Catalysts Promoted with Niobium Oxide for Air Pollution Abatement

Pt-containing catalysts are currently used commercially to catalyze the conversion of carbon monoxide (CO) and hydrocarbon (HC) pollutants from stationary chemical and petroleum plants. It is well known that Pt-containing catalysts are expensive and have limited availability. The goal of this research is to find alternative and less expensive catalysts to replace Pt for these applications. This study found that niobium oxide (Nb2O5), as a carrier or support for certain transition metal oxides, promotes oxidation activity while maintaining stability, making them candidates as alternatives to Pt. The present work reports that the orthorhombic structure of niobium oxide (formed at 800 °C in air) promotes Co3O4 toward the oxidation of both CO and propane, which are common pollutants in volatile organic compound (VOC) applications. This was a surprising result since this structure of Nb2O5 has a very low surface area (about 2 m2/g) relative to the more traditional Al2O3 support, with a surface area of 150 m2/g. The results reported demonstrate that 1% Co3O4/Nb2O5 has comparable fresh and aged catalytic activity to 1% Pt/γ-Al2O3 and 1% Pt/Nb2O5. Furthermore, 6% Co3O4/Nb2O5 outperforms 1% Pt/Al2O3 in both catalytic activity and thermal stability. These results suggest a strong interaction between niobium oxide and the active component—cobalt oxide—likely by inducing an oxygen defect structure with oxygen vacancies leading to enhanced activity toward the oxidation of CO and propane

Probing the role of a non-thermal plasma (NTP) in the hybrid NTP catalytic oxidation of methane

Three recurring hypotheses are often used to explain the effect of non-thermal plasmas (NTPs) on NTP catalytic hybrid reactions; namely, modification or heating of the catalyst or creation of new reaction pathways by plasma-produced species. NTP-assisted methane (CH4) oxidation over Pd/Al2O3 was investigated by direct monitoring of the X-ray absorption fine structure of the catalyst, coupled with end-of-pipe mass spectrometry. This in situ study revealed that the catalyst did not undergo any significant structural changes under NTP conditions. However, the NTP did lead to an increase in the temperature of the Pd nanoparticles; although this temperature rise was insufficient to activate the thermal CH4 oxidation reaction. The contribution of a lower activation barrier alternative reaction pathway involving the formation of CH3(g) from electron impact reactions is proposed

The Role of Ruthenium in CO2 Capture and Catalytic Conversion to Fuel by Dual Function Materials (DFM)

Development of sustainable energy technologies and reduction of carbon dioxide in the atmosphere are the two effective strategies in dealing with current environmental issues. Herein we report a Dual Function Material (DFM) consisting of supported sodium carbonate in intimate contact with dispersed Ru as a promising catalytic solution for combining both approaches. The Ru-Na2CO3 DFM deposited on Al2O3 captures CO2 from a flue gas and catalytically converts it to synthetic natural gas (i.e., methane) using H2 generated from renewable sources. The Ru in the DFM, in combination with H2, catalytically hydrogenates both adsorbed CO2 and the bulk Na2CO3, forming methane. The depleted sites adsorb CO2 through a carbonate reformation process and in addition adsorb CO2 on its surface. This material functions well in O2- and H2O-containing flue gas where the favorable Ru redox property allows RuOx, formed during flue gas exposure, to be reduced during the hydrogenation cycle. As a combined CO2 capture and utilization scheme, this technology overcomes many of the limitations of the conventional liquid amine-based CO2 sorbent technology

The application of inelastic neutron scattering to investigate the ‘dry’ reforming of methane over an alumina-supported nickel catalyst operating under conditions where filamentous carbon formation is prevalent

The use of CO2 in reforming methane to produce the industrial feedstock syngas is an economically and environmentally attractive reaction. An alumina-supported nickel catalyst active for this reaction additionally forms filamentous carbon. The catalyst is investigated by inelastic neutron scattering as well as elemental analysis, temperature-programmed oxidation, temperature-programmed hydrogenation, X-ray diffraction, transmission electron microscopy and Raman scattering. Isotopic substitution experiments, using 13CO2 for 12CO2, show the oxidant to contribute to the carbon retention evident with this sample. At steady-state operation, a carbon mass balance of 95 % is observed. A kinetic scheme is proposed to account for the trends observed

Deactivation study of the hydrodeoxygenation of p-methylguaiacol over silica supported rhodium and platinum catalysts

