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 CH 4 and CO 2 into syngas for downstream Fischer–Tropsch synthesis. However, Ni catalysts deactivate rapidly by coking and sintering at high temperatures. Here we report a Ni 3 Zn/MgAl 2 O 4 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 CH 4 and CO 2 conversions, while the carbon deposition rate was reduced to 1/28 of that on the Ni/MgAl 2 O 4 catalyst. Combined experimental and theoretical studies reveal that Zn incorporation redistributes charge to generate polarized Ni δ- -Zn δ+ sites, which weaken CO binding and promote cooperative CH 4 and CO 2 activation. Simultaneously, CH 4 -derived carbon migrates into the Ni 3 Zn lattice, reversibly forming a carbide phase (Ni 3 ZnC 0.7 ) 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.