Constructing High‐Active Surface of Plasmonic Tungsten Oxide for Photocatalytic Alcohol Dehydration

Abstract Plasmonic semiconductors with broad spectral response hold significant promise for sustainable solar energy utilization. However, the surface inertness limits the photocatalytic activity. Herein, a novel approach is proposed to improve the body crystallinity and increase the surface oxygen vacancies of plasmonic tungsten oxide by the combination of hydrochloric acid (HCl) regulation and light irradiation, which can promote the adsorption of tert‐butyl alcohol (TBA) on plasmonic tungsten oxide and overcome the hindrance of the surface depletion layer in photocatalytic alcohol dehydration. Additionally, this process can concentrate electrons for strong plasmonic electron oscillation on the near surface, facilitating rapid electron transfer within the adsorbed TBA molecules for C‐O bond cleavage. As a result, the activation barrier for TBA dehydration is significantly reduced by 93% to 6.0 kJ mol −1 , much lower than that of thermocatalysis (91 kJ mol −1 ). Therefore, an optimal isobutylene generation rate of 1.8 mol g −1 h −1 (selectivity of 99.9%) is achieved. A small flow reaction system is further constructed, which shows an isobutylene generation rate of 12 mmol h −1 under natural sunlight irradiation. This work highlights the potential of plasmonic semiconductors for efficient photocatalytic alcohol dehydration, thereby promoting the sustainable utilization of solar energy.