Template‐free Fabrication of Hierarchical Macro‐/mesoporous N‐doped TiO2/graphene Oxide Composites with Enhanced Visible‐light Photocatalytic Activity

Hierarchical macro‐/mesoporous N‐doped TiO₂/graphene oxide (N‐TiO₂/GO) composites were prepared without using templates by the simple dropwise addition mixed solution of tetrabutyl titanate and ethanol containg graphene oxide (GO) to the ammonia solution, and then calcined at 350 °C. The as‐prepared samples were characterized by scanning electron microscopy (SEM), Brunauer‐Emmett‐Teller (BET) surface area, X‐ray diffraction (XRD), Raman spectroscopy, X‐ray photoelectron spectroscopy (XPS), and UV‐Vis absorption spectroscopy. The photocatalytic activity was evaluated by the photocatalytic degradation of methyl orange in an aqueous solution under visible‐light irradiation. The results show that N‐TiO₂/GO composites exhibited enhanced photocatalytic activity. GO content exhibited an obvious influence on photocatalytic performance, and the optimal GO addition content was 1 wt%. The enhanced photocatalytic activity could be attributed to the synergetic effects of three factors including the improved visible light absorption, the hierarchical macro‐mesoporous structure, and the efficient charge separation by GO.     

Preparation of ZnFe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles by mechanical alloying and annealing for sensitizing C-modified TiO<Subscript>2</Subscript> and acquirement of efficient photocatalyst

ZnFe₂O₄ nanoparticles sensitized by C-modified TiO₂ hybrids (ZnFe₂O₄–TiO₂/C) were successfully prepared by a feasible method. The ZnFe₂O₄ nanoparticles were prepared by mechanical alloying and annealing. The residual organic compounds in the synthetic process of TiO₂ were selected as the carbon source. The as-prepared composites were characterized by X-ray diffraction, Raman spectroscopy, X-ray fluorescence, transmission electron microscopy, X-ray photoelectron spectroscopy, ultraviolet–visible light diffuse reflectance spectroscopy (UV–Vis) and N₂ adsorption–desorption analysis. The photocatalytic activity of the photocatalysts was measured by degradation of methyl orange under ultraviolet (UV) light and simulated solar irradiation, respectively. The results show that the carbon did not enter the TiO₂ lattice but adhered to the surface of TiO₂. The photocatalytic activity of the as-prepared C-modified TiO₂ (TiO₂/C) improved both under UV and simulated solar light irradiation, but the improvement was not dramatic. Introduction of ZnFe₂O₄ into the TiO₂/C could enhance the absorption spectrum range. The ZnFe₂O₄–TiO₂/C hybrids exhibited a higher photocatalytic activity both than that of the pure TiO₂ and TiO₂/C under either UV or simulated solar light irradiation. The complex synergistic effect plays an important role in improving the photocatalytic performance of ZnFe₂O₄–TiO₂/C composites. The optimum photocatalytic performance was obtained from the ZnFe₂O₄(0.8 wt%)–TiO₂/C sample.     

Photocatalytic activity of polyaniline/Fe-doped TiO2 composites by in situ polymerization method

This study was focused on the photocatalytic activity of polyaniline (Pani)/iron doped titanium dioxide (Fe–TiO₂) composites for the degradation of methylene blue as a model dye. TiO₂ nanoparticles were doped with iron ions (Fe) using the wet impregnation method and the doped nanoparticles were further combined with Pani via an in situ polymerization method. For comparison purposes, Pani composites were also synthesized in the presence undoped TiO₂. The photocatalyst and the composites were characterized by standard analytical techniques such as FTIR, XRD, SEM, EDX and UV–Vis spectroscopies. Fe–TiO₂ and its composites exhibited enhanced photocatalytic activity under ultraviolet light irradiation. Improved photocatalytic activity of Fe–TiO₂ was attributed to the dopant Fe ions hindering the recombination of the photoinduced charge carriers. Pani/Fe–TiO₂ composite with 30?wt.% of TiO₂ nanoparticles achieved 28% dye removal and the discoloration rate of methylene blue for the sample was 0.0025?min^?1. FTIR, XRD, SEM, EDX and UV–Vis spectroscopies supported the idea that Fe ions integrated into TiO₂ crystal structure and Pani composites were successfully synthesized in the presence of the photocatalyst nanoparticles. The novelty of this study was to investigate the photocatalytic activity of Pani composites, containing iron doped TiO₂ and to compare their results with that of Pani/TiO₂.     

