Selective permeation and separation of steam from water–methanol–hydrogen gas mixtures through mordenite membrane

Separation properties of a mordenite membrane for water–methanol–hydrogen mixtures were studied in the temperature range from 423 to 523 K under pressurized conditions. The mordenite membrane was prepared on the outer surface of a porous alumina tubular support by a secondary-growth method. It was found that water was selectively permeated through the membrane. The separation factor of water/hydrogen and water/methanol were 49–156 and 73–101, respectively. Even when only hydrogen was fed at 0.5 MPa, its permeance was as low as 10⁻⁹ mol m⁻² s⁻¹ Pa⁻¹ up to 493 K, possibly suggesting that water pre-adsorbed in the micropores of mordenite hindered the permeation of hydrogen. The hydrogen permeance dramatically increased to 6.5 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ at 503 K and reached to 1.4 × 10⁻⁶ mol m⁻² s⁻¹ Pa⁻¹ at 523 K because of the formation of cracks in the membrane. However, the membrane was thermally stabilized in the presence of steam and/or methanol.     

In situ FTIR study on reaction pathways in Ni(CO)4/CH3OK catalytic system for low-temperature methanol synthesis in a liquid medium

An in situ infrared spectroscopic study was conducted to elucidate the reaction pathways for low-temperature methanol synthesis in a catalytic system composed of Ni(CO)₄ and CH₃OK (denoted as Ni(CO)₄/CH₃OK). The reaction was conducted in a liquid medium at 313–333 K with an initial pressure of 3.0 MPa. When CH₃OK was added to Ni(CO)₄ solution at 293 K, different carbonylnickelates, [Ni₅(CO)₁₂]²⁻, [Ni₆(CO)₁₂]²⁻ and [Ni(CO)₃(COOCH₃)]⁻, were immediately formed from Ni(CO)₄. The species and the composition of the carbonylnickel complexes varied with temperature. The variations in concentrations of methanol (MeOH) and methyl formate (MF) during the run, which were determined from their IR absorptions, indicated a pattern characteristic of consecutive reactions with MF as an intermediate. Thus, it was shown that methanol was produced through the carbonylation of MeOH to MF and the subsequent hydrogenation of MF to MeOH. Stable hydridocarbonylnickel anions, [HNi(CO)₃]⁻ and/or [HNi₂(CO)₆]⁻, were observed together with a small amount of Ni(CO)₄ throughout the methanol synthesis. Since Ni(CO)₄ alone showed no activity for the hydrogenation of MF, the hydridocarbonylnickel anions generated in the presence of CH₃OK must be responsible for the reaction. The dual role of CH₃OK in the catalytic system was stated.     

Effect of hydrogen peroxide on the destruction of organic contaminants-synergism and inhibition in a continuous-mode photocatalytic reactor

The effect of hydrogen peroxide on the photocatalytic degradation of organic contaminants in water was investigated using a TiO₂-rotating disk photocatalytic reactor (RDPR) operated in a continuous-mode and at steady state. The experiments were performed at pH 3.0, in the presence of near-UV radiation, and using 4-chlorobenzoic acid (4-CBA) as a model non-volatile organic contaminant at influent concentration of 300 μmol l⁻¹. Experiments were performed at concentrations of hydrogen peroxide in the range 0–10.74 mmol l⁻¹. Addition of hydrogen peroxide at small concentrations (<2 mmol l⁻¹) had a synergistic effect and increased considerably the rates of photocatalytic reactions. An optimum influent hydrogen peroxide concentration was observed at 1.6 mmol l⁻¹, which caused an increased in the rates of 4-CBA degradation and total organic carbon (TOC) mineralization by 1.72 and 2.13 times, respectively. This corresponded to an optimum oxidant to contaminant molar ratio of 5.33. At higher concentrations, hydrogen peroxide was found to cause an inhibiting effect on the photocatalytic reactions. The synergistic and inhibiting effects of hydrogen peroxide were rationalized based on the reaction rate constants between relevant radical species.     

