A polyoxometalate@covalent triazine framework as a robust electrocatalyst for selective benzyl alcohol oxidation coupled with hydrogen production

Electrocatalytic oxidation has been proven as a sustainable and promising alternative to traditional chemical transformation, but its further development is limited by the use of noble-metal electrocatalysts. Herein, a polyoxometalate-based electrode material,H₅PMo₁₀V₂O₄₀@CTF(denoted asPMo₁₀V₂@CTF), has been successfully fabricated through electrostatic assembly of a molecular polyoxometalate catalyst,PMo₁₀V₂, with a porous cationic covalent triazine framework (CTF), which, to our knowledge, represents the first combination of polyoxometalate with a cationic CTF. The resultingPMo₁₀V₂@CTFexhibits high activity for the selective electrocatalytic oxidation of alcohols to aldehydes, achieving 99% conversion of benzyl alcohol, over 99% selectivity of benzyl aldehyde, and at the same time near unity H₂production. Notably, the reported electrocatalytic system presents good atom economy, high energy conversion (96% faradaic efficiency), remarkable catalytic activity and robustness for at least eight recycles. Based on the various experimental and spectroscopic analyses, a possible catalytic mechanism was proposed, revealing that such excellent electrocatalytic performance is attributed to the versatile redox ability ofPMo₁₀V₂and the good porosity and adsorption property of the CTF in the constructedPMo₁₀V₂@CTFcomposite.