Stable Co-valorization of Carbon Dioxide and Methane via Dynamic Reconstruction of a Metal Oxide Solid Solution Catalyst

Dry reforming of methane (DRM) is a process that converts two greenhouse gases (methane and carbon dioxide) into syngas, a mixture of H₂ and CO, that can lead to a variety of value-added chemicals. Owing to its endothermic nature, high reaction temperatures up to 800 °C are typically required, and the grand challenge lies in developing robust catalysts without sintering and coking-induced deactivation during the long-term on-stream operation. Toward this aim, herein, a robust complex oxide-supported NiCu alloy catalyst was generated in situ during DRM. By leveraging the configurational stability of a solid oxide solution precursor, tightly anchored NiCu bimetallic nanoparticles were in situ exsoluted and acted as the active sites in DRM. The as-afforded catalyst exhibited stable performance for DRM due to the ability to repel coke off the surface as the reaction proceeds. Kinetic experiments along with top surface characterization detail the reconstruction behavior of the solid oxide solution under the DRM reaction conditions. The fundamental insights from this work provide guidance on generating resistant and flexible catalysts via in situ active site formation from easily synthesized metal oxide solid solutions.