Plasmonic Ni-doped W18O49 with dual active sites drives efficient methanol dehydration to dimethyl ether.

Photocatalytic methanol dehydration to dimethyl ether (DME) offers a sustainable alternative to energy-intensive thermocatalysis, yet its practical application remains constrained by low efficiency. Herein, we designed Ni-doped plasmonic W18O49 nanowires that synergistically integrates low-coordinated W and Ni dual active sites with surface plasmon resonance for enhanced photocatalytic performance. The synergistic effect of W and Ni dual sites is amplified by plasmonic electron oscillations to facilitate the C-O bond cleavage and C-O-C coupling, driving efficient methanol-to-DME conversion. The optimized Ni0.66-W18O49 achieves a DME yield of 133.7 ± 3.3 mmol g-1 h-1 with 98.7% selectivity under 400 mW cm-2 illumination. The versatility of the catalyst is demonstrated through C2+ alcohol dehydration, achieving 40-80% rate enhancements and a recorded isobutylene yield of 3.7 mol g-1 h-1. This study highlights the huge potential of rationally engineered plasmonic semiconductors in solar-driven chemical synthesis, particularly for C-O bond activation and coupling reactions.