Promotion of surface SOx on the selective catalytic reduction of NO by hydrocarbons over Ag/Al2O3

The promotion of sulfur oxides on the selective catalytic reduction (SCR) of NO by hydrocarbons in the presence of a low concentration of sulfur oxides over Ag/Al₂O₃ has been investigated by a flow reaction test and in situ infrared spectroscopy. When the C₃H₆ (or C₁₀H₂₂) + NO + O₂ feed-flow reaction was tested, maximum NO reduction was below 30% over fresh Ag/Al₂O₃. After the addition of SO₂ to the feed flow, conversion increased slightly. Conversion increased further after SO₂ was cut-off from the feed flow. This demonstrated that the increase in NO reduction activity of the catalyst was related to SO_x adsorbed on the catalyst. SO_x adsorbed on the catalytic surface (1375 cm⁻¹) was detected by IR spectroscopy and was stable within the temperature range. NCO species, as an intermediate in NO reduction, on SO_x-adsorbed Ag/Al₂O₃ in a C₃H₆ + NO + O₂ feed flow was observed in in situ IR spectra during the elevation of the reaction temperature from 473 to 673 K, while it was only observed at 673 K on fresh Ag/Al₂O₃ under the same experimental conditions. We suggest that SO_x in low concentrations depressed the combustion of reductants by contaminating hydrocarbon combustion active sites on the catalyst, resulting in an increase in NO reduction efficiency of the reductants.     

硫酸催化乙二醛气体相水化反应机理和速率常数理论计算研究

采用M06-2X和CCSD(T)高阶量化计算和传统过渡态理论研究硫酸催化乙二醛气体相水化反应.对HCOCHO+H₂O, HCOCHO+H₂O+H₂O, HCOCHO+H₂O+H₂O, HCOCHO+H₂O...H₂SO₄和HCOCHO+H₂O+H₂SO₄五个路径的反应机理和速率常数进行了研究.计算结果表明硫酸具有较强的催化能力,能显著减小乙二醛水化反应的能垒,在CCSD(T)/6-311++G(3df,3pd)//M06-2X/6-311++G(3df,3pd)理论水平,当硫酸分子参与乙二醛水化反应时,反应能垒从37.15 kcal/mol减少至7.08 kcal/mol.在室温条件下,硫酸催化乙二醛水化反应的反应速率1.34×10^-11 cm³/(molecule.s),是等量水分子参与乙二醛水化反应的速率的10¹²倍,大于乙二醛与OH自由基反应的反应速率1.10×10^-11 cm³/(molecule.s).这表明大气条件下,硫酸催化乙二醛水化反应可以发生,同乙二醛与OH自由基反应相竞争.     

Heterogeneous adsorption and catalytic oxidation of benzene, toluene and xylene over spent and chemically regenerated platinum catalyst supported on activated carbon

The heterogeneous adsorption and catalytic oxidation of benzene, toluene and o-xylene (BTX) over the spent platinum catalyst supported on activated carbon (Pt/AC) as well as the chemically treated spent catalysts were studied to understand their catalytic and adsorption activities. Sulfuric aqueous acid solution (0.1N, H₂SO₄) was used to regenerate the spent Pt/AC catalyst. The physico-chemical properties of the catalysts in the spent and chemically treated states were analyzed by using nitrogen adsorption-desorption isotherm and elemental analysis (EDX). The gravimetric adsorption and the light-off curve analysis were employed to study the BTX adsorption and oxidation on the spent catalyst and its modified Pt/AC catalysts. The experimental results indicate that the spent Pt/AC catalyst treated with the H₂SO₄ aqueous solution has a higher toluene adsorption and conversion ability than that of the spent Pt/AC catalyst. A further studies of H₂SO₄ treated Pt/AC catalyst on their catalytic and heterogeneous adsorption behaviours for BTX revealed that the activity of the H₂SO₄ treated Pt/AC catalyst follows the sequence of benzene > toluene > o-xylene. The adsorption equilibrium isotherms of BTX on the H₂SO₄ treated Pt/AC were measured at different temperatures ranging from 120 to 180 °C. To correlate the equilibrium data and evaluate their adsorption affinity for BTX, the two sites localized Langmuir (L2m) isotherm model was employed. The heterogeneous surface feature of the H₂SO₄ treated Pt/AC was described in detail with the information obtained from the results of isosteric enthalpy of adsorption and adsorption energy distributions. Furthermore, the activity of H₂SO₄ treated Pt/AC about BTX was found to be directly related to the Henry's constant, isosteric enthalpy of adsorption and adsorption energy distribution functions.     

