LED light-induced enhanced photocatalytic hydrogen evolution on Au@TiO2 core–shell modified by nitrogen doping and reduced graphene oxide

This study focused on the large band gap of TiO₂ for its use as a photocatalyst under light emitting diode (LED) light irradiation. The photocatalytic activities of core–shell structured Au@TiO₂ nanoparticles (NPs), nitrogen doped Au@TiO₂ NPs, and Au@TiO₂/rGO nanocomposites (NCs) were investigated under various light intensities and sacrificial reagents. All the materials showed better photocatalytic activity under white LED light irradiation than under blue LED light. The N-doped core–shell structured Au@TiO₂ NPs (Au@N–TiO₂) and Au@TiO₂/rGO NCs showed enhanced photocatalytic activity with an average H₂ evolution rate of 9205 μmol h^?1g^?1 and 9815 μmol h^?1g^?1, respectively. All these materials showed an increasing rate of hydrogen evolution with increasing light intensity and catalyst loading. In addition, methanol was more suitable as a sacrificial reagent than lactic acid. The rate of hydrogen evolution increased with increasing methanol concentration up to 25% in DI water and decreased at higher concentrations. Overall, Au@TiO₂ core–shell-based nanocomposites can be used as an improved photocatalyst in photocatalytic hydrogen production.     

Boosting photocatalytic hydrogen generation by the combination of tunable cobaloxime and covalent organic framework

Here, we have investigated the photocatalytic activities of substituted Schiff-based COFs as photosensitizes and molecular cobaloximes as non-noble metal co-catalysts for the hydrogen production from water under visible light irradiation. The steric and electronic properties of the functional group at the backbone of COFs, and cobaloximes, have a pronounced effect on the photocatalytic performance of the photocatalytic system. We established that the methyl-substituted COF (COF-AD₁) as a photosensitizer, chloro (p-N,N-dimethylpyridine) cobaloxime (Co-2) as co-catalyst and triethanolamine (TEOA) sacrificial electron donor form a highly active photocatalytic system which exhibited a record hydrogen production rate of 7072 μmolg^?1h^?1 with a quantum efficiency of 51.4%, TOF of 35.6, TON of 462.4 for 20 h in a 4:1 acetonitrile/water mixture.     

Visible light induced dye-sensitized photocatalytic hydrogen production over platinized TiO2 derived from decomposition of platinum complex precursor

Pt/TiO₂ derived from complete decomposition of the surface-anchored Pt(dcbpy)Cl₂ (dcbpy = 4,4′-dicarboxy-2,2′-bipyridine) precursor (denoted as C-Pt/TiO₂) was prepared to serve as photocatalyst in visible light region. For dye-sensitized hydrogen production experiments, the photocatalyst was sensitized by Ru(2,2′-bipyridine-4,4′-dicarboxylic)₂(NCS)₂ (the N3 dye) and Ru(2,2′bipyridyl-4,4′-dicarboxylic) (4,4′- dinonyl-2,2′bipyridine) (NCS)₂ (the Z907 dye) to induce hydrogen evolution in the presence of sacrificial electron donor, triethanolamine (TEA). The hydrogen generation results showed that C-Pt/TiO₂ was found to be a much more active photocatalyst when compared to P-Pt/TiO₂, prepared by conventional method of photochemical deposition of H₂PtCl₆ (denoted as P-Pt/TiO₂). For further investigation, the photodegradation experiments in visible region were also confirmed the better photocatalytic activity of C-Pt/TiO₂. The enhanced catalytic activity is due to efficient interparticle electron transfer with the small-size and high-disperse platinum particles generated from photodeposition of Pt(dcbpy)Cl₂, which was verified by the transmission electron microscopy (TEM) measurement.     

Formation of multilayer-Eosin Y-sensitized TiO2 via Fe coupling for efficient visible-light photocatalytic hydrogen evolution

An efficient visible-light active photocatalyst of multilayer-Eosin Y-sensitized TiO₂ is prepared through linkage of Fe³⁺ between not only TiO₂ and Eosin Y but also different Eosin Y molecules to form three-dimensional polymeric dye structure. The multilayer-dye-sensitized photocatalyst is found to have high light harvesting efficiency and photocatalytic activity for hydrogen evolution under visible light irradiation (λ > 420 nm). On the optimum conditions (1:1 initial molar ratio of Eosin Y to Fe(NO₃)₃, initial 10 × 10⁻³ M Eosin Y, and 1.0 wt% Pt deposited by in situ photoreduction), its maximal apparent quantum yield for hydrogen evolution is 19.1% from aqueous triethanolamine solution (TEOA aq). The present study highlights linking between dye molecules via metal ions as a general way to develop efficient visible-light photocatalyst.     

