Adsorption and Reactions of CH2I2 on Clean and Oxygen-Modified Ag(111): a RAIRS and TPD Study

The surface chemistry of CH₂I₂ on Ag(111) in the presence and absence of pre-adsorbed O, produced by NO₂ adsorption at elevated temperature, has been examined using temperature-programmed desorption and reflection absorption infrared spectroscopy. There is good evidence for the formation of adsorbed methylene, CH₂(a), that reacts with another CH₂(a) to form and desorb ethylene, C₂H₄(g), in a reaction-limited process. Increasing the surface coverage of CH₂I₂ hinders both the dissociation and recombination processes indicated by the upward temperature shift in the formation of C₂H₄. Co-adsorbed O atoms strengthen the bonding of CH₂I₂ to the surface; the increased thermal stability is up to 60 K. The formation of C₂H₄ decreases with increasing amounts of pre-adsorbed O; the main reaction product is CH₂O produced in a reaction-limited process. CH₂O forms either on the chemisorbed or on the oxide phase with desorption peak temperatures of 225 and 270 K, respectively. The formation of gas-phase carbon dioxide suggests that a formate intermediate is involved in a secondary reaction pathway.     

Photocatalytic reduction of N2O on metal-supported TiO2 powder at room temperature in the presence of H2O and CH3OH vapor

Ag- and Cu-supported TiO₂ photocatalysts showed high activity for the reduction of N₂O to N₂ at room temperature in the presence of CH₃OH and H₂O vapor. The suppression by H₂O on the activity was not observed in the present photocatalyst system. The remarkable behavior of the Ag and Cu co-catalysts for TiO₂ photocatalysts agreed well with that of electro- and thermal catalyses. This revised version was published online in July 2006 with corrections to the Cover Date.     

A comparative study of the thermal stability and reactions of CH2, CH3 and C2H5 species on the Pd(100) surface

Adsorbed CH₂, CH₂ and C₂H₅ moieties were produced on Pd(100) at 90 K by photoinduced dissociation of the corresponding iodo compounds, and their thermal reactions were established.This laboratory is a part of the Center of Catalysis, Surface and Material Science at the University of Szeged.     

The effects of a potassium overlayer on the reaction pathway of CH2 and C2H5 on Rh(111)

The effect of potassium on the reaction pathways of adsorbed CH₂ and C₂H₅ species on Rh(111) was investigated by means of reflection absorption infrared spectroscopy (RAIRS) and temperature programmed desorption (TDS). Hydrocarbon fragments were produced by thermal and photo-induced dissociation of the corresponding iodo compounds. Potassium adatoms markedly stabilized the adsorbed CH₂ and converted it into C₂H₄, the formation of which was not observed for K-free Rh(111). New routes of the surface reactions of C₂H₅ have been also opened in the presence of potassium, namely its transformation into butane and butene.     

Catalytic Performance of Pt/ZrO2 and Pt/Ce-ZrO2 Catalysts on CO2 Reforming of CH4 Coupled with Steam Reforming or Under High Pressure

CO₂ reforming of methane was performed on Pt/ZrO₂ and Pt/Ce-ZrO₂ catalysts at 1073K under different reactions conditions: (i) atmospheric pressure and CH₄:CO₂ ratio of 1:1 and 2:1; (ii) in the presence of water and CH₄:CO₂ ratio of 2:1; (iii) under pressure (105 and 190 psig) and CH₄:CO₂ ratio of 2:1. The Pt supported on ceria-promoted ZrO₂ catalyst was more stable than the Pt/ZrO₂ catalyst under all reaction conditions. We ascribe this higher stability to the higher density of oxygen vacancies on the promoted support, which favors the cleaning mechanism of the metal particle. The increase of either the CH₄:CO₂ ratio or total pressure causes a decrease in activity for both catalysts, because under either case the rate of methane decomposition becomes higher than the rate of oxygen transfer. The Pt/Ce-ZrO₂ catalyst was always more stable than the Pt/ZrO₂ catalyst, demonstrating the important role of the support on this reaction.     

