Small-molecule aqueous electrocatalytic transformation powered by renewable electricity is a sustainable and eco-friendly energy utilization technique for producing compounds with added value from renewable feedstocks. Although an aqueous solution can directly contribute a hydrogen/oxygen source via water splitting to the transformation process, the single active source results in fewer available reaction pathways and a narrower range of products. To overcome this difficulty, we have here summarized a three-stage electrocatalytic method for valuing aqueous small molecules based on benefit increments and different reaction pathways: (1) the primary hydrogen/oxygen as the active species participated in small-molecule selective transformation processes, (2) the external nucleophile/electrophile induced small-molecule electrocatalytic coupling transformation process, and (3) multiple steps of small-molecule electrocatalytic cascade transformation via coupling electrocatalysis with electro/thermo/biocatalysis processes. Finally, we discuss the present challenges and knowledge gaps, thus setting the trajectory for future advances in aqueous electrocatalytic small-molecule valorization.

由可再生电力驱动的小分子水电催化转化是一种可持续且环保的能源利用技术，用于从可再生原料中生产具有附加值的化合物。虽然水溶液可以通过水分解直接为转化过程提供氢/氧源，但单一的活性源导致可用的反应途径更少，产物范围更窄。为了克服这一困难，我们在此总结了一种基于效益增量和不同反应途径评价水性小分子的三阶段电催化方法：（1）初级氢/氧作为活性物种参与小分子选择性转化过程， （2）外部亲核/亲电试剂诱导的小分子电催化耦合转化过程，以及（3）通过电催化与电/热/生物催化过程耦合的小分子电催化级联转化的多个步骤。最后，我们讨论了当前的挑战和知识差距，从而为水性电催化小分子增值的未来进展设定了轨迹。