Connective tissue inspired elastomer-based hydrogel for artificial skin via radiation-indued penetrating polymerization.

Robust hydrogels offer a candidate for artificial skin of bionic robots, yet few hydrogels have a comprehensive performance comparable to real human skin. Here, we present a general method to convert traditional elastomers into tough hydrogels via a unique radiation-induced penetrating polymerization method. The hydrogel is composed of the original hydrophobic crosslinking network from elastomers and grafted hydrophilic chains, which act as elastic collagen fibers and water-rich substances. Therefore, it successfully combines the advantages of both elastomers and hydrogels and provides similar Young's modulus and friction coefficients to human skin, as well as better compression and puncture load capacities than double network and polyampholyte hydrogels. Additionally, responsive abilities can be introduced during the preparation process, granting the hybrid hydrogels shape adaptability. With these unique properties, the hybrid hydrogel can be a candidate for artificial skin, fluid flow controller, wound dressing layer and many other bionic application scenarios.

Selective CO2 reduction to CH3OH over atomic dual-metal sites embedded in a metal-organic framework with high-energy radiation.

The efficient use of renewable X/γ-rays or accelerated electrons for chemical transformation of CO2 and water to fuels holds promise for a carbon-neutral economy; however, such processes are challenging to implement and require the assistance of catalysts capable of sensitizing secondary electron scattering and providing active metal sites to bind intermediates. Here we show atomic Cu-Ni dual-metal sites embedded in a metal-organic framework enable efficient and selective CH3OH production (~98%) over multiple irradiated cycles. The usage of practical electron-beam irradiation (200 keV; 40 kGy min-1) with a cost-effective hydroxyl radical scavenger promotes CH3OH production rate to 0.27 mmol g-1 min-1. Moreover, time-resolved experiments with calculations reveal the direct generation of CO2•‒ radical anions via aqueous electrons attachment occurred on nanosecond timescale, and cascade hydrogenation steps. Our study highlights a radiolytic route to produce CH3OH with CO2 feedstock and introduces a desirable atomic structure to improve performance.

Radiolytic Water Splitting Sensitized by Nanoscale Metal-Organic Frameworks.

High-energy radiation that is compatible with renewable energy sources enables direct H2 production from water for fuels; however, the challenge is to convert it as efficiently as possible, and the existing strategies have limited success. Herein, we report the use of Zr/Hf-based nanoscale UiO-66 metal-organic frameworks as highly effective and stable radiation sensitizers for purified and natural water splitting under γ-ray irradiation. Scavenging and pulse radiolysis experiments with Monte Carlo simulations show that the combination of 3D arrays of ultrasmall metal-oxo clusters and high porosity affords unprecedented effective scattering between secondary electrons and confined water, generating increased precursors of solvated electrons and excited states of water, which are the main species responsible for H2 production enhancement. The use of a small quantity (<80 mmol/L) of UiO-66-Hf-OH can achieve a γ-rays-to-hydrogen conversion efficiency exceeding 10% that significantly outperforms Zr-/Hf-oxide nanoparticles and the existing radiolytic H2 promoters. Our work highlights the feasibility and merit of MOF-assisted radiolytic water splitting and promises a competitive method for creating a green H2 economy.

Superior Anticorrosion Performance of Well-Dispersed MXene-Polymer Composite Coatings Enabled by Covalent Modification and Ambient Electron-Beam Curing.

MXene-reinforced composite coatings have recently shown promise for metal anticorrosion due to their large aspect ratio and antipermeability; however, the challenges of the poor dispersion, oxidation, and sedimentation of MXene nanofillers in a resin matrix that are often encountered in the existing curing methods have greatly limited practical applications. Herein, we reported an efficient, ambient, and solvent-free electron beam (EB) curing technology to fabricate PDMS@MXene filled acrylate-polyurethane (APU) coatings for anticorrosion of 2024 Al alloy, a common aerospace structural material. We showed that the dispersion of MXene nanoflakes modified by PDMS-OH was dramatically improved in EB-cured resin and enhanced the water resistance through the additional water-repellent groups of PDMS-OH. Moreover, the controllable irradiation-induced polymerization enabled a unique high-density cross-linked network, presenting a large physical barrier against corrosive media. The newly developed APU-PDMS@MX1 coatings achieved excellent corrosion-resistance with the highest protection efficiency of 99.9957%. The coating filled with uniformly distributed PDMS@MXene promoted the corrosion potential, corrosion current density, and corrosion rate to be -0.14 V, 1.49 × 10-9 A/cm2, and 0.0004 mm/year, respectively, and the impedance modulus was increased by 1-2 orders of magnitude compared to that of APU-PDMS coating. This work combining 2D material with EB curing technology broadens the avenue for designing and fabricating composite coatings for metal corrosion protection.

Electrically driven single microwire-based single-mode microlaser.