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.     

Photocatalytic Degradation of Organic Reactive Dyes over MnTiO3/TiO2 Heterojunction Composites Under UV‐Visible Irradiation

In this study, the photocatalytic degradation of organic reactive dyes have been investigated using MnTiO₃/TiO₂ heterojunction composites in the presence of electron acceptors under UV‐Visible light irradiation. This MnTiO₃/TiO₂ heterojunction composites were prepared by annealing different mass ratios of pyrophanite MnTiO₃ (3–11 wt%) and TiO₂ at 300°C. All the MnTiO₃/TiO₂ heterojunction composites were characterized by spectral techniques like X‐ray diffraction (XRD), scanning electron microscope (SEM) and diffused reflectance UV‐visible spectroscopic analysis (DRS). Among them, 9 wt% MnTiO₃/TiO₂ heterojunction composites exhibited higher photocatalytic activity for the degradation of Reactive Blue 4 (RB 4). The photocatalytic efficiency of 9 wt% MnTiO₃/TiO₂ heterojunction composites was further enhanced by the addition of substantial amount of electron acceptors like hydrogen peroxide (H₂O₂) and ammonium peroxydisulfate ([NH₄]₂S₂O₈). The presence of oxidants (electron acceptors) facilitates the fast degradation of dye solution even in higher concentration upto 200 mg/L. The photocatalytic activity of MnTiO₃/TiO₂ heterojunction composites was also studied for the degradation of other four different structured reactive dyes. The extent of mineralization of these organic reactive dyes during photocatalytic degradation was estimated from COD analysis. MnTiO₃/TiO₂ heterojunction composites was also found to have good photostability in the presence of oxidants.     

Preparation of CdS–TiO2/Fe3O4 photocatalyst and its photocatalytic properties

The CdS modified TiO₂/Fe₃O₄ photocatalysts were prepared by sol–gel and immersion methods. The morphological, structural and optical properties of as-prepared samples were characterized by X-ray diffraction (XRD), UV–Vis absorption spectra, X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The TEM observation showed that the surface of magnetite particles (Fe₃O₄) were coated by CdS–TiO₂ layer as loose clusters, and average diameter of composites particles was about 250 nm. UV–Vis absorption spectra indicated that CdS–TiO₂/Fe₃O₄ composites had pronounced red-shift compared with that of TiO₂/Fe₃O₄. The CdS–TiO₂/Fe₃O₄ composites exhibit higher photocatalytic activity than pure TiO₂ and TiO₂/Fe₃O₄ for the degradation of Reactive Brilliant Red X-3B dye (X-3B) aqueous solution under simulated sunlight, and the optimum content of CdS is 1.0 % (mol ratio of CdS to TiO₂). In addition, a gradual loss of photocatalytic activity can be observed in reusability test of CdS–TiO₂/Fe₃O₄ composites, and degradation of X-3B reached still to 78.9 % after five runs.     

