Manufacturable Conducting Rubber Ambers and Stretchable Conductors from Copper Nanowire Aerogel Monoliths

We report on a low-cost, simple yet efficient strategy to fabricate ultralightweight aerogel monoliths and conducting rubber ambers from copper nanowires (CuNWs). A trace amount of poly(vinyl alcohol) (PVA) substantially improved the mechanical robustness and elasticity of the CuNW aerogel while maintaining a high electrical conductivity. The resistivity was highly responsive to strains manifesting two distinct domains, and both followed a power law function consistent with pressure-controlled percolation theory. However, the values of the exponents were much less than the predicted value for 3D systems, which may be due to highly porous structures. Remarkably, the CuNW-PVA aerogels could be further embedded into PDMS resin, forming conducting rubber ambers. The ambers could be further manufactured simply by cutting into any arbitrary 1D, 2D, and 3D shapes, which were all intrinsically conductive without the need of external prewiring, a condition required in the previous aerogel-based conductors. The outstanding electrical conductivity in conjunction with high mechanical compliance enabled prototypes of the elastic piezoresistivity switches and stretchable conductors

Free-Standing Bilayered Nanoparticle Superlattice Nanosheets with Asymmetric Ionic Transport Behaviors

Natural cell membranes can directionally and selectively regulate the ion transport, which is critical for the functioning of living cells. Here, we report on the fabrication of an artificial membrane based on an asymmetric nanoparticle superlattice bilayered nanosheet, which exhibits similar ion transport characteristics. The superlattice nanosheets were fabricated <i>via</i> a drying-mediated self-assembly of polystyrene-capped gold nanoparticles at the liquid–air interface. By adopting a layer-by-layer assembly process, an asymmetric nanomembrane could be obtained consisting of two nanosheets with different nanoparticle size. The resulting nanomembranes exhibit an asymmetric ion transport behavior, and diode-like current–voltage curves were observed. The asymmetric ion transport is attributed to the cone-like nanochannels formed within the membranes, upon which a simulation map was established to illustrate the relationship between the channel structure and the ionic selectivity, in consistency with our experimental results. Our superlattice nanosheet-based design presents a promising strategy for the fabrication of next-generation smart nanomembranes for rationally and selectively regulating the ion transport even at a large ion flux, with potential applications in a wide range of fields, including biosensor devices, energy conversion, biophotonics, and bioelectronics

Two-Dimensional Bipyramid Plasmonic Nanoparticle Liquid Crystalline Superstructure with Four Distinct Orientational Packing Orders

Anisotropic plasmonic nanoparticles have been successfully used as constituent elements for growing ordered nanoparticle arrays. However, orientational control over their spatial ordering remains challenging. Here, we report on a self-assembled two-dimensional (2D) nanoparticle liquid crystalline superstructure (NLCS) from bipyramid gold nanoparticles (BNPs), which showed four distinct orientational packing orders, corresponding to horizontal alignment (H-NLCS), circular arrangement (C-NLCS), slanted alignment (S-NLCS), and vertical alignment (V-NLCS) of constituent particle building elements. These packing orders are characteristic of the unique shape of BNPs because all four packing modes were observed for particles with various sizes. Nevertheless, only H-NLCS and V-NLCS packing orders were observed for the free-standing ordered array nanosheets formed from a drying-mediated self-assembly at the air/water interface of a sessile droplet. This is due to strong surface tension and the absence of particle–substrate interaction. In addition, we found the collective plasmonic coupling properties mainly depend on the packing type, and characteristic coupling peak locations depend on particle sizes. Interestingly, surface-enhanced Raman scattering (SERS) enhancements were heavily dependent on the orientational packing ordering. In particular, V-NLCS showed the highest Raman enhancement factor, which was about 77-fold greater than the H-NLCS and about 19-fold greater than C-NLCS. The results presented here reveal the nature and significance of orientational ordering in controlling plasmonic coupling and SERS enhancements of ordered plasmonic nanoparticle arrays

Shape Transformation of Constituent Building Blocks within Self-Assembled Nanosheets and Nano-origami

Self-assembly of nanoparticles represents a simple yet efficient route to synthesize designer materials with unusual properties. However, the previous assembled structures whether by surfactants, polymer, or DNA ligands are “static” or “frozen” building block structures. Here, we report the growth of transformable self-assembled nanosheets which could enable reversible switching between two types of nanosheets and even evolving into diverse third generation nanosheet structures without losing pristine periodicity. Such <i>in situ</i> transformation of nanoparticle building blocks can even be achieved in a free-standing two-dimensional system and three-dimensional origami. The success in such <i>in situ</i> nanocrystal transformation is attributed to robust “plant-cell-wall-like” ion-permeable reactor arrays from densely packed polymer ligands, which spatially define and confine nanoscale nucleation/growth/etching events. Our strategy enables efficient fabrication of nanocrystal nanosheets with programmable building blocks for innovative applications in adaptive tactile metamaterials, optoelectronic devices, and sensors

