Enhanced visible-light photodegradation of fluoroquinolone-based antibiotics and E. coli growth inhibition using Ag–TiO2 nanoparticles

Antibiotics in wastewater represent a growing and worrying menace for environmental and human health fostering the spread of antimicrobial resistance. Titanium dioxide (TiO₂) is a well-studied and well-performing photocatalyst for wastewater treatment. However, it presents drawbacks linked with the high energy needed for its activation and the fast electron–hole pair recombination. In this work, TiO₂ nanoparticles were decorated with Ag nanoparticles by a facile photochemical reduction method to obtain an increased photocatalytic response under visible light. Although similar materials have been reported, we advanced this field by performing a study of the photocatalytic mechanism for Ag–TiO₂ nanoparticles (Ag–TiO₂ NPs) under visible light taking in consideration also the rutile phase of the TiO₂ nanoparticles. Moreover, we examined the Ag–TiO₂ NPs photocatalytic performance against two antibiotics from the same family. The obtained Ag–TiO₂ NPs were fully characterised. The results showed that Ag NPs (average size: 23.9 ± 18.3 nm) were homogeneously dispersed on the TiO₂ surface and the photo-response of the Ag–TiO₂ NPs was greatly enhanced in the visible light region when compared to TiO₂ P25. Hence, the obtained Ag–TiO₂ NPs showed excellent photocatalytic degradation efficiency towards the two fluoroquinolone-based antibiotics ciprofloxacin (92%) and norfloxacin (94%) after 240 min of visible light irradiation, demonstrating a possible application of these particles in wastewater treatment. In addition, it was also proved that, after five Ag–TiO₂ NPs re-utilisations in consecutive ciprofloxacin photodegradation reactions, only a photocatalytic efficiency drop of 8% was observed. Scavengers experiments demonstrated that the photocatalytic mechanism of ciprofloxacin degradation in the presence of Ag–TiO₂ NPs is mainly driven by holes and ˙OH radicals, and that the rutile phase in the system plays a crucial role. Finally, Ag–TiO₂ NPs showed also antibacterial activity towards Escherichia coli (E. coli) opening the avenue for a possible use of this material in hospital wastewater treatment.

Ag nanoparticles decorated-TiO₂ P25 are a viable alternative for the degradation, through a rutile-mediated mechanism, of fluoroquinolone-based antibiotics under visible light irradiation and, at the same time, for bacteria inactivation in water.     

Enhanced charge separation in TiO2/nanocarbon hybrid photocatalysts through coupling with short carbon nanotubes

The interfacial contact between TiO₂ and graphitic carbon in a hybrid composite plays a critical role in electron transfer behavior, and in turn, its photocatalytic efficiency. Herein, we report a new approach for improving the interfacial contact and delaying charge carrier recombination in the hybrid by wrapping short single-wall carbon nanotubes (SWCNTs) on TiO₂ particles (100 nm) via a hydration-condensation technique. Short SWCNTs with an average length of 125 ± 90 nm were obtained from an ultrasonication-assisted cutting process of pristine SWCNTs (1–3 μm in length). In comparison to conventional TiO₂–SWCNT composites synthesized from long SWCNTs (1.2 ± 0.7 μm), TiO₂ wrapped with short SWCNTs showed longer lifetimes of photogenerated electrons and holes, as well as a superior photocatalytic activity in the gas-phase degradation of acetaldehyde. In addition, upon comparison with a TiO₂–nanographene “quasi-core–shell” structure, TiO₂-short SWCNT structures offer better electron-capturing efficiency and slightly higher photocatalytic performance, revealing the impact of the dimensions of graphitic structures on the interfacial transfer of electrons and light penetration to TiO₂. The engineering of the TiO₂–SWCNT structure is expected to benefit photocatalytic degradation of other volatile organic compounds, and provide alternative pathways to further improve the efficiency of other carbon-based photocatalysts.

The interfacial contact between TiO₂ and graphitic carbon in a hybrid composite plays a critical role in electron transfer behavior, and in turn, its photocatalytic efficiency.     

