Synergistic effect of Cu2O/TiO2 heterostructure nanoparticle and its high H2 evolution activity

Cu₂O/TiO₂ nanoparticles were prepared by solvothermal method, which formed the heterostructure of Cu₂O/TiO₂. Due to the heterostructure, the H₂ evolution rate under simulated solar irradiation was increasingly promoted. Meanwhile a certain amount of Cu particles which were confirmed by Transmission Electro Microscopy (TEM) and X-Ray Photoelectron Spectroscopy (XPS), formed on the surface of Cu₂O/TiO₂, and the photoactivity was accordingly further enhanced. The stabilized activity was maintained after many times irradiation. It is interesting that after a few hours irradiation the amount of Cu particles on the surface kept unchanged in the presence of Cu₂O and TiO₂. The Cu particles that formed during hydrogen generation reaction play a key role in the further enhancement of the hydrogen production activity. In this study, it is the first time to study the details on the formation of the stable ternary structure under simulated solar irradiation and their synergistic effect on the photoactivity of the water splitting.     

Cu2O/Cu/TiO2 nanotube Ohmic heterojunction arrays with enhanced photocatalytic hydrogen production activity

Cu₂O/Cu/TiO₂ nanotube heterojunction arrays were prepared by assembling Cu@Cu₂O core-shell nanoparticles on TiO₂ nanotube arrays (NTAs) using a facile impregnation-reduction method. SEM and TEM results show that Cu@Cu₂O plate-like nanoparticles with tens of nanometers in size are confined inside TiO₂ NTAs. Only the outmost several nanometers of the nanoparticles are Cu₂O and the predominant inner of the nanoparticles are Cu metals. Cu L₃VV Auger spectra of Cu₂O/Cu/TiO₂ NTAs suggest that Cu metals are enveloped by at least several nanometers Cu₂O on the surface, which further confirms the Cu@Cu₂O core shell structure of Cu nanoparticles. The ability of light absorption of Cu₂O/Cu/TiO₂ NTAs is enhanced. The range of absorption wavelengths changes from 400 to 700 nm due to the surface plasmon response of Cu metals core and Cu₂O nanoparticles shell. The photocatalytic hydrogen production rate of Cu₂O/Cu/TiO₂ heterojunction arrays is enhanced when compared with those of Cu₂O/TiO₂ NTAs and TiO₂ NTAs under UV light. Moreover, a stable H₂ generation property was obtained under visible light (λ gt; 400 nm). The Cu metal core is believed to play a key role in the enhancement of photocatalytic properties of Cu₂O/Cu/TiO₂ nanotube heterojunction arrays.     

Controllable proton and CO2 photoreduction over Cu2O with various morphologies

Simultaneous photocatalytic reduction of water to H₂ and CO₂ to CO was observed over Cu₂O photocatalyst under both full arc and visible light irradiation (>420 nm). It was found that the photocatalytic reduction preference shifts from H₂ (water splitting) to CO (CO₂ reduction) by controlling the exposed facets of Cu₂O. More interestingly, the low index facets of Cu₂O exhibit higher activity for CO₂ photoreduction than high index facets, which is different from the widely-reported in which the facets with high Miller indices would show higher photoactivity. Improved CO conversion yield could be further achieved by coupling the Cu₂O with RuO_x to form a heterojunction which slows down fast charge recombination and relatively stabilises the Cu₂O photocatalyst. The RuO_x amount was also optimised to maximise the junction's photoactivity.     

The influence of the electrodeposition potential on the morphology of Cu2O/TiO2 nanotube arrays and their visible-light-driven photocatalytic activity for hydrogen evolution

The influence of the electrodeposition potential on the morphology of Cu₂O/TiO₂ nanotube arrays (Cu₂O/TNA) and their visible-light-driven photocatalytic activity for hydrogen evolution have been investigated for the first time in this work. The photocatalytic hydrogen evolution rate of the as-prepared Cu₂O/TNA at the deposition potential of −0.8 V was about 42.4 times that of the pure TNA under visible light irradiation. This work demonstrated a feasible and simple electrodeposition method to fabricate an effective and recyclable visible-light-driven photocatalyst for hydrogen evolution.     