Omnidirectional Hydrogen Generation Based on a Flexible Black Gold Nanotube Array

Solar-driven hydrogen generation is emerging as an economical and sustainable means of producing renewable energy. However, current photocatalysts for hydrogen generation are mostly powder-based or rigid-substrate-supported, which suffer from limitations, such as difficulties in catalyst regeneration or poor omnidirectional light-harvesting. Here, we report a two-dimensional (2D) flexible photocatalyst based on elastomer-supported black gold nanotube (GNT) arrays with conformal CdS coating and Pt decoration. The highly porous GNT arrays display a strong light-trapping effect, leading to near-complete absorption over almost the entire range of the solar spectrum. In addition, they offer high surface-to-volume ratios promoting efficient photocatalytic reactions. These structural features result in high H2 generation efficiencies. Importantly, our elastomer-supported photocatalyst displays comparable photocatalytic activity even when being mechanically deformed, including bending, stretching, and twisting. We further designed a three-dimensional (3D) tree-like flexible photocatalytic system to mimic Nature’s photosynthesis, which demonstrated omnidirectional H2 generation. We believe our strategy represents a promising route in designing next-generation solar-to-fuel systems that rival natural plants

Unconventional Janus Properties of Enokitake-like Gold Nanowire Films

We report on unconventional Janus material properties of vertically aligned gold nanowire films that conduct electricity and interact with light and water in drastically different ways on its two opposing sides. These Janus-like properties originate from enokitake-like nanowire structures, causing the nanoparticle side (“head”) to behave like bulk gold, yet the opposing nanowire side (“tail”) behaves as discontinuous nanophases. Due to this Janus film structure, its head side is hydrophilic but its tail side is hydrophobic; its head side reflects light like bulk gold, yet its tail side is a broadband superabsorber; its tail side is less conductive but with tunable resistance. More importantly, the elastomer-bonded Janus film exhibits unusual mechatronic properties when being stretched, bent, and pressed. The tail-bonded elastomeric sheet can be stretched up to ∼800% strain while remaining conductive, which is about 10-fold that of head-bonded film. In addition, it is also more sensitive to bending forces and point loads than the corresponding tail-bonded film. We further demonstrate the versatility of nanowire-based Janus films for pressure sensors using bilayer structures in three different assembly layouts

Unconventional Janus Properties of Enokitake-like Gold Nanowire Films

We report on unconventional Janus material properties of vertically aligned gold nanowire films that conduct electricity and interact with light and water in drastically different ways on its two opposing sides. These Janus-like properties originate from enokitake-like nanowire structures, causing the nanoparticle side (“head”) to behave like bulk gold, yet the opposing nanowire side (“tail”) behaves as discontinuous nanophases. Due to this Janus film structure, its head side is hydrophilic but its tail side is hydrophobic; its head side reflects light like bulk gold, yet its tail side is a broadband superabsorber; its tail side is less conductive but with tunable resistance. More importantly, the elastomer-bonded Janus film exhibits unusual mechatronic properties when being stretched, bent, and pressed. The tail-bonded elastomeric sheet can be stretched up to ∼800% strain while remaining conductive, which is about 10-fold that of head-bonded film. In addition, it is also more sensitive to bending forces and point loads than the corresponding tail-bonded film. We further demonstrate the versatility of nanowire-based Janus films for pressure sensors using bilayer structures in three different assembly layouts

Large-Scale Self-Assembly and Stretch-Induced Plasmonic Properties of Core–Shell Metal Nanoparticle Superlattice Sheets

We report on a facile interfacial self-assembly approach to fabricate large-scale metal nanoparticle superlattice sheets from nonspherical core–shell nanoparticles, which exhibited reversible plasmonic responses to repeated mechanical stretching. Monodisperse Au@Ag nanocubes (NCs) and Au@Ag nanocuboids (NBs) could be induced to self-assembly at the hexane/water interface, forming uniform superlattices up to at least ∼13 cm² and giving rise to mirror-like reflection. Such large-area mirror-like superlattice sheets exhibited reversible plasmonic responses to external mechanical strains. Under stretching, the dominant plasmonic resonance peak for both NB and NC superlattice sheets shifted to blue, following a power-law function of the applied strain. Interestingly, the power-law exponent (or the decay rate) showed a strong shape dependence, where a faster rate was observed for NB superlattice sheets than that for NC superlattice sheets