Nonmetallic plasmonic Al-doped W<sub>18</sub>O<sub>49</sub> drives pure CO production from formic acid dehydration.

Ji, Guanrui; Zhang, Zhen; Li, Juan; Liu, Xiaolei; Wang, Zeyan; Mao, Liang; Chen, Xincheng; Wei, Wei et al. · Nat Commun · 2026

basic_science · Level V

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Abstract

As a vital industrial feedstock, carbon monoxide (CO) is widely employed in pharmaceutical, electronic and fine chemical synthesis, yet its efficient production in high purity remains challenging. Here we report a solar-driven route to high-purity CO from formic acid using a nonmetallic plasmonic photocatalyst based on aluminum-doped tungsten oxide (Al-W<sub>18</sub>O<sub>49</sub>). Plasmon-derived hot electrons drive the cleavage of C-H in adsorbed formic acid, while a concomitant photothermal effect markedly accelerates the overall kinetics. This synergistic mechanism lowers the apparent activation energy of HCOOH dehydration to 10.5 kJ mol<sup>-1</sup>, substantially below its thermocatalytic barrier of 80.6 kJ mol<sup>-1</sup>, and enables a CO production rate of 1.88 mol g<sup>-1</sup> h<sup>-1</sup> under 1 W cm<sup>-2</sup> irradiation. A continuous-flow reactor operated stably for 350 hours, delivering CO at a maximum rate of 2000 L m<sup>-2</sup> h<sup>-1</sup> under concentrated sunlight. This work develops a practical photocatalytic system for the sustainable production of high-purity CO.