Ion engineering techniques for the preparation of the highly effective TiO<Subscript>2</Subscript> photocatalysts operating under visible light irradiation

The successful application of ion engineering techniques for the development of TiO₂ photocatalysts operating under visible and/or solar light irradiations has been summarized in this review article. First, we have physically doped various transition metal ions within a TiO₂ lattice on an atomic level by using an advanced metal ion implantation method. The metal ion implanted TiO₂ could efficiently work as a photocatalyst under visible light irradiation. Some field tests under solar light irradiation clearly revealed that the Cr or V ions implanted TiO₂ samples showed 2–3 times higher photocatalytic reactivity than the un-implanted TiO₂. Second, we have developed the visible light responsive TiO₂ thin film photocatalyst by a single process using an RF-magnetron sputtering (RF-MS) deposition method. The vis-type TiO₂ thin films showed high photocatalytic reactivity for various reactions such as reduction of NOx, degradation of organic compounds, and splitting of H₂O under visible and/or solar light irradiations.     

TiO2光催化剂的形貌与晶面调控

二氧化钛（TiO₂）具有化学稳定性高、无毒、价格低廉、来源广泛及光电性能优异等优点,被广泛应用于太阳能电池和光催化等领域,尤其是在污染物的光催化降解方面,可很好地解决当前的环境污染问题。但一方面受带隙宽度限制,使其对太阳光的利用率不足5%,不能充分利用太阳光中的可见光;另一方面由于光生电子-空穴容易结合,催化效率低,从而使TiO₂的实际应用受到限制。因此必须采取合适的措施,一方面要增强TiO₂对可见光的吸收,提高对太阳光的利用率;另一方面要抑制光生电子-空穴的复合,提高光催化效率。目前越来越多的科学家通过控制TiO₂的形貌、晶型、特殊晶面暴露等手段来提高TiO₂光生电子-空穴的传输速率和光电转换效率。本文主要综述了近年来在TiO₂光催化剂的特殊形貌和特殊晶面暴露等方面的研究进展,对未来的研究和发展方向作了展望。     

TiO_2光催化剂的形貌与晶面调控

二氧化钛(TiO2)具有化学稳定性高、无毒、价格低廉、来源广泛及光电性能优异等优点,被广泛应用于太阳能电池和光催化等领域,尤其是在污染物的光催化降解方面,可很好地解决当前的环境污染问题。但一方面受带隙宽度限制,使其对太阳光的利用率不足5%,不能充分利用太阳光中的可见光;另一方面由于光生电子-空穴容易结合,催化效率低,从而使TiO2的实际应用受到限制。因此必须采取合适的措施,一方面要增强TiO2对可见光的吸收,提高对太阳光的利用率;另一方面要抑制光生电子-空穴的复合,提高光催化效率。目前越来越多的科学家通过控制TiO2的形貌、晶型、特殊晶面暴露等手段来提高TiO2光生电子-空穴的传输速率和光电转换效率。本文主要综述了近年来在TiO2光催化剂的特殊形貌和特殊晶面暴露等方面的研究进展,对未来的研究和发展方向作了展望。     

In‐situ Platinum Plasmon Resonance Effect Prompt Titanium Dioxide Nanocube Photocatalytic Hydrogen Evolution

Herein, Pt‐decorated TiO₂ nanocube hierarchy structure (Pt‐TNCB) was fabricated by a facile solvothermal synthesis and in‐situ photodeposition strategy. The Pt‐TNCB exhibits an excellent solar‐driven photocatalytic hydrogen evolution rate (337.84 μmol h^?1), which is about 37 times higher than that of TNCB (9.19 μmol h^?1). Interestingly, its photocatalytic property is still superior to TNCB with post modification Pt (1 wt %) (208.11 μmol h^?1). The introduction of Pt efficiently extends the photoresponse of the composite material from UV to visible light region, simultaneously boosting their solar‐driven photocatalytic performance, which attribute to the porous structure, the sub size TNCB, the SPR effect of Pt NPs and strong interaction of two components. In fact, Pt NPs can enhance collective oscillations on delocalized electrons, which is conducive to capture electrons and hinder the recombination of photogenerated electron‐hole pairs, leading to the longer lifetime of photogenerated charges. The fabrication of Pt‐TNCB photocatalyst with SPR effect may provide a promising method to improve visible‐light photocatalytic activities for traditional photocatalysts.     

