Robust Metallic Actuators Based on Nanoporous Gold Rapidly Dealloyed from Gold–Nickel Precursors

Dealloyed nanoporous gold (np-Au) has applications as oxygen reduction catalysis in Li-air batteries and fuel cells, or as actuators to convert electricity into mechanical energy. However, it faces the challenges of coarsening-induced structure instability, mechanical weakness due to low relative densities, and slow dealloying rates. Here, monolithic np-Au is dealloyed from a single-phase Au₂₅Ni₇₅ solid-solution at a one-order faster dealloying rate, ultra-low residual Ni content, and importantly, one-third more relative density than np-Au dealloyed from conventional Au₂₅Ag₇₅. The small atomic radius and low dealloying potential of the sacrificing element Ni are intrinsically beneficial to fast produce high relative density np-Au, as predicted by a general model for dealloying of binary alloys and validated by experiments. Stable, durable, and reversible actuation of np-Au takes place under cyclic potential triggering in alkaline and acidic electrolytes with negligible coarsening-induced strain-shift. The thermal and mechanical robustness of bulk np-Au is confirmed by two-order slower ligament coarsening rates during annealing at 300 °C and 45 MPa macroscopic yielding strength distinctive from the typical early onset of plastic yielding. This article opens a rich direction to achieve high relative density np-Au which is essential for porous network connectivity, mechanical strength, and nanostructure robustness for electrochemical functionality.     

Fe82Nb6B12合金表面纳米多孔结构的形成及电催化析氢性能的研究

目的增加条带表面积,提高电催化析氢活性。方法采用真空激冷装置制备Fe_(82)Nb_6B_(12)前驱体条带,通过控制铜辊转速得到α-Fe纳米晶/非晶双相结构。利用α-Fe纳米晶与非晶基体在0.5 mol/L H_2SO_4溶液中腐蚀性能的差异,通过脱合金法得到非晶纳米多孔结构。使用XRD、DSC、SEM、EDS等表征手段以及电化学测试方法,研究铜辊转速、脱合金时间对物相、成分、形貌及电催化析氢性能的影响。结果 1kr/min样品完全晶化,2~3 kr/min样品为α-Fe纳米晶/非晶双相合金,且随着铜辊转速增大,前驱体条带中α-Fe纳米晶含量减少。脱合金后成功制备了非晶纳米多孔结构,铜辊转速越大,孔径越小,比表面积越小。4 kr/min样品为非晶态,脱合金后没有得到多孔结构。2 kr/min多孔结构的析氢性能最好,在电流密度为10 mA/cm~2时的过电位为220 mV,塔菲尔斜率为105 mV/dec。结论采用甩带法可以制备具有α-Fe纳米晶/非晶双相结构的Fe_(82)Nb_6B_(12)合金。通过α-Fe纳米晶的选择性腐蚀,在条带表面得到纳米多孔结构,条带比表面积显著改善,从而提高了其析氢性能。     

Controlled synthesis of one-dimensional Au-Ag porous nanostructures

The fabrication of a new type of one-dimensional Au-Ag porous nanotube (NPT) structure was presented based on a facile combination of nanocrystal growth and surface modification. Ag nanowires with various diameters were firstly served as the chemical plating templates via a polyol-process. Then, one-dimensional (1D) Au-Ag porous nanostructures with tailored structural features could be prepared by controlling the individual steps involved in this process, such as nanowire growth, surface modification, thermal diffusion, and dealloying. Structural characterizations reveal these Au-Ag porous nanotubes, non-porous nanotubes and porous nanowires possess novel nano-architectures with multimodal open porosity and excellent structural continuity and integrity, which make them particularly desirable as novel 1D nanocarriers for biomedical, drug delivery and sensing applications.     

Localized dissolution initiated at single and clustered intermetallic particles during immersion of Al–Cu–Mg alloy in sodium chloride solution

Aiming at understanding how intermetallic phases response when AA2024-T3 aluminium alloy is exposed to chloride-containing aqueous medium, scanning electron microscopy was employed to provide morphological information on alloy surface before and after corrosion testing. Energy dispersive X-ray spectroscopy was carried out to determine compositional change in intermetallic particles. Atomic force microscopy was used to examine topographical variation introduced by the reactions of intermetallic phases. Transmission electron microscopy combined with ultramicrotomy was carried out on dealloyed Al₂CuMg particles and their periphery region. It is found that dealloyed Al₂CuMg particles exhibited porous, polycrystalline structure comprised of body-centred cubic copper particles with sizes of 5 to 20 nm. Aluminium matrix started to trench in the periphery of Al₂CuMg particles at the early stage of dealloying. Development of trenching in Al–Cu–Fe–Mn–(Si) particle's periphery was not uniform and took longer time to initiate than Al₂CuMg dealloying. Localized corrosion at a cluster of Al₂CuMg and Al₂Cu particles was mainly associated with Al₂CuMg particles.     

