Atomic scale visualizations of low-angle grain boundary mediated plasticity by coupled dislocation climb and glide in nanoporous gold

Grain boundaries(GBs),as a prevalent structural characteristic,play a crucial role in the deformation of nanoporous metals with nanosized grains and ligaments.However,the fundamental understanding of GB-mediated deformation is still lacking because the plastic behavior of discrete ligaments involving GBs remains to be unknown.Here,we report atomic scale visualizations of coupled GB dislocation climb and glide in nanoporous gold ligaments with low-angle GBs via in situ tensile straining inside a Cs-corrected transmission electron microscope.The zig-zag motion paths of GB dislocations are precisely determined by real-time tracking of the movements of dislocation cores.The concurrent climb and glide of the dislocation arrays are confined to a narrow GB region,greatly enhancing GB diffusion in the bicrystal ligament.Our findings of coupled dislocation climb and glide shine a light on the room-temperature deformation of nanoporous metals and provide a time-dependent atomic-level physical image for GB engineering.

Self-supporting nanoporous gold-palladium overlayer bifunctional catalysts toward oxygen reduction and evolution reactions

The oxygen reduction reaction （ORR） and oxygen evolution reaction （OER） are crucial processes for energy conversion/storage systems, such as fuel cells, metal-air batteries, and water splitting. However, both reactions are severely restricted by their sluggish kinetics, thus requiring highly active, cost-effective, and durable electrocatalysts. Herein, we develop novel bifunctional nanocatalysts through surface nanoengineering of dealloying-driven nanoporous gold （NPG）. Pd overlayers were precisely deposited onto the NPG ligament surface by epitaxial layer-by-layer growth. More importantly, the obtained NPG-Pd overlayer nanocatalysts exhibit remarkably enhanced electrocatalytic activities toward both the ORR and OER in alkaline media, benchmarked against a state- of-the-art Pt/C catalyst. The improved electrocatalytic performance is rationalized by the unique three-dimensional nanoarchitecture of NPG, enhanced Pd utilization efficiency from precise control of the Pd overlayers, and change in electronic structure, as revealed by density functional theory calculations.

Highly coordinated Pd overlayers on nanoporous gold for efficient formic acid electro-oxidation

Design and fabrication of highly efficient and stable electrocatalysts remain key challenges in green energy technologies such as low-temperature direct liquid fuel cells.Based on in-depth theoretical calculations,here we demonstrate that surface Pd atoms with high coordination numbers(HCNs)can effectively modulate their adsorption energies for CO and OH,and thus achieve very high performance for formic acid electro-oxidation reaction(FAOR).Based on epitaxial coating Pd atomic layers onto nanoporous gold(NPG)thin membranes and a slight further decoration of Au clusters on top,the resulted core-shell structured NPG-Pd-Au electrocatalyst can demonstrate Pd intrinsic and mass activities of 8.62 mA·cm^(-2)and 27.25 A·mg^(-1)respectively at the peak potential around 0.33 V versus saturated calomel electrode toward FAOR,which are far better than those of commercial Pd/C catalysts(1.09 mA·cm^(-2)and 0.32 A·mg^(-1))tested under the same conditions.Moreover,the membrane electrode assemblies based on these low precious metal loading electrodes can achieve an anode Pd power efficiency over 10 W·mg^(-1)in a direct formic acid fuel cell,which is two orders of magnitude higher than that of the commercial Pd/C.These results provide new inspirations for the development of revolutionary electrodes for energy technologies in a rational manner.