A novel multifunctional Ag and Sr2+ co-doped TiO2@rGO ternary nanocomposite with enhanced p-nitrophenol degradation,and bactericidal and hydrogen evolution activity

In the present study, a novel multifunctional Sr²⁺/Ag–TiO₂@rGO ternary hybrid photocatalyst was prepared via facile sol–gel and hydrothermal methods. The prepared catalyst was well characterized by UV-vis, XRD, Raman, HRTEM and XPS. The synthesized composite was utilised for p-NP degradation, E. coli disinfection and H₂ generation under visible light. The Sr²⁺/Ag–TiO₂@rGO catalyst showed enhanced photocatalytic H₂ evolution rate (64.3 μmol h⁻¹) compared with Ag–TiO₂@rGO (30.1 μmol h⁻¹) and TiO₂ (no activity). Nearly complete degradation of 15 mg l⁻¹p-NP was achieved over Sr²⁺/Ag–TiO₂@rGO after 3 h, while only 66% and 5% was achieved by Ag–TiO₂@rGO and TiO₂ respectively. Furthermore, TEM analysis was carried out on Escherichia coli (E. coli) before and after visible light irradiation to understand the inactivation mechanism and DNA analysis indicated no fragmentation during inactivation. Radical quantification experiments and ESR analysis suggested that ·OH and O₂˙⁻ were the main ROS in the degradation and disinfection processes. The superior photocatalytic H₂ evolution rate of Sr²⁺/Ag–TiO₂@rGO was attributed to the synergetic effect between the Ag, Sr²⁺ and TiO₂ components on the rGO surface. The localized SPR effect of Ag induced visible light generated charge carriers into the conduction band of the TiO₂ and Sr²⁺ which further transfer to the rGO for the reduction of H⁺ ions into H₂. The results suggest that Sr²⁺/Ag–TiO₂@rGO structures could not only induce separation and migration efficiency of charge carries, but also improve charge collection efficiency for enhanced catalytic activity. Thus, we believe that this work could provide new insights into multifunctional nanomaterials for applications in solar photocatalytic degradation of harmful organics and pathogenic bacteria with clean energy generation during wastewater treatment.

In the present study, a novel multifunctional Sr²⁺/Ag–TiO₂@rGO ternary hybrid photocatalyst was prepared via facile sol–gel and hydrothermal methods.     

Construction of H4xK2xSn2−xS4+x/TiO2 nanocomposites with enhanced visible light-driven photocatalytic performance

In this paper, a new photocatalyst with TiO₂ nanospheres decorated on ultrathin layered thiostannate H_4xK_2xSn_2−xS_4+x (X = 0.5–0.6, HKTS) nanosheets was successfully synthesized by a facile solvothermal method combined with the hydrolysis of tetrabutyl titanate and it was denoted as HKTS/TiO₂. By adjusting the content of tetrabutyl titanate, composites with different Sn/Ti molar ratios were prepared. The composites were applied for RhB degradation under visible light irradiation, and the optimum proportion of HKTS/TiO₂ was obtained. The results of X-ray diffraction, Raman spectroscopy, Fourier transform infrared spectroscopy and scanning electron microscopy confirmed that TiO₂ was successfully decorated on HKTS nanosheets. The combination of TiO₂ and HKTS extended the absorption wavelength of TiO₂ from UV to visible light range, and the separation efficiency of photoexcited electron–hole pairs was also enhanced. The photocatalytic degradation rate of RhB over HKTS/TiO₂-1.0 was almost 97.9% after 60 min illumination, which was higher than those of HKTS and pure TiO₂. The photocatalyst exhibited excellent reusability and stability as the degradation rate of RhB was 95.7% even after three cycles. The photocatalytic mechanism experiment indicated that ·O₂⁻ and h⁺ played a dominant role in the photocatalytic process. All these results indicate that the newly fabricated HKTS/TiO₂ composites provide a high-performance photocatalyst for waste water treatment, and the application of thiostannate can be extended to the field of photocatalytic materials.