Ultrasonic spray pyrolysis synthesis of Ag/TiO2 nanocomposite photocatalysts for simultaneous H2 production and CO2 reduction

Simultaneous photocatalytic hydrogen production and CO₂ reduction (to form CO and CH₄) from water using methanol as a hole scavenger were investigated using silver-modified TiO₂ (Ag/TiO₂) nanocomposite catalysts. A simple ultrasonic spray pyrolysis (SP) method was used to prepare mesoporous Ag/TiO₂ composite particles using TiO₂ (P25) and AgNO₃ as the precursors. The material properties and photocatalytic activities were compared with those prepared by a conventional wet-impregnation (WI) method. It was found that the samples prepared by the SP method had a larger specific surface area and a better dispersion of Ag nanoparticles on TiO₂ than those prepared by the WI method, and as a result, the SP samples showed much higher photocatalytic activities toward H₂ production and CO₂ reduction. The optimal Ag concentration on TiO₂ was found to be 2 wt%. The H₂ production rate of the 2% Ag/TiO₂–SP sample exhibited a six-fold enhancement compared with the 2% Ag/TiO₂–WI sample and a sixty-fold enhancement compared with bare TiO₂. The molar ratio of H₂ and CO in the final products can be tuned in the range from 2 to 10 by varying the reaction gas composition, suggesting a viable way of producing syngas (a mixture of H₂ and CO) from CO₂ and water using the prepared Ag/TiO₂ catalysts with energy input from the sun.     

Highly efficient TiO2 nanotube photocatalyst for simultaneous hydrogen production and copper removal from water

1-D mesoporous TiO₂ nanotube (TNT) with large BET surface area was successfully synthesized by a hydrothermal-calcination process, and employed for simultaneous photocatalytic H₂ production and Cu²⁺ removal from water. Cu²⁺, across a wide concentration range of 8-800 ppm, was removed rapidly from water under irradiation. The removed Cu²⁺ then combined with TNT to produce efficient Cu incorporated TNT (Cu-TNT) photocatalyst for H₂ production. Average H₂ generation rate recorded across a 4 h reaction was between 15.7 and 40.2 mmol h⁻¹ g⁻¹_catalyst, depending on initial Cu²⁺/Ti ratio in solution, which was optimized at 10 atom%. In addition, reduction process of Cu²⁺ was also a critical factor in governing H₂ evolution. In comparison with P25, its large surface area and 1-D tubular structure endowed TNT with higher photocatalytic activity in both Cu²⁺ removal and H₂ production.     

In2O3:Sn/TiO2/CdS heterojunction nanowire array photoanode in photoelectrochemical cells

The design of photoanode with highly efficient light harvesting and charge collection properties is important in photoelectrochemical (PEC) cell performance for hydrogen production. Here, we report the hierarchical In₂O₃:Sn/TiO₂/CdS heterojunction nanowire array photoanode (ITO/TiO₂/CdS-nanowire array photoanode) as it provides a short travel distance for charge carrier and long light absorption pathway by scattering effect. In addition, optical properties and device performance of the ITO/TiO₂/CdS-nanowire array photoanode were compared with the TiO₂ nanoparticle/CdS photoanode. The photocatalytic properties for water splitting were measured in the presence of sacrificial agent such as SO₃²⁻ and S²⁻ ions. Under illumination (AM 1.5G, 100 mW/cm²), ITO/TiO₂/CdS-nanowire array photoanode exhibits a photocurrent density of 8.36 mA/cm² at 0 V versus Ag/AgCl, which is four times higher than the TiO₂ nanoparticle/CdS photoanode. The maximum applied bias photon-to-current efficiency for the ITO/TiO₂/CdS-nanowire array and the TiO₂ nanoparticle/CdS photoanode were 3.33% and 2.09%, respectively. The improved light harvesting and the charge collection properties due to the increased light absorption pathway and reduced electron travel distance by ITO nanowire lead to enhancement of PEC performance.     

