Hybrid Aeromaterials for Enhanced and Rapid Volumetric Photothermal Response.

Conversion of light into heat is essential for a broad range of technologies such as solar thermal heating, catalysis and desalination. Three-dimensional (3D) carbon nanomaterial-based aerogels have been shown to hold great promise as photothermal transducer materials. However, until now, their light-to-heat conversion is limited by near-surface absorption, resulting in a strong heat localization only at the illuminated surface region, while most of the aerogel volume remains unused. We present a fabrication concept for highly porous (>99.9%) photothermal hybrid aeromaterials, which enable an ultrarapid and volumetric photothermal response with an enhancement by a factor of around 2.5 compared to the pristine variant. The hybrid aeromaterial is based on strongly light-scattering framework structures composed of interconnected hollow silicon dioxide (SiO2) microtubes, which are functionalized with extremely low amounts (in order of a few µg cm-3) of reduced graphene oxide (rGO) nanosheets, acting as photothermal agents. Tailoring the density of rGO within the framework structure enables us to control both light scattering and light absorption and thus the volumetric photothermal response. We further show that by rapid and repeatable gas activation, these transducer materials expand the field of photothermal applications, like untethered light-powered and light-controlled microfluidic pumps and soft pneumatic actuators.

Overcoming Water Diffusion Limitations in Hydrogels via Microtubular Graphene Networks for Soft Actuators.

Hydrogel-based soft actuators can operate in sensitive environments, bridging the gap of rigid machines interacting with soft matter. However, while stimuli-responsive hydrogels can undergo extreme reversible volume changes of up to ≈90%, water transport in hydrogel actuators is in general limited by their poroelastic behavior. For poly(N-isopropylacrylamide) (PNIPAM) the actuation performance is even further compromised by the formation of a dense skin layer. Here it is shown, that incorporating a bioinspired microtube graphene network into a PNIPAM matrix with a total porosity of only 5.4% dramatically enhances actuation dynamics by up to ≈400% and actuation stress by ≈4000% without sacrificing the mechanical stability, overcoming the water transport limitations. The graphene network provides both untethered light-controlled and electrically powered actuation. It is anticipated that the concept provides a versatile platform for enhancing the functionality of soft matter by combining responsive and 2D materials, paving the way toward designing soft intelligent matter.

Synthesis and Nanostructure Investigation of Hybrid ß-Ga2 O3 /ZnGa2 O4 Nanocomposite Networks with Narrow-Band Green Luminescence and High Initial Electrochemical Capacity.

The material design of functional "aero"-networks offers a facile approach to optical, catalytical, or and electrochemical applications based on multiscale morphologies, high large reactive area, and prominent material diversity. Here in this paper, the synthesis and structural characterization of a hybrid ß-Ga2 O3 /ZnGa2 O4 nanocomposite aero-network are presented. The nanocomposite networks are studied on multiscale with respect to their micro- and nanostructure by X-ray diffraction (XRD) and transmission electron microscopy (TEM) and are characterized for their photoluminescent response to UV light excitation and their electrochemical performance with Li-ion conversion reaction. The structural investigations reveal the simultaneous transformation of the precursor aero-GaN(ZnO) network into hollow architectures composed of ß-Ga2 O3 and ZnGa2 O4 nanocrystals with a phase ratio of ≈1:2. The photoluminescence of hybrid aero-ß-Ga2 O3 /ZnGa2 O4 nanocomposite networks demonstrates narrow band (λem  = 504 nm) green light emission of ZnGa2 O4 under UV light excitation (λex  = 300 nm). The evaluation of the metal-oxide network performance for electrochemical application for Li-ion batteries shows high initial capacities of ≈714 mAh g-1 at 100 mA g-1 paired with exceptional rate performance even at high current densities of 4 A g-1 with 347 mAh g-1 . This study provides is an exciting showcase example of novel networked materials and demonstrates the opportunities of tailored micro-/nanostructures for diverse applications a diversity of possible applications.