Constructing Ordered Three‐Dimensional TiO2 Channels for Enhanced Visible‐Light Photocatalytic Performance in CO2 Conversion Induced by Au Nanoparticles

As a typical photocatalyst for CO₂ reduction, practical applications of TiO₂ still suffer from low photocatalytic efficiency and limited visible‐light absorption. Herein, a novel Au‐nanoparticle (NP)‐decorated ordered mesoporous TiO₂ (OMT) composite (OMT‐Au) was successfully fabricated, in which Au NPs were uniformly dispersed on the OMT. Due to the surface plasmon resonance (SPR) effect derived from the excited Au NPs, the TiO₂ shows high photocatalytic performance for CO₂ reduction under visible light. The ordered mesoporous TiO₂ exhibits superior material and structure, with a high surface area that offers more catalytically active sites. More importantly, the three‐dimensional transport channels ensure the smooth flow of gas molecules, highly efficient CO₂ adsorption, and the fast and steady transmission of hot electrons excited from the Au NPs, which lead to a further improvement in the photocatalytic performance. These results highlight the possibility of improving the photocatalysis for CO₂ reduction under visible light by constructing OMT‐based Au‐SPR‐induced photocatalysts.     

Surface Modifications and Optoelectronic Characterization of TiO2‐Nanoparticles: Design of New Photo‐Electronic Materials

TiO₂ nanoparticles are of great current interest for applications in photo‐electronic materials including light‐energy conversion, artificial photosynthetic systems as well as photocatalysis. The success of these applications relies on the exciton recombination dynamics and visible‐light sensitivity of the TiO₂ nanomaterials. Thus, in order to develop the highly efficient photo‐electronic materials absorbing visible light, different low dimensional TiO₂ nanostructures such as nanodiscs, nanofibers and nanochains were synthesized, and thereafter their surfaces were modified by incorporating with Sn‐porphyrins and heteropoly acid. The optoelectronic properties of the surface‐modified nanomaterials were investigated with regard to the optical properties and the surface exciton dynamics by using both steady‐state and ultrafast time‐resolved laser spectroscopic techniques including single nanoparticle photoluminescence technique. These results were correlated with the photo‐electronic properties including photocatalytic activities and solar cell efficiencies, indicating that the electron transfer mechanism in the modified nanostructures may be similar to the “Z‐scheme” of the plant photosynthetic system so that both photocatalytic activity and solar cell efficiencies were synergistically enhanced by using two color illumination.     

Microwave‐Hydrothermal Preparation and Visible‐Light Photoactivity of Plasmonic Photocatalyst Ag‐TiO2 Nanocomposite Hollow Spheres

Visible‐light‐driven plasmonic photocatalyst Ag‐TiO₂ nanocomposite hollow spheres are prepared by a template‐free chemically‐induced self‐transformation strategy under microwave‐hydrothermal conditions, followed by a photochemical reduction process under xenon lamp irradiation. The prepared samples are characterized by using scanning electron microscopy, transmission electron microscopy, X‐ray diffraction, N₂ adsorption‐desorption isotherms, X‐ray photoelectron spectroscopy, UV/Vis and Raman spectroscopy. Production of ?OH radicals on the surface of visible‐light illuminated TiO₂ was detected by using a photoluminescence method with terephthalic acid as the probe molecule. The photocatalytic activity of as‐prepared samples was evaluated by photocatalytic decolorization of Rhodamine B (RhB) aqueous solution at ambient temperature under visible‐light irradiation. The results show that the surface plasmon absorption band of the silver nanoparticles supported on the TiO₂ hollow spheres was red shifted, and a strong surface enhanced Raman scattering effect for the Ag‐TiO₂ nanocomposite sample was observed. The prepared nanocomposite hollow spheres exhibits a highly visible‐light photocatalytic activity for photocatalytic degradation of RhB in water, and their photocatalytic activity is higher than that of pure TiO₂ and commercial Degussa P25 (P25) powders. Especially, the as‐prepared Ag‐TiO₂ nanocomposite hollow spheres at the nominal atomic ratio of silver to titanium ( R ) of 2 showed the highest photocatalytic activity, which exceeds that of P25 by a factor of more than 2.     

