Synergistic Promotion Strategies for Ni-Based Catalysts in Methane Dry Reforming: Suppressing Sintering and Carbon Deposition

Methane dry reforming (DRM) represents a promising route for the simultaneous valorization of CH₄ and CO₂ into syngas; however, conventional Ni-based catalysts suffer from rapid deactivation due to sintering and carbon deposition. In this work, we present a synergistically engineered Ni-based catalyst integrating hierarchical SiC confinement, Pd promotion via oleic-acid-assisted complexation, and MgO surface modification to overcome these challenges. Under optimized reaction conditions (CH₄/CO₂ = 1:1, 750 °C, GHSV = 36,000 mL g⁻¹ h⁻¹), the multifunctional NiPd/Si–xMg catalyst achieved steady-state conversions of 85% for CH₄ and 84% for CO₂, maintaining an H₂/CO ratio close to 1.0 over 100 h of continuous operation without noticeable deactivation. In contrast, the reference Ni/SiC and Ni/MgO catalysts exhibited initial conversions of 75–80% but declined by more than 50% within the same period, confirming the superior durability of the optimized system. Thermogravimetric analysis (TGA) revealed a drastic reduction in carbon deposition—from 119.0 mg C g⁻¹ for Ni/SiC to 81.4 mg C g⁻¹ for NiPd/Si-xMg—indicating enhanced coke resistance. Transmission electron microscopy (TEM) confirmed uniform Ni dispersion with an average particle size of 7.2 ± 1.8 nm, while H₂-TPR and CO₂-TPD analyses demonstrated improved reducibility and surface basicity. The combination of SiC confinement, Pd-induced hydrogen spillover, and MgO-mediated CO₂ activation effectively mitigated sintering and carbon accumulation, resulting in high activity, stability, and carbon tolerance. This integrated catalyst design provides a robust pathway toward industrially viable DRM systems for sustainable syngas production.