Failure analysis of brass portions of dielectric unions

Persistent failures (leakage) were observed in the brass portion of dielectric unions after a relatively short service period. Metallographic examination revealed evidence of severe stress-corrosion cracking within the brass as well as dealloying on the surface. Evaluations using stress calculations and the dynamics of freezing water indicated that the unions were not overtightened during installation, and the water passing through the unions did not freeze. The subject copper alloy was shown to have been insufficient for the intended application due to high susceptibility to corrosion.     

Nanoporous Al‐Ni‐Co‐Ir‐Mo High‐Entropy Alloy for Record‐High Water Splitting Activity in Acidic Environments

Ir‐based binary and ternary alloys are effective catalysts for the electrochemical oxygen evolution reaction (OER) in acidic solutions. Nevertheless, decreasing the Ir content to less than 50 at% while maintaining or even enhancing the overall electrocatalytic activity and durability remains a grand challenge. Herein, by dealloying predesigned Al‐based precursor alloys, it is possible to controllably incorporate Ir with another four metal elements into one single nanostructured phase with merely ≈20 at% Ir. The obtained nanoporous quinary alloys, i.e., nanoporous high‐entropy alloys (np‐HEAs) provide infinite possibilities for tuning alloy's electronic properties and maximizing catalytic activities owing to the endless element combinations. Particularly, a record‐high OER activity is found for a quinary AlNiCoIrMo np‐HEA. Forming HEAs also greatly enhances the structural and catalytic durability regardless of the alloy compositions. With the advantages of low Ir loading and high activity, these np‐HEA catalysts are very promising and suitable for activity tailoring/maximization.     

脱合金法制备Fe基纳米多孔材料及其催化性能

近年来,纳米多孔金属材料成为催化和传感器等领域的研究热点。本研究将铁基非晶合金和脱合金工艺相结合,制备具有催化性能的纳米多孔材料。采用真空感应熔炼装置和真空急冷甩带装置制备宽1mm×厚25μm的Fe_(60)Pd_(20)P_(20)非晶合金条带,并借助X射线衍射仪(XRD)、扫描电镜(SEM)、能谱仪(EDS)对非晶合金条带进行表征。将Fe60Pd_(20)P_(20)非晶合金作为电化学脱合金的前驱体材料,在25℃、1mol/L H_2SO4电解液中进行1h恒电位脱合金处理,成功制备出具有均匀三维连通孔道结构的纳米多孔金属材料。经电化学测试表明,恒电位0.72V获得的纳米多孔材料,在0.5mol/L H_2SO4+0.5mol/L HCOOH溶液的循环伏安曲线中,较原非晶合金的氧化峰电压负移约0.4V,氧化峰电流密度提高约15倍,该纳米多孔材料对甲酸的分解有明显的催化性能。     

Vapor Phase Dealloying Derived Nanoporous Co@CoO/RuO2 Composites for Efficient and Durable Oxygen Evolution Reaction (Adv. Funct. Mater. 17/2023)

The development of low-cost and effective oxygen evolution reaction (OER) electrocatalysts to expedite the slow kinetics of water splitting is crucial for increasing the efficiency of energy conversion from electricity to hydrogen fuel. Herein, 3D bicontinuous nanoporous Co@CoO/RuO₂ composites with tunable sizes and chemical compositions are fabricated by introducing vapor phase dealloying of cobalt-based alloys. The influence of physical parameters on the formation of nanoporous Co substrates with various feature ligament sizes is systematically investigated. The CoO/RuO₂ shell is constructed by integrating a thin layer of RuO₂ on the inner surface of nanoporous Co, where the CoO interlayer is formed by annealing oxidization. The composite catalyst delivers an ultralow overpotential of 198 mV at 10 mA cm⁻², Tafel slope of 57.1 mV dec⁻¹, and long-term stability of 50 h. The superior OER activity and fast reaction kinetics are attributed to charge transfer through the coupling of Co O Ru bonds at the interface and the excellent nanopore connectivity, while the durability originates from the highly stable CoO/RuO₂ interface.