Efficient and Robust Cu/TiO2 Nanorod Photocatalysts for Simultaneous Removal of Cr(VI) and Methylene Blue under Solar Light

Because of its large bandgap, TiO₂ can function only under UV light. TiO₂ surface modification with noble metal nanoparticles can extend the light absorption from UV to visible light region and enhance the photocatalytic quantum yield. In this work, TiO₂ nanorods (Cu/TiO₂) modified by copper nanoparticles were prepared by a one‐step solvothermal method at low cost. The resultant Cu/TiO₂ nanorods show excellent synergistic effect in the oxidation of methylene blue (MB) and the reduction of aqueous Cr(VI) under solar light irradiation. Mechanistic investigation suggests that the Cr(VI) species could effectively scavenge the electrons from MB in the presence of the as‐prepared photocatalyst, leading to the simultaneous removal of both pollutants. Being economically viable, environmentally sustainable, and highly efficient, the proposed photocatalyst holds promise for technologies involving simultaneous organic degradation and heavy metal removal in wastewater treatment.     

TiO2 Nanotube Arrays Modified with Cr‐Doped SrTiO3 Nanocubes for Highly Efficient Hydrogen Evolution under Visible Light

In recent decades, solar‐driven hydrogen production over semiconductors has attracted tremendous interest owing to the global energy and environmental crisis. Among various semiconductor materials, TiO₂ exhibits outstanding photocatalytic properties and has been extensively applied in diverse photocatalytic and photoelectric systems. However, two major drawbacks limit practical applications, namely, high charge‐recombination rate and poor visible‐light utilization. In this work, heterostructured TiO₂ nanotube arrays grafted with Cr‐doped SrTiO₃ nanocubes were fabricated by simply controlling the kinetics of hydrothermal reactions. It was found that coupling TiO₂ nanotube arrays with regular SrTiO₃ nanocubes can significantly improve the charge separation. Meanwhile, doping Cr cations into SrTiO₃ nanocubes proved to be an effective and feasible approach to enhance remarkably the visible‐light response, which was also confirmed by theoretical calculations. As a result, the rate of photoelectrochemical hydrogen evolution of these novel heteronanostructures is an order of magnitude larger than those of TiO₂ nanotube arrays and other previously reported SrTiO₃/TiO₂ nanocomposites under visible‐light irradiation. Furthermore, the as‐prepared Cr‐doped SrTiO₃/TiO₂ heterostructures exhibit excellent durability and stability, which are favorable for practical hydrogen production and photoelectric nanodevices.     

Effect of Erbium on the Photocatalytic Activity of TiO2/Ag Nanocomposites under Visible Light Irradiation

Erbium co‐doped TiO₂/Ag catalysts are synthesized by using a simple, one‐step solvothermal method and characterized by X‐ray diffraction, field‐emission scanning electron microscopy, transmission electron microscopy, Raman analysis, X‐ray photoelectron spectroscopy, and diffuse reflectance spectroscopy. The catalysts exhibit anatase crystal structures with increased visible light absorption compared with pure TiO₂. Enhanced photocatalytic activity is observed with Er co‐doped TiO₂/Ag nanocomposites for Rhodamine B degradation under visible light irradiation. The photocatalytic activity of 1 % Er co‐doped TiO₂/Ag is much higher than that of TiO₂/Ag, TiO₂/Er, pure TiO₂, and commercial Degussa P25. The kinetics of the degradation process are studied and the pseudo‐first‐order rate constant (k) and half‐life time (t_1/2) of the reaction are calculated. The enhanced activity might be accredited to the efficient separation of electron–hole pairs by silver and higher visible light absorption of TiO₂ induced by Er.     

Photo Catalytic Degradation of Azo Dyes over Mn2+ Doped TiO2 Catalyst under UV/Solar Light:An Insight to the Route of Electron Transfer in the Mixed Phase of Anatase and Rutile

Mn²⁺ ion was doped into the TiO₂ matrix and its photocatalytic activity was evaluated for the degradation of a mono azo dye methyl orange (MO) and a di‐azo dye brilliant yellow (BY) under UV/solar light. X‐ray diffraction results revealed the phase transformation from anatase to rutile due to the inclusion of Mn²⁺ ion into the TiO₂ matrix. All the doped catalysts showed a red shift in the band gap to the visible region. The degradation reaction of the dyes was found to be dependent on its structure. It was found that mono azo dye degrades faster than di azo dye under UV/solar light. The rate constant under identical conditions calculated for the degradation of MO is 2.4 times (under UV light) and 4.5 times (under solar light) higher compared to BY. Among the photocatalysts studied, Mn²⁺(0.06 at.%)‐TiO₂ showed higher activity under both UV and solar light illumination. The synergestic effect in the bicrystalline framework of anatase and rutile effectively suppresses the charge carrier recombination and enhances the photocatalytic activity. The degradation reaction was followed by UV‐visible spectroscopy and the photoproducts formed were analyzed by GC‐MS techniques.     

