C–O bond activation using ultralow loading of noble metal catalysts on moderately reducible oxides
Abstract
Selective C–O activation of multifunctional molecules is essential for many important chemical processes. Although reducible metal oxides are active and selective towards reductive C–O bond scission via the reverse Mars–van Krevelen mechanism, the most active oxides undergo bulk reduction during reaction. Here, motivated by the enhanced oxide reducibility by metals, we report a strategy for C–O bond activation by doping the surface of moderately reducible oxides with an ultralow loading of noble metals. We demonstrate the principle using highly dispersed Pt anchored onto TiO2 for furfuryl alcohol conversion to 2-methylfuran. A combination of density functional theory calculations, catalyst characterization (scanning transmission electron microscopy, electron paramagnetic resonance, Fourier-transform infrared spectroscopy and X-ray absorption spectroscopy), kinetic experiments and microkinetic modelling expose substantial C–O activation rate enhancement, without bulk catalyst reduction or unselective ring hydrogenation. A methodology is introduced to quantify various types of sites, revealing that the cationic redox Pt on the TiO2 surface is more active than metallic sites for C–O bond activation.
- Authors:
-
[1];
[3];
[3];
[3]
- Univ. of Delaware, Newark, DE (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Univ. of Delaware, Newark, DE (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
- Bruker BioSpin Corporation, Billerica, MA (United States)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI); Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1615721
- Report Number(s):
- BNL-213861-2020-JAAM
Journal ID: ISSN 2520-1158
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Catalysis
- Additional Journal Information:
- Journal Volume: 3; Journal Issue: 5; Journal ID: ISSN 2520-1158
- Publisher:
- Springer Nature
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 77 NANOSCIENCE AND NANOTECHNOLOGY
Citation Formats
Fu, Jiayi, Lym, Jonathan, Zheng, Weiqing, Alexopoulos, Konstantinos, Mironenko, Alexander V., Li, Na, Boscoboinik, J. Anibal, Su, Dong, Weber, Ralph T., and Vlachos, Dionisios G. C–O bond activation using ultralow loading of noble metal catalysts on moderately reducible oxides. United States: N. p., 2020.
Web. doi:10.1038/s41929-020-0445-x.
Fu, Jiayi, Lym, Jonathan, Zheng, Weiqing, Alexopoulos, Konstantinos, Mironenko, Alexander V., Li, Na, Boscoboinik, J. Anibal, Su, Dong, Weber, Ralph T., & Vlachos, Dionisios G. C–O bond activation using ultralow loading of noble metal catalysts on moderately reducible oxides. United States. https://doi.org/10.1038/s41929-020-0445-x
Fu, Jiayi, Lym, Jonathan, Zheng, Weiqing, Alexopoulos, Konstantinos, Mironenko, Alexander V., Li, Na, Boscoboinik, J. Anibal, Su, Dong, Weber, Ralph T., and Vlachos, Dionisios G. Mon .
"C–O bond activation using ultralow loading of noble metal catalysts on moderately reducible oxides". United States. https://doi.org/10.1038/s41929-020-0445-x. https://www.osti.gov/servlets/purl/1615721.
@article{osti_1615721,
title = {C–O bond activation using ultralow loading of noble metal catalysts on moderately reducible oxides},
author = {Fu, Jiayi and Lym, Jonathan and Zheng, Weiqing and Alexopoulos, Konstantinos and Mironenko, Alexander V. and Li, Na and Boscoboinik, J. Anibal and Su, Dong and Weber, Ralph T. and Vlachos, Dionisios G.},
abstractNote = {Selective C–O activation of multifunctional molecules is essential for many important chemical processes. Although reducible metal oxides are active and selective towards reductive C–O bond scission via the reverse Mars–van Krevelen mechanism, the most active oxides undergo bulk reduction during reaction. Here, motivated by the enhanced oxide reducibility by metals, we report a strategy for C–O bond activation by doping the surface of moderately reducible oxides with an ultralow loading of noble metals. We demonstrate the principle using highly dispersed Pt anchored onto TiO2 for furfuryl alcohol conversion to 2-methylfuran. A combination of density functional theory calculations, catalyst characterization (scanning transmission electron microscopy, electron paramagnetic resonance, Fourier-transform infrared spectroscopy and X-ray absorption spectroscopy), kinetic experiments and microkinetic modelling expose substantial C–O activation rate enhancement, without bulk catalyst reduction or unselective ring hydrogenation. A methodology is introduced to quantify various types of sites, revealing that the cationic redox Pt on the TiO2 surface is more active than metallic sites for C–O bond activation.},
doi = {10.1038/s41929-020-0445-x},
journal = {Nature Catalysis},
number = 5,
volume = 3,
place = {United States},
year = {Mon Mar 23 00:00:00 EDT 2020},
month = {Mon Mar 23 00:00:00 EDT 2020}
}
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Dataset for C-O bond activation using ultra-low loading noble metal catalysts on moderately reducible oxides
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Dataset for C-O bond activation using ultra-low loading noble metal catalysts on moderately reducible oxides
dataset, January 2020
- Fu, Jiayi
- Mendeley