Synthesis and Characterizations of Titanium Tungstosilicate and Tungstophosphate Mesoporous Materials

The work reports a development approach for the synthesis of novel multi-components mesoporous materials of titanium tungstate (meso-TiW) titanium tungstosilicate (meso-TiWSi) and tungstophosphate (meso-TiWP) mixed oxides that have high surface area and ordered mesoporous structures at nanometer length scale. Using the solvent evaporation-induced self-assembly (EISA) new oxides of bi- and tri-component of meso-TiW, meso-TiWSi and meso-TiWP oxides with different compositions and porosity were achieved. The physicochemical properties of the mesoporous oxides were characterized by X-ray diffraction, BET surface area analyzer, scanning, and transmission electron microscopes. Subject to the oxide composition, the obtained meso-TiW, meso-TiWSi and meso-TiWP exhibits high surface area, ordered 2D hexagonal mesostructured with order channels extended over a large area. The produced meso-TiW, meso-TiWSi, and meso-TiWP adsorbents exhibit good adsorption efficiency for the removal of Pb(II), Cd(II) and Hg(II) ions from water solution due to the presence of high surface area and accessibility of surface active sites. The adsorption efficiency of these mesoporous oxide reaches up to 95% and is found to be dependent contact time and adsorbents dose. The synthesis strategy is particularly advantageous for the production of new complex (multi-component) inorganic mesoporous materials that might have an application in the field of environmental, catalysis or energy storage and production

Exploiting the synergistic catalytic effects of CoPi nanostructures on Zr-doped highly ordered TiO2 nanotubes for efficient solar water oxidation

Photoelectrochemical (PEC) catalysis offers promising strategies for sustainable development. This study demonstrated the synergistic catalytic behavior of ZrO2 and a cobalt phosphate on anodized TiO2 nanotubes (TNTs), which significantly enhanced the PEC performance for visible-light-driven water splitting reactions. The sequential addition of ZrO2/CoPi-decorated TNTs was performed via electrodeposition and photoassisted electrodeposition. The substitution of Zr4+ by Ti4 can lead to the creation of oxygen vacancies, enabling electron trapping, reducing charge recombination, and thereby enhancing the charge transfer efficiency. Further, in the case of TNTs/ZrO2/CoPi photoanode, the CoPi WOC functioned as a hole-transfer relay to promote the water-splitting reaction. Specifically, incorporating ZrO2/CoPi rushes the surface reaction kinetics of TNTs and considerably improves charge transfer efficiency (ηCT = 90%), photocurrent density (0.86 mA/cm2 at 1.23 VRHE) and durability were obtained. Further, the mechanistic examination by impedance measurements showed the enhanced charge transfer, and surface conductivity for prepared materials. The proposed method can be widely used to develop electrodes made of other materials to produce solar fuels

Photoelectrochemical performance of strontium titanium oxynitride photo-activated with cobalt phosphate nanoparticles for oxidation of alkaline water

Photoelectrochemical (PEC) solar water splitting is favourable for transforming solar energy into sustainable hydrogen fuel using semiconductor electrodes. Perovskite-type oxynitrides are attractive photocatalysts for this application due to their visible light absorption features and stability. Herein, strontium titanium oxynitride (STON) containing anion vacancies of SrTi(O,N)3−δ was prepared via solid phase synthesis and assembled as a photoelectrode by electrophoretic deposition, and their morphological and optical properties and PEC performance for alkaline water oxidation are investigated. Further, cobalt-phosphate (CoPi)-based co-catalyst was photo-deposited over the surface of the STON electrode to boost the PEC efficiency. A photocurrent density of ~138 μA/cm at 1.25 V versus RHE was achieved for CoPi/STON electrodes in presence of a sulfite hole scavenger which is approximately a four-fold enhancement compared to the pristine electrode. The observed PEC enrichment is mainly due to the improved kinetics of oxygen evolution because of the CoPi co-catalyst and the reduced surface recombination of the photogenerated carriers. Moreover, the CoPi modification over perovskite-type oxynitrides provides a new dimension for developing efficient and highly stable photoanodes in solar-assisted water-splitting reactions

Structure and electrochemical activity of nickel aluminium fluoride nanosheets during urea electro-oxidation in an alkaline solution

