Enhancement of Oxidation Efficiency of Elemental Mercury by CeO2/TiO2 at Low Temperatures Governed by Different Mechanisms.
ABSTRACT: This study aims to investigate the photothermal oxidation removal of Hg0 in simulated flue gases using photothermal catalysts at relatively low temperatures of 120-160 °C in two phases: the first phase applied the sol-gel method to prepare TiO2 and CeO2/TiO2 photothermal catalysts and characterized surface properties by specific surface area analysis, X-ray diffraction, X-ray photoelectron spectroscopy (XPS), and photoluminescence spectroscopy. The second phase investigated the effects of operating parameters on Hg0 oxidation efficiency at lower temperatures of 100-160 °C. The operating parameters included reaction temperatures and modified concentrations of CeO2. Experimental results indicated that TiO2 prepared by the sol-gel method was mainly in the anatase phase. XPS analysis showed that Ce mostly existed in the form of Ce4+. The content of surface-chemisorbed oxygen increased with the modification amount of CeO2. Photothermal catalytic oxidation results indicated that CeO2/TiO2 had a much higher oxidation efficiency of Hg0 at 120-160 °C than neat TiO2, which increased from 30-60 to >90%. 7%CeO2/TiO2 not only had the best photothermal performance but also maintained high efficiency at a relatively higher reaction temperature of 160 °C.
Project description:Whilst the highest power conversion efficiency (PCE) perovskite solar cell (PSC) devices that have reported to date have been fabricated by high temperature sintering (>500 °C) of mesoporous metal oxide scaffolds, lower temperature processing is desirable for increasing the range of substrates available and also decrease the energy requirements during device manufacture. In this work, titanium dioxide (TiO2) mesoporous scaffolds have been compared with metal oxide oxidation catalysts: cerium dioxide (CeO2) and manganese dioxide (MnO2). For MnO2, to the best of our knowledge, this is the first time a low energy band gap metal oxide has been used as a scaffold in the PSC devices. Thermal gravimetric analysis (TGA) shows that organic binder removal is completed at temperatures of 350 °C and 275 °C for CeO2 and MnO2, respectively. By comparison, the binder removal from TiO2 pastes requires temperatures >500 °C. CH3NH3PbBr3 PSC devices that were fabricated while using MnO2 pastes sintered at 550 °C show slightly improved PCE (? = 3.9%) versus mesoporous TiO2 devices (? = 3.8%) as a result of increased open circuit voltage (Voc). However, the resultant PSC devices showed no efficiency despite apparently complete binder removal during lower temperature (325 °C) sintering using CeO2 or MnO2 pastes.
Project description:To eliminate nitrogen oxides (NOx), a series of highly ordered mesoporous WO3(?)-CeO2 nanomaterials (? represents the mole ratio of W/Ce) were synthesized by using KIT-6 as a hard template, which was used for selective catalytic reduction (SCR) to remove NOx with NH3 at low temperatures. Moreover, the nanomaterials were characterized by TEM, XRD, Raman, XPS, BET, H2-TPR, NH3-TPD and in situ DRIFTS. It can be found that all of the prepared mesoporous WO3(?)-CeO2 (? = 0, 0.5, 0.75, 1 and 1.25) showed highly ordered mesoporous channels. Furthermore, mesoporous WO3(1)-CeO2 exhibited the best removal efficiency of NOx, and its NOx conversion ratio could reach 100% from 225 ° C to 350 ° C with a gas hourly space velocity of 30 000 h-1, which was due to higher Ce3+ concentrations, abundant active surface oxygen species and Lewis acid sites based on XPS, H2-TPR, NH3-TPD and in situ DRIFTS. In addition, several key performance parameters of mesoporous WO3(1)-CeO2, such as superior water resistance, better alkali metal resistance, higher thermal stability and N2 selectivity, were systematically studied, indicating that the synthesized mesoporous WO3(1)-CeO2 has great potential for industrial applications.
Project description:In this work, we compare the CO oxidation performance of Pt single atom catalysts (SACs) prepared via two methods: (1) conventional wet chemical synthesis (strong electrostatic adsorption-SEA) with calcination at 350?°C in air; and (2) high temperature vapor phase synthesis (atom trapping-AT) with calcination in air at 800?°C leading to ionic Pt being trapped on the CeO2 in a thermally stable form. As-synthesized, both SACs are inactive for low temperature (<150?°C) CO oxidation. After treatment in CO at 275?°C, both catalysts show enhanced reactivity. Despite similar Pt metal particle size, the AT catalyst is significantly more active, with onset of CO oxidation near room temperature. A combination of near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) and CO temperature-programmed reduction (CO-TPR) shows that the high reactivity at low temperatures can be related to the improved reducibility of lattice oxygen on the CeO2 support.
