Temperature-Dependent Separation of CO2 from Light Hydrocarbons in a Porous Self-Assembly of Vertexes Sharing Octahedra.

Design of flexible porous materials where the diffusion of guest molecules is regulated by the dynamics of contracted pore aperture is challenging. Here, a flexible porous self-assembly consisting of 1D channels with dynamic bottleneck gates is reported. The dynamic pendant naphthimidazolylmethyl moieties at the channel necks provide kinetic gate function, that enables unusual adsorption for light hydrocarbons. The adsorption for CO2 is mainly dominated by thermodynamics with the uptakes decreasing with increasing temperature, whereas the adsorptions for larger hydrocarbons are controlled by both thermodynamics and kinetics resulting in an uptake maximum at a temperature threshold. Such an unusual adsorption enables temperature-dependent separation of CO2 from the corresponding hydrocarbons.

In Situ Raman Probing of Hot-Electron Transfer at Gold-Graphene Interfaces with Atomic Layer Accuracy.

Plasmonic metals under photoexcitation can generate energetic hot electrons to directly induce chemical reactions. However, the capability and fundamental insights of the transportation of these hot electrons at plasmonic metal-2D material interfaces remain unclear. Herein, hot-electron transfer at Au-graphene interfaces has been in situ studied using surface-enhanced Raman spectroscopy (SERS) with atomic layer accuracy. Combining in situ SERS studies with density functional theory calculations, it is proved that hot electrons can be injected from plasmonic Au nanoparticles to graphene and directly penetrate graphene to trigger photocatalytic reactions. With increasing graphene layers, the transportation of hot electrons decays rapidly and would be completely blocked after five layers of graphene. Moreover, the transfer of hot electrons can be modulated by applying an external electric field, and the hot-electron transfer efficiency under electrochemical conditions is improved by over three times in the presence of a monolayer of graphene.

High-Performance Piezo-Electrocatalytic Sensing of Ascorbic Acid with Nanostructured Wurtzite Zinc Oxide.

Nanostructured piezoelectric semiconductors offer unprecedented opportunities for high-performance sensing in numerous catalytic processes of biomedical, pharmaceutical, and agricultural interests, leveraging piezocatalysis that enhances the catalytic efficiency with the strain-induced piezoelectric field. Here, a cost-efficient, high-performance piezo-electrocatalytic sensor for detecting l-ascorbic acid (AA), a critical chemical for many organisms, metabolic processes, and medical treatments, is designed and demonstrated. Zinc oxide (ZnO) nanorods and nanosheets are prepared to characterize and compare their efficacy for the piezo-electrocatalysis of AA. The electrocatalytic efficacy of AA is significantly boosted by the piezoelectric polarization induced in the nanostructured semiconducting ZnO catalysts. The charge transfer between the strained ZnO nanostructures and AA is elucidated to reveal the mechanism for the related piezo-electrocatalytic process. The low-temperature synthesis of high-quality ZnO nanostructures allows low-cost, scalable production, and integration directly into wearable electrocatalytic sensors whose performance can be boosted by otherwise wasted mechanical energy from the working environment, for example, human-generated mechanical signals.

Protecting the Nanoscale Properties of Ag Nanowires with a Solution-Grown SnO2 Monolayer as Corrosion Inhibitor.

The chemical reactivity and/or the diffusion of Ag atoms or ions during thermal processing can cause irreversible structural damage, hindering the application of Ag nanowires (NWs) in transparent conducting films and other applications that make use of the material's nanoscale properties. Here, we describe a simple and effective method for growing monolayer SnO2 on the surface of Ag nanowires under ambient conditions, which protects the Ag nanowires from chemical and structural damage. Our results show that Sn2+ and Ag atoms undergo a redox reaction in the presence of water. First-principle simulations suggest a reasonable mechanism for SnO2 formation, showing that the interfacial polarization of the silver by the SnO2 can significantly reduce the affinity of Ag to O2, thereby greatly reducing the oxidation of the silver. The corresponding values (for example, before coating: 17.2 Ω/sq at 86.4%, after coating: 19.0 Ω/sq at 86.6%) show that the deposition of monolayer SnO2 enables the preservation of high transparency and conductivity of Ag. In sharp contrast to the large-scale degradation of pure Ag-NW films including the significant reduction of its electrical conductivity when subjected to a series of harsh corrosion environments, monolayer SnO2 coated Ag-NW films survive structurally and retain their electrical conductivity. Consequently, the thermal, electrical, and chemical stability properties we report here, and the simplicity of the technology used to achieve them, are among the very best reported for transparent conductor materials to date.