An electrocatalyst of potassium nickel aluminium hexafluoride (KNiAlF6) nanosheets has been prepared using solid-phase synthesis at 900 °C. X-ray diffraction, scanning electron microscopy, and conductivity studies confirmed the formation of KNiAlF6 nanosheets having a cubic defect pyrochlore structure with an average thickness of 60–70 nm and conductivity of 1.297 × 103 S m−1. The electrochemical catalytic activity of the KNiAlF6 nanosheets was investigated for urea oxidation in alkaline solution. The results show that the KNiAlF6 nanosheets exhibit a mass activity of ∼395 mA cm−2 mg−1 at 1.65 V vs. HRE, a reaction activation energy of 4.02 kJ mol−1, Tafel slope of 22 mV dec−1 and an oxidation onset potential of ∼1.35 V vs. HRE which is a significant enhancement for urea oxidation when compared with both bulk Ni(OH)2 and nickel hydroxide-based catalysts published in the literature. Chronoamperometry and impedance analysis of the KNiAlF6 nanosheets reveal lower charge transfer resistance and long-term stability during the prolonged urea electro-oxidation process, particularly at 60 °C. After an extended urea electrolysis process, the structure and morphology of the KNiAlF6 nanosheets were significantly changed due to partial transformation to Ni(OH)2 but the electrochemical activity was sustained. The enhanced electrochemical surface area and the replacement of nickel in the lattice by aluminium make KNiAlF6 nanosheets highly active electrocatalysts for urea oxidation in alkaline solution

Mesoporous Tungsten Trioxide Photoanodes Modified with Nitrogen-Doped Carbon Quantum Dots for Enhanced Oxygen Evolution Photo-Reaction

Nanostructured photoanodes are attractive materials for hydrogen production via water photo-electrolysis process. This study focused on the incorporation of carbon quantum dots doped with nitrogen as a photosensitizer into mesoporous tungsten trioxide photoanodes (N-CQD/meso-WO3) using a surfactant self-assembly template approach. The crystal structure, composition, and morphology of pure and N-CQD- modified mesoporous WO3 photoanodes were investigated using scanning electron and transmission microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. Due to their high surface area, enhanced optical absorption, and charge-carrier separation and transfer, the resulting N-CQD/meso-WO3 photoanodes exhibited a significantly enhanced photocurrent density of 1.45 mA cm−2 at 1.23 V vs. RHE under AM 1.5 G illumination in 0.5 M Na2SO4 without any co-catalysts or sacrificial reagent, which was about 2.23 times greater than its corresponding pure meso-WO3. Moreover, the oxygen evolution onset potential of the N-CQD/meso-WO3 photoanodes exhibited a negative shift of 95 mV, signifying that both the charge-carrier separation and transfer processes were promoted

Characteristics of the voltammetric behavior of the hydroxide ion oxidation at disordered mesoporous titanium dioxide electrocatalyst

The alkaline water electrochemical splitting reactions need economical, very energetic, and durable catalysts. Here, a disordered mesoporous and highly defected titanium dioxide (dom-TiO2) electrocatalyst for the oxidation of hydroxide ion was prepared via ligand-assisted evaporation-induced self-assembly. The (dom-TiO2) electrocatalyst showed significant electrocatalytic performance for the oxidation of hydroxide ion compared to that of non-porous TiO2 (bare-TiO2) and highly-ordered hexagonal mesoporous (hm-TiO2) electrodes. The chemical and electrochemical parameters of the diffusion (D), concentration in the bulk (Cb), the number of transferred electrons (n), rate constant of heterogeneous electron transfer (ks), redox potential (E°), and homogeneous chemical rate constant (kc) for the oxidation of hydroxide ion reaction at the porous TiO2 electrodes were determined via the convolution–deconvolution voltammetry and competed against that of non-porous (bare-TiO2) and hm-TiO2 and catalysts. In addition to the effect of dom-TiO2 film thickness and the type of supporting electrolytes on the electrochemical parameters of the electrocatalytic oxidation of OH– ions have been estimated. The convolutive–deconvoluted results show that the dom-TiO2 electrode catalyst exhibits a superior reaction rate constant among the studied electrodes that depend on the film thickness and type of supporting electrolyte

Bifunctional Electrocatalyst of Low-Symmetry Mesoporous Titanium Dioxide Modified with Cobalt Oxide for Oxygen Evolution and Reduction Reactions

Hybrids of low-symmetry (disordered) mesoporous titanium dioxide modified with different weight ratios of cobalt oxide nanoparticles (Co3O4(x)/lsm-TiO2) are prepared using a one-pot self-assembly surfactant template. The physicochemical characterization of Co3O4(x)/lsm-TiO2 hybrids by scanning and transmission electron microscopy, X-ray diffraction, N2 adsorption–desorption isotherms, and X-ray photoelectron spectroscopy confirm the successful incorporation of cobalt oxide nanoparticles (2–3 nm in diameter) with preservation of the highly mesoporous structure of titanium dioxide substrate. Among these mesoporous hybrids, the ~3.0 wt.% Co3O4/lsm-TiO2 exhibits the best performance toward both the oxygen evolution (OER) and reduction (ORR) reactions in alkaline solution. For the OER, the hybrid shows oxidation overpotential of 348 mV at 10 mA cm−2, a turnover frequency (TOF) of 0.034 s−1, a Tafel slope of 54 mV dec−1, and mass activity of 42.0 A g−1 at 370 mV. While for ORR, an onset potential of 0.84 V vs. RHE and OER/ORR overpotential gap (ΔE) of 0.92 V are achieved which is significantly lower than that of commercial Pt/C, hexagonal mesoporous, and bulk titanium dioxide analogous. The Co3O4/lsm-TiO2 hybrid demonstrates significantly higher long-term durability than IrO2. Apparently, such catalytic activity performance originates from the synergetic effect between Co3O4 and TiO2 substrate, in addition to higher charge carrier density and the presence of disordered mesopores which provide short ions diffusion path during the electrocatalytic process