Azo dyes degradation using TiO2-Pt/graphene oxide and TiO2-Pt/reduced graphene oxide photocatalysts under UV and natural sunlight irradiation

The photocatalytic degradation of azo dyes with different structures (amaranth, sunset yellow and tartrazine) using TiO₂-Pt nanoparticles (TPt), TiO₂-Pt/graphene oxide (TPt-GO) and TiO₂-Pt/reduced graphene oxide (TPt-rGO) composites were investigated in the presence of UV and natural sunlight irradiation. The composites were prepared by a combined chemical-thermal method and characterized by Transmission Electron Microscopy (TEM), X-ray powder diffraction (XRD), Infrared (FTIR) and UV–Vis spectroscopy. The modification of TiO₂-Pt with graphene oxide shifted its optical absorption edge towards the visible region and increased its photocatalytic activity under UV and natural sunlight irradiation. The efficiency of catalysts on azo dyes degradation (in similar conditions) reached high values (above 99%) under sunlight conditions, proving the remarkable photocatalytic activities of obtained composites. TPt-GO nanocomposite exhibited higher photoactivity than TPt or TPt-rGO, demonstrating degradation efficiencies of 99.56% for amaranth, 99.15% for sunset yellow and 96.23% for tartrazine. The dye photodegradation process follows a pseudo-first-order kinetic with respect to the Langmuir-Hinshelwood reaction mechanism. A direct dependence between azo dyes degradation rate and chemical structure of dyes has been observed.     

Solvothermal synthesis of WO3/TiO2/carbon fiber composite photocatalysts for enhanced performance under sunlight illumination

Carbon fiber (CF)‐based WO₃/TiO₂ composite catalysts (WO₃/TiO₂/CF) were successfully synthesized by solvothermal method. The catalysts were characterized by XPS, SEM, BET, XRD, FTIR, Raman and UV–Vis. The analyses confirmed the WO₃/TiO₂ nanoparticles with high crystallinity deposited on the carbon structure. The photocatalytic degradation of Orange II azo dye under UV and sunlight illumination with the synthesized catalyst was explored. The composite catalyst displayed high performance (85%) for Orange II degradation while that of for WO₃/TiO₂ was found as 76%. The effects of CF amount, solution pH, initial dye concentration and catalyst dose on photocatalytic performance were studied. It was found that the degradation efficiency increased from 68% to 90% with the increasing CF amount from 3 wt% to 5 wt%, while the further increase in CF amount (7–10 wt%) decreased the photodegradation due to the blocking the active sites of WO₃/TiO₂. The enhanced photocatalytic efficiency was mainly attributed to the electrical properties of the CF and reduced bandgap.     

Preparation and characterization of ZnTiO<Subscript>3</Subscript>–TiO<Subscript>2</Subscript>/pillared montmorillonite composite catalyst for enhanced photocatalytic activity

ZnTiO₃–TiO₂/organic pillared montmorillonite (pMt) composite catalyst was successfully prepared in this paper by immobilizing ZnTiO₃–TiO₂ onto pMt. The composition and texture of the prepared composite catalyst were characterized by X-ray diffraction, Raman spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscopy, energy dispersive spectrometry, ultraviolet–visible light (UV–Vis) diffuse reflectance spectroscopy and X-ray photoelectron spectroscopy. The photocatalytic activity was tested via photocatalytic degradation of methyl blue (MB) under both visible irradiation and UV light. The results indicated that the ZnTiO₃–TiO₂/pMt composite catalyst had an apparent absorption at the area of visible irradiation, and exhibited a higher efficiency of photocatalytic degredation of MB under visible irradiation. This was due to the heterostructure of ZnTiO₃–TiO₂, and the mesoporous structure and specific surface area of the ZnTiO₃–TiO₂/pMt composite. In addition, the results of the radical scavenging experiments showed that the holes and superoxide radicals are responsible for the degradation of MB under visible irradiation.     