The enhanced visible light photocatalytic performance of a newly fabricated nanostructure combined TiO₂ with HKTS.     

The three-dimensional ordered macroporous structure of the Pt/TiO2–ZrO2 composite enhanced its photocatalytic performance for the photodegradation and photolysis of water

Using polystyrene (PS) spheres as a template, three-dimensional ordered macroporous Pt/TiO₂–ZrO₂ (3DOM Pt/TiO₂–ZrO₂) composites were prepared by vacuum impregnation combined with photoreduction. The crystal structure, composition, morphology, optical absorption, and surface physicochemical properties of the as-synthetized samples were characterized by X-ray diffraction (XRD), UV-visible diffuse reflectance spectroscopy (UV-vis/DRS), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and N₂ adsorption–desorption analyses. The results showed that the 3DOM Pt/TiO₂–ZrO₂ composites were mainly composed of anatase TiO₂ and tetragonal ZrO₂ crystal phases, in which Pt mainly existed as a single species. In addition, the as-synthesized composites had open, three-dimensionally ordered macroporous structures that could enhance their multi-mode photocatalytic degradation performance under UV, visible light, simulated solar light, and microwave-assisted irradiation. Moreover, the 3DOM Pt/TiO₂–ZrO₂ composites exhibited the best photocatalytic water splitting performance as compared to other systems.

Using polystyrene spheres as templates, 3DOM Pt/TiO₂–ZrO₂ composites were prepared by the vacuum impregnation combined with photoreduction method, which exhibited an enhanced photodegradation and water splitting performance.     

Enhanced photocatalytic activity of TiO2/UiO-67 under visible-light for aflatoxin B1 degradation

TiO₂ has great potential in photocatalytic degradation of organic pollutants, but poor visible light response and low separation efficiency of photogenerated electron–hole pairs limit its wide applications. In this study, we have successfully prepared TiO₂/UiO-67 photocatalyst through an in situ solvothermal method. The degradation rate of aflatoxin B1 (AFB1) is 98.9% in only 80 min, which is superior to the commercial P25, commercial TiO₂ and most of reported photocatalysts under visible light irradiation. In addition, the TiO₂/UiO-67 photocatalyst showed excellent recyclability. We demonstrated that the enhanced photocatalytic mechanism was owing to the heterojunction between TiO₂ and UiO-67, which enhanced effectively the separation photogenerated charge carriers and visible light response. The free radical trapping tests demonstrated that superoxide radicals (˙O₂⁻), holes (h⁺) and hydroxyl radicals (˙OH) were the main active species and then oxidized AFB1 to some small molecules.

Enhanced photocatalytic activity of TiO₂/UiO-67 under visible-light for aflatoxin B1 degradation.     

Highly crystalline anatase TiO2 nanocuboids as an efficient photocatalyst for hydrogen generation

Highly crystalline anatase titanium dioxide (TiO₂) nanocuboids were synthesized via a hydrothermal method using ethylenediamine tetraacetic acid as a capping agent. The structural study revealed the nanocrystalline nature of anatase TiO₂ nanocuboids. Morphological study indicates the formation of cuboid shaped particles with thickness of ∼5 nm and size in the range of 10–40 nm. The UV-visible absorbance spectra of TiO₂ nanocuboids showed a broad absorption with a tail in the visible-light region which is attributed to the incorporation of nitrogen atoms into the interstitial positions of the TiO₂ lattice as well as the formation of carbonaceous and carbonate species on the surface of TiO₂ nanocuboids. The specific surface areas of prepared TiO₂ nanocuboids were found to be in the range of 85.7–122.9 m² g⁻¹. The formation mechanism of the TiO₂ nanocuboids has also been investigated. Furthermore, the photocatalytic activities of the as-prepared TiO₂ nanocuboids were evaluated for H₂ generation via water splitting under UV-vis light irradiation and compared with the commercial anatase TiO₂. TiO₂ nanocuboids obtained at 200 °C after 48 h exhibited higher photocatalytic activity (3866.44 μmol h⁻¹ g⁻¹) than that of commercial anatase TiO₂ (831.30 μmol h⁻¹ g⁻¹). The enhanced photoactivity of TiO₂ nanocuboids may be due to the high specific surface area, good crystallinity, extended light absorption in the visible region and efficient charge separation.

