Structuring and Shaping of Mechanically Robust and Functional Hydrogels toward Wearable and Implantable Applications.

Hydrogels possess unique features such as softness, wetness, responsiveness, and biocompatibility, making them highly suitable for biointegrated applications that have close interactions with living organisms. However, conventional man-made hydrogels are usually soft and brittle, making them inferior to the mechanically robust biological hydrogels. To ensure reliable and durable operation of biointegrated wearable and implantable devices, mechanical matching and shape adaptivity of hydrogels to tissues and organs are essential. Recent advances in polymer science and processing technologies have enabled mechanical engineering and shaping of hydrogels for various biointegrated applications. In this review, polymer network structuring strategies at micro/nanoscales for toughening hydrogels are summarized, and representative mechanical functionalities that exist in biological materials but are not easily achieved in synthetic hydrogels are further discussed. Three categories of processing technologies, namely, 3D printing, spinning, and coating for fabrication of tough hydrogel constructs with complex shapes are reviewed, and the corresponding hydrogel toughening strategies are also highlighted. These developments enable adaptive fabrication of mechanically robust and functional hydrogel devices, and promote application of hydrogels in the fields of biomedical engineering, bioelectronics, and soft robotics.

Giant polarization ripple in transverse pyroelectricity.

Pyroelectricity originates from spontaneous polarization variation, promising in omnipresent non-static thermodynamic energy harvesting. Particularly, changing spontaneous polarization via out-of-plane uniform heat perturbations has been shown in solar pyroelectrics. However, these approaches present unequivocal inefficiency due to spatially coupled low temperature change and duration along the longitudinal direction. Here we demonstrate unconventional giant polarization ripples in transverse pyroelectrics, without increasing the total energy input, into electricity with an efficiency of 5-fold of conventional longitudinal counterparts. The non-uniform graded temperature variation arises from decoupled heat localization and propagation, leading to anomalous in-plane heat perturbation (29-fold) and enhanced thermal disequilibrium effects. This in turn triggers an augmented polarization ripple, fundamentally enabling unprecedented electricity generation performance. Notably, the device generates a power density of 38 mW m-2 at 1 sun illumination, which is competitive with solar thermoelectrics and ferrophotovoltaics. Our findings provide a viable paradigm, not only for universal practical pyroelectric heat harvesting but for flexible manipulation of transverse heat transfer towards sustainable energy harvesting and management.

Substrate-Friendly Growth of Large-Sized Ni(OH)2 Nanosheets for Flexible Electrochromic Films.

Large-area, 2D, anisotropic, direct growth of nanostructures is considered an effective and straightforward way to readily fulfill transparent, flexible technology requirements. In addition, formation of thin hybrid structures by combining with another 2D material brings about dimensional advantages, such as intimate heterostructure functionalities, large specific area, and optical transparency. Here, we demonstrate 2D planar growth of thin Ni(OH)2 nanosheets on arbitrary rigid and soft supports, by exploiting the growth strategies of oriented attachment induced by interfacial chemistry and the intrinsic driving force of layered structure constitution. Moreover, large-scale 2D heterohybrids have successfully been prepared by direct conformal growth of Ni(OH)2 nanosheets overlying MoO3 nanobelts. Unlike the exfoliation and transfer of 2D materials technique, this approach minimizes multiple process contamination and physical-handling structural defects. Accordingly, proof-of-concept flexible electrochromism is demonstrated in view of its prerequisite to the access of a large homogeneous material coating. The as-synthesized 2D layered structure affirms its optical and electrochemical superiority through the display of wide optical modulation, high coloration efficiency, good cyclic stability, and flexibility.

Self-Biased Hybrid Piezoelectric-Photoelectrochemical Cell with Photocatalytic Functionalities.

Utilizing solar energy for environmental and energy remediations based on photocatalytic hydrogen (H2) generation and water cleaning poses great challenges due to inadequate visible-light power conversion, high recombination rate, and intermittent availability of solar energy. Here, we report an energy-harvesting technology that utilizes multiple energy sources for development of sustainable operation of dual photocatalytic reactions. The fabricated hybrid cell combines energy harvesting from light and vibration to run a power-free photocatalytic process that exploits novel metal-semiconductor branched heterostructure (BHS) of its visible light absorption, high charge-separation efficiency, and piezoelectric properties to overcome the aforementioned challenges. The desirable characteristics of conductive flexible piezoelectrode in conjunction with pronounced light scattering of hierarchical structure originate intrinsically from the elaborate design yet facile synthesis of BHS. This self-powered photocatalysis system could potentially be used as H2 generator and water treatment system to produce clean energy and water resources.

