Electrochemical conversion of light alkanes to high-value oxygenates provides an attractive avenue for eco-friendly utilization of these hydrocarbons. However, such conversion under ambient conditions remains exceptionally challenging due to the high energy barrier of C–H bond cleavage. Herein, we investigated theoretically the partial oxidation of propane on a series of single atom alloys by using active intermediates generated during water oxidation as the oxidant. We show that by controlling the potential and pH, stable surface oxygen atoms can be maintained under water oxidation conditions. The free energy barrier for C–H bond cleavage by the surface oxygen can be as small as 0.54 eV, which can be surmounted easily at room temperature. Our calculations identified three promising surfaces as effective propane oxidation catalysts. Our complementary experiments demonstrated the partial oxidation of propane to acetone on Ni-doped Au surfaces. We also investigated computationally the steps leading to acetone formation. These studies show that the concept of exploiting intermediates generated in water oxidation as oxidants provides a fruitful strategy for electrocatalyst design to efficiently convert hydrocarbons into value-added chemicals.

中文翻译：

---

利用水氧化过程中产生的中间体选择性活化丙烷

轻链烷烃电化学转化为高价值的含氧化合物为这些碳氢化合物的环保利用提供了诱人的途径。但是，由于C–H键断裂的高能垒，在环境条件下进行这种转化仍然具有极大的挑战性。本文中，我们使用水氧化过程中产生的活性中间体作为氧化剂，对丙烷在一系列单原子合金上的部分氧化进行了理论研究。我们表明，通过控制电势和pH值，可以在水氧化条件下保持稳定的表面氧原子。由表面氧裂解C–H键的自由能势垒可小至0.54 eV，在室温下可以轻易克服。我们的计算确定了三个有希望的表面作为有效的丙烷氧化催化剂。我们的补充实验表明，在掺Ni的金表面上丙烷部分氧化为丙酮。我们还通过计算研究了导致丙酮形成的步骤。这些研究表明，利用水氧化过程中产生的中间体作为氧化剂的概念为电催化剂设计提供了卓有成效的策略，以有效地将碳氢化合物转化为增值化学品。