Abstract
Photoelectrochemical (PEC) technology has emerged as a promising platform for sustainable energy conversion and chemical synthesis, utilizing solar energy to facilitate redox reactions. While PEC systems have been extensively studied for water splitting, CO(2) reduction, nitrogen reduction for value-added compounds synthesis, the sluggish oxygen evolution reaction (OER) on the anode side and the less economic value of O(2) limit system efficiency. To address this, researchers have explored paired chemical upgrading strategies, coupling selective anodic organic oxidation reactions (OORs) with cathodic reduction reactions. This approach enabled the simultaneous production of high-value chemicals and fuels, enhancing the PEC system efficiency and economic viability. In this Perspective, we highlight the latest advancements and milestones in coupling anode OORs and cathode reduction reactions within PEC cells. Particular emphasis is placed on the key design principles, catalyst development, reaction mechanisms, and the performance of paired PEC cells. In addition, challenges and perspectives are provided for the future development of this emerging and sustainable technology.