Shielding active Fe oxide by surface oxide overlayers for harsh high-temperature water-gas shift reaction

doi:10.1016/S1872-2067(25)64900-X

Abstract

Abstract:

Oxide supports are well known to significantly influence the structure and properties of active oxide overlayers through strong oxide-support interactions. However, the effect of oxide overlayers on the underlying active oxide substrates remains poorly understood. Here, we report the controllable formation of ceria (CeO₂) overlayers on a hematite (Fe₂O₃) surface (CeO₂/Fe₂O₃) via a melting-wetting method. Submonolayer CeO₂ patches facilitate the partial reduction of surrounding Fe₂O₃ to active magnetite (Fe₃O₄) while effectively suppress further reduction of Fe₃O₄ to inactive metallic iron (Fe⁰) under harsh high-temperature water-gas shift (HT-WGS) conditions. We demonstrate this stabilization effect of surface oxide patches (MO_x, M = Ce, Cr, Mn, Mg, Al and Zn) on surrounding active Fe oxide sites via creating a shielding zone around each oxide patch. As a result, Fe₂O₃ catalysts covered with a small amount of CeO₂ surface overlayers (~1.8 wt%) exhibit remarkable stability at 450 °C for over 100 h, in contrast to rapid deactivation observed in pure Fe₂O₃ and industrial iron-chromium (6.5 wt% Cr) catalysts. Building on these findings, we have developed an advanced HT-WGS process that utilizes Cr-free catalysts and significantly reduces steam consumption. This study highlights the critical role of surface oxide overlayers in modulating the redox behavior and reactivity of underlying active oxide substrates, developing an interface confinement strategy for the design of robust and efficient oxide catalysts.

Key words: Surface oxide overlayers, Strong oxide-support interaction, Interface confinement effect, Fe₂O₃, High-temperature water-gas shift

Rongtan Li, Xiangze Du, Xiaohui Feng, Jianyang Wang, Na Ta, Qiang Fu, Xinhe Bao. Shielding active Fe oxide by surface oxide overlayers for harsh high-temperature water-gas shift reaction[J]. Chinese Journal of Catalysis, 2026, 82: 327-336.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64900-X

https://www.cjcatal.com/EN/Y2026/V82/I3/327

Figures/Tables 4

Fig. 1. Preparation and structure of CeOx/Fe2O3 catalysts. (a) Schematic diagram of preparation of CeOx/Fe2O3 catalysts by the melting-wetting method. (b) XRD patterns of CeOx/Fe2O3 catalysts. (c) Monolayer dispersion threshold of CeOx on Fe2O3 determined by XRD and XPS. (d) STEM and EDX mapping images of 2CeOx/Fe2O3 catalyst.

Fig. 2. Interface-dependent reduction behavior of CeOx/Fe2O3 catalysts. (a) CO-TPR of CeOx/Fe2O3 catalysts. CO MS signal (m/z = 28 5%CO/Ar balance. (b) Quasi in-situ Fe 2p3/2 XPS spectra of CeOx/Fe2O3 catalysts after CO-TPR at 330 and 600 °C. (c) ToF-SIMS spectra of CeOx/Fe2O3 catalysts. (d) Correlation of IFe2+/IFe and IFe0/IFe calculated from XPS results with IFe-O-Ce/IFe-O-Fe.

Fig. 3. Effect of surface oxide overlayers on the reduction behavior of surrounding Fe2O3. (a) Quasi in-situ Fe 2p3/2 XPS spectra of oxide/Fe2O3 catalysts after HT-WGS at 450 °C; 10%CO/10%H2O/80%N2, 30000 mL/(h·gcat). (b) In-situ XRD spectra of Fe2O3, 2CeOx/Fe2O3 and 2NiOx/Fe2O3 catalysts in simulated HT-WGS reaction gases at 450 °C for 1 h (the bottom line represents t = 0 and the upper line represents t = 1 h); 10%CO2/10%H2/80%N2, 60000 mL/(h·gcat). (c) Quasi in-situ XPS spectra of metal elements from oxide overlayers of oxide/Fe2O3 catalysts after HT-WGS at 450 °C; 10%CO/10%H2O/80%N2, 30000 mL/(h·gcat).

Fig. 4. Activity, long-term stability and structural evolution of oxide/Fe2O3 catalysts. CO conversion of CeOx/Fe2O3 catalysts at temperatures from 350 to 450 °C (a) and oxide/Fe2O3 catalysts (b) at t = 3 min and 10 h, at 450 °C. (c) Stability test of Oxide/Fe2O3 and industrial FeCrOx catalysts at 450 °C. Reaction conditions in (a-c): 10%CO/10%H2O/80%N2, 36000 mL/(h·gcat). (d) Quasi in-situ Fe 2p XPS spectra of the spent CrOx/Fe2O3 and industrial FeCrOx catalysts after stability test at 450 °C for 5 h. In-situ XRD patterns of industrial FeCrOx (e) and CrOx/Fe2O3 (f) catalysts in simulated HT-WGS reaction gases at 450 °C for 1 h (the bottom line represents t = 0 h and the upper line represents t = 1 h), 10%CO2/10%H2/80%N2, 60000 mL/(h·gcat).

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