Resistive switching and polarization reversal of hydrothermal-method-grown undoped zinc oxide nanorods by using scanning probe microscopy techniques.

This paper reports the localized electrical, polarization reversal, and piezoelectric properties of the individual hexagonal ZnO nanorods, which are grown via the hydrothermal method and textured with [0001] orientation. The studies are conducted with conductive atomic force microscopy (c-AFM) and piezoresponse force microscopy (PFM) techniques. The correlation between the resistance switching and polarization reversal is discussed. The c-AFM results show that there is less variation on the set or reset voltage in nanorod samples, compared to that of the ZnO thin film. With increasing aspect ratio of the nanorods, both set and reset voltages are decreased. The nanorods with low aspect ratio show unipolar resistance switching, whereas both unipolar and bipolar resistance switching are observed when the aspect ratio is larger than 0.26. The PFM results further show the ferroelectric-like property in the nanorods. Comparing with that of the ZnO thin film, the enhanced piezoresponse in the nanorods can be attributed to the size effect. In addition, the piezoresponse force spectroscopy (PFS) experiments are conducted in ambient air, synthetic air, and argon gas. It shows that the depolarization field in the nanorod may be due to the moisture in the environment; moreover, the increased piezoresponse may relate to the absence of oxygen in the environment. It is also shown that the piezoelectric responses increase nonlinearly with the aspect ratio of the nanorods. By comparing the piezoresponse hysteresis loops obtained from the nanorod samples of as-grown, air-annealed and vacuum-annealed, it is found that the oxygen vacancies are the origin of the polarization reversal in ZnO nanorods. Finally, the tradeoff between the electrical and ferroelectric-like properties is also observed.

Tuning of multifunctional Cu-doped ZnO films and nanowires for enhanced piezo/ferroelectric-like and gas/photoresponse properties.

The prospect of tuning and enhancing multiple properties of ZnO from optical, electrical, piezo to ferroelectricity/magnetism with Cu dopants will certainly spur the pursuit of facile doping methodology to immensely advance this field of research. Here, a one-step aqueous synthesis of Cu-doped ZnO nanostructured materials with effective controllability over the morphology (film to nanowire) and doping concentrations both on rigid and flexible substrates has been developed. High structural integrity Cu-doped ZnO films and nanowires were achieved without multiple/harsh post-processing which tends to degrade their functional properties. Comprehensive investigations of varying doping concentrations on the enhancement and tunability of room temperature piezo/ferroelectricity to gas/photosensing multifunctional properties were systematically reported for the first time.

Metal nanoparticle-loaded hierarchically assembled ZnO nanoflakes for enhanced photocatalytic performance.

We have demonstrated an environmentally friendly and template-free aqueous synthesis of hierarchically assembled 3D ZnO nanoflakes. The ZnO nanoflakes self-assembled to expose highly interconnected networks of well-defined catalytic active {0001} facets. Well dispersed Pt, Ag and Au metal nanoparticles were loaded to form hybrid ZnO nanoflakes for enhanced photocatalytic activity. The enhanced photocatalytic activity may be attributed to the synergetic effects of well-structured ZnO crystal facets, high metal nanoparticles dispersity, enhanced light absorption and charge-transfer kinetics which leads to high photocatalytic degradation.

Ammonia plasma modification towards a rapid and low temperature approach for tuning electrical conductivity of ZnO nanowires on flexible substrates.

Though the fabrication of ZnO nanostructures is economical and low temperature, the lack of a facile, reliable and low temperature methodology to tune its electrical conductivity has prevented it from competing with other semiconductors. Here, we carried out surface modification of ZnO nanowires using ammonia plasma with no heat treatment, and studied their electrical properties over an extended time frame of more than a year. The fabrication of flexible devices was demonstrated via various methods of transferring and aligning as-synthesized ZnO nanowires onto plastic substrates. Hall measurements of the plasma modified ZnO nanowires revealed p-type conductivity. The N1s peak was present in the X-ray photoelectron spectrum of the surface modified ZnO, showing the presence of ammonia complexes. Low temperature photoluminescence showed evidence of acceptor-bound exciton emission. The resulting electrical devices, a chemical sensor and p-n homojunction, show the tunable electrical response of the surface modified ZnO nanowires.