Reductive decomposition of nitrate ion to nitrogen in water on a unique hollandite photocatalyst

Photocatalysis of a hollandite compound K_xGa_xSn_8−xO₁₆ (x = ca. 1.8) was examined for the reduction of nitrate ion with a reducing agent of methanol in water under UV irradiation. Hollandites have a characteristic one-dimensional tunnel structure. The hollandite powder, which was prepared by the sol–gel method and unloaded with any additives like metals, was used as the photocatalyst and its photocatalytic reaction was analyzed quantitatively by using ion chromatography and on-line mass spectrometry, and its reaction mechanism was analyzed by in-situ FT-IR. The hollandite photocatalyst showed a significant activity for the formation of N₂ from NO₃⁻. The nitrate was reduced to N₂ and NO₂⁻, while the reducing agent methanol was partly oxidized to change to formic acid. The conversion of NO₃⁻was proportional to the yields of N₂, NO₂⁻, and HCOO⁻. The present photocatalyzed decomposition of NO₃⁻ to N₂ would be a useful photocatalysis for the environmental protection of water.     

Investigation on the partial oxidation of methane to syngas in a tubular Ba0.5Sr0.5Co0.8Fe0.2O3−δ membrane reactor

A perovskite material of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF), with both electronic and ionic conductivity, was synthesized by a combined citrate–EDTA complexing method. The dense membrane tube made of BSCF was fabricated using the plastic extrusion method. The partial oxidation of methane (POM) to syngas was performed in the tubular BSCF membrane reactor packed with a LiLaNiO/γ–Al₂O₃ catalyst. The reaction performance of the membrane reactor was investigated as functions of temperature, air flow rate in the shell side and methane concentration in the tube side. The mechanism of POM in the membrane reactor was discussed in detail. It was found that in the tubular membrane reactor, combustion reaction of methane with permeated oxygen took place in the reaction zone close to the surface of the membrane, then followed by steam and CO₂ reforming of methane in the middle zone of the tube side. The membrane tube can be operated steadily for 500 h in pure methane with 94% methane conversion and higher than 95% CO selectivity, and higher than 8.0 ml/cm² min oxygen permeation flux.     

The condensation/polymerisation of dimethyl siloxane fluids in a three-phase trickle flow monolith reactor

For the production of siloxane fluids, the viability of using a multi-channel monolith as a catalyst support system in a three-phase reactor has been studied. The catalyst was tripotassium phosphate (K₃PO₄). Experiments were performed in a single-channel flow reactor (15 mm i.d. and 500 mm catalyst coated length). The rate of reaction was followed by monitoring the disappearance of the hydroxyl group (–OH). Reaction experiments were performed at a hydroxyl group concentration range from 150 to 170 mol m⁻³, T=373–413 K and P=7.9 kPa with a nitrogen purge. The maximum temperature of operation was restricted to 413 K to avoid the formation of undesirable by-products. In the regime controlled by chemical kinetics, reaction was of an apparent first order with respect to –OH concentration, and in the apparent rate constant, the pre-exponential factor was 4.19×10⁻⁴ ms⁻¹, and the apparent activation energy was 16.1 kJ mol⁻¹. These are only valid for the operating pressure and purge gas flowrate used, as both of these are shown to affect water removal from the liquid phase and, hence, reaction rates. Mass transfer coefficients from the liquid to the catalyst surface were estimated and these increased rapidly with flowrate and were higher than expected for a falling liquid film.     

Oxidative gas phase carbonylation of methanol to dimethyl carbonate over chloride-free Cu-impregnated zeolite Y catalysts at elevated pressure

Incipient wetness impregnation of zeolite Y with copper(II) nitrate solution and inert activation at 650 °C led to active catalysts for the oxidative carbonylation of methanol to dimethyl carbonate in the gas phase. Activities were measured under elevated pressure (0.4–1.6 MPa) with feed compositions of CO/MeOH/O₂ = 40/20/6–1.5 vol.% (balanced by N₂) over zeolite Y loaded with 10–17 wt.% copper. It could be shown that inert activation at 650 °C enhanced the activity, and that Cu loading of 14–17 wt.% gave the best performance. By combined XRD, TEM, TPR and DRIFT characterization it was found that the inert activation initiated dispersion of crystalline CuO, auto-reduction of Cu²⁺ to Cu⁺ and redistribution of copper ions with enrichment inside the supercages of the zeolite. The O₂ content of the feed was found to control the selectivity to dimethyl carbonate. Dimethyl carbonate selectivities of 70–75% were achieved within the temperature range of 140–170 °C at an O₂ content of 1.5 vol.%. This allowed space-time yields of dimethyl carbonate up to 632 g l_cat⁻¹ h⁻¹ at methanol conversions of 5–12%. Formation of the main side product, dimethoxymethane, was surprisingly affected by CO, which is not in line with suggested reaction pathways. A mechanism is proposed including formation of surface carbonate structures as common intermediate.     

