Enhanced Methane Dry Reforming Stability Under Concentrated Feedstocks Through Engineering Nickel‐Vanadium Hydroxyapatite Interactions

In dry reforming of methane (DRM) processes, carbon deposition and metal sintering are major causes of catalytic deactivation. Herein, we deliberately introduced cerium species into vanadium hydroxyapatite to support Ni nanoparticles (Ni/VAP‐Ce) for enhanced DRM stability. Under a concentrated feedstock of 50 vol% CH 4 /50 vol% CO 2 , CH 4 conversion decreases only from 75.1% to 61.9% within 900 h over Ni/VAP‐Ce, with a deactivation rate of only 0.01%/h. High‐angle annular dark‐field scanning transmission electron microscopy characterization reveals that Ni nanoparticles on Ni/VAP‐Ce only slightly grow to 12.5 ± 5.5 nm after 900 h long‐term reaction, while Ni/VAP counterpart suffers from severe sintering with Ni particle size reaching 17.0 ± 6.1 nm after only 20 h of DRM reaction. In addition, comprehensive characterizations confirm that the stronger Ni and VAP‐Ce interaction endows the catalyst with improved intrinsic coke resistance and enhanced coke elimination ability, which collectively account for the outstanding long‐term DRM stability. This work provides a practical support engineering strategy to alleviate the persistent challenge of insufficient long‐term stability for non‐noble DRM catalysts under industrially relevant concentrated feed conditions, and also offers a valuable reference for the design of robust catalysts toward high‐temperature greenhouse gas valorization.