Liu Siqi, Li Ruhao, Tyagi Madhusudan, Akcora Pinar
1 Castle Point on Hudson, Department of Chemical Engineering and Materials Science, Stevens Institute of Technology, McLean Hall 415, 07030, Hoboken, NJ, USA.
NIST Center for Neutron Research, 100 Bureau Dr, 20899, Gaithersburg, MD, USA.
Chemphyschem. 2022 Sep 16;23(18):e202200219. doi: 10.1002/cphc.202200219. Epub 2022 Jul 14.
Ionic liquid mixed with poly(methyl methacrylate)-grafted Fe O nanoparticle aggregates at low particle concentrations was found to exhibit different dynamics and ionic conductivity than that of pure ionic liquid in our previous studies. In this work, we report on the quasi-elastic neutron scattering results of ionic liquid containing polymer-grafted Fe O nanoparticles at higher particle concentrations. The diffusivity of imidazolium (HMIM ) cations of 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (HMIM-TFSI) in the presence of poly(methyl methacrylate)-grafted Fe O nanoparticles is discussed through the confinement. Analysis of the elastic incoherent structure factor revealed that the confinement radius decreased with the addition of grafted particles in HMIM-TFSI/solvent mixture. We propose the confinement that is induced by the high concentration of grafted particles shrinks the HMIM-TFSI restricted volume. We further conjecture that this enhanced diffusivity occurs as a result of the local ordering of cations within aggregates of poly(methyl methacrylate)-grafted Fe O nanoparticles.
在我们之前的研究中发现,在低颗粒浓度下,离子液体与聚甲基丙烯酸甲酯接枝的Fe₃O₄纳米颗粒聚集体混合时,其动力学和离子电导率与纯离子液体不同。在这项工作中,我们报告了在较高颗粒浓度下含聚合物接枝Fe₃O₄纳米颗粒的离子液体的准弹性中子散射结果。通过受限效应讨论了1-己基-3-甲基咪唑双(三氟甲基磺酰)亚胺(HMIM-TFSI)中咪唑鎓(HMIM⁺)阳离子在聚甲基丙烯酸甲酯接枝的Fe₃O₄纳米颗粒存在下的扩散率。对弹性非相干结构因子的分析表明,在HMIM-TFSI/溶剂混合物中,随着接枝颗粒的加入,受限半径减小。我们提出,高浓度接枝颗粒引起的受限效应会使HMIM-TFSI的受限体积缩小。我们进一步推测,这种扩散率的增强是由于聚甲基丙烯酸甲酯接枝的Fe₃O₄纳米颗粒聚集体内阳离子的局部有序排列所致。