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Title: Carboxyl intermediate formation via an in situ-generated metastable active site during water-gas shift reaction

Abstract

Definitive experimental proof for catalytic pathways and active sites during the low-temperature water-gas shift reaction remains elusive. Herein, we combine spectroscopic, kinetic, and computational analyses to address the decades-long mechanistic controversy by studying the reverse water-gas shift over Pd/Al2O3. Isotopic transient kinetic analysis clearly established the minor role of the formate (HCOO) intermediate. Moreover, hydrogen titration experiments unambiguously confirmed the intermediacy of carboxyl (COOH) for the first time. The ability to decouple the parallel formate and carboxyl pathways led to the identification of a distinct active site exhibiting regio- and chemoselective H-addition to CO2 to yield carboxyl. The metastable active site is formed in situ, resulting in hydroxylation of the metal-support interface and electronic restructuring of Pd via reduced coordination. Parallel atomistic simulations of the active site electronic structure and mechanistic landscape provided a framework consistent with experimental observations. Our study highlights the dynamic creation of a coordinatively unsaturated metal site caused by substrate adsorption on an adjacent support site.

Authors:
 [1];  [1]; ORCiD logo [1];  [1];  [1]
  1. BATTELLE (PACIFIC NW LAB)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1577844
Report Number(s):
PNNL-SA-141247
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Nature Catalysis
Additional Journal Information:
Journal Volume: 2; Journal Issue: 10
Country of Publication:
United States
Language:
English

Citation Formats

Nelson, Nicholas C., Nguyen, Manh Thuong, Glezakou, Vassiliki-Alexandra, Rousseau, Roger J., and Szanyi, Janos. Carboxyl intermediate formation via an in situ-generated metastable active site during water-gas shift reaction. United States: N. p., 2019. Web. doi:10.1038/s41929-019-0343-2.
Nelson, Nicholas C., Nguyen, Manh Thuong, Glezakou, Vassiliki-Alexandra, Rousseau, Roger J., & Szanyi, Janos. Carboxyl intermediate formation via an in situ-generated metastable active site during water-gas shift reaction. United States. doi:10.1038/s41929-019-0343-2.
Nelson, Nicholas C., Nguyen, Manh Thuong, Glezakou, Vassiliki-Alexandra, Rousseau, Roger J., and Szanyi, Janos. Tue . "Carboxyl intermediate formation via an in situ-generated metastable active site during water-gas shift reaction". United States. doi:10.1038/s41929-019-0343-2.
@article{osti_1577844,
title = {Carboxyl intermediate formation via an in situ-generated metastable active site during water-gas shift reaction},
author = {Nelson, Nicholas C. and Nguyen, Manh Thuong and Glezakou, Vassiliki-Alexandra and Rousseau, Roger J. and Szanyi, Janos},
abstractNote = {Definitive experimental proof for catalytic pathways and active sites during the low-temperature water-gas shift reaction remains elusive. Herein, we combine spectroscopic, kinetic, and computational analyses to address the decades-long mechanistic controversy by studying the reverse water-gas shift over Pd/Al2O3. Isotopic transient kinetic analysis clearly established the minor role of the formate (HCOO) intermediate. Moreover, hydrogen titration experiments unambiguously confirmed the intermediacy of carboxyl (COOH) for the first time. The ability to decouple the parallel formate and carboxyl pathways led to the identification of a distinct active site exhibiting regio- and chemoselective H-addition to CO2 to yield carboxyl. The metastable active site is formed in situ, resulting in hydroxylation of the metal-support interface and electronic restructuring of Pd via reduced coordination. Parallel atomistic simulations of the active site electronic structure and mechanistic landscape provided a framework consistent with experimental observations. Our study highlights the dynamic creation of a coordinatively unsaturated metal site caused by substrate adsorption on an adjacent support site.},
doi = {10.1038/s41929-019-0343-2},
journal = {Nature Catalysis},
number = 10,
volume = 2,
place = {United States},
year = {2019},
month = {10}
}

Works referenced in this record:

Water Gas Shift Catalysis
journal, September 2009


Challenges in the Greener Production of Formates/Formic Acid, Methanol, and DME by Heterogeneously Catalyzed CO 2 Hydrogenation Processes
journal, May 2017


Mechanism of CO 2 Hydrogenation on Pd/Al 2 O 3 Catalysts: Kinetics and Transient DRIFTS-MS Studies
journal, September 2015


Highly active copper-ceria and copper-ceria-titania catalysts for methanol synthesis from CO2
journal, July 2014


Kinetic and mechanistic studies of the water–gas shift reaction on Pt/TiO2 catalyst
journal, June 2009

