Direct Z-scheme anatase/rutile bi-phase nanocomposite TiO2 nanofiber photocatalyst with enhanced photocatalytic H2-production activity

Design and preparation of direct Z-scheme anatase/rutile TiO₂ nanofiber photocatalyst to enhance photocatalytic H₂-production activity via water splitting is of great importance from both theoretical and practical viewpoints. Herein, we develop a facile method for preparing anatase and rutile bi-phase TiO₂ nanofibers with changing rutile content via a slow and rapid cooling of calcined electrospun TiO₂ nanofibers. The phase structure and composition, surface morphology, specific surface area, surface chemical composition and element chemical states of TiO₂ nanofibers were analyzed by X-ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), nitrogen adsorption and X-ray photoelectron spectroscopy (XPS). By a rapid cooling of 500 °C-calcined electrospun TiO₂ precursor, anatase/rutile bi-phase TiO₂ nanofibers with a roughly equal weight ratio of 55 wt.% anatase and 45 wt.% rutile were prepared. The enhanced H₂ production performance was observed in the above obtained anatase/rutile composite TiO₂ nanofibers. A Z-scheme photocatalytic mechanism is first proposed to explain the enhanced photocatalytic H₂-production activity of anatase/rutile bi-phase TiO₂ nanofibers, which is different from the traditional heterojunction electron–hole separation mechanism. This report highlights the importance of phase structure and composition on optimizing photocatalytic activity of TiO₂-based material.     

Review of surface photovoltage spectra of nano-sized semiconductor and its applications in heterogeneous photocatalysis

Heterogeneous photocatalysis is a promising technique valuable for environmental purification. Nano-sized semiconductors such as ZnO and TiO₂, which is one of the most basic functional materials, have emerged as effective photocatalyst materials. The surface photovoltage spectra (SPS) can be an effective method for quickly evaluating the photocatalytic activity of semiconductor materials since it can provide a rapid, non-destructive monitor of the semiconductor surface properties such as surface band bending, surface and bulk carrier recombination and surface states, mainly showing the carrier separation and transfer behavior with the aid of light, especially the electric-field-induced surface photovoltage spectra (EFISPS), in which SPS is combined with the electric-field-modified technique. In this review, the basic principles, measurement and applications of the SPS and EFISPS are mainly discussed together with some fundamental aspects like the electric properties of semiconductor surface and the principle of electric field effect. In particular, the applications of SPS to nano-sized semiconductors such as ZnO and TiO₂ in heterogeneous photocatalysis are emphasized, which involve mainly evaluating the photocatalytic activity by analyzing semiconductor surface properties such as the separation efficiency of photoinduced carriers under illumination by the SPS measurement, highlighting our own contributions. The results show that the weaker the surface photovoltage signal is, the higher the photocatalytic activity is in the case of nano-sized semiconductor photocatalysts.     

TiO2-rutile/anatase homojunction with enhanced charge separation for photoelectrochemical water splitting

The mismatched interfaces of heterojunction usually have lots of defects, deriving in recombination of generated electron-hole pairs. On the other hand, homojunction interfaces are considered to be beneficial to the separation of charge carriers due to the similar characteristics in two sides of homojunction. TiO₂ have rutile and anatase two typical photoactive phases in nature. In this work, TiO₂-rutile/anatase (TiO₂-R/A) homojunction photoanode is fabricated by in situ growth of anatase TiO₂ on TiO₂-R surface. By contrast with TiO₂-rutile/rutile (TiO₂-R/R) photoanode, TiO₂-R/A displays higher photocurrent density (1.70 mA cm^?2 at 0.6 V vs. SCE). Deep insight into the mechanism suggests that TiO₂-R/A homojunction has intense band bending and enhanced surface area, which facilitate the charge separation and transmission. This study offers some novel insights to design and fabricate semiconductors photoanodes for highly efficient photocatalytic reactions.     

