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Considering the small amount of CO2 as a contaminant in industrial gas mixtures, developing CO2‐selective adsorbents exhibit advantages in directly obtaining pure C2H2 in one‐step to reduce the energy consumption. However, it is still a great challenge due to the essential molecular feature of C2H2, including the triple bond and high polarizability. Herein, a simple but effective CO2‐facilitated transport...