Cathodic‐Potential‐Induced Amorphous TiO _x Layer for Glycerol Valorization

Abstract

ABSTRACT Electrochemical oxidation offers a low‐carbon pathway for glycerol valorization, yet it remains constrained by the inherent trade‐off between activity and selectivity toward high value‐added products. Here, we create H doped amorphous layer (H‐a‐TiO x ) on anatase TiO 2 , thus enabling 992 mmol m − 2 h − 1 glycerol‐to‐glyceraldehyde conversion with >80% selectivity while demonstrating scalable and economically sustainable performance. X‐ray absorption spectroscopy and solid‐state 1 H magic angle spinning NMR spectra reveal that H‐a‐TiO x exhibits reduced Ti–O coordination due to oxygen stripping, along with strengthened second shell Ti─Ti coordination arising from interstitial hydrogen incorporation. Mechanistic investigations indicate that hydrogen‐bond strengthening around adsorbed hydroxyl (*OH) raises the energy barrier for C─C bond cleavage, whereas enhanced localization of *OH lowers that for C─H bond activation, thereby overcoming the activity–selectivity trade‐off for glyceraldehyde production. This work outlines a practical phase‐engineering strategy that enables sustainable electrosynthesis with earth‐abundant metal oxides.