Partial oxidation of methane in Ba0.5Sr0.5Co0.8Fe0.2O3−δ membrane reactor at high pressures

Oxygen permeation fluxes through dense disk-shaped Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCFO) membranes were investigated as a function of temperature (973–1123 K), pressure (2–10 atm), and membrane thickness (1–2 mm) under an air/helium gradient. A high oxygen permeation flux of 2.01 ml/cm² min was achieved at 1123 K and 10 atm under an air/He oxygen partial pressure gradient. Based on the dependence of the oxygen permeation flux on the oxygen partial pressure difference across the membrane and the membrane thickness, it is assumed that bulk diffusion of oxygen ions was the rate-controlling step in the oxygen transport across the BSCFO membrane disk under an air/He gradient. The partial oxidation of methane (POM) to syngas using LiLaNiO_x/γ-Al₂O₃ as catalyst in a BSCFO membrane reactor was successfully performed at high pressure (5 atm). Ninety-two percent methane conversion, 90% CO selectivity, and 15.5 ml/cm² min oxygen permeation flux were achieved in steady state at a temperature of 1123 K and a pressure of 5 atm. A syngas production rate of 79 ml/cm² min was obtained. Characterization of the membrane surface by SEM and XRD after reaction showed that the surface exposed to the air side preserved the Perovskite structure while the surface exposed to the reaction side was eroded.     

Catalytic performance of quaternary ammonium salts in the reaction of butyl glycidyl ether and carbon dioxide

The synthesis of cyclic carbonate from butyl glycidyl ether (BGE) and carbon dioxide was performed in the presence of quaternary ammonium salt catalysts. Quaternary ammonium salts of different alkyl group (C₃, C₄, C₆ and C₈) and anions (Cl⁻, Br⁻ and I⁻) were used for this reaction carried out in a batch autoclave reactor at 60–120 °C. The catalytic activity increased with increasing alkyl chain length in the order of C₃ < C₄ < C₆. But, the quaternary ammonium salt with longer alkyl chain length (C₈) decreased the conversion of BGE because it is too bulky to form an intermediate with BGE. For the counter anion of the tetrabutyl ammonium salt catalysts, the BGE conversion decreased in the order Cl⁻ > Br⁻ > I⁻. The effects of carbon dioxide pressure and reaction temperature on this reaction were also studied to better understand the reaction mechanism.     

Photocatalytic degradation kinetics of di- and tri-substituted phenolic compounds in aqueous solution by TiO2/UV

In this study, photocatalytic degradation of 2,4,6-trimethylphenol (TMP), 2,4,6-trichlorophenol (TCP), 2,4,6-tribromophenol (TBP), 2,4-dimethylphenol (DMP), 2,4-dichlorophenol (DCP) and 2,4-dibromophenol (DBP) has been studied by TiO₂/UV. Although degraded phenolic compound concentration increased by increasing initial concentration photocatalytic decomposition rates of di- and tri-substituted phenols at 0.1–0.5 mM initial concentrations decreased when the initial concentration increased. The fastest degradation observed for TCP and the slowest for TMP. Photodegradation kinetics of the compounds has been explained in terms of Langmuir–Hinshelwood kinetics model. Degradation rate constants have been observed to be extremely depended on electronegativity of the substituents on phenolic ring. Degradation rate constant and adsorption equilibrium constant of TCP were calculated as k 0.0083 mM min⁻¹ and K 9.03 mM⁻¹. For TBP and TMP the values of k and K were obtained as 0.0040 mM min⁻¹, 19.20 mM⁻¹, and 0.0017 mM min⁻¹, 51.68 mM⁻¹, respectively. Degradation rate constant of DBP was similar as DCP (0.0029 mM min⁻¹ for DBP and 0.0031 mM min⁻¹ for DCP) whereas adsorption equilibrium constants differed (48.40 mM⁻¹ for DBP and 30.52 mM⁻¹ for DCP). K and k of DMP found as 83.68 mM⁻¹ and 0.0019 mM min⁻¹, respectively. The adsorption equilibrium constants in the dark were ranged between 1.11 and 3.28 mM⁻¹ which are lower than those obtained in kinetics. Adsorption constants have inversely proportion with degradation rate constants for all phenolic compounds studied.     

