skip to main content


Title: Activation and deactivation of the commercial‐type CuO–Cr 2 O 3 –Fe 2 O 3 high temperature shift catalyst
Abstract

This work elucidates the structural evolution of a commercial‐type iron oxide‐based high temperature water–gas shift (HT‐WGS) catalyst during activation and deactivation stages. The findings highlight the importance of Cu–FeOxinterfaces. Based on the new insights, future improvement of commercial iron‐based catalysts should focus on stabilization of the active Cu–FeOxinterface. Much effort has been devoted to understanding the structure, mechanism, and promotion of the commercial‐type CuO–Cr2O3–Fe2O3catalyst for the high temperature water–gas shift (HT‐WGS) reaction. However, structural evolution of the catalyst during the activation and deactivation stages was rarely reported. Herein, catalyst characterization, temperature‐programmed studies, and kinetic analysis were conducted on iron oxide‐based HT‐WGS catalysts. Addition of Cu was found to accelerate both the bulk (Fe2O3 → Fe3O4) and surface (active FeOx–Cu interface) transformations during the catalyst activation stage. During catalyst deactivation, Cu accelerated both sintering of the Fe3O4bulk phase and unfavorable encapsulation of the metallic Cu particles with a substantial FeOxoverlayer. The loss of the initial active Cu–FeOxinterfacial sites reversed the promotional effect of Cu.

 
more » « less
NSF-PAR ID:
10455616
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
AIChE Journal
Volume:
66
Issue:
1
ISSN:
0001-1541
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Super‐Earths ranging up to 10 Earth masses (ME) with Earth‐like density are common among the observed exoplanets thus far, but their measured masses and radii do not uniquely elucidate their internal structure. Exploring the phase transitions in the Mg‐silicates that define the mantle‐structure of super‐Earths is critical to characterizing their interiors, yet the relevant terapascal conditions are experimentally challenging for direct structural analysis. Here we investigated the crystal chemistry of Fe3O4as a low‐pressure analog to Mg2SiO4between 45–115 GPa and up to 3000 K using powder and single crystal X‐ray diffraction in the laser‐heated diamond anvil cell. Between 60–115 GPa and above 2000 K, Fe3O4adopts an 8‐fold coordinated Th3P4‐type structure (I‐43d,Z = 4) with disordered Fe2+and Fe3+into one metal site. This Fe‐oxide phase is isostructural with that predicted for Mg2SiO4above 500 GPa in super‐Earth mantles and suggests that Mg2SiO4can incorporate both ferric and ferrous iron at these conditions. The pressure‐volume behavior observed in this 8‐fold coordinated Fe3O4indicates a maximum 4% density increase across the 6‐ to 8‐fold coordination transition in the analog Mg‐silicate. Reassessment of the FeO—Fe3O4fugacity buffer considering the Fe3O4phase relationships identified in this study reveals that increasing pressure and temperature to 120 GPa and 3000 K in Earth and planetary mantles drives iron toward oxidation.

     
    more » « less
  2. Abstract

    An ultra-thin overcoating of zirconium oxide (ZrO2) film on CuO-ZnO-Al2O3(CZA) catalysts by atomic layer deposition (ALD) was proved to enhance the catalytic performance of CZA/HZSM-5 (H form of Zeolite Socony Mobil-5) bifunctional catalysts for hydrogenation of CO2to dimethyl ether (DME). Under optimal reaction conditions (i.e. 240 °C and 2.8 MPa), the yield of product DME increased from 17.22% for the bare CZA/HZSM-5 catalysts, to 18.40% for the CZA catalyst after 5 cycles of ZrO2ALD with HZSM-5 catalyst. All the catalysts modified by ZrO2ALD displayed significantly improved catalytic stability of hydrogenation of CO2to DME reaction, compared to that of CZA/HZSM-5 bifunctional catalysts. The loss of DME yield in 100 h of reaction was greatly mitigated from 6.20% (loss of absolute value) to 3.01% for the CZA catalyst with 20 cycles of ZrO2ALD overcoating. Characterizations including hydrogen temperature programmed reduction, x-ray powder diffraction, and x-ray photoelectron spectroscopy revealed that there was strong interaction between Cu active centers and ZrO2.

     
    more » « less
  3. Doped perovskite metal oxide catalysts of the form A(BxM1-x)O3-δhave been instrumental in the development of solid oxide electrolyzers/fuel cells. In addition, this material class has also been demonstrated to be effective as a heterogeneous catalyst. Co-doped barium niobate perovskites have shown remarkable stability in highly acidic CO2sensing measurements/environments (1). However, the reason for their chemical stability is not well understood. Doping with transition metal cations for B site cations often leads to exsolution under reducing conditions. Many perovskites used for the oxidative coupling of methane (OCM) or the electrochemical oxidative coupling of methane (E-OCM) either lack long term stability, or catalytic activity within these highly reducing methane environments. The Mg and Fe co-doped barium niobate BaMg0.33Nb0.67-xFexO3-δshown activity in E-OCM reactors over long periods (2) (>100 hrs) with no iron metal exsolution observed by diffraction or STEM EDX measurements. In contrast, iron decorated BaMg0.33Nb0.67O3showed little C2 conversion activity.

     
    more » « less
  4. Abstract

    Gold (Au) on ceria–zirconia is one of the most active catalysts for the low‐temperature water–gas shift reaction (LTS), a key stage of upgrading H2reformate streams for fuel cells. However, this catalyst rapidly deactivates on‐stream and the deactivation mechanism remains unclear. Using stop–start scanning transmission electron microscopy to follow the exact same area of the sample at different stages of the LTS reaction, as well as complementary X‐ray photoelectron spectroscopy, we observed the activation and deactivation of the catalyst at various stages. During the heating of the catalyst to reaction temperature, we observed the formation of small Au nanoparticles (NPs; 1–2 nm) from subnanometer Au species. These NPs were then seen to agglomerate further over 48 h on‐stream, and most rapidly in the first 5 h when the highest rate of deactivation was observed. These findings suggest that the primary deactivation process consists of the loss of active sites through the agglomeration and possible dewetting of Au NPs.

     
    more » « less
  5. Abstract

    Gold (Au) on ceria–zirconia is one of the most active catalysts for the low‐temperature water–gas shift reaction (LTS), a key stage of upgrading H2reformate streams for fuel cells. However, this catalyst rapidly deactivates on‐stream and the deactivation mechanism remains unclear. Using stop–start scanning transmission electron microscopy to follow the exact same area of the sample at different stages of the LTS reaction, as well as complementary X‐ray photoelectron spectroscopy, we observed the activation and deactivation of the catalyst at various stages. During the heating of the catalyst to reaction temperature, we observed the formation of small Au nanoparticles (NPs; 1–2 nm) from subnanometer Au species. These NPs were then seen to agglomerate further over 48 h on‐stream, and most rapidly in the first 5 h when the highest rate of deactivation was observed. These findings suggest that the primary deactivation process consists of the loss of active sites through the agglomeration and possible dewetting of Au NPs.

     
    more » « less