TiO2/ZnO Supported on Sepiolite: Preparation,Structural Characterization,and Photocatalytic Degradation of Flumequine Antibiotic in Aqueous Solution

In this study, TiO₂, ZnO, TiO₂/ZnO (Ti/Zn), and TiO₂/ZnO/Sep (Ti/Zn/Sep) catalysts have been synthesized using sol–gel and chemical precipitation method. Their photocatalytic performances have been compared using Flumequine (FLQ) antibiotic. X-ray diffraction (XRD), Fourier transform infrared spectra (FTIR), scanning electron microscopy (SEM), N₂-adsorption, and the determination of a zero point charge has been used to characterize the synthesized catalysts. The degradation studies showed that the catalytic efficiency of Ti/Zn/Sep is higher than that for other catalysts. The operational parameters such as pH, initial FLQ concentration, and catalyst dosage were evaluated. UV–vis and high-resolution mass spectroscopy (HRMS) analyses were used to determine the degradation efficiency and products. ZnO played a major role in the FLQ degradation process, and sepiolite contributed to adsorption of FLQ on the catalyst surface enormously. The catalysts exhibited 11%, 23%, 63%, and 85% degradation efficiency for ZnO, TiO₂, Ti/Zn, and Ti/Zn/Sep in the decomposition of FLQ, respectively.     

Isotope effect of H2/D2 and H2O/D2O for the PROX reaction of CO on the FeOx/Pt/TiO2 catalyst

The oxidation reaction of CO with O₂ on the FeOx/Pt/TiO₂ catalyst is markedly enhanced by H₂ and/or H₂O, but no such enhancement occurs on the Pt/TiO₂ catalyst. Isotope effects were studied by H₂/D₂ and H₂O/D₂O on the FeOx/Pt/TiO₂ catalyst, and almost the same magnitude of isotope effect of ca. 1.4 was observed for the enhancement of the CO conversion by H₂/D₂ as well as by H₂O/D₂O at 60 °C. This result suggests that the oxidation of CO with O₂ via such intermediates as formate or bicarbonate in the presence of H₂O, in which H₂O or D₂O acts as a molecular catalyst to promote the oxidation of CO as described below.      

ZnO/Cr2O3 catalyst for reverse-water-gas-shift reaction of CAMERE process

The stability and the activity of Fe₂O₃/Cr₂O₃ and ZnO/Cr₂O₃ catalysts were examined for a reverse-watergas-shift reaction (RWReaction). The initial activities of those catalysts were quite high so that the conversion reached close to equilibrium. The activity of Fe₂O₃/Cr₂O₃ catalyst decreased from 33.5 to 29.8% during the RWReaction for 75 h at 873 K with GHSV (ml/gcat · h) of 100,000. Moreover, the coke formation on the Fe₂O₃/Cr₂O₃ catalyst caused clogging in the RWReactor of the CAMERE process. On the other hand, the ZnO/Cr₂O₃ catalyst showed no coke formation and no deactivation for the RWReaction at 873 K with GHSV (ml/gcat · h) of 150,000. The ZnO/Cr₂O₃ was a good catalyst for the RWReaction of the CAMERE process.     

Stoichiometric photocatalytic decomposition of pure water in Pt/TiO2 aqueous suspension system

The influence of the direction of ultraviolet irradiation upon the yields of the photocatalytic decomposition of pure water has been investigated in Pt/TiO₂ aqueous suspension system. The yields of the photocatalytic decomposition irradiated from the top of the reaction cell are about 10³ times higher than those irradiated from the bottom. The difference seems due to the reverse reaction of the formed H₂ and O₂ in the suspension.     

Nb–TiO2 supported platinum nanocatalyst for oxygen reduction reaction in alkaline solutions