Atomic-Scale Control of Silicon Expansion Space as Ultrastable Battery Anodes.

Development of electrode materials with high capability and long cycle life are central issues for lithium-ion batteries (LIBs). Here, we report an architecture of three-dimensional (3D) flexible silicon and graphene/carbon nanofibers (FSiGCNFs) with atomic-scale control of the expansion space as the binder-free anode for flexible LIBs. The FSiGCNFs with Si nanoparticles surrounded by accurate and controllable void spaces ensure excellent mechanical strength and afford sufficient space to overcome the damage caused by the volume expansion of Si nanoparticles during charge and discharge processes. This 3D porous structure possessing built-in void space between the Si and graphene/carbon matrix not only limits most solid-electrolyte interphase formation to the outer surface, instead of on the surface of individual NPs, and increases its stability but also achieves highly efficient channels for the fast transport of both electrons and lithium ions during cycling, thus offering outstanding electrochemical performance (2002 mAh g(-1) at a current density of 700 mA g(-1) over 1050 cycles corresponding to 3840 mAh g(-1) for silicon alone and 582 mAh g(-1) at the highest current density of 28 000 mA g(-1)).

Synthesis and surface plasmonic properties of ultra-thick silver nanowires.

Metallic nanowires (NWs) possess significant potential for applications in integrated photonic and electronic devices at the nanoscale. Considering the manipulation of NWs and energy loss associated with surface plasmon polaritons (SPPs) modes which serve as signal carriers in the nanophotonic devices, NWs with large diameters are significant. In this work, we report a successive multi-step polyol process approach for the synthesis of ultra-thick silver nanowires (Ag NWs) and investigate their energy loss. Thin Ag NWs prepared in the first step are used as seeds for the further growth of thick Ag NWs in the subsequent steps, where Ag NWs with diameter as large as 1820 nm have been prepared. We further investigate the SPP propagation properties of these thick Ag NWs, and find that energy loss is decreased in Ag NWs with improved diameter. Our experimental results are important for the design and fabrication of SPP-based nanophotonic components and circuits.

Triboelectric sensor as self-powered signal reader for scanning probe surface topography imaging.

We report a self-powered signal reading mechanism for imaging surface topography using a triboelectric sensor (TES) without supplying an external power or light source. A membrane-structured triboelectric nanogenerator (TENG) is designed at the root of a whisker (probe); the deflection of the whisker causes the two contacting surfaces of the TENG to give an electric output current/voltage that responds to the bending degree of the whisker when it scans over a rough surface. A series of studies were carried out to characterize the performance of the TES, such as high sensitivity of 0.45 V mm(-1), favorable repeating of standard deviation 8 mV, high Z-direction resolution of 18 µm, as well as lateral resolution of 250 µm by using a probe of size 11 mm in the length and 120 µm in radius. It not only can recognize the surface feature and size but also can perform a surface topography imaging in scanning mode. This work shows the potential of a TES as a self-powered tactile sensor for applications at relatively low spatial resolution.

In vivo powering of pacemaker by breathing-driven implanted triboelectric nanogenerator.

The first application of an implanted triboelectric nanogenerator (iTENG) that enables harvesting energy from in vivo mechanical movement in breathing to directly drive a pacemaker is reported. The energy harvested by iTENG from animal breathing is stored in a capacitor and successfully drives a pacemaker prototype to regulate the heart rate of a rat. This research shows a feasible approach to scavenge biomechanical energy, and presents a crucial step forward for lifetime-implantable self-powered medical devices.

Complementary power output characteristics of electromagnetic generators and triboelectric generators.

