TiO<Subscript>2</Subscript> porous ceramic/Ag–AgCl composite for enhanced photocatalytic degradation of dyes under visible light irradiation

TiO₂ porous ceramic/Ag–AgCl composite was prepared by incorporating AgCl nanoparticles within the bulk of TiO₂ porous ceramic followed by reducing Ag⁺ in the AgCl particles to Ag⁰ species under visible light irradiation. The porous TiO₂ ceramic was physically robust and chemically durable, and the porous structure facilitated the implantation of AgCl NPs. Compared with the bare TiO₂ ceramic, TiO₂ porous ceramic/Ag–AgCl composite exhibited higher photocatalytic performance for the degradation of MO and RhB under visible light irradiation. The reaction rate constants k of MO and RhB degradation over TiO₂ porous ceramic/Ag–AgCl composite was respectively 6.25 times and 3.62 times higher than those recorded over the bare TiO₂ porous ceramic. The photocatalytic activity showed virtually no decline after four times cyclic experiments under visible light irradiation. Scanning electron microscopy, energy dispersive X-ray analysis, X-ray diffraction, UV–Vis diffuse reflectance spectroscopy, photoluminescence spectra and X-ray photoelectron spectroscopy were used to characterize the TiO₂ porous ceramic/Ag–AgCl composite.     

Effect of different iron precursors on the synthesis and photocatalytic activity of Fe–TiO2 nanotubes under visible light

Fe–TiO₂ nanotubes (Fe-TNTs) were developed to entitled photocatalytic reactions using a visible range of the solar spectrum. This work reports on the effect of different Fe precursors on the synthesis, characterization, kinetic study, material and photocatalytic properties of Fe-TNTs prepared by electrochemical method using three different Fe precursors i.e. (iron nitrate [Fe(NO₃)₃⋅9H₂O], iron sulfate [FeSO₄⋅7H₂O], and potassium iron ferricyanide [K₃Fe(CN)₆]). X-ray diffraction, X-ray photoelectron spectroscopy, field emission scanning electron microscopy, and Fourier transform infrared spectroscopy are used to examine the influence of the Fe precursor on the Fe-TNTs material characterization. Different Fe-TNT properties, such as enhanced photoactivity, good crystallization, and composition of titania structures (anatase and rutile) could be acquired from different iron precursors. Among the three iron precursors, Fe(NO₃)₃ provided with the only anatase phase, yields the highest photocatalytic activity. Congo red is used as a model compound to check the photocatalytic efficiency of synthesized materials because it has a complex aromatic structure which makes it difficult to be biodegraded or oxidized with the aid of chemicals. The photocatalytic efficiency of all Fe-TNT can be arranged in the following order: TNT-FeN > TNT-FeS > TNT-FeK > TNT. The kinetic rate constant of congo red degradation using the Fe-TNT with Fe(NO₃)₃ was 0.44 h⁻¹ with a half-life of 1.57 h⁻¹     

AgBr@Ag/TiO2 core–shell composite with excellent visible light photocatalytic activity and hydrothermal stability

AgBr@Ag/TiO₂ core–shell photocatalysts were fabricated by a facile green route. TiO₂ was uniformly coated on the surface of cubic AgBr, making AgBr@Ag/TiO₂ core–shell photocatalyst show excellent hydrothermal stability. Beneficial from that Ag nanoparticles and AgBr can respond to visible light and core–shell structure can effectively separate the photogenerated electrons and holes, AgBr@Ag/TiO₂ core–shell composites exhibited outstanding visible light photocatalytic activity for the degradation of acid orange 7. The activity of AgBr@Ag/TiO₂ is related to the thickness of TiO₂ shell, and the optimal shell thickness for obtaining the highest activity is 10 nm.     