  • Kalamaras, Christos M.; Panagiotopoulou, Paraskevi; Kondarides, Dimitris I.
  • Journal of Catalysis, Vol. 264, Issue 2
  • DOI: 10.1016/j.jcat.2009.03.002

Studies of the water-gas-shift reaction on ceria-supported Pt, Pd, and Rh: Implications for oxygen-storage properties
journal, January 1998


Identification of active sites in CO oxidation and water-gas shift over supported Pt catalysts
journal, September 2015


Active Nonmetallic Au and Pt Species on Ceria-Based Water-Gas Shift Catalysts
journal, August 2003


A Common Single-Site Pt(II)–O(OH) x – Species Stabilized by Sodium on “Active” and “Inert” Supports Catalyzes the Water-Gas Shift Reaction
journal, March 2015

  • Yang, Ming; Liu, Jilei; Lee, Sungsik
  • Journal of the American Chemical Society, Vol. 137, Issue 10
  • DOI: 10.1021/ja513292k

Water-gas shift reaction: finding the mechanistic boundary
journal, January 1995


On the Mechanism of Low-Temperature Water Gas Shift Reaction on Copper
journal, January 2008

  • Gokhale, Amit A.; Dumesic, James A.; Mavrikakis, Manos
  • Journal of the American Chemical Society, Vol. 130, Issue 4
  • DOI: 10.1021/ja0768237

Microkinetic analysis and mechanism of the water gas shift reaction over copper catalysts
journal, July 2011


Optimizing Binding Energies of Key Intermediates for CO 2 Hydrogenation to Methanol over Oxide-Supported Copper
journal, September 2016

  • Kattel, Shyam; Yan, Binhang; Yang, Yixiong
  • Journal of the American Chemical Society, Vol. 138, Issue 38
  • DOI: 10.1021/jacs.6b05791

On the Importance of the Associative Carboxyl Mechanism for the Water-Gas Shift Reaction at Pt/CeO 2 Interface Sites
journal, March 2014

  • Aranifard, Sara; Ammal, Salai Cheettu; Heyden, Andreas
  • The Journal of Physical Chemistry C, Vol. 118, Issue 12
  • DOI: 10.1021/jp5000649

Water-Gas Shift Reaction on a Highly Active Inverse CeO x /Cu(111) Catalyst: Unique Role of Ceria Nanoparticles
journal, October 2009

  • Rodriguez, José A.; Graciani, Jesús; Evans, Jaime
  • Angewandte Chemie International Edition, Vol. 48, Issue 43
  • DOI: 10.1002/anie.200903918

Fundamental studies of methanol synthesis from CO2 hydrogenation on Cu(111), Cu clusters, and Cu/ZnO(0001̄)
journal, January 2010

  • Yang, Yixiong; Evans, Jaime; Rodriguez, Jose A.
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 33
  • DOI: 10.1039/c001484b

Water Gas Shift Reaction on Cu and Au Nanoparticles Supported on CeO2(111) and ZnO(000): Intrinsic Activity and Importance of Support Interactions
journal, February 2007

  • Rodriguez, José A.; Liu, Ping; Hrbek, Jan
  • Angewandte Chemie International Edition, Vol. 46, Issue 8
  • DOI: 10.1002/anie.200603931

Activity of CeOx and TiOx Nanoparticles Grown on Au(111) in the Water-Gas Shift Reaction
journal, December 2007


Importance of the Metal-Oxide Interface in Catalysis: In Situ Studies of the Water-Gas Shift Reaction by Ambient-Pressure X-ray Photoelectron Spectroscopy
journal, April 2013

  • Mudiyanselage, Kumudu; Senanayake, Sanjaya D.; Feria, Leticia
  • Angewandte Chemie International Edition, Vol. 52, Issue 19
  • DOI: 10.1002/anie.201210077

Alkali-Stabilized Pt-OHx Species Catalyze Low-Temperature Water-Gas Shift Reactions
journal, September 2010


A New Type of Strong Metal–Support Interaction and the Production of H 2 through the Transformation of Water on Pt/CeO 2 (111) and Pt/CeO x /TiO 2 (110) Catalysts
journal, May 2012

  • Bruix, Albert; Rodriguez, José A.; Ramírez, Pedro J.
  • Journal of the American Chemical Society, Vol. 134, Issue 21
  • DOI: 10.1021/ja302070k

Counting electrons on supported nanoparticles
journal, December 2015

  • Lykhach, Yaroslava; Kozlov, Sergey M.; Skála, Tomáš
  • Nature Materials, Vol. 15, Issue 3
  • DOI: 10.1038/nmat4500

Metallic Corner Atoms in Gold Clusters Supported on Rutile Are the Dominant Active Site during Water−Gas Shift Catalysis
journal, October 2010

