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Deactivation from coke deposition on Ni catalysts in the dry reforming of methane (DRM) remains an intractable problem at low temperatures, particularly for biogas with a high CH 4 /CO 2 ratio often above 1. Herein, we engineer a bifunctional catalyst composed of a Ni 3 ZnC 0.7 core for CH 4 activation and an external CaO promoter with high dispersion for CO 2 capture and activation. Remarkably, the optimal catalyst exhibits outstanding activation capability through the in situ -induced formation of the Ni 3 ZnC 0.7 structure, enabling low-temperature H 3 C–H bond cleavage, while CaCO 3 intermediates synergistically enhanced methane activation kinetics. The optimized system achieved CH 4 and CO 2 conversions of 47.7 and 71.6% with a H 2 /CO ratio of 1.02 at 600 °C in CH 4 -rich DRM. Notably, the system maintained thermodynamic control over H 2 /CO ratios above 550 °C, effectively inhibiting the reverse water–gas shift reaction. This atomic- to system-level design establishes a paradigm for stable DRM catalysis without energy-intensive pretreatment.
Li et al. (Mon,) studied this question.