Fullerol–Titania Charge‐Transfer‐Mediated Photocatalysis Working under Visible Light

The development of visible‐light‐active photocatalysts is being investigated through various approaches. In this study, C₆₀‐based sensitized photocatalysis that works through the charge transfer (CT) mechanism is proposed and tested as a new approach. By employing the water‐soluble fullerol (C₆₀(OH)_x) instead of C₆₀, we demonstrate that the adsorbed fullerol activates TiO₂ under visible‐light irradiation through the “surface–complex CT” mechanism, which is largely absent in the C₆₀/TiO₂ system. Although fullerene and its derivatives have often been utilized in TiO₂‐based photochemical conversion systems as an electron transfer relay, their successful photocatalytic application as a visible‐light sensitizer of TiO₂ is not well established. Fullerol/TiO₂ exhibits marked visible photocatalytic activity not only for the redox conversion of 4‐chlorophenol, I^?, and Cr^VI, but also for H₂ production. The photoelectrode of fullerol/TiO₂ also generates an enhanced anodic photocurrent under visible light as compared with the electrodes of bare TiO₂ and C₆₀/TiO₂, which confirms that the visible‐light‐induced electron transfer from fullerol to TiO₂ is particularly enhanced. The surface complexation of fullerol/TiO₂ induced a visible absorption band around 400–500 nm, which was extinguished when the adsorption of fullerol was inhibited by fluorination of the surface of TiO₂. The transient absorption spectroscopic measurement gave an absorption spectrum ascribed to fullerol radical cations (fullerol^.+) the generation of which should be accompanied by the proposed CT. The theoretical calculation regarding the absorption spectra for the (TiO₂ cluster+fullerol) model also confirmed the proposed CT, which involves excitation from HOMO (fullerol) to LUMO (TiO₂ cluster) as the origin of the visible‐light absorption.     

Modification of the Optical and Electronic Properties of TiO<Subscript>2</Subscript> By N Anion-Doping for Augmentation of the Visible Light Assisted Photocatalytic Performance

In this work, a nitrogen-doped anatase TiO₂ nanocrystal is prepared by a modified sol-gel preparation method using the nonionic surfactant (polyoxyethylene sorbitan monooleate) as a structural controller and a soft template. The as-prepared samples are characterized by X-ray diffraction, Raman spectroscopy, UVVis diffuse reflectance spectroscopy, and X-ray photoelectron spectroscopy techniques. Then the photocatalytic activity of these samples is assessed by the photocatalytic oxidation of phenol under visible light irradiation. The phenol concentration is measured using a UV-Vis spectrometer. Experimental results show that N-doping leads to an excellent visible light photocatalytic activity of the TiO₂ nanocatalyst. Furthermore, the formation energy and electronic structure of pure and N-doped anatase TiO₂ are described by density functional theory (DFT) calculations. It is found that N-doping narrowed the band gap of bare TiO₂, which leads to an excellent visible light photocatalytic activity of N–TiO₂ nanocatalysts. Therefore, the prepared N–TiO₂ photocatalyst is expected to find the use in organic pollutant degradation under solar light illumination.     

Broadband Light Harvesting and Unidirectional Electron Flow for Efficient Electron Accumulation for Hydrogen Generation

The efficiency of solar hydrogen evolution closely depends on the multiple electrons accumulation on the catalytic center for two‐electron‐involved water reduction. Herein, we report an effective approach to enable broadband light absorption and unidirectional electron flow for efficiently accumulating electrons at active sites for hydrogen evolution by rationally engineering the nanostructure of Pt nanoparticles (NPs), TiO₂, and SiO₂ support. In addition to Schottky‐junction‐driven electron transfer from TiO₂ to Pt, Pt NPs also produce hot electrons by recycling the scattered visible and near‐infrared (vis‐NIR) light of the support. Unidirectional electron flow to active sites is realized by tuning the components spatial distribution. These features collectively accumulate multiple electrons at catalytic Pt sites, thereby affording enhanced activity toward hydrogen evolution under simulated sunlight.     

