| 1. |
- Martin, Natalia Mihaela, 1984, et al.
(författare)
-
A LEIS and in situ XAS study of supported Pd-Pt catalysts for CH4 oxidation
- 2016
-
Konferensbidrag (övrigt vetenskapligt/konstnärligt)abstract
- It is of vital importance to remove methane (CH4) from the exhausts of natural gas and biogas fueled engines as CH4 is a strong greenhouse gas. So far Pd-based catalysts have been used almost exclusively but their high sensitivity to sulfur and water pushes research to explore other materials. Among these are Pd-Pt catalysts [1-4], which exhibit a slight increase in CH4 oxidation activity with time and higher long-term stability than the Pd-only counterpart [5-7]. Still, however, little is known about the oxidation-reduction behaviour of the Pd-Pt nanoclusters and how this impacts the catalytic activity. This study aims at increase the understanding of the catalytic activity of Al2O3-supported Pd-Pt nanoclusters for low-temperature CH4 oxidation under transient, although generally lean, conditions.
|
|
| 2. |
- Martin, Natalia Mihaela, 1984, et al.
(författare)
-
Characterization of Surface Structure and Oxidation/Reduction Behaviour of Pd-Pt/Al2O3 Model Catalysts
- 2016
-
Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 120:49, s. 28009-28020
-
Tidskriftsartikel (refereegranskat)abstract
- Structural and morphological characterisation of bimetallic Pd-Pt/Al2O3 model cat- alysts are performed using X-ray diffraction, X-ray absorption spectroscopy, transmis- sion electron microscopy and CO chemisorption. Further, the catalysts were studied under oxidising and reducing conditions using both X-ray absorption spectroscopy and low-energy ion scattering spectroscopy. For the as-prepared catalysts, the existence of alloyed bimetallic Pd-Pt particles and of (tetragonal) PdO were found for the samples calcined at 800 C. PdO is present in form of crystals at the surface of the Pd-Pt par- ticles or as isolated PdO crystals on the support oxide. Bimetallic Pd-Pt nanoparticles were only formed on the Pd-Pt catalysts after calcination at 800 C. The results show that the Pd-Pt nanoparticles undergo reversible changes in surface structure composi- tion and chemical state in response to oxidising or reducing conditions. Under oxidising conditions Pd segregates to the shell and oxidises forming PdO, while under reducing conditions regions with metallic Pd and Pd-Pt alloys were observed at the surface. No bimetallic Pd-Pt nanoparticles were observed for the sample initially calcined at 500 C, but instead isolated monometallic particles, where small Pt particles are easily oxidised under O2 treatment. In the monometallic catalysts, the Pd is found to be com- pletely oxidised already after calcination and to consist of metallic Pd after reductive treatment.
|
|
| 3. |
- Martin, Natalia Mihaela, 1984, et al.
(författare)
-
CO Oxidation and Site Speciation for Alloyed Pd-Pt Model Catalysts Studied by In Situ FTIR Spectroscopy
- 2017
-
Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 121:47, s. 26321-26329
-
Tidskriftsartikel (refereegranskat)abstract
- In situ Fourier transform infrared spectroscopy was used to study transient CO oxidation over a series of bimetallic Pd-Pt catalysts with different Pd:Pt molar ratios. The catalysts were found to contain both alloyed PdPt nanoparticles (particle sizes 25-35 nm) and monometallic Pd nanoparticles (sizes below 10 nm). For oxygen-free conditions, CO reduces the surface while simultaneously function as a chemical probe molecule whereby the CO adsorption sites can be characterised. Under these conditions it is shown that adsorbed carbonyl species form both on the Pd and Pt. On platinum, CO adsorbs predominantly linearly on top, whereas on palladium it adsorbes in bridged configurations. This behaviour is used for site speciation of the catalysts. The spectra from the bimetallic Pd-Pt catalysts are more complicated than a direct superposition of the spectra for the monometallic catalysts as a consequence of alloy formation and enrichment of Pd at the surface of the reduced catalysts. The temperature programmed CO oxidation results show that the addition of Pd to the Pt catalyst supported on alumina shifts the CO-poisoned state to lower temperatures therefore increasing the temperature range for the CO oxidation at low temperatures.
|
|
| 4. |
|
|
| 5. |
- Martin, Natalia Mihaela, 1984, et al.
