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Hierarchical-structure materials hold great promise for numerous applied domains such as fuel cell, sensor, and optic. However, the developments are significantly impeded by the lack of efficient strategy permitting precise and efficient decoration of specific confined space. Here, an in-situ precise hybridization strategy is proposed to efficiently manipulate the nanostructure of membrane nanochannels. Typically, Nafion ionic nanochannels are impregnated with precursors via heat swelling, followed by microwave-assisted condensation to form polymer quantum dot network. The formation of polymer quantum dot network significantly improves the stability and functionality of ionic nanophase (i.e., ionic nanochannel). This helps hybrid membrane achieving enhanced proton conduction and methanol barrier properties, resulting in over ten times increase in proton/methanol selectivity. These then impart prominent device performances for both hydrogen and methanol fuel cells with the elevation of ~ 100%. Importantly, such function manipulation of ionic nanochannels is achieved with fully maintaining function of backbone nanophase. Besides, the regulation of physical topology and chemical environment of ionic nanochannel also brings optimization of gas and ion separation properties. This facile and versatile strategy may open up a new avenue for decorating confined space of many hierarchical-structure materials.
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