State Key Laboratory of Heavy Oil Processing, College of Science, China University of Petroleum, Beijing, 102249, PR China.
Unconventional Natural Gas Institute, China University of Petroleum, Beijing, 102249, PR China.
Chemosphere. 2022 May;295:133846. doi: 10.1016/j.chemosphere.2022.133846. Epub 2022 Feb 1.
To pursue the adsorptivity of versatile vermiculite (Na-Vt)-based adsorbent targeted at emerging pharmaceuticals (mefenamic acid and ibuprofen, corresponding to MEA and IBP, respectively), a quinoline-based gemini surfactant (DHQU) with multi-functional groups is applied as modifier on Na-Vt. Enhanced hydrophobicity, enlarged interlayer space and decreased surface area of DHQU-Vt are obtained, whose modifier availability (the mole ratio of modifier intercalated to added) reaches up to 84.18% as characterized by FT-IR, XRD, TG-DTG, EA and BET analysis. Efficient adsorption of MEA/IBP (123.71/240.69 mg/g) is achieved under an extremely low DHQU dosage (0.2 CEC lower than the usual saturated dosage of organo-Vts), with all the processes fitting satisfactorily with pseudo-second order and Freundlich isotherm models accompanied by an exothermic nature. Acid pickling testifies a stable and reliable reusability process of DHQU-Vt even after 3 cycles. Multiple interactions (i.e., partition process, XH-π interaction, π-π interaction, π-π stacking and electrostatic interaction) are revealed and compared from not only characterization results, but also simulation of frontier orbital analysis, the adsorption configuration and bonding analysis: (i) The greater molecular flexibility of the adsorbate, the greater intra particle diffusion effect. (ii) π-π stacking between isolated aromatic rings is stronger than that between parallelly connected aromatic rings. (iii) The strength of multiple active sites provided by quinoline (CH-π, NH-π and π-π interactions) are comparable but weaker than electrostatic interaction/intra particle diffusion.
为了研究针对新兴药物(甲芬那酸和布洛芬,分别对应 MEA 和 IBP)的多功能蛭石(Na-Vt)基吸附剂的吸附性能,我们将一种具有多功能基团的基于喹啉的双子表面活性剂(DHQU)用作 Na-Vt 的改性剂。通过 FT-IR、XRD、TG-DTG、EA 和 BET 分析,得到了增强的疏水性、扩大的层间距和减小的表面积的 DHQU-Vt,其改性剂利用率(插层到添加的改性剂的摩尔比)高达 84.18%。在非常低的 DHQU 剂量(比通常的有机-Vt 饱和剂量低 0.2 CEC)下,实现了 MEA/IBP(123.71/240.69 mg/g)的有效吸附,所有过程都非常符合准二级和 Freundlich 等温模型,并伴随着放热性质。酸浸实验证明了 DHQU-Vt 在经过 3 次循环后仍然具有稳定可靠的可重复使用性。从表征结果以及前沿轨道分析、吸附构象和键合分析的模拟中,揭示并比较了多种相互作用(即分配过程、XH-π 相互作用、π-π 相互作用、π-π 堆积和静电相互作用):(i)吸附物的分子柔性越大,内部粒子扩散效应越大。(ii)孤立芳环之间的π-π 堆积比平行连接的芳环之间的更强。(iii)喹啉(CH-π、NH-π 和 π-π 相互作用)提供的多个活性位点的强度可与静电相互作用/内部粒子扩散相媲美,但较弱。