期刊
JOURNAL OF CATALYSIS
卷 326, 期 -, 页码 82-91出版社
ACADEMIC PRESS INC ELSEVIER SCIENCE
DOI: 10.1016/j.jcat.2015.03.011
关键词
Bronsted acid; Dehydration; Molybdenum carbide; Interstitial carbide; Bifunctional catalyst; Site density; Oxophilic; Transition metal
资金
- Office of Basic Energy Sciences, the U.S. Department of Energy [DE-SC0008418]
- MRSEC program of the National Science Foundation [DMR-1420013]
- NSF through the MRSEC program
Acid site densities could be reversibly tuned by a factor of similar to 30 using an O-2 co-feed, which reversibly creates Bronsted acid sites on the carbide surface without altering the bulk crystal structure of 2-5 nm MO2C crystallites. Unimolecular isopropanol (IPA) dehydration at 415 K, a probe reaction, occurred on Bronsted acid sites of these oxygen-modified carbides with an intrinsic activation energy of 93 +/- 1.3 kJ mole(-1) via an E-2 elimination mechanism with a kinetically-relevant step of beta-hydrogen scission. Site densities were estimated via in situ 2,6-di-tert-butylpyridine (DTBP) titration and used to calculate a turnover frequency (TOF) of 0.1 s(-1), which was independent of site density. Oxygen co-processing allows for facile in situ tunability of acidic and metallic sites on highly oxophilic metal carbides. (C) 2015 Elsevier Inc. All rights reserved.
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