Au nanorods decorated TiO2 nanobelts with enhanced full solar spectrum photocatalytic antibacterial activity and the sterilization file cabinet application

TiO₂ photocatalysts have been widely studied and applied for removing bacteria, but its antibacterial efficiency is limited to the ultraviolet (UV) range of the solar spectrum. In this work, we use the gold (Au) nanorods to enhance the visible and near-infrared (NIR) light absorption of TiO₂ NBs, a typical UV light photocatalyst, thus the enhancement of its full solar spectrum (UV, visible and NIR) photocatalytic antibacterial properties is achieved. Preliminary surface plasmon resonance (SPR) enhancement photocatalytic antibacterial mechanism is suggested. On one hand, transverse and longitudinal SPR of Au NRs is beneficial for visible and NIR light utilization. On the other hand, Au NRs combined with TiO₂ NBs to form the heterostructure, which can improve the photogenerated carrier separation and direct electron transfer increases the hot electron concentration while Au NRs as the electron channel can well restrain charge recombination, finally produces the high yield of radical oxygen species and exhibits a superior antibacterial efficiency. Furthermore, we design a sterilization file cabinet with Au NR/TiO₂ NB heterostructures as the photocatalytic coating plates. Our study reveals that Au NR/TiO₂ NB heterostructure is a potential candidate for sterilization of bacteria and archives protection.     

Ag‐Enhanced TiO2–x/C Composites with Metal‐Organic Frameworks as Precursors for Photodegradation of Methyl Blue

A series of Ag‐enhanced TiO_2–x/C composites (Ag/TiO_2–x/C composites) with metal‐organic frameworks (MOFs) as precursors were prepared, and their photocatalytic activities were evaluated by the UV‐light driven photodegradation behaviors of methyl blue (MB). The as‐obtained samples were characterized by several techniques such as SEM, XRD, N₂‐adsorption, XPS, UV/Vis spectrophotometry and UV/Vis diffuse‐reflectance spectra. The best photocatalytic performance was achieved in Ag/TiO_2–x/C composite pyrolyzed at 1000 °C (ATC‐P10) due to rapid capture of electrons caused by silver doping, higher density of TiO_2–x lattice oxygen vacancies for better trapping of electrons, and high surface area due to reduction and evaporation of metallic Zn. No obvious deactivation was observed after 10 cycles of UV‐light degradation of MB under the same experimental conditions. This report reveals a new approach to prepare stable and highly efficient UV‐light‐driven photocatalysts for organic pollutants in water.     

Investigation of Electron Behavior in Nano‐TiO2 Photocatalysis by Using In Situ Open‐Circuit Voltage and Photoconductivity Measurements

The in situ open‐circuit voltages (V_oc) and the in situ photoconductivities have been measured to study electron behavior in photocatalysis and its effect on the photocatalytic oxidation of methanol. It was observed that electron injection to the conduction band (CB) of TiO₂ under light illumination during photocatalysis includes two sources: from the valence band (VB) of TiO₂ and from the methanol molecule. The electron injection from methanol to TiO₂ is slower than that directly from the VB, which indicates that the adsorption mode of methanol on the TiO₂ surface can change between dark and illuminated states. The electron injection from methanol to the CB of TiO₂ leads to the upshift of the Fermi level of electrons in TiO₂, which is the thermodynamic driving force of photocatalytic oxidation. It was also found that the charge state of nano‐TiO₂ is continuously changing during photocatalysis as electrons are injected from methanol to TiO₂. Combined with the apparent Langmuir–Hinshelwood kinetic model, the relation between photocatalytic kinetics and electrons in the TiO₂ CB was developed and verified experimentally. The photocatalytic rate constant is the variation of the Fermi level with time, based on which a new method was developed to calculate the photocatalytic kinetic rate constant by monitoring the change of V_oc with time during photocatalysis.     

The Visible‐Light Photocatalytic Activity and Antibacterial Performance of Ag/AgBr/TiO2 Immobilized on Activated Carbon