Highly crystalline TiO₂ nanocuboids have been prepared and their photocatalytic hydrogen generation activity was evaluated via water splitting.     

Coating-free TiO2@β-SiC alveolar foams as a ready-to-use composite photocatalyst with tunable adsorption properties for water treatment

Coating-free TiO₂@β-SiC photocatalytic composite foams gathered within a ready-to-use shell/core alveolar medium the photocatalytically active TiO₂ phase and the β-SiC foam structure were prepared via a multi-step shape memory synthesis (SMS) replica method. They were fabricated following a sequential two-step carburization approach, in which an external TiC skin was synthesized at the surface of a β-SiC skeleton foam obtained from a pre-shaped polyurethane foam during a first carburization step. The adsorption behaviour of the shell/core TiO₂@β-SiC composite foams towards the Diuron pollutant in water was tuned by submitting the carbide foams to a final calcination treatment within the 550–700 °C temperature range. The controlled calcination step allowed (i) the selective oxidation of the TiC shell into a TiO₂ crystallite shell owing to the β-SiC resistance to oxidation and (ii) the amount of residual unreacted carbon in the foams to be tuned. The lower the calcination temperature, the more pronounced the adsorption profiles of the composites and the higher the Diuron amount removed by adsorption on the residual unreacted carbon. The ready-to-use TiO₂@β-SiC composite foams were active in the degradation of the Diuron pesticide, without any further post-synthesis immobilization or synthesis process at the foam surface. They displayed good reusability with test cycles and benefitted from an enhanced stability in terms of the titania release to water.

Coating-free TiO₂@β-SiC photocatalytic composite foams gathering within a ready-to-use shell/core alveolar medium the TiO₂ photocatalyst and the β-SiC foam structure were prepared via a multi-step shape memory synthesis (SMS) replica method.     

The effect of heat treatment on the anatase–rutile phase transformation and photocatalytic activity of Sn-doped TiO2 nanomaterials

Sn-doped TiO₂ nanomaterials with different amounts of Sn (1, 2.5, 5, 10, and 15 at%) were prepared by a sol–gel method and characterized by XRD, TG, DTA, EDS, XPS, DRS, SEM, BET, and PL. The photocatalytic activity of the prepared samples was investigated by measuring the degradation of rhodamine B in aqueous solution under UV light. The experimental results indicate that doping with Sn promotes phase transformation from anatase to rutile. The photocatalytic activity of TiO₂ is influenced by both the heat treatment temperature and the Sn doping concentration. 1% Sn–TiO₂ exhibits the highest degradation rate at 350 °C and 5% Sn–TiO₂ exhibits the best photocatalytic activity at 500 °C and 650 °C. The enhancement of the photocatalytic activity can be ascribed to a larger surface area and a better hydration ability, as well as less recombination of the photogenerated pairs.

Sn incorporation into TiO₂ lattices promotes anatase/rutile transformation and Sn–TiO₂ exhibits better photocatalytic activity at different temperatures.     

Coatings of magnetic composites of iron oxide and carbon nitride for photocatalytic water purification

