Evidence of redox cycling as a sub-mechanism in hydrogen production during ethanol steam reforming over La 0.7 Sr 0.3 MnO 3-x perovskite oxide catalysts
Ethanol steam reforming (ESR) is of societal interest. Here, in this work, experiments were conducted to ascertain if some of the H 2 is produced by a redox cycle involving H 2 O filling oxygen vacancies over reducible oxide catalysts. Redox cycling experiments were performed over La 0.7 Sr 0.3 MnO 3-x (100) in ultra-high vacuum. It was found that H 2 was produced from redox cycling with alternating ethanol and water exposures over La 0.7 Sr 0.3 MnO 3-x (100), with both half-cycles occurring at temperatures ≤800 K. In the first half-cycle, ethanol ‘directly’ reduced the surface to create oxygen vacancies (not by a CO intermediate), and in the second half-cycle water filled oxygen vacancies to make H 2 . The H 2 production during the water exposure has a half-cycle turnover frequency of >3.2 × 10 -2 molecules site -1 s -1 in the temperature range of 700–800 K, which is fast enough to be part of the ESR full catalytic cycle. Flowing both reactant gases together, ethanol and water, over La 0.7 Sr 0.3 MnO 3-x (100) and La 0.7 Sr 0.3 MnO 3-x powders significantly increases hydrogen production compared to pure ethanol. The results suggest that steady state ESR includes a sub-mechanism of ethanol ‘directly’ reducing the surface to create oxygen vacancy, and water filling oxygen vacancy to make some of the H 2 by a Mars van Krevelen type mechanism.