Effects of SO2 on selective catalytic reduction of NO with NH3 over a TiO2 photocatalyst

Abstract

The effect of SO₂ gas was investigated on the activity of the photo-assisted selective catalytic reduction of nitrogen monoxide (NO) with ammonia (NH₃) over a TiO₂ photocatalyst in the presence of excess oxygen (photo-SCR). The introduction of SO₂ (300 ppm) greatly decreased the activity of the photo-SCR at 373 K. The increment of the reaction temperature enhanced the resistance to SO₂ gas, and at 553 K the conversion of NO was stable for at least 300 min of the reaction. X-ray diffraction, FTIR spectroscopy, thermogravimetry and differential thermal analysis, x-ray photoelectron spectroscopy (XPS), elemental analysis and N₂ adsorption measurement revealed that the ammonium sulfate species were generated after the reaction. There was a strong negative correlation between the deposition amount of the ammonium sulfate species and the specific surface area. Based on the above relationship, we concluded that the deposition of the ammonium sulfate species decreased the specific surface area by plugging the pore structure of the catalyst, and the decrease of the specific surface area resulted in the deactivation of the catalyst.     

Photo-fixation of SO2 in nanocrystalline TiO2 films prepared by reactive DC magnetron sputtering

We report on photo-fixation of SO₂ onto nanostructured TiO₂ thin films prepared by reactive DC magnetron sputtering. The films were exposed to 50 ppm SO₂ gas mixed in synthetic air and illuminated with UV light at 298 and 473 K. The evolution of the adsorbed SO_x species was monitored by in situ Fourier transform infrared specular reflection spectroscopy. Significant photo-fixation occurred only in the presence of UV illumination. The SO₂ uptake was dramatically enhanced at elevated temperatures and then produced strongly bonded surface-coordinated SO_x complexes. The total SO_x uptake is consistent with Langmuir adsorption kinetics. The sulfur doping at saturation was estimated from X-ray photoelectron spectroscopy to be ~ 2.2 at.% at 473 K. These films were pale yellowish and had an optical absorption coefficient being ~ 3 times higher than in undoped film. The S-doped films exhibit interesting oleophobic properties, exemplified by the poor adherence of stearic acid. Our results suggest a new method for sulfur doping of TiO₂ to achieve combined anti-grease and photocatalytic properties.     

Promotional effects of carbon nanotubes on V2O5/TiO2 for NOX removal

A series of V₂O₅/TiO₂-carbon nanotube (CNT) catalysts were synthesized by sol-gel method, and their activities for NO_X removal were compared. A catalytic promotional effect was observed by adding CNTs to V₂O₅/TiO₂. The catalyst V₂O₅/TiO₂-CNTs (10 wt.%) showed an NO_X removal efficiency of 89% at 300 °C under a GHSV of 22,500 h⁻¹. Based on X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, NH₃-temperature-programmed desorption, temperature-programmed reduction, Brunauer-Emmett-Teller surface area measurements, differential scanning calorimetry, and thermogravimetric analysis, the increased acidity and reducibility, which could promote NH₃ adsorption and oxidation of NO to NO₂, respectively, contributed to this promotion.     

High-throughput technology for novel SO2 oxidation catalysts

We review the state of the art and explain the need for better SO₂ oxidation catalysts for the production of sulfuric acid. A high-throughput technology has been developed for the study of potential catalysts in the oxidation of SO₂ to SO₃. High-throughput methods are reviewed and the problems encountered with their adaptation to the corrosive conditions of SO₂ oxidation are described. We show that while emissivity-corrected infrared thermography (ecIRT) can be used for primary screening, it is prone to errors because of the large variations in the emissivity of the catalyst surface. UV-visible (UV-Vis) spectrometry was selected instead as a reliable analysis method of monitoring the SO₂ conversion. Installing plain sugar absorbents at reactor outlets proved valuable for the detection and quantitative removal of SO₃ from the product gas before the UV-Vis analysis. We also overview some elements used for prescreening and those remaining after the screening of the first catalyst generations.     

