Doped TiO2 Photocatalysts for the Photocatalytic Degradation Efficiency of Methylene Blue and Humic Acid under Solar Light

I n various advanced oxidation processes, photocatalysis is a promising and efficient way? to remove natural organic matter consisting of humic acids and fulvic acids. The principle of this method involves both usage of a semiconductor photocatalyst and O2 for the generation of radicals. Among them, TiO2 photocatalysis is the most popular and studied one since TiO has unique properties such as being chemically inert, photocatalytically stable, Phone: +90 386 280 3104cheap, non-toxic, environmentally benign and exhibiting high oxidative power. However, despite all the advantages of using TiO2 as a photocatalyst, there is a major disadvantage. Since TiO2 has a broad band gap, its usage widely under solar light is limited and only allows to be active under UV light. Doping is one of the most popular methods to enhance the photocatalytic activity of TiO2 via using metal or non-metal species as dopants. In this respect, solar light sensitive TiO2 photocatalyst, C, N, S, Se doped and S/N codoped TiO2 photocatalysts were synthesized by using wet-impregnation method. These doped photocatalysts were characterized by Raman spectroscopy to determine the crystal surface morphology. Moreover, methylene blue was used to investigate the photocatalytic performance of prepared doped TiO2 photocatalysts in the presence or absence of organic matrix. Photocatalytic experiments were performed using a solar light simulating photoreactor. Humic acid characterization was monitored by UV-vis and fluorescence spectroscop

Preparation of PANI modified TiO2 and characterization under pre- and post- photocatalytic conditions

Polyaniline (PANI) is a promising conducting polymer for surface modification of TiO2 to overcome limitations of the use of visible light and attain increased photocatalytic efficiency for the removal of organic contaminants. In this study, a series of polyaniline modified TiO2 (PANI-TiO2) composites were prepared by using "in-situ" chemical oxidation polymerization method. The composites were systematically characterized by Fourier transform infrared spectroscopy (equipped with an attenuated total reflection accessory, FTIR-ATR), Raman spectroscopy, X-ray diffractometry (XRD), scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDAX), X-ray photoelectron spectroscopy (XPS), ultraviolet–visible diffuse reflectance spectroscopy (UV-DRS), photoluminescence spectroscopy (PL), nitrogen (N2) physisorption (Brunauer − Emmett − Teller surface area (SBET) and Barrett-Joyner-Halenda (BJH) pore size analysis), thermogravimetry-derivative thermogravimetry (TG-DTG) techniques. XRD patterns of PANI-TiO2 composites confirmed both the amorphous phase of PANI and the crystalline character of TiO2. TG/DTG analysis complemented the XRD profiles that the interactions between PANI and TiO2 resulted in a more stable PANI-TiO2 matrix. SEM images displayed the dominant morphology as dandelion-like shapes of PANI being more pronounced with increasing PANI ratios in PANI-TiO2 composites. UV-DRS profiles revealed that the band gap energies of the composites were lower than bare TiO2 expressing a shift to the visible light region. Both PL and UV-DRS analyses confirmed the band-gap reduction phenomenon of PANI modification of TiO2. The incorporation of PANI into TiO2 resulted in a reduction of the surface area of TiO2. The composites were subsequently subjected to photocatalytic activity assessment tests using humic acid (HA) as a model of refractory organic matter (RfOM) under simulated solar irradiation (Uyguner-Demirel et al. Environ Sci Pollut Res 30 85626-85638, 2023). The morphological and structural changes attained upon application of photocatalysis were also evaluated by FTIR-ATR, Raman spectroscopy, XRD, and SEM-EDAX methods in a comparable manner. The FTIR-ATR spectral features of PANI, RfOM and all composites displayed peaks with slight shifts under pre- and post- photocatalytic conditions as well as following dark surface interactions. Besides exhibiting noticeable photocatalytic performance, PANI-TiO2 composites were also proven to maintain stability under non-selective oxidation conditions in the presence of a complex organic matrix. The prepared PANI-TiO2 composites overcoming the limitations of UVA light active bare TiO2 photocatalysis could possibly find a beneficial use as potential catalysts in solar photocatalytic applications. © 2023, The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature

Preparation of PANI Modified ZnO Composites via Different Methods: Structural, Morphological and Photocatalytic Properties

Polyaniline modified zinc oxide (PANI-ZnO) photocatalyst composites were synthesized by focusing on dissolution disadvantage of ZnO. In-Situ chemical oxidation polymerization method was performed under neutral conditions (PANI-ES) whereas in hybridization method physical blending was applied using emeraldine base of polyaniline (PANI-EB). PANI-ZnO composites were prepared in various ratios of aniline (ANI) to ZnO as 1%, 3%, 6% and 9%. The alterations on the structural and morphological properties of PANI-ZnO composites were compared by Fourier Transform Infrared (FT-IR), Raman Spectroscopy, X-ray Diffraction (XRD) and Scanning Electron Microscopy-Energy Dispersive X-ray Analysis Unit (SEM-EDAX) techniques. FT-IR and Raman spectroscopy confirmed the presence of PANI in all composites. SEM images revealed the morphological differences of PANI-ZnO composites based on PANI presence and preparation methods. Photocatalytic performances of PANI-ZnO specimens were investigated by following the degradation of methylene blue (MB) in aqueous medium under UVA irradiation. The effects of catalyst dose and initial dye concentration were also studied. MB degradation was followed by both decolorization extents and removal of aromatic fractions. PANI-ZnO composites expressed enhanced photocatalytic performance (~95% for both methods) as compared to sole ZnO (~87%). The hybridization method was found to be more efficient than the In-Situ chemical oxidation polymerization method emphasizing the significance of the neutral medium

