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

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

Journal Article · 22 March 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.

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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

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

References (60)

Dataset for C-O bond activation using ultra-low loading noble metal catalysts on moderately reducible oxides Fu, Jiayi Mendeley https://doi.org/10.17632/pgmcmfb243	dataset	January 2020
Directing Reaction Pathways through Controlled Reactant Binding at Pd-TiO ₂ Interfaces Zhang, Jing; Wang, Bingwen; Nikolla, Eranda Angewandte Chemie, Vol. 129, Issue 23 https://doi.org/10.1002/ange.201703669	journal	May 2017
Exploring the Reaction Pathways of Bioglycerol Hydrodeoxygenation to Propene over Molybdena-Based Catalysts Zacharopoulou, Vasiliki; Vasiliadou, Efterpi S.; Lemonidou, Angeliki A. ChemSusChem, Vol. 11, Issue 1 https://doi.org/10.1002/cssc.201701605	journal	December 2017
Computational study on the reactions of H2O2 on TiO2 anatase (101) and rutile (110) surfaces Huang, Wen-Fei; Raghunath, P.; Lin, M. C. Journal of Computational Chemistry, Vol. 32, Issue 6 https://doi.org/10.1002/jcc.21686	journal	November 2010
High selective production of tetrahydrofurfuryl alcohol: Catalytic hydrogenation of furfural and furfuryl alcohol Merat, Nadine; Godawa, Christine; Gaset, Antoine Journal of Chemical Technology & Biotechnology, Vol. 48, Issue 2 https://doi.org/10.1002/jctb.280480205	journal	January 1990
Conversion of Guaiacol over Supported Ru Catalysts Boonyasuwat, Sunya; Omotoso, Taiwo; Resasco, Daniel E. Catalysis Letters, Vol. 143, Issue 8 https://doi.org/10.1007/s10562-013-1033-3	journal	June 2013
The H2 Pressure Dependence of Hydrodeoxygenation Selectivities for Furfural Over Pt/C Catalysts Luo, Jing; Monai, Matteo; Yun, Hongseok Catalysis Letters, Vol. 146, Issue 4 https://doi.org/10.1007/s10562-016-1705-x	journal	February 2016
Kinetics and Mechanism of Ketonization of Acetic Acid on Ru/TiO2 Catalyst Pham, Tu N.; Shi, Dachuan; Resasco, Daniel E. Topics in Catalysis, Vol. 57, Issue 6-9 https://doi.org/10.1007/s11244-013-0227-7	journal	November 2013
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Catalytic performance and mechanism of a Pt/TiO2 catalyst for the oxidation of formaldehyde at room temperature Zhang, Changbin; He, Hong; Tanaka, Ken-ichi Applied Catalysis B: Environmental, Vol. 65, Issue 1-2 https://doi.org/10.1016/j.apcatb.2005.12.010	journal	May 2006
Surface structures and thermodynamics of low-index of rutile, brookite and anatase – A comparative DFT study Esch, Tobit R.; Gadaczek, Immanuel; Bredow, Thomas Applied Surface Science, Vol. 288 https://doi.org/10.1016/j.apsusc.2013.10.021	journal	January 2014
A Python Multiscale Thermochemistry Toolbox (pMuTT) for thermochemical and kinetic parameter estimation Lym, Jonathan; Wittreich, Gerhard R.; Vlachos, Dionisios G. Computer Physics Communications, Vol. 247 https://doi.org/10.1016/j.cpc.2019.106864	journal	February 2020
Selective conversion of furfural to methylfuran over silica-supported NiFe bimetallic catalysts Sitthisa, Surapas; An, Wei; Resasco, Daniel E. Journal of Catalysis, Vol. 284, Issue 1 https://doi.org/10.1016/j.jcat.2011.09.005	journal	November 2011
Aqueous-phase ketonization of acetic acid over Ru/TiO2/carbon catalysts Pham, Tu Nguyet; Shi, Dachuan; Sooknoi, Tawan Journal of Catalysis, Vol. 295 https://doi.org/10.1016/j.jcat.2012.08.012	journal	November 2012
Acetic acid ketonization on tetragonal zirconia: Role of surface reduction Tosoni, Sergio; Pacchioni, Gianfranco Journal of Catalysis, Vol. 344 https://doi.org/10.1016/j.jcat.2016.10.002	journal	December 2016
Catalytic carbon dioxide hydrogenation to methane: A review of recent studies Su, Xiong; Xu, Jinghua; Liang, Binglian Journal of Energy Chemistry, Vol. 25, Issue 4 https://doi.org/10.1016/j.jechem.2016.03.009	journal	July 2016
Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles Liu, Lichen; Corma, Avelino Chemical Reviews, Vol. 118, Issue 10 https://doi.org/10.1021/acs.chemrev.7b00776	journal	April 2018
Mechanistic Insights into Metal Lewis Acid-Mediated Catalytic Transfer Hydrogenation of Furfural to 2-Methylfuran Gilkey, Matthew J.; Panagiotopoulou, Paraskevi; Mironenko, Alexander V. ACS Catalysis, Vol. 5, Issue 7 https://doi.org/10.1021/acscatal.5b00586	journal	June 2015
