Modulating Metal Support Interactions for Durable and Selective CO2 Hydrogenation Reaction: An Operando Transmission Electron Microscopy Study

Microscopy and Microanalysis, vol. 31

Abstract

Carbon dioxide (CO2) hydrogenation is a promising route to generate clean high-value fuels and chemicals, for example CO, CH4, CH3OH, and C2+ hydrocarbons [1]. Heterogeneous metal-support catalysts have emerged as prime candidates for this reaction, effectively dissociating H2 to facilitate CO2 conversion [2]. While considerable effort has focused on tailoring the size, morphology, and composition of both supports and metal nanoparticles, achieving high activity, selectivity, and stability remains a significant challenge [3]. Crucially, metal-support interactions (MSI) are now recognized as playing a decisive role, as the interface provides active sites and oxygen vacancies that influence gas adsorption, activation, and product formation. Therefore, directly observing these dynamic MSI under realistic reaction conditions is essential for understanding catalytic mechanisms and designing advanced catalysts. While various in-situ techniques have been employed to probe CO2 hydrogenation, recent advances in MEMS-based sample carriers and corresponding transmission electron microscopy (TEM) holders, coupled with residual gas analysis, have enabled in-situ TEM studies of near-atmospheric pressure reactions [4,5]. As TEM provides the opportunity to perform simultaneous high-resolution imaging, chemical composition mapping, and local electronic structure studies, in-situ TEM allows for real-time observation of MSI dynamics and correlation with reaction products, providing unprecedented insights into the catalytic processes [6]. In this work, by comparing different types of metal-substrate interaction, we will uncouple the effect of substrate during CO2 hydrogenation (Figure 1) [7]. Our study would contribute to deepening the understanding of high temperature (co)electrolysis processes, leading to the design of high-performance electrode materials. Time series of TEM images showing the evolution of nickel nanoparticles around surface edges of the substrate.

Authors 8

1. Hongkui Zheng

   Denssolutions (Netherlands)

   Affiliation as printed

   DENSsolutions B.V., Informaticalaan 12 , Delft ,

2. Pritam Kishore Chakraborty Aachen Institute of Physical Chemistry

   Forschungszentrum Jülich · RWTH Aachen University

   Affiliation as printed

   Institute of Energy Technologies - Fundamental Electrochemistry (IET-1) , Forschungszentrum Jülich GmbH, Jülich ,

   Institute of Physical Chemistry, RWTH Aachen University , Aachen ,

3. Ronald G. Spruit

   Denssolutions (Netherlands)

   Affiliation as printed

   DENSsolutions B.V., Informaticalaan 12 , Delft ,

4. Yevheniy V. Pivak

   Denssolutions (Netherlands)

   Affiliation as printed

   DENSsolutions B.V., Informaticalaan 12 , Delft ,

5. Hongyu Sun corresponding

   Denssolutions (Netherlands)

   Affiliation as printed

   DENSsolutions B.V., Informaticalaan 12 , Delft ,

6. Shibabrata Basak corresponding

   Forschungszentrum Jülich

   Affiliation as printed

   Institute of Energy Technologies - Fundamental Electrochemistry (IET-1) , Forschungszentrum Jülich GmbH, Jülich ,

7. Rüdiger‐A. Eichel Aachen Faculty of Mechanical Engineering Institute of Physical Chemistry

   Forschungszentrum Jülich · RWTH Aachen University

   Affiliation as printed

   Faculty of Mechanical Engineering, RWTH Aachen University , Aachen ,

   Institute of Energy Technologies - Fundamental Electrochemistry (IET-1) , Forschungszentrum Jülich GmbH, Jülich ,

   Institute of Physical Chemistry, RWTH Aachen University , Aachen ,

8. H. Hugo Pérez Garza corresponding

   Denssolutions (Netherlands)

   Affiliation as printed

   DENSsolutions B.V., Informaticalaan 12 , Delft ,