Breaking the Activity‐Stability Trade‐Off in Dry Reforming of Methane via Heteroenergetic Support Engineering

ABSTRACT Nickel‐based catalysts are promising for dry reforming of methane (DRM) owing to their high C─H bond activation ability and low cost, while highly susceptible to coke deposition and sintering. Here, we report a heteroenergetic Ce 0.75 Ti 0.25 O 2‐x support that simultaneously regulates Ni nanoparticle stabilization, DRM activity, and oxygen‐mediated carbon removal. Neural‐network‐based molecular dynamics (NN‐MD) simulations and electron microscopy show that partial Ti substitution in CeO 2 transforms the strong Ni‐CeO 2 interaction and weak Ni‐TiO 2 interaction into an intermediate wetting regime with a Ni‐support contact angle close to 90°, suppressing both particle migration/coalescence‐ and Ostwald ripening‐induced sintering while preserving a coupled population of active interfacial and metallic Ni sites. Characterizations and Bader charge analysis further reveal that Ce 0.75 Ti 0.25 O 2‐x moderates Ni‐support electronic coupling and improves oxygen vacancy concentration and lattice oxygen mobility. These coupled structural and chemical effects facilitate methane activation and transient carbon removal through synergistic Mars‐van Krevelen and Langmuir‐Hinshelwood pathways. As a result, Ni/Ce 0.75 Ti 0.25 O 2‐x achieves highly competitive DRM performance with near‐equilibrium CH 4 and CO 2 conversions of 93.8% and 94.3%, respectively, at 750°C and remains stable over 120 h without noticeable deactivation. This work establishes heteroenergetic support engineering as an effective strategy that reconciles high activity with long‐term stability in thermally demanding catalytic reactions.