Role of the Support and Reaction Conditions on the Vapor-Phase Deoxygenation of m -Cresol over Pt/C and Pt/TiO ₂ Catalysts Griffin, Michael B.; Ferguson, Glen A.; Ruddy, Daniel A. ACS Catalysis, Vol. 6, Issue 4 https://doi.org/10.1021/acscatal.5b02868	journal	March 2016
Mechanisms for High Selectivity in the Hydrodeoxygenation of 5-Hydroxymethylfurfural over PtCo Nanocrystals Luo, Jing; Yun, Hongseok; Mironenko, Alexander V. ACS Catalysis, Vol. 6, Issue 7 https://doi.org/10.1021/acscatal.6b00750	journal	May 2016
Mechanistic Study of the Direct Hydrodeoxygenation of m -Cresol over WO _x -Decorated Pt/C Catalysts Wang, Cong; Mironenko, Alexander V.; Raizada, Abhishek ACS Catalysis, Vol. 8, Issue 9 https://doi.org/10.1021/acscatal.8b01746	journal	July 2018
Structure Sensitivity of Acetylene Semi-Hydrogenation on Pt Single Atoms and Subnanometer Clusters Kuo, Chun-Te; Lu, Yubing; Kovarik, Libor ACS Catalysis, Vol. 9, Issue 12 https://doi.org/10.1021/acscatal.9b02840	journal	October 2019
DFT Study of Furfural Conversion to Furan, Furfuryl Alcohol, and 2-Methylfuran on Pd(111) Vorotnikov, Vassili; Mpourmpakis, Giannis; Vlachos, Dionisios G. ACS Catalysis, Vol. 2, Issue 12 https://doi.org/10.1021/cs300395a	journal	October 2012
Ketonization of Carboxylic Acids in Biomass Conversion over TiO ₂ and ZrO ₂ Surfaces: A DFT Perspective Pacchioni, Gianfranco ACS Catalysis, Vol. 4, Issue 9 https://doi.org/10.1021/cs500791w	journal	July 2014
Structure-sensitivity and ensemble effects in reactions of strongly adsorbed intermediates: catalytic dehydrogenation and dehydration of formic acid on nickel Iglesia, Enrique; Boudart, Michel The Journal of Physical Chemistry, Vol. 95, Issue 18 https://doi.org/10.1021/j100171a053	journal	September 1991
Selective Hydrogenation of the CO Bond in Acrolein through the Architecture of Bimetallic Surface Structures Murillo, Luis E.; Goda, Amit M.; Chen, Jingguang G. Journal of the American Chemical Society, Vol. 129, Issue 22 https://doi.org/10.1021/ja070264m	journal	June 2007
Atomically Dispersed Au–(OH) _x Species Bound on Titania Catalyze the Low-Temperature Water-Gas Shift Reaction Yang, Ming; Allard, Lawrence F.; Flytzani-Stephanopoulos, Maria Journal of the American Chemical Society, Vol. 135, Issue 10 https://doi.org/10.1021/ja312646d	journal	March 2013
Remarkable Performance of Ir ₁ /FeO _x Single-Atom Catalyst in Water Gas Shift Reaction Lin, Jian; Wang, Aiqin; Qiao, Botao Journal of the American Chemical Society, Vol. 135, Issue 41 https://doi.org/10.1021/ja408574m	journal	October 2013
Conjugation-Driven “Reverse Mars–van Krevelen”-Type Radical Mechanism for Low-Temperature C–O Bond Activation Mironenko, Alexander V.; Vlachos, Dionisios G. Journal of the American Chemical Society, Vol. 138, Issue 26 https://doi.org/10.1021/jacs.6b02871	journal	June 2016
Catalyst Architecture for Stable Single Atom Dispersion Enables Site-Specific Spectroscopic and Reactivity Measurements of CO Adsorbed to Pt Atoms, Oxidized Pt Clusters, and Metallic Pt Clusters on TiO ₂ DeRita, Leo; Dai, Sheng; Lopez-Zepeda, Kimberly Journal of the American Chemical Society, Vol. 139, Issue 40 https://doi.org/10.1021/jacs.7b07093	journal	September 2017
Hydrogen Adsorption and Diffusion on the Anatase TiO ₂ (101) Surface: A First-Principles Investigation Islam, Mazharul M.; Calatayud, Monica; Pacchioni, Gianfranco The Journal of Physical Chemistry C, Vol. 115, Issue 14 https://doi.org/10.1021/jp200408v	journal	March 2011
Single-atom catalysis of CO oxidation using Pt1/FeOx Qiao, Botao; Wang, Aiqin; Yang, Xiaofeng Nature Chemistry, Vol. 3, Issue 8 https://doi.org/10.1038/nchem.1095	journal	July 2011
MoS2 monolayer catalyst doped with isolated Co atoms for the hydrodeoxygenation reaction Liu, Guoliang; Robertson, Alex W.; Li, Molly Meng-Jung Nature Chemistry, Vol. 9, Issue 8 https://doi.org/10.1038/nchem.2740	journal	March 2017
Identification of active sites on supported metal catalysts with carbon nanotube hydrogen highways Briggs, Nicholas M.; Barrett, Lawrence; Wegener, Evan C. Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-06100-9	journal	September 2018
