Methane Oxidation on Palladium and Platinum Catalysts - A SSITKA Study

The catalytic process of total methane oxidation presents itself as an extremely favorable alternative to flame combustion, as it helps to reduce the production of NOx, CO emissions and non-oxidized hydrocarbons into the Earth’s atmosphere.

Some of the most dynamic catalytic materials for total methane oxidation are supported palladium and platinum catalysts. Showing great selectivity and activity, these materials demonstrate adequate levels of resistance to heat and mechanical damage.

On the other hand, there are still unanswered questions that need to be addressed before these catalysts become widely used in the industry. One such issues includes the reaction mechanism of total methane oxidation over palladium and platinum catalysts. This study employed the Steady State Isotopic Transient Kinetic Analysis method (SSITKA) to explore this potential obstacle further.

Using SSITKA to Analyze Heterogeneous Catalytic Reactions

This method makes it possible to obtain useful new data relating to the mechanisms of a number of heterogeneous catalytic reactions, as well as other matters of comparable importance, including: surface concentrations of reagents, intermediates and products of the catalytic reaction, the quantity of active centers on the surface of the catalyst, and the average surface life-span.

To successfully carry out the SSITKA study, access to accurate and high-quality equipment was essential. In a study like this, it is especially important to have a system of dosing and quick switching of reagent streams, as well as a mass spectrometer that allows users to analyze miniscule variations in the concentration of isotopes.

For this study, the switches between reaction streams including 12CH4/Ar/O2/He and 13CH4/Kr/O2/He were carried out, as well as those between 16O2/Ar/CH4/He and 18O2/Kr/CH4/He. Fig. 1 illustrates the examples of the findings for the Pd-Pt/Al2O3 catalyst.

Effect of the switching between reaction streams including 16O2/Ar/CH4/He and 18O2/Kr/CH4/He (X is the conversion of methane).

Figure 1. Effect of the switching between reaction streams including 16O2/Ar/CH4/He and 18O2/Kr/CH4/He (X is the conversion of methane).


Following a thorough analysis based on these results (full details of which can be found in the reference paper below), it has been suggested that two different types of active centers (α – more active, but less abundant, and β – less active, but more abundant) are present on the catalyst surface, and the process of methane oxidation takes place concurrently, according to two different reaction mechanisms (by Mars-van Krevelen and Langmuir-Hinshelwood).

The degree of their participation in methane oxidation varies depending on the reaction temperature. Furthermore, the process of methane oxidation takes place not only simultaneously - according to two different reaction mechanisms - but also with differing rates of reaction, as determined by the variety of active centers.


Rotko, A. Machocki, G. Słowik (2014) “The mechanism of the CH4/O2 reaction on the Pd-Pt/γ-Al2O3 catalyst: A SSITKA study” Applied Catalysis B: Environmental, 160-161 298-306

This information has been sourced, reviewed and adapted from materials provided by Hiden Analytical.

For more information on this source, please visit Hiden Analytical.

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