The relationship of the catalytic activity and the open-circuit potential of Pt interfaced with YSZ

This study deals with the relationship between open-circuit potential and catalytic activity of the system Pt/YSZ. Temperature-programmed desorption (TPD) of oxygen was carried out in order to investigate the link between the oxygen coverage and the potential. Then, catalytic activity in parallel with the potential value was measured between 200 °C and 500 °C for NO oxidation, C₃H₈ combustion, C₃H₆ combustion and the selective catalytic reduction (SCR) of NO by C₃H₆ in the presence of oxygen. It was found that potential measurement can give precious information on the competitive adsorption between oxygen and other reactants. Finally, it seems to be also a good way to anticipate the NEMCA behavior for reactions, which involve oxygen. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

Capture of pure toxic gases through porous materials from molecular simulations

ABSTRACT

In the last three decades, the air pollution is the main problem to affect human health and the environment in China and its contaminants include SO_2, NH_3, H₂S, NO₂, NO and CO. In this work, we employed grand canonical Monte Carlo simulations to investigate the adsorption capability of metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) for these toxic gases. Eighty-nine MOFs and COFs were studied, and top-10 adsorption materials were screened for each toxic gas at room temperature. Dependence of the adsorption performance on the geometry and constructed element of MOFs/COFs was determined and the adsorption conditions were optimised. The open metal sites have mainly influenced the adsorption of NH₃, H₂S, NO₂ and NO. Especially, the X-DOBDC and XMOF-74 (X = Mg, Co, Ni, Zn) series of materials containing open metal sites are all best performance for adsorption of NH₃ to illustrate the importance of electrostatic interaction. Our simulation results also showed that ZnBDC and IRMOF-13 are good candidates to capture the toxic gases NH_3, H₂S, NO₂, NO and CO. This work provides important insights in screening MOF and COF materials with satisfactory performance for toxic gas removal.     

Effect of combination of noble metals and metal oxide supports on catalytic reduction of NO by H2

We investigated the effects of combination of noble metals M (Rh, Pd, Ir, Pt) and metal oxide supports S (Al₂O₃, SiO₂, ZrO₂, CeO₂) on the NO + H₂ reaction using planar catalysts with M/S two layered thin films on Si substrate. In this study, NO reduction ability per metal atom were evaluated with a specially designed apparatus employing pulse valves for the injection of reactant molecules onto catalysts and a time-of-flight mass spectrometer to measure multiple transient products: NH₃, N₂ and N₂O simultaneously as well as with an atomic force microscopy to observe the surface area of metal particles. The catalytic performances of Rh and Ir catalysts were hardly affected by a choice of a metal oxide support, while Pd and Pt catalysts showed different catalytic activity and selectivity depending on the metal oxide supports. This assortment is consistent with ability to dissociate NO depending on metals without the effect of any support materials. There, the metals to the left of Rh and Ir on the periodic table favor dissociation of NO and those to the right of Pd and Pt tend to show molecular adsorption of NO. Therefore, the catalytic property of noble metals could be assorted into two groups, i.e. Rh and Ir group whose own property would mainly dominate the catalytic performance, and Pd and Pt group whose interaction with metal oxides supports would clearly contribute to the reaction of NO with H₂. NO reduction activity of Pd and Pt was found to be promoted above that of Rh and Ir, provided that Pd and Pt were supported by CeO₂ and ZrO₂.     

