聚电解质
反离子
凝聚
化学
化学物理
化学工程
离子
聚合物
有机化学
色谱法
工程类
作者
Binghui Xue,Yuyan Lai,Yuan Liu,Mu Li,Xinpei Li,Panchao Yin
标识
DOI:10.1016/j.jcis.2023.03.105
摘要
Nano-ions can complex with polyelectrolytes for coacervates with hierarchical structures; however, the rational design of functional coacervations is still rare due to the poor understanding of their structure-property relationship from their complex interaction. Herein, 1 nm anionic metal oxide clusters, PW12O403-, with well-defined, mono-disperse structures are applied to complex with cationic polyelectrolyte and the system shows tunable coacervation via the alternation of counterions (H+ and Na+) of PW12O403-. Suggested from Fourier transform infrared spectroscopy (FT-IR) and isothermal titration studies, the interaction between PW12O403- and cationic polyelectrolytes can be modulated by the bridging effect of counterions via hydrogen bonding or ion-dipole interaction to carbonyl groups of polyelectrolytes. The condensed structures of the complexed coacervates are explored by small angle X-ray and neutron scattering techniques, respectively. The coacervate with H+ as counterions shows both crystallized and discrete PW12O403- clusters, with a loose polymer-cluster network in comparison to the system of Na+ which shows a dense packing structure with aggregated nano-ions filling the meshes of polyelectrolyte networks. The bridging effect of counterions helps understand the super-chaotropic effect observed in nano-ion system and provides avenues for the design of metal oxide cluster-based functional coacervates.
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