Kinetics and selectivity of methane oxidation on an IrO2(110) film

Undercoordinated, bridging O-atoms (Obr) are highly active as H-acceptors in alkane dehydrogenation on IrO2(110) surfaces but transform to HObr groups that are inactive toward hydrocarbons. The low C-H activity and high stability of the HObr groups cause the kinetics and product selectivity during CH4 oxidation on IrO2(110) to depend sensitively on the availability of Obr atoms prior to the onset of product desorption. From temperature programmed reaction spectroscopy (TPRS) and kinetic simulations, we identified two Obr-coverage regimes that distinguish the kinetics and product formation during CH4 oxidation on IrO2(110). Under excess Obr conditions, when the initial Obr coverage is greater than that needed to oxidize all the CH4 to CO2 and HObr groups, complete CH4 oxidation is dominant and produces CO2 in a single TPRS peak between 450 and 500 K. However, under Obr-limited conditions, nearly all the initial Obr atoms are deactivated by conversion to HObr or abstracted after only a fraction of the initially adsorbed CH4 oxidizes to CO2 and CO below 500 K. Thereafter, some of the excess CHx groups abstract H and desorb as CH4 above ~500 K while the remainder oxidize to CO2 and CO at a rate that is controlled by the rate at which Obr atoms are regenerated from HObr during the formation of CH4 and H2O products. We also show that chemisorbed O-atoms (“on-top O”) on IrO2(110) enhance CO2 production below 500 K by efficiently abstracting H from Obr atoms and thereby increasing the coverage of Obr atoms available to completely oxidize CHx groups at low temperature. Our results provide new insights for understanding factors which govern the kinetics and selectivity during CH4 oxidation on IrO2(110) surfaces.

Influence of Cs Promoter on Ethanol Steam-Reforming Selectivity of Pt/m-ZrO2 Catalysts at Low Temperature

The decarboxylation pathway in ethanol steam reforming ultimately favors higher selectivity to hydrogen over the decarbonylation mechanism. The addition of an optimized amount of Cs to Pt/m-ZrO2 catalysts increases the basicity and promotes the decarboxylation route, converting ethanol to mainly H2, CO2, and CH4 at low temperature with virtually no decarbonylation being detected. This offers the potential to feed the product stream into a conventional methane steam reformer for the production of hydrogen with higher selectivity. DRIFTS and the temperature-programmed reaction of ethanol steam reforming, as well as fixed bed catalyst testing, revealed that the addition of just 2.9% Cs was able to stave off decarbonylation almost completely by attenuating the metallic function. This occurs with a decrease in ethanol conversion of just 16% relative to the undoped catalyst. In comparison with our previous work with Na, this amount is—on an equivalent atomic basis—just 28% of the amount of Na that is required to achieve the same effect. Thus, Cs is a much more efficient promoter than Na in facilitating decarboxylation.

Physicochemical Properties of MoVTeNb Mixed Oxide Catalysts Synthesized using Different Vanadium Sources

The use of different vanadium sources in the synthesis of multi-metal MoVTeNb oxide catalysts has been investigated for their effect on the physicochemical properties of catalysts. Metal oxides were synthesized by slurry method assisted with a microwave irradiation. Vanadium pentoxide (V2O5), vanadyl sulphate (VOSO4) and ammonium metavanadate (NH4VO3) were used as the vanadium sources, respectively. X-ray diffraction (XRD) pattern showed the existence of orthorhombic (M1) phases in all catalysts. The catalyst prepared using V2O5 produced the highest formation of the phase. This was further supported by Inductive Couple Plasma-Atomic Emission Spectroscopy (ICP-AES), which showed that the V2O5 catalyst has the highest V: Mo ratio, mainly responsible for the high catalytic activity. Temperature Programmed Reduction in Hydrogen (H2-TPR) showed better reducibility for the catalyst when compared to the others. Temperature Programmed Reaction (TPRn) confirmed that the oxidants active for propane conversion into acrylic acid were originated from the lattice of the catalyst.

