RESUMEN
Resulting from the dense packing of subnanometer molecular clusters, molecular granular materials (MGMs) are shown to maintain high elasticity far above their apparent glass transition temperature (Tg*). However, our microscopic understanding of their structure-property relationship is still poor. Herein, 1 nm polyhedral oligomeric silsesquioxanes (POSSs) are appended to a backbone chain in a brush configuration with different flexible linker chains. Assemblies of these brush polymers exhibit hierarchical relaxation dynamics with the glass transition arising from the cooperative dynamics of packed POSSs. The interaction among the assemblies can be strengthened by increasing the rigidity of linkers with the MGM relaxation modes changing from colloid- to polymer chain-like behavior, rendering their tunable viscoelasticity. This finally contributes to the decoupling of mechanical and thermal properties by showing elasticity dominant mechanical properties at a temperature 150 K above the Tg*.
RESUMEN
The developments of mixed matrix membranes (MMMs) are severely hindered by the complex inter-phase interaction and the resulting poor utilization of inorganics' microporosity. Herein, a dual porosity framework is constructed in MMMs to enhance the accessibility of inorganics' microporosity to external gas molecules for the effective application of microporosity for gas separation. Nanocomposite organogels are first prepared from the supramolecular complexation of rigid polymers and 2 nm microporous coordination nanocages (CNCs). The network structures can be maintained with microporous features after solvent removal originated from the rigid nature of polymers, and the strong coordination and hydrogen bond between the two components. Moreover, the strong supramolecular attraction reinforces the frustrated packing of the rigid polymers on CNC surface, leading to polymer networks' extrinsic pores and the interconnection of CNCs' micro-cavities for the fast gas transportation. The gas permeabilities of the MMMs are 869 times for H2 and 1099 times for CO2 higher than those of pure polymers. The open metal sites from nanocage also contribute to the enhanced gas selectivity and the overall performance surpasses 2008 H2/CO2 Robeson upper bound. The supramolecular complexation reinforced packing frustration strategy offers a simple and practical solution to achieve improved gas permselectivity in MMMs.
RESUMEN
As the key component of various energy storage and conversion devices, proton exchange membranes (PEMs) have been attracting significant interest. However, their further development is limited by the high cost of perfluorosulfonic acid polymers and the poor stability of acid-dopped non-fluorinated polymers. Recently, a new group of PEMs has been developed by hybridizing polyoxometalates (POMs), a group of super acidic sub-nanoscale metal oxide clusters, with polymers. POMs can serve simultaneously as both proton sponges and stabilizing agents, and their complexation with polymers can further improve polymers' mechanical performance and processability. Enormous efforts have been focused on studying supramolecular complexation or covalent grafting of POMs with various polymers to optimize PEMs in terms of cost, mechanical properties and stabilities. This concept summarizes recent advances in this emerging field and outlines the design strategies and application perspectives employed for using POM-polymer hybrid materials as PEMs.
RESUMEN
The granular materials of soft particles (SPs) demonstrate unique viscoelasticity distinct from general colloidal and polymer systems. Exploiting dynamic light scattering measurements, together with molecular dynamics simulations, we study the diffusive dynamics of soft particle clusters (SPCs) with spherical and cylindrical brush topologies, respectively, in the melts of SPs. A topologically constrained relaxation theory is proposed by quantitatively correlating the relaxation time to the topologies of the SPCs, through the mean free space (Va) of tethered SPs in the cluster. The tethered SPs in SPCs are crowded by SPs of the melts to form the cage zones, and the cooperative diffusion of the tether SPs in the zones is required for the diffusive motion of SPCs. The cage zone serves as an entropic barrier for the diffusion of SP clusters, while its strength is determined by Va. Three characteristic modes can be confirmed: localized non-diffusive mode around critical Va, diffusive mode with Va deviating far from the critical value, and a sub-diffusive mode as an interlude between two limits. Our studies raise attention to the emergent physical properties of materials based on SPs via a topological design while opening new avenues for the design of soft structural materials.
RESUMEN
Cost-effective, non-fluorinated polymer proton exchange membranes (PEMs) are highly desirable in emerging hydrogen fuel cells (FCs) technology; however, their low proton conductivities and poor chemical and dimension stabilities hinder their further development as alternatives to commercial Nafion®. Here, we report the inorganic-organic hybridization strategy by facilely complexing commercial polymers, polyvinyl butyral (PVB), with inorganic molecular nanoparticles, H3 PW12 O40 (PW) via supramolecular interaction. The strong affinity among them endows the obtained nanocomposites amphiphilicity and further lead to phase separation for bi-continuous structures with both inter-connected proton transportation channels and robust polymer scaffold, enabling high proton conductivities, mechanical/dimension stability and barrier performance, and the H2 /O2 FCs equipped with the composite PEM show promising power densities and long-term stability. Interestingly, the hybrid PEM can be fabricated continuously in large scale at challenging ~10â µm thickness via typical tape casting technique originated from their facile complexing strategy and the hybrids' excellent mechanical properties. This work not only provides potential material systems for commercial PEMs, but also raises interest for the research on hybrid composites for PEMs.