Microscopic insight into catalytic HCN removal over the CuO surface in chemical looping combustion

Hydrogen cyanide (HCN) is well-accepted as a main nitrogen-containing precursor from fuel nitrogen to nitrogen oxides. When using coal as fuel with a CuO-based oxygen carrier in chemical looping combustion (CLC), complex heterogeneous reactions exist among the system of HCN, O₂, NO, H₂O, and CuO particles. This work performs density functional theory (DFT) calculations to systematically probe the microscopic HCN heterogeneous reactions over the CuO particle surface. The results indicate that HCN is chemisorbed on the CuO surface, and the third dissociation step within the consecutive three-step HCN dissociations (HCN*→CN*→NCO*→N*) is the rate-determining step. Namely, the CN*/NCO* radicals can be deemed as an indicator of the performance of HCN removal due to their quite higher dissociation energies. With the existence of O₂, H₂O, and NO, the reaction mechanism of HCN conversion becomes extremely complex. Both DFT calculations and kinetic analyses determine that O₂, NO, and H₂O all significantly accelerate the consumption of CN*/NCO* radicals to produce various N-containing species (NOx or NH₃) to different extents. Finally, a skeletal reaction network in a system of O₂/NO/H₂O/HCN is concluded, which clearly elucidates that CuO exhibits excellent catalytic activity toward HCN removal.     

One‐Pot Synthesis of Algae‐Like MoS2/PPy Nanocomposite: A Synergistic Catalyst with Superior Peroxidase‐Like Catalytic Activity for H2O2 Detection

A facile one‐pot synthetic route is reported to prepare algae‐like molybdenum disulfide/polypyrrole (MoS₂/PPy) nanocomposite through a redox reaction between ammonium tetrathiomolybdate and pyrrole monomer under a hydrothermal condition without any other templates. The as‐prepared unique algae‐like MoS₂/PPy nanocomposites are composed of few layer MoS₂ nanosheets, which are covered with PPy. Structural and morphological characterizations of this unique nanocomposite are investigated by Fourier‐transform infrared spectra, Raman spectra, X‐ray diffraction pattern, X‐ray photoelectron spectra, energy‐dispersive X‐ray spectroscopy, and transmission electron microscopy. The as‐prepared MoS₂/PPy nanocomposites exhibit an excellent peroxidase‐like catalytic activity toward the oxidation of 3,3,5,5‐tetramethylbenzidine (TMB) in the presence of hydrogen peroxide (H₂O₂) in acetate buffer solution (pH 4.0), which provides a facile strategy for the colorimetric detection of H₂O₂ with a high sensitivity.     

The role of co-adsorbed O2 on the catalytic reduction of NO with C2H5OH on the surface of Pt(3 3 2)

The influence of pre-dosed O₂ on the catalytic reduction of NO with ¹³C₂H₅OH on the surface of stepped Pt(3 3 2) was investigated using Fourier transform infra red reflection-absorption spectroscopy (FTIR-RAS) and thermal desorption spectroscopy (TDS). We show that the oxidation of ¹³C₂H₅OH with O₂ is a very effective reaction, occurring at 150 K and giving rise to acetate. The presence of NO does not lead to any evident oxidation of ¹³C₂H₅OH irrespective of the annealing temperature. For the case of O₂ + ¹³C₂H₅OH + NO co-adlayers, oxidation of ¹³C₂H₅OH also takes place at 150 K. However, no new surface species that are supposed to be an intermediate for the production of N₂ are detected.The influence of O₂ on the production and desorption of N₂ is intimately related to both O₂ and ¹³C₂H₅OH coverage. The presence of pre-dosed O₂ does not greatly promote N₂ desorption. In fact, N₂ desorption is suppressed quantitatively with increasing O₂ coverage, after which unreacted, or left-over O atoms appear and remain on steps. It is concluded that the presence of pre-dosed O₂ does not play a role of activating reactants in the catalytic reduction of NO with ¹³C₂H₅OH on the surface of Pt(3 3 2).     