Promoting the Selectivity of Pt/m-ZrO2 Ethanol Steam Reforming Catalysts with K and Rb Dopants

The ethanol steam reforming reaction (ESR) was investigated on unpromoted and potassium- and rubidium-promoted monoclinic zirconia-supported platinum (Pt/m-ZrO2) catalysts. Evidence from in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) characterization indicates that ethanol dissociates to ethoxy species, which undergo oxidative dehydrogenation to acetate followed by acetate decomposition. The acetate decomposition pathway depends on catalyst composition. The decarboxylation pathway tends to produce higher overall hydrogen selectivity and is the most favored route at high alkali loading (2.55 wt.% K and higher or 4.25 wt.% Rb and higher). On the other hand, decarbonylation is a significant route for the undoped catalyst or when a low alkali loading (e.g., 0.85% K or 0.93% Rb) is used, thus lowering the overall H2 selectivity of the process. Results of in situ DRIFTS and the temperature-programmed reaction of ESR show that alkali doping promotes forward acetate decomposition while exposed metallic sites tend to facilitate decarbonylation. In previous work, 1.8 wt.% Na was found to hinder decarbonylation completely. Due to the fact that 1.8 wt.% Na is atomically equivalent to 3.1 wt.% K and 6.7 wt.% Rb, the results show that less K (2.55% K) or Rb (4.25% Rb) is needed to suppress decarbonylation; that is, more basic cations are more efficient promoters for improving the overall hydrogen selectivity of the ESR process.

Decomposition of Formic Acid over Orthorhombic Molybdenum Carbide

The decomposition of formic acid is investigated on the β-Mo₂C (100) catalyst surface using density functional theory. The dehydration and dehydrogenation mechanism for the decomposition is simulated, and the thermochemistry and kinetics are discussed. The potential energy landscape of the reaction shows a thermodynamically favourable cleavage of H-COOH to form CO; however, the kinetics show that the dehydrogenation mechanism is faster and CO₂ is continuously formed. The effect of HCOOH adsorption on the surface is also analysed, in a temperature-programmed reaction, with the decomposition proceeding at under 350 K and desorption of CO₂ observed.

Decomposition of Formic Acid over Orthorhombic Molybdenum Carbide

The decomposition of formic acid is investigated on the β-Mo₂C (100) catalyst surface using density functional theory. The dehydration and dehydrogenation mechanism for the decomposition is simulated, and the thermochemistry and kinetics are discussed. The potential energy landscape of the reaction shows a thermodynamically favourable cleavage of H-COOH to form CO; however, the kinetics show that the dehydrogenation mechanism is faster and CO₂ is continuously formed. The effect of HCOOH adsorption on the surface is also analysed, in a temperature-programmed reaction, with the decomposition proceeding at under 350 K and desorption of CO₂ observed.

On Catalytic Behavior of Bulk Mo2C in the Hydrodenitrogenation of Indole over a Wide Range of Conversion Thereof

The catalytic activity of bulk molybdenum carbide (Mo2C) in the hydrodenitrogenation (HDN) of indole was studied. The catalyst was synthesized using a temperature-programmed reaction of the respective oxide precursor (MoO3) with the carburizing gas mixture of 10 vol.\% CH4/H2. The resultant material was characterized using X-ray diffraction, CO chemisorption, and nitrogen adsorption. The catalytic activity was studied in the HDN of indole over a wide range of conversion thereof and in the presence of a low amount of sulfur (50 ppm), which was used to simulate the processing of real petroleum intermediates. The molybdenum carbide has shown high activity under the tested operating conditions. Apparently, the bulk molybdenum carbide turned out to be selective towards the formation of aromatic products such as ethylbenzene, toluene, and benzene. The main products of HDN were ethylbenzene and ethylcyclohexane. After 99% conversion of indole HDN was reached (i.e., lack of N-containing compounds in the products was observed), the hydrogenation of ethylbenzene to ethylcyclohexane took place. Thus, the catalytic behavior of bulk molybdenum carbide for the HDN of indole is completely different compared to previously studied sulfide-based systems.