Tuning the Surface Structure of Nitrogen‐Doped TiO2 Nanofibres—An Effective Method to Enhance Photocatalytic Activities of Visible‐Light‐Driven Green Synthesis and Degradation

Nitrogen‐doped TiO₂ nanofibres of anatase and TiO₂(B) phases were synthesised by a reaction between titanate nanofibres of a layered structure and gaseous NH₃ at 400–700 °C, following a different mechanism than that for the direct nitrogen doping from TiO₂. The surface of the N‐doped TiO₂ nanofibres can be tuned by facial calcination in air to remove the surface‐bonded N species, whereas the core remains N doped. N‐Doped TiO₂ nanofibres, only after calcination in air, became effective photocatalysts for the decomposition of sulforhodamine B under visible‐light irradiation. The surface‐oxidised surface layer was proven to be very effective for organic molecule adsorption, and the activation of oxygen molecules, whereas the remaining N‐doped interior of the fibres strongly absorbed visible light, resulting in the generation of electrons and holes. The N‐doped nanofibres were also used as supports of gold nanoparticle (Au NP) photocatalysts for visible‐light‐driven hydroamination of phenylacetylene with aniline. Phenylacetylene was activated on the N‐doped surface of the nanofibres and aniline on the Au NPs. The Au NPs adsorbed on N‐doped TiO₂(B) nanofibres exhibited much better conversion (80 % of phenylacetylene) than when adsorbed on undoped fibres (46 %) at 40 °C and 95 % of the product is the desired imine. The surface N species can prevent the adsorption of O₂ that is unfavourable for the hydroamination reaction, and thus, improve the photocatalytic activity. Removal of the surface N species resulted in a sharp decrease of the photocatalytic activity. These photocatalysts are feasible for practical applications, because they can be easily dispersed into solution and separated from a liquid by filtration, sedimentation or centrifugation due to their fibril morphology.     

Controlling the Selectivity of the Surface Plasmon Resonance Mediated Oxidation of p‐Aminothiophenol on Au Nanoparticles by Charge Transfer from UV‐excited TiO2

Although catalytic processes mediated by surface plasmon resonance (SPR) excitation have emerged as a new frontier in catalysis, the selectivity of these processes remains poorly understood. Here, the selectivity of the SPR‐mediated oxidation of p‐aminothiophenol (PATP) employing Au NPs as catalysts was controlled by the choice of catalysts (Au or TiO₂‐Au NPs) and by the modulation of the charge transfer from UV‐excited TiO₂ to Au. When Au NPs were employed as catalyst, the SPR‐mediated oxidation of PATP yielded p,p‐dimercaptobenzene (DMAB). When TiO₂‐Au NPs were employed as catalysts under both UV illumination and SPR excitation, p‐nitrophenol (PNTP) was formed from PATP in a single step. Interestingly, PNTP molecules were further reduced to DMAB after the UV illumination was removed. Our data show that control over charge‐transfer processes may play an important role to tune activity, product formation, and selectivity in SPR‐mediated catalytic processes.     

Design of unique titanium oxide photocatalysts by an advanced metal ion-implantation method and photocatalytic reactions under visible light irradiation

The metal ion-implantation of titanium oxide with various transition metal ions was carried out by applying by high voltage acceleration. The subsequent calcination of the implanted TiO₂ in oxygen at around 723 K resulted in a large shift in the absorption spectra of the TiO₂ toward visible light regions, its extent being dependent on the amount and the kind of metal ions implanted. Such metal ion-implanted titanium oxide catalysts were active in carrying out various photocatalytic reactions such as the decomposition of NO into N₂, O₂ and N₂O at 275 K under irradiation with visible light longer than 450 nm. The application of this advanced, high energy metal ion-implantation method enables the novel design of titanium oxide photocatalysts which can absorb and initiate vital reactions under visible light and will contribute to the development of catalytic systems utilizing solar energy.     

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.     

