Mechanism insights into CO oxidation over transition metal modified V2O5/TiO2 catalysts: A theoretical study.

The V2O5/TiO2 based selective catalytic reduction (SCR) catalysts possess not only promising capability on the denitrification of nitrogen oxides (NOx), but also certain effects on the oxidation of carbon monoxide (CO) in the flue gas. Modification of traditional SCR catalysts with certain transition metals can further improve their catalytic oxidation ability of CO. Therefore, it is of great significance to reveal the catalytic oxidation mechanism of CO for developing modified SCR catalysts to achieve the co-removal of CO and NOx. Theoretical calculations based on density functional theory (DFT) were performed to probe the comprehensive reaction mechanism of CO oxidation on M doped V2O5/TiO2 catalysts (M = Mo, Fe, and Co). The whole CO oxidation cycles include three stages, i.e., the first CO oxidation, the re-oxidation of the surface, and the second CO oxidation. The terminal oxygen and the surface oxygen formed by the adsorbed O2 all play vital roles in the whole CO oxidation cycles. The activation barriers of the rate-determining steps for CO oxidation on Fe-V2O5/TiO2 and Co-V2O5/TiO2 are much lower than that of Mo-V2O5/TiO2, which indicates Fe and Co dopants can apparently promote the CO oxidation activities of the modified SCR catalysts. Meanwhile, the electronic structure analysis confirms that Fe and Co dopants can cause electron distribution change with strong oxidation ability at the active oxygen sites.

Like Cures like: Detoxification Effect between Alkali Metals and Sulfur over the V2O5/TiO2 deNOx Catalyst.

The V2O5/TiO2 (VTi) catalyst has been widely employed for the NH3 selective catalytic reduction (NH3-SCR) reaction, and sulfur (S) and alkali metals (K) were usually considered as poisons during this reaction. In this work, the synergistic effect of S and K over the VTi catalyst for the NH3-SCR reaction was analyzed and discussed. It is surprisingly observed that the synergistic effects of S and K exhibited a detoxification effect on the NH3-SCR reaction. That is, although the VTi catalyst exhibited moderate resistance to S poisoning and unsatisfactory resistance to K deactivation, the SCR activity was restored to close to fresh VTi when K and S coexisted. This detoxification effect also could occur between other alkali metals (e.g., Ca and Na) and sulfur. X-ray photoelectron spectroscopy and charge density difference studies both indicate that the introduction of K could significantly affect the electronic structure of V, but this toxic effect was recovered by the further addition of S because of the strong interaction between S and K. Therefore, this detoxification effect can occur in the practical reaction atmosphere, which alleviates the alkali metal poisoning of commercial catalysts.

Dynamic Change of Active Sites of Supported Vanadia Catalysts for Selective Catalytic Reduction of Nitrogen Oxides.

Selective catalytic reduction of NOx by ammonia (NH3-SCR) on V2O5/TiO2 catalysts is a widely used commercial technology in power plants and diesel vehicles due to its high elimination efficiency for NOx removal. However, the mechanistic aspects of the NH3-SCR reaction, especially the active sites on the V2O5/TiO2 catalysts, are still a puzzle. Herein, using combined operando spectroscopy and density functional theory calculations, we found that the reactivity of the Lewis acid site was significantly overestimated due to its conversion to the Brønsted acid site. Such interconversion makes it challenging to measure the intrinsic reactivity of different acid sites accurately. In contrast, the abundant V-OH Brønsted acid sites govern the overall NOx reduction rate in realistic exhaust containing water vapor. Moreover, the vanadia species cycle between V5+═O and V4+-OH during NOx reduction, and the re-oxidation of V4+ species to form V5+ is the rate-determining step.

Photo- and thermo-catalytic mechanisms for elemental mercury removal by Ce doped commercial selective catalytic reduction catalyst (V2O5/TiO2).

