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Synthesis and characterization of silica doped alumina catalyst support with superior thermal stability and unique pore properties

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Abstract

A facile, solvent-deficient, one-pot synthesis of a thermally stable silica-doped alumina, having high surface area, large pore volume and uniquely large pores, has been developed. Silica-doped alumina (SDA) was synthesized by adding 5 wt% silica from tetraethyl orthosilicate (TEOS) to aluminum isoproxide (AIP), a 1:5 mol ratio AIP to water, and a 1:2 mol ratio TEOS to water in the absence of a template. The structure of silica-doped alumina was studied by in situ high-temperature powder XRD, nitrogen adsorption, thermogravimetric analysis, solid-state NMR, and TEM. The addition of silica significantly increases the stability of γ-Al2O3 phase to 1200 °C while maintaining a high surface area, a large pore volume and a large pore diameter. After calcination at 1100 °C for 2 h, a surface area of 160 m2/g, pore volume of 0.99 cm3/g, and a bimodal pore size distribution of 23 and 52 nm are observed. Compared to a commercial silica-doped alumina, after calcination for 24 h at 1100 °C, the surface area, pore volume, and pore diameter SDA are higher by 46, 155, and 94 %, respectively. Results reveal that Si stabilizes the porous structure of γ-Al2O3 up to 1200 °C, while unstabilized alumina is stable to only 900 °C. From our data, we infer that Si enters tetrahedral vacancies in the defect spinel structure of alumina without moving Al from tetrahedral positions and forms a silica–alumina interface.

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Acknowledgments

This work was supported by the U.S. Department of Energy under grant DE-FG02-05ER15666 and National Science Foundation under CHE-0959862. The solid state NMR (TMA) was performed at Sandia National Laboratories which is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-AC04-94AL85000. We also thank Dr. Jeff Farrer and the BYU microscopy lab for their assistance with the TEM imaging.

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT, 84602, USA

    Maryam Khosravi Mardkhe, Baiyu Huang & Brian F. Woodfield

  2. Department of Chemical Engineering, Brigham Young University, Provo, UT, 84602, USA

    Calvin H. Bartholomew

  3. Department of Electronic, Optical and Nanostructured Materials, Sandia National Laboratories, Albuquerque, NM, 87185, USA

    Todd M. Alam

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  1. Maryam Khosravi Mardkhe
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Correspondence to Brian F. Woodfield.

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Mardkhe, M.K., Huang, B., Bartholomew, C.H. et al. Synthesis and characterization of silica doped alumina catalyst support with superior thermal stability and unique pore properties. J Porous Mater 23, 475–487 (2016). https://doi.org/10.1007/s10934-015-0101-z

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