Preparation of cobalt coated TiO2 and WO3–TiO2 nanotube films via photo-assisted deposition with enhanced photocatalytic activity under visible light illumination

Highly ordered TiO₂ and WO₃–TiO₂ nanotubes were prepared by one-step electrochemical anodizing method and cobalt has been successfully deposited on these nanotubes by photo-assisted deposition process. The morphology, crystal structure, elemental composition and light absorption capability of samples were characterized by field emission scanning electron microscope, X-ray diffraction, energy dispersive X-ray spectrometer and ultraviolet–visible spectroscopy methods. All cobalt loaded samples show an appearance of red shift relative to the unloaded samples. The degradation of methylene blue was used as a model reaction to evaluate the photocatalytic activity of these novel visible-light-responsive photocatalysts. Results showed that the photocatalytic activity of bare WO₃–TiO₂ samples is higher than that with undoped TiO₂ sample. Compared with unmodified TiO₂ and WO₃–TiO₂, the Co/TiO₂ and Co/WO₃–TiO₂ samples exhibited enhanced photocatalytic activity in the degradation of methylene blue. Kinetic research showed that the reaction rate constant of Co/WO₃–TiO₂ is approximately 2.26 times higher than the apparent reaction rate constant of bare WO₃–TiO₂. This work provides an insight into designing and synthesizing new TiO₂–WO₃ nanotubes-based hybrid materials for effective visible light-activated photocatalysis. The catalysts prepared in this study exhibit industrially relevant interests due to the low cost and high photocatalytic activity.     

Li–Y doped and codoped TiO2 thin films: Enhancement of photocatalytic activity under visible light irradiation

Sol−gel synthesis based on the self-assembling template method has been applied to synthesize Li–Y doped and co-doped TiO₂ not only to improve simultaneously the structural and electronic properties of TiO₂ nanomaterials but also to achieve Li–Y doping of titania with high photocatalytic reactivity. The characterization of the samples was performed by GXRD, GSDR, FT-IR, and Raman spectroscopy. According to the GXRD patterns, all the observed reflections can be indexed using the anatase form of TiO₂, Which is confirmed by ground state diffuse reflectance and micro-Raman spectra. The Li–Y doped titania materials immobilized as nanostructured thin films on glass substrates exhibit high photocatalytic efficiency for the degradation of toluidine and benzoic acid under visible light irradiation. The development of these visible light-activated nanocatalysts has the potential of providing environmentally benign routes for water treatment.     

Green synthesis of nickel oxide coupled copper hexacyanoferrate (NiO2–CuHCF) nanocomposites for efficient and highly stable natural sunlight-driven photocatalytic degradation of wastewater pollutants

Metal hexacyanoferrates are found to be the promising candidates utilized to degrade toxic dyes from waste water under natural sunlight irradiation. Coupling of metal hexacyanoferrate with metal oxide enhances the degradation efficacy. In present work, nickel oxide coupled copper hexacyanoferrate nanocomposites (NiO₂–CuHCF) are synthesized by employing facile co-precipitation route. XRD reveals the incorporation of NiO₂ with CuHCF. SEM confirms the sheet like structures of NiO₂–CuHCF nanocomposite. TEM demonstrates the even distribution of elements present in the NiO₂–CuHCF nanocomposite. XPS shows the active participation of constituents having different valence states. The UV–Vis (DRS) is employed to measure the optical properties. The band gap of nickel oxide coupled copper hexacyanoferrate nanocomposite (NiO₂–CuHCF) decreases in comparison with pure copper hexacyanoferrate (CuHCF) from 1.23 to 1.14 eV. 97% degradation of Methyl blue (MB) is observed in just 110 min by NiO₂–CuHCF nanocomposite when exposed to natural sunlight. Moreover, it also retains 92% photocatalytic efficiency over 6 cycles which shows its excellent stability and reusability. The improved photocatalytic performance of NiO₂–CuHCF nanocomposite is attributed to their sheet resembling morphologies which may provide adequate active sites responsible to transport more charge carriers and also reduce charge recombination. In general, this research may open new avenue to use CuHCF with the addition of NiO₂ in future as an efficient degradation agent at industrial level.     

Sol–gel reverse micelle preparation and characterization of N-doped TiO2: Efficient photocatalytic degradation of methylene blue in water under visible light

A series of N-substituted titanium (IV) 2-ethyl-1,3-hexanediolate Ti(C₃₂H₆₈O₈) precursor were synthesized by the sol–gel reverse micelle (SGRM) method. The ethylene diaminetetraacetic acid (Na₂EDTA) has been used as a source of nitrogen n species. The obtained solids were calcined at 500 ?C for 1 h to obtain photoactive phases. The effect of nitrogen content (N/Ti = 0.025; 0.03; 0.05 atomic ratios) is examined. The materials were characterized by XRD, BET, TG/DTA and UV–vis reflectance spectroscopy (DRS). Photocatalytic decolourisation of methylen blue (MB) in aqueous solution was carried out using nano, doped TiO₂. Experimental results revealed that N/Ti = 0.05 atomic ratio N-doped TiO₂ required shorter irradiation time for complete decolourisation of MB than pure nano TiO₂ and commercial (Degussa P-25) TiO₂.     

