(251e) Tailoring Catalytic Activity in Dry Methane Reforming Via Atomic-Level Support Modification

Dry methane reforming (DRM) is a promising strategy for CO₂ utilization and greenhouse gas reduction, converting CO₂ and CH₄ into syngas, a key feedstock for synthetic fuels and chemicals. However, severe catalyst deactivation due to sintering and coke deposition at high temperatures limits its industrial application. To address this, innovative catalyst design strategies are required to enhance both activity and stability.

Atomic layer deposition (ALD) enables precise atomic-scale control of catalyst structures, improving stability under harsh conditions. While conventional ALD studies have primarily focused on overcoating active metals to prevent deactivation, this study employs liquid-phase ALD (L-ALD) to modify the electronic properties of the support by depositing only a few atoms. By tuning the electronic density of the support rather than forming a protective shell, we demonstrate that even a single atomic layer of Al₂O₃ significantly enhances catalytic activity. This approach leads to notable improvements in reaction performance compared to bulk-phase Al₂O₃-modified supports reported in previous studies.

To elucidate the impact of ALD modifications, we synthesized MgO–Al₂O₃–Ni catalysts with precisely controlled Al₂O₃ layers via L-ALD and characterized them using H₂-TPR, XPS, DRIFTS, and CO₂-TPD. The results reveal how atomic-level modifications influence reaction chemistry, contributing to enhanced stability and activity. This study highlights a novel catalyst design approach using ALD beyond conventional overcoating strategies, providing insights into rational catalyst engineering for high-temperature reactions and carbon utilization technologies.