Comparison of optical and structural properties of nanostructure TiO2 thin film doped by Sn and Nb

The thin films of TiO₂ doped by Sn or Nb were prepared by sol–gel method under process control. The effects of Sn and Nb doping on the structural, optical and photo-catalytic properties of applied thin films have been studied by X-ray diffraction (XRD) high resolution transmission electron microscopy and UV–Vis absorption spectroscopy. Surface chemical state of thin films was examined by atomic X-ray photoelectron spectroscopy. XRD results suggest that adding impurities has a great effect on the crystallinity and particle size of TiO₂. Titania rutile phase formation in thin film was promoted by Sn⁴⁺ addition but was inhibited by Nb⁵⁺ doping. The activity of the photocatalyst was evaluated by photocatalytic degradation kinetics of aqueous methylene blue under UV and Visible radiation. The results show that the photocatalytic activity of the Sn-doped TiO₂ thin film have a larger degradation efficiency than Nb-doped TiO₂ under visible light, but under UV light photocatalytic activity of the Nb-doped TiO₂ thin film is better.     

Single-step solvothermal synthesis of mesoporous anatase TiO<Subscript>2</Subscript>-reduced graphene oxide nanocomposites for the abatement of organic pollutants

In the present work, we have fabricated a novel mesoporous TiO₂–rGO nanocomposite by a facile one-step solvothermal method using titanic sulfate as the TiO₂ source. The as-prepared composites were characterized by transmission electron microscopy, X-ray diffraction; UV–Vis diffuse reflectance spectra, X-ray photoelectron spectroscopy and photoluminence spectra. In situ nucleation and anchoring of TiO₂ nanoparticles onto a graphene sheet is favorable fpr forming an intimate interfacial contact, and the chemically bonded TiO₂–rGO nanocomposites commendably enhanced their photocatalytic activity in the photodegradation of rhodamine B and phenol. The high photocatalytic activity of the as-synthesized nanocomposites are primarily ascribed to the mesoporous structure, efficient charge transportation and separation with enhanced visible light absorption, which come from the appealing nanoarchitecture, for instance, ultra-dispersed and ultra-small TiO₂ nanocrystals along with intimate and absolute interfacial contact between the TiO₂ nanocrystals and the graphene sheet.     

A novel approach for the synthesis of visible-light-active nanocrystalline N-doped TiO2 photocatalytic hydrosol

A visible-light-active nitrogen doped nanocrystalline titanium dioxide (N–TiO₂) hydrosol was prepared by precipitation–peptization method and following with hydrothermal crystallization at 110 °C holding for 6 h. XPS results show that nitrogen ions have been doped into the TiO₂ lattice successfully and the UV–Vis absorption spectra indicate that the light absorption edge of the N-doped TiO₂ has been red-shifted into visible light region. The photocatalytic performance of the N-doped TiO₂ thin film prepared from the synthesized hydrosol was evaluated by photodegrading the gaseous formaldehyde (HCHO) under visible light irradiation. The photodegradation ratio of HCHO reached up to 90% within 24 h and the degradation ratio was stable for ten degradation cycles, indicating the prepared hydrosol has good reusable performance in photodegrading gaseous pollutants.     

Synthesis of anatase TiO2 in a vinyl-containing ionic liquid and its enhanced photocatalytic activity

TiO₂ microspheres were synthesized by the sol–gel method using the ionic liquid (IL) 1-vinyl-3-propylimidazolium iodide (VPIM⁺I^?) as a reaction medium, then calcined at 500 °C. The samples were characterized by X-ray diffraction, scanning electron microscopy, and ultraviolet–visible (UV–Vis) diffuse reflectance spectroscopy. The phase of TiO₂ microspheres is anatase, and VPIM⁺I^? is able to favor the growth of anatase phase and prevents the collapse of small pores. The photocatalytic activity of TiO₂-IL was tested by degradation of 2-nitrophenol under UV light illumination. The photocatalytic activity of TiO₂-IL was higher than that of samples prepared in the reaction medium without VPIM⁺I^?.     

