Fully exposed Pt<sub>n</sub> cluster catalysts enable cascade oxidation of polyol to dicarboxylic acid.
basic_science · Level V
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- Record sourced from PubMed, PMID 40745176.
- Also identified by DOI 10.1038/s41467-025-62192-0 and PMC identifier 12314095.
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Abstract
The polyol oxidation to dicarboxylic acid, a crucial value-accretive reaction, is still challenging due to the paradoxical relationship between efficient activation of C-H bond and rapid desorption of carboxylic acid. Herein, we break this contradiction by constructing fully exposed Pt<sub>n</sub> cluster supported on hydroxyapatite (Pt<sub>n</sub>/HAP) to promote two primary hydroxyl groups of polyol oxidation to dicarboxylic acid. Such fully exposed Pt<sub>n</sub> cluster with an average Pt-Pt coordination number of ∼3.4 exhibits unique electronic properties between Pt<sub>1</sub> single atom and nanoparticle Pt<sub>p</sub>. Specifically, gradient charge distribution in fully exposed Pt<sub>n</sub> cluster shows a special synergistic effect in the C-H bond activation. Moreover, the d-band centre of fully exposed Pt<sub>n</sub> cluster moderately far from the Fermi level weakens the adsorption of C = O bond in dicarboxylic acid product. As a result, fully exposed Pt<sub>n</sub>/HAP with better catalytic activity (turnover frequency: 619.1 h<sup>-</sup><sup>1</sup>) shows nearly 10 times and 1.5 times of tartronic acid selectivity than Pt<sub>1</sub> single atom and nanoparticle Pt<sub>p</sub> catalysts, respectively. The system is also applicable to other polyol oxidation to dicarboxylic acids with noteworthy catalytic results.