Structural properties of CuO/TiO2 nanorod in relation to their catalytic activity for simultaneous hydrogen production under solar light

CuO was introduced into porous TiO₂ nanorod through impregnation method. Before the impregnation step, TiO₂ nanorod was hydrothermally synthesized from TiO₂ powder in aqueous NaOH solution and followed by thermal treatment at 450 °C. The structures and properties of impregnated samples were characterized using various techniques, including XRD, BET, XAS, TEM, and UV-DRS. Their photocatalytic performance on simultaneous hydrogen production from pure water and aqueous methanol solution was also investigated under solar light. It was found that CuO/TiO₂ nanorod possessed a high surface area, good photocatalytic property and excellent hydrogen generation activity. Incorporation of Cu ions into the lattice framework of anatase TiO₂ nanorod enhanced the efficiency in visible region at 438–730 nm. Moreover, the XAS results showed that some Cu ions formed solid solution in the TiO₂ nanorod (Cu_xT_1−xO₂). However, the excessive incorporation of Cu ions did not improve any ability of anatase TiO₂ nanorod for production of hydrogen from pure water splitting. This could be due to the excessive CuO agglomeration at outside-pores which blocked the sensitization of TiO₂ nanorod. Only 1% Cu/TiO₂ nanorod was found to be a remarkable and an efficient photocatalyst for hydrogen production under solar light from both pure water and sacrificial methanol splitting. The highest rate of hydrogen production of 139.03 μmol h⁻¹ g_catalyst⁻¹ was found in sacrificial methanol which was 3.24% higher than in pure water.     

The design of a hierarchical photocatalyst inspired by natural forest and its usage on hydrogen generation

A novel photocatalyst was designed from the inspiration of natural forest's high efficient on light harvesting and energy conversion. This novel “forest-like” photocatalyst was successfully synthesized by a facile continuously-conducted three steps methods: electrospinning TiO₂ nanofiber acts as the trunks, hydrothermal growth ZnO nanorods on the surface of TiO₂ nanofiber acts as the branches, while photodeposition of Cu nanoparticles on the surface of TiO₂ nanofiber and ZnO nanorods act as the leaves. This novel photocatalyst demonstrated higher photocatalytic hydrogen generation rate than most of semiconductor catalysts and many newly developed catalysts such as Pt/TiO₂ catalyst and artificial leaves Pt/N–TiO₂ catalyst in a water/methanol sacrificial reagent system under the light irradiation as a result of its enhanced light absorption ability, enlarged specific surface area promoting mass transfer and providing more reaction sites and its potential on anti-recombination of electrons and holes. Meanwhile, it is interesting to note that the photocatalytic hydrogen generation activity has a liner relationship with the hierarchy of materials, which means higher hierarchy materials display higher photocatalytic hydrogen generation activity. It is reasonable to believe that this natural mimic photocatalyst without noble metals will benefit the energy generation and novel materials development.     

Enhanced surface electron transfer by fabricating a core/shell Ni@NiO cluster on TiO2 and its role on high efficient hydrogen generation under visible light irradiation

A Ni@NiO core/shell cluster was fabricated on TiO₂ surface (Ni@NiO/TiO₂) and its roles on surface electron transfer and the enhancement on hydrogen evolution under visible light irradiation were investigated. For a comparison, the Ni/TiO₂ and NiO/TiO₂ catalysts were fabricated, respectively. By photosensitization using Eosin Y as an antenna molecule, (1.6 wt%)Ni@NiO/TiO₂ exhibited the highest activity (364.1 μmol h⁻¹) in comparison with (1.6 wt%)Ni/TiO₂ and (1.6 wt%)NiO/TiO₂ and the corresponding apparent quantum efficiency reached 28.6% at 460 nm. The photoluminescence spectra and photoelectrochemical characterization results confirmed that the Ni@NiO core/shell structure could promote the photogenerated electrons transferring from TiO₂ conduction band to Ni@NiO clusters, resulting in the quicker separation of electron–hole pairs. In addition, part of NiO shell can be reduced into metallic Ni during the photoreaction and vice versa. Cyclic voltammogram characterization verified that the transformation between Ni and NiO was a dynamic balance process, which can not only provide reacting channels for electrons and protons but also ensure the photocatalytic hydrogen evolution proceeding continuously. This study discloses structure-dependent effect of non-noble metal cocatalyst on semiconductor photocatalysts in photocatalytic water reduction, and gives an insight into designing high-efficient non-noble metal/semiconductor hybrid photocatalysts.     

