Steering selectivity of electrocatalysts towards upgrading cellulosic biomass-derived platform compounds

The accelerating global energy crisis and increasing environmental concerns are intensifying the demand for renewable alternatives to fossil fuels. Cellulose-derived platform molecules such as glucose, 5-hydroxymethylfurfural, and glycerol represent promising feedstocks for the sustainable production of fuels, polymer precursors, and fine chemicals. Electrocatalytic conversion of these molecules allows for precise control of reaction pathways under mild conditions, offering advantages over conventional thermocatalytic methods. Despite advances in catalytic activity, achieving precise selectivity in the conversion of cellulose and its derivatives remains a fundamental challenge. A profound mechanistic understanding of product selectivity remains critically underdeveloped. This review systematically addresses this knowledge gap by analyzing reaction pathways of cellulose-derived compounds and exploring how catalyst structure influences selectivity. Key factors include electronic states tuned by heteroatom doping, interfacial and dynamic reconstruction, single-atom confinement, and defect engineering, all of which impact adsorption properties. The review also highlights the role of morphological and mesoscale designs, including nanowires, porous scaffolds, and layered double hydroxides, in enhancing mass transfer and accessibility of active sites. Additionally, operational strategies such as optimizing electrolyte composition, adjusting pH, and applying dynamic potential are discussed for their effectiveness in suppressing competing reactions. This review formulates design principles for electrocatalysts with targeted selectivity, offering a blueprint for efficient biomass valorization.