Magnetic composites of iron oxide (α-Fe₂O₃ and Fe₃O₄) and carbon nitride materials (CN) were synthesized via a microwave assisted hydrothermal method starting from iron salts and CN, which was obtained by thermal decomposition of dicyandiamide. The as-prepared composites with iron oxide loadings of 0.5 ω%–6 ω% were characterized by powder X-ray diffraction (PXRD), diffuse reflectance UV-vis spectroscopy, magnetization measurements, nitrogen adsorption measurements and thermogravimetric analyzes (TGA). The composites were examined for the degradation rate of an aqueous rhodamine B (RhB) solution under visible light irradiation. The magnetic composite α-Fe₂O₃(3 ω%)/CN enables 82% degradation of RhB within 90 min. Therefore, this material was selected for an immobilization approach and deposited using a spray coating technique on a magnetic polymer substrate. Coatings with loadings from 1.1 mg to 3.6 mg were compared with regard to their activity for the photocatalytic degradation of RhB under visible light irradiation. The substrate loaded with 0.4 mg cm⁻² catalyst enables a RhB degradation of 61% within 8 h. Photocatalytic degradation of triclosan and ethinyl estradiol was also successful and both compounds were degraded with up to 46% of the initial concentration within 8 h. ICP-MS measurements of the pollutant solutions after photocatalytic treatment showed that leaching does not occur.

Photocatalytic degradation of organic pollutants with spray coated iron oxide/CN composite films.     

Deposition of platinum on boron-doped TiO2/Ti nanotube arrays as an efficient and stable photocatalyst for hydrogen generation from water splitting

An efficient photocatalyst of boron-doped titanium dioxide/titanium nanotube array-supported platinum particles (Pt–B/TiO₂/Ti NTs) was fabricated for photocatalytic water splitting for hydrogen production through a two-step route. First, B/TiO₂/Ti NTs were prepared by anodic oxidation using hydrofluoric acid as electrolyte and boric acid as a B source. Then, Pt particles were deposited on the surface of B/TiO₂/Ti NTs by photo-assisted impregnation reduction. The structure and properties of Pt–B/TiO₂/Ti NTs were characterized by various physical measurements which showed the successful fabrication of Pt–B/TiO₂/Ti NTs. The Pt–B/TiO₂/Ti NTs, with a B-doping content of 15 mmol L⁻¹, showed the highest photocatalytic activity and exhibited a photocatalytic hydrogen-production rate of 384.9 μmol g⁻¹ h⁻¹, which was 9.2-fold higher than that of unmodified TiO₂/Ti NTs (41.7 μmol g⁻¹ h⁻¹). This excellent photocatalytic performance was ascribed mainly to the synergistic effect of Pt and B, which could enhance the photocatalytic activity of TiO₂/Ti NTs.

Pt–B/TiO₂/Ti NTs, prepared by anodic oxidation and photo-deposition methods, showed excellent photocatalytic activity.     

New insights into the surface plasmon resonance (SPR) driven photocatalytic H2 production of Au–TiO2

The Surface Plasmon Resonance (SPR) driven photocatalytic H₂ production upon visible light illumination (≥500 nm) was investigated on gold-loaded TiO₂ (Au–TiO₂). It has been clearly shown that the Au-SPR can directly lead to photocatalytic H₂ evolution under illumination (≥500 nm). However, there are still some open issues about the underlying mechanism for the SPR-driven photocatalytic H₂ production, especially the explanation of the resonance energy transfer (RET) theory and the direct electron transfer (DET) theory. In this contribution, by means of the EPR and laser flash photolysis spectroscopy, we clearly showed the signals for different species formed by trapped electrons and holes in TiO₂ upon visible light illumination (≥500 nm). However, the energy of the Au-SPR is insufficient to overcome the bandgap of TiO₂. The signals of the trapped electrons and holes originate from two distinct processes, rather than the simple electron–hole pair excitation. Results obtained by Laser Flash Photolysis spectroscopy evidenced that, due to the Au-SPR effect, Au NPs can inject electrons to the conduction band of TiO₂ and the Au-SPR can also initiate e⁻/h⁺ pair generation (interfacial charge transfer process) upon visible light illumination (≥500 nm). Moreover, the Density Functional Theory (DFT) calculation provided direct evidence that, due to the Au-SPR, new impurity energy levels occurred, thus further theoretically elaborating the proposed mechanisms.

The Surface Plasmon Resonance (SPR) driven photocatalytic H₂ production upon visible light illumination (≥500 nm) was investigated on gold-loaded TiO₂ (Au–TiO₂).     

