Plasmonic Ni-doped W<sub>18</sub>O<sub>49</sub> with dual active sites drives efficient methanol dehydration to dimethyl ether.

Tian, Dehua; Liang, Yinlan; Zheng, Zhaoke; Mao, Liang; Cai, Xiaoyan; Chen, Yizhen; Wang, Xiangxian; Liu, Xiaolei et al. · Nat Commun · 2025

basic_science · Level V

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Abstract

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 W<sub>18</sub>O<sub>49</sub> 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 Ni<sub>0.66</sub>-W<sub>18</sub>O<sub>49</sub> achieves a DME yield of 133.7 ± 3.3 mmol g<sup>-1</sup> h<sup>-1</sup> with 98.7% selectivity under 400 mW cm<sup>-2</sup> illumination. The versatility of the catalyst is demonstrated through C<sub>2+</sub> alcohol dehydration, achieving 40-80% rate enhancements and a recorded isobutylene yield of 3.7 mol g<sup>-1</sup> h<sup>-1</sup>. 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.