Synthesis and photocatalytic activity of nanocrystalline TiO2 co-doped with nitrogen and cobalt(II)

Nitrogen-modified cobalt-doped TiO₂ materials were successfully prepared via a modified sol–gel method. The structure and properties of the catalysts were characterized via X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM, ultraviolet–visible light diffuse reflectance spectra (UV–Vis DRS), N₂ adsorption–desorption isotherms, and energy-dispersive X-ray spectroscopy. The XRD patterns of the pure and co-doped TiO₂ samples indicate that the predominant phase was anatase. The average grain size obtained from TEM was approximately 10 nm. The Brunauer–Emmett–Teller analysis results indicate that the specific surface area was 77.7 m² g^?1. The UV–Vis DRS results for the co-doped sample reveal an absorption edge that had been red-shifted to 500 nm. The photocatalytic activities of the samples were evaluated through photodegradation of papermaking wastewater under UV and visible light irradiation. Compared with the cobalt-doped TiO₂ sample and Degussa P25, the 3 mol% N-doped mesoporous N/Co-TiO₂ photocatalyst exhibited the highest photocatalytic activity, which can be ascribed to the synergistic effect of the N and Co co-doping.     

Optimal TiO2–Graphene Oxide Nanocomposite for Photocatalytic Activity under Sunlight Condition: Synthesis,Characterization, and Kinetics

TiO₂–graphene oxide nanocomposites have been fabricated by the sol–gel technique for degradation of a typical cationic dye solution. The prepared photocatalysts were characterized by X‐ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric‐differential analyses, Brunauer–Emmett–Teller surface area measurement, and scanning and transmission electron microscopy. In addition, the photocatalytic activities of samples were evaluated by degradation of methylene blue aqueous solution under the sunlight irradiation. The change in color of solution was evaluated by the UV–vis spectroscopy, and the maximum photocatalytic decoloration (94%) was achieved within 60 min, which exceeded that of pure anatase under the same conditions. The results show that the nanocomposite containing 9.0 wt% of graphene oxide has the superior photocatalytic performance to either single‐phase anatase or other composites containing different amounts of graphene oxide. The experimental degradation data obtained from the batch tests were analyzed by a modified kinetic model, which predicted the performance with higher regression coefficients and lower relative errors. The distribution of TiO₂ nanoparticles (<20 nm) on graphene oxide sheets is proposed to be the efficient factor in the homogeneous degradation of dye which can concomitantly improve the photocatalytic activity.     

Improved Photodegradation of Organic Contaminants Using Nano‐TiO2 and TiO2–SiO2 Deposited on Portland Cement Concrete Blocks

The photocatalytic activity of TiO₂ nanoparticles (nano‐TiO₂) and its hybrid with SiO₂ (nano‐TiO₂–SiO₂) for degradation of some organic dyes on cementitious materials was studied in this work. Nanohybrid photocatalysts were prepared using an inorganic sol–gel precursor and then characterized using XRD, SEM and UV–Vis. The grain sizes were estimated by Scherrer's equation to be around 10 nm. Then, a thin layer was applied to Portland cement concrete (PCC) blocks by dipping them into nano‐TiO₂ and nano‐TiO₂–SiO₂ solution. The efficiency of coated PCC blocks for the photocatalytic decomposition of two dyes, Malachite Green oxalate (MG) and Methylene Blue (MB), was examined under UV and visible irradiation and then monitored by the chemical oxygen demand tests. The results showed that more than 80% and 92% of MG and MB were decomposed under UV–Vis irradiation using blocks coated with nano‐TiO₂–SiO₂. TiO₂/PCC and TiO₂–SiO₂/PCC blocks showed a significant ability to oxidize dyes under visible and UV lights and TiO₂–SiO₂/PCC blocks require less time for dye degradation. Based on these results, coated blocks have increased photocatalytic activity which can make them commercially accessible photocatalysts.     

