Although graphene aerogels (GA) have been attracted great attention, the easy-operation and large-scale production of GA are still challenges. Further, most GA have a monolith-like appearance, limiting their application-specific needs. Herein, we highlight graphene aerogel spheres with controllable hollow structures (HGAS) that are delicately designed and manufactured via coaxial electrospinning coupled with freeze-drying and calcination. The HGAS exhibit a spherical configuration at the macroscale, while the construction elements of graphene on the microscale showing an interconnected radial microchannel structure. Further, ball-in-ball graphene aerogel spheres (BGAS) are obtained by reference to the triaxial electrospinning technology. The as-prepared spheres possess the controllable integrated conductive networks, leading to the effective dielectric loss and impedance matching, thus bringing on high-performance microwave absorption. The as-obtained HGAS shows a minimum reflection loss of −52.7 dB, and a broad effective absorption bandwidth (f E ) of 7.0 GHz with thickness of 2.3 mm. Further, the f E reaches 9.3 GHz for BGAS with thickness of 3.4 mm. Aforementioned superior microwave absorption of HGAS and BGAS confirms combination of multiaxial electrospinning and freeze-drying on the multiscale is an effective strategy for scalable fabrication of advanced microwave absorbing functional graphene aerogel spheres.
Hierarchical structure has exhibited an important influence in the fields of supercapacitors, catalytic applications, and tissue engineering. The hot dog, a popular food, is composed of bread and sausage with special structures. In this study, inspired by the structure of a hot dog, the strategy of combining direct ink writing 3D printing with bidirectional freezing is devised to prepare hot dog‐like scaffolds with hierarchical structure. The scaffolds are composed of hollow bioceramic tubes (mimicking the “bread” in hot dogs, pore size: ≈1 mm) embedded by bioceramic rods (mimicking the “sausage” in hot dogs, diameter: ≈500 µm) and the sausage‐like bioceramic rods possess uniformly aligned lamellar micropores (lamellar pore size: ≈30 µm). By mimicking the functions of hierarchical structure of bone tissues for transporting and storing nutrients, the prepared hot dog‐like scaffolds show excellent properties for loading and releasing drugs and proteins as well as for improving the delivery and differentiation of tissue cells. The in vivo study further demonstrates that both the hierarchical structure itself and the controlled drug delivery in hot dog‐like scaffolds significantly contribute to the improved bone‐forming bioactivity. This study suggests that the prepared hot dog‐like scaffolds are a promising biomaterial for drug delivery, tissue engineering, and regenerative medicine.
Graphene metamaterials with a radial-like structure and negative Poisson’s ratio (NPR) were assembled using a unique centripetal freezing technique. Driven by the centripetal temperature gradient, ice crystals were grown toward the center of an aqueous graphene dispersion and form a radially arranged skeleton. A reentrant structure was formed at the diagonal of the monolith as the ice crystals sublimate. The obtained centripetal graphene metamaterial (CGM) was endowed with NPR response. CGM maintained NPR under 50% compression, which reached a minimum (−0.18) at 10% strain. After 50 compressive cycles at 50% strain, CGM retained approximately 96% of the original compressive strength. The radial channels endowed CGM with fast absorption kinetics, and the NPR response effectively accommodated the damage caused by volume shrinkage during repeated adsorption-regeneration cycles. This strategy is an effective method for achieving NPR response and improving the mechanical properties of porous materials.
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