Phys Chem Chem Phys. 2015 Dec 14;17(46):31297-307. doi: 10.1039/c5cp05583k.

Methane partial oxidation using FeO(x)@La(0.8)Sr(0.2)FeO(3-δ) core-shell catalyst--transient pulse studies.

Physical chemistry chemical physics : PCCP

Arya Shafiefarhood, Joseph Clay Hamill, Luke Michael Neal, Fanxing Li

PMID: 26549423 DOI: 10.1039/c5cp05583k

Abstract

The chemical looping reforming (CLR) process, which utilizes a transition metal oxide based redox catalyst to partially oxidize methane to syngas, represents a potentially efficient approach for methane valorization. The CLR process inherently avoids costly cryogenic air separation by replacing gaseous oxygen with regenerable ionic oxygen (O(2-)) from the catalyst lattice. Our recent studies show that an [email protected]δ core-shell redox catalyst is effective for CLR, as it combines the selectivity of an LSF shell with the oxygen capacity of an iron oxide core. The reaction between methane and the catalyst is also found to be highly dynamic, resulting from changes in lattice oxygen availability and surface properties. In this study, a transient pulse injection approach is used to investigate the mechanisms of methane partial oxidation over the Fe2O3@LSF redox catalyst. As confirmed by isotope exchange, the catalyst undergoes transitions between reaction "regions" with markedly different mechanisms. While oxygen evolution maintains a modified Mars-van Krevelen mechanism throughout the reaction with O(2-) conduction being the rate limiting step, the mechanism of methane conversion changes from an Eley-Rideal type in the first reaction region to a Langmuir-Hinshelwood-like mechanism in the third region. Availability of surface oxygen controls the reduction scheme of the catalyst and the underlying reaction mechanism.

Publication Types

• Journal Article
• Research Support, Non-U.S. Gov't
• Research Support, U.S. Gov't, Non-P.H.S.