Project description:Ag-based catalysts with different supports (TiO2, Al2O3 and CeO2) were prepared by impregnation method and subsequently tested for the catalytic oxidation of formaldehyde (HCHO) at low temperature. The Ag/TiO2 catalyst showed the distinctive catalytic performance, achieving the complete HCHO conversion at around 95 °C. In contrast, the Ag/Al2O3 and Ag/CeO2 catalysts displayed much lower activity and the 100% conversion was reached at 110 °C and higher than 125 °C, respectively. The Ag-based catalysts were next characterized by several methods. The characterization results revealed that supports have the dramatic influence on the Ag particle sizes and dispersion. Kinetic tests showed that the Ag based catalyst on the TiO2, Al2O3 or CeO2 supports have the similar apparent activation energy of 65 kJ mol(-1), indicating that the catalytic mechanism keep immutability over these three catalysts. Therefore, Ag particle size and dispersion was confirmed to be the main factor affecting the catalytic performance for HCHO oxidation. The Ag/TiO2 catalyst has the highest Ag dispersion and the smallest Ag particle size, accordingly presenting the best catalytic performance for HCHO oxidation.
Project description:Titanium dioxide doped with the Pt ion (Pt-TiO2) was synthesized by a sol-gel method using only water as the solvent and conducting dialysis. The photocatalytic activity for the degradation of 4-chlorophenol (4-CP) on Pt-TiO2 was not affected by the Brunauer-Emmett-Teller specific surface area under visible light (VL) irradiation. X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure measurements revealed that only the Pt(IV) ion existed in the TiO2 bulk and both Pt(II) and Pt(IV) were present near the Pt-TiO2 surface. Pt(IV) is most likely substituted in the Ti(IV) site of the TiO2 lattice because of their similar ionic sizes. Quantitative analysis of Pt(II) was performed in the XPS measurements, indicating that the amount of Pt(II) on the surface increased with an increase in the doping amount from 0.2 to 1.0 atom %. We synthesized 0.5 atom % Pt-TiO2 with various Pt(II)/Pt(IV) ratios by changing the Ti(OC3H7)4 concentration used in the sol-gel synthesis. The 4-CP conversion on Pt-TiO2 increased linearly with an increase in the Pt(II)/Pt(IV) ratios. A similar relationship was obtained with Pt-TiO2, which was prepared by a conventional sol-gel method in ethanol-water mixed solvent. Therefore, the Pt(II)/Pt(IV) ratio is a key factor affecting the photocatalytic activity of Pt-TiO2 under VL irradiation. Our results indicate that controlling the mixed valence states of the doped metal ions is a new strategy to developing highly active metal-ion-doped TiO2 under VL irradiation.
Project description:Nd-modified TiO2 photocatalysts have been obtained via hydrothermal (HT) and sol-hydrothermal (SHT) methods. The as-prepared samples were characterized by X-ray diffraction (XRD), BET surface area measurements, scanning electron microscopy (SEM), diffuse reflectance spectroscopy (DRS), luminescence spectroscopy and X-ray photoelectron spectroscopy (XPS). The photocatalytic activity of the synthesized samples was evaluated by the degradation of phenol in aqueous solution under irradiation with UV-vis (λ > 350 nm) and vis (λ > 420 nm) light, as well as by the degradation of gaseous toluene under irradiation with vis (λmax = 415 nm) light. It was found that Nd-modified TiO2 is an efficient photocatalyst for the degradation of phenol and toluene under visible light. XPS analysis revealed that the photocatalyst prepared via HT method contains a three-times higher amount of hydroxy groups at the surface layer and a two-times higher amount of surface defects than that obtained by the SHT method. The photocatalytic efficiency of phenol and toluene degradation under vis irradiation in the presence of 0.25% Nd-TiO2(HT) reached 0.62 and 3.36 μmol·dm-1·min-1, respectively. Photocatalytic activity tests in the presence of Nd-TiO2 and scavenger confirm that superoxide radicals were responsible for the visible light-induced degradation of the model pollutant in aqueous solution.