New evidence for the regulation of photogenerated electron transfer on surface potential energy controlled co-catalyst on TiO2 – The investigation of hydrogen production over selectively exposed Au facet on Au/TiO2

In this study, Au/TiO₂ samples with different exposed facets ({100}, {100/111}, and {111}) of Au were employed as catalysts for the examination of facet-dependent catalytic activity toward photocatalytic hydrogen evolution from water. By photosensitized using Eosin Y as antenna molecule, Au/TiO₂ series photocatalysts exhibited different photocatalytic hydrogen evolution performances under visible light irradiation. Au{111}/TiO₂ photocatalyst presented the highest photocatalytic hydrogen generation activity among Au/TiO₂ series samples. As evidenced by photoluminescence spectra, photocurrent, electrochemical impedance spectra, and Mott–Schottky characterizations, the difference in photocatalytic activities resulted from the different electron transfer rates from the conduction band of TiO₂ to Au nanoparticles. Au nanoparticles with exposed {111} facets were more effective in trapping electrons due to their higher Fermi level. In addition, the apparent activation energy of Au{111}/TiO₂ sample was the lowest, resulted from the biggest uncoordinated numbers of Au atoms on Au{111} nanoparticles, which was favor in forming the hydrogen–metal bond. This study discloses the facet-dependent effect of noble-metal cocatalyst on semiconductor photocatalysts in photocatalytic water reduction, and will give an insight into design and synthesis of high-efficient noble metal/semiconductor hybrid photocatalysts.     

Green synthesized carbon quantum dots as TiO2 sensitizers for photocatalytic hydrogen evolution

Carbon quantum dots (CQDs) have attracted growing interest due to their superior luminescent properties, which make them excellent photosensitizers for TiO₂. This study presents the green-synthesis of CQDs from edible mushroom Agaricus bisporus through microwave irradiation. In the study as-synthesized CQDs were used as a sensitizer for TiO₂ in photocatalytic hydrogen evolution in aqueous triethanolamine (sacrificial reagent) under visible-light irradiation. Photocatalytic hydrogen production activity of CQD-sensitized TiO₂ was found to be 472 μmol g⁻¹ h⁻¹ (without loading any noble metal co-catalyst) and 1458 μmol g⁻¹ h⁻¹ (with loading Pt co-catalyst). The study revealed that the CQDs from mushroom A. bisporus can be used as an efficient sensitizer for TiO₂ in photocatalytic hydrogen production.     

Preparation and photocatalytic properties of HLaNb2O7/(Pt,TiO2) perovskite intercalated nanomaterial

A novel perovskite intercalated nanomaterial HLaNb₂O₇/(Pt, TiO₂) is fabricated by successive intercalated reaction of HLaNb₂O₇ with [Pt(NH₃)₄]Cl₂ aqueous solution, n-C₆H₁₃NH₂/C₂H₅OH organic solution and acidic TiO₂ colloid solution, followed by ultraviolet light irradiation. The gallery height and the band gap energy of HLaNb₂O₇/(Pt, TiO₂) is less than 0.6 nm and 3.14 eV, respectively. The photocatalytic activity of HLaNb₂O₇/TiO₂ is superior to that of unsupported TiO₂ and is enhanced by the co-incorporation of Pt. The photocatalytic hydrogen evolution based on HLaNb₂O₇/(Pt, TiO₂) is 240 cm³ h⁻¹ g⁻¹ using methanol as a sacrificial agent under irradiation with wavelength more than 290 nm from a 100-W mercury lamp. High photocatalytic activity of HLaNb₂O₇/(Pt, TiO₂) may be due to the host with rare earth La element and perovskite structure, the quantum size effect of intercalated semiconductor and the coupling effect between host and guest.     

