Zn1.2H0.6PW12O40 Nanotubes with Double Acid Sites as Heterogeneous Catalysts for the Production of Biodiesel from Waste Cooking Oil

Abstract
Out of the frying pan: A ZnPW nanotube catalyst containing Brønsted and Lewis double acid sites promotes the conversion of waste cooking oil into biodiesel. The catalytic activity of the ZnPW nanotubes is stable to the presence of free fatty acids or water in the feedstock. The high catalytic activity of the ZnPW nanotubes is attributed to the synergistic effect of Lewis acid sites and Brønsted acid sites. Zinc dodecatungstophosphate (Zn1.2H0.6PW12O40; ZnPW) nanotubes, which feature Lewis acid and Brønsted acid sites, were prepared using cellulose fibers as templates. The structure, acid properties, and catalytic activity of the nanotubes as heterogeneous catalysts for biodiesel production were then studied in detail. The ZnPW nanocatalyst exhibited higher catalytic activities for the simultaneous esterification and transesterification of palmitic acid than the parent acid catalyst 12-tungstophosphoric acid (H3PW12O40). Moreover, the doubly acidic nanotubes led to markedly enhanced yields of methyl esters in the conversion of waste cooking oil (containing 26.89 wt % free fatty acids and 1 % moisture) to biodiesel. The catalyst could be recycled and reused with negligible loss in activity over five cycles. The ZnPW nanocatalyst is acid- and water-tolerant and is an environmentally benign heterogeneous catalyst for the production of biodiesel from low-quality feedstocks.