C–O bond activation using ultralow loading of noble metal catalysts on moderately reducible oxides

Fu, Jiayi; Lym, Jonathan; Zheng, Weiqing; Alexopoulos, Konstantinos; Mironenko, Alexander V.; Li, Na; Boscoboinik, J. Anibal; Su, Dong; Weber, Ralph T.; Vlachos, Dionisios G.

doi:10.1038/s41929-020-0445-x

C–O bond activation using ultralow loading of noble metal catalysts on moderately reducible oxides

Journal Article · Mon Mar 23 00:00:00 EDT 2020 · Nature Catalysis

DOI:https://doi.org/10.1038/s41929-020-0445-x· OSTI ID:1615721

Fu, Jiayi ^[1]; ^[1]; Zheng, Weiqing ^[1]; Alexopoulos, Konstantinos ^[1]; Mironenko, Alexander V. ^[1]; Li, Na ^[2]; ^[3]; ^[3]; Weber, Ralph T. ^[4]; ^[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)

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.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012704

OSTI ID:: 1615721

Alternate ID(s):: OSTI ID: 1637958
OSTI ID: 1690044

Report Number(s):: BNL--213861-2020-JAAM

Journal Information:: Nature Catalysis, Journal Name: Nature Catalysis Journal Issue: 5 Vol. 3; ISSN 2520-1158

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

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