Hydrodeoxygenation of para-methylguaiacol using silica supported Rh or Pt catalysts was investigated using a fixed-bed reactor at 300 °C, under 4 barg hydrogen and a WHSV of 2.5 h−1. The activity, selectivity and deactivation of the catalysts were examined in relation to time on stream. Three catalysts were tested: 2.5% Rh/silica supplied by Johnson Matthey (JM), 2.5% Rh/silica and 1.55% Pt/silica both prepared in-house. The Rh/silica (JM) showed the best stability with steady-state reached after 6 h on stream and a constant activity over 3 days of reaction. In contrast the other two catalysts did not reach steady state within the timeframe of the tests, with continuous deactivation over the time on stream. Nevertheless higher coking was observed on the Rh/silica (JM) catalyst, while all three catalysts showed evidence of sintering. The Pt catalyst (A) showed higher selectivity for the production of 4-methylcatechol while the Rh catalysts were more selective toward the cresols. In all cases, complete hydrodeoxygenation of the methylguaiacol to methylcyclohexane was not observed

Influence of different palladium precursors on the properties of solution-combustion-synthesized palladium/ceria catalysts for methane combustion

A series of Pd/CeO2 catalysts was prepared by solution combustion synthesis (SCS) using different Pd precursors. The powders were characterized by complementary techniques such as BET surface area measurements, X-Ray diffraction analysis, X-Ray photoelectron spectroscopy, temperature-programmed reduction, temperature-programmed oxidation, and high-resolution TEM. The results obtained evidenced the formation of a Pd-Ce solid solution on all SCS samples. This solid solution is in the form of an ordered supercell structure only in the SCS catalyst prepared from palladium nitrate. This was correlated to the heat of reaction between Pd(NO3)(2) and the fuel. The samples were tested for methane catalytic combustion, and the reaction rates on all SCS samples were approximately twice that of the impregnated counterpart, irrespective of the precursor. This was attributed to the presence of the Pd-O-Ce solid solution, which gave rise to strong Pd-ceria interactions.Postprint (author's final draft

Platinum Inhibits Low‐Temperature Dry Lean Methane Combustion through Palladium Reduction in Pd−Pt/Al2O3: An In Situ X‐ray Absorption Study

NSERCPeer ReviewedPalladium–platinum bimetallic catalysts supported on alumina with palladium/platinum molar ratios ranging from 0.25 to 4 are studied in dry lean methane combustion in the temperature range of 200 to 500 °C. Platinum addition decreases the catalyst activity, which cannot be explained by the decrease in dispersion or the structure sensitivity of the reaction. In situ X‐ray absorption near‐edge structure and extended X‐ray absorption fine structure spectroscopy measurements have been conducted for monometallic Pd, Pt, and 2:1 Pd−Pt catalysts. Monometallic palladium is fully oxidized in the full temperature range, whereas platinum addition promotes palladium reduction, even in a reactive oxidizing environment. The Pd/PdO weight ratio in bimetallic Pd−Pt 2:1 catalysts decreases from 98/2 to 10/90 in the 200–500 °C temperature range under the reaction conditions. Thus, platinum promotes the formation of the reduced palladium phase with a significantly lower activity than that of oxidized palladium. The study sheds light on the effect of platinum on the state of the active palladium surface under low‐temperature dry lean methane combustion conditions, which is important for methane‐emission control devices

Phosphorus poisoning during wet oxidation of methane over Pd@CeO2/graphite model catalysts

10siThe influence of phosphorus and water on methane catalytic combustion was studied over Pd@CeO2 model catalysts supported on graphite, designed to be suitable for X-ray Photoelectron Spectroscopy/Synchrotron Radiation Photoelectron Spectroscopy (XPS/SRPES) analysis. In the absence of P, the catalyst was active for the methane oxidation reaction, although introduction of 15% H2O to the reaction mixture did cause reversible deactivation. In the presence of P, both thermal and chemical aging treatments resulted in partial loss of activity due to morphological transformation of the catalyst, as revealed by Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM) analysis. At 600 °C the combined presence of PO43− and water vapor caused a rapid, irreversible deactivation of the catalyst. XPS/SRPES analysis, combined with operando X-ray Absorption Near Edge Structure (XANES) and AFM measurements, indicated that water induces severe aggregation of CeO2 nanoparticles, exposure of CePO4 on the outer layer of the aggregates and incorporation of the catalytic-active Pd nanoparticles into the bulk. This demonstrates a temperature-activated process for P-poisoning of oxidation catalysts in which water vapor plays a crucial role.partially_openembargoed_20171009Monai, Matteo; Montini, Tiziano; Melchionna, Michele; Duchoň, Tomáš; Kúš, Peter; Tsud, Nataliya; Prince, Kevin C.; Matolin, Vladimir; Gorte, Raymond J.; Fornasiero, PaoloMonai, Matteo; Montini, Tiziano; Melchionna, Michele; Duchoň, Tomáš; Kúš, Peter; Tsud, Nataliya; Prince, Kevin C.; Matolin, Vladimir; Gorte, Raymond J.; Fornasiero, Paol