Platinum based nanocatalyst at home made Nb–TiO₂ support was synthesized and characterized as the catalyst for oxygen reduction reaction in 0.1 mol dm⁻³ NaOH, at 25 °C. Nb doped TiO₂ catalyst support, containing 5% of Nb, has been synthesized by modified acid-catalyzed sol–gel procedure in non-aqueous medium. BET and X-ray diffraction (XRD) techniques were applied for characterization of synthesized supporting material. XRD analysis revealed only presence of anatase TiO₂ phase in synthesized support powder. Existence of any peaks belonging to Nb compounds has not been observed, indicating Nb incorporated into the lattice.Nb–TiO₂ supported Pt nanocatalyst synthesized, using borohydride reduction method, was characterized by TEM and HRTEM techniques. Platinum nanoparticles distribution, over Nb doped TiO₂ support, was quite homogenous. Mean particle size of about 4 nm was found with no pronounced particle agglomeration. Electrochemical techniques: cyclic voltammetry and linear sweep voltammetry at rotating disc electrode were applied in order to study kinetics and estimate catalytic activity of this new catalyst for the oxygen reduction reaction in alkaline solution. Two different Tafel slopes were found: one close to −90 mV dec⁻¹ in low current density region and other approximately −200 mV dec⁻¹ in high current density region, which is in good accordance with literature results for oxygen reduction at Pt single crystals, as well as Pt nanocatalysts in alkaline solutions. Similar specific catalytic activity (expressed in term of kinetic current density per real surface area) of Nb(5%)–TiO₂/Pt catalyst for oxygen reduction reaction in comparison with the carbon supported platinum (Vulcan/Pt) nanocatalyst, was found.     

Infrared study of crotonaldehyde and CO adsorption on a Pt/TiO2 catalyst

A Pt/TiO₂ catalyst has been subjected to reduction in hydrogen at 473, 573 and 773 K and the various degrees of metal-support interaction (SMSI) confirmed by means of CO and H₂ chemisorption, FTIR of CO and the hydrogenation of crotonaldehyde. Coadsorption of CO and crotonaldehyde were performed to identify the preferred adsorption site and mode of adsorption of the unsaturated aldehyde. Results which appear to suggest shifts to lower frequencies of bands due to adsorbed carbonyls are not due to electronic effects induced by coadsorption, but rather indicate displacement of CO from the weaker bonding sites which eliminate dipole coupling effects between different carbonyl clusters, and consequently removes intensity transfer phenomena leading to enhancement in intensity at lower frequencies. This revised version was published online in August 2006 with corrections to the Cover Date.     

A Novel Catalyst Pt/CoAl2O4/Al2O3 for Combination CO2 Reforming and Partial Oxidation of CH4

Pt/CoAl₂O₄/Al₂O₃, Pt/CoO_x/Al₂O₃, CoAl₂O₄/Al₂O₃ and CoO_x/Al₂O₃ catalysts were studied for combination CO₂ reforming and partial oxidation of CH₄. The results indicate that Pt/CoAl₂O₄/Al₂O₃ is the most effective, and XRD results indicate that Pt species are well dispersed over the Pt/CoAl₂O₄/Al₂O₃. High dispersion is related to the presence of CoAl₂O₄, formed during calcining at high temperature before Pt addition. In the presence of Pt, CoAl₂O₄ in the catalyst could be reduced partially at 973 K. Based on these results, it appears that zerovalent platinum with high dispersion and zerovalent cobalt resulting from CoAl₂O₄ reduction are responsible for high activity in the Pt/CoAl₂O₄/Al₂O₃ catalyst.     

Improvement of Pt/ZrO2 by CeO2 for high pressure CH4/CO2 reforming

CH₄/CO₂ reforming over Pt/ZrO₂, Pt/CeO₂ and Pt/ZrO₂ with CeO₂ was investigated at 2 MPa. Pt/ZrO₂, which shows stable activity under 0.1 MPa, and Pt/CeO₂ showed gradual deactivation with time at the high pressure. The deactivation was suppressed drastically on Pt/ZrO₂ with CeO₂ prepared by different impregnation order (co-impregnation of Pt and CeO₂ on ZrO₂, and consecutive impregnation of Pt and CeO₂ on ZrO₂). The amount of coke deposition was found insignificant and similar among all the catalysts (including Pt/ZrO₂ and Pt/CeO₂). Catalytic activity after the reaction for 24 h was in agreement with Pt particle size after the reaction for same period, indicating that the difference of the catalytic stability is mainly dependent on the extent of Pt aggregation through catalyst preparation, H₂ reduction, and the CH₄/CO₂ reforming. Pt aggregation and the amount of coke deposition were least pronounced on (Pt–Ce)/ZrO₂ prepared by impregnation of CeO₂ on Pt/ZrO₂ and the catalyst showed highest stability.     

