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Title: 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]; ORCiD logo [1];  [1];  [1];  [1];  [2]; ORCiD logo [3]; ORCiD logo [3];  [4]; ORCiD logo [3]
  1. Univ. of Delaware, Newark, DE (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Univ. of Delaware, Newark, DE (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. 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 Lab. (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. doi: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. doi: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 = {2020},
month = {3}
}

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