Covalent Triazine Framework Nanosheets for Efficient Energy Storage and Conversion

Two-dimensional crystalline covalent triazine frameworks(CTFs) have received much attention because of their unique triazine structure, which endows CTFs with high thermal and chemical stability, high proportion of nitrogen and permanent porosity. Based on this unique structure characteristic, CTFs have shown great potential in energy storage and conversion due to the intrinsically strong conjugated structure, delocalized electron and rich active sites. However, charge carrier(electron, hole or ion) transport can't reach the deep active sites and charge diffusion was impeded by defects in bulk CTFs. Hence, to break through this barrier, increasing attention has been paid to get few layered CTFs or CTFs nanosheets in order to shorten the pathways of charge diffusion and expose more active sites. This review summarizes the synthetic methodologies of CTFs nanosheets and the potential application in photocatalytic and electrochemical energy storage and conversion.     

Synthesis of N-TiO2@NH2-MIL-88(Fe) Core-shell Structure for Efficient Fenton Effect Assisted Methylene Blue Degradation Under Visible Light

Core-shell TiO₂-based photocatalysts with specific composition, morphology, and functionality have attracted considerable attention for their excellent degradation properties on organic pollutants via a photocatalytic oxidation process. Herein, a N-TiO₂@NH₂-MIL-88(Fe) core-shell structure was prepared by coating NH₂-MIL-88(Fe) on nitrogen-doped TiO₂(N-TiO₂) nanoparticles. Introduction of heteroatom nitrogen to pure TiO₂ expands the spectral response range, leading to enhanced quantum efficiency of photocatalyst. Furthermore, loading NH₂-MIL-88(Fe) on N-TiO₂ improved the adsorption ability of the nanocomposites due to the porous tunnels of NH₂-MIL-88(Fe). The resulted core-shell N-TiO₂@NH₂-MIL-88(Fe) nanocomposites realized the transfer of photo excited electrons from N-TiO₂ to NH₂-MIL-88(Fe) rapidly, partially reduced Fe³⁺ to Fe²⁺ in NH₂-MIL-88(Fe), and further enhanced the Fenton effect on efficiently degrading methylene blue dye(MB) under visible light(λ ≥ 420 nm) with the assistance of H₂O₂.     

In situ Carbon Modification of g-C3N4 from Urea co-Crystal with Enhanced Photocatalytic Activity Towards Degradation of Organic Dyes Under Visible Light

An in situ strategy was introduced for synthesizing carbon modified graphitic carbon nitride(g-C₃N₄) by using urea/4-aminobenzoic acid(PABA) co-crystal(PABA@Urea) as precursor materials. Via co-calcination of the PABA co-former and the urea in PABA@Urea co-crystals, C guest species were generated and compounded into g-C₃N₄ matrix in situ by replacing the lattice N of the carbon nitride and forming carbon dots onto its layer surface. The carbon modification dramatically enhanced visible-light harvesting and charge carrier separation. Therefore, visible light photo-catalytic oxidation of methylene blue(MB) pollution in water over the carbon modified g-C₃N₄(C/g-C₃N₄) was notably improved. Up to 99% of methylene blue(MB) was eliminated within 60 min by the optimal sample prepared from the PABA@Urea co-crystal with a PABA content of 0.1%(mass ratio), faster than the degradation rate over bare g-C₃N₄. The present study demonstrates a new way to boost up the photocatalysis performance of g-C₃N₄, which holds great potential concerning the degradation of organic dyes from water.     

Combinatıon of a Box-Behnken design technique with response surface methodology for optimization of the photocatalytic mineralization of C.I. Basic Red 46 dye from aqueous solution

The photodegradation of an industrial azo dye C.I Basic Red 46 was examined in a fixed-bed photoreactor using UV-lamps simulated to the solar irradiation. In our photodecolorization study, the UV/TiO₂ process was optimized using the Box-Behnken approach to evaluate the synergistic effects of three independent parameters (initial concentration of the dye, flow rate, and UV intensity) on mineralization effectiveness. The response surface methodology was in good promise with the prediction model (coefficients of determination of decolorization and mineralization were R²_Dec = 0.997 and R²_TOC = 0.994, respectively). The effects of the factors could be estimated from a second–order polynomial equation and student’s t-test. The optimal parameters of decolorization and mineralization were as follows: initial concentration of colorant 25 mg L⁻¹, rate of fluid flow 0.3 L min⁻¹, and ultraviolet light intensity 38.1 W m⁻². The decolorization and mineralization removal efficiency under these optimal conditions were 100% and 57.63% respectively. These results indicate that optimization using response surface methodology, based on the Box-Behnken approach, is an excellent tool for determining the optimal conditions, and the process can be easily extrapolated for a specific treatment of real waste water containing the azo dye C.I Basic Red 46. Also, the intermediates that were produced during photodegradation process of Basic Red 46 were determined by GC/MS.     