Evaporation kinetics in highly porous tetrapodal zinc oxide networks studied using in situ SRµCT.

Tetrapodal zinc oxide (t-ZnO) is used to fabricate polymer composites for many different applications ranging from biomedicine to electronics. In recent times, macroscopic framework structures from t-ZnO have been used as a versatile sacrificial template for the synthesis of multi-scaled foam structures from different nanomaterials such as graphene, hexagonal boron nitride or gallium nitride. Many of these fabrication methods rely on wet-chemical coating processes using nanomaterial dispersions, leading to a strong interest in the actual coating mechanism and factors influencing it. Depending on the type of medium (e.g. solvent) used, different results regarding the homogeneity of the nanomaterial coating can be achieved. In order to understand how a medium influences the coating behavior, the evaporation process of water and ethanol is investigated in this work using in situ synchrotron radiation-based micro computed tomography (SRµCT). By employing propagation-based phase contrast imaging, both the t-ZnO network and the medium can be visualized. Thus, the evaporation process can be monitored non-destructively in three dimensions. This investigation showed that using a polar medium such as water leads to uniform evaporation and, by that, a homogeneous coating of the entire network.

Macroscopic Silicone Microchannel Matrix for Tailored Drug Release and Localized Glioblastoma Therapy.

Localized therapy of the highly malignant brain tumor glioblastoma multiforme (GBM) could help to drastically improve the treatment efficiency and increase the patient's median survival. Here, a macroscopic PDMS matrix composed of interconnected microchannels for tailored drug release and localized GBM therapy is introduced. Based on a simple bottom-up fabrication method using a highly versatile sacrificial template, the presented strategy solves the scaling problem associated with the previously developed microchannel-based drug delivery systems, which were limited to two dimensions due to the commonly employed top-down microfabrication methods. Additionally, tailoring of the microchannel density, the fraction of drug-releasing microchannels and the macroscopic size of the drug delivery systems enabled precise adjustment of the drug release kinetics for more than 10 days. As demonstrated in a long-term GBM in vitro model, the release kinetics of the exemplarily chosen GBM drug AT101 could be tailored by variation of the microchannel density and the initial drug concentration, leading to diffusion-controlled AT101 release. Adapting a previously developed GBM treatment plan based on a sequential stimulation with AT101, measured anti-tumorigenic effects of free versus PDMS-released AT101 were comparable in human GBM cells and demonstrated efficient biological activity of PDMS-released AT101.

Wet-Chemical Assembly of 2D Nanomaterials into Lightweight, Microtube-Shaped, and Macroscopic 3D Networks.

Despite tremendous efforts toward fabrication of three-dimensional macrostructures of two-dimensional (2D) materials, the existing approaches still lack sufficient control over microscopic (morphology, porosity, pore size) and macroscopic (shape, size) properties of the resulting structures. In this work, a facile fabrication method for the wet-chemical assembly of carbon 2D nanomaterials into macroscopic networks of interconnected, hollow microtubes is introduced. As demonstrated for electrochemically exfoliated graphene, graphene oxide, and reduced graphene oxide, the approach allows for the preparation of highly porous (> 99.9%) and lightweight (<2 mg cm-3) aeromaterials with tailored porosity and pore size as well as tailorable shape and size. The unique tubelike morphology with high aspect ratio enables ultralow-percolation-threshold graphene composites (0.03 S m-1, 0.05 vol%) which even outperform most of the carbon nanotube-based composites, as well as highly conductive aeronetworks (8 S m-1, 4 mg cm-3). On top of that, long-term compression cycling of the aeronetworks demonstrates remarkable mechanical stability over 10 000 cycles, even though no chemical cross-linking is employed. The developed strategy could pave the way for fabrication of various macrostructures of 2D nanomaterials with defined shape, size, as well as micro- and nanostructure, crucial for numerous applications such as batteries, supercapacitors, and filters.