A novel TiO2 − xNx/BN composite photocatalyst: Synthesis,characterization and enhanced photocatalytic activity for Rhodamine B degradation under visible light

A novel TiO_2 − xN_x/BN composite photocatalyst was prepared via a facile method using melamine–boron acid adducts (M·2B) and tetrabutyl titanate as reactants. The morphological results confirmed that nitrogen-doped TiO₂ nanoparticles were uniformly coated on the surface of porous BN fibers. A red shift of absorption edge from 400 nm (pure TiO₂) to 520 nm (TiO_2 − xN_x/BN composites) was observed in their UV–Vis light absorption spectra. The TiO_2 − xN_x/BN photocatalysts exhibited enhanced photocatalytic activity for the degradation of Rhodamine B (RhB) and the highest photocatalytic degradation efficiency reached 97.8% under visible light irradiation for 40 min. The mechanism of enhanced photocatalytic activity was finally proposed.     

Enhanced structural,optical, and photocatalytic activity of novel Cd–Zn co-doped Mg0.25 Fe1.75O4 for degradation of RhB dye under visible light irradiation

Cd_xZn_1-xMg_0.25Fe_1.75O₄ (where x = 0.00, 0.25, 0.50, 0.75, 1.00) have been successfully produced by a facile hydrothermal technique for a thorough comparison of structural, optical, and photocatalytic properties (degradation of Rhodamine B -RhB dye under visible light irradiation). X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) confirmed the formation of cubic spinel structure for all of the samples. Fourier transform infrared (FTIR) spectroscopy verified the presence of metal-oxygen (M–O) bonding in the prepared samples with two frequency bands corresponding to phonon vibrational stretching in both the octahedral and tetrahedral lattice positions. UV–Visible Spectrophotometer and photoluminescence (PL) spectroscopy investigated the bandgap variation (2.7 eV-1.7 eV) and emission spectrum peaks appearing in the range of 405–471 nm region. The comparison in the photo-degradation of Rhodamine B (RhB) revealed the superior performance (98% degradation of RhB dye in 80 min having a K value of 0.04966 with excellent reusability) of Cd_0.50Zn_0.50Mg_0.25Fe_1.75O₄ sample having 50/50 dopant ratio of Cd and Zn in the parent Mg Ferrite, attributed to the lowest bandgap, longer lifetime of charge carriers, active octahedral lattice site, electron/hole pair recombination preventions, and the least value of ohmic impedance at higher frequency.     

A highly active and stable Fischer–Tropsch synthesis cobalt/silica catalyst with bimodal cobalt particle distribution

Silica-supported cobalt (20 wt%) catalysts were prepared by incipient wetness impregnation of silica with different cobalt nitrate solution. The catalyst prepared from dehydrated ethanol solution exhibited highest activity and very low methane selectivity. The catalyst prepared from cyclohexanol had the lowest activity and highest methane selectivity. The catalyst prepared from aqueous solution, a most conventional catalyst, exhibited moderate reaction behavior. The catalyst prepared from dehydrated ethanol had cobalt particles with two different size where the large particles showed low bulk density with cluster-like structure.     

A simple oxidation–reduction process for the activation of a stainless steel surface to synthesize multi-walled carbon nanotubes and its application to phenol degradation in water

Aligned multi-walled carbon nanotubes (MWCNTs) were synthesized directly on a stainless steel surface by surface activation by intense oxidation in air followed by a moderate reduction in H₂ without any wet process. This method is extremely simple compared with conventional ways that need catalyst loading steps or acid pre-etching steps to synthesize carbon nanotubes on stainless steel surfaces. It was found that the length of MWCNT bundles could reach 80 μm when the oxidation step was properly controlled. It was demonstrated that MWCNTs synthesized on stainless steel meshes could be used as a catalyst support to enhance ozone oxidation in the decomposition of phenol in water.     