Nano-structured Cu2O solar cells fabricated on sparse ZnO nanorods

Nano-structured Cu₂O/ZnO nanorod (NR) heterojunction solar cells fabricated on indium tin oxide (ITO)-coated glass are studied. Substrate film and NR density have a strong influence on the preferred growth of the Cu₂O film. The X-ray diffractometer (XRD) analysis results show that highly (2 0 0)-preferred Cu₂O film was formed when plating on plain ITO substrate. However, a highly (1 1 1)-preferred Cu₂O film was obtained when plating on sparse ZnO NRs. SEM, TEM and XRD studies on sparse NR samples indicate that the Cu₂O nano-crystallites mostly initiate its nucleation on the peripheral surfaces of the ZnO NRs, and are also highly (1 1 1)-oriented. Solar cells with ZnO NRs yielded much higher efficiency than those without. In addition, ZnO NRs plated on a ZnO-coated ITO glass significantly improve the shunt resistance and open-circuit voltage (V_oc) of the devices, with consistently much higher efficiency obtained than when ZnO NRs are directly plated on ITO film. However, longer NRs do not improve the efficiency due to low short-circuit current (J_sc) and slightly higher series resistance. The best conversion efficiency of 0.56% was obtained from a Cu₂O/ZnO NRs heterojunction solar cell fabricated on a 80 nm ZnO-coated ITO glass with V_oc=0.514 V, J_sc=2.64 mA/cm² and 41.5% fill factor.     

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.     

H2 evolution from a photoelectrochemical cell with n-Cu2O photoelectrode under visible light irradiation

H₂ evolution was observed for the first time from a photoelectrochemical cell using an n-type Cu₂O photoelectrode under visible light irradiation. Three-electrode configuration was used in the photoelectrochemical cell to observe H₂ evolution. AgCl/Ag calomel electrode and a platinum plate were used as the reference and counter electrodes, respectively. Fe²⁺/Fe³⁺ redox couple was used as the electrolyte. H₂ evolution was visible on the platinum electrode in the photoelectrochemical cell.     

Photocatalytic hydrogen production from aqueous methanol solution with CuO/Al2O3/TiO2 nanocomposite

The photocatalytic hydrogen production from aqueous methanol solution was investigated with ZnO/TiO₂, SnO/TiO₂, CuO/TiO₂, Al₂O₃/TiO₂ and CuO/Al₂O₃/TiO₂ nanocomposites. A mechanical mixing method, followed by the solid-state reaction at elevated temperature, was used for the preparation of nanocomposite photocatalyst. Among these nanocomposite photocatalysts, the maximal photocatalytic hydrogen production was observed with CuO/Al₂O₃/TiO₂ nanocomposites. A variety of components of CuO/Al₂O₃/TiO₂ photocatalysts were tested for the enhancement of H₂ formation. The optimal component was 0.2 wt% CuO/0.3 wt% Al₂O₃/TiO₂. The activity exhibited approximately tenfold enhancement at the optimum loading, compared with that with pure P-25 TiO₂. Nano-sized TiO₂ photocatalytic hydrogen technology has great potential for low-cost, environmentally friendly solar-hydrogen production to support the future hydrogen economy.     

High photocatalytic hydrogen production over the band gap-tuned urchin-like Bi2S3-loaded TiO2 composites system

A new system using Bi₂S₃-loaded TiO₂ photocatalysts (Bi₂S₃/TiO₂) was developed to enhance the production of hydrogen. The Bi₂S₃ (5, 10, 15 wt%) particles in an urchin-like morphology with a length of about 2∼3 μm and a diameter of 15–20 nm, which can absorb all wavelengths in UV–visible radiation, were prepared by solvothermal method and loaded onto nano-sized TiO₂ (10∼15 nm) for photocatalysis on hydrogen production. The evolution of H₂ from methanol/water (1:1) photo splitting over the Bi₂S₃/TiO₂ composite in the liquid system was enhanced, compared with that over pure TiO₂ and Bi₂S₃. In particular, 14.2 ml of H₂ gas was produced after 12 h when 0.5 g of a 10 wt% Bi₂S₃/TiO₂ composite was used. On the basis of cyclic voltammetry (CV) results, the high photoactivity was attributed to the increase of band gap in the Bi₂S₃/TiO₂ composite, due to the decreased recombination between the excited electrons and holes.     