Simultaneous absorption of NOx and SO2 from flue gas with pyrolusite slurry combined with gas-phase oxidation of NO using ozone

NO was oxidized into NO₂ first by injecting ozone into flue gas stream, and then NO₂ was absorbed from flue gas simultaneously with SO₂ by pyrolusite slurry. Reaction mechanism and products during the absorption process were discussed in the followings. Effects of concentrations of injected ozone, inlet NO, pyrolusite and reaction temperature on NO_x/SO₂ removal efficiency and Mn extraction rate were also investigated. The results showed that ozone could oxidize NO to NO₂ with selectivity and high efficiency, furthermore, MnO₂ in pyrolusite slurry could oxidize SO₂ and NO₂ into MnSO₄ and Mn(NO₃)₂ in liquid phase, respectively. Temperature and concentrations of injected ozone and inlet NO had little impact on both SO₂ removal efficiency and Mn extraction rate. Specifically, Mn extraction rate remained steady at around 85% when SO₂ removal efficiency dropped to 90%. NO_x removal efficiency increased with the increasing of ozone concentration, inlet NO concentration and pyrolusite concentration, however, it remained stable when reaction temperature increased from 20 °C to 40 °C and decreased when the flue gas temperature exceeded 40 °C. NO_x removal efficiency reached 82% when inlet NO at 750 ppm, injected ozone at 900 ppm, concentration of pyrolusite at 500 g/L and temperature at 25 °C.     

Effects of particulates, heavy metals and acid gas on the removals of NO and PAHs by V2O5–WO3 catalysts in waste incineration system

This study investigated the activities of prepared and commercial V₂O₅–WO₃ catalysts for simultaneous removals of NO and polycyclic aromatic hydrocarbons (PAHs) and the influences of particulates, heavy metals, SO₂, and HCl on the performances of catalysts. The experiments were carried out in a laboratory-scale waste incineration system equipped with a catalyst reactor. The DREs of PAHs by prepared and commercial V₂O₅–WO₃ catalysts were 64% and 72%, respectively. Increasing the particulate concentrations in flue gas suppressed the DRE of PAHs, but increasing the carbon content on surface of catalysts promotes the NO conversions. The DRE of PAHs by the catalysts was significantly decreased by the increased concentrations of heavy metal Cd, but was promoted by high concentration of Pb. The influence level of SO₂ was higher than HCl on the performances of V₂O₅–WO₃ catalysts for PAHs removal, but was lower than HCl for NO removal. Prepared and commercial V₂O₅–WO₃ catalysts have similar trends on the effects of particulates, heavy metals, SO₂, and HCl. The results of ESCA analysis reveal that the presences of these pollutants on the surface of catalysts did not change the chemical state of V and W.     

Effect of Co-Mo catalyst preparation and CH4/H2 flow on carbon nanotube synthesis

Abstract

Supported Co-Mo catalysts with a given ratio of metals were prepared from polyoxomolybdate Mo₁₂O₂₈(μ₂-OH)₁₂{Со(H₂O)₃}₄ using impregnation and combustion methods. Effects of the type of catalyst and the ratio and flow of methane and hydrogen gases on the structure of carbon nanotubes (CNTs) synthesized by catalytic chemical vapor deposition (CCVD) method were studied using transmission electron microscopy and Raman spectroscopy. The catalyst prepared by combustion method yielded mainly individualized CNTs, while the CNTs were highly entangled or bundled when impregnation method was used. In both cases, addition of hydrogen to methane led to reduction of the CNT yield. The samples synthesized using two different catalysts and the same CH₄/H₂ ratio and flow of gases were tested in electrochemical capacitors. A higher specific surface area of the CNTs grown over impregnation-prepared catalyst caused a better performance at scan rates from 2 to 1000?mV/s.     

One-pot synthesis of intestine-like SnO2/TiO2 hollow nanostructures

In the present study the intestine-like binary SnO₂/TiO₂ hollow nanostructures are one-pot synthesized in aqueous phase at room temperature via a colloid seeded deposition process in which the intestine-like hollow SnO₂ spheres and Ti(SO₄)₂ are used as colloid seeds and Ti-source, respectively. The novel core (SnO₂ hollow sphere)-shell (TiO₂) nanostructures possess a large surface area of 122 m²/g (calcined at 350 °C) and a high exposure of TiO₂ surface. The structural change of TiO₂ shell at different temperatures was investigated by means of X-ray diffraction and Raman spectroscopy. It was observed that the rutile TiO₂ could form even at room temperature due to the presence of SnO₂ core and the unique core-shell interaction.     

Visible light-induced degradation of acetone over SO4/MoOx/MgF2 catalysts

A visible light active photodegration catalyst was prepared by doping MoO₃ into MgF₂ matrix. The addition of SO₄²⁻ into MoO_x/MgF₂ could improve the catalytic activity greatly and an acetone conversion of 96.1% under visible light was obtained on the SO₄²⁻/5% MoO_x/MgF₂ (SMM) catalyst. By BET, XRD, Raman, FT-IR, XPS, UV–vis technology the specific area, structure and photoadsorption ability of the catalysts were characterized. The high photocatlaytic activity of the SMM catalyst is attributed to its large specific area, the high dispersal of MoO₃ domains in MgF₂ and the inhibiting effect of MgF₂ matrix on the electron–hole pair recombination.     

