Zhang Xiaoqing, Li Shihao, Wang Yuelin, Shen Jiwei, Wei Yinmao, Wang Chaozhan
Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an 710127, China.
Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an 710127, China.
J Hazard Mater. 2025 May 5;488:137405. doi: 10.1016/j.jhazmat.2025.137405. Epub 2025 Jan 31.
Given the pervasive existence and toxicity of organic dyes, it is imperative to develop effective methods for their removal and detection. High-performance adsorbents competent for broad spectrum removal of organic dyes are highly expected. In this manuscript, we demonstrate the preparation of porous hypercrosslinked polymers (MAP-BCMBP-HCP) for the removal of anionic dyes, cationic dyes, and amphoteric dyes from water, through a simple Friedel-Crafts alkylation using m-aminophenol as a monomer and 4,4'-bis(chloromethyl)biphenyl (BCMBP) as a cross-linking agent. It exhibits high capacity for adsorption of the organic dyes, with maximum adsorption capacity of 299, 254, 388, 521, 111, 86, 962, 329, 173, and 153 mg/g to bromothymol blue, chromium black T, alizarin red S, chromium azurite S, methylene blue, crystal violet, rhodamine B, congo red, methyl orange, and caustic bright blue, which is superior to the majority of previously reported adsorbents. The removal efficiency of these dyes can reach 91-99 %, this may be attributed to the high specific surface area of the adsorbent, the rich pore structure, and the presence of abundant functional groups on the surface. Furthermore, MAP-BCMBP-HCP exhibited fast adsorption kinetics, enabling the rapid and highly efficient removal of organic dyes within 10-40 min. Chemisorption plays a predominant role in the overall adsorption process. Additionally, the analysis of adsorption thermodynamics demonstrates that this process occurs spontaneously. A combination of experimental and density functional theory (DFT) studies revealed that the dye adsorption on MAP-BCMBP-HCP was governed by hydrogen bonding interaction, hydrophobic interaction, π-π interaction, and pore-filling. The adsorption of the dyes did not change remarkably with variation in pH and salt concentration, as well as the coexistence of various anions and cations. The good performance of MAP-BCMBP-HCP for organic dye removal was validated using simulated wastewater. In addition, the polymer shows a good ability to remove other pollutants including naphthalene and its derivatives, bisphenols, and polyfluorinated benzoic acids, indicating its potential for broad-spectrum organic pollutants. MAP-BCMBP-HCP can be readily reused at least six times without a notable decline in adsorption efficacy. All these features lay a solid foundation for the application of MAP-BCMBP-HCP in practical industrial wastewater treatment.
鉴于有机染料的普遍存在及其毒性，开发有效的去除和检测方法势在必行。人们高度期望有能高效去除多种有机染料的高性能吸附剂。在本论文中，我们展示了一种多孔超交联聚合物（MAP-BCMBP-HCP）的制备方法，该聚合物通过以间氨基酚为单体、4,4'-双(氯甲基)联苯（BCMBP）为交联剂的简单傅克烷基化反应，用于从水中去除阴离子染料、阳离子染料和两性染料。它对有机染料具有高吸附容量，对溴百里酚蓝、铬黑T、茜素红S、铬天青S、亚甲基蓝、结晶紫、罗丹明B、刚果红、甲基橙和烧碱亮蓝的最大吸附容量分别为299、254、388、521、111、86、962、329、173和153 mg/g，优于大多数先前报道的吸附剂。这些染料的去除效率可达91 - 99%，这可能归因于吸附剂的高比表面积、丰富的孔结构以及表面存在大量官能团。此外，MAP-BCMBP-HCP表现出快速的吸附动力学，能够在10 - 40分钟内快速高效地去除有机染料。化学吸附在整个吸附过程中起主要作用。此外，吸附热力学分析表明该过程是自发进行的。实验和密度泛函理论（DFT）研究相结合表明，染料在MAP-BCMBP-HCP上的吸附受氢键相互作用、疏水相互作用、π-π相互作用和孔填充作用控制。染料的吸附在pH值、盐浓度以及各种阴离子和阳离子共存时变化不明显。使用模拟废水验证了MAP-BCMBP-HCP在去除有机染料方面的良好性能。此外，该聚合物对包括萘及其衍生物、双酚和多氟苯甲酸在内的其他污染物也具有良好的去除能力，表明其在去除广谱有机污染物方面的潜力。MAP-BCMBP-HCP可以很容易地重复使用至少六次，而吸附效果没有明显下降。所有这些特性为MAP-BCMBP-HCP在实际工业废水处理中的应用奠定了坚实基础。