The elemental mercury was catalytically removed by V2O5/TiO2 and Ce doped V2O5/TiO2 catalysts under the UV irradiation at 30-160 °C to determine whether the catalysts could simultaneously have both thermo- and photo-catalytic activities. The physicochemical properties of catalysts were characterized by XRD, SEM, EDX, BET, XPS, UV-visible, PER and EIS. The experimental results demonstrated that V2O5/TiO2 and Ce-doped catalysts possessed both thermo- and photo-catalytic reactivities. A suitable reaction temperature (120 °C) and UV light had promoting effects on mercury removal efficiency. In addition, owing to the high oxidation capability as well good oxygen storage performance of Ce4+, Ce doping could greatly improve the mercury removal properties of the catalyst, reduce the inhibition of SO2 and make NO the component with enhanced effect. Ce doping also had the capability of enhancing the light absorption intensity in the UV region as well as the separation rate of photoinduced carriers. Finally, DFT calculations of V-Ti and Ce-V-Ti for Hg0 removal were investigated to further verify the experimental conclusion.

Precise control of heat-treatment conditions to improve the catalytic performance of V2O5/TiO2 for H2S removal.

The purpose of this study is to investigate the influences of atmospheric gas and temperature while preparing V2O5/TiO2 catalysts to find a suitable heat-treatment method to improve catalytic performance during the process of H2S removal. The catalysts prepared by wet-impregnation were heat-treated at different temperatures (400 or 600 â„ƒ) under various atmospheres (Air, N2, or H2). The catalytic tests demonstrated that the catalyst heat-treated at 400 â„ƒ under N2 atmosphere (N-400) possessed excellent catalytic activities regarding H2S conversion (96.4%) and sulfur yield (89.1%). The characterization results revealed that the mild reducing condition employed for N-400 led to the formation of partially reduced V2O5 crystals and a strong V-Ti interaction owing to the anatase TiO2 phase, resulting in the high oxygen vacancies on the catalyst surface. However, severe reducing conditions (H2 or N2 with 600 â„ƒ) or the higher temperature (600 â„ƒ) induced highly reduced V2O5-x or rutile TiO2 related to a weak V-Ti interaction, respectively, which facilitated lower oxygen vacancies. This study is the first to demonstrate the significance of a precisely controlled heat-treatment to enhance catalytic performance for H2S removal.

Ti3+ doped V2O5/TiO2 catalyst for efficient selective catalytic reduction of NOx with NH3.

The effect of self-doping Ti3+ into V2O5/TiO2 catalysts on the activity of the catalysts was assessed by the selective catalytic reduction of NOX with NH3 (NH3-SCR). 0.2-V2O5/TiO2 (Al(acac)3:TBOT = 0.2%) catalyst had the highest catalytic activity at low-temperature range. The as-prepared catalysts are characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), H2 temperature-programmed reduction (H2-TPR), NH3 temperature-programmed desorption (NH3-TPD), surface area and pore structure. XPS and EPR were used to confirm the existence of Ti3+ and oxygen vacancy in the catalysts. The specific surface area, surface acidity, reducibility and valence state of the active components of the catalysts are significantly affected by the self-doping of Ti3+. This work would lead to a new strategic design of Ti3+ self-doped catalysts with fine structure and that can efficiently improve low-temperature SCR performance.

Porous V2O5/TiO2 Nanoheterostructure Films with Enhanced Visible-Light Photocatalytic Performance Prepared by the Sparking Method.

Porous V2O5/TiO2 nanoheterostructure films with different atomic ratios of Ti/V (4:1, 2:1, 1:1, and 1:2) were synthesized by a sparking method for the first time. The sparking method, which is a simple and cost-effective process, can synthesize highly porous and composite films in one step. Field-emission scanning electron microscope (FE-SEM) images revealed the porosity morphology of all prepared samples. V2O5/TiO2 nanoheterostructure films were confirmed by Raman spectroscopy, high-resolution transmission electron microscopy (HRTEM), and X-ray photoelectron spectroscopy (XPS). The secondary particle size and band gap of the samples were highly correlated to the V2O5 proportion, resulting in enhanced visible-light absorbance. V2O5/TiO2 nanoheterostructure films at an atomic ratio of 1:1 showed the highest photocatalytic performance, which improved the degradation rate up to 24% compared to pure TiO2 film. It is believed that the formed nanoheterostructure and greater portion of V4+ ions are reflected by this ratio.

