Catalysts consisting of Au, Pd and their alloys have been shown to be active oxidation catalysts. These materials can use dioxygen or hydrogen peroxide as the oxidant with CO and activated organic molecules using O₂(g) while more challenging cases, such as methane to partial oxygenates, relying on H₂O₂. Although H₂O₂ is a green oxidant, the incorporation of dioxygen greatly reduces overall cost and so there is an incentive to find new ways to reduce the reliance on H₂O₂. In this study we use DFT calculations to discuss the direct synthesis of H₂O₂ from H₂(g) and O₂(g) and use this understanding to identify the important surface species derived from dioxygen. We cover the adsorption of oxygen, hydrogen and water to model Au and Pd nanoclusters and the oxidation of the metals, since reduction of any oxides formed will consume H₂. We then turn to the production of a surface hydroperoxy species; the first step in the synthesis of H₂O₂. This can occur via hydrogenation of O₂(ads) with H₂(ads) or via protonation of O₂(ads) by solvent water. Both routes are found to be energetically reasonable, but the latter is likely to be favoured under experimental conditions.

由 Au、Pd 及其合金组成的催化剂已被证明是活性氧化催化剂。这些材料可以使用分子氧或过氧化氢作为氧化剂，CO 和使用 O ₂ (g) 的活化有机分子，而更具挑战性的情况，例如甲烷到部分氧化，依赖于 H ₂ O ₂。虽然 H ₂ O ₂是一种绿色氧化剂，但加入分子氧大大降低了总成本，因此有动力寻找新的方法来减少对 H ₂ O ₂的依赖。在这项研究中，我们使用DFT计算来讨论H的直接合成₂ Ø ₂选自H ₂（G）和O ₂(g) 并使用这种理解来识别源自分子氧的重要表面物种。我们涵盖了氧、氢和水的吸附以模拟 Au 和 Pd 纳米团簇以及金属的氧化，因为形成的任何氧化物的还原都会消耗 H ₂。然后我们转向生产表面过氧化氢物质；H ₂ O ₂合成的第一步。这可以通过O ₂ (ads) 与H ₂ (ads) 的氢化或通过溶剂水的O ₂ (ads)质子化而发生。发现这两条路线在能量上都是合理的，但后者在实验条件下可能更受欢迎。