 anatase nanoparticles at room temperature using SiCl4 and air containing water without the use of a catalyst. The morphology of the CVD-grown SiO2 layers was found to be strongly dependent on the initial surface states of the TiO2 nanopowders, which could be altered by applying a simple heat pretreatment. The deposition on untreated TiO2 resulted in granular films, whereas on preheated TiO2 highly uniform and conformal SiO2 layers were obtained. By varying the SiCl4 precursor dosing time and the number of CVD cycles, the thickness of the SiO2 could be controlled at the nanometer level, which allowed us to investigate the influence of film thickness on the photocatalytic suppression ability. We found that a conformal SiO2 layer with a thickness of 3 nm could sufficiently suppress the photocatalytic activity of anatase TiO2 nanoparticles, which was demonstrated by the photodegradation of Rhodamine B. Our approach offers a simple, fast, feasible and low-temperature deposition method which can be directly applied to SiO2 coating on nanoparticles in pigments and other fields, particularly heat-sensitive materials, and further developed for large-scale production.@en