H4SiW12O40-catalyzed oxidation of nitrobenzene in supercritical water: kinetic and mechanistic aspects

The catalytic effect of a heteropolyacid, H₄SiW₁₂O_40, on nitrobenzene (20 and 30 μM) oxidation in supercritical water was investigated. A capillary flow-through reactor was operated at varying temperatures (T=400–500 °C; P=30.7 MPa) and H₄SiW₁₂O₄₀ concentrations (3.5–34.8 μM) in an attempt to establish global power-law rate expressions for homogenous H₄SiW₁₂O₄₀-catalyzed and uncatalyzed supercritical water oxidation. Oxidation pathways and reaction mechanisms were further examined via primary oxidation product identification and the addition of various hydroxyl radical scavengers (2-propanol, acetone, acetone-d₆, bromide and iodide) to the reaction medium. Under our experimental conditions, nitrobenzene degradation rates were significantly enhanced in the presence of H₄SiW₁₂O₄₀. The major differences in temperature dependence observed between catalyzed and uncatalyzed nitrobenzene oxidation kinetics strongly suggest that the reaction path of H₄SiW₁₂O₄₀-catalyzed supercritical water oxidation (average activation E_a=218 kJ/mol; k=0.015–0.806 s⁻¹ energy for T=440–500 °C; E_a=134 kJ/mol for the temperature range T=470–490 °C) apparently differs from that of uncatalyzed supercritical water oxidation (E_a=212 kJ/mol; k=0.37–6.6 μM s⁻¹). Similar primary oxidation products (i.e. phenol and 2-, 3-, and 4-nitrophenol) were identified for both treatment systems. H₄SiW₁₂O₄₀-catalyzed homogenous nitrobenzene oxidation kinetics was not sensitive to the presence of OH√ scavengers.     

Oxidative coupling of methane in a mixed-conducting perovskite membrane reactor

Ionic-electronic mixed-conducting perovskite-type oxide La_0.6Sr_0.4Co_0.8Fe_0.2O₃ was applied as a dense membrane for oxygen supply in a reactor for methane coupling. The oxygen permeation properties were studied in the p_O2-range of 10⁻³−1 bar at 1073–1273 K, using helium as a sweeping gas at the permeate side of the membrane. The oxygen semi-permeability has a value close to 1 mmol m⁻² s⁻¹ at 1173 K with a corresponding activation energy of 130–140 kJ/mol. The oxygen flux is limited by a surface process at the permeate side of the membrane. It was found that the oxygen flux is only slightly enhanced if methane is admixed with helium. Methane is converted to ethane and ethene with selectivities up to 70%, albeit that conversions are low, typically 1–3% at 1073–1173 K. When oxygen was admixed with methane rather than supplied through the membrane, selectivities obtained were found to be in the range 30–35%. Segregation of strontium was found at both sides of the membrane, being seriously affected by the presence of an oxygen pressure gradient across it. The importance of a surface limited oxygen flux for application of perovskite membranes for methane coupling is emphasized.     

Optimisation of degradation conditions of 1,8-diazabicyclo[5.4.0]undec-7-ene in water and reaction kinetics analysis using a cocurrent downflow contactor photocatalytic reactor

The photocatalytic degradation of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, a non-biodegradable nitrogenous organic compound) in water was optimised under UV radiation using titanium dioxide photocatalyst. The reactor used was a pilot scale cocurrent downflow contactor photocatalytic reactor (CDCPR), a system offering very high mass transfer efficiency. The effect of photocatalyst loading, initial substrate concentration, temperature, pH, and different combinations of UV, O₂, H₂O₂ and TiO₂ on the photocatalytic oxidation of DBU was investigated. The TiO₂ photocatalyst used was Degussa VP Aeroperl P25/20, a granulated form of Degussa P-25, recently developed to ameliorate downstream catalyst separation problems. The CDCPR was fitted with an internally and vertically mounted 1.0 kW UV lamp. The reactions were carried out at 40–60 °C and 1 barg, with the reactor being operated in closed loop recycle mode and suspended photocatalyst being re-circulated. Optimisation of reaction conditions using a combination of TiO₂, UV radiation and O₂ gave the most rapid degradation and mineralisation of the DBU in comparison with other processes. Under optimised conditions, 100% degradation of DBU was achieved in 45 min, with a quantum yield of 7.39, using a 1 kW lamp, 0.5 g/dm³ TiO₂, 100 mg/dm³ DBU, 1 barg, 50 °C and pH of 3.17. Investigating the reaction pathway and its modelling showed a first order dependency, incorporating the effect of first intermediates of degradation. The activation energy was found to be 54.68 kJ mol⁻¹ showing a significant influence of temperature on the photocatalytic degradation of DBU.     