Synergistic effect of {101} crystal facet and bulk/surface oxygen vacancy ratio on the photocatalytic hydrogen production of TiO2

Anatase titanium dioxide (TiO₂) nanocrystals with different percentages (up to 95%) of exposed {101} facet and different concentration ratios of bulk single-electron-trapped oxygen vacancies (SETOVs) to surface oxygen vacancies (SOVs) were prepared by alcohol-thermal method with nanotube titanic acid as the precursor in combination with solid-state reduction by NaBH₄. The as-prepared TiO₂ nanocrystals were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, electron spin resonance spectroscopy, and ultraviolet–visible light spectrometry. The effects of the percentage of crystal facets and the concentration ratio of bulk SETOVs/SOVs on the photocatalytic hydrogen production rate of TiO₂ nanocrystals were investigated with positron annihilation lifetime spectroscopy as well as photocurrent test. Findings indicate that the percentage of the exposed {101} facets of the as-prepared TiO₂ nanocrystals and their concentration ratios of bulk SETOVs/SOVs can be well tuned by properly adjusting the amount of NaBH₄ and the reduction reaction time as well. Increasing percentage of the {101} facet of anatase TiO₂ nanocrystals contributes to improving their photocatalytic hydrogen production activity, because the {101} facets of the anatase TiO₂ nanocrystals possess enriched electrons and can act as the reduction sites to enhance the reduction reaction of H⁺ affording H₂ in the sacrifice system of splitting water. Both the bulk SETOVs and SOVs contribute to the improvement of the light absorption while SOVs can facilitate the separation of photogenerated charges, thereby adding to the photocatalytic activity. However, the bulk SETOVs and excessive SOVs are also the combination centers of photogenerated charges, which means it is essential to maintain a suitable concentration ratio of the bulk SETOVs/SOVs so as to enhance the light absorption and achieve the best separation efficiency of photogenerated charges and achieve the best photocatalytic activity for hydrogen production. Particularly, when anatase TiO₂ nanocrystal with a high percentage (95%) of exposed {101} facet is reduced by NaBH₄ at a mass ratio of 2: 1 for 20 min, the resultant reduced H-TiO₂ nanocrystal (denoted as H-TiO₂-R20(2:1)) provides the highest photocatalytic hydrogen productive rate. Furthermore, the combination of 0.5% Pt/H-TiO₂-R20(2:1) with 0.5% Pt/WO₃ can split water to simultaneously produce H₂ and O₂, showing promising potential for splitting water affording hydrogen and oxygen.     

Single crystalline TiO2 nanorods with enhanced visible light activity for solar hydrogen generation

Single crystalline TiO₂ nanorods and polycrystalline nanotubes were fabricated with same length to investigate the effects of their nanostructures on photocatalytic properties for splitting water. In order to enhance the visible light absorbance, TiO₂ nanorods and nanotubes were sensitized with semiconductor nanoparticles such as CdS, CdSe, and CdS/CdSe, and compared in viewpoint of solar hydrogen generation. It was observed that single-crystalline nanorods showed superior photocatalytic properties to polycrystalline nanotubes, and also the potential level of the nanorods with rutile phase was measured as lower than that of the nanotubes with mixture of anatase and rutile. Further improvement of photo-conversion efficiency was obtained by subsequent heat treatments of the sensitized photoelectrodes. It turns out that the improvement is attributed to the improved crystallinity and the increased size of the nanoparticles during the post-annealing treatments. It was demonstrated that TiO₂ nanorods with lower potential level and a single crystalline phase on FTO glass were advantageous for effective charge injection from the sensitized nanoparticles and transport without recombination lost at grain boundaries.     

Influence of oxygen and water related surface defects on the dye sensitized TiO2 solar cell

Oxygen- and water-related surface defects on porous TiO₂ (anatase) can be well controlled by the oxygen and water partial pressures and therefore such defects are of technological relevance for dye sensitized TiO₂ solar cells. We investigated the action of oxygen and water-related surface defects in situ by impedance spectroscopy, photoconductivity, photoluminescence, and optical transmission as well as by characterizing solar cells which were prepared under respective conditions. Oxygen loss from the TiO₂ surface leads to electrical doping by Ti³⁺/oxygen donor states. Such defects create recombination paths for injected electrons back into the electrolyte. Pre-treatment of porous TiO₂ by chemisorption of water increases the open circuit voltage of the solar cells without altering the short circuit current. Water-related surface defects decrease the saturation current of the diode, probably by raising the barrier height at the TiO₂/electrolyte interface.     

