Domino Effect of Catalysis: Coherence between Reaction Network and Catalyst Restructuring Accelerating Surface Carburization for CO2 Hydrogenation.

Dynamic carburization is a common and important phenomenon in many industrial reactions. Finding the critical factor governing this process is significant for catalyst optimization, which is complicated due to the coherence between catalyst dynamics and reaction dynamics. In this work, we manipulate the in situ formation of fast carburization on the Pd-FeOx surface by revealing a domino effect between the reaction network and catalyst restructuring during long-term CO2 hydrogenation reaction. We prepared catalysts of three sizes (5Pd-FeOx, 0.5Pd-FeOx, 0.05Pd-FeOx) and found that the large size of Pd NP (5Pd-FeOx) induces the reactive metal-support interaction, following the in situ Pd3Fe formation, the reaction route change, the fast surface carburization (Fe5C2), and finally the superior catalytic performance. Among these changes, we identify that in situ alloying instead of the apparent size difference is crucial for the formation of the active Fe5C2 phase. As a proof of concept, we further design a presynthesized Pd3Fe alloy on FeOx and find an enhanced activity with reduced Pd loading by controlled fast carburization. This work not only demonstrates the controllability of dynamic carburization but also presents a benchmark of optimizing catalysts through the comprehensive understanding of in situ catalyst changes.