Chemical manufacturing industries are plagued with energy- and cost-intensive processes, employing harsh reaction conditions and toxic/expensive catalysts to drive chemical conversions. Furthermore, the resultant product distributions are complex, introducing difficulty for isolation of respective constituents. In this regard, electrosynthesis starting from biomass-derived platform chemicals (i.e., glycerol, 5-hydroxymethylfurfural, levulinic acid, and muconic acid), serves as a promising avenue for driving specific molecular transformations and direct synthesis of high-value chemicals. Here, our focused review highlights fundamental perspectives concerning electrosynthesis (proton/electron transfer processes, oxygenation, and hydrogenation mechanisms), bottlenecks in achieving selective product generation, and recent advancements in the field. We rationalize the design of electrochemical systems through noting influence of setups and catalyst design strategies in correlation to product selectivity. Operational analysis/characterizations and theoretical calculations are discussed to achieve understanding of mechanistic pathways and intermediate/product generations. Finally, we provide a succinct outlook for deriving these promising electrochemical technologies.

化学制造行业受到能源和成本密集型过程的困扰，它们采用苛刻的反应条件和有毒/昂贵的催化剂来推动化学转化。此外，所得的产品分布复杂，导致难以分离各个成分。在这方面，从生物质衍生的平台化学品（即甘油，5-羟甲基糠醛，乙酰丙酸和粘康酸）开始的电合成，是驱动特定分子转化和直接合成高价值化学品的有前途的途径。在这里，我们的重点综述重点介绍了有关电合成（质子/电子转移过程，氧合和氢化机理），实现选择性产物生成的瓶颈以及该领域的最新进展的基本观点。我们通过注意装置和催化剂设计策略对产品选择性的影响来合理化电化学系统的设计。讨论了操作分析/特性和理论计算，以了解机械路径和中间/产品生成。最后，我们为衍生出这些有前途的电化学技术提供了简洁的前景。