Photocatalytic Degradation of Humic Acids Using LaFeO₃

TiO2 photocatalytic degradation of dissolved organic matter (DOM), namely humic substances composed of humic (HA) and fulvic acids, has been investigated for decades. However, the application of non-TiO2 photocatalysis for this purpose has only received recent attention. Aiming to fill this gap, this study was performed to elucidate the photocatalytic degradation of HAs using the novel photocatalyst LaFeO3 (LF) under simulated solar light irradiation. HA was selectively fractionated by ultrafiltration to two different molecular size fractions representing high molecular fraction as 100 kDa and lower molecular size fraction comprised of humic components expressing size fractions smaller than 30 kDa. Photocatalyst LF was prepared by the citrate auto-combustion method and characterized by using various techniques and Brunauer⁻Emmett⁻Teller (BET) surface area. Ultraviolet-visible (UV-vis) and excitation-emission matrix (EEM) fluorescence spectroscopic features were used to characterize the treated HA and photocatalytic mineralization extend was followed by dissolved organic carbon (DOC) contents. Photocatalytic performance of LF was compared to the metal modified version as Cu-doped LF. Highest mineralization was achieved upon the use of a photocatalyst dose of 0.25 mg/mL of LaFe0.90Cu0.10O3−δ (Cu-LF) for 30 kDaHA, whereas lowest mineralization was attained for 100 kDaHA upon the use of LF. Photocatalytic degradation kinetics indicated the possible use of LF and Cu-LF for the degradation of HA

Influence of Se/N Codoping on the Structural, Optical, Electronic and Photocatalytic Properties of TiO2

Se4+ and N3− ions were used as codopants to enhance the photocatalytic activity of TiO2 under sunlight irradiation. The Se/N codoped photocatalysts were prepared through a simple wet-impregnation method followed by heat treatment using SeCl4 and urea as the dopant sources. The prepared photocatalysts were well characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV-diffuse reflectance spectroscopy (UV-DRS), scanning electron microscopy (SEM) and Raman spectroscopy. The codoped samples showed photoabsorption in the visible light range from 430 nm extending up to 580 nm. The photocatalytic activity of the Se/N codoped photocatalysts was evaluated by degradation of 4-nitrophenol (4-NP). The degradation of 4-NP was highly increased for the Se/N codoped samples compared to the undoped and single doped samples under both UV-A and sunlight irradiation. Aiming to determine the electronic structure and dopant locations, quantum chemical modeling of the undoped and Se/N codoped anatase clusters was performed using Density Functional Theory (DFT) calculations with the hybrid functional (B3LYP) and double-zeta (LanL2DZ) basis set. The results revealed that Se/N codoping of TiO2 reduces the band gap due to mixing of N2p with O2p orbitals in the valence band and also introduces additional electronic states originating from Se3p orbitals in the band gap

Photocatalytic Bactericidal Performance of LaFeO3 under Solar Light in the Presence of Natural Organic Matter: Spectroscopic and Mechanistic Evaluation

Solar photocatalytic inactivation (SPCI) of E. coli as the indicator microorganism using LaFeO3 (LF) has already been investigated under various experimental conditions, excluding any role of natural organic matter (NOM). However, comprehensive information about the behavior of E. coli and its inactivation mechanism in the presence of NOM, as well as the behavior of NOM components via solar photocatalysis using LF as a photocatalyst, has prime importance in understanding real natural water environments. Therefore, in this study, further assessment was devoted to explore the influence of various NOM representatives on the SPCI of E. coli by using LF as a novel non-TiO2 photocatalyst. The influence of NOM as well as its sub-components, such as humic acids (HA) and fulvic acids (FA), was also investigated to understand different NOM-related constituents of real natural water conditions. In addition to spectroscopic and mechanistic investigations of cell-derived organics, excitation emission matrix (EEM) fluorescence spectra with parallel factor multiway analysis (PARAFAC) modeling revealed further information about the occurrence and/or disappearance of NOM-related and bacteria-related fluorophores upon LF SPCI. Both the kinetics as well as the mechanism of the LF SPCI of E. coli in the presence of NOM compounds displayed substrate-specific variations under all conditions

Influence of Se/N Codoping on the Structural, Optical, Electronic and Photocatalytic Properties of TiO2

Se4+ and N3− ions were used as codopants to enhance the photocatalytic activity of TiO2 under sunlight irradiation. The Se/N codoped photocatalysts were prepared through a simple wet-impregnation method followed by heat treatment using SeCl4 and urea as the dopant sources. The prepared photocatalysts were well characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV-diffuse reflectance spectroscopy (UV-DRS), scanning electron microscopy (SEM) and Raman spectroscopy. The codoped samples showed photoabsorption in the visible light range from 430 nm extending up to 580 nm. The photocatalytic activity of the Se/N codoped photocatalysts was evaluated by degradation of 4-nitrophenol (4-NP). The degradation of 4-NP was highly increased for the Se/N codoped samples compared to the undoped and single doped samples under both UV-A and sunlight irradiation. Aiming to determine the electronic structure and dopant locations, quantum chemical modeling of the undoped and Se/N codoped anatase clusters was performed using Density Functional Theory (DFT) calculations with the hybrid functional (B3LYP) and double-zeta (LanL2DZ) basis set. The results revealed that Se/N codoping of TiO2 reduces the band gap due to mixing of N2p with O2p orbitals in the valence band and also introduces additional electronic states originating from Se3p orbitals in the band gap