TiO2–Au composite nanofibers for photocatalytic hydrogen evolution

TiO₂-based materials for photocatalytic hydrogen (H₂) evolution have attracted much interest as a renewable approach for clean energy applications. TiO₂–Au composite nanofibers (NFs) with an average fiber diameter of ∼160 nm have been fabricated by electrospinning combined with calcination treatment. In situ reduced gold nanoparticles (NPs) with uniform size (∼10 nm) are found to disperse homogenously in the TiO₂ NF matrix. The TiO₂–Au composite NFs catalyst can significantly enhance the photocatalytic H₂ generation with an extremely high rate of 12 440 μmol g⁻¹ h⁻¹, corresponding to an adequate apparent quantum yield of 5.11% at 400 nm, which is 25 times and 10 times those of P25 (584 μmol g⁻¹ h⁻¹) and pure TiO₂ NFs (1254 μmol g⁻¹ h⁻¹), respectively. Furthermore, detailed studies indicate that the H₂ evolution efficiency of the TiO₂–Au composite NF catalyst is highly dependent on the gold content. This work provides a strategy to develop highly efficient catalysts for H₂ evolution.

The H₂ production rate of TiO₂–Au nanofibers is dramatically improved to 12 440 μmol g⁻¹ h⁻¹, 10 times that of pure TiO₂.     

Highly efficient visible light active Cu–ZnO/S-g-C3N4 nanocomposites for efficient photocatalytic degradation of organic pollutants

The photocatalytic activity of photocatalysts is severely hampered by limited visible light harvesting and unwanted fast recombination of photogenerated e⁻ and h⁺. In the current study, the photocatalytic efficiency of Cu–ZnO/S-g-C₃N₄ (CZS) nanocomposites was investigated against MB dye. The composite materials were designed via chemical co-precipitation method and characterised by important analytical techniques. Distinctive heterojunctions developed between S-g-C₃N₄ and Cu–ZnO in the CZS composite were revealed by TEM. The synthesized composites exhibit a huge number of active sites, a large surface area, a smaller size and better visible light absorption. The considerable enhancement in the photocatalytic activity of CZS nanocomposites might be accredited to the decay in the e–h pair recombination rate and a red shift in the visible region, as observed by PL and optical analysis, respectively. Furthermore, the metal (Cu) doping into the S-g-C₃N₄/ZnO matrix created exemplary interfaces between ZnO and S-g-C₃N₄, and maximized the photocatalytic activity of CZS nanocomposites. In particular, CZS nanocomposites synthesized by integrating 25% S-g-C₃N₄ with 4% Cu–ZnO (CZS-25 NCs) exhibited the 100% photocatalytic degradation of MB in 60 minutes under sunlight irradiation. After six cycles, the photocatalytic stability of CZS-25 NCs was excellent. Likewise, a plausible MB degradation mechanism is proposed over CZS-25 NCs based on photoluminescence and reactive species scavenger test observation. The current research supports the design of novel composites for the photocatalytic disintegration of organic contaminants.

The photocatalytic activity of photocatalyst is severely hampered by limited visible light harvesting and unwanted fast recombination of photogenerated e⁻ and h⁺.     

Fabrication of Ag/AgBr/Ag3VO4 composites with high visible light photocatalytic performance

Herein, Ag/AgBr/Ag₃VO₄ composites were synthesized by a simple continuous precipitation method. The obtained composites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy and photoluminescence spectroscopy (PL). Photocatalytic performance of the composites was assessed by the degradation of methyl orange (MO) and tetracycline hydrochloride (TC) under visible light, and the effects of different nominal mass ratios of AgBr and Ag₃VO₄ on the photocatalytic activity were investigated. The results showed that after 20 min of visible light irradiation (λ > 420 nm), the removal rate of MO in the presence of a 5 : 1 sample reached 98.6%. The EIS and photocurrent results demonstrated that the enhancement of the visible light photocatalytic activity was attributed to the efficient electron–hole pair separation. In addition, the scavenging reactions conducted via the addition of different scavengers confirmed that h⁺ and ·O²⁻ were the main active species in the reaction. The present study offers potential for the degradation of contaminants.

