Dynamic Carbon Migration and Dual-Site Ni–Zn Synergy Enable Coke-Resistant Ni 3 Zn/MgAl 2 O 4 Catalysts for Dry Reforming of Methane

Dry reforming of methane (DRM) converts the greenhouse gases CH4 and CO2 into syngas for downstream Fischer–Tropsch synthesis. However, Ni catalysts deactivate rapidly by coking and sintering at high temperatures. Here we report a Ni3Zn/MgAl2O4 catalyst that achieves exceptional stability by integrating dynamic carbon migration with dual-site electronic modulation. At 650 °C, the catalyst sustains stable operation for 90 h, delivering nearly double CH4 and CO2 conversions, while the carbon deposition rate was reduced to 1/28 of that on the Ni/MgAl2O4 catalyst. Combined experimental and theoretical studies reveal that Zn incorporation redistributes charge to generate polarized Niδ--Znδ+ sites, which weaken CO binding and promote cooperative CH4 and CO2 activation. Simultaneously, CH4-derived carbon migrates into the Ni3Zn lattice, reversibly forming a carbide phase (Ni3ZnC0.7) that prevents surface carbon accumulation. This synergy between electronic modulation and dynamic carbon accommodation provides a robust strategy for designing durable, coke-resistant Ni-based catalysts for DRM and related high-temperature reactions.