Efficient H2 production by water-splitting using indium–tin-oxide/V-doped TiO2 multilayer thin film photocatalyst

In order to sensitize TiO₂ in visible light and to reduce photo-induced charge recombination, the multilayer films of Indium-Tin Oxide (ITO)/V-doped TiO₂ were synthesized by radio-frequency magnetron sputtering. V-doped TiO₂ thin films showed red shift in TiO₂ absorption edge with increasing dopant concentration and, most importantly, the dopant energy levels are formed in the TiO₂ band gap due to V⁵⁺/V⁴⁺ ions as confirmed by UV-Visible and XPS spectra. Multilayer films with different numbers of ITO/V-doped TiO₂ (6 at.%) bilayers (namely, 2-, 3-, 4-, 5-, 6- and 7-bilayers) were deposited, in order to reduce the charge recombination rate, by keeping the total thickness of TiO₂ constant in each multilayer film. In multilayer films, when exposed to visible light the photocurrent increases as function of the number of bilayers by reaching the maximum with 6-bilayers of ITO/V-doped TiO₂. The measured enhanced photocurrent is attributed to: 1) ability of V-doped TiO₂ to absorb visible light, 2) number of space-charge layers in form of ITO/TiO₂ interfaces in multilayer films, and 3) generation of photoelectrons just in/or near to the space-charge layer by decreasing the V-doped TiO₂ layer thickness. The reduced charge recombination rate in multilayer films was also confirmed by the photocurrent kinetic curves. The superior photocatalytic efficiency of the 6-bilayers film is also reflected in hydrogen production rate through water-splitting: we obtained indeed 31.2 μmol/h of H₂ production rate.     

Photocatalytic properties of redox-treated Pt/TiO2 photocatalysts for H2 production from an aqueous methanol solution

The influence of redox-treated Pt/TiO₂ photocatalysts on H₂ production is investigated. Catalyst characterizations are performed by TEM, XPS, XRD, BET, and UV–vis/DR spectroscopy techniques. In terms of production rate, the oxidation treatment shows higher reactivity than the reduction treatment. The reduction treatment allows the formation of metallic Pt(0), which more easily catalyzes the transition of TiO₂ from the anatase to the rutile phases. Reduction-treated Pt/TiO₂ photocatalysts have lower S_BET values than oxidation-treated Pt/TiO₂ photocatalysts due to the higher percentage of TiO₂ in the rutile phase. Combining the results of XPS and optical analyses, PtO/TiO₂ shows a higher energy band gap than metallic Pt(0)/TiO₂, indicating that oxidation-treated Pt/TiO₂ is more capable of achieving water splitting for H₂ production. According to the results of this study, the oxidation treatment of Pt/TiO₂ photocatalysts can significantly enhance the reactivity of photocatalytic H₂ production because of their homogenous distribution, lower phase transition, higher S_BET, and higher energy band gap.     

The role of CuO in promoting photocatalytic hydrogen production over TiO2

Low cost semiconductor photocatalysts that can efficiently harvest solar energy to generate H₂ from water or biofuels will be critical to future hydrogen economies. In this study, low cost CuO/TiO₂ photocatalysts (CuO loadings 0–15 wt.%) were prepared, characterized and evaluated for H₂ production from ethanol–water mixtures (80 vol.% ethanol, 20 vol.% H₂O) under UV excitation. TEM, XRF, EDAX, EPR, Raman, TGA, XPS and Cu L-edge NEXAFS data showed that at CuO loadings <5 wt.%, Cu(II) was highly dispersed over the TiO₂ support, possibly as a sub-monolayer CuO species. At higher loadings, CuO crystallites of diameter 1–2 nm were identified. The photocatalytic activity of CuO/TiO₂ photocatalysts was highly dependent on the CuO loading, with 1.25 wt.% CuO being optimal (H₂ production rate = 20.3 mmol g⁻¹ h⁻¹). Results suggest that sub-monolayer coverages of Cu(II) or CuO on TiO₂ are highly beneficial for H₂ generation from ethanol–water mixtures and support the development of a sustainable H₂ economy.     