Development and introduction of a highly efficient catalyst for the butane–butylene fraction oligomerization process for the production of a high-octane automobile gasoline compound

The main stages in developing a technology for the production of high-silica ZSM-5 zeolite-based catalyst for the butane–butylene fraction (BBF) oligomerization process are described. The application of a new zeolite surface modification procedure allows the attainment of higher selectivity and target product yields (compared to familiar analogs) and the synthesis of more branched (and thus more high-octane) oligomers at lower pressures. The introduction of promoting metal Ga raises the target gasoline fraction yield by 0.9%, compared to the unpromoted catalyst. Comparative pilot tests of industrial (BAK-70U) and the developed (Ga-ZSM-5/Al₂O₃) BBF oligomerization catalysts are performed under the following conditions: pressure, 1.5 MPa; initial working temperature, 300°C; feedstock hourly space velocity (FHSV), 1.5 mL BBF/(mL cat h). It is shown that using modified ZSM-5 based catalyst results in a gasoline fraction yield 7% higher than with BAK-70U. The higher quality of the oligomerizate obtained on Ga-ZSM-5/Al₂O₃ is observed throughout the period of tests (191 h): MON is 2 points higher, and the concentration of gums is 50% lower. The results from these studies and tests are used for the development and industrial implementation of a technology for the production of the KOB-1 zeolite oligomerization catalyst: 2.5 t of industrial catalyst has been produced by September of 2016 at the industrial facilities of ZAO Redkino Catalyst Plant. The next important stage in the implementation of the Gazprom Netf innovative development strategy in oil refining is a pilot run of the new oligomerization catalyst in the combined industrial MTBE–oligomerizate production plant of Gazprom Neft Moscow Oil Refinery. The introduction of the KOB-1 catalyst at the Gazprom Neft Oil Refinery will be an important step in improving the efficiency of technologies for the production of high-margin products, especially compounds of commercial automobile gasoline.     

Enhanced the photocatalytic activity of B–C–N–TiO2 under visible light:Synergistic effect of element doping and Z-scheme interface heterojunction constructed with Ag nanoparticles

In order to enhance the photocatalytic activity of TiO₂ under visible light, Ag nanoparticles were introduced into tridoped B–C–N–TiO₂ (TT) catalyst by photoreduction deposition. Ag/B–C–N–TiO₂ (ATT) catalysts with the functions of reducing band gap and carrier recombination were prepared. At the same time, the effect of the amount of Ag on the photocatalytic performance of ATT catalyst was investigated. Through XRD, XPS, PL and other characterization methods, the (211)/(101)/Ag interface heterojunction mechanism similar to the traditional Z-scheme heterojunction was proposed. The intervention of Ag nanoparticles changed the P–N interface heterojunction between (211)/(101) to the (211)/(101)/Ag Z-scheme interface heterojunction. The results show that ATT catalyst exhibits the highest photocatalytic activity when the molar amount of Ag is 0.005% with the MB degradation rate of the ATT catalyst (0.01707 min^?1), which is 14.59 times of TiO₂ (0.00117 min^?1) and 2.02 times of TT (0.00847 min^?1). In addition, the four cycles efficiencies of ATT for MB degradation were all above 94.00%.This study reveals the possibility of construction of Z-scheme heterojunctions between precious metal nanoparticles and different interfaces of TiO₂, and provides a reference for the construction of Z-scheme interface heterojunctions.     

Polyoxometalate–molybdenylacetylacetonate hybrid complex: A reusable and efficient catalyst for oxidation of alkenes with tert-butylhydroperoxide

The hybrid complex consist of molybdenylacetylacetonate complex covalently linked to a lacunary Keggin-type polyoxometalate, K₈[SiW₁₁O₃₉] (POM), was synthesized and characterized by elemental analysis, SEM, XRD, diffuse reflectance UV–Vis and FT-IR spectroscopic methods. The hybrid complex, [MoO₂(acac)–POM] (1), was used for alkene epoxidation with tert-BuOOH in 1,2-dichloroethane as solvent. The complex (1) can catalyze epoxidation of various olefins including non-activated terminal olefins. The effect of reaction parameters such as oxidant, solvent, and temperature on the epoxidation of cyclooctene was also investigated. This heterogeneous catalyst was reused several times in the oxidation of cyclooctene.     

