Partial oxidation of methanol is a promising reaction for on-board production of high purity H₂ streams for fuel cell applications. In the present work, the influence of Cu oxidation state on the selectivity of POM catalyzed by Cu/ZnO was investigated via the use of a microreactor and X-ray photoelectron spectroscopy. A strong correlation between H₂ selectivity and the metallic copper (Cu°) content of the catalyst was observed, while, surprisingly, the CO₂ selectivity was not significantly affected by the catalyst oxidation state. Instead, CO₂ selectivity showed a strong correlation with O₂ partial pressure, which could be explained by differences in the energy barriers between CO desorption and CO₂ formation from CO* on Cu₂O surfaces calculated via first-principles calculations. Our results indicate that maintaining metallic Cu catalyst during methanol oxidation could maximize H₂ production for use in fuel cells or other clean energy applications.

甲醇的部分氧化是用于燃料电池应用的高纯度H ₂流的机载生产的有前途的反应。在本工作中，通过使用微反应器和X射线光电子能谱研究了Cu氧化态对Cu / ZnO催化POM选择性的影响。观察到H ₂选择性与催化剂的金属铜（Cu°）含量之间有很强的相关性，令人惊讶的是，CO ₂选择性不受催化剂氧化态的显着影响。取而代之的是，CO _2的选择性与O _2的分压有很强的相关性，这可以用CO解吸和CO之间的能垒差异来解释。₂从CO生成*对Cu ₂ ö面经由第一原理计算来计算。我们的结果表明，在甲醇氧化过程中保持金属Cu催化剂可使H _2的产量最大化，可用于燃料电池或其他清洁能源应用。