Ag/AgBr/Ag₃VO₄ composites were synthesized by a simple continuous precipitation method, which were used to degrade organic pollutants and found to have excellent photocatalytic properties.     

Enhanced photocatalytic hydrogen evolution and ammonia sensitivity of double-heterojunction g-C3N4/TiO2/CuO

The performance of semiconductor photocatalysts has been limited by rapid electron–hole recombination. One strategy to overcome this problem is to construct a heterojunction structure to improve the survival rate of electrons. In this context, a novel g-C₃N₄/TiO₂/CuO double-heterojunction photocatalyst was developed and characterized. Its photocatalytic activity for hydrogen production from water–methanol photocatalytic reforming was explored. Methanol is always used to eliminate semiconductor holes. The g-C₃N₄/TiO₂/CuO double-heterojunction photocatalyst with a narrow bandgap of ∼1.38 eV presented excellent photocatalytic activity for hydrogen evolution (97.48 μmol (g h)⁻¹) under visible light irradiation. Compared with g-C₃N₄/TiO₂ and CuO/TiO₂, the photocatalytic activity of g-C₃N₄/TiO₂/CuO for hydrogen production was increased approximately 7.6 times and 1.8 times, respectively. Below 240 °C, the sensitivity of g-C₃N₄/TiO₂/CuO to ammonia was approximately 90% and 46% higher than that of g-C₃N₄/TiO₂ and CuO/TiO₂, respectively. The enhancement of the photocatalytic activity and gas sensing properties of the g-C₃N₄/TiO₂/CuO composite resulted from the close interface contact established by the double heterostructure. The trajectory of electrons in the double heterojunction conformed to the S-scheme. UV-vis, PL, and transient photocurrent characterization showed that the double heterostructure effectively inhibited the recombination of e⁻/h⁺ pairs and enhanced the migration of photogenerated electrons.

The trajectory of electrons in the g-C3N4/TiO2/CuO double-heterojunction conforms to the S-scheme.     

Enhanced photocatalytic activity of a B12-based catalyst co-photosensitized by TiO2 and Ru(ii) towards dechlorination

A novel hybrid photocatalyst denoted as B₁₂–TiO₂–Ru(ii) was prepared by co-immobilizing a B₁₂ derivative and trisbipyridine ruthenium (Ru(bpy)₃²⁺) on the surface of a mesoporous anatase TiO₂ microspheres and was characterized by DRS, XRD, SEM and BET et al. By using the hybrid photocatalyst, DDT was completely didechlorinated and a small part of tridechlorinated product was also detected in the presence of TEOA only after 30 min of visible light irradiation. Under simulated sunlight, the hybrid exhibited a significantly enhanced photocatalytic activity for dechlorination compared with B₁₂–TiO₂ under the same condition or itself under visible light irradiation due to the additivity in the contribution of UV and visible part of the sunlight to the electron transfer. In addition, this hybrid catalyst can be easily reused without loss of catalytic efficiency. This is the first report on a B₁₂-based photocatalyst co-sensitized by two photosensitizers with wide spectral response.

The additivity of the contribution of the UV and visible parts of sunlight to electron transfer was confirmed in the B₁₂–TiO₂–Ru(ii) photocatalytic system.     

Synthesis of TiO2–Ag3PO4 photocatalyst material with high adsorption capacity and photocatalytic activity: application in the removal of dyes and pesticides

The photocatalytic activity of TiO₂ can be enhanced by coupling it with other semiconductors and the semiconductor composites may find useful application in water treatment technologies. TiO₂–Ag₃PO₄ composites were synthesized and characterized with XRD, SEM-EDX and DRS. The synthesized TiO₂–Ag₃PO₄ showed high photocatalytic activity in the presence UV-vis light on rhodamine B, methylene blue and the pesticides imidacloprid, atrazine and pyrimethanil. LC-MS analysis of the photodegraded pyrimethanil led to the identification of hydroxylated and aliphatic derivatives of pyrimethanil. The photocatalytic activity of the coupled semiconductor was higher than that of the bare TiO₂ and Ag₃PO₄ and this was attributed to the unique band matching between TiO₂ and Ag₃PO₄ which resulted in efficient charge separation and subsequent reduction in the electron–hole recombination. In addition, the synthesized TiO₂–Ag₃PO₄ showed strong adsorption for water soluble dyes implying that TiO₂–Ag₃PO₄ can remove pollutants through photocatalysis and adsorption. The results from the study showed the potential application of TiO₂–Ag₃PO₄ composite in water treatment technologies.

