Recent Advances in the Synthesis and Pore Structure Regulation of Macro–Mesoporous Alumina

Porous alumina is widely utilized as a catalyst or support in the petrochemical industry owing to its high surface area, thermal stability, tunable acidity/basicity, and adjustable pore structure. Pore architecture—especially macro–mesopores (10 nm < pore size < 50 nm)—critically influences diffusion efficiency and coke resistance in catalytic reactions. This review systematically outlines formation mechanisms and synthesis strategies for macro–mesoporous alumina, covering nanocasting, templating (surfactant/nonsurfactant, microemulsion), self‐assembly, phase separation, microwave‐assisted, and template‐free methods. Key factors affecting pore structure—such as aluminum source, precursor phase, aging, drying, and calcination—are analyzed. Technical pathways for precise pore control, including grain size regulation, pore‐forming agents, surfactants, solvents, hydrothermal treatment, and doping, are emphasized. The advantages and limitations of each method are compared in terms of pore size range, cost, and environmental impact. Finally, prospects are provided for the scalable and stable fabrication of tailored macro–mesoporous alumina, offering guidance for the rational design and industrial production of high‐performance alumina materials.