CeO2 nanofibers-CdS nanostructures n–n junction with enhanced visible-light photocatalytic activity

In the present work, the n-cerium (IV) oxide (CeO₂)/n-cadmium sulfide (CdS) composite nanofibers were successfully synthesized via a facile electrospinning and hydrothermal synthesis strategy. The physicochemical properties of the synthesized composite nanofibers were investigated by using X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), energy Dispersive X-Ray Spectroscopy (EDS), diffuse Reflectance Spectroscopy (DRS), Fourier-transform infrared (FTIR), photoluminescence (PL), Brunauer–Emmett–Teller (BET) and Raman spectroscopy analysis. The activities of the CeO₂/CdS were evaluated through the photocatalytic degradation of Rose Bengal (RB) in an aqueous solution under blue LED light radiation. CeO₂/CdS composites exhibit higher photocurrent density in photocurrent response experiment and smaller charge-transfer resistance in electrochemical impedance spectroscopy (EIS). Overall, the results confirmed higher charge separation efficiency in CeO₂/CdS composites compared to pristine CeO₂ nanofibers, and CdS, which is related to intimately contact among the CeO₂, and CdS. The present work provides a new approach to construct n-n heterojunction photocatalysts based on electrospinning and a deeper insight for the photocatalytic degradation activity. In addition, possible degradation mechanism and pathways were proposed according to the identified intermediates.     

Effect of synthesis pH on the physicochemical properties of a synthesized Bi2WO6 and the type of substrate chosen,in assessing its photo-catalytic activities

Crystalline orthorhombic Bi₂WO₆ powders were synthesized by a hydrothermal method from aqueous solutions of Bi(NO₃)₃·5H₂O and Na₂WO₄·2H₂O over a range of three selected pH values (2.0, 5.0 and 7.0), using NaOH as precipitating agent. The as-prepared catalysts were characterized by XRD, BET, FE-SEM, TEM, XPS and UV-vis spectroscopy. The effect of pH-synthesis on crystallinity, morphologies, surface area and optical absorption properties, were investigated. Although the pH has a marked influence on morphology, the nature of the precipitating agent (NaOH or TEA) also influences the morphology and surface structure composition, as it is observed in the present work. Three different probe molecules were used to evaluate the photo-catalytic properties under two illumination conditions (UV and Visible): Methyl Orange and Rhodamine B were chosen as dye substrates and Phenol as a transparent substrate. The photo-catalytic activities are strongly dependent not only on the pH used in the synthesis but also on the nature of the chosen substrate in assessing the photo-catalytic activities. Results were compared with those obtained when using TiO₂(P25, Evonik) in the same experimental conditions. The photo-catalytic activity of one of the synthesised samples has been evaluated by exposing a mixture of Rhodamine B and Phenol in water, to different illumination conditions. Our results provide new evidences about the issue of whether dyes are suitable substrates to assess the activity of a photo-catalyst.     

CFTS-3/In2S3/SnO2:F heterojunction structure as eco-friendly photocatalytic candidate for removing organic pollutants

In this paper, quaternary chalcogenide Cu₂FeSnS₄ (CFTS) thin films were synthesized by spray pyrolysis using multilayer deposition technique in which the number (N) of sequential deposition runs (DR) is N = 1, 2, 3 and 4. The delivered volume in each sample is (N × 300 ml). Correspondingly, samples are named CFTS-N. Chemical composition, morphological, structural, optical and electrical properties were characterized using dispersive X-ray spectrometry (EDX), scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, spectrophotometer and Hall Effect measurements. XRD and Raman spectroscopy show a purer phase and better crystalline quality of CFTS-3 than other films. Average particle size increases with DR and reaches a maximum value of about 60 nm for N = 3. Optical results show high absorption coefficient value about 10⁵ cm⁻¹ in visible range, with an optical band gap of about 1.47 eV. Electrical resistivity of CFTS-3 equals to 5.82 10⁻³ Ω cm which is the lowest value of these four samples. We have investigated the photocatalysis activity of various thin films by measuring the degradation of methylene blue (MB) and Rhodamine (RhB) as pollutant dyes. In particular we have compared the candidates: CFTS-3/SnO₂:F, CFTS-3/In₂S₃ and CFTS-3/In₂S₃/SnO₂:F. Under sun light irradiation, CFTS-3/In₂S₃/SnO₂:F heterojunction exhibits the best photodegradation rate (96%) of MB dye.     