Simultaneous catalytic ozonation of NO and dichloromethane on Mn/H-ZSM-5 catalysts: Interaction effect and mechanism

Catalytic ozonation is a promising method for simultaneous removal of NO_x and Cl-VOCs, but needs to clarify their interaction mechanism and the influence of catalyst acidity. In this paper, the simultaneous catalytic ozonation of NO and dichloromethane (DCM) on Mn/H-ZSM-5 molecular sieve catalysts were investigated experimentally. Results show that the overall acidity, acid sites type and intensity have a significant impact on the degradation efficiency, the conversion path of Cl element, and the interaction of NO/DCM adsorption-degradation. Nevertheless, regardless of catalysts, NO could be preferentially oxidized by ozone to generate NO₂ in co-ozonation process, which inhibited and even shielded DCM ozonation at O₃/DCM ratio <1.7. In addition, the highly active oxidizing species such as NO₃/N₂O₅, produced by the deep ozonation of NO₂, exhibited a synergistic effect on the conversion of DCM and intermediates, which in turn weakened NO₂ deep oxidation. Specifically, NO addition caused a general decrease in the HCl selectivity, and a slight increase in the CHCl₃ selectivity of all samples, while the Cl₂ selectivity was determined by the overall catalyst acidity. The samples with higher overall acidity exhibited lower activity for DCM degradation. In particular, for samples with the weak overall acidity but strong acid sites, the sum selectivity of HCl, Cl₂, and CHCl₃ was significantly improved under the interplay effect of NO, indicating that strong acidic sites were beneficial to the complete degradation of DCM. In-situ DRIFTS revealed that aldehydes and carboxylates were the key intermediates of DCM ozonation. In the co-ozonation, NO and its oxidation products (such as nitrates) could promote the formation and conversion of these intermediates, and further converted into CO and CO₂ by the active oxidant from ozone. Finally, the interference of H₂O and SO₂ on the NO/DCM co-ozonation were revealed.     

Plasma-activated core-shell gold nanoparticle films with enhanced catalytic properties

Catalytically active gold nanoparticle films have been prepared from core-shell nanoparticles by plasma-activation and characterized by high-resolution transmission electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. Methane can be selectively oxidized into formic acid with an O₂–H₂ mixture in a catalytic wall reactor functionalized with plasma-activated gold nanoparticle films containing well-defined Au particles of about 3.5 nm in diameter. No catalytic activity was recorded over gold nanoparticle films prepared by thermal decomposition of core-shell nanoparticles due to particle agglomeration.     

Electrochemical promotion of NO reduction by C3H6 and CO on Rh/YSZ catalyst — Electrodes

The selective catalytic reduction of NO by propylene or CO in the presence of excess oxygen is a system of great technological importance. The effect of Electrochemical Promotion (or Non-faradaic Electrochemical Modification of Catalytic Activity — NEMCA) was used to promote this reaction (C₃H₆ or CO/NO/O₂) on Rh/YSZ catalyst-electrodes. It was found that both the catalytic activity and the selectivity of the Rh catalyst-electrode is affected dramatically upon varying its potential with respect to a Au pseudoreference electrode. Catalytic rate enhancements up to 15000% and 6000% were observed in the case of NO reduction by propylene, while the product selectivity to N₂ production is affected significantly (up to 200%) upon positive potential application. Remarkable promotion of the catalytic activity was also observed in the case of NO reduction by CO, since up to 20-fold increases both in catalytic rates and in NO conversion were obtained under NEMCA conditions. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Differences in catalytic properties between mesoporous and nanoparticulate platinum

Conventional Pt/Al₂O₃ catalysts prepared by wet-impregnation are composed of Pt nanoparticles exposing convex and facetted surfaces deposited on high-surface area γ-Al₂O₃ supports. A hexagonal phase mesoporous Pt material (denoted H₁-Pt) prepared by chemical reduction in the aqueous domains of a lyotropic liquid crystalline template exposes however mainly a concave surface with expected different catalytic properties. A series of Pt/Al₂O₃ catalysts were prepared using H₁-Pt, Pt-black or wet-impregnated Pt, and the samples were characterized by SEM-EDX and TEM, and finally evaluated for CO oxidation. The H₁-Pt/Al₂O₃ catalyst showed an ignition profile for CO oxidation at lower temperatures and thus appeared less sensitive to CO poisoning than the two other types of samples. This difference may be related to the differences in surface curvature.     