Photoelectrocatalytic and photocatalytic disinfection of E. coli suspensions by titanium dioxide

This paper reports studies of the photoelectrocatalytic and photocatalytic disinfection of E. coli suspensions by titanium dioxide in a sparged photoelectrochemical reactor.

Two types of titanium dioxide electrode have been used. ‘Thermal’ electrodes were made by oxidation of titanium metal mesh; ‘sol–gel’ electrodes were made by depositing and then heating a layer of titania gel on titanium mesh. Cyclic voltammetry was used to carry out an initial characterisation and optimisation of both electrode types. The best ‘thermal electrodes’—i.e. those with the highest photocurrents—were prepared by heating titanium mesh at 700 °C in air. For sol–gel derived electrodes, optimum performance was obtained by heating at 600 °C. These electrodes were then used, in a gas sparged reactor, to disinfect E. coli suspensions with an initial concentration of 10⁷ colony forming units (cfu) ml⁻¹. Films prepared by the oxidation of titanium metal were shown to be superior to sol–gel derived films. Direct experimental comparison demonstrates that the photoelectrochemical system is more efficient than photocatalytic disinfection effected by slurries of Degussa P25 titanium dioxide.

Since in practical systems the TiO₂ would be exposed to a variety of species additional to those that are targeted, we also examined the effects of H₂PO₄⁻ and HCO₃⁻ ions on the measured disinfection rates. Phosphate addition poisons both the electrode and particulate-slurry systems and is only partially reversible. By contrast, although bicarbonate addition affects all three systems, the effects are reversible.     

Kinetic studies of CH4 oxidation over Pt–NiO/δ-Al2O3 in a fluidised bed reactor

The oxidation of CH₄ over Pt–NiO/δ-Al₂O₃ has been studied in a fluidised bed reactor as part of a major project on an autothermal (combined oxidation–steam reforming) system for CH₄ conversion. The kinetic data were collected between 773 and 893 K and 101 kPa total pressure using CH₄ and O₂ compositions of 10–35% and 8–30%, respectively. Rate–temperature data were also obtained over alumina-supported monometallic catalysts, Pt and NiO. The bimetallic Pt–NiO system has a lower activation energy (80.8 kJ mol⁻¹) than either Pt (86.45 kJ mol⁻¹) and NiO (103.73 kJ mol⁻¹). The superior performance of the bimetallic catalyst was attributed to chemical synergy. The reaction rate over the Pt–NiO catalyst increased monotonically with CH₄ partial pressure but was inhibited by O₂. At low partial pressures (<30 kPa), H₂O has a detrimental effect on CH₄ conversion, whilst above 30 kPa, the rate increased dramatically with water content.     

Performance of microchannel reactor combined with combustor for methanol steam reforming

The microchannel reactor with combustor for methanol steam reforming was fabricated to produce hydrogen for onboard proton exchange membrane (PEM) fuel cell device. A commercial copper-containing catalyst (Cu/ZnO/Al₂O₃) and Pt/ZrO₂ were used as a catalyst for methanol steam reforming and combustion reaction, respectively. It was found that catalyst layer with zirconia sol solution in microchannel showed no crack on the surface of catalyst layer and an excellent adherence to stainless steel microchannel even after reaction. The temperature of combustor could be controlled between 200 and 300 °C depending on the methanol feed rate. The hydrogen flow of 3.9 l h⁻¹ hydrogen was obtained with the reforming feed flow rate of 3.65 ml h⁻¹ at 270 °C.     

Kinetics of the water–gas shift reaction over nanostructured copper–ceria catalysts

Water–gas shift reaction was studied over two nanostructured Cu_xCe_1−xO_2−y catalysts: a Cu_0.1Ce_0.9O_2−y catalyst prepared by a sol–gel method and a Cu_0.2Ce_0.8O_2−y catalyst prepared by co-precipitation method. A commercial low temperature water–gas shift CuO–ZnO–Al₂O₃ catalyst was used as reference. The kinetics was studied in a plug flow micro reactor at an atmospheric pressure in the temperature interval between 298 and 673 K at two different space velocities: 5.000 and 30.000 h⁻¹, respectively. Experimentally estimated activation energy, E_af, of the forward water–gas shift reaction at CO/H₂O = 1/3 was 51 kJ/mol over the Cu_0.1Ce_0.9O_2−y, 34 kJ/mol over the Cu_0.2Ce_0.8O_2−y and 47 kJ/mol over the CuO–ZnO–Al₂O₃ catalyst. A simple rate expression approximating the water–gas shift process as a single reversible surface reaction was used to fit the experimental data in order to evaluate the rate constants of the forward and backward reactions and of the activation energy for the backward reaction.     