Synthesis and characterization of novel InVO<Subscript>4</Subscript>–TiO<Subscript>2</Subscript> thin films using the low temperature sol

The InVO₄ sol was obtained by a mild hydrothermal treatment (the precursor precipitation solution at 423 K, for 4 h). Novel visible-light activated photocatalytic InVO₄–TiO₂ thin films were synthesized through a sol–gel dipping method from the composite sol, which was obtained by mixing the low temperature InVO₄ sol and TiO₂ sol. The photocatalytic activities of the new InVO₄–TiO₂ thin films under visible light irradiation were investigated by the photocatalytic discoloration of methyl orange aqueous solution. The thin films were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and UV–Vis absorption spectroscopy (UV–Vis). The results revealed that the InVO₄ doped thin films enhanced the methyl orange degradation rate under visible light irradiation, 3.0 wt% InVO₄–TiO₂ thin films reaching 80.1% after irradiated for 15 h.     

Cellulose-TiO2 nanocomposite with enhanced UV–Vis light absorption

TiO₂/N-cellulose nanocomposite was successfully prepared in the (cyclohexyl)hexyl-dimethylammonium acetate–dimethyl sulfoxide solution. The obtained composite was characterized with various techniques like UV–Vis/DR, FTIR/DRS, X-ray diffraction, thermogravimetric analysis, DLS method and BET SSA measurements. TiO₂/N-cellulose nanocomposite exhibited high UV–Vis light absorption with energy gap shifted to the visible region. Additive of TiO₂/N photocatalyst to cellulose-IL-DMSO solution leads to obtaining the material with higher thermostability and limited photoactivity.     

Cooperation among N,F and Fe in tri-doped TiO<Subscript>2</Subscript> photocatalyst

TiO₂ photocatalysts tri-doped with N, F and Fe were synthesized by a sol–gel method. The cooperation of N, F and Fe in tri-doped TiO₂ was verified by monitoring NH₃ decomposition, X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and ultraviolet–visible (UV–Vis) absorption spectroscopy, and by the simulation based on the density functional theory (DFT). The results from NH₃ decomposition revealed that the cooperation of N, F and Fe broadened the optical response of TiO₂ to the visible light range and also enhanced the photocatalytic activity of TiO₂ under UV light. The reusability of the tri-doped TiO₂ sample after three cycles under UV and visible light irradiation was very good. XRD patterns and SEM and HRTEM images indicated that the tri-doped sample was nanometric anatase with a small amount of rutile with an average particle size of 18 nm. Tri-doping with N, F and Fe suppressed the phase transition from anatase to rutile and also resulted in some more lattice defects. XPS analysis showed that the N, F and Fe atoms were doped into the TiO₂ lattice. UV–Vis absorption spectra of the tri-doped TiO₂ showed that its optical absorption edge was moved up to 640 nm and its UV absorption was also enhanced. The DFT results confirmed that the cooperation of Fe 3d and N 2p orbits narrowed the band gap of TiO₂ and the F 2p orbit broadened the upper valence bands. The synergistic electron density around N, F and Fe in tri-doped TiO₂ was capable of enhancing the photochemical stability and reusability of TiO₂.     

Preparation of SnO2–TiO2/Fly Ash Cenospheres and its Application in Phenol Degradation

SnO₂–TiO₂/fly ash cenospheres (FAC) were prepared via hydrothermal method and used as an active photocatalyst in a photocatalytic system. Scanning electron microscopy, X‐ray diffraction analysis, UV–Vis diffuse reflectance spectroscopy, Fourier transform infrared spectroscopy and N₂ adsorption–desorption measurements were used to determine the structure and optical property of SnO₂–TiO₂/FAC. Phenol was selected as the model substance for photocatalytic reactions to evaluate catalytic ability. Results showed that the degradation efficiency of phenol by SnO₂–TiO₂/FAC was 90.7% higher than that decomposed by TiO₂/FAC. Increased efficiency could be due to the enhanced synergistic effect of semiconductors and FAC could provide more adsorption sites for the pollutant in the photocatalytic reaction. Furthermore, SnO₂–TiO₂/FAC composites exhibited excellent photocatalytic stability in four reuse cycles. Radical‐trapping experiments further revealed the dominating functions of holes in the photocatalytic reaction.