Efficient CO2 adsorbents are crucial for addressing the global climate crisis. In this study the novel adsorbents were synthesized using an impregnation precipitation method with MCM-48 as the silica source and Li2CO3 as the lithium source. By doping alkali metal carbonate (Na2CO3), the ML-Na2CO3 adsorbent was created for high-temperature CO2 capture. The results showed that the maximum adsorption capacity of 35.63 wt% was achieved at 600℃ in the mixture (15 vol% CO2, the balance being N2)when the adsorbent contained 15 wt% Na2CO3, representing a 4.49 wt% increase compared to the undoped ML adsorbent. The adsorption kinetics analysis confirmed a good fit with the biexponential model. Density Functional Theory (DFT) simulations revealed that the adsorption energy increased by an average of 0.1035 eV and Oslab exhibited high activity in chemisorbing CO2, forming CO32−. Na2CO3 doping modified the electronic structure of Oslab and Lislab, resulting in increased high-energy electrons, reflective activity, and improved CO2 adsorption energy. Overall, incorporating Na2CO3 enhanced carbon dioxide adsorption performance by 114.42 %, indicating a promising potential for real flue gas CO2 adsorption applications.