Recently, a triboelectric generator (TEG) has been invented to convert mechanical energy into electricity by a conjunction of triboelectrification and electrostatic induction. Compared to the traditional electromagnetic generator (EMG) that produces a high output current but low voltage, the TEG has different output characteristics of low output current but high output voltage. In this paper, we present a comparative study regarding the fundamentals of TEGs and EMGs. The power output performances of the EMG and the TEG have a special complementary relationship, with the EMG being a voltage source and the TEG a current source. Utilizing a power transformed and managed (PTM) system, the current output of a TEG can reach as high as ∼3 mA, which can be coupled with the output signal of an EMG to enhance the output power. We also demonstrate a design to integrate a TEG and an EMG into a single device for simultaneously harvesting mechanical energy. In addition, the integrated NGs can independently output a high voltage and a high current to meet special needs.

Theoretical comparison, equivalent transformation, and conjunction operations of electromagnetic induction generator and triboelectric nanogenerator for harvesting mechanical energy.

Triboelectric nanogenerator (TENG) is a newly invented technology that is effective using conventional organic materials with functionalized surfaces for converting mechanical energy into electricity, which is light weight, cost-effective and easy scalable. Here, we present the first systematic analysis and comparison of EMIG and TENG from their working mechanisms, governing equations and output characteristics, aiming at establishing complementary applications of the two technologies for harvesting various mechanical energies. The equivalent transformation and conjunction operations of the two power sources for the external circuit are also explored, which provide appropriate evidences that the TENG can be considered as a current source with a large internal resistance, while the EMIG is equivalent to a voltage source with a small internal resistance. The theoretical comparison and experimental validations presented in this paper establish the basis of using the TENG as a new energy technology that could be parallel or possibly equivalently important as the EMIG for general power application at large-scale. It opens a field of organic nanogenerator for chemists and materials scientists who can be first time using conventional organic materials for converting mechanical energy into electricity at a high efficiency.

Transparent triboelectric nanogenerators and self-powered pressure sensors based on micropatterned plastic films.

Transparent, flexible and high efficient power sources are important components of organic electronic and optoelectronic devices. In this work, based on the principle of the previously demonstrated triboelectric generator, we demonstrate a new high-output, flexible and transparent nanogenerator by using transparent polymer materials. We have fabricated three types of regular and uniform polymer patterned arrays (line, cube, and pyramid) to improve the efficiency of the nanogenerator. The power generation of the pyramid-featured device far surpassed that exhibited by the unstructured films and gave an output voltage of up to 18 V at a current density of ∼0.13 µA/cm(2). Furthermore, the as-prepared nanogenerator can be applied as a self-powered pressure sensor for sensing a water droplet (8 mg, ∼3.6 Pa in contact pressure) and a falling feather (20 mg, ∼0.4 Pa in contact pressure) with a low-end detection limit of ∼13 mPa.

Light propagation in curved silver nanowire plasmonic waveguides.

Plasmonic waveguides made of metal nanowires (NWs) possess significant potential for applications in integrated photonic and electronic devices. Energy loss induced by bending of a NW during light propagation is critical in affecting its performance as a plasmonic waveguide. We report the characterization of the pure bending loss in curved crystalline silver NW plasmonic waveguides by decoupling the energy loss caused by bending and propagation. The energy attenuation coefficiency due purely to bending was also determined, which exhibited an exponential relationship with the bending radius. Finite-difference-time-domain (FDTD) methods were utilized for theoretical simulations, which matched the experimental results well.

A density functional theory approach to mushroom-like platinum clusters on palladium-shell over Au core nanoparticles for high electrocatalytic activity.