Synthesis, structure, and photovoltaic property of a nanocrystalline 2H perovskite-type novel sensitizer (CH3CH2NH3)PbI3

A new nanocrystalline sensitizer with the chemical formula (CH₃CH₂NH₃)PbI₃ is synthesized by reacting ethylammonium iodide with lead iodide, and its crystal structure and photovoltaic property are investigated. X-ray diffraction analysis confirms orthorhombic crystal phase with a = 8.7419(2) Å, b = 8.14745(10) Å, and c = 30.3096(6) Å, which can be described as 2 H perovskite structure. Ultraviolet photoelectron spectroscopy and UV-visible spectroscopy determine the valence band position at 5.6 eV versus vacuum and the optical bandgap of ca. 2.2 eV. A spin coating of the CH₃CH₂NH₃I and PbI₂ mixed solution on a TiO₂ film yields ca. 1.8-nm-diameter (CH₃CH₂NH₃)PbI₃ dots on the TiO₂ surface. The (CH₃CH₂NH₃)PbI₃-sensitized solar cell with iodide-based redox electrolyte demonstrates the conversion efficiency of 2.4% under AM 1.5 G one sun (100 mW/cm²) illumination.     

The influence of MSI (metal–support interactions) on activity and selectivity in the hydrogenation of aldehydes and ketones

The vapor–phase hydrogenation of a group of aldehydes and ketones which contain unsaturated C=C bonds has been studied over a family of supported Pt catalysts. Turnover frequencies, activation energies and reaction orders for crotonaldehyde, benzaldehyde, phenylacetaldehyde and acetophenone are provided and compared to those for butyraldehyde, benzyl alcohol, 1–phenylethanol, acetylcyclohexane and acetone. Metal–support interactions (MSI) induced in Pt/TiO₂ not only enhance specific activity but also markedly shift selectivity because hydrogenation of the carbonyl bond is favored. The retention of high selectivity to the intermediate unsaturated alcohols shows that adsorption properties, as well as kinetic parameters, are altered. A model is discussed which describes the sites responsible for this behavior. This revised version was published online in June 2006 with corrections to the Cover Date.     

Catalytic reaction of CH4 with CO2 over alumina-supported Pt metals

The dissociation of CH₄ and CO₂, as well as the reaction between CH₄ and CO₂ at 723–823 K have been studied over alumina supported Pt metals. In the high temperature interaction of CH₄ with catalyst surface small amounts of C₂H₆ were detected. In the reaction of CH₄+CO₂, CO and H₂ were produced with different ratios. The specific activities of the catalysts decreased in the order: Ru, Pd, Rh, Pt and Ir, which agreed with their activity order towards the dissociation of CO₂.This laboratory is a part of the Center for Catalysis, Surface and Material Science at the University of Szeged.     

Electro-oxidation of coal on NiO and/or Co3O4 modified TiO2/Pt electrodes

A TiO₂/Pt based electrode exhibited better activity for the oxidation of coal in a basic system compared to Ti/Pt, TiO₂–Cu/Pt and pure metal electrodes. The surface morphologies and composition of the electrodes were studied by SEM and XRD, respectively. Linear sweep voltammetry was employed to investigate the catalytic effects of electrodes, and the product of coal oxidization was determined by a gas collection test. The TiO₂/Pt electrodes that were modified with NiO and/or Co₃O₄ exhibited higher average currents and a lower decrease in mass during electrolysis compared to the other electrodes; this finding indicated that NiO and Co₃O₄ play important roles as catalysts.     