(författare)
-
Study of methane oxidation over alumina supported Pd-Pt catalysts using operando DRIFTS/MS and in situ XAS techniques
- 2017
-
Ingår i: Catalysis, Structure and Reactivity. - 2055-0758. ; 3:1-2, s. 24-32
-
Tidskriftsartikel (refereegranskat)abstract
- Methane oxidation over Pd–Pt/Al2O3 model catalysts calcined at three different conditions is investigated using operando diffuse reflectance infrared Fourier transform spectroscopy and mass spectrometry, and in situ X-ray absorption spectroscopy while cycling the feed gas stoichiometry between lean (net-oxidising) and rich (net-reducing) conditions. When calcined in air, alloy Pd–Pt nanoparticles are present only on catalysts subjected to elevated temperature (800 ◦C) whereas calcination at lower temperature (500◦C) leads to segregated Pt and Pd nanoparticles on the support. Here, we show that the alloy Pd–Pt nanoparticles undergo reversible changes in surface structure and composition during transient methane oxidation exposing a PdO surface during lean conditions and a metallic Pd–Pt surface (Pd enriched) under rich conditions. Alloyed particles seem more active for methane oxidation than their monometallic counterparts and, furthermore, an increased activity for methane oxidation is clearly observed under lean conditions when PdO has developed on the surface, analogous to monometallic Pd catalysts. Upon introducing rich conditions, partial oxidation of methane dominates over total oxidation forming adsorbed carbonyls on the noble metal particles. The carbonyl spectra for the three samples show clear differences originating from different surfaces exposed by alloyed vs. non-alloyed particles. The kinetics of the noble metal oxidation and reduction processes as well as carbonyl formation during transient methane oxidation are discussed.
|
|
| 6. |
|
|
| 7. |
- Mihai, Oana, 1975, et al.
(författare)
-
The effect of water on methane oxidation over Pd/Al2O3 under lean, stoichiometric and rich conditions
- 2017
-
Ingår i: Catalysis Science and Technology. - : Royal Society of Chemistry (RSC). - 2044-4753 .- 2044-4761. ; 7:14, s. 3084-3096
-
Tidskriftsartikel (refereegranskat)abstract
- In this study, the effect of oxygen concentration and the presence of water on methane oxidation were examined over a Pd/Al2O3 catalyst. The physicochemical properties of the catalyst were investigated in detail using BET, XRD, STEM, O-2-TPO and CH4-TPR. Ramping experiments from 150 to 700 degrees C were conducted using rich, stoichiometric and lean gas mixtures in the absence and presence of water. It was found that increasing the oxygen concentration in a dry atmosphere resulted in higher methane oxidation activity, which can be connected to the facilitation of palladium oxide formation. The TPO data showed that only minor amounts of PdO up to 700 degrees C were decomposed; however, in the stoichiometric and rich reaction mixture, PdO was still decomposed because of the oxygen limitation. This fact resulted in a "negative activation" during cooling, with increased activity because of palladium re-oxidation. Moreover, methane steam reforming and water gas shift reactions were important reactions under rich conditions over the metallic palladium sites. A significant inhibiting effect of water on the Pd-catalyst with loss of methane activity was found. Interestingly, the inhibition effect was much greater using high oxygen concentration in the gas mixture (500 ppm CH4, 8% O-2, 5% H2O) than that at lower oxygen levels (800-1200 ppm) and we propose that the hydroxyl species formation, which blocks the active sites, are facilitated by a large oxygen excess. In addition, the re-oxidation of palladium occurring during the cooling ramp in dry feed using rich and stoichiometric gas mixtures was also significantly suppressed in the presence of a large amount of water. Thus, water impedes the oxidation of palladium, which significantly deactivates the Pd catalyst.
|
|
| 8. |
- Sadokhina, Nadezda, 1985, et al.
