Highly dispersed CoOx in layered double oxides for oxidative dehydrogenation of propane: guest-host interactions

摘要

Co-Al layered-double-oxides (LDOs) derived from inorganic anion (nitrate, carbonate, sulfate and phosphate) pillared Co-Al layered-double-hydroxides (LDHs) were synthesized. These LDO samples exhibited impressive catalytic performances in oxidative dehydrogenation of propane (ODHP) at low temperatures. Characterization techniques such as XRD, TEM, H-2-TPR and O-2-TPD were used to measure the physicochemical properties of the samples. The results showed that the LDO samples consisted of homogeneously mixed cobalt spinel oxides (Co2AlOx) containing both Co(III) and Co(II). Co(III) instead of Co(II) was linked with the active sites for ODHP at low temperatures. The sulfate and phosphate anions were preserved in the corresponding LDO samples, unlike the nitrate and carbonate pillars. Sulfate (phosphate) around the cobalt decreased the size of the spinel oxide particles more relative to nitrate and carbonate, and so the dispersion of CoOx in the LDO and the selectivity to propylene in ODHP over these catalysts were improved. Both surface adsorbed oxygen species and surface lattice oxygen species were significantly found over the phosphate-pillared LDO, but only lattice oxygen species were available over the sulfate-pillared LDO. Different mechanisms of propane activation were exhibited over these LDO samples for ODHP.