Decomposition and oxidation of CH3 13CH2OH on A12O3, Pd/Al2O3, and PdO/Al2O3 catalysts

Temperature-programmed desorption (TPD) and oxidation (TPO) were used to investigate the decomposition and oxidation of ethanol on Al₂O₃, Pd/Al₂O₃, and PdO/Al₂O₃. Ethyl--¹³C alcohol (CH₃ ¹³CH₂OH) was adsorbed on the catalysts so that reaction pathways of the two carbons could be distinguished. Alumina was mainly a dehydration catalyst, but dehydrogenation was also observed and some carbon remained on the surface. In the presence of O₂, A1₂O₃ oxidized the decomposition products and the-carbon was oxidized faster. Ethanol, which was adsorbed on A1₂O₃, decomposed much faster on Pd/A1₂O₃ by diffusing to Pd and undergoing CO elimination to form CH₄,¹³CO, H₂, and surface carbon. On PdO/A1₂O₃, the decomposition was slower than on Pd/A1₂O₃ until lattice oxygen was extracted above 450 K; the decomposition products were oxidized by lattice oxygen. In the presence of gas phase O₂, Pd/Al₂O₃ was an active oxidation catalyst at low temperature, but lattice oxygen had to be extracted from PdO/A1₂O₃ before it had significant oxidation activity.     

An HREM study of the WO3/TiO2 monolayer catalyst system. Proposals for the overlayer structure

High resolution electron microscopy (HREM) has been used to characterise the WO₃/TiO₂ (anatase) catalyst system. Comparisons between pure samples of TiO₂ in the uncalcined and calcined states with titania in the catalyst (loaded with 10 wt% WO₃) indicate that the tungsten oxide overlayer preserves the surface roughness of the support (as observed in the pure uncalcined material). The calcination of pure anatase results in significant grain growth and surface smoothing. In the electron microscope, the tungsten oxide overlayer is revealed as 2D pseudo-hexagonal shaped clusters which appear to be epitaxially related to the support. After noting that the anatase support predominantly exposes {112}, {011}, {110} and (001) type facets we have combined this information with structural data on the overlayer derived from a previous EXAFS and XANES study by Hilbrig et al. that reported the presence of WO₄ species and six-coordinate WO₅ groups. By considering the arrangement of terminating oxygen atoms on each of the aforementioned anatase surfaces, we suggest ways in which the WO _x species may be linked together to form the tungsten oxide overlayer. This approach has led us to conclude that, with the exception of the (001) surface, the overlayer may consist of WO₄ dimers rather than chains of linked WO₅ groups terminated by WO₄ species.     

The combination of photocatalysis process (UV/TiO2(P25) and UV/ZnO) with activated sludge culture for the degradation of sulfamethazine

The major factors affecting the removal efficiency of sulfamethazine (SMT) by photocatalysis process in the presence of TiO₂ P25 or ZnO, namely the pH, the amount of catalyst and the initial SMT concentration were examined. The obtained results showed the absence of adsorption of SMT on the catalysts and the absence of degradation of SMT by direct photolysis under UV light in the absence of catalyst. The variation of the pH solution in the range 4–9 did not cause any significant degradation of SMT. The optimal amounts of each catalyst were, respectively, 0.5 and 0.25 g/L for TiO₂ P25 and ZnO. Increasing the initial SMT concentration impacted negatively the removal efficiency, which decreased from 31% to 13% and from 100% to 27% in the presence of TiO₂ P25 and ZnO in the presence of 10 mg/L and 50 of SMT after 30-min reaction time, respectively. The obtained results showed better efficiency of ZnO than TiO₂ P25 regarding both removal efficiency and chemical oxygen demand (COD) abatement. However, removal efficiency and COD abatement were not complete, even after 7 h of photocatalysis, about 92% and 41%, respectively. The biodegradability was examined after photocatalysis performed in the following conditions: [SMT]₀ = 50 mg/L, pH = 6, T = 25°C, ω = 360 rpm and 0.5 g/L of TiO₂ P25 or 0.25 g/L of ZnO. In these conditions, the removal efficiencies were, respectively, 26% and 41% in the presence of TiO₂ P25 and 55 and 92% in the presence of ZnO after 4 and 7 h of pretreatment times, respectively. The BOD₅/COD ratio increased substantially and, respectively, from 0 to 0.25 and from 0 to 0.16 in the presence of TiO₂ P25 and ZnO after 7 h of irradiation. Even if the limit of biodegradability (0.4) was not achieved, a subsequent biological treatment was considered in the presence of TiO₂ P25, leading to 58% COD abatement after a 28-day culture.