Slice Thickness Optimization for the Focused Ion Beam-Scanning Electron Microscopy 3D Tomography of Hierarchical Nanoporous Gold

The combination of focused ion beam (FIB) with scanning electron microscopy (SEM), also known as FIB-SEM tomography, has become a powerful 3D imaging technique at the nanometer scale. This method uses an ion beam to mill away a thin slice of material, which is then block-face imaged using an electron beam. With consecutive slicing along the z-axis and subsequent imaging, a volume of interest can be reconstructed from the images and further analyzed. Hierarchical nanoporous gold (HNPG) exhibits unique structural properties and has a ligament size of 15–110 nm and pore size of 5–20 nm. Accurate reconstruction of its image is crucial in determining its mechanical and other properties. Slice thickness is one of the most critical and uncertain parameters in FIB-SEM tomography. For HNPG, the slice thickness should be at least half as thin as the pore size and, in our approach, should not exceed 10 nm. Variations in slice thickness are caused by various microscope and sample parameters, e.g., converged ion milling beam shape, charging effects, beam drift, or sample surface roughness. Determining and optimizing the actual slice thickness variation appear challenging. In this work, we examine the influence of ion beam scan resolution and the dwell time on the mean and standard deviation of slice thickness. After optimizing the resolution and dwell time to achieve the target slice thickness and lowest possible standard deviation, we apply these parameters to analyze an actual HNPG sample. Our approach can determine the thickness of each slice along the z-axis and estimate the deviation of the milling process along the y-axis (slow imaging axis). For this function, we create a multi-ruler structure integrated with the HNPG sample.

Ni(OH)_2 nanoflakes supported on 3D hierarchically nanoporous gold/Ni foam as superior electrodes for supercapacitors

The increasing demand for portable electronic devices and hybrid electric vehicles stimulates the develop- ment of supercapacitors as an advanced energy storage system. Here, we demonstrate a binder-free nickel hydroxide@nano- porous gold/Ni foam （Ni（OH）2@NPG/Ni foam） electrode for high-performance supercapacitors, which is prepared by a facile three-step fabrication route including electrodeposition of Au-Sn alloy on Ni foam, chemical dealloying of Sn and electrodepostion of Ni（OH）2 on NPG/Ni foam. Such Ni（OH）2@NPG/Ni foam electrode is composed of a thin layer of conformable Ni（OH）2 nanoflakes supported on three-di- mensional （3D） hierarchically porous NPG/Ni foam substrate. The resulting Ni（OH）2@NPG/Ni foam electrode can offer highways for both electron transfer and ion transport and lead to an excellent electrochemical performance with an ultrahigh specific capacitance of 3,380 F g-1 at a current density of 2 A g-1. Even when the current density was increased to 50 A g-1, it still retained a high capacitance of 1,927 F g-1. The promising performance of the Ni（OH）2@NPG/Ni foam elec- trode is mainly ascribed to the 3D hierarchical porosity and the highly conductive network on the NPG/Ni foam composite current collector, as well as the conformal electrodeposition of Ni（OH）2 active material on the NPG/Ni foam, which induces the formation of interconnected porosity both on the top surface and on the inner surface of the electrode. This in- spiring electrochemical performance would make the as-de- signed electrode material become one of the most promising candidates for future electrochemical energy storage systems.

Bottom-up fabrication of three-dimensional nanoporous gold from Au nanoparticles using nanowelding

Three-dimensional(3D)nanoporous gold(NPG)shows promising applications in various fields.However,its most common fabrication strategy(i.e.,dealloying)faces the problems of high energy consumption,resource waste,the use of corrosive solvent,and residue of the sacrificial component.Here,we report a general bottom-up nanowelding strategy to fabricate high-purity NPG from Au nanoparticles(NPs),accomplished via interfacial self-assembly of the Au NPs into monolayer Au NP film,its subsequent layer-by-layer transfer onto a solid substrate,and direct current(DC)nanowelding.We show that the DC nanowelding process can gradually evolve the layered Au NP film into NPG at low temperatures within 10 s,while not damaging their spherical structure.This is because during the nanowelding,electrons are preferred to be localized at the high-resistance NP/NP junctions,whose electrostatic repulsion in turn strengthens their surface atom diffusion to initiate a mild solid-state diffusion nanowelding.Furthermore,when using differently sized Au NPs as the starting building blocks,this strategy allows readily tuning the thickness,ligament size,and pore size,thereby offering great flexibility to create functional porous nanomaterials,e.g.,electrocatalyst for methanol electrooxidation.Surely,low-temperature nanowelding can play a role for the production of diverse nanoporous materials from other NPs beyond Au NPs.