Enhanced photocatalytic hydrogen evolution from reduced graphene oxide-defect rich TiO2-x nanocomposites

Solar-driven photocatalytic hydrogen generation by splitting water molecules requires an efficient visible light active photocatalyst. This work reports an improved hydrogen evolution activity of visible light active TiO_2-x photocatalyst by introducing reduced graphene oxide via an eco-friendly and cost-effective hydrothermal method. This process facilitates graphene oxide reduction and incorporates intrinsic defects in TiO₂ lattice at a one-pot reaction process. The characteristic studies reveal that RGO/TiO_2-x nanocomposites were sufficiently durable and efficient for photocatalytic hydrogen generation under the visible light spectrum. The altered band gap of TiO_2-x rationally promotes the visible light absorption, and the RGO sheets present in the composites suppresses the electron-hole recombination, which accelerates the charge transfer. Hence, the noble metal-free RGO/TiO_2-x photocatalyst exhibited hydrogen production with a rate of 13.6 mmol h^?1g^?1_cat. under solar illumination. The appreciable photocatalytic hydrogen generation activity of 947.2 μmol h^?1g^?1_cat with 117 μAcm^?2 photocurrent density was observed under visible light (>450 nm).     

TiO2 nanoparticles modified with 2D MoSe2 for enhanced photocatalytic activity on hydrogen evolution

As an emerging two-dimensional (2D) nanomaterial, 2D MoSe₂ nanosheets has the advantages of wide light response and rapid charge migration ability. In this work, 2D MoSe₂/TiO₂ nanocomposites were successfully synthesized through a simple hydrothermal method. The microstructure and photocatalytic activity of the nanocomposites were systematically investigated and determined. The corresponding Raman peaks and crystal planes of MoSe₂ were analysed by Raman spectroscopy and transmission electron microscopy respectively, demonstrating the successful combination of the MoSe₂ nanosheets and TiO₂ nanoparticles. UV-vis diffused reflectance spectra demonstrated that the introduction of MoSe₂ did increase the light absorption ability of the nanocomposites. A lower recombination of electrons and holes was demonstrated for the MoSe₂/TiO₂ heterojunction from photoluminescence results. The photocatalytic hydrogen evolution test showed that the hydrogen production rate was 4.9 μmol h⁻¹ for the sample with 0.1 wt.% MoSe₂, 2 times higher than that of bare TiO₂. This work provides a novel strategy for improving the photocatalytic properties of semiconductor photocatalyst.     

CuWO4 as a novel Z-scheme partner to construct TiO2 based stable and efficient heterojunction for photocatalytic hydrogen generation

Synthesis of highly efficient, stable, visible active CuWO₄ nanoparticles through a simple methodology, paves a feasible path for enhancing the efficiency of TiO₂. A novel nanocomposite of CuWO₄ NP loaded TiO₂ NR heterojunction was mounted through a direct Z-scheme mechanism. Optimized composite CWT-3, advances the photocatalytic hydrogen production rates of TiO₂ to 106.7 mmol h^?1 g^?1_cat. CuWO₄ incorporation as OEP compensates inefficiency of WO₃ and other Z-scheme combinations reported so far, on limiting the charge carrier recombination followed by the generation of a greater number of excitons. Specific amounts of catalyst loading, study on the effect of sacrificial reagents, and understanding the effect of the light source, are the three pivotal steps that helped here to hamper the density of overall back reactions. The formation of Z-scheme heterojunction was evidently confirmed on determining the position of CBM and VBM, PL and photoelectrochemical analysis. Recyclability studies further proved the stable and efficient outcomes of CWT-3 for five consecutive cycles. Based on photocatalytic activity, employing BDF by-product glycerol as an optimized sacrificial reagent serves the oxidation demands and triggered 53.26% solar to hydrogen conversion efficiency under natural sunlight irradiation.     