Effects of MoO3 and CeO2 doping on the decomposition and reactivity of NH4HSO4 on V2O5/TiO2 catalysts.

The deposition of NH4HSO4 on catalysts is one of the key issues for selective catalytic reduction of NOx. In this study, NH4HSO4 was preloaded on catalysts, and the effects of MoO3 and CeO2 doping on the decomposition and reactivity of NH4HSO4 on V2O5/TiO2 catalysts are studied. The results show that the introduction of MoO3 and CeO2 significantly promoted NOx conversion on the V2O5/TiO2 catalysts. Doping with MoO3 could effectively enhance the S and H2O resistance of the catalysts. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analysis indicate that it is the strong chemical interactions between NH4HSO4 and the catalysts that are adverse to the decomposition of NH4HSO4. However, doping with MoO3 apparently inhibits these interactions, which significantly decrease the decomposition temperature of NH4HSO4. In situ FTIR experiments show that the NH4+ in preloaded NH4HSO4 could react with gaseous NO on catalysts, and doping with MoO3 could facilitate the reaction rate.

Modeling and optimization of V2O5/TiO2 nanocatalysts for NH3-Selective catalytic reduction (SCR) of NOx by RSM and ANN techniques.

In the present study, two statistical methods including the response surface method (RSM) and artificial neural network (ANN), were employed for modeling and optimization of selective catalytic reduction of NOx with NH3 (NH3-SCR) over V2O5/TiO2 nanocatalysts. The relationship between catalyst preparation variables, such as metal loading, impregnation temperature, and calcination temperature on NO conversion were investigated. The R2 value of 0.9898 was obtained for quadratic a RSM model, which proves the high agreement of the model with the experimental data. The results of Pareto analysis revealed that three factors including calcination temperature, V loading, and impregnation temperature have a considerable impact on the response. Deduced from the established RSM model, the order of influence on the NO conversion was as follows: calcination followed by V loading and impregnation temperature. The optimum condition of catalyst preparation for maximum NO conversion over V2O5/TiO2 nanocatalysts was predicted to be at 0.0051 mol of V loading, an impregnation temperature of 50 °C and a calcination temperature of 491 °C. Moreover, an ANN model was created by a feed-forward back propagation network (with the topology 4, 12 and 1) to model the relation between the selected catalyst preparation variables and NH3-SCR process temperature. The R2 values for training, validation as well as test sets, were 0.99, 0.9810 and 0.9733. These high values proved the accuracy of the AAN model in modeling and estimating the NO conversion over V2O5/TiO2 nanocatalysts. According to the ANN model, the relative significance of each variable on NO conversion is calcination temperature, process temperature loading, and impregnation temperature from high to low importance, respectively, corroborating the obtained results from RSM.

Chemisorption and kinetic mechanisms of elemental mercury on immobilized V2O5/TiO2 at low temperatures.

To investigate the effect of low temperature and catalyst filling pattern on the adsorption of Hg° by DeNOx equipment, the chemisorption and kinetic mechanisms of Hg° adsorption on 5-30%V2O5/TiO2 immobilized on glass beads at 100-160 °C were investigated. The effects of the reaction temperature, influent Hg° concentration, and V2O5 doping amount on the adsorption efficiency and capacity for Hg° were explored. The active sites for Hg° adsorption were further identified. Additionally, the adsorption kinetics were modelled using the linear driving force approximation, Fick's diffusion model, and pseudo-second-order kinetic model. Finally, the influence of immobilization on the adsorption of Hg° was also investigated. Experimental results showed that the bridged oxygen atom of V-O-V played a key role in the adsorption of Hg°. The Hg° adsorption efficiencies decreased from >90% to 40% as the reaction temperature increased from 120 °C to 160 °C for 20%V2O5/TiO2, while the adsorptive capacities for Hg° were highly influenced by the influent Hg° concentration and V2O5 doping amount. 20%V2O5/TiO2 had the highest adsorptive capacity of 2547 µg Hg°/g V2O5/TiO2 at 160 °C. The kinetic results showed that the linear driving force approximation model fit the Hg° adsorption better than the other models. The diffusion resistance increased significantly for the immobilized catalysts because the external mass transfer coefficient decreased by more than 1200-fold.

