Developing of fast and efficient adsorbents for removal of low concentration refractory organics in water is significant. Herein, a novel calix[4]arene-based porous organic polymer CaPy is constructed through Sonogashira-Hagihara cross-coupling polycondensation. The strong polar sulfonate is further anchored onto the polymer skeleton of CaPy and three sulfonate-modified anionic polymers CaPy-S1, CaPy-S2, and CaPy-S3 were obtained and fully characterized. The adsorption isotherms showed that the maximum adsorption capacities of CaPy, CaPy-S1, CaPy-S2, and CaPy-S3 toward methylene blue (MB) were 270, 1454, 558 and 1381 mg g⁻¹, whereas those for Rhodamine B (RhB) were 183, 2653, 1132, and 1796 mg g⁻¹, respectively. The maximum adsorption capacity toward RhB was the highest reported vale among the currently used synthetic adsorbents. In addition, the pseudo-second-order rate constants of CaPy, CaPy-S1, CaPy-S2, and CaPy-S3 toward MB were 0.00572, 0.488, 2.24, and 0.192 g mg⁻¹ min⁻¹, respectively, and those toward RhB were 0.000234, 0.138, 0.0819, and 0.203 g mg⁻¹ min⁻¹, respectively. The pseudo-second-order rate constant of CaPy-S2 toward MB was 2.24 g mg⁻¹ min⁻¹ indicating one of the highest adsorption speeds. The activation energy of CaPy-S1 for RhB and MB were 121 and 109 kJ mol⁻¹, respectively, demonstrating that the adsorption of both dyes on CaPy-S1 was chemisorption process. Further, the obtained values of Gibbs free energy were negative, revealing that the adsorption process was spontaneous. This work provides an effective approach for improving adsorption performance via post-modification.

开发用于去除水中低浓度难降解有机物的快速高效吸附剂具有重要意义。在此，通过Sonogashira-Hagihara交叉偶联缩聚构建了一种新型的杯[4]芳烃基多孔有机聚合物CaPy。强极性磺酸盐进一步锚定在 CaPy 的聚合物骨架上，获得并充分表征了三种磺酸盐改性的阴离子聚合物 CaPy-S1、CaPy-S2 和 CaPy-S3。吸附等温线表明，CaPy、CaPy-S1、CaPy-S2 和 CaPy-S3 对亚甲蓝 (MB) 的最大吸附量分别为 270、1454、558 和 1381 mg g ^-1，而对罗丹明 B (RhB ) 分别为 183、2653、1132 和 1796 mg g ^-1， 分别。对 RhB 的最大吸附容量是目前使用的合成吸附剂中报道的最高值。此外，CaPy、CaPy-S1、CaPy-S2 和 CaPy-S3 对 MB 的准二级速率常数分别为 0.00572、0.488、2.24 和 0.192 g mg ^-1 min ^-1，向RhB 分别为 0.000234、0.138、0.0819 和 0.203 g mg ^-1 min ^-1。CaPy-S2 对 MB 的准二级速率常数为 2.24 g mg ^-1 min ^-1，表明吸附速度最高之一。CaPy-S1 对 RhB 和 MB 的活化能分别为 121 和 109 kJ mol ^-1, 分别表明两种染料在 CaPy-S1 上的吸附是化学吸附过程。此外，得到的吉布斯自由能值为负，表明吸附过程是自发的。这项工作为通过后改性提高吸附性能提供了一种有效的方法。