Efficient Pt<sub>1</sub>Ni single-atom alloy catalyst for hydrogen-free catalytic fractionation of lignocellulose.

Zhou, Hao; Xiang, Qian; Guo, Zhiruo; Song, Kepeng; Shakouri, Mohsen; Guo, Yong; Liu, Xiaohui; Hu, Yongfeng et al. · Nat Commun · 2026

basic_science · Level V

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Abstract

The production of monophenols from lignocellulose with cellulose intact without exogenous hydrogen via self-hydrogen supplied fractionation is promising, yet requires high metal loadings and yields saturated products. Herein, we report a single-atom alloyed Pt<sub>1</sub>Ni catalyst that achieves 50.9 wt% yield of phenolic monomers from birch sawdust with about 50% selectivity to valuable propenyl side-chained products under mild conditions (140 °C, 1 atm N<sub>2</sub>), while preserving cellulose intact. Reaction pathway studies and density functional theory calculations based on a β-O-4 model compound reveal three coexisting pathways. The Pt<sub>1</sub>Ni alloy preferentially promotes the dehydroxylation of C<sub>α</sub>-OH and forms a key C<sub>α</sub> = C<sub>β</sub> intermediate due to the oxygen affinity of Ni sites, and ultimately, enhance the production of valuable propenyl products via the synergistic effect of Pt and Ni. This work provides a strategy for maximizing Pt utilization and producing unsaturated chemicals from biomass under hydrogen-free conditions, advancing sustainable biorefining.