Effect of Cl− anions on photocatalytic decomposition of gaseous ozone over Au @ Ag/TiO2 catalyst

Au core Ag shell composite structure nanoparticles were prepared using a sol method. The Au core Ag shell composite nanoparticles were loaded on TiO₂ nanoparticles as support using a modified powder–sol method, enabling the generation of Au @ Ag/TiO₂ photocatalysts for photocatalytic decomposition and elimination of ozone. The sols were characterized by means of ultraviolet–visible light (UV–Vis) reflection spectrometry, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The activity of the Au @ Ag/TiO₂ photocatalysts for photocatalytic decomposition and elimination of ozone was evaluated and the effect of Cl^? anions on the photocatalytic activity of the catalysts was highlighted. Results showed that Au @ Ag/TiO₂ prepared via the modified powder–sol route in the presence of an appropriate amount of NaCl solid as demulsifier had better activity in the photocatalytic decomposition and elimination of ozone. At the same time, Au @ Ag/TiO₂ catalysts had better ability to resist poisonous Cl^? anions than conventional Au/TiO₂ catalyst. The reasons could be, first, that NaCl was capable of reducing the concentration of free Ag⁺ by adsorption on the surface of Ag particles forming AgCl and enhancing the formation of Au core Ag shell particles, leading to a better resistance to Cl^? anions of the catalysts, and, second, AgCl took part in the photocatalytic decomposition of ozone together with Au @ Ag/TiO₂ catalysts and had a synergistic effect on the latter, resulting in better photocatalytic activity of Au @ Ag/TiO₂ catalysts.     

Size‐Dependence of the Activity of Gold Nanoparticle‐Loaded Titanium(IV) Oxide Plasmonic Photocatalyst for Water Oxidation

Mesoporous TiO₂ nanocrystalline film was formed on fluorine‐doped tin oxide electrode (TiO₂/FTO) and gold nanoparticles (NPs) of different sizes were loaded onto the surface with the loading amount kept constant (Au/TiO₂/FTO). Visible‐light irradiation (λ>430 nm) of the Au/TiO₂/FTO photoanode in a photoelectrochemical cell with the structure of photoanode|0.1 m NaClO4 aqueous solution|Ag/AgCl (reference electrode)|glassy carbon (cathode) leads to the oxidation of water to oxygen (O₂). We show that the visible‐light activity of the Au/TiO₂/FTO anode increases with a decrease in Au particle size (d) at 2.9≤d≤11.9 nm due to the enhancement of the charge separation and increasing photoelectrocatalytic activity.     

Hydrothermal oxidation synthesis of rod‐like ZnO and the influence of oxygen vacancy on photocatalysis

Rod‐like ZnO nanoparticles (NPs ) were synthesized from zinc powder by a simple hydrothermal oxidation method. The presence of acetylacetone could promote the oxidation reaction of Zn and the formation of hexagonal nanorods. Then, the as‐prepared samples were annealed in N₂ , O₂ , and air atmosphere at 550°C for 2 h to control the number of oxygen vacancies in the samples. The samples were characterized by X‐ray diffraction, scanning electron microscopy, X‐ray photoelectron spectroscopy, and UV –vis spectroscopy. The correlation between the oxygen vacancies and the photocatalytic activity was investigated. The results reveal that the annealing process alters the samples’ bandgap and number of the oxygen vacancies, thereby improving the photocatalytic activity. The enhancement of photodegradation efficiency arising from the appropriate content of oxygen vacancies is discussed.     

Surface species and gas phase products in the preferential oxidation of CO on TiO2-supported Au-Rh bimetallic catalysts

The oxidation of CO in the presence of hydrogen (PROX process) was investigated on bimetallic Au-Rh catalysts at 300–373 K by Fourier transform infrared spectroscopy and mass spectroscopy. The effects of catalyst composition, reaction temperature and composition of the reacting gas mixtures have been studied. The IR studies revealed the formation of bi- and monodentate carbonates, bicarbonates and hydrocarbonates on the catalysts surfaces; these surface species proved to be not involved in the surface reactions. The formation of adsorbed formaldehyde was observed on all surfaces, except 1% (0.25Au+0.75Rh)/TiO₂. Adsorbed CO₂ (as the surface product of CO oxidation) was not detected on any surface. The presence of both O₂ and H₂ reduced the surface concentration of CO adsorbed on the metallic sites. Mass spectroscopic analysis of the gas phase showed that gaseous CO₂ was formed in the highest amount in the CO+O₂ mixture, the presence of H₂ suppressed the amount of CO₂ produced. This negative effect of H₂ was the lowest on the 1% Rh/TiO₂ and 1% (0.25Au+0.75Rh)/TiO₂ catalysts.     

