Tetravalent (Zr, Ti, Ce, Sn) metals promoted highly stable γ‐Al ₂ O ₃ for production of linear long‐chain α ‐olefins

Gamma‐Aluminum oxide (γ‐A 2 O 3 ) is a promising catalyst for producing linear long‐chain α‐olefins via dehydration of biomass‐derived n‐alcohols but suffers from hydration‐induced phase transformation and deactivation. Herein, the concept of M 4+ incorporated octahedral cationic vacancies to boost activity and structure stability was established, particularly for Zr 4+ . Extended X‐ray absorption fine structure and density functional theory (DFT) analyses reveal that Zr preferentially occupies octahedral sites, leading to hydroxyl consumption, formation of Zr–O–Al bonds, and lattice expansion due to the large ionic radius of Zr 4+ . Zr incorporation increases surface acidity owing to its electron‐deficient state. Under optimized conditions, the catalyst achieves 100% conversion and 96.4% selectivity toward C₁₆ α‐olefins. In‐situ FTIR elucidates the dehydration pathway and reaction mechanism. The modified catalyst exhibits excellent stability for over 375 h, attributed to reduced surface hydrophilicity and strengthened Al–O bonds that suppress hydration‐induced phase transition and carbon deposition.