Influence of reduction temperature on Ni particle size and catalytic performance of Ni/Mg(Al)O catalyst for CO2 reforming of CH4

Hydrotalcite-derived Ni/Mg(Al)O is promising for CH4-CO2 reforming. However, the catalysts reported so far suffer from sever coking at low temperatures. In this work, we demonstrate that a significant improvement of coke-resistance of Ni/Mg(Al)O can be achieved by fine tuning the Ni particle size through adjusting the reduction condition of catalyst. Ni particles having average size within 4.0-7.1 nm are in situ generated by reducing the catalyst at a selected temperature within 923-1073 K. Controllability of Ni particle size is related to the formation of Mg(Ni,Al)O solid solution upon hydrotalcite decomposition. It is found that the catalyst reduced at 973 K exhibits high activity, stability, and coke-resistance even at reaction temperature as low as 773 K. In contrast, the catalyst reduced at 923 K has low activity and deactivates due to Ni oxidation, while those reduced at 1023 and 1073 K suffer from sintering and severe coking. STEM and O-2-TPO reveal that coke deposition is directly proportional to the Ni particle size but becomes negligible at a size below 6.2 nm. It is evidenced that a critical size of about 6 nm is required to inhibit coking effectively. CO2 temperature-programmed surface reaction indicates that the deposited carbon on small Ni particles can be easily removed by the CO2 activated at the Ni-Mg(Al)O interfaces, accounting for the better resistance to coking. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.