Elucidation of the Reaction Mechanism for High-Temperature Water Gas Shift over an Industrial-Type Copper–Chromium–Iron Oxide Catalyst

Polo-Garzon, Felipe; Fung, Victor; Nguyen, Luan; Tang, Yu; Tao, Franklin; Cheng, Yongqiang; Daemen, Luke L.; Ramirez-Cuesta, Anibal J.; Foo, Guo Shiou; Zhu, Minghui; Wachs, Israel E.; Jiang, De-en; Wu, Zili

doi:10.1021/jacs.9b03516

Title: Elucidation of the Reaction Mechanism for High-Temperature Water Gas Shift over an Industrial-Type Copper–Chromium–Iron Oxide Catalyst

Journal Article · Thu Apr 25 00:00:00 EDT 2019 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.9b03516· OSTI ID:1513371

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Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Univ. of California, Riverside, CA (United States)
Univ. of Kansas, Lawrence, KS (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); W. L. Gore and Associates, Newark, DE (United States)
Lehigh Univ., Bethlehem, PA (United States); East China Univ. of Science and Technology, Shanghai (China)
Lehigh Univ., Bethlehem, PA (United States)
Univ. of California, Riverside, CA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

The water gas shift (WGS) reaction is of paramount importance for the chemical industry, as it constitutes, coupled with methane reforming, the main industrial route to produce hydrogen. Copper–chromium–iron oxide-based catalysts have been widely used for the high-temperature WGS reaction industrially. The WGS reaction mechanism by the CuCrFeOx catalyst has been debated for years, mainly between a “redox” mechanism involving the participation of atomic oxygen from the catalyst and an “associative” mechanism proceeding via a surface formate-like intermediate. In the present work, advanced in situ characterization techniques (infrared spectroscopy, temperature-programmed surface reaction (TPSR), near-ambient pressure XPS (NAP-XPS), and inelastic neutron scattering (INS)) were applied to determine the nature of the catalyst surface and identify surface intermediate species under WGS reaction conditions. The surface of the CuCrFeOx catalyst is found to be dynamic and becomes partially reduced under WGS reaction conditions, forming metallic Cu nanoparticles on Fe3O4. Neither in situ IR not INS spectroscopy detect the presence of surface formate species during WGS. TPSR experiments demonstrate that the evolution of CO2 and H2 from the CO/H2O reactants follows different kinetics than the evolution of CO2 and H2 from HCOOH decomposition (molecule mimicking the associative mechanism). Steady-state isotopic transient kinetic analysis (SSITKA) (CO + H216O → CO + H218O) exhibited significant 16O/18O scrambling, characteristic of a redox mechanism. Computed activation energies for elementary steps for the redox and associative mechanism by density functional theory (DFT) simulations indicate that the redox mechanism is favored over the associative mechanism. The combined spectroscopic, computational, and kinetic evidence in the present study finally resolves the WGS reaction mechanism on the industrial-type high-temperature CuCrFeOx catalyst that is shown to proceed via the redox mechanism.

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Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: AC05-00OR22725; AC02-05CH11231

OSTI ID:: 1513371

Alternate ID(s):: OSTI ID: 1542620

Journal Information:: Journal of the American Chemical Society, Vol. 141, Issue 19; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 42 works

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Activation and deactivation of the commercial‐type CuO–Cr ₂ O ₃ –Fe ₂ O ₃ high temperature shift catalyst Zhu, Minghui; Tian, Pengfei; Chen, Jiacheng AIChE Journal, Vol. 66, Issue 1 https://doi.org/10.1002/aic.16846	journal	November 2019
Ultra-stable metal nano-catalyst synthesis strategy: a perspective Cao, Xiao-Qing; Zhou, Jun; Li, Song Rare Metals, Vol. 39, Issue 2 https://doi.org/10.1007/s12598-019-01350-y	journal	December 2019
The catalytic mechanism of the Au@TiO _2−x /ZnO catalyst towards a low-temperature water-gas shift reaction Liu, Ning; Yin, Pan; Xu, Ming Catalysis Science & Technology, Vol. 10, Issue 3 https://doi.org/10.1039/c9cy02077b	journal	January 2020

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Water-gas shift
reaction mechanism
iron oxide-based catalyst
NAP-XPS
FTIR
neutron scattering
TPSR
SSITKA
DFT.

Title: Elucidation of the Reaction Mechanism for High-Temperature Water Gas Shift over an Industrial-Type Copper–Chromium–Iron Oxide Catalyst

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