Engineering the lasing-mode oscillations effectively within a laser cavity is a relatively updated attentive study and perplexing issue in the field of laser physics and applications. Herein, we report a realization of electrically driven single-mode microlaser, which is composed of gallium incorporated zinc oxide microwire (ZnO:Ga MW) with platinum nanoparticles (PtNPs, d ~ 130 nm) covering, a magnesium oxide (MgO) nanofilm, a Pt nanofilm, and a p-type GaN substrate. The laser cavity modes could resonate following the whispering-gallery mode (WGM) among the six side surfaces by total internal reflection, and the single-mode lasing wavelength is centered at 390.5 nm with a linewidth of about 0.18 nm. The cavity quality factor Q is evaluated to about 2169. In the laser structure, the usage of Pt and MgO buffer layers can be utilized to engineer the band alignment of ZnO:Ga/GaN heterojunction, optimize the p-n junction quality and increase the current injection. Thus, the well-designed device structure can seamlessly unite the electron-hole recombination region, the gain medium, and optical microresonator into the PtNPs@ZnO:Ga wire perfectly. Such a single MW microlaser is essentially single-mode regardless of the gain spectral bandwidth. To study the single-mode operation, PtNPs working as superabsorber can engineering the multimode lasing actions of ZnO:Ga MWs even if their dimensions are typically much larger than that of lasing wavelength. Our findings can provide a straightforward and effective scheme to develop single-mode microlaser devices based on one-dimensional wire semiconductors.

Improved optical properties of perovskite solar cells by introducing Ag nanopartices and ITO AR layers.

Embedded noble metal nanostructures and surface anti-reflection (AR) layers affect the optical properties of methylammonium lead iodide (CH3NH3PbI3) perovskite solar cells significantly. Herein, by employing a combined finite element method and genetic algorithm approach, we report five different types of CH3NH3PbI3 perovskite solar cells by introducing embedded Ag nanoparticles within the CH3NH3PbI3 layer and/or top ITO cylinder grating as an AR layer. The maximum photocurrent was optimized to reach 23.56 mA/cm2, which was 1.09/1.17 times higher than Tran's report/ flat cases. It is also comparable with values (23.6 mA/cm2) reported in the literature. The calculations of the electric field and charge carrier generation rate of the optimized solar cell further confirms this improvement than flat cases. It attributes to the synergistic effect of the embedded Ag nanoparticles and ITO AR layer. The results obtained herein hold great promise for future boosting the optical efficiency of perovskite solar cells.

Energy funnelling within multichromophore architectures monitored with subnanometre resolution.

The funnelling of energy within multichromophoric assemblies is at the heart of the efficient conversion of solar energy by plants. The detailed mechanisms of this process are still actively debated as they rely on complex interactions between a large number of chromophores and their environment. Here we used luminescence induced by scanning tunnelling microscopy to probe model multichromophoric structures assembled on a surface. Mimicking strategies developed by photosynthetic systems, individual molecules were used as ancillary, passive or blocking elements to promote and direct resonant energy transfer between distant donor and acceptor units. As it relies on organic chromophores as the elementary components, this approach constitutes a powerful model to address fundamental physical processes at play in natural light-harvesting complexes.

An electrically induced probe of the modes of a plasmonic multilayer stack.

A new single-image acquisition technique for the determination of the dispersion relation of the propagating modes of a plasmonic multilayer stack is introduced. This technique is based on an electrically-driven, spectrally broad excitation source which is nanoscale in size: the inelastic electron tunnel current between the tip of a scanning tunneling microscope (STM) and the sample. The resulting light from the excited modes of the system is collected in transmission using a microscope objective. The energy-momentum dispersion relation of the excited optical modes is then determined from the angle-resolved optical spectrum of the collected light. Experimental and theoretical results are obtained for metal-insulator-metal (MIM) stacks consisting of a silicon oxide layer (70, 190 or 310 nm thick) between two gold films (each with a thickness of 30 nm). The broadband characterization of hybrid plasmonic-photonic transverse magnetic (TM) modes involved in an avoided crossing is demonstrated and the advantages of this new technique over optical reflectivity measurements are evaluated.

Directional light beams by design from electrically driven elliptical slit antennas.

We report on the low-energy, electrical generation of light beams in specific directions from planar elliptical microstructures. The emission direction of the beam is determined by the microstructure eccentricity. A very simple, broadband, optical antenna design is used, which consists of a single elliptical slit etched into a gold film. The light beam source is driven by an electrical nanosource of surface plasmon polaritons (SPP) that is located at one focus of the ellipse. In this study, SPPs are generated through inelastic electron tunneling between a gold surface and the tip of a scanning tunneling microscope.

Surface plasmon polariton beams from an electrically excited plasmonic crystal.

Surface plasmon polariton (SPP) beams with an in-plane angular spread of 8° are produced by electrically exciting a 2D plasmonic crystal using a scanning tunneling microscope (STM). The plasmonic crystal consists of a gold nanoparticle (NP) array on a thin gold film on a glass substrate and it is the inelastic tunnel electrons (IET) from the STM that provide a localized and spectrally broadband SPP source. Surface waves on the gold film are shown to be essential for the coupling of the local, electrical excitation to the extended NP array, thus leading to the creation of SPP beams. A simple model of the scattering of SPPs by the array is used to explain the origin and direction of the generated SPP beams under certain conditions. In order to take into account the broadband spectrum of the source, calculations realized using finite-difference time-domain (FDTD) methods are obtained, showing that bandgaps for SPP propagation exist for certain wavelengths and indicating how changing the pitch of the NP array may enhance the SPP beaming effect.