Project description:The performance of dye-sensitized solar cells (DSCs) critically depends on the efficiency of electron transport within the TiO2-dye-electrolyte interface. To improve the efficiency of the electron transfer the conventional structure of the working electrode (WE) based on TiO2 nanoparticles (NPs) was replaced with TiO2 nanotubes (NTs). Sol-gel method was used to prepare undoped and Nb-doped TiO2 NPs and TiO2 NTs. The crystallinity and morphology of the WEs were characterized using XRD, SEM and TEM techniques. XPS and PL measurements revealed a higher concentration of oxygen-related defects at the surface of NPs-based electrodes compared to that based on NTs. Replacement of the conventional NPs-based TiO2 WE with alternative led to a 15% increase in power conversion efficiency (PCE) of the DSCs. The effect is attributed to the more efficient transfer of charge carriers in the NTs-based electrodes due to lower defect concentration. The suggestion was confirmed experimentally by electrical impedance spectroscopy measurements when we observed the higher recombination resistance at the TiO2 NTs-electrolyte interface compared to that at the TiO2 NPs-electrolyte interface. Moreover, Nb-doping of the TiO2 structures yields an additional 14% PCE increase. The application of Nb-doped TiO2 NTs as photo-electrode enables the fabrication of a DSC with an efficiency of 8.1%, which is 35% higher than that of a cell using a TiO2 NPs. Finally, NTs-based DSCs have demonstrated a 65% increase in the PCE value, when light intensity was decreased from 1000 to 10 W/m2 making such kind device be promising alternative indoor PV applications when the intensity of incident light is low.
Project description:Ultraviolet (UV)-durable superhydrophobic nanocomposite thin films have been successfully fabricated on aluminum substrates by embedding cobalt stearate (CoSA)-coated TiO2 nanoparticles in a hydrophobic polymethylhydrosiloxane (PMHS) matrix (PMHS/TiO2@CoSA) using the sol-gel process. When compared to the sharp decrease of water contact angle (WCA) on the superhydrophobic PMHS/TiO2 thin films, the PMHS/TiO2@CoSA superhydrophobic thin films exhibited a nearly constant WCA of 160° under continuous UV irradiation for more than 1 month. The designed scheme of the TiO2@CoSA core-shell structure not only increased the hydrophobic properties of the TiO2 nanoparticle surface but also confined the photocatalytic efficiency of TiO2 nanoparticles. A plausible model has been suggested to explain the UV-durable mechanism of the superhydrophobic nanocomposite thin films based on PMHS/TiO2@CoSA. Furthermore, the elongated lifetime in the exposure of the solar light imparts this superhydrophobic nanocomposite thin film with potential practical applications where UV-resistant properties are emphasized including corrosion-resistant building walls, anti-icing airplanes, self-cleaning vehicles, and so forth.
Project description:In this study, the in situ sol-gel method has been deployed to prepare the titanium dioxide/multiwalled carbon nanotubes (TiO2/MWCNTs) nanocomposite (NCs) powders with varying content of MWCNTs (0.01-1.0 wt %), to construct the dye-sensitized solar cells (DSSCs). First, binder-free NCs were deposited on a transparent-conducting F:SnO2 (FTO) glass substrate by a doctor-blade technique and then anchored with Ru(II)-based dyes to either N719 or ruthenium phthalocyanine (RuPc). The structural and optical properties and interconnectivity of the materials within the composite are investigated thoroughly by various spectral techniques (XRD, XPS, Raman, FT-IR, and UV-vis), electron microscopy (HRTEM), and BET analysis. The experimental results suggest that the ratio of MWCNTs and TiO2 in NCs, morphology, and their interconnectivity influenced their structural, optical, and photovoltaic properties significantly. Finally, the photovoltaic performances of the assembled DSSCs with different content of MWCNTs to TiO2 films anchored with two different dyes were tested under one sun irradiation (100 mW/cm2). The measured current-voltage (IV) curve and incident photon-to-current conversion efficiency (IPCE) spectra of TiO2/0.1 wt % MWCNTs (T@0.1 C) for N719 dye show three times more power conversion efficiency (? = 6.21%) which is opposed to an efficiency (? = 2.07%) of T@0.1 C for RuPc dye under the same operating conditions.
Project description:Ordered nanoperforated TiO2 monolayers fabricated through sol-gel chemistry were used to grow isolated particles of Prussian blue analogues (PBA). The elaboration of the TiO2/CoFe PBA nanocomposites involves five steps. The samples were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), infrared spectroscopy and X-ray photoelectron spectroscopy (XPS) all along the synthesis process. Selected physico-chemical parameters have been varied in order to determine the key steps of the synthesis process and to optimize it. This study is an important step towards the full control of the fabrication process.