Enhanced dry reforming of methane over nickel catalysts supported on zirconia coated mesoporous silica

Dry reforming of methane (DRM) offers a sustainable route to convert CH₄ and CO₂ into syngas, addressing both greenhouse gas emissions and energy demand. However, catalyst deactivation due to sintering and coking limits practical applications. In this work, we developed a mesoporous Ni-based catalyst (Ni/ZrSBA-15-OH) featuring abundant Ni-ZrO₂ interfaces and small Ni nanoparticles (5.6 nm) confined within a stable silica framework. This catalyst showed excellent performance, achieving 80% CH₄ and 87% CO₂ conversions at 750°C, with minimal coke formation (0.4 mg g_cat⁻¹ h⁻¹) and high durability (1.3% CH₄ conversion loss over 20 h). Advanced characterizations (X-ray absorption spectroscopy [XAS], transmission electron microscopy [TEM], H₂-temperature programmed reduction [H₂-TPR], and temperature-programmed surface reaction [TPSR]) revealed that the metal-oxide interface enhances the activation of reactants and stabilizes active sites. Density functional theory (DFT) calculations confirmed that the Ni-ZrO₂ interface increases the energy barrier for CH∗ dehydrogenation, effectively suppressing carbon deposition. This study provides a rational strategy for designing structurally robust and coke-resistant Ni-based catalysts for efficient DRM.