FEMS EUROMAT 2023
Lecture
04.09.2023
In-Situ and Operando TEM for CO2 catalytic conversion investigation
JR

Josephine Rezkallah (Ph.D.)

Centre national de la recherche scientifique (CNRS)

Rezkallah, J. (Speaker)¹; Moldovan, S.¹; Sauvage, X.¹; Witulski, B.²
¹GPM Laboratory, CNRS UMR 6634, Rouen University, Normandy, Saint Etienne du Rouvray (France); ²LCMT Laboratory, CNRS UMR 6507, ENSICAEN & Caen University, Normandy
Vorschau
20 Min. Untertitel (CC)

A potential solution for the rise in CO2 emissions is to convert CO2 into valuable chemical compounds and fuels utilizing renewable energy. Due to their high reactivity, Pt-based nanoparticles are interesting candidates as catalysts for fuel cells, CO2 hydrogenation, oxygen reduction reaction, etc. Important catalysts transformations that can occur during a chemical reaction may lead to catalyst deactivation (coalescence of particles, surface poisoning, etc). This study utilizes an environmental cell TEM holder to follow the materials microstructure evolution under controlled gaseous environment, high temperature and pressure, providing a better understanding of the catalyst behavior during the reaction and its relation to the catalytic reaction products. Pt-Co hollow nanospheres (HNS) with mean outer diameter of 15 nm±2nm and a shell thickness of 2-3nm have been synthesized using a well-defined ratio of Pt salts (H2PtCl6) and Co NPs as precursors. The electron tomography (ET) essays confirmed the complex 3D structure of the HNS with the shell constituted by small nanoparticles (NPs) with diameters of 2 nm. Moreover, the ET allowed one to identify the presence of pores within the shell, which is an indication of an augmentation of the active surface area as the accessibility to the inner surface of the nanosphere is ensured. The catalysts morphological evolution was monitored using a closed cell experimental device (Protochips: Atmospehere) under CO2 and H2 mixture (H2/CO2=4 instead of a ratio of 3 as most ex situ experiments, since increasing the H2/CO2 input ratio would boost the conversion at low temperatures) at the atmospheric pressure and by varying the temperature with a rate of 20°C/min. In the same time, the evolution of the reaction products (HCO2H, CH3OH and H2O) was monitored. As expected, the growth of the shell NPs via Ostwald ripening mechanism was identified, such that at 240°C, a continuous shell is formed. Although the accessibility to the inner surface is blocked the reaction was still occurring on the outer surface of the nanospheres up to 450°C. Beyond this temperature, the nanospherical microstructure starts collapsing, process accompanied by the increase of the reaction products. This suggests that a part of the reaction products is encapsulated within the HNS inner volume and released upon their collapse.

Abstract

Abstract

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