Electrochemical characterisation of the Pt/YSZ interface exposed to a reactive gas phase

The Pt/yttria-stabilized cubic zirconia (YSZ) interface exposed to a reactive gas was characterised by solid electrolyte potentiometry and cyclic voltammetry. The catalytic reactions included total combustion of C₃H₈ and C₃H₆ to CO₂ and H₂O as well as NO reduction by C₃H₆ in the presence of O₂ under oxygen-rich and stoichiometric conditions. The solid electrolyte potentiometry as a function of the temperature in C₃H_x/O₂ (with x=6 or 8) reflected the catalytic properties of Pt for C₃H_x oxidation. In C₃H₆/NO/O₂, the reduction of NO was evidenced below 300 °C. The cyclic voltammetry evidenced the formation of an oxygen chemisorbed layer on the Pt surface under anodic potential. Propane had no effect on this chemisorbed layer, whereas propene weakened significantly the strength of this Pt–O bond. Addition of NO to C₃H₆/O₂ led to the disappearing of this chemisorbed layer. The use of solid electrolyte potentiometry in conjunction with cyclic voltammetry allowed us to determine the surface oxidation state of Pt during the catalytic reactions.     

Langmuir-Blodgett self-assembly and electrochemical catalytic property of FePt magnetic nano-monolayer

Dispersed-well FePt nanoparticles with particle size ~5 nm have been prepared by hydrazine hydrate reduction of H₂PtCl₆·6H₂O and FeCl₂·4H₂O in ethanol–water system. By employing as-synthesized FePt nanoparticles, the monolayer can be formed by LB Technique. The structural, magnetic properties and electrochemical properties of FePt monolayer were respectively studied by XRD, TEM, VSM and CHI 820 electrochemical workstation. The as-synthesized particle has a chemically disordered fcc structure and can be transformed into chemically ordered fct structure after annealing treatment above 400°C. The coercivity of ordered fct FePt phase can be up to 2515Oe. CVs of 0.5 M H₂SO₄/0.5M CH₃OH on GCE modified with FePt nanoparticles monolayer films illustrate that the as-synthesized FePt is a kind of active electrochemical catalyst.     

Pseudo-capacitance on exfoliated carbon fiber in sulfuric acid electrolyte

The specific capacitance of exfoliated carbon fibers (ExCF) which were synthesized from pitch-based carbon fibers showed a strong dependence with the concentration of sulfuric acid electrolyte and reached 1.4 F/m² in 18 M H₂SO₄ solution. Since the capacitance value is quite large compared with the case of conventional activated carbons, faradic reactions (charge transfer reactions) are the cause of pseudo-capacitance. ExCF, however, gave a featureless cyclic voltammogram in 18 M H₂SO₄ solution. In the case of exfoliated natural graphite, the intercalation of H₂SO₄ molecules is evidenced by redox peaks observed in the voltammograms in the same conditions. Therefore, a strong interaction between the H₂SO₄ molecules and the ExCF surface might be the reason for the origin of pseudo-capacitance with ExCF in H₂SO₄ electrolyte. PACS 81.05.Uw; 82.45.Fk; 82.47.Uv     

Influences of water vapor and fly ash addition on NO and SO2 gas conversion efficiencies enhanced by pulsed corona discharge

The NO and SO₂ gas conversion processes in a pulsed corona discharge field have been studied. The experiments were conducted to investigate the influences of water vapor and fly ash addition on the conversion efficiencies of NO and SO₂. Experimental results show that positive pulsed corona discharge can facilitate NO and SO₂ conversion processes, and the conversion efficiencies of NO and SO₂ are primarily dependent on the radicals OH, O and the active species O₃, HO₂, H₂O₂, etc. With water vapor addition, SO₂ conversion efficiency is improved, but NO conversion process is restrained. Low fly ash concentration helps to enhance the conversion of NO and SO₂; however, the conversion efficiencies of NO and SO₂ are drastically degraded by high fly ash concentration addition. The synergistic effects of water vapor and fly ash addition strengthen the chemical adsorption ability of the fly ash surface, which results in a considerable improvement in the conversion of NO and SO₂. Furthermore, the specific input energy plays an important role in NO and SO₂ conversion efficiencies. Measured conversion efficiencies of NO and SO₂ reach about 60% and 90%, respectively, under the conditions tested.     

