Deng Shuai,Mao Xi,Wang Mian,Deng Renhua,Zhu Jintao
Block copolymer (BCP) photonic crystals (PCs) have great potential in color decoration, optical encryption, and smart sensing because of their excellent flexibility and stimuli-responses. Supramolecular BCPs (SBCPs) provide a versatile platform for engineering structural colors through reversible non-covalent interactions, yet their precise dynamic modulation under confined environments remains underexplored. Here, we develop an integrated real-time monitoring system to elucidate the temperature-solvent synergistic annealing strategy to regulate the disorder-to-order transition of hydrogen-bonded comb-like SBCPs and homopolymers binary co-assembly system, which can yield a lamellar structure and exhibit structural color. Systematic investigation revealed that increasing solvent content accelerates ordering kinetics and induces a red-shift of structural color in their swollen states, while the equilibrium structural color remains solvent-independent upon solvent removal. Unexpectedly, elevating the temperature decelerates ordering kinetics and induces a blue-shift in both swollen and dry states. This counterintuitive phenomenon can be attributed to thermally reduced solvent uptake (by SBCPs) and partial hydrogen-bond dissociation, diminishing the molecular weight and rigidity of SBCPs. These findings elucidate the critical role of swelling and dynamic hydrogen-bond interactions in governing assembly pathways, structure and optical properties of SBCPs, providing a versatile platform for designing stimuli-responsive PC materials with on-demand colors and color switching.
Mesoporous carbon microparticles (MCMPs) with anisotropic shapes and ordered structures are attractive materials that remain challenging to access. In this study, a facile yet versatile route is developed to prepare anisotropic MCMPs by combining neutral interface-guided 3D confined self-assembly (3D-CSA) of block copolymer (BCP) with a self-templated direct carbonization strategy. This route enables pre-engineering BCP into microparticles with oblate shape and hexagonal packing cylindrical mesostructures, followed by selective crosslinking and decorating of their continuous phase with functional species (such as platinum nanoparticles, Pt NPs) via in situ growth. To realize uniform in situ growth, a “guest exchange” strategy is proposed to make room for functional species and a pre-crosslinking strategy is developed to preserve the structural stability of preformed BCP microparticles during infiltration. Finally, Pt NP-loaded MCMPs are derived from the continuous phase of BCP microparticles through selective self-templated direct carbonization without using any external carbon source. This study introduces an effective concept to obtain functional species-loaded and N -doped MCMPs with oblate shape and almost hexagonal structure ( p6mm ), which would find important applications in fuel cells, separation, and heterogeneous catalysis.
Membrane separation technology has garnered significant interest due to its energy efficiency, environmental benefits, and molecular sieving capabilities. Polymeric membranes, despite their cost-effectiveness and processability, face challenges in balancing water permeance and selectivity, primarily due to non-uniform or sparse pore structures. Block copolymer (BCP)-based isoporous membranes, fabricated via strategies like the self-assembly and non-solvent-induced phase separation (SNIPS), offer improved pore uniformity and separation performance. This work introduces an alternative strategy to produce isoporous membranes by combining phase separation and surface tension driven micelle spreading at the air/water interface. The resulting membranes feature ordered isopores ( ca. 10 nm) and exceptional water permeance ( ca. 1450 L m −2 h −1 bar −1 ), enabling precise nanoparticle separation. The membrane demonstrates stability under 20 psi pressure, with tunable thickness (via micellar solution volume) and pore size (via water temperature). The work advances the design of high-performance isoporous membranes, offering potential applications in ultrafiltration, biotechnology, and environmental remediation.
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