Efficient indium tin oxide/Cr-doped-TiO2 multilayer thin films for H2 production by photocatalytic water-splitting

Cr-doped-TiO₂ thin films, with three different Cr concentrations (2, 5.5, and 9 at.%), have been synthesized by radio-frequency magnetron sputtering in order to sensitize TiO₂ in visible light. UV–visible spectra showed that maximum narrowing (2.1 eV) of the TiO₂ band gap is obtained for the highest Cr concentration. However, negligible photocurrent was measured with Indium Tin Oxide (ITO)/Cr-doped-TiO₂ (9 at.%) single bilayer sample due to the increased recombination rate of the photo-generated charges on the defects associated to the Cr³⁺ ions. To lower the charge recombination rate in the Cr-doped-TiO₂, multilayer films with different numbers of ITO/Cr-doped-TiO₂ (9 at.%) bilayers (namely, 3-, 4-, 5-, 6- and 7-bilayers) were deposited by keeping the total thickness of TiO₂ constant in each multilayer film. When the multilayer films were exposed to visible light, we observed that the photocurrent increases as function of the number of bilayers by reaching the maximum with 6-bilayers of ITO/Cr-doped-TiO₂. The enhanced photocurrent is attributed to: 1) higher absorption of visible light by Cr-doped-TiO₂, 2) number of space charge layers in form of ITO/TiO₂ interfaces in multilayer films, and 3) generation of photoelectrons just in/or near to the space charge layer by decreasing the Cr-doped-TiO₂ layer thickness. The reduced charge recombination rate in multilayer films was also confirmed by studying the photocurrent kinetic curve. The superior photocatalytic efficiency of the 6-bilayers film implies higher hydrogen production rate through water-splitting: we obtained indeed 24.4 μmol/h of H₂ production rate, a value about two times higher than that of pure TiO₂ (12.5 μmol/h).     

Cu(OH)2-modified TiO2 nanotube arrays for efficient photocatalytic hydrogen production

Cu(OH)₂/TNAs photocatalyst was prepared by loading Cu(OH)₂ nanoparticles on TiO₂ nanotube arrays (TNAs) using a chemical bath deposition method. The amount of Cu(OH)₂ loaded on the arrays was controlled by the repeated deposition times. The prepared catalyst was used to generate hydrogen under simulated solar light irradiation, and the results demonstrated that the hydrogen yield of Cu(OH)₂/TNAs was 20.3 times that of the pure TNAs. Furthermore, the photocatalytic efficiency for hydrogen production decreased only 5.8% after five cycles, indicating that Cu(OH)₂/TNAs photocatalyst showed excellent stability and reusability. This work presents an applicable and facile method to fabricate a highly active and stable photocatalyst for hydrogen production.     

Facile preparation and size-dependent photocatalytic activity of Cu2O nanocrystals modified titania for hydrogen evolution

Degussa TiO₂ powder (P25) with Cu₂O nanocrystals of different sizes deposited on the surface were prepared by a facile ethanol-induced deposition followed with a calcination process at 350 °C and characterized by XRD, XPS, HRTEM and UV–Vis diffuse reflectance spectra, respectively. In our protocol, Cu₂O nanocrystals is formed by reducing Cu(II) with the ethanol adsorbed on the surface of P25. The absorption edge as well as photocatalytic activity for H₂ evolution are closely related to the size of the Cu₂O nanocrystals depending on the Cu content in the as-prepared composites. The 0.9 mol% Cu₂O/TiO₂ composite with ca. 4 nm Cu₂O nanocrystals exhibits the highest photocatalytic H₂ evolution rate of 318 μmol h⁻¹ under the illumination of simulant solar light and an apparent quantum efficiency of 28.6% at 365 nm, 397 times higher than that of P25. This enhancement is mainly attributed to the quantum confinement effect of quantum-sized Cu₂O nanocrystals (q-Cu₂O), which can upgrade the conduction band bottom of q-Cu₂O, and thus facilitates the effective separation of photogenerated charge carriers to enhance the photocatalytic activity. The results provided here not only offers a green and simple way for depositing q-Cu₂O on the surfaces of P25 to get the photocatalyst with an excellent photocatalytic activity for H₂ evolution, but also sheds a new insight for the fabrication of efficient p–n heterojunctions for the separation of electron-hole pairs by quantum confinement effect.     