Promoted Fixation of Molecular Nitrogen with Surface Oxygen Vacancies on Plasmon‐Enhanced TiO2 Photoelectrodes

A hundred years on, the energy‐intensive Haber–Bosch process continues to turn the N₂ in air into fertilizer, nourishing billions of people while causing pollution and greenhouse gas emissions. The urgency of mitigating climate change motivates society to progress toward a more sustainable method for fixing N₂ that is based on clean energy. Surface oxygen vacancies (surface O_vac) hold great potential for N₂ adsorption and activation, but introducing O_vac on the very surface without affecting bulk properties remains a great challenge. Fine tuning of the surface O_vac by atomic layer deposition is described, forming a thin amorphous TiO₂ layer on plasmon‐enhanced rutile TiO₂/Au nanorods. Surface O_vac in the outer amorphous TiO₂ thin layer promote the adsorption and activation of N₂, which facilitates N₂ reduction to ammonia by excited electrons from ultraviolet‐light‐driven TiO₂ and visible‐light‐driven Au surface plasmons. The findings offer a new approach to N₂ photofixation under ambient conditions (that is, room temperature and atmospheric pressure).     

Catalytic Role of TiO2 Terminal Oxygen Atoms in Liquid‐Phase Photocatalytic Reactions: Oxidation of Aromatic Compounds in Anhydrous Acetonitrile

On the basis of experiments carried out with controlled amounts of residual oxygen and water, or by using oxygen‐isotope‐labeled Ti¹⁸O₂ as the photocatalyst, we demonstrate that ¹⁸O_s atoms behave as real catalytic species in the photo‐oxidation of acetonitrile‐dissolved aromatic compounds such as benzene, phenol, and benzaldehyde with TiO₂. The experimental evidence allows a terminal‐oxygen indirect electron‐transfer (TOIET) mechanism to be proposed, which is a new pathway that involves the trapping of free photogenerated valence‐band holes at O_s species and their incorporation into the reaction products, with simultaneous generation of oxygen vacancies at the TiO₂ surface and their subsequent healing with oxygen atoms from either O₂ or H₂O molecules that are dissolved in the liquid phase. According to the TOIET mechanism, the TiO₂ surface is not considered to remain stable, but is continuously changing in the course of the photocatalytic reaction, challenging earlier interpretations of TiO₂ photocatalytic phenomena.     

Au‐TiO2/Graphene Nanocomposite Film for Electrochemical Sensing of Hydrogen Peroxide and NADH

We describe a simple method for preparing Au‐TiO₂/graphene (GR) nanocomposite by deposition of Au nanoparticles (NPs) on TiO₂/GR substrates. The as‐prepared Au‐TiO₂/GR was characterized by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The presence of Au NPs on TiO₂/GR surface remarkably improves the electrocatalytic activity towards the oxidation of hydrogen peroxide (H₂O₂) and β‐nicotinamide adenine dinucleotide (NADH). The Au‐TiO₂/GR modified glassy carbon (GC) electrode exhibits good amperometric response to H₂O₂ and NADH, with linear range from 10 to 200 µM and 10 to 240 µM, and detection limit of 0.7 and 0.2 µM, respectively.     

Structure and chemical activity of transition metal and metal oxide catalysts: An insight from theoretical DFT studies

The present theoretical DFT study discusses the structure and chemical activity of transition metal and metal oxide catalysts within the well-known cluster approach. Selective oxidation of carbon monoxide on gold supported on titania (Au/TiO₂ (110)) as well as some key points in understanding the effect of non-metal doping on TiO2 with the aim to increase its photocatalytic functionality have been briefly discussed. It was shown that Au (with formal oxidation state equal to plus one) stabilized on water-assisted and vacancy containing TiO₂ (110) can explain selective oxidation of CO. Here binding of O₂ with the vacancy site is energetically preferable than its adsorption on an Au site. Conversely, CO adsorbs on an Au center of Au/TiO₂ (110) which is energetically much more profitable than its interaction with the oxygen vacancy site. Also, carbon and nitrogen doping on TiO₂ (110) leads to two different structures. Energetically most profitable is that carbon occupies an interstitial position in deep bulk while nitrogen replaces the protruded oxygen atom and forms a surface N-H group.     