  • Williams, W. Damion; Shekhar, Mayank; Lee, Wen-Sheng
  • Journal of the American Chemical Society, Vol. 132, Issue 40
  • DOI: 10.1021/ja1064262

In Situ Characterization of Cu/CeO 2 Nanocatalysts for CO 2 Hydrogenation: Morphological Effects of Nanostructured Ceria on the Catalytic Activity
journal, May 2018

  • Lin, Lili; Yao, Siyu; Liu, Zongyuan
  • The Journal of Physical Chemistry C, Vol. 122, Issue 24
  • DOI: 10.1021/acs.jpcc.8b03596

Dynamic formation of single-atom catalytic active sites on ceria-supported gold nanoparticles
journal, March 2015

  • Wang, Yang-Gang; Mei, Donghai; Glezakou, Vassiliki-Alexandra
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7511

Size-dependent dynamic structures of supported gold nanoparticles in CO oxidation reaction condition
journal, July 2018

  • He, Yang; Liu, Jin-Cheng; Luo, Langli
  • Proceedings of the National Academy of Sciences, Vol. 115, Issue 30
  • DOI: 10.1073/pnas.1800262115

Palladium-Catalyzed Ligand-Directed C−H Functionalization Reactions
journal, February 2010

  • Lyons, Thomas W.; Sanford, Melanie S.
  • Chemical Reviews, Vol. 110, Issue 2
  • DOI: 10.1021/cr900184e

Trends in Formic Acid Decomposition on Model Transition Metal Surfaces: A Density Functional Theory study
journal, November 2014

  • Herron, Jeffrey A.; Scaranto, Jessica; Ferrin, Peter
  • ACS Catalysis, Vol. 4, Issue 12
  • DOI: 10.1021/cs500737p

The critical role of water at the gold-titania interface in catalytic CO oxidation
journal, September 2014


Gold Atoms Stabilized on Various Supports Catalyze the Water–Gas Shift Reaction
journal, November 2013

  • Flytzani-Stephanopoulos, Maria
  • Accounts of Chemical Research, Vol. 47, Issue 3
  • DOI: 10.1021/ar4001845

Electronic factors determining the reactivity of metal surfaces
journal, December 1995


Scaling Properties of Adsorption Energies for Hydrogen-Containing Molecules on Transition-Metal Surfaces
journal, July 2007


A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

  • Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
  • DOI: 10.1063/1.1329672

A diagnostic test of the kinetic regime in a packed bed reactor
journal, March 1967


Design and operating characteristics of a transient kinetic analysis catalysis reactor system employing in situ transmission Fourier transform infrared
journal, September 2006

  • Yang, Yong; Disselkamp, R. S.; Szanyi, J.
  • Review of Scientific Instruments, Vol. 77, Issue 9
  • DOI: 10.1063/1.2349602

Discovering the Active Sites for C3 Separation in MIL-100(Fe) by Using Operando IR Spectroscopy
journal, August 2012

  • Wuttke, Stefan; Bazin, Philippe; Vimont, Alexandre
  • Chemistry - A European Journal, Vol. 18, Issue 38
  • DOI: 10.1002/chem.201201006

Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach
journal, April 2005

  • VandeVondele, Joost; Krack, Matthias; Mohamed, Fawzi
  • Computer Physics Communications, Vol. 167, Issue 2
  • DOI: 10.1016/j.cpc.2004.12.014

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

A hybrid Gaussian and plane wave density functional scheme
journal, October 1997

  • Lippert, By GERALD; Parrinello, JURG HUTTER and MICHELE
  • Molecular Physics, Vol. 92, Issue 3
  • DOI: 10.1080/002689797170220

Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases
journal, September 2007

  • VandeVondele, Joost; Hutter, Jürg
  • The Journal of Chemical Physics, Vol. 127, Issue 11
  • DOI: 10.1063/1.2770708

Dipole correction for surface supercell calculations
journal, May 1999


Highly active and stable MgAl2O4-supported Rh and Ir catalysts for methane steam reforming: A combined experimental and theoretical study
journal, July 2014


Dissecting the steps of CO 2 reduction: 1. The interaction of CO and CO 2 with γ-Al 2 O 3 : an in situ FTIR study
journal, January 2014

  • Szanyi, János; Kwak, Ja Hun
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 29
  • DOI: 10.1039/C4CP00616J

Dissecting the steps of CO 2 reduction: 2. The interaction of CO and CO 2 with Pd/γ-Al 2 O 3 : an in situ FTIR study
journal, January 2014

  • Szanyi, János; Kwak, Ja Hun
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 29
  • DOI: 10.1039/C4CP00617H