离子液体中阴阳离子的特性对其吸收二氧化硫的影响

SO_2是一种无色、有强烈刺激性气味的气体,弥散在空气中的SO_2对人体健康、生态环境有着严重的危害,是导致空气质量不断恶化的主要大气污染物之一。人为造成的SO_2污染物的主要来源有燃料燃烧、工业生产、交通运输等,其中燃料燃烧占70%。因此,削减和控制燃料燃烧所产生的SO_2的排放是我国能源利用和环保领域的重要研究方向,烟气脱硫是应对烟气中SO_2排放的有效途径。湿法烟气脱硫是目前应用最广泛的方法,占世界安装烟气脱硫机组总容量的85%,采用该方法处理的烟气占总处理量的80%。在湿法烟气脱硫技术中比较实用的主要包括钙法脱硫、有机胺脱硫、海水脱硫。其中,钙法脱硫的脱硫效率高,对煤种的适应性较强,但是脱硫会产生CaSO_4沉淀,降低经济效益;有机胺脱硫的系统腐蚀性小,副产品可生产硫酸,但是胺易挥发,造成吸收剂损失和环境污染;海水法脱硫的工艺简单、运行可靠,但其应用受到地域的影响,并且对环境也会产生一定的影响。离子液体是一种新兴的绿色介质,它具有环保、可再生、结构可调控的优点,为解决传统工艺中的污染问题提供了新方案。在离子液体吸收气体的过程中,吸收液不会因其挥发性而蒸发进入气相,并且可以在较低的温度下完成吸收解吸循环。离子液体的这些优良特性使其在SO_2吸收方面有着极广阔的应用前景。目前,研究者们已合成了一系列胍盐类、咪唑类、醇胺类、吡啶类等离子液体,探究其吸收SO_2的性能与机理,并根据其结构可设计的特点,在离子液体中的阴阳离子上引入各类官能团(如氰基、醚基、氨基、卤素),合成满足特定需求的离子液体,使其高效、可逆、低耗地吸收SO_2。本文总结了近年来各类离子液体吸收SO_2的性能和机理,为系统地认识离子液体在SO_2分离领域的应用提供了帮助;重点阐明了离子液体中阴阳离子的种类、官能化,尤其是酸碱性对其吸收SO_2的影响,这为调整离子液体酸碱性、合理设计离子液体的结构,探索离子液体吸收SO_2的机理,改善其对SO_2的吸收性能有着重要的价值。最后指出了目前研究中存在的问题并且对未来新型离子液体的合成进行了展望。     

A scheme for solving strongly coupled chemical reaction equations appearing in the removal of SO2 and NOx from flue gases

The removal of NO_x from mixtures of NO-NO₂-N₂ and NO-NO₂-O₂-H₂O is discussed theoretically in this study, and the removal of ₂SO and xNO is further discussed when a gas system of NO_x-N₂-O₂-H₂O contains CO₂ and SO₂. The involved chemical reaction rate equations in the process of SO₂/NO_x removal are solved numerically using Treanor's method, in which a scheme separating chemical reactions into fast and slow groups has been proposed for improving the numerical stability. Numerical results show that the contribution of ion reactions to xNO removal is negligible, and that high temperature is not beneficial for the NO oxidation. However, high concentration of O₂ is conducive to the NO oxidation. Addition of water facilitates the NO_x removal, and increasing water vapor concentration enhances the NO_x removal efficiency; inclusion of CO₂ and SO₂ into the system favors the NO removal.     

High-throughput technology for novel SO2 oxidation catalysts

Abstract

We review the state of the art and explain the need for better SO₂ oxidation catalysts for the production of sulfuric acid. A high-throughput technology has been developed for the study of potential catalysts in the oxidation of SO₂ to SO₃. High-throughput methods are reviewed and the problems encountered with their adaptation to the corrosive conditions of SO₂ oxidation are described. We show that while emissivity-corrected infrared thermography (ecIRT) can be used for primary screening, it is prone to errors because of the large variations in the emissivity of the catalyst surface. UV-visible (UV-Vis) spectrometry was selected instead as a reliable analysis method of monitoring the SO₂ conversion. Installing plain sugar absorbents at reactor outlets proved valuable for the detection and quantitative removal of SO₃ from the product gas before the UV-Vis analysis. We also overview some elements used for prescreening and those remaining after the screening of the first catalyst generations.     

