Extremely efficient crystallization of HKUST-1 and Keggin-loaded related phases through the epoxide route

Abstract

Highly crystalline HKUST-1 and COK-16-like phases were obtained based on a mild in situ alkalinization one-pot epoxide driven method. A slurry composed of finely ground trimesic acid, H₃BTC, dispersed in a CuCl₂ aqueous solution quantitatively developed well crystallized HKUST-1 after the addition of propylene oxide. The use of solid H₃BTC ensures a low concentration of free linker, favoring crystalline growth over the precipitation of amorphous or metastable impurities. An extreme space-time yield of 2.1 × 10⁵ kg m⁻³ day⁻¹ was reached, with no linker excess and minimum use of solvent. The method was equally efficient in the achievement of pure NENU/COK-16 phases, containing [PW₁₂O₄₀]³⁻, [PMo₁₂O₄₀]³⁻ and [SiMo₁₂O₄₀]⁴⁻ polyoxometalates.