Remarkable promotion of photocatalytic hydrogen evolution from water on TiO2-pillared titanoniobate

TiO₂-pillared titanoniobate TiO₂/HTiNbO₅ as an efficient photocatalyst was prepared via an exfoliation–restacking route. The as-prepared nanohybrid is mesoporous with a high specific surface area of 171 m²/g and a gallery height of 1.55 nm. Under a 300 W Xe lamp irradiation, the nanohybrid exhibited a high photocatalytic activity of 219 μmol/h/(g cat) in splitting water into hydrogen, which is 12 times as high as its parent HTiNbO₅ (18 μmol/h/g) and 24 times as TiO₂ (9 μmol/h/g). Enlarged surface area and effective electronic coupling between the host and the guest components contribute to the high photocatalytic activity of TiO₂/HTiNbO₅. Its photocatalytic activity was further improved through platinizing, and 5 wt% Pt-loaded TiO₂/HTiNbO₅ gave a remarkable hydrogen evolution rate of 4735 μmol/h/g. A photoexcitation model of the semiconductor–semiconductor pillared photocatalyst was proposed based on the results of XPS and UV–vis.     

Further studies of photodegradation and photocatalytic hydrogen production over Nafion-coated Pt/P25 sensitized by rhodamine B

TiO₂ is an excellent photocatalyst in photodegradation and hydrogen production. Herein, through simple modification of Pt/TiO₂ (P25) by Nafion (Nf), photocatalyst Nf/Pt/P25 was prepared and characterized. Photodegradation of rhodamine B (RhB) and photocatalytic hydrogen production over the Nf/Pt/P25 were investigated and compared with those of Nf/P25, P25 and Pt/P25. The results showed the Nf coating caused remarkable improvements in RhB degradation and hydrogen production with RhB as sensitizer. Especially, for the first time, the influence of sacrificial reagent (SR) on hydrogen production performance was studied in detail and the results indicated replacing disodium ethylene-diamine tetraacetate (EDTA) used in literature with triethanolamine (TEOA) leads to a significant enhancement in activity. The H₂-evolving rate of RhB-Nf/Pt/P25-TEOA system is up to 12 times that of RhB-Nf/Pt/P25-EDTA. Besides, other H₂ evolution parameters were optimized and cycling H₂ evolution tests over the Nf/Pt/P25 were conducted. The results confirmed that concurrent H₂ evolution and RhB degradation can be achieved even with very few RhB. Finally, reasons for the enhanced H₂ production performance were proposed. It addressed the importance of selecting a suitable SR and will be very helpful for further work on photocatalytic hydrogen production and photodegradation.     

Biomass-derived hierarchical porous CdS/M/TiO2 (M = Au,Ag, pt,pd) ternary heterojunctions for photocatalytic hydrogen evolution

We demonstrate a general method for the synthesis of biomass-derived hierarchical porous CdS/M/TiO₂ (M = Au, Ag, Pt, Pd) ternary heterojunctions for efficient photocatalytic hydrogen evolution. A typical biomass—wood are used as the raw sources while five species of wood (Fir, Ash, White Pine, Lauan and Shiraki) are chosen as templates for the synthesis of hierarchical porous TiO₂. The as-obtained products inherited the hierarchical porous features with pores ranging from micrometers to nanometers, with improved photocatalytic hydrogen evolution activity than non-templated counterparts. Noble metals M (M = Pt, Au, Ag, Pd) and CdS are loaded via a two-step photodeposition method to form core (metal)/shell (CdS) structures. The photocatalytic modules—CdS(shell)/metal (core)/TiO₂ heterostructures, have demonstrated to increase visible light harvesting significantly and to increase the photocatalytic hydrogen evolution activity. The H₂ evolution rates of CdS/Pd/TiO₂ ternary heterostructures are about 6.7 times of CdS/TiO₂ binary heterojunctions and 4 times higher than Pd/CdS/TiO₂ due to the vertical electron transfer process. The design of such system is beneficial for enhanced activity from morphology control and composition adjustment, which would provide some new pathways for the design of promising photocatalytic systems for enhanced performance.     

Photodeposition of AuNPs on metal oxides: Study of SPR effect and photocatalytic activity

Effect of photodeposition of AuNPs (gold nanoparticles) on TiO₂, CeO₂, Cu₂O and Fe₃O₄ supports has been illustrated on sacrificial donor based hydrogen evolution. The synthesized samples were characterized by diffuse reflectance spectroscopy (DRS), and transmission electron microscopy (TEM). Highest photocatalytic activity was exhibited by Au/TiO₂ followed by Au/Fe₃O₄, Au/CeO₂ and Au/Cu₂O. Au/TiO₂ under optimized conditions has shown significantly high photocatalytic activity under both UV–visible and visible radiation. Au/TiO₂ shows hydrogen evolution rate of 920 μmol h⁻¹ and 32.4 μmol h⁻¹ under UV–visible and visible radiation, respectively. Significant enhancement in hydrogen evolution rate under visible light is very encouraging and may be attributed to polydispersed nature of AuNPs wherein larger particles facilitate light absorption and the smaller function as catalytic sites. Further studies are in progress to study the influence of various parameters on photocatalytic activity of Au/TiO_2.     