A facile nonaqueous route for preparing mixed-phase TiO2 with high activity in photocatalytic hydrogen generation

A facile and simple method was developed to prepare amorphous titanium oxalate from nonaqueous reaction of tetrabutyl titanate and oxalic acid in ethanol at room temperature. This complex was converted to mixed-phase TiO₂ (anatase/rutile) by calcinations. The mixed-phase TiO₂ obtained at the optimum calcination temperature (600 °C) consisting of 67 wt% anatase and 33 wt% rutile exhibited superior photocatalytic hydrogen production activity (1026 μmol h^?1) with high stability, which can be ascribed to the phase-junctions (anatase/rutile) and high crystalline.     

Mesoporous plasmonic Au–TiO2 nanocomposites for efficient visible-light-driven photocatalytic water reduction

The mesoporous Au–TiO₂ nanocomposites with different Au concentrations were prepared via a co-polymer assisted sol–gel method. The structures have been characterized by powder X-Ray diffraction, N₂ adsorption–desorption isotherms, diffuse reflectance UV–Vis spectroscopy, X-ray photoemission spectroscopy, transmission electron microscopy. Most generated Au nanoparticles were embedded in the mesoporous TiO₂ matrix. The prepared Au–TiO₂ nanocomposites exhibit remarkable visible-light activity for H₂ evolution from photocatalytic water reduction in the presence of ascorbic acid as the electron donor. By comparing with Pt–TiO₂ samples, we found that the visible-light activity of the Au–TiO₂ nanocomposites could be partially contributed by the defects/impurity states in the TiO₂ matrix, while the gold surface plasmons could significantly enhance the weak visible-light excitation of TiO₂ matrix. In addition, further studies by controlling irradiation wavelengths suggest that some plasmon-excited electrons could transfer from Au nanoparticles to the contacting TiO₂ to reduce water for H₂ generation. We believe that these Au–TiO₂ nanocomposites as well as the mechanistic studies would have considerable impact on future development of metal-semiconductor hybrid photocatalysts for efficient solar hydrogen production.     

Electrospun TiO2/SnO2 nanofibers with innovative structure and chemical properties for highly efficient photocatalytic H2 generation

Innovative TiO₂/SnO₂ nanofibers were fabricated via electrospinning an innovated precursor solution and used for photocatalytic H₂ generation. The nanofibers exhibited greatly enhanced H₂ evolution rate compared to bare TiO₂ nanofiber and P25. The enhanced efficiency of the TiO₂/SnO₂ nanofibers was attributed to its excellent synergistic properties: (1) its good mesoporosity; (2) the red-shift of absorbance spectra to enhance light absorbance capability; (3) its long nanofibrous structure and (4) anatase TiO₂ – rutile TiO₂ – rutile SnO₂ ternary junctions favorable for the separation of electrons and holes. Based on our experimental results, the optimum ratio of TiO₂/SnO₂ nanofibers with 3% Sn demonstrated the highest efficiency in H₂ generation.     

Single-step fabrication of phase-controllable nanocrystalline TiO2 films for enhanced photoelectrochemical water splitting and dye-sensitized solar cells

We introduce a single-step procedure for growing a phase-controllable bilayer-structured TiO₂ film directly onto transparent conductive oxide glass by precipitation from hydrolysis of TiCl₄ in acid solution containing sulfate ions. The obtained bilayer-structured film with anatase nanoparticles in the inner layer which provide high surface area, and an outer layer of larger rutile particles for incident light scattering. In both the water splitting and the dye-sensitized solar cells under AM 1.5 simulated solar light, the bilayer-structured film outperformed the single layer-structured films with either anatase or rutile TiO₂ alone by at least 50%.     

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.     