Photocatalytic decomposition of liquid-water on the Pt-loaded TiO2 catalysts: Effects of the oxidation states of Pt species on the photocatalytic reactivity and the rate of the back reaction

The photocatalytic decomposition of liquid water on Pt-loaded TiO₂ (Pt/TiO₂) catalysts was investigated. The results obtained by XPS and XRD measurements of the catalysts as a function of the calcination temperature as well as the photocatalytic decomposition reactions of H₂O clearly indicate that controlling the oxidation state of Pt as well as the amount of loaded Pt species are both important factors in the design of water-splitting photocatalysts having high efficiency and stoichiometry.     

Synthesis of W‐doped TiO2 by low‐temperature hydrolysis: Effects of annealing temperature and doping content on the surface microstructure and photocatalytic activity

A series of tungsten‐doped Titania photocatalysts were synthesized using a low‐temperature method. The effects of dopant concentration and annealing temperature on the phase transitions, crystallinity, electronic, optical, and photocatalytic properties of the resulting material were studied. The X‐ray patterns revealed that the doping delays the transition of anatase to rutile to a high temperature. A new phase W_yTi_1‐yO₂ appeared for 5.00 wt% W‐TiO₂ annealed at 900 °C. Raman and diffuse reflectance UV–Vis spectroscopy showed that band gap values decreased slightly up to 700 °C. X‐ray photoelectron spectroscopy showed that surface species viz. Ti³⁺, Ti⁴⁺, O^2?, oxygen‐vacancies, and adsorbed OH groups vary depending on the preparation conditions. The photocatalytic activity was evaluated via the degradation of methylene blue using LED white light. The degradation rate was affected by the percentage of dopants. The best photocatalytic activity was achieved with the sample labeled 5.00 wt% W‐TiO₂ annealed at 700 °C.     

低温静电自组装法制备贵金属修饰TiO_2纳米结构薄膜及其增强的光催化性能(英文)

以碱-水热法在金属Ti片上原位生长了TiO2纳米结构(纳米花和纳米线)薄膜,并采用低温静电自组装方法将超细贵金属(金、铂、钯)纳米颗粒均匀沉积于多孔TiO2薄膜上.负载于Ti片上的贵金属/TiO2纳米结构薄膜具有一体化结构、多孔架构和高光催化活性.超高分辨率场发射扫描电子显微镜(FESEM)直接观察表明贵金属纳米颗粒在TiO2表面分布均匀,且颗粒之间相互分离,金、铂、钯纳米颗粒的平均粒径分别约为4.0、2.0和10.0nm.俄歇电子能谱(AES)纵深成分分析表明贵金属不仅沉积于薄膜表面,且大量分布于TiO2纳米结构薄膜内部,其深度超过580 nm.X射线光电子能谱(XPS)分析表明,经300°C下在空气中热处理后,纳米金仍保持金属态,纳米铂部分被氧化成PtOabs,而钯粒子则完全被氧化成氧化钯(PdO).以低温静电自组装法沉积贵金属,贵金属负载量可通过调节组装时间与溶胶pH值来控制.光催化降解甲基橙的结果表明,沉积的纳米金和铂能显著增加TiO2纳米结构薄膜的光催化活性,说明金和铂粒子可促进光生载流子的分离;但负载的PdO对TiO2薄膜的光催化性能增强几乎无作用.     

Photocatalytic degradation of organophosphate flame retardant TBEP: kinetics and identification of transformation products by orbitrap mass spectrometry

The photocatalytic degradation of tris (2–butoxyethyl) phosphate (TBEP) flame retardant using visible light response catalysts TiO₂/V₂O₅, (N,F-doped)-TiO₂/V₂O₅, and N-doped-SrTiO₃ has been studied by high-resolution orbitrap mass spectrometry. TBEP degradation followed first-order kinetics with half-life values ranging between 9.8 and 83.5 min. N-doped-SrTiO₃ was the catalyst with better photocatalytic performance while activity for TiO₂/V₂O₅ composites followed the trend: N, F- TiO₂/V₂O₅ > N-TiO₂/V₂O₅> TiO₂/V₂O₅. The identified degradation products (DPs) revealed hydroxylation, further oxidation and dealkylation as major degradation pathways. Based on the identified DPs and scavenging experiments, ^?OH radical-mediated reactions can be considered for the degradation of TBEP using TiO₂ and SrTiO₃-based photocatalytic materials.     