Synthesis scheme of the Ag₃PO₄–TiO₂ nanocomposite.     

Titania/chitosan–lignin nanocomposite as an efficient photocatalyst for the selective oxidation of benzyl alcohol under UV and visible light

Developing functional materials from biomass is a significant research subject due to its unique structure, abundant availability, biodegradability and low cost. A series of chitosan–lignin (CL) composites were prepared through a hydrothermal method by varying the weight ratio of chitosan and lignin. Subsequently, these CL composites were combined with titania (T) to form a nanocomposite (T/CL) using sol–gel and hydrothermal based methods. T/CL nanocomposites exhibited improved photocatalytic performance in comparison with sol–gel and hydrothermally prepared pristine titania (SGH-TiO₂), towards the selective oxidation of benzyl alcohol (BnOH) to benzaldehyde (Bnald) under UV (375 nm) and visible light (515 nm). More specifically, the 75T/CL(25 : 75) nanocomposite (a representative photocatalyst from the 75T/CL nanocomposite series) showed very high selectivity (94%) towards Bnald at 55% BnOH conversion under UV light. Whereas, SGH-TiO₂ titania exhibited much lower (68%) selectivity for Bnald at similar BnOH conversion. Moreover, the 75T/CL(25 : 75) nanocomposite also showed excellent Bnald selectivity (100%) at moderate BnOH conversion (19%) under visible light. Whereas, SGH-TiO₂ did not show any activity for BnOH oxidation under visible light. XPS studies suggest that the visible light activity of the 75T/CL(25 : 75) nanocomposite is possibly related to the doping of nitrogen into titania from chitosan. However, according to UV-visible-DRS results, no direct evidence pertaining to the decrease in band-gap energy of titania was found upon coupling with the CL composite and the visible light activity was attributed to N-doping of titania. Overall, it was found that T/CL nanocomposites enhanced the photocatalytic performance of titania via improved light harvesting and higher selectivity through mediation of active radical species.

Combining titania with chitosan–lignin composites results in an active and selective photocatalyst for the oxidation of benzyl alcohol to benzaldehyde under green light (515 nm).     

CNT modified layered α-MnO2 hybrid flame retardants: preparation and their performance in the flame retardancy of epoxy resins

In this paper, CNT modified layered α-MnO₂ hybrid flame retardants (α-MnO₂–CNTs) were synthesized through one-pot preparation. The structure and composition of the α-MnO₂–CNTs hybrid flame retardants were investigated by X-ray diffraction, TEM and SEM. Subsequently, the α-MnO₂–CNTs hybrids were then incorporated into epoxy resin (EP) to improve the fire safety properties. Compared with pure EP and the composites with CNTs or α-MnO₂, EP/α-MnO₂–CNTs composites exhibited improved flame retardancy and smoke suppression properties. With the incorporation of only 2.0 wt% of α-MnO₂–CNTs hybrid flame retardants, the peak heat release rate and total heat release of the composites showed 34% and 10.7% reduction respectively. In addition, the volatile gases such as CO and CO₂ were reduced and the smoke generation was also effectively inhibited. The improved fire safety of the composites is generally due to the network structures and the synergistic effect of α-MnO₂ and CNTs, the catalyzing charring effect, smoke suppression and the physical barrier effect of α-MnO₂ nanosheets.

In this paper, CNT modified layered α-MnO₂ hybrid flame retardants (α-MnO₂–CNTs) were synthesized through one-pot preparation.