Bifunctional H2WO4/TS-1 catalysts for direct conversion of cyclohexane to adipic acid: Active sites and reaction steps

Abstract

Adipic acid production may account for 10% of the annual increase in atmospheric nitrous oxide level. Here we developed a hollow H2WO4/TS-1 bifunctional catalyst with excellent catalytic activity for the direct transformation of cyclohexane to adipic acid with 30% hydrogen peroxide by a non-HNO3 route. XRD diffraction, N2 physisorption, TEM, NH3-TPD and Raman, XPS, Infrared, and UV–visible spectroscopies were used to characterize catalysts to increase understanding of the structure of active species on the hollow TS-1 support. The enhanced catalytic activity in comparison of reference catalysts (H2WO4, H2WO4/Silicate-1 and TS-1) was explained in terms of their bifunctional catalytic sites and perfect hollow morphology with large intraparticle voids. Experimental results on the product distribution indicated that the tetrahedral Ti and surface W sites played important roles in the synergistic effect: tetrahedral Ti worked in oxidation of cyclohexane to intermediates (cyclohexanone and cyclohexanol) and surface W worked in further oxidation of late intermediates to adipic acid. Theoretical calculation results on catalytic activity of the TiOOH and WOOH active sites in the H2WO4/TS-1 for different reaction steps validate the experimental results. The catalytic activity was also correlated to the strong interaction between W sites and HTS-1 surface induced increase in acidity of the materials. Increasing calcination temperature led to structural evolution of supported active species and subsequent activity change. A cyclohexane conversion of 31% with 78% adipic acid selectivity was achieved over this catalyst calcinated at 500 ∘C. Based on the catalytic and characterization results, possible reaction pathways were thus proposed to explain high adipic acid yield over hollow H2WO4/TS-1 catalysts.