Furfural–acetone aldol condensation over polyethylene terephthalate-derived amorphous mesoporous Zr coordination materials

The aldol condensation of furfural with acetone is an important C–C bond-forming route to C₈–C₁₃ oxygenated intermediate for fuel and chemical production, but its performance over solid catalysts is often limited by acid-site accessibility, diffusion of bulky products and competitive self-condensation of acetone. Here we report a one-step strategy to transform polyethylene terephthalate (PET) into amorphous mesoporous Zr coordination materials, denoted PET-Zr-X. The obtained PET-Zr incorporates PET-derived linker fragments into defective UiO-66-like Zr-oxo/hydroxyl motifs, creating abundant Brønsted and Lewis acid sites. In furfural–acetone aldol condensation, it shows a turnover frequency of 25.0 h⁻¹ at 80 °C, about four times higher than that of crystalline UiO-66, with high selectivity to the mono-condensation product. Via analysis of reaction kinetics, furfural adsorption, IR and TPD of adsorbed CD₃CN, and product desorption, we reveal that preferential adsorption of furfural over acetone and rapid intrapore transport of primary condensation product jointly enhance catalytic activity and selectivity, and suppress secondary over condensation and acetone self-condensation.