Abstract The electrosynthesis from 5‐hydroxymethylfurfural (HMF) is considered a green strategy to achieve biomass‐derived high‐value chemicals. As the molecular structure of HMF is relatively complicated, understanding the HMF adsorption/catalysis behavior on electrocatalysts is vital for biomass‐based electrosynthesis. The electrocatalysis behavior can be modulated by tuning the adsorption energy of the reactive molecules. In this work, the HMF adsorption behavior on spinel oxide, Co 3 O 4 is discovered. Correspondingly, the adsorption energy of HMF on Co 3 O 4 is successfully tuned by decorating with single‐atom Ir. It is observed that compared with bare Co 3 O 4 , single‐atom‐Ir‐loaded Co 3 O 4 (Ir‐Co 3 O 4 ) can enhance adsorption with the CC groups of HMF. The synergetic adsorption can enhance the overall conversion of HMF on electrocatalysts. With the modulated HMF adsorption, the as‐designed Ir‐Co 3 O 4 exhibits a record performance (with an onset potential of 1.15 V RHE ) for the electrosynthesis from HMF.

Tuning the Selective Adsorption Site of Biomass on Co3O4 by Ir Single Atoms for Electrosynthesis