Structural evolution of atomically dispersed Pt catalysts dictates reactivity DeRita, Leo; Resasco, Joaquin; Dai, Sheng Nature Materials, Vol. 18, Issue 7 https://doi.org/10.1038/s41563-019-0349-9	journal	April 2019
Operando NAP-XPS unveils differences in MoO3 and Mo2C during hydrodeoxygenation Murugappan, Karthick; Anderson, Eric M.; Teschner, Detre Nature Catalysis, Vol. 1, Issue 12 https://doi.org/10.1038/s41929-018-0171-9	journal	November 2018
Fundamentals of C–O bond activation on metal oxide catalysts Goulas, Konstantinos A.; Mironenko, Alexander V.; Jenness, Glen R. Nature Catalysis, Vol. 2, Issue 3 https://doi.org/10.1038/s41929-019-0234-6	journal	February 2019
Optimization methods for finding minimum energy paths Sheppard, Daniel; Terrell, Rye; Henkelman, Graeme The Journal of Chemical Physics, Vol. 128, Issue 13 https://doi.org/10.1063/1.2841941	journal	April 2008
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
A generalized solid-state nudged elastic band method Sheppard, Daniel; Xiao, Penghao; Chemelewski, William The Journal of Chemical Physics, Vol. 136, Issue 7 https://doi.org/10.1063/1.3684549	journal	February 2012
Selective Hydrogenation of α,β-Unsaturated Aldehydes Gallezot, P.; Richard, D. Catalysis Reviews, Vol. 40, Issue 1-2 https://doi.org/10.1080/01614949808007106	journal	February 1998
The atomic simulation environment—a Python library for working with atoms Hjorth Larsen, Ask; Jørgen Mortensen, Jens; Blomqvist, Jakob Journal of Physics: Condensed Matter, Vol. 29, Issue 27 https://doi.org/10.1088/1361-648X/aa680e	journal	June 2017
Single-atom catalyst: a rising star for green synthesis of fine chemicals Zhang, Leilei; Ren, Yujing; Liu, Wengang National Science Review, Vol. 5, Issue 5 https://doi.org/10.1093/nsr/nwy077	journal	August 2018
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium Kresse, G.; Hafner, J. Physical Review B, Vol. 49, Issue 20, p. 14251-14269 https://doi.org/10.1103/PhysRevB.49.14251	journal	May 1994
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
VESTA : a three-dimensional visualization system for electronic and structural analysis Momma, Koichi; Izumi, Fujio Journal of Applied Crystallography, Vol. 41, Issue 3 https://doi.org/10.1107/S0021889808012016	journal	May 2008
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data Momma, Koichi; Izumi, Fujio Journal of Applied Crystallography, Vol. 44, Issue 6 https://doi.org/10.1107/S0021889811038970	journal	October 2011
Structural and thermal parameters for rutile and anatase Howard, C. J.; Sabine, T. M.; Dickson, F. Acta Crystallographica Section B Structural Science, Vol. 47, Issue 4 https://doi.org/10.1107/S010876819100335X	journal	August 1991
An object-oriented scripting interface to a legacy electronic structure code Bahn, S. R.; Jacobsen, K. W. Computing in Science & Engineering, Vol. 4, Issue 3 https://doi.org/10.1109/5992.998641	journal	January 2002
Control of Metal Nanocrystal Size Reveals Metal-Support Interface Role for Ceria Catalysts Cargnello, M.; Doan-Nguyen, V. V. T.; Gordon, T. R. Science, Vol. 341, Issue 6147 https://doi.org/10.1126/science.1240148	journal	July 2013
Identification of active sites in CO oxidation and water-gas shift over supported Pt catalysts Ding, K.; Gulec, A.; Johnson, A. M. Science, Vol. 350, Issue 6257 https://doi.org/10.1126/science.aac6368	journal	September 2015
Thermally stable single-atom platinum-on-ceria catalysts via atom trapping Jones, J.; Xiong, H.; DeLaRiva, A. T. Science, Vol. 353, Issue 6295 https://doi.org/10.1126/science.aaf8800	journal	July 2016
Dataset for C-O bond activation using ultra-low loading noble metal catalysts on moderately reducible oxides Fu, Jiayi Mendeley https://doi.org/10.17632/pgmcmfb243	dataset	January 2020
Dataset for C-O bond activation using ultra-low loading noble metal catalysts on moderately reducible oxides Fu, Jiayi Mendeley https://doi.org/10.17632/pgmcmfb243.1	dataset	January 2020
Topology of the pyroxenes as a function of temperature, pressure, and composition as determined from the procrystal electron density Downs, Robert T. American Mineralogist, Vol. 88, Issue 4 https://doi.org/10.2138/am-2003-0409	journal	April 2003
CHEMKIN-III: A FORTRAN chemical kinetics package for the analysis of gas-phase chemical and plasma kinetics Kee, R. J.; Rupley, F. M.; Meeks, E. https://doi.org/10.2172/481621	report	May 1996

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