“One-pot” synthesis of phosphorylated mesoporous carbon heterogeneous catalysts with tailored surface acidity

• Published in: Catalysis today 2012-06, Vol.186 (1), p.12-19
• Main Authors: Fulvio, Pasquale F., Mayes, Richard T., Bauer, John C., Wang, Xiqing, Mahurin, Shannon M., Veith, Gabriel M., Dai, Sheng
• Format: Article
• Language: English
• Subjects: acidity; ADSORPTION; AMMONIA; Ammonia-TPD; CARBON; Catalysis; CATALYSTS; catalytic activity; Chemistry; Colloidal state and disperse state; DEHYDRATION; DESORPTION; energy; Exact sciences and technology; gels; GENERAL AND MISCELLANEOUS//MATHEMATICS, COMPUTING, AND INFORMATION SCIENCE; General and physical chemistry; hydrochloric acid; Isopropanol dehydration; isopropyl alcohol; Mesoporous carbon; MIXTURES; NITRIC ACID; NITROGEN; PH VALUE; PHOSPHATES; PHOSPHORIC ACID; PHOSPHORYLATION; PLURONICS; Porous materials; Soft-templating; SPECIFIC SURFACE AREA; spectroscopy; SURFACE AREA; Surface physical chemistry; SYNTHESIS; temperature; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; TRANSMISSION ELECTRON MICROSCOPY; X-radiation; X-RAY PHOTOELECTRON SPECTROSCOPY; X-RAY SPECTROSCOPY
• ISSN: 0920-5861; 1873-4308
• DOI: 10.1016/j.cattod.2011.08.004

. Highly active acid catalysts supported on mesoporous carbon were successfully synthesized and tested for dehydration reaction. [Display omitted] ► Mesoporous carbons containing phosphate sites and tailored surface acidity. ► Adsorption and structural properties modified by phosphoric acid ratios. ► Number of surface phosphate sites determined by phosphoric acid ratios in synthesis. ► Control over activity for isopropanol dehydration and conversion temperatures. Soft-templated phosphorylated mesoporous carbons with homogeneous distributions of phosphate groups were prepared by a “one-pot” synthesis method using mixtures of phosphoric acid with hydrochloric, or nitric acids in the presence of Pluronic F127 triblock copolymer. Adjusting the various ratios of phosphoric acid used in these mixtures resulted in carbons with distinct adsorption, structural and surface acidity properties. The pore size distributions (PSDs) from nitrogen adsorption at −196°C showed that mesoporous carbons exhibit specific surface areas as high as 551m2/g and mesopores as large as 13nm. Both structural ordering of the mesopores and the final phosphate contents were strongly dependent on the ratios of H3PO4 in the synthesis gels, as shown by transmission electron microscopy (TEM), X-ray photoelectron (XPS) and energy dispersive X-ray spectroscopy (EDS). The number of surface acid sites determined from temperature programmed desorption of ammonia (NH3–TPD) were in the range of 0.3–1.5mmol/g while the active surface areas are estimated to comprise 5–54% of the total surface areas. Finally, the conversion temperatures for the isopropanol dehydration were lowered by as much as 100°C by transitioning from the least acidic to the most acidic catalysts surface.