Surfactant Directionally Assembled at the Electrode‐Electrolyte Interface for Facilitating Electrocatalytic Aldehyde Hydrogenation

Abstract Electrocatalytic hydrogenation of unsaturated aldehydes to unsaturated alcohols is a promising alternative to conventional thermal processes. Both the catalyst and electrolyte deeply impact the performance. Designing the electrode‐electrolyte interface remains challenging due to its compositional and structural complexity. Here, we employ the electrocatalytic hydrogenation of 5‐hydroxymethylfurfural (HMF) as a reaction model. The typical cationic surfactant, cetyltrimethylammonium bromide (CTAB), and its analogs are employed as electrolyte additives to tune the interfacial microenvironment, delivering high‐efficiency hydrogenation of HMF and inhibition of the hydrogen evolution reaction (HER). The surfactants experience a conformational transformation from stochastic distribution to directional assembly under applied potential. This oriented arrangement hampers the transfer of water molecules to the interface and promotes the enrichment of reactants. In addition, near 100 % 2,5‐bis(hydroxymethyl)furan (BHMF) selectivity is achieved, and the faradaic efficiency (FE) of the BHMF is improved from 61 % to 74 % at −100 mA cm −2 . Notably, the microenvironmental modulation strategy applies to a range of electrocatalytic hydrogenation reactions involving aldehyde substrates. This work paves the way for engineering advanced electrode‐electrolyte interfaces and boosting unsaturated alcohol electrosynthesis efficiency.