Avoiding Self‐Poisoning: A Key Feature for the High Activity of Au/Mg(OH)2 Catalysts in Continuous Low‐Temperature CO Oxidation

Au/Mg(OH)₂ catalysts have been reported to be far more active in the catalytic low‐temperature CO oxidation (below 0 °C) than the thoroughly investigated Au/TiO₂ catalysts. Based on kinetic and in situ infrared spectroscopy (DRIFTS) measurements, we demonstrate that the comparatively weak interaction of Au/Mg(OH)₂ with CO₂ formed during the low‐temperature reaction is the main reason for the superior catalyst performance. This feature enables rapid product desorption and hence continuous CO oxidation at temperatures well below 0 °C. At these temperatures, Au/TiO₂ also catalyzes CO₂ formation, but does not allow for CO₂ desorption, which results in self‐poisoning. At higher temperatures (above 0 °C), however, CO₂ formation is rate‐limiting, which results in a much higher activity for Au/TiO₂ under these reaction conditions.     

The Influence of Defects on Mo‐Doped TiO2 by First‐Principles Studies

TiO₂ doped with transition metals shows improved photocatalytic efficiency. Herein the electronic and optical properties of Mo‐doped TiO₂ with defects are investigated by DFT calculations. For both rutile and anatase phases of TiO₂, the bandgap decreases continuously with increasing Mo doping level. The 4d electrons of Mo introduce localized states into the forbidden band of TiO₂, and this shifts the absorption edge into the visible‐light region and enhances the photocatalytic activity. Since defects are universally distributed in TiO₂ or doped TiO₂, the effect of oxygen deficiency due to oxygen vacancies or interstitial Mo atoms is systemically studied. Oxygen vacancies associated with the Mo dopant atoms or interstitial Mo will reduce the spin polarization and magnetic moment of Mo‐doped TiO₂. Moreover, oxygen deficiency has a negative impact on the improved photocatalytic activity of Mo‐doped TiO₂. The current results indicate that substitutional Mo, interstitial Mo, and oxygen vacancy have different impacts on the electronic/optical properties of TiO₂ and are suited to different applications.     

Sub-nanometer-thick Al2O3 Overcoat Remarkably Enhancing Thermal Stability of Supported Gold Catalysts

Supported gold nanoparticle catalysts show extraordinarily high activity in many reactions. While the relative poor thermal stability of Au nanoparticles against sintering at elevated temperatures severely limits their practical applications. Here atomic layer deposition (ALD) of TiO₂ and Al₂O₃ was performed to deposit an Au/TiO₂ catalyst with precise thickness con-trol, and the thermal stability was investigated. We surprisingly found that sub-nanometer-thick Al₂O₃ overcoat can su ciently inhibit the aggregation of Au particles up to 600 C in oxygen. On the other hand, the enhancement of Au nanoparticle stability by TiO₂ overcoat is very limited. Di use reffectance infrared Fourier transform spectroscopy (DRIFTS) of CO chemisorption and X-ray photoelectron spectroscopy measurements both con rmed the ALD overcoat on Au particles surface and suggested that the presence of TiO₂ and Al₂O₃ ALD overcoat on Au nanoparticles does not considerably change the electronic properties of Au nanoparticles. The catalytic activities of the Al₂O₃ overcoated Au/TiO₂ catalysts in CO oxidation increased as increasing calcination temperature, which suggests that the embed-ded Au nanoparticles become more accessible for catalytic function after high temperature treatment, consistent with our DRIFTS CO chemisorption results.     

Photocatalytic performance of TiO2 nanocrystals with/without oxygen defects

To investigate the role of oxygen defects on the photocatalytic activity of TiO₂, the TiO₂ nanocrystals with/without oxygen defects are successfully synthesized by the hydrothermal and sol-gel methods, respectively. The as-prepared TiO₂ nanocrystals with defects are light blue and the absorption edge of light is towards the visible light region (～420 nm). Raman and X-ray photoelectron spectroscopy (XPS) measurements all confirm that the concentration of oxygen vacancies in the TiO₂ synthesized by the sol-gel method is less than that synthesized through the hydrothermal route. The introduction of oxygen defects contributes to a new state in the band gap that narrows the band gap, which is the reason for the extension of light absorption into the visible light region. The photocurrent results confirm that this band-gap narrowing enhances the photocurrent response under simulated solar light irradiation. The TiO₂ with oxygen defects shows a higher photocatalytic activity for decomposition of a methylene blue solution compared with that of the perfect TiO₂ sample. The photocatalytic mechanism is discussed based on the density functional theory calculations and photoluminescence spectroscopy measurements.