Synthesis and characterization of novel nanostructured fishbone-like Cu(OH)2 and CuO from Cu4SO4(OH)6

The Cu₄SO₄(OH)₆ was synthesized by a simple hydrothermal reaction with a yield of ~ 90%. Using Cu₄SO₄(OH)₆ as the starting material, novel fishbone-like Cu(OH)₂ was produced by a direct reaction of Cu₄SO₄(OH)₆ with NaOH solution. The Cu(OH)₂ consists of many needle-like nanorods parallel to each other and perpendicular to the direction of backbone, forming fishbone-like structure. Using the fishbone-like Cu(OH)₂ as the sacrificial precursor, CuO with similar size and morphology was obtained through a simple heat treatment. X-ray diffraction, scanning electron microscopy, energy dispersive X-ray, X-ray photoelectron spectroscopy, BET nitrogen adsorption, and UV-Vis absorption spectroscopy were employed to characterize the as-prepared samples. The conversion of the Cu₄SO₄(OH)₆ to the fishbone-like Cu(OH)₂ was visualized by time-dependent SEM images. A mechanism was also proposed based on the observed results.     

Preparation of nitrogen co-doped SiO2/TiO2 thin films on ceramic with enhanced photocatalytic activity under visible-light irradiation

In this study, we have successfully deposited N-doped SiO₂/TiO₂ thin films on ceramic tile substrates by sol–gel method for auto cleaning purpose. After dip coating and annealing process the film was transparent, smooth and had a strong adhesion on the ceramic tile surface. The synthesised catalysts were then characterised by using several analytical techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscope (AFM) and UV-vis absorption spectroscopy (UV-vis). The analytical results revealed that the optical response of the synthesised N-doped SiO₂/TiO₂ thin films was shifted from the ultraviolet to the visible light region. The nitrogen substituted some of the lattice oxygen atoms. The surface area of co-doped catalyst increased, and its photocatalytic efficiency was enhanced. The photocatalytic tests indicated that nitrogen co-doped SiO₂/TiO₂ thin films demonstrated higher than of the SiO₂/TiO₂ activity in decolouring of methylene blue under visible light. The enhanced photocatalytic activity was attributed to an increasing of the surface area and a forming of more hydroxyl groups in the doped catalyst.     

Chemical vapor deposition of NiSi using Ni(PF3)4 and Si3H8

NiSi_x films were deposited using chemical vapor deposition (CVD) with a Ni(PF₃)₄ and Si₃H₈/H₂ gas system. The step coverage quality of deposited NiSi_x was investigated using a horizontal type of hot-wall low pressure CVD reactor, which maintained a constant temperature throughout the deposition area. The step coverage quality improved as a function of the position of the gas flow direction, where PF₃ gas from decomposition of Ni(PF₃)₄ increased. By injecting PF₃ gas into the Ni(PF₃)₄ and Si₃H₈/H₂ gas system, the step coverage quality markedly improved. This improvement in step coverage quality naturally occurred when PF₃ gas was present, indicating a strong relationship. The Si/Ni deposit ratio at 250 °C is larger than at 180 °C. It caused a decreasing relative deposition rate of Ni to Si. PF₃ molecules appear to be adsorbed on the surface of the deposited film and interfere with faster deposition of active Ni deposition species.     

Self-catalytic formation and characterization of Zn2SnO4 nanowires

Mass production of transparent semiconducting ternary oxide Zn₂SnO₄ nanowires is successfully synthesized by the thermal evaporation method without any catalyst. The as-synthesized products are characterized with field-emission scanning electron microscope (FE-SEM), X-ray powder diffraction (XRD), energy-dispersive spectroscopy (EDS), high-resolution transmission electron microscope (HR-TEM) and selected area electron diffraction (SEAD). A formation of Zn₂SnO₄ nanowires based on a self-catalytic VLS growth mechanism is discussed. The photoluminescence spectrum (PL) of the nanowires shows a broad blue-green emission around the 300-600 nm wavelengths with a maximum center at 580 nm under room temperature.     

