Tao Shanwen, Irvine John T S, Plint Steven M
School of Chemistry, University of St. Andrews, Fife KY16 9ST, Scotland, United Kingdom.
J Phys Chem B. 2006 Nov 2;110(43):21771-6. doi: 10.1021/jp062376q.
Because of its widespread availability, natural gas is the most important fuel for early application of stationary fuel cells, and furthermore, methane containing biogases are one of the most promising renewable energy alternatives; thus, it is very important to be able to efficiently utilize methane in fuel cells. Typically, external steam reforming is applied to allow methane utilization in high temperature fuel cells; however, direct oxidation will provide a much better solution. Recently, we reported good electrochemical performance for an oxide anode La0.75Sr0.25Cr0.5Mn0.5O3 (LSCM) in low moisture (3% H2O) H2 and CH4 fuels without significant coking in CH4. Here, we investigate the catalytic activity of this oxide with respect to its ability to utilize methane. This oxide is found to exhibit fairly low reforming activity for both H2O and CO2 reforming but is active for methane oxidation. LSCM is found to be a full oxidation catalyst rather than a partial oxidation catalyst as CO2 production dominates CO production even in CH4-rich CH4/O2 mixtures. X-ray adsorption spectroscopy was utilized to confirm that Mn was the redox active species, clearly demonstrating that this material has the oxidation catalytic behavior that might be expected from a Mn perovskite and that the Cr ion is only present to ensure stability under fuel atmospheres.
由于天然气广泛可得,它是固定式燃料电池早期应用中最重要的燃料,此外,含甲烷的生物气是最有前景的可再生能源替代品之一;因此,能够在燃料电池中高效利用甲烷非常重要。通常,外部蒸汽重整用于在高温燃料电池中实现甲烷利用;然而,直接氧化将提供更好的解决方案。最近,我们报道了氧化物阳极La0.75Sr0.25Cr0.5Mn0.5O3(LSCM)在低湿度(3% H2O)的H2和CH4燃料中具有良好的电化学性能,且在CH4中无明显积碳。在此,我们研究该氧化物对甲烷的利用能力的催化活性。发现该氧化物对H2O和CO2重整均表现出相当低的重整活性,但对甲烷氧化具有活性。发现LSCM是一种全氧化催化剂而非部分氧化催化剂,因为即使在富含CH4的CH4/O2混合物中,CO2的生成也主导着CO的生成。利用X射线吸附光谱证实Mn是氧化还原活性物种,清楚地表明该材料具有锰钙钛矿预期的氧化催化行为,且Cr离子仅用于确保在燃料气氛下的稳定性。