Preparation and characterization of H4SiW12O40@MIL-100(Fe) and its catalytic performance for synthesis of 4,4′-MDA

Abstract

Abstract The catalytic performance of commonly used heteropolyacids (H 3 PW 12 O 40 , H 4 SiW 12 O 40 and H 3 PMo 12 O 40 ) for the synthesis of 4,4′-methylenedianiline (4,4′-MDA) from aniline and formaldehyde was evaluated and the result showed that H 4 SiW 12 O 40 with moderate acid strength exhibited the best catalytic performance. Then H 4 SiW 12 O 40 @MIL-100(Fe) was prepared by encapsulating H 4 SiW 12 O 40 within the pores of MIL-100(Fe) to facilitate its recovery and reuse. The prepared H 4 SiW 12 O 40 @MIL-100(Fe) was characterized by means of FT-IR, N 2 adsorption–desorption, XRD, TG and then the catalytic performance was evaluated. The result showed that H 4 SiW 12 O 40 was highly dispersed in the pores of MIL-100(Fe), and both the Keggin structure of H 4 SiW 12 O 40 and the crystal skeleton structure of MIL-100(Fe) could be effectively preserved. Furthermore, H 4 SiW 12 O 40 @MIL-100(Fe) showed excellent catalytic performance under the following reaction conditions: a molar ratio of aniline to formaldehyde = 5, a mass ratio of catalyst to formaldehyde = 1.2, a reaction temperature of 120 °C and a reaction time of 6 h. Under the above reaction conditions, the conversion of aniline was 41.1%, and the yield and selectivity of 4,4′-MDA were 81.6% and 79.2%, respectively. Unfortunately, an appreciable loss in the catalytic activity of the recovered H 4 SiW 12 O 40 @MIL-100(Fe) was observed because of the blocking of the pores and the change of the acidity resulted from the adsorption of alkaline organics such as aniline and 4,4′-MDA. The adsorbed alkaline organics could be cleaned up when the recovered catalyst was washed by methanol and DMF. Then the catalyst was effectively reused up to three cycles without much loss in its activity.