Visible‐light‐driven Ag/AgBr/TiO₂/activated carbon (AC) composite was prepared by solgel method coupled with photoreduction method. For comparison, TiO₂, TiO₂/AC, and Ag/AgBr/TiO₂ were also synthesized. Their characteristics were analyzed by XRD, SEM‐EDS, TG‐DSC and UV–vis techniques. Photocatalytic activity and antibacterial performance under visible‐light irradiation were investigated by ICP‐AES, ATR‐FT‐IR and spectrophotometry methods using methylene blue and Escherichia coli as target systems, respectively. The results showed that Ag/AgBr was successfully deposited on anatase TiO₂/AC surface, and exhibited a distinct light absorption in the visible region. Ag/AgBr/TiO₂/AC displayed excellent antibacterial performance both in dark and under visible‐light illumination. The growth of E. coli cell was inhibited in the presence of Ag/AgBr/TiO₂/AC in dark. Moreover, upon visible‐light illumination, a significant damage of cell membrane was noticed. Ag/AgBr/TiO₂/AC was also shown higher photocatalytic efficiency for methylene blue degradation than those of TiO₂, TiO₂/AC, and Ag/AgBr/TiO₂. This is attributed to the synergetic effect between AC and Ag/AgBr/TiO₂, of which AC acts as the role of increasing reaction areas, continuous enriching, and transferring the adsorbed MB molecules to the surface of supported photocatalysts, and the Ag/AgBr/TiO₂ acts as a highly active photocatalyst for degrading MB molecules under visible‐light irradiation.     

Ionic‐Liquid‐Assisted Synthesis of Uniform Fluorinated B/C‐Codoped TiO2 Nanocrystals and Their Enhanced Visible‐Light Photocatalytic Activity

Exploiting advanced photocatalysts under visible light is of primary significance for the development of environmentally relevant photocatalytic decontamination processes. In this study, the ionic liquid (IL), 1‐butyl‐3‐methylimidazolium tetrafluoroborate, was employed for the first time as both a structure‐directing agent and a dopant for the synthesis of novel fluorinated B/C‐codoped anatase TiO₂ nanocrystals (T_IL) through hydrothermal hydrolysis of tetrabutyl titanate. These T_IL nanocrystals feature uniform crystallite and pore sizes and are stable with respect to phase transitions, crystal ripening, and pore collapse upon calcination treatment. More significantly, these nanocrystals possess abundant localized states and strong visible‐light absorption in a wide range of wavelengths. Because of synergic interactions between titania and codopants, the calcined T_IL samples exhibited high visible‐light photocatalytic activity in the presence of oxidizing Rhodamine B (RhB). In particular, 300 °C‐calcined T_IL was most photocatalytically active; its activity was much higher than that of TiO_1.98N_0.02 and reference samples (T_W) obtained under identical conditions in the absence of ionic liquid. Furthermore, the possible photocatalytic oxidation mechanism and the active species involved in the RhB degradation photocatalyzed by the T_IL samples were primarily investigated experimentally by using different scavengers. It was found that both holes and electrons, as well as their derived active species, such as ^.OH, contributed to the RhB degradation occurring on the fluorinated B/C‐codoped TiO₂ photocatalyst, in terms of both the photocatalytic reaction dynamics and the reaction pathway. The synthesis of the aforementioned novel photocatalyst and the identification of specific active species involved in the photodegradation of dyes could shed new light on the design and synthesis of semiconductor materials with enhanced photocatalytic activity towards organic pollutants.     

Photocatalytic Activity for Water Decomposition to Hydrogen over Nitrogen‐doped TiO2 Nanoparticle

Nitrogen-doped TiO2 nanoparticle photocatalysts were obtained by an annealing method with gaseous ammonia and nitrogen. The influence of dopant N on the crystal structure was characterized by XRD, XPS, BET, TEM and UV-Vis spectra. The results of XRD indicate that, the crystal phase transforms from anatase to rutile structure gradually with increase of annealing temperature from 300 to 700 ℃. XPS studies indicate that the nitrogen atom enters the TiO2 lattice and occupies the position of oxygen atom. Agglomeration of particles is found in TEM images after annealing. BET results show that the specific surface areas of N-doped samples from 44.61 to 38.27 m2/g are smaller than that of Degussa TiO2. UV-Vis spectra indicate that the absorption threshold shifts gradually with increase of annealing temperature, which shows absorption in the visible region. The influence of annealing condition on the photocatalytic property has been researched over water decomposition to hydrogen, indicating that nitrogen raises the photocatalytic activity for hydrogen evolution, and the modified TiO2 annealed for 2 h at 400 ℃ under gas of NH3/N2 (V/V＝1/2) mixture shows better efficiency of hydrogen evolution. Furthermore, the N-doped TiO2 nanoparticle catalysts have obvious visible light activity, evidenced by hydrogen evolution under visible light (λ＞400 nm) irradiation. However, the catalytic activity under visible light irradiation is absent for Degussa as reference and the N-doped TiO2 annealed at 700 ℃.