On the Selection of Catalysts’ Support with High Oxygen Delivery Capacity for DRM Application: Interest of Praseodymium as Dopant of Ceria

In the present work, a series of supports with varying compositions (ranging from pure CeO2 to pure PrO2-y) was designed to investigate their ability to release oxygen (with the concomitant formation of oxygen vacancies) under diverse reducing atmospheres: hydrogen (H2), helium (He), and in the presence of a carbonaceous substance that mimics eventual carbon deposits formed under practical reaction conditions (DRM). Oxygen vacancies were generated effectively in all three atmospheres (following the order He < H2 < carbon material). With regard to the influence of the composition, the capability to generate oxygen vacancies clearly increased with the Pr content, for whatever the conditions tested. Notably, the non-stoichiometry obtained with the support of pure praseodymia in both inert and reducing atmospheres is very remarkable, as it approaches the maximum non-stoichiometry value of the well-established theoretical Bevan cluster. This leads to consider this formulation as a very promising support for applications in catalysis and other fields where oxygen vacancies play a crucial role. Dry Reforming of Methane requires catalytic supports that possess highly mobile oxygen, enabling it to actively participate in the reactions step involved or potentially gasify undesirable carbon deposits generated during parallel reactions. Consequently, designing and elucidating the behavior of ceria-praseodymium-based supports with high reducibility and generation of oxygen vacancies (oxygen storage and release capacity) holds particular relevance in this context. Actually, the very preliminary results comparing two counterpart formulations (5%Ni/PrO2-y versus 5%Ni/Al2O3) already confirm the suitability of the choice of pure praseodymia in terms of activity, stability and very high selectivity towards H2 and CO, reaching a very close value to the ideal H2/CO ratio of 1.

Open Access funding provided thanks to the CRUE-CSIC agreement with Springer Nature. L.H.S. and A.G.G gratefully acknowledge the financial support of Generalitat Valenciana through a PROMETEO project (CIPROM/2021/070 project) and through the co-financing Organism PRTR—NextGeneration EU (INVEST/2022/253). The financial support from the Ministry of Science and Innovation is also acknowledged (PID2019-105542RB-I00/AEI/https://doi.org/10.13039/501100011033 project). Finally, the authors acknowledge ELECMI-ICTS (code of proposal: ELC181-2023) for the hours allocated allowing the use of the node: TEM/DME Cádiz/TALOS F200X.