Electrocatalytic water-to-oxygenates conversion: redox-mediated versus direct oxygen transfer.

Electrocatalytic oxygenation of hydrocarbons with high selectivity has attracted much attention for its advantages in the sustainable and controllable production of oxygenated compounds with reduced greenhouse gas emissions. Especially when utilizing water as an oxygen source, by constructing a water-to-oxygenates conversion system at the anode, the environment and/or energy costs of producing oxygenated compounds and hydrogen energy can be significantly reduced. There is a broad consensus that the generation and transformation of oxygen species are among the decisive factors determining the overall efficiency of oxygenation reactions. Thus, it is necessary to elucidate the oxygen transfer process to suggest more efficient strategies for electrocatalytic oxygenation. Herein, we introduce oxygen transfer routes through redox-mediated pathways or direct oxygen transfer methods. Especially for the scarcely investigated direct oxygen transfer at the anode, we aim to detail the strategies of catalyst design targeting the efficient oxygen transfer process including activation of organic substrate, generation/adsorption of oxygen species, and transformation of oxygen species for oxygenated compounds. Based on these examples, the significance of balancing the generation and transformation of oxygen species, tuning the states of organic substrates and intermediates, and accelerating electron transfer for organic activation for direct oxygen transfer has been elucidated. Moreover, greener organic synthesis routes through heteroatom transfer and molecular fragment transfer are anticipated beyond oxygen transfer.