Recently, it was found that Pt clusters deposited on Pd shell over Au core nanoparticles (Au@Pd@Pt NPs) exhibit unusually high electrocatalytic activity for the electro-oxidation of formic acid (P. P. Fang, S. Duan, et al., Chem. Sci., 2011, 2, 531-539). In an attempt to offer an explanation, we used here carbon monoxide (CO) as probed molecules, and applied density functional theory (DFT) to simulate the surface Raman spectra of CO at this core-shell-cluster NPs with a two monolayer thickness of Pd shell and various Pt cluster coverage. Our DFT results show that the calculated Pt coverage dependent spectra fit the experimental ones well only if the Pt clusters adopt a mushroom-like structure, while currently the island-like structure is the widely accepted model, which follows the Volmer-Weber growth mode. This result infers that there should be a new growth mode, i.e., the mushroom growth mode as proposed in the present work, for Au@Pd@Pt NPs. We suggest that such a mushroom-like structure may offer novel active sites, which accounts for the observed high electrocatalytic activity of Au@Pd@Pt NPs.

ZnO nanotube-based dye-sensitized solar cell and its application in self-powered devices.

High-density vertically aligned ZnO nanotube arrays were fabricated on FTO substrates by a simple and facile chemical etching process from electrodeposited ZnO nanorods. The nanotube formation was rationalized in terms of selective dissolution of the (001) polar face. The morphology of the nanotubes can be readily controlled by electrodeposition parameters for the nanorod precursor. By employing the 5.1 microm-length nanotubes as the photoanode for a dye-sensitized solar cell (DSSC), a full-sun conversion efficiency of 1.18% was achieved. Furthermore, we show that the DSSC unit can serve as a robust power source to drive a humidity sensor, with a potential for self-powered devices.

Atomic structure of Au-Pd bimetallic alloyed nanoparticles.

Using a two-step seed-mediated growth method, we synthesized bimetallic nanoparticles (NPs) having a gold octahedron core and a palladium epitaxial shell with controlled Pd-shell thickness. The mismatch-release mechanism between the Au core and Pd shell of the NPs was systematically investigated by high-resolution transmission electron microscopy. In the NPs coated with a single atomic layer of Pd, the strain between the surface Pd layer and the Au core is released by Shockley partial dislocations (SPDs) accompanied by the formation of stacking faults. For NPs coated with more Pd (>2 nm), the stacking faults still exist, but no SPDs are found. This may be due to the diffusion of Au atoms into the Pd shell layers to eliminate the SPDs. At the same time, a long-range ordered L1(1) AuPd alloy phase has been identified in the interface area, supporting the assumption of the diffusion of Au into Pd to release the interface mismatch. With increasing numbers of Pd shell layers, the shape of the Au-Pd NP changes, step by step, from truncated-octahedral to cubic. After the bimetallic NPs were annealed at 523 K for 10 min, the SPDs at the surface of the NPs coated with a single atomic layer of Pd disappeared due to diffusion of the Au atoms into the surface layer, while the stacking faults and the L1(1) Au-Pd alloyed structure remained. When the annealing temperature was increased to 800 K, electron diffraction patterns and diffraction contrast images revealed that the NPs became a uniform Au-Pd alloy, and most of the stacking faults disappeared as a result of the annealing. Even so, some clues still support the existence of the L1(1) phase, which suggests that the L1(1) phase is a stable, long-range ordered structure in Au-Pd bimetallic NPs.

Facet-selective epitaxial growth of heterogeneous nanostructures of semiconductor and metal: ZnO nanorods on Ag nanocrystals.

We demonstrate a new approach for synthesizing Ag-ZnO heterogeneous nanostructures in which single-crystalline ZnO nanorods were selectively grown on {111} rather than {100} facets of single-crystalline Ag truncated nanocubes. We have identified the fine structure of the Ag-ZnO heterostructures and proposed a mechanism indicating that structure match plays a critically important role in this type of facet-selective growth. These heterogeneous nanostructures are of special interest and have potential applications in electrical contacts, functional devices, biological sensors, and catalysis.

Epitaxial growth of heterogeneous metal nanocrystals: from gold nano-octahedra to palladium and silver nanocubes.

With octahedral Au nanocrystals as seeds, highly monodisperse Au@Pd and Au@Ag core-shell nanocubes were synthesized by a two-step seed-mediated method in aqueous solution. Accordingly, we have preliminarily proposed a general rule that the atomic radius, bond dissociation energy, and electronegativity of the core and shell metals play key roles in determining the conformal epitaxial layered growth mode.