Morphological effect of MoS2 nanoparticles on catalytic oxidation and vacuum lubrication

The closed layered MoS₂ nano-balls and the opened layered MoS₂ nano-slices were prepared by decomposing MoS₃ in hydrogen atmosphere. The obtained MoS₂ nanoparticles were respectively used as catalysts for S²⁻ oxidation into SO₄²⁻ and lubricating fillers in polyoxymethylene (POM) plastic. Only basal surface could be found in the closed layered MoS₂ nano-balls, which represented very low catalytic efficiency for S²⁻ oxidation into SO₄²⁻. However, the opened layered MoS₂ nano-slices were of both basal surface and rim-edge surface and showed excellent catalytic properties. Moreover, it was shown that MoS₂ nano-balls could improve the self-lubrication of POM plastic in vacuum. However, MoS₂ nano-slices led to the obvious degradation of POM, implying it is not a proper additive for POM. The high activity of MoS₂ nano-slices for catalyzing S²⁻oxidation and degrading POM was ascribed to their small sizes and partly wedge-like shapes, which led to a considerable increase in the rim sites. The weak catalysis and excellent lubrication of MoS₂ nano-balls were resulted from its closed structure and chemical inertness.     

Surface modification of carbon nanotubes for enhancing BTEX adsorption from aqueous solutions

Carbon nanotubes (CNTs) were fabricated by the catalytic chemical vapor deposition method and oxidized by HCl, H₂SO₄, HNO₃ and NaOCl solutions for enhancing benzene, toluene, ethylbenzene and p-xylene (BTEX) adsorption in an aqueous solution. The surface nature of CNTs was changed after the H₂SO₄, HNO₃ and NaOCl oxidation, which makes CNTs that adsorb more BTEX. The NaOCl-oxidized CNTs show the greatest enhancement in BTEX adsorption, followed by the HNO₃-oxidized CNTs, and then the H₂SO₄-oxidized CNTs. The adsorption mechanism of BTEX via CNTs is mainly attributed to the π-π electron-donor-acceptor interaction between the aromatic ring of BTEX and the surface carboxylic groups of CNTs. The NaOCl-oxidized CNTs have superior adsorption performance of BTEX as compared to many types of carbon and silica adsorbents reported in the literature. This suggests that the NaOCl-oxidized CNTs are efficient BTEX adsorbents and that they possess good potential applications for BTEX removal in wastewater treatment.     

Effects of impurities containing phosphorus on the surface properties and catalytic activity of TiO2 nanotube arrays

TiO₂ nanotube arrays were prepared by titanium anodic oxidation with either HF or H₃PO₄/NH₄F aqueous electrolyte solutions. The samples were characterized by means of X-ray diffraction (XRD), infrared spectroscopy (IR), Raman spectroscope, photoluminescence spectra (PL) and photocurrent response. Aqueous solutions of methylene blue or Cr(VI) ions were used as the target pollutants to compare catalytic activities of the two nanotube array types. The amorphous impurities containing phosphorus were confirmed by XRD and IR, for the sample synthesized with H₃PO₄/NH₄F electrolytes. They closed a portion of the active sites, acted as recombination centers of photo-generated charges, and were also involved in the negative reactions of competing photo-generated holes or OH radicals. The TiO₂ nanotube arrays formed in the H₃PO₄/NH₄F electrolytes exhibited a stronger fluorescence spectrum, a weaker photocurrent and a lower catalytic activity than the sample fabricated with HF electrolyte without phosphorus impurities.