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Porous carbon materials have gained increasing attention in catalysis applications due to their tailorable surface properties, large specific surface area, excellent thermal stability, and low cost. Even though porous carbon materials have been employed for thermal-catalytic dry reforming of methane (DRM), the structure–function relationship, especially the critical factor affecting catalytic performance, is still under debate. Herein, various porous carbon-based samples with disparate pore structures and surface properties are prepared by alkali (K₂CO₃) etching and the following CO₂ activation of low-cost petroleum pitch. Detailed characterization clarifies that the quinone/ketone carbonyl functional groups on the carbon surface are the key active sites for DRM. Density functional theory (DFT) calculations also show that the C=O group have the lowest transition state energy barrier for CH₄* cleavage to CH₃* (2.15 eV). Furthermore, the cooperative interplay between the specific surface area and quinone/ketone carbonyl is essential to boost the cleavage of C-H and C-O bonds, guaranteeing enhanced DRM catalytic performance. The MC-600-800 catalyst exhibited an initial CH₄ conversion of 51% and a reaction rate of 12.6 mmol_CH4 g_cat.⁻¹ h⁻¹ at 800 °C, CH₄:CO₂:N₂= 1:1:8, and GHSV = 6000 mL g_cat.⁻¹ h⁻¹. Our work could pave the way for the rational design of metal-free carbon-based DRM catalysts and shed new light on the high value-added utilization of heavy oils.