Tailored interfaces promoting photo-activation of molecular enclosed CO₂ on MOF-derived Ni/CeZrO₂ for photothermal synergistic dry reforming of methane

Photothermal synergistic catalysis dry reforming of methane (PTSC-DRM) has attracted considerable interest due to its capability to convert CH₄ and CO₂ into syngas under mild conditions. The development of high-performance catalysts that efficiently harness both light and heat while resisting carbon deposition remains challenging. In this study, we present a Ni/CeZrO₂ catalyst derived from metal-organic frameworks (MOF). Characterization techniques such as TEM confirmed the presence of abundant interface sites, which enhance the metal-support interactions. This configuration facilitates the establishment of a CO₂ molecular fence around nickel nanoparticles, thereby increasing reaction rates and mitigating carbon deposition through enhanced CO₂ photoactivation. At 650 °C, the conversion rates of CH₄ and CO₂ reached 63.9 % and 71.1 %, respectively. In situ DRFITS and CO₂-TPD characterization, along with theoretical calculations, revealed superior CO₂ adsorption at the Ni-O-Zr sites, promoting the formation of carbon-tolerant intermediates (CH_xO*) under light irradiation, which are subsequently oxidized by OH* to produce CO and H₂. This remarkable light-induced decarbonization mechanism allows the catalyst to effectively suppress carbon deposition and accelerate carbon oxidation. At 600 °C, unlike the severe carbon accumulation observed with Ni/CeO₂ during 70 h of online testing, the Ni/CeZrO₂ catalyst maintains stable PTSC-DRM activity for over 250 h without significant performance degradation.