Growth, Structure, and Photocatalytic Properties of Hierarchical V2O5-TiO2 Nanotube Arrays Obtained from the One-step Anodic Oxidation of Ti-V Alloys.

V2O5-TiO2 mixed oxide nanotube (NT) layers were successfully prepared via the one-step anodization of Ti-V alloys. The obtained samples were characterized by scanning electron microscopy (SEM), UV-Vis absorption, photoluminescence spectroscopy, energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (DRX), and micro-Raman spectroscopy. The effect of the applied voltage (30-50 V), vanadium content (5-15 wt %) in the alloy, and water content (2-10 vol %) in an ethylene glycol-based electrolyte was studied systematically to determine their influence on the morphology, and for the first-time, on the photocatalytic properties of these nanomaterials. The morphology of the samples varied from sponge-like to highly-organized nanotubular structures. The vanadium content in the alloy was found to have the highest influence on the morphology and the sample with the lowest vanadium content (5 wt %) exhibited the best auto-alignment and self-organization (length = 1 µm, diameter = 86 nm and wall thickness = 11 nm). Additionally, a probable growth mechanism of V2O5-TiO2 nanotubes (NTs) over the Ti-V alloys was presented. Toluene, in the gas phase, was effectively removed through photodegradation under visible light (LEDs, λmax = 465 nm) in the presence of the modified TiO2 nanostructures. The highest degradation value was 35% after 60 min of irradiation. V2O5 species were ascribed as the main structures responsible for the generation of photoactive e- and h⁺ under Vis light and a possible excitation mechanism was proposed.

Removal of elemental mercury by TiO2doped with WO3 and V2O5 for their photo- and thermo-catalytic removal mechanisms.

The catalytic removal of Hg(0) was investigated to ascertain whether the catalysts could simultaneously possess both thermo- and photo-catalytic reactivity. The immobilized V2O5/TiO2 and WO3/TiO2 catalysts were synthesized by sol-gel method and then coated on the surface of glass beads for catalytic removal of Hg(0). They were also characterized by SEM, BET, XRD, UV-visible, and XPS analysis, and their catalytic reactivity was tested under 100-160 °C under the near-UV irradiation. The results indicated that V2O5/TiO2 solely possessed the thermo-catalytic reactivity while WO3/TiO2 only had photo-catalytic reactivity. Although the synthesis catalytic reactivity has not been found for these catalysts up to date, but compared with TiO2, the removal efficiencies of Hg(0) at 140 and 160 °C were enhanced; particularly, the efficiency was improved from 20 % at 160 °C by TiO2 to nearly 90 % by WO3/TiO2 under the same operating conditions. The effects of doping amount of V2O5 and WO3 were also investigated, and the results showed that 10 % V2O5 and 5 % WO3/TiO2 were the best immobilized catalysts for thermo- and photo-catalytic reactivity, respectively. The effect of different influent concentrations of Hg(0) was demonstrated that the highest concentration of Hg(0) led to the best removal efficiencies for V2O5/TiO2 and WO3/TiO2 at 140 and 160 °C, because high Hg(0) concentration increased the mass transfer rate of Hg(0) toward the surface of catalysts and drove the reaction to proceed. At last, the effect of single gas component on the removal of Hg(0) was also investigated.

Effects of PbCl2 on selective catalytic reduction of NO with NH3 over vanadia-based catalysts.

The effects of PbCl2 on the selective catalytic reduction of NO with NH3 over vanadia-based catalysts were studied with BET, XRD, SEM, XPS, NH3-TPD, NH3 chemisorption, FT-IR and catalytic activity measurements. The results showed that PbCl2 deactivated the catalysts to a very high extent. The doping of PbCl2 could decrease the surface acidity, especially that of Brønsted acid sites. XPS characterization reveals that the presence of PbCl2 resulted in the transformation of V(5+) into V(4+), which decreased the reducibility of vanadia species. Based on the analysis of physical and chemical properties of the catalysts, the PbCl2-poisoning mechanism model of the vanadia-based SCR catalysts was proposed.