Photocatalytic hydrogen evolution over CuCrO2

We have been studying the technical feasibility of a photochemical H₂ evolution based on a dispersion of CuCrO₂ powder in aqueous electrolytes containing various reducing agents (S²⁻, and ). The title oxide combines a fair resistance to corrosion with an optimal band gap E_g of 1.32 eV. The intercalation of a small amount of oxygen should be accompanied by a partial oxidation of Cu⁺ into Cu²⁺ implying a p-type semiconductivity. The S²⁻ oxidation inhibits the photocorrosion and the H₂ evolution increases parallel to polysulfides formation. Most of H₂ is produced when p-CuCrO₂ is connected to n-Cu₂O formed in situ. H₂ liberation proceeds mostly on CuCrO₂ while the oxidation of S²⁻ takes place over Cu₂O surface and the hetero system Cu₂O/CuCrO₂ is optimized with respect to some physical parameters. The photoactivity is dependent on preparation conditions and lowering the synthesis temperature through nitrate route leads to an increase in specific surface area S_sp. The photoelectrochemical H₂ production is a multistep process where the rate determining step is the arrival of electrons at the interface because of their low mobility. Prolonged irradiation (>80 min) leads to a pronounced decrease of the photoactivity; the tendency toward saturation is due to the undesired back reduction of polysulfides in a closed system and to their strong absorption in the visible region (λ_max = 520 nm).     

Low-temperature preparation of AgIn5S8/TiO2 heterojunction nanocomposite with efficient visible-light-driven hydrogen production

AgIn₅S₈ and AgIn₅S₈/TiO₂ heterojunction nanocomposite with efficient photoactivity for H₂ production were prepared by a low-temperature water bath deposition process. The resultant AgIn₅S₈ shows an absorption edge at ∼720 nm, corresponding to a bandgap of ∼1.72 eV, and its visible-light-driven photoactivity (100.1 μmol h⁻¹) for H₂ evolution is 9 times higher than that (11 μmol h⁻¹) of the product derived from a hydrothermal process, while the obtained AgIn₅S₈/TiO₂ heterojunction nanocomposites prepared by using commercially available TiO₂ nanoparticles (P25) as TiO₂ source exhibit remarkably improved photoactivity as compared to the pristine AgIn₅S₈, and the AgIn₅S₈/TiO₂ nanocomposite with molar ratio of 1:10 shows a maximum photocatalytic H₂ evolution rate (371.1 μmol h⁻¹), which is 4.3 times higher than that (85 μmol h⁻¹) of the corresponding AgIn₅S₈/TiO₂ nanocomposite derived from a hydrothermal method. This significant enhancement in the photocatativity of the present AgIn₅S₈/TiO₂ nanocomposite can be ascribed to the better dispersion of the AgIn₅S₈ formed on TiO₂ nanoparticle surfaces and the more intimate AgIn₅S₈/TiO₂ heterojunction structure during the water bath deposition process under continuously stirring as compared to the corresponding nanocomposite derived from a hydrothermal method. This configuration of nanocomposite results in fast diffusion of the photogenerated carriers in AgIn₅S₈ towards TiO₂, which is beneficial for separating spatially the photogenerated carriers and improving the photoactivity. The present findings shed light on the tuning strategy of spectral responsive region and photoactivity of photocatalysts for efficient light-to-energy conversion.