Induced Restructuring of a Supramolecular Metal‒Organic Framework Into a Cu─Zn Alloy Catalyst for Reverse Water–Gas Shift

ABSTRACT In Cu–Zn catalysts used for the reverse water–gas shift (RWGS) reaction, Cu and Zn phases remain dispersed, while the Cu–Zn interphase is widely regarded as the catalytically active site. Herein, we engineered a ZnO‐decorated Cu‐rich Cu–Zn alloy using a mixed Cu/Zn oxalate‐based supramolecular metal–organic framework precursor with compositionally homogeneous Cu/Zn mixing. The resulting Cu–Zn catalyst (Cu–Zn|C‐oxo|R) maintained >99% CO selectivity and, at 550°C, delivered a Cu‐normalized CO space–time yield (STY) of 1580 mmol CO g Cu −1 h −1 , higher than those of the Cu‐only and commercial Cu–Zn–Al benchmarks. Under a high space velocity test, the Cu–Zn|C‐oxo|R catalyst remained stable for >50 h at 550°C. Operando Cu K‐edge x‐ray absorption spectroscopy shows that Cu is reduced to a predominantly metallic local environment that persists under RWGS conditions. Complementary in situ x‐ray diffraction and electron microscopy identify Cu‐rich Cu–Zn alloy domains in contact with ZnO, while in situ diffuse reflectance infrared Fourier transform spectroscopy is consistent with an associative formate‐mediated RWGS pathway at these interfaces. Density functional theory calculations further revealed that these interfacial sites favor the formate reaction pathway, providing a molecular‐level rationale for the enhanced catalytic activity.

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Publication Details

Journal
Angewandte Chemie
Published
2026-09-30
DOI
https://doi.org/10.1002/ange.4933664
Primary Topic
Metal-Organic Frameworks: Synthesis and Applications
Type
article
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article

Induced Restructuring of a Supramolecular Metal‒Organic Framework Into a Cu─Zn Alloy Catalyst for Reverse Water–Gas Shift

Pedro Castaño, Bambar Davaasuren, Seba AlAreeqi, Óscar Castillo et al.
Angewandte Chemie
Metal-Organic Frameworks: Synthesis and Applications
article

Induced Restructuring of a Supramolecular Metal‒Organic Framework Into a Cu─Zn Alloy Catalyst for Reverse Water–Gas Shift

Pedro Castaño, Bambar Davaasuren, Seba AlAreeqi, Óscar Castillo, Jon Pascual-Colino, Mohamed Ben Hassine, Pia Dally, Abdallah Nassereddine, Antonio Aguilar‐Tapia, Natalia Morlanés, Enrique V. Ramos–Fernández, Sandra Mena-Gutiérrez, Xueqin Bai, David Trueba, Quaid Johar Samun Virpurwala, Vijay Kumar Velisoju, Hend Mohamed
article en

Abstract

ABSTRACT In Cu–Zn catalysts used for the reverse water–gas shift (RWGS) reaction, Cu and Zn phases remain dispersed, while the Cu–Zn interphase is widely regarded as the catalytically active site. Herein, we engineered a ZnO‐decorated Cu‐rich Cu–Zn alloy using a mixed Cu/Zn oxalate‐based supramolecular metal–organic framework precursor with compositionally homogeneous Cu/Zn mixing. The resulting Cu–Zn catalyst (Cu–Zn|C‐oxo|R) maintained >99% CO selectivity and, at 550°C, delivered a Cu‐normalized CO space–time yield (STY) of 1580 mmol CO g Cu −1 h −1 , higher than those of the Cu‐only and commercial Cu–Zn–Al benchmarks. Under a high space velocity test, the Cu–Zn|C‐oxo|R catalyst remained stable for >50 h at 550°C. Operando Cu K‐edge x‐ray absorption spectroscopy shows that Cu is reduced to a predominantly metallic local environment that persists under RWGS conditions. Complementary in situ x‐ray diffraction and electron microscopy identify Cu‐rich Cu–Zn alloy domains in contact with ZnO, while in situ diffuse reflectance infrared Fourier transform spectroscopy is consistent with an associative formate‐mediated RWGS pathway at these interfaces. Density functional theory calculations further revealed that these interfacial sites favor the formate reaction pathway, providing a molecular‐level rationale for the enhanced catalytic activity.

Angewandte Chemie
Centre National de la Recherche Scientifique (FR), University of the Basque Country (ES), Basque Center for Materials, Applications and Nanostructures (ES), Département de Chimie Moléculaire (FR), Institut Néel (FR), Institut de Chimie Moléculaire de Grenoble (FR), King Abdullah University of Science and Technology (SA), Université Grenoble Alpes (FR)
Clean water and sanitation
Openalex Percentile: Top 27%
Metal-Organic Frameworks: Synthesis and Applications
DOISourceOpenAlex
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