This study investigates the capture of single Ag atoms through high-temperature-induced crystal plane reconstruction on γ-Al₂O₃. By controlling the calcination temperature, the exposed crystal face of γ-Al₂O₃ transitions from (110) to (100), increasing the number of terminal hydroxyl groups, which serve as anchoring sites for Ag species. Experimental results, combined with AIMD and DFT simulations, show that high-temperature calcination leads to atomic rearrangement on the (110) crystal face, forming a structure similar to the (100) crystal face, thereby enhancing the dispersion of Ag species and enabling single-atom dispersion. This results in the development of a stable and efficient single-atom Ag-based catalyst. The study highlights the role of terminal hydroxyl groups in anchoring Ag on metal oxides, particularly on γ-Al₂O₃ and CeO₂. The type of exposed crystal facet significantly affects the content of terminal hydroxyl groups, influencing the dispersion of Ag. The "terminal hydroxyl group anchoring mechanism" is applicable not only to Ag but also to other non-precious metals like Fe, Co, Ni, and Mn on Al₂O₃. On CeO₂, terminal hydroxyl groups also serve as anchoring sites for Ag, forming a dumbbell structure. The study demonstrates that high-temperature calcination induces crystal plane transformation, leading to increased terminal hydroxyl groups and enhanced Ag dispersion. The Ag/(Al-900) sample exhibits better catalytic activity in HC-SCR and O₃ decomposition compared to the Ag/(Al-500) sample. The results show that terminal hydroxyl groups on oxide surfaces are crucial for anchoring metals, and the type of exposed crystal facet significantly affects the content of terminal hydroxyl groups, thus influencing the dispersion of the metal. The study provides insights into designing thermally stable single-atom catalysts by creating additional anchor points for single-atom capture at high temperatures.This study investigates the capture of single Ag atoms through high-temperature-induced crystal plane reconstruction on γ-Al₂O₃. By controlling the calcination temperature, the exposed crystal face of γ-Al₂O₃ transitions from (110) to (100), increasing the number of terminal hydroxyl groups, which serve as anchoring sites for Ag species. Experimental results, combined with AIMD and DFT simulations, show that high-temperature calcination leads to atomic rearrangement on the (110) crystal face, forming a structure similar to the (100) crystal face, thereby enhancing the dispersion of Ag species and enabling single-atom dispersion. This results in the development of a stable and efficient single-atom Ag-based catalyst. The study highlights the role of terminal hydroxyl groups in anchoring Ag on metal oxides, particularly on γ-Al₂O₃ and CeO₂. The type of exposed crystal facet significantly affects the content of terminal hydroxyl groups, influencing the dispersion of Ag. The "terminal hydroxyl group anchoring mechanism" is applicable not only to Ag but also to other non-precious metals like Fe, Co, Ni, and Mn on Al₂O₃. On CeO₂, terminal hydroxyl groups also serve as anchoring sites for Ag, forming a dumbbell structure. The study demonstrates that high-temperature calcination induces crystal plane transformation, leading to increased terminal hydroxyl groups and enhanced Ag dispersion. The Ag/(Al-900) sample exhibits better catalytic activity in HC-SCR and O₃ decomposition compared to the Ag/(Al-500) sample. The results show that terminal hydroxyl groups on oxide surfaces are crucial for anchoring metals, and the type of exposed crystal facet significantly affects the content of terminal hydroxyl groups, thus influencing the dispersion of the metal. The study provides insights into designing thermally stable single-atom catalysts by creating additional anchor points for single-atom capture at high temperatures.