Li2O–ZnO–Co3O4–TiO2 composite thin-film electrocatalyst for efficient water oxidation catalysis

Thin films of different Li₂O–ZnO–Co₃O₄–TiO₂ (LZCT) compositions were prepared and employed as electrocatalysts (i.e., anodes) to perform water oxidation reaction (WOR). The electrocatalytic activities of these thin films were compared with those exhibited by the sodium salt of cobalt phosphate (Na₂CoP₂O₇) (CP) thin-film electrocatalyst, which is a well-known water oxidation catalyst (WOC). These results suggest that the 10Li₂O–10ZnO–40Co₃O₄–40TiO₂ composition exhibits a better catalytic activity in terms of higher faradaic efficiency (>98%), lower over potentials (<400?mV), higher reaction stability (up to 30 continuous cyclic voltammetry (CV) cycles), and the rate of O₂ and H₂ gas evolution in terms of current density (about 1?mA/cm²) in comparison with those exhibited by CP thin-film electrocatalyst. Furthermore, these LZCT thin films exhibited very high specific surface area values and due to the unique microstructure of ZnCo₂O₄ phase evolved out of these LZCT compositions at a calcination temperature of 550°C for 30?min it has been found to be responsible for the higher specific surface area values measured for these thin-film compositions.     

Nitrogen and europium doped TiO2 anodized films with applications in photocatalysis

Micro-arc oxidation method is a useful process for mesoporous titanium dioxide films. In order to improve the photocatalytic activity of the TiO₂ film, N-Eu co-doped titania catalyst was synthesized by micro-arc oxidation in the H₂SO₄/Eu(NO₃)₃ mixture solution.The specific surface area and the roughness of the anodic titania film fabricated in the H₂SO₄/Eu(NO₃)₃ electrolyte, were increased compared to that of the anodic TiO₂ film prepared in H₂SO₄ solution. The absorbance response of N-Eu titania film shows a higher adsorption onset toward visible light region, and the incorporated N and Eu ions during anodization as a dopant in the anodic TiO₂ film significantly enhanced the photocatalytic activity for dye degradation. After dye decomposition test for 3 h, dye removal rates for the anodic TiO₂ film were 60.7% and 90.1% for the N-Eu doped titania film. The improvement of the photocatalytic activity was ascribed to the synergistic effects of the surface enlargement and the new electronic state of the TiO₂ band gap by N and Eu co-doping.     

Preparation and characterization of Co-doped TiO2 materials for solar light induced current and photocatalytic applications

Different amounts of Co-doped TiO₂ powders and thin films were prepared by following a conventional co-precipitation and sol–gel dip coating technique, respectively. The synthesized powders and thin films were subjected to thermal treatments from 400 to 800 °C and were thoroughly investigated by means of X-ray diffraction, X-ray photoelectron spectroscopy, energy dispersive analysis with X-rays, FT-infrared, FT-Raman, diffuse reflectance spectroscopy, ultraviolet–visible spectroscopy, BET surface area, zeta potential, flat band potential measurements, band-gap energy, etc. The photocatalytic ability of the powders was evaluated by methylene blue (MB) degradation studies. The thin films were characterized by photocurrent and ultraviolet–visible (UV–Vis) spectroscopy techniques. The characterization results suggest that the Co-doped TiO₂ powders synthesized in this study consist mainly anatase phase, and possess reasonably high specific surface area, low band gap energy and flat band potentials amenable to water oxidation in photoelectrochemical (PEC) cells. The photocatalytic degradation of MB over Co-doped TiO₂ powders followed the Langmuir–Hinshelwood first order reaction rate relationship. The 0.1 wt.% Co-doped TiO₂ composition provided the higher photocurrent, n-type semi-conducting behavior and higher photocatalytic activity among various Co-doped TiO₂ compositions and pure TiO₂ investigated.     

Influence of effective surface area on gas sensing properties of WO3 sputtered thin films

WO₃ thin films having different effective surface areas were deposited under various discharge gas pressures at room temperature by using reactive magnetron sputtering. The microstructure of WO₃ thin films was investigated by X-ray diffraction, scanning electron microscopy, and by the measurement of physical adsorption isotherms. The effective surface area and pore volume of WO₃ thin films increase with increasing discharge gas pressure from 0.4 to 12 Pa. Gas sensors based on WO₃ thin films show reversible response to NO₂ gas and H₂ gas at an operating temperature of 50-300 °C. The peak sensitivity is found at 200 °C for NO₂ gas and the peak sensitivity appears at 300 °C for H₂ gas. For both kinds of detected gases, the sensor sensitivity increases linearly with an increase of effective surface area of WO₃ thin films. The results demonstrate the importance of achieving high effective surface area on improving the gas sensing performance.