Mechanical properties of nanocrystalline nanoporous gold complicated by variation of grain and ligament: A molecular dynamics simulation

A series of large-scale molecular dynamics(MD) simulations has been performed to study the effects of grain size and ligament diameter on the mechanical properties of nanocrystalline nanoporous gold. Such simulations indicate that the principal deformation mechanism is a combination of grain boundary sliding, grain rotation and dislocation movement. The results of uniaxial tensile tests reveal the presence of a reverse Hall-Petch relation between strength and nominal grain size, rather than the conventional Hall-Petch relationship in the present range of nominal grain size(7.9–52.7 nm). An increase of flow stress may possibly attribute to the lower total proportion of grain boundary sliding and grain rotation in the deformation of samples with larger grain size. The Young's modulus shows a linear relation with the reciprocal of nominal grain size, which depends largely on the volume fraction of grain boundaries and thus decreasing grain size leads to relatively lower Young's modulus. MD simulations on samples with ligament diameter ranging from 4.07 to 8.10 nm are also carried out and results show that the increasing ligament diameter resulted in decreased flow stress and increased Young's modulus.

Electrochemical synthesis of silver nanoparticles-coated gold nanoporous film electrode and its application to amperometric detection for trace Cr(VI)

A simple and rapid approach for the electrochemical synthesis of Ag nanoparticles-coated gold nanoporous film (AgGNF) on a gold substrate was reported. The solid gold electrode (SGE) was directly anodized under a high potential of 5 V, and then reduced to obtain gold nanoporous film (AuNF) by freshly prepared ascorbic acid. The Ag nanoparticles (AgNPs) were grown on the AuNF electrode by potential-step electrodeposition. The resulting AgGNF composites electrodes were characterized by scanning electron microscopy (SEM), energy dispersive X-ray (EDX) spectroscopy and cyclic voltammetry (CV). As-prepared AgGNF electrode was used as a kind of superior sensor for Cr(VI) detection, which exhibited better electrocatalytic behavior than those of AuNF and SGE under identical conditions. Such a designed AgGNF nanocomposites electrode showed outstanding sensitivity (about 0.15 nA/ppb) and favorable reproducibility for Cr(VI) detection. The dependence of reduction current on Cr(VI) concentration is linear from 2 to 370 ppb with a low detection limit of 0.65 ppb. Interferences from other heavy metals ions (Cr3+, Cu2+, Pb2+, As3+ and Hg2+) associated with Cr(VI) analysis could be effectively diminished. The present method proves to be rapid, reliable, sensitive and low-cost.

Sensitive and Specific Y-Shaped Ratio Biosensor for Detecting Serum mi R-18a:Potential Early Scanning Tool for Non-Small Cell Lung Cancer

miR-18a has been identified as a significantly expressed microRNA(miRNA)in non-small cell lung cancer(NSCLC)and plays a vital role in cancer cell transformation,metastasis,and carcinogenesis.Herein,a pair of binary probes from numerous probe pairs based on single nucleotide polymorphism analyses of miR-18a and miR-18b was first designed and screened to develop a Y-shaped ratio biosensor for accurate detection of serum miR-18a in NSCLC.The special structure of the binary probes combined with the hairpin showed strong specificity for miR-18a,which was confirmed by polyacrylamide gel electrophoresis assay and square wave voltammetry assay.Furthermore,it is beneficial to immobilize single-stranded DNA(ssDNA)probes due to the large specific surface area of nanoporous gold,thereby improving the sensitivity of the biosensor.The Y-shaped ratio biosensor exhibited a wide detection range and can quantify the concentration of miR-18a in the range of 10 fmol/L–100 pmol/L,with a limit of detection of 0.211 fmol/L(S/N=3).Moreover,it exhibits excellent detection capabilities in serum samples since the biosensor showed a high selectivity toward the coexistence of miR-18a and miR-18b.Therefore,the prepared Y-shaped ratio biosensor is a highly sensitive and specific miR-18a detection tool,capable of identifying microscopic amounts of miR-18a in serum samples,providing great potential for early screening of NSCLC.