A new and efficient catalytic system for synthesis of diphenyl carbonate with W–Mo-heteropolyacids as a cocatalyst

A new catalytic system, which consists of Pd(OAc)₂ as the catalyst and W–Mo-containing heteropolyacids (HPAs)/Mn(OAc)₂ as the bicomponent cocatalysts, has been found to be very efficient in the oxidative carbonylation of phenol to diphenyl carbonate at low pressure in the absence of solvent. The efficiency of the catalytic system is dependent on the ratio of W/Mo in the HPAs, being best in a ratio of 6/6. The synergistic effect between W–Mo-containing HPAs and Mn(OAc)₂ has been observed in the catalysis. This revised version was published online in July 2006 with corrections to the Cover Date.     

A green and facile one-pot synthesis of Ag–ZnO/RGO nanocomposite with effective photocatalytic activity for removal of organic pollutants

In this study, Ag–ZnO/reduced graphene oxide (Ag–ZnO/RGO) composite was synthesized by a green and facile one-step hydrothermal process. Aqueous suspension containing Ag and ZnO precursors with graphene oxide (GO) sheets was heated at 140 °C for 2 h. The morphology and structure of as-synthesized particles were characterized by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy, and Photoluminescence (PL) spectroscopy which revealed the formation of composite of metal, metal oxide and RGO. It was observed that the presence of Ag precursor and GO sheets in the hydrothermal solution could sufficiently decrease the size of ZnO flowers. The hybrid nanostructure, with unique morphology, obtained from this convenient method (low temperature, less time, and less number of reagents) was found to have good photocatalytic and antibacterial activity. The perfect recovery of catalyst after reaction and its unchanged efficiency for cyclic use showed that it will be an economically and environmentally friendly photocatalyst.     

Synthesis of Zn0·1Cd0·9S heterostructure with N-doped graphene quantum dots and graphene for enhancing photoelectric performance in UV–visible light

In the present study, a heterostructure based on Zn_0·1Cd_0·9S, N-doped graphene quantum dots (N-GQDs), and graphene was successfully prepared by a simple method. Various analyses are conducted to determine the structure, morphology, and materials performance of the synthesized composite. The results exhibit that the Zn_0·1Cd_0·9S/N-GQDs/graphene heterostructure presents excellent photoelectric performance with a high photocurrent of 4.43 × 10⁻⁵ A/cm² and 3.43 × 10⁻⁵ A/cm² under light irradiation of 365 nm and 405 nm, respectively. It demonstrates a two-fold photocurrent enhancement in comparison to blank Zn_0·1Cd_0.9S. This remarkable improvement is ascribed to a mechanism in which the N-GQDs act as photosensitizers, enhancing the absorption ability. Concurrently, graphene serves as a carrier mobility substrate, facilitating the separation of the photogenerated electron–hole pairs. The synergetic effect between Zn_0·1Cd_0·9S, the N-GQDs, and graphene enhances the photoelectric performance. The Zn_0·1Cd_0·9S/N-GQDs/graphene heterostructure provides a new route for the enhancement of the photoelectric performance of a semiconductor under UV–visible light.     

A one-pot method for the preparation of graphene–Bi2MoO6 hybrid photocatalysts that are responsive to visible-light and have excellent photocatalytic activity in the degradation of organic pollutants

Graphene–Bi₂MoO₆ (G–Bi₂MoO₆) hybrid photocatalysts were prepared by a simple one-step process in which the reduction of graphene oxide (GO) and the growth of Bi₂MoO₆ crystals occurred simultaneously. The material was characterized by X-ray diffraction, scanning electron microscopy, nitrogen adsorption–desorption isotherms, X-ray photoelectron spectroscopy, UV–vis diffuse reflectance spectroscopy and Raman spectroscopy. The photocatalytic activity was investigated by the degradation of reactive brilliant red dye X-3B. An increase in photocatalytic activity was observed for G–Bi₂MoO₆ hybrids compared with pure Bi₂MoO₆ under visible light. This improvement was attributed to the following two reasons: increased migration efficiency of photo-induced electrons and increased adsorption activity for dye molecules. A study of the effect of the amount of graphene on the photocatalytic activity showed that there was an optimum amount of 2.5% (initial GO weight).