Facile synthesis of anatase/rutile TiO2/g-C3N4 multi-heterostructure for efficient photocatalytic overall water splitting

Rational design of high-efficiency heterostructure photocatalyst is an effective strategy to realize photocatalytic H₂ evolution from pure water, but remains still a considerable challenge. Herein, an anatase/rutile TiO₂/g-C₃N₄ (A/R/CN) multi-heterostructure photocatalyst was prepared by a facile thermoset hybrid method. The combination of two type-II semiconductor heterostructures (i.e., A/R and R/CN) significantly improve the separation and transfer efficiency of photogenerated carriers of anatase TiO₂, rutile TiO₂ and g-C₃N₄, and A/R/CN photocatalyst with high activity is obtained. The optimal A/R/CN photocatalyst exhibits significantly increased photocatalytic overall water splitting activity with a rate of H₂ evolution of 374.2 μmol g⁻¹h⁻¹, which is about 8 and 4 times that of pure g-C₃N₄ and P25. Moreover, it is demonstrated to be stable and retained a high activity (ca. 91.2%) after the fourth recycling experiment. This work comes up with an innovative perspective on the construction of multi-heterostructure interfaces to improve the overall photocatalytic water splitting performance.     

In-situ synthesis of novel plate-like Co(OH)2 co-catalyst decorated TiO2 nanosheets with efficient photocatalytic H2 evolution activity

Efficient separation of photo-generated electrons and holes is a crucial aspect for photocatalytic hydrogen evolution. Herein, novel plate-like Co(OH)₂ decorated TiO₂ nanosheets for photocatalytic water splitting were synthesized by a facile in-situ synthetic method. The results of X-ray diffractometry (XRD), transmission electron microscope (TEM), UV–Vis diffusion reflectance spectroscopy (DRS) and X-ray photoelectron spectroscopy (XPS) indicate the successfully incorporation of Co(OH)₂ co-catalysts onto the surface of TiO₂ nanosheet photocatalysts. Further photocatalytic hydrogen evolution experiments illustrate that all Co(OH)₂ decorated TiO₂ samples show higher rate of hydrogen production performance than pure TiO₂ sample and the composite sample with Co(OH)₂ loading amount of 0.5mol% presents the highest photocatalytic hydrogen production activity of 746.93 μmol g^?1·h^?1. It is indicated that plate-like Co(OH)₂ particle act as an electron collector, which leads to photo-generated electrons transfer from TiO₂ to Co(OH)₂, and therefore enhance the photocatalytic activity. Based on above results, a possible mechanism is proposed and further verified by surface photovoltage spectra (SPV).     

A comparison of microwave and conventional heat treatments of nanocrystalline TiO2

TiO₂ thin films are an important component of dye-sensitized solar cells. For these solar cells, the TiO₂ film must be sintered to achieve crystallization and good interparticle connections. Microwave processing may allow a reduction in the required temperature and time for this heat treatment. Therefore, microwave heating of nanocrystalline TiO₂ has been investigated. No significant difference was found between microwave and conventional heating in the sintering of TiO₂, but microwave heating promotes the phase transformation from anatase to rutile. Microwave heating improved the solar cell performance when a surface treatment of the TiO₂ film with titanium isopropoxide was applied.     

Activity and stability of TiO2 samples with different phase compositions in the decomposition of formaldehyde in SCW

TiO₂ samples with different crystal sizes and compositions were synthesized using a sol-gel method at different calcination temperatures (350–900 °C). The activity and stability of TiO₂ samples were determined by the gasification of formaldehyde in supercritical water (SCW) and by treatment in SCW. Increasing calcination temperature and SCW gasification (SCWG)/SCW treatment decreased the surface area of anatase TiO₂ samples due to growing crystallite size via agglomeration and sintering. Among anatase TiO₂ samples, the TiO₂ calcinated at 450 °C was found as the most suitable material under SCW conditions. However, the surface area of rutile TiO₂ slightly increased from 17.2 m² g^?1 to 19.8 m² g^?1 with the weakly crumbling of particles during SCWG. The highest hydrogen formation (63%) from formaldehyde in the SCW was obtained in the presence of anatase TiO₂ calcined at 350 °C and rutile TiO₂ calcined at 800 °C. CO₂ formation in the presence of anatase TiO₂ is higher than rutile TiO₂ because of the presence of active lattice oxygen species (O^?, O^2?) based on O₂-TPD.     

