Conjugated microporous polymers (CMPs) are potential materials for gas uptake, pollutant adsorption and photocatalysis. However, their relatively wide pore size distribution (PSD) makes it hard to establish the relationship between adsorption capacities and pore structure. Here, we synthesized two CMPs with similar chemical structure based on carbazole and ferrocene units. Poly[1,1′-di(9-carbazolyl)ferrocene] (PDCF) showed hierarchical pore structure with pore sizes distributed in three regions: 0.7–0.85 nm, 1–3 nm and 10–100 nm, while the pore sizes of poly{1,1′-di[4-(9-carbazolyl))phenyl]ferrocene} (PDCPF) were mostly less than 3 nm. The results of gas uptake and dye adsorption capacities show that the extra mesopores of PDCF exhibit better adsorption capacities to adsorbates with larger sizes. Besides, dye molecules adsorbed in the micropores are harder to desorption than that in the mesopores. The intermolecular forces between porous polymers and adsorbates were used to explain these results successfully. Our findings indicate that designing the right pore sizes for porous polymers when adsorbing gases or dyes with a specific molecules size is very important in the future.

共轭微孔聚合物 (CMP) 是用于气体吸收、污染物吸附和光催化的潜在材料。然而，它们相对较宽的孔径分布（PSD）使得很难建立吸附容量和孔结构之间的关系。在这里，我们基于咔唑和二茂铁单元合成了两种具有相似化学结构的 CMP。聚[1,1'-二(9-咔唑基)二茂铁] (PDCF) 显示出分级孔结构，孔径分布在三个区域：0.7-0.85 nm、1-3 nm 和 10-100 nm，而孔径为聚{1,1'-二[4-(9-咔唑基))苯基]二茂铁}(PDCPF)大多小于3nm。气体吸收和染料吸附能力的结果表明，PDCF 的额外介孔对较大尺寸的吸附物表现出更好的吸附能力。除了，吸附在微孔中的染料分子比在中孔中更难解吸。多孔聚合物和吸附物之间的分子间作用力被用来成功解释这些结果。我们的研究结果表明，在吸附特定分子大小的气体或染料时，为多孔聚合物设计正确的孔径在未来非常重要。