Facile Synthesis, Characterization, Photocatalytic Activity, and Cytotoxicity of Ag-Doped MgO Nanoparticles

Due to unique physicochemical properties, magnesium oxide nanoparticles (MgO NPs) have shown great potential for various applications, including biomedical and environmental remediation. Moreover, the physiochemical properties of MgO NPs can be tailored by metal ion doping that can be utilized in photocatalytic performance and in the biomedical field. There is limited study on the photocatalytic activity and biocompatibility of silver (Ag)-doped MgO NPs. This study was planned for facile synthesis, characterization, and photocatalytic activity of pure and silver (Ag)-doped MgO NPs. In addition, cytotoxicity of pure and Ag-doped MgO NPs was assessed in human normal umbilical vein endothelial cells (HUVECs). Pure MgO NPs and Ag-doped (1, 2, 5, and 7.5 mol%) MgO NPs were prepared via a simple sol-gel procedure. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR), photoluminescence (PL), and X-ray photoelectron spectroscopy (XPS) were used to characterize the prepared samples. XRD results showed the preparation of highly crystalline NPs with no impurity peaks. TEM and SEM studies indicate smooth surfaces with almost spherical morphology of MgO NPs, and Ag-doping did not change the morphology. Elemental composition study suggested that Ag is uniformly distributed in MgO particles. Intensity of the PL spectra of MgO NPs decreased with increasing the concentration of Ag dopants. In comparison to pure MgO NPs, Ag-MgO NPs showed higher degradation of methylene blue (MB) dye under UV irradiation. The improved photocatalytic activity of Ag-MgO NPs was related to the effect of dopant concentration on reducing the recombination between electrons and holes. Cytotoxicity studies showed good biocompatibility of pure and Ag-doped MgO NPs with human normal umbilical vein endothelial cells (HUVECs). These results highlighted the potential of Ag-doped MgO NPs in environmental remediation

Boosting the Photoelectrochemical Water Oxidation Performance of TiO2 Nanotubes by Surface Modification Using Silver Phosphate

Photoelectrocatalytic approaches are fascinating options for long-lasting energy storage through the transformation of solar energy into electrical energy or hydrogen fuel. Herein, we report a facile method of fabricating a composite electrode of well-aligned TiO2 nanotubes (TNTs) decorated with photodeposited silver phosphate (Ag3PO4) nanoparticles. Assessment of the optical, physiochemical and photoelectrochemical features demonstrated that the fabricated TNTs/Ag3PO4 films showed a substantially boosted photocurrent response of 0.74 mA/cm2, almost a 3-fold enrichment in comparison with the pure TNTs. Specifically, the applied bias photon-to-current efficiency of the fabricated TNTs/Ag3PO4 composite electrode was 2.4-fold superior to that of the pure TNTs electrode. In these TNTs/Ag3PO4 photoanodes, the introduction of Ag3PO4 over TNTs enhanced light absorption and improved charge transfer and surface conductivity. The developed process can be generally applied to designing and developing efficient contact interfaces between photoanodes and numerous cocatalysts

Boosting the Photoelectrochemical Water Oxidation Performance of TiO₂ Nanotubes by Surface Modification Using Silver Phosphate

Photoelectrocatalytic approaches are fascinating options for long-lasting energy storage through the transformation of solar energy into electrical energy or hydrogen fuel. Herein, we report a facile method of fabricating a composite electrode of well-aligned TiO2 nanotubes (TNTs) decorated with photodeposited silver phosphate (Ag3PO4) nanoparticles. Assessment of the optical, physiochemical and photoelectrochemical features demonstrated that the fabricated TNTs/Ag3PO4 films showed a substantially boosted photocurrent response of 0.74 mA/cm2, almost a 3-fold enrichment in comparison with the pure TNTs. Specifically, the applied bias photon-to-current efficiency of the fabricated TNTs/Ag3PO4 composite electrode was 2.4-fold superior to that of the pure TNTs electrode. In these TNTs/Ag3PO4 photoanodes, the introduction of Ag3PO4 over TNTs enhanced light absorption and improved charge transfer and surface conductivity. The developed process can be generally applied to designing and developing efficient contact interfaces between photoanodes and numerous cocatalysts