Role of molecular oxygen on the synthesis of Ni(OH)2/TiO2 photocatalysts and its effect on solar hydrogen production activity

Molecular oxygen performs a vital role in the photocatalytic activity of anatase TiO₂, but there is a little experimental insight into the role of molecular oxygen on the synthesis of TiO₂ based photocatalysts. Herein, we have shown that Ni(OH)₂/TiO₂ prepared in the presence and absence of molecular oxygen results in significantly varied hydrogen production activity. The sample synthesized in the presence of O₂ and N₂ produced 6624 μmol/h/g and 4468 μmol/h/g of hydrogen under direct solar light exposure. Additionally, the samples prepared in the presence of light irradiation produced 8289 μmol/h/g of hydrogen, a 72 fold jump in hydrogen production compared to TiO₂. XPS, FTIR, Raman, and ESR measurements were carried out to investigate the underlined mechanism for such variation in the photocatalytic activity. Our results suggest that the presence of molecular oxygen during Ni(OH)₂/TiO₂ synthesis causes the formation of terminal OH and reduced the oxygen vacancies on the surface of TiO₂, which can significantly alter the H₂ production. Also, the reusability of the photocatalysts is greatly affected by the synthesis conditions, namely the presence of light and molecular oxygen.     

Concentrated solar photocatalysis for hydrogen generation from water by titania-containing gold nanoparticles

Photocatalysis is an effective way to utilize solar energy to produce hydrogen from water. Au/TiO₂ nanoparticles (NPs) have a better performance in photocatalytic hydrogen generation because of the localized surface plasmon resonance (LSPR) effect of Au/TiO₂ NPs. In the photocatalytic hydrogen generation experiments, it was found that light intensity plays a key role in the photocatalytic reaction rate of Au/TiO₂ NPs. At a light intensity of 0–7 kW/m², the reaction rate has a super-linear law dependence on the light intensity (Rate ∝ Intensityⁿ, with n > 1). However, at a light intensity of 7–9 kW/m², the dependency becomes sub-linear (n < 1). This means that the increase rate of photocatalytic rate is smaller than that of light intensity when the light intensity exceeds 7 kW/m². In addition, the finite element method (FEM) was utilized to further elucidate the role of light intensity by calculating the absorption power and nearfield intensity mapping of a Au/TiO₂ nanoparticle. The variation trend of the calculated total absorption power agrees with the photocatalytic experimental results for different light intensities. These results shed light on the utilization of concentrated solar photocatalysis to increase the solar-to-hydrogen performance of Au/TiO₂ NPs.     

Photocatalytic hydrogen generation by WO3 in synergism with hematite-anatase heterojunction

The present study reports about exploration of a multi-component photocatalytic system comprising of WO₃, TiO₂ and Fe₂O₃ with tandem n-n heterojunctions. The ternary WO₃/TiO₂/Fe₂O₃ nanocomposite with WO₃ nanoparticles over the interfaces of Fe₂O₃ and TiO₂ is synthesized by wet precipitation followed by thermal decomposition. The WO₃/TiO₂/Fe₂O₃ nanocomposite has an enhanced photocatalytic performance towards hydrogen generation by water splitting reaction under visible light irradiation, when compared to the Fe₂O₃/TiO₂ system. A band gap of 2.10 eV, favouring visible light absorption was achieved with the distribution of WO₃ nanopartcles over the interfaces of Fe₂O₃ and TiO_2. The as prepared WTF heterojunction exhibited a maximum hydrogen production rate of 10.2 mL h⁻¹ for a catalyst loading of 0.025 g mL⁻¹. The enhanced photocatalytic performance is tested in presence of various sacrificial agents and proton source. In both cases, the higher photocatalytic efficiency is attributed to the more visible light harnessing ability and pronounced charge separation owing to the tandem n-n heterojunctions generated between TiO₂ with WO₃ and TiO₂ with Fe₂O₃ semiconductors and enhancing the lifetime of the photogenerated electron-hole pairs.