BiVO4/TiO2 core-shell heterostructure: wide range optical absorption and enhanced photoelectrochemical and photocatalytic performance

In the present study, pristine BiVO₄, TiO₂ and BiVO₄/TiO₂ core-shell heterostructured nanoparticles are prepared by hydrothermal methods and studied for structural, morphological, optical, photoelectrochemical water splitting and photocatalytic degradation of methylene blue as an organic pollutant. Both pristine BiVO₄ and TiO₂ exhibit poor PEC and PC performance under visible light illumination. However, an enhanced PEC and PC activity in BiVO₄/TiO₂ core-shell heterostructure is observed due to high solar energy absorption and superior charge separation properties in core-shell nanoparticles. The photoelectrode prepared using BiVO₄/TiO₂ core-shell nanoparticles exhibit a photocathode behavior and produced cathodic photocurrent, however, the pristine BiVO₄ and TiO₂ photoelectrodes act as photoanode and produced anodic photocurrent. This behavior of change in current direction is also observe in the Mott-Schottky analysis where the BiVO₄/TiO₂ core-shell nanoparticles photoelectrode exhibits the positive slow showing p-type semiconducting behavior. The change in cathodic photoresponse in core-shell nanoparticles in comparison to anodic photoresponse of BiVO₄ and TiO₂ nanoparticles is explained in terms of the variations in the work function values. These results highlight the advantages of core-shell nanoparticle of suitable materials for photocatalytic and photoelectrochemical applications.     

Characterization and activity of visible-light-driven TiO2 photocatalyst codoped with lanthanum and iodine

The novel visible-light-activated La/I/TiO₂ nanocomposition photocatalyst was successfully synthesized using precipitation-dipping method, and characterized by X-ray powder diffraction (XRD), the Brunauer-Emmett-Teller (BET) method, transmission electron microscopy (TEM), thermogravimetry-differential scanning calorimetry (TG-DSC) and UV-vis diffuse reflectance spectroscopy (UV-vis DRS). The photocatalytic activity of La/I/TiO₂ was evaluated by studying photodegradation of reactive blue 19 as a probe reaction under simulated sunlight irradiation. Photocatalytic experiment results showed that the maximum specific photocatalytic activity of the La/I/TiO₂ photocatalyst appeared when the molar ratio of La/Ti was 2.0 at%, calcined at 350 °C for 2 h, due to the sample with good crystallization, high BET surface area and small crystal size. Under simulated sunlight irradiation, the degradation of reactive blue 19 aqueous solution reached 98.6% in 80 min, which showed La/I/TiO₂ photocatalyst to be much higher photocatalytic activity compared to standard Degussa P25 photocatalyst. The higher visible light activity is due to the codoping of lanthanum and iodine.     

Synthesis and photocatalytic property of N-doped TiO2 nanorods and nanotubes with high nitrogen content

Nano N-doped TiO₂ nanotubes were fabricated by hydrothermally treating N-doped TiO₂ nanorods in a 8 M NaOH solution at 110 °C for 20 h. The N-doped TiO₂ nanorods were synthesized by a solvothermal process with precursor solution containing titanium sulfate, urea, and dichloroethane. The N-doped TiO₂ nanorods and nanotubes were characterized with X-ray diffraction, transmission electron microscopy, and UV-vis spectrophotometry. The nitrogen contents of the N-doped TiO₂ nanorods and nanotubes were reached to high values of 36.9 at.% and 25.7 at.%, respectively. The nitrogen doping narrowed the band gap of the N-doped TiO₂ nanorods and nanotubes and introduced indirect band gap to the powders, which respectively extended the absorption edge to visible light and infrared region. The nanotubes showed larger specific surface area and greater degradation efficiency to methyl orange than the nanorods.