Ultrathin nanoporous metal-semiconductor heterojunction photoanodes for visible light hydrogen evolution

Plasmonic metal-semiconductor nano-heterojuncfions （NHJs）, with their superior photocatalytic performance, provide opportunities for the efficient utilization of solar energy. However, scientific significance and technical challenges remain in the development of suitable metal-semiconductor NHJ photoelectrodes for new generation flexible optoelectronic devices, which often require complex processing. Herein, we report integrated three-dimensional （3D） NHJ photoelectrodes by conformally coating cadmium sulfide （CdS） nanolayers onto ultrathin nano- porous gold （NPG） films via a facile electrodeposition method. Localized surface plasmon resonance （LSPR） of NPG enhances the electron-hole pair generation and separation. Moreover, the direct contact interface and high conductive framework structure of the NHJs boosts the photogenerated carrier separation and transport. Hence, the NHJs exhibit evidently enhanced photocurrent density and hydrogen evolution rate relative to CdS deposited on either gold （Au） foil or fluorine-doped tin oxide （FTO） at 0 V vs. SCE （saturated calomel electrode） under visible-light irradiation. Moreover, they demonstrate a surprisingly stable photoelectrochemical hydrogen evolution （PEC-HE） activity over 104 s of continuous irradiation.

Ultra-thin layer structured anodes for highly durable Iow-Pt direct formic acid fuel cells

Direct formic acid fuel cells （DFAFCs） allow highly efficient low temperature conversion of chemical energy into electricity and are expected to play a vital role in our future sustainable society. However, the massive precious metal usage in current membrane electrode assembly （MEA） technology greatly inhibits their actual applications. Here we demonstrate a new type of anode constructed by confining highly active nanoengineered catalysts into an ultra-thin catalyst layer with thickness around 100 nm. Specifically, an atomic layer of platinum is first deposited onto nanoporous gold （NPG） leaf to achieve high utilization of Pt and easy accessibility of both reactants and electrons to active sites. These NPG-Pt core/shell nanostructures are further decorated by a sub-monolayer of Bi to create highly active reaction sites for formic acid electro-oxidation. Thus obtained layer-structured NPG-Pt-Bi thin films allow a dramatic decrease in Pt usage down to 3 ~tg.cm-2, while maintaining very high electrode activity and power performance at sufficiently low overall precious metal loading. Moreover, these electrode materials show superior durability during half-year test in actual DFAFCs, with remarkable resistance to common impurities in formic acid, which together imply their great potential in applications in actual devices.

Long-lived electron emission reveals localized plasmon modes in disordered nanosponge antennas

We report long-lived,highly spatially localized plasmon states on the surface of nanoporous gold nanoparticles—nanosponges—with high excitation efficiency.It is well known that disorder on the nanometer scale,particularly in two-dimensional systems,can lead to plasmon localization and large field enhancements,which can,in turn,be used to enhance nonlinear optical effects and to study and exploit quantum optical processes.Here,we introduce promising,three-dimensional model systems for light capture and plasmon localization as gold nanosponges that are formed by the dewetting of gold/silver bilayers and dealloying.We study light-induced electron emission from single nanosponges,a nonlinear process with exponents of n≈5...7,using ultrashort laser pulse excitation to achieve femtosecond time resolution.The long-lived electron emission process proves,in combination with optical extinction measurements and finite-difference time-domain calculations,the existence of localized modes with lifetimes of more than 20 fs.These electrons couple efficiently to the dipole antenna mode of each individual nanosponge,which in turn couples to the far-field.Thus,individual gold nanosponges are cheap and robust disordered nanoantennas with strong local resonances,and an ensemble of nanosponges constitutes a meta material with a strong polarization independent,nonlinear response over a wide frequency range.