Dharmaraj Kanakarasu, Sanjay Kumar Mohandas, Palanisami Nallasamy, Prakash Muthuramalingam, Loganathan Pushparaj, Shanmugan Swaminathan
Department of Chemistry, Faculty of Engineering and Technology, SRM Institute of Science and Technology, Kattankulathur-603 203, Chengalpattu, Tamil Nadu, India.
Computational Chemistry Research Laboratory (CCRL), Department of Chemistry, Faculty of Engineering and Technology, SRM Institute of Science and Technology, Kattankulathur-603 203, Chengalpattu, Tamil Nadu, India.
Dalton Trans. 2024 Aug 13;53(32):13602-13616. doi: 10.1039/d4dt01397b.
The degradation of water bodies caused by organic pollutants from industrial wastewater discharge has made it necessary to develop new functional materials like hydrophobic-oleophilic materials that can efficiently remediate water. It is factual that many of the synthetic methods for creating hydrophobic-oleophilic materials involve the use of toxic or harmful reactants, such as fluorine or sulfur compounds. However, these methods often have significant drawbacks, including being hazardous to the environment, expensive, and complex to utilize. Therefore, there is an urgent need to develop a hydrophobic/oleophilic material that is non-toxic and eco-friendly in order to overcome the existing drawbacks. In this regard, we have proposed a modest and eco-friendly approach for constructing a hydrophobic-oleophilic Ph-POSS@HKUST-1 composite material by solution-assisted self-assembly for the conversion of hydrophilic HKUST-1 into hydrophobic HKUST-1 for separation applications. The incorporation of fluorine-free, low surface energy and hydrophobic POSS into HKUST-1 increased the hydrophobicity and oleophilicity of the system. The synthesized Ph-POSS@HKUST-1 composite material has been thoroughly characterized through FT-IR, PXRD, HR-SEM, BET, and thermogravimetric analysis. It has been observed that the material exhibits a contact angle of 137 ± 4° and shows high selectivity and absorption capacity towards organic solvents and oils from water mixtures. Concurrently, the Ph-POSS@HKUST-1@PDA@sponge has been effectively utilized for the separation of solvents and oils and it has shown more than 95% separation efficiency for up to 15 cycles. It is interesting to note that Ph-POSS@HKUST-1 and the Ph-POSS@HKUST-1@PDA@sponge have outstanding stability in abrasive chemical environments which is due to the presence of a mechanically and chemically stable inorganic-organic hybrid POSS nanocage. In addition, and DFT calculations elicit that the Ph-POSS@HKUST-1 composite is stabilized through π⋯π stacking instead of the C-H⋯π mode of interaction at the HKUST-1⋯Ph-POSS interface. Further electron density features confirm the interfacial interaction at the interface. Our latest research has led us to propose an eco-friendly and non-toxic hybrid composite material for efficiently tackling the issue of organic solvent and oil pollution in water mixtures.
工业废水排放中的有机污染物导致水体退化，因此有必要开发新型功能材料，如疏水性亲油性材料，以有效修复水体。事实上，许多制备疏水性亲油性材料的合成方法都涉及使用有毒或有害的反应物，如氟或硫化合物。然而，这些方法往往存在重大缺陷，包括对环境有害、成本高以及使用复杂。因此，迫切需要开发一种无毒且环保的疏水性/亲油性材料，以克服现有缺陷。在这方面，我们提出了一种适度且环保的方法，通过溶液辅助自组装构建疏水性亲油性Ph-POSS@HKUST-1复合材料，将亲水性HKUST-1转化为疏水性HKUST-1用于分离应用。将无氟、低表面能且疏水的POSS掺入HKUST-1中，增加了体系的疏水性和亲油性。通过傅里叶变换红外光谱（FT-IR）、粉末X射线衍射（PXRD）、高分辨率扫描电子显微镜（HR-SEM）、比表面积分析仪（BET）和热重分析对合成的Ph-POSS@HKUST-1复合材料进行了全面表征。据观察，该材料的接触角为137±4°，对水混合物中的有机溶剂和油表现出高选择性和吸收能力。同时，Ph-POSS@HKUST-1@PDA@海绵已有效地用于溶剂和油的分离，在多达15个循环中显示出超过95%的分离效率。有趣的是，Ph-POSS@HKUST-1和Ph-POSS@HKUST-1@PDA@海绵在苛刻的化学环境中具有出色的稳定性，这是由于存在机械和化学稳定的无机-有机杂化POSS纳米笼。此外，密度泛函理论（DFT）计算表明，Ph-POSS@HKUST-1复合材料是通过π⋯π堆积而不是HKUST-1⋯Ph-POSS界面处的C-H⋯π相互作用模式稳定的。进一步的电子密度特征证实了界面处的相互作用。我们的最新研究使我们提出了一种环保且无毒的杂化复合材料，以有效解决水混合物中有机溶剂和油污染的问题。