Reaction and oxygen permeation studies in Sm0.4Ba0.6Fe0.8Co0.2O3 − δ membrane reactor for partial oxidation of methane to syngas

A disk-type Sm_0.4Ba_0.6Co_0.2Fe_0.8O_3 − δ perovskite-type mixed-conducting membrane was applied to a membrane reactor for the partial oxidation of methane to syngas (CO + H₂). The reaction was carried out using Rh (1 wt%)/MgO catalyst by feeding CH₄ diluted with Ar. While CH₄ conversion increased and CO selectivity slightly decreased with increasing temperature, a high level of CH₄ conversion (90%) and a high selectivity to CO (98%) were observed at 1173 K. The oxygen flux was increased under the conditions for the catalytic partial oxidation of CH₄ compared with that measured when Ar was fed to the permeation side. We investigated the reaction pathways in the membrane reactor using different membrane reactor configurations and different kinds of gas. In the membrane reactor without the catalyst, the oxygen flux was not improved even when CH₄ was fed to the permeation side, whereas the oxygen flux was enhanced when CO or H₂ was fed. It is implied that the oxidation of CO and H₂ with the surface oxygen on the permeation side improves the oxygen flux through the membrane, and that CO₂ and H₂O react with CH₄ by reforming reactions to form syngas.     

Influence of exchanged cations (Na, Cs, Sr and Ba) on xylene permeation through ZSM-5/SS tubular membranes

Na-ZSM-5 membranes were synthesized by secondary growth on the outer surface of stainless steel porous tubes. The membranes were ion-exchanged with Cs⁺, Ba²⁺ and Sr²⁺ to investigate their effect upon the separation of p-xylene from m-xylene and o-xylene. The permeation through the membranes was measured between 150 and 400 °C using each xylene isomer separately and a ternary mixture. All the membranes were selective to p-xylene in the temperature range studied. N₂ and xylene permeation measurements together with SEM observations were used to determine whether or not cracks and/or pinholes developed after exposure to the xylene isomers at high temperature (400 °C). Neither pore blockage nor extra-zeolitic pores developed after the ion exchange procedure and subsequent calcination. Furthermore, duplicate synthesized membranes of each cation form had similar separation factors and permeances. The duplicate values differ much less than the measurement error. The p-xylene permeation flux decreased in the order: Na-ZSM-5 > Ba-ZSM-5 > Sr-ZSM-5  Cs-ZSM-5 while the permeation flux of the m- and o-xylene decreased in the order Na-ZSM-5 > Sr-ZSM-5 > Ba-ZSM-5 > Cs-ZSM-5. The membrane that exhibited the best performance was Ba-ZSM-5, with a maximum p/o separation factor of 8.4 and a p-xylene permeance of 0.54 × 10⁻⁷ mol s⁻¹ m⁻² Pa⁻¹ at 400 °C.     

Photocatalytic oxidation of CO with various oxidants by Mo oxide species highly dispersed on SiO2 at 293 K

The photocatalytic oxidation of CO into CO₂ with oxidants such as NO, N₂O and O₂ proceeded efficiently on a Mo/SiO₂ with high Mo dispersion under UV light irradiation. It was found that the reaction rate greatly depended on the kind and concentration of the oxidant. Photoluminescence investigations reveal the close relationship between the reaction rate and the relative concentration of the photo-excited Mo⁶⁺-oxide species, i.e. charge transfer–excited–triplet state (Mo⁵⁺–O⁻)^*, under steady-state reaction conditions. Moreover, the photocatalytic oxidation of CO with O₂ in excess H₂ was carried out to test suitability for applications to supplying pure H₂. This reaction was seen to proceed efficiently on Mo/SiO₂ with a high CO conversion of 100% and CO selectivity of 99% after 180 min under UV light irradiation, showing higher photocatalytic performance than TiO₂ (P-25) photocatalyst. UV–vis, XAFS, photoluminescence and FT-IR investigations revealed that the high reactivity of the charge transfer–excited–triplet state (Mo⁵⁺–O⁻)^*, with CO as well as the high reactivity of the photoreduced Mo-oxide species (Mo⁴⁺-species) with O₂ to produce the original Mo-oxide species (Mo⁶⁺O²⁻), played a crucial role in the reactions.