Selective Activation of Propane Using Intermediates Generated during Water Oxidation

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.