RESUMEN
The large sizes of granular particles lead to their slow diffusive dynamics and significant interparticle friction, bringing enormous difficulty to tune the mechanical properties and processability of the granular materials (GMs). Herein, 1 nm polyhedral oligomeric silsesquioxane (POSS) particles functionalized with azobenzene are designed as structural units, and the obtained GMs show unique photoswitchable viscoelasticity. The azobenzene group can undergo a reversible trans-cis conformation switch while the π-π stacking among the azobenzene fragments is only favored by the trans-conformation due to molecular geometrical requirements. The POSS units from neighboring assemblies close pack to form microdomains, and the POSS is under confinement by both the supramolecular bonding and the other POSS in the microdomains. The simultaneous breaking of the two types of confinement is difficult and, therefore, the free diffusion of POSS is hindered, leading to the elasticity of the GMs of trans-POSS. For cis-POSS, the interparticle supramolecular interaction is weak and the POSS unit can undergo free diffusion, contributing to their high flowability at room temperature. The photoswitching viscoelasticity of GMs is further used for self-healing and photoswitchable adhesion. This work paves new pathways for the regulation of material viscoelasticity and the design of GM-based smart materials.
RESUMEN
Metallo-supramolecular polymer networks (MSPNs) are fabricated from the crosslinking of polymers by discrete supramolecular coordination complexes. Due to the availability of various coordination complexes, e. g., 2D macrocycles and 3D nanocages, the MSPNs have been recently developed with broadly tunable visco-elasticity and enriched functions inherited from the coordination complexes. The coordination complexes possess enriched topologies and unique structural relaxation dynamics, rendering them the capability to break the traditional tradeoffs of polymer systems for the design of materials with enhanced mechanical performance. The structure-property relationship studies are critical for the material-by-design of MSPNs, while the spatiotemporal investigations are desired for the exploration of dynamics information. The work summarizes recent studies on the unique ligand-exchange kinetics and the multi-level structural relaxation dynamics of MSPNs. The MSPNs' mechanical properties can be quantitatively correlated with the dynamics for understanding the structure-property relationship. This concept will not only serve to attract more researchers to engage in the study of the structure-activity relationship of MSPNs but also inspire innovative research findings pertaining to the application of MSPNs.
RESUMEN
The rod-like viruses show anomalously rapid diffusion in bio-tissue networks originated from the rotation-facilitated transportation; however, the experimental investigation of the correlation of the rotational and translational dynamics is still in blank. Herein, typical rod-like and spherical gold nanoparticles (NPs) are dispersed in the classical Tetra-PEG gels, respectively, as model systems for light scattering studies. The contributions from translational and rotational diffusive dynamics, and network fluctuation dynamics can be well-resolved and the stretch exponent of rotational dynamics at 0.25 is proven to be the fingerprint for the coupled rotational and translational dynamics of nanorods. The rotation facilitated re-orientation finally leads to the fast transportation of nanorods. The discoveries are confirmed to be valid for rod-like biomacromolecule systems by studying the diffusive dynamics of Tobacco mosaic virus in gels. The work can be inspiring for the development of protocols to prevent infection of microorganism and regulate the transportation of nano-medicines.
RESUMEN
The search for alternative chemical systems other than polymers with chain topologies for soft structural materials raises general interests in fundamental materials and chemical sciences. It is also appealing from an engineering perspective for the urgent need to resolve the typical trade-offs of polymer systems. Herein, a subnanometer molecular cluster, polyhedral oligomeric silsesquioxanes, is assembled into molecular nanoparticles (MNPs) with star topology. Broadly tunable viscoelasticity can be realized by fine-tuning the MNPs' deformability. Being analogous to polymeric systems, the hierarchical structural relaxation dynamics can be observed, and their relaxation time and temperature dependence are dominated by the linker flexibilities. This not only provides microscopic understanding on MNP's unique viscoelasticity but also offers enormous opportunities for modulating their mechanical properties via linker engineering. Our work proves the possibility of applying structural units with particle topologies for the design of soft structural materials.
RESUMEN
The high-speed impact-resistanct materials are of great significance while their development is hindered by the intrinsic tradeoff between mechanical strength and energy dissipation capability. Herein, the new chemical system of molecular granular material (MGM) is developed for the design of impact-resistant materials from the supramolecular complexation of sub-nm molecular clusters (MCs) and hyper-branched polyelectrolytes. Their hierarchical aggregation provides the origin of the decoupling of mechanical strengths and structural relaxation dynamics. The MCs' intrinsic fast dynamics afford excellent high-speed impact-resistance, up to 5600 s-1 impact in a typical split-Hopkinson pressure bar test while only tiny boundary cracks can be observed even under 7200 s-1 impact. The high loadings of MCs and their hierarchical aggregates provide high-density sacrificial bonding for the effective dissipation of the impact energy, enabling the protection of fragile devices from the direct impact of over 200 m s-1 bullet. Moreover, the MGMs can be conveniently processed into protective coatings or films with promising recyclability due to the supramolecular interaction feature. The research not only reveals the unique relaxation dynamics and mechanical properties of MGMs in comparison with polymers and colloids, but also develops new chemical systems for the fabrication of high-speed impact-resistant materials.