The optical absorption and hydrogen production by water splitting of (Si,Fe)-codoped anatase TiO2 photocatalyst

The electronic and optical properties are studied using the density functional theory in (Si,Fe)-codoped anatase TiO₂. The calculated results suggest that the synergistic effects of (Si,Fe) codoping can effectively induce the redshift of optical absorption edge, which leads to higher visible-light photocatalytic activity for hydrogen production by water splitting than pure anatase TiO₂. To verify the reliability of our calculated results, nanocrystalline (Si,Fe)-codoped TiO₂ is synthesized by a sol-gel-solvothermal method, and excellent absorption performance and photocatalytic activity for hydrogen production by water splitting are observed in our experiments.     

Preparations and photocatalytic hydrogen evolution of N-doped TiO2 from urea and titanium tetrachloride

Nitrogen (N)-doped TiO₂ samples with high specific surface areas were directly prepared by heating the mixture of urea and TiO₂, where the TiO₂ was obtained with titanium tetrachloride as precursor. The absorption spectrum of the N-doped TiO₂ shifted to wavelength up to 600 nm with increasing urea contents. X-ray photoelectron spectroscopic measurements showed that the N presented in TiO₂ was in the state of both molecularly chemisorbed N₂ and substituted N. While both of them contribute to the response to visible light, the latter gave the prepared samples with hydrogen evolution under visible light. The apparent photocatalytic activity of water splitting demonstrated as high amount of H₂ evolution was partly due to the phase transformation from anatase to rutile for the N-doped TiO₂.     

Photocatalytic hydrogen production with aid of simultaneous metal deposition using titanium dioxide from aqueous glucose solution

The photocatalytic hydrogen production with aid of simultaneous metal deposition using TiO₂ was investigated in biomass glucose solution. Because the hydrogen production was very trace with pure TiO₂, the simultaneous metal deposition was applied into the glucose solution. The photocatalytic H₂ production activity with TiO₂ was significantly enhanced by simultaneous metal deposition for Au and Pd. The experimental factors such as glucose concentration, metal ion concentration and reaction temperature were investigated. The photocatalytic hydrogen production increased with increasing the concentration of glucose, and it followed Langmuir–Hinshelwood mechanism. Under the optimal conditions, the photocatalytic hydrogen generations from aqueous glucose solution with in-situ Au and Pd deposited TiO₂ were about 203 and 362 times larger compared with those observed with pure TiO₂. The enhanced photocatalytic activity could be explained in terms of reduced electron hole recombination via electron transfer from conductance band of TiO₂ to metal.     

Nickel sulfide as co-catalyst on nanostructured TiO2 for photocatalytic hydrogen evolution

In this study, TiO₂ photocatalysts with nickel sulfide cocatalyst are prepared by loading nickel sulfide on TiO₂ with solvothermal synthesis approach. The materials were prepared by glycol solvothermal method using anatase, nickel nitrate, thiourea as precursor. The prepared catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), ultraviolet–visible diffuse reflectance spectroscopy (UV–vis DRS), and X-ray photoelectron spectroscopy (XPS). This is the first time to report that NiS is used as a cocatalyst with TiO₂ for the photocatalytic production of H₂. The results revealed that the structure and the amount of the cocatalyst loaded on TiO₂ play important roles in the photocatalytic activity of NiS/TiO₂ composite. The maximum evolution of H₂ was obtained when NiS had hexagonal structure with content in the composite of 7 at% in relation to TiO₂. The rate of H₂ evolution was increased up to about 30 times than that of TiO₂ alone.     

Ab initio study on the effects of dopant–defect cluster on the electronic properties of TiO2-based photocatalysts

We present a first-principles study on the electronic properties of TiO₂ containing both dopants and defects on the basis of density-functional theory. We show that the formation energies of defects can be reduced by up to 80% in N-doped TiO₂ (N substitutes O), as compared to those in perfect TiO₂, but the H-doping (H substitutes O) has less effect on the defect formation. We predict that dopant-interstitial Ti cluster plays an important role in the narrowing of band gap of N-doped anatase and brookite TiO₂, and H-doped rutile TiO₂. Importantly, the defect bands within the band gaps can enhance the visible-light absorption and improve the photocatalytic performance of the systems due to the reduced gap between the bands. The dopant–defect cluster in the doped TiO₂ may be responsible for the observed visible-light absorption in experiments. The present study provides a new route to enhance the performance of photocatalyst.