(författare)
-
An Experimental and Kinetic Modelling Study for Methane Oxidation over Pd-based Catalyst: Inhibition by Water
- 2017
-
Ingår i: Catalysis Letters. - : Springer Science and Business Media LLC. - 1572-879X .- 1011-372X. ; 147:9, s. 2360-2371
-
Tidskriftsartikel (refereegranskat)abstract
- The water inhibition of methane oxidation over a bimetallic Pt-Pd on CeO2-Al2O3 catalyst was investigated and the experimental data were used to develop a kinetic model, consisting of only three reaction steps. In the model, the water effect was assigned to the adsorption of H2O on surface sites, as well as to the formation and accumulation of surface hydroxyl groups. These two effects were accounted by the model, which could well describe the experimental data obtained under various conditions.
|
|
| 9. |
- Sadokhina, Nadezda, 1985, et al.
(författare)
-
The influence of gas composition on Pd-based catalyst activity in methane oxidation - inhibition and promotion by NO
- 2017
-
Ingår i: Applied Catalysis B: Environmental. - : Elsevier BV. - 0926-3373 .- 1873-3883. ; 200, s. 351-360
-
Tidskriftsartikel (refereegranskat)abstract
- The individual influence, as well as the combined effect of H2O and NO on the activity of Pd/Al2O3, PtPd/Al2O3 and PtPd/CeAl2O3 catalysts in complete methane oxidation under lean conditions were investigated. Under temperature-programmed ramping experiments the activity was severely inhibited in the presence of 5 vol.% H2O in the reaction mixture. We propose that this is due to blocking by both water and hydroxyl species. Under the influence of NO without water in the gas flow, it was found that the methane oxidation activity was partly suppressed, due to blocking of active sites. Indeed TPD performed after ramping experiments showed NOx storage on the catalyst. Contrary to the negative effect of NO in the dry case, the promotional NO effect on the activity was observed when water was co-fed, comparing the case with only water presence. The promotional NO effect was confirmed with isothermal experiments, where e.g. the methane conversion decreased from initial 96% to 25% after 10 h of exposure in CH4-O-2-H2O mixture at 450 degrees C over the Pd/Al2O3 sample, while the decrease was only from 88% to 60% when catalyst was exposed to CH4-O-2-H2O-NO mixture. We propose that the reason is that the NO reacts with the hydroxyl species to form HNO2, which reduces the water deactivation effect.
|
|
| 10. |
- Velin, Peter, 1989, et al.
(författare)
-
Water Inhibition in Methane Oxidation over Alumina Supported Palladium Catalysts
- 2019
-
Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 123:42, s. 25724-25737
-
Tidskriftsartikel (refereegranskat)abstract
- In situ diffuse reflectance infrared Fourier transform spectroscopy has been used to distinguish surface hydroxyl groups on Al2O3 and PdO/Al2O3 model catalysts calcined at 500-900 °C. Employing the operando approach, the formation of surface hydroxyl groups has been correlated to the methane oxidation activity for PdO/Al2O3 catalysts using a PdO powder sample as reference. The results show that the alumina support stabilizes active PdO particles leading to enhanced apparent methane turnover frequency (TOF), which decreases slowly in dry conditions due to alumina hydroxylation. Wet conditions cause severe hydroxylation that is detrimental for the methane TOF. The hydroxylation follows two different routes, i.e., spillover of hydrogen-containing species to the PdO-Al2O3 boundary and/or the close proximity of the supported PdO particles and under wet conditions also dissociation of gas phase water on the entire alumina surface. Both hydroxylation routes obey varying kinetics such that near saturation is reached quickly (minutes) followed by a continuous slow growth for prolonged exposure times (hours). At low temperatures, inhibition of palladium active sites on the rim of the PdO particles close to alumina seems to be of particular importance for the observed detrimental effect of water, whereas water induced morphological changes (no sintering observed) of the PdO particles play a minor role.
|
|
