Cu–Co Synergism in Cu 1− xCo xFe 2O 4—Catalysis and XPS Aspects

Abstract

A systematic study on catalytic methylation of phenol is carried out with methanol as a function of reaction temperature and catalyst composition on a Cu 1− x Co x Fe 2O 4 ( x=0.0 to 1.0) ferrospinel system. Phenol methylation gives two major products, namely o-cresol and 2,6-xylenol. Large phenol conversion and 2,6-xylenol production are observed at 350°C and x=0.5 shows good catalytic performance. Increase in selectivity of 2,6-xylenol at the expense of o-cresol demonstrates that the phenol methylation is sequential. X-ray diffraction of fresh catalysts reveals the formation of the spinel phase along with a mixture of CuO and α-Fe 2O 3 phases at x=0.0, while trace amounts of α-Fe 2O 3 are found for x≥0.25. Spent catalysts display better crystallinity, hinting at the integrity of the structure. X-ray photoelectron spectroscopy and X-ray-induced Auger electron spectroscopy reveal the presence of Cu 2+, Fe 3+, Co 2+, and Co 3+ species on fresh catalysts. Metal ions reduce partially to lower oxidation states on spent catalysts. Reducibility of Cu 2+ species decreases with increasing x. Valence band photoemission studies demonstrate a clear change in the overlap between 3d bands of Cu, Co, and Fe from fresh to spent catalysts. The better catalytic results observed with x=0.5 are attributed to an optimum distribution of Cu species with heteroatom neighbors on the surface, and the maximum overlap between the Cu and Co 3d bands makes the ferrospinel integrate chemically and electronically.