Nanoporous Surface High-Entropy Alloys as Highly Efficient Multisite Electrocatalysts for Nonacidic Hydrogen Evolution Reaction

Electrocatalytic hydrogen evolution in alkaline and neutral media offers the possibility of adopting platinum-free electrocatalysts for large-scale electrochemical production of pure hydrogen fuel, but most state-of-the-art electrocatalytic materials based on nonprecious transition metals operate at high overpotentials. Here, a monolithic nanoporous multielemental CuAlNiMoFe electrode with electroactive high-entropy CuNiMoFe surface is reported to hold great promise as cost-effective electrocatalyst for hydrogen evolution reaction (HER) in alkaline and neutral media. By virtue of a surface high-entropy alloy composed of dissimilar Cu, Ni, Mo, and Fe metals offering bifunctional electrocatalytic sites with enhanced kinetics for water dissociation and adsorption/desorption of reactive hydrogen intermediates, and hierarchical nanoporous Cu scaffold facilitating electron transfer/mass transport, the nanoporous CuAlNiMoFe electrode exhibits superior nonacidic HER electrocatalysis. It only takes overpotentials as low as ≈240 and ≈183 mV to reach current densities of ≈1840 and ≈100 mA cm⁻² in 1 m  KOH and pH 7 buffer electrolytes, respectively; ≈46- and ≈14-fold higher than those of ternary CuAlNi electrode with bimetallic Cu–Ni surface alloy. The outstanding electrocatalytic properties make nonprecious multielemental alloys attractive candidates as high-performance nonacidic HER electrocatalytic electrodes in water electrolysis.     

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.     

纳米多孔金电化学传感器构建及其对饮品中抗坏血酸的检测

基于纳米多孔金（nanoporous gold，NPG）对抗坏血酸的强电催化氧化作用，通过酸腐蚀制备NPG，构建纳米多孔电极（NPG/GCE）检测饮料中的抗坏血酸。通过循环伏安法和差分脉冲伏安（differential pulse voltammetry，DPV）法对抗坏血酸检测条件进行优化，确定最佳检测条件为pH 4.0的柠檬酸缓冲液。在优化条件下，利用DPV法对抗坏血酸进行检测，结果表明：在6.652 8～160 μg/mL的范围内，峰电流密度与抗坏血酸质量浓度呈良好的线性关系；该电极制备简单、灵敏度高、稳定性和抗干扰能力强，对饮料中抗坏血酸的快速检测有良好的应用潜力。     

Nanoporous copper sonocatalysts prepared by dealloying Cu–Al–Ti amorphous ribbons

ABSTRACT

Nanoporous copper (NPC) with a controllable ligament width was prepared by chemically dealloying Cu₄₅Al₄₅Ti₁₀ amorphous ribbons in dilute HCl solution. X-ray diffraction and scanning electron microscopy analysis confirmed the 3D, bicontinuous, nanoporous structure constituting fcc-Cu ligaments of 39–79?nm thickness. The coarsening of NPC ligaments increased significantly with an increase of HCl concentration, reaction temperature or time. The surface diffusivity and activation energy of NPC were also calculated. Finally, the catalytic activity of NPC was validated with the ultrasound and H₂O₂-assisted degradation of methyl orange (MO), where 99% MO was degraded within 15?min.     

基于正交实验优化不锈钢表面纳米孔结构制备工艺

目的通过正交实验优化不锈钢表面纳米孔制备工艺。方法通过田口实验方法设计正交试验优化工艺。采用含有氯化钠和硫脲的硝酸溶液阳极氧化制备纳米孔,在含有氯化钠、盐酸和硫酸的水溶液中进行扩孔处理。通过扫描电子显微镜、能谱仪对表面处理后的试样表面形貌和元素进行分析,应用软件统计SEM图片孔隙率,并将孔隙率作为响应指标,利用极差分析和方差分析研究阳极氧化工艺和扩孔时间对表面形貌及孔隙率的影响,并优化工艺参数。结果 SEM照片和5个水平的均值表明,硝酸浓度的提高有利于提高孔隙率,较高的硫脲浓度有利于形成均匀有序的纳米孔结构,氯化钠浓度、氧化时间、氧化电压和扩孔时间对表面形貌和孔隙率影响不明显。元素分析表明,纳米孔的材料仍然是不锈钢,而不是金属氧化物。正交实验优化的工艺参数是:硝酸的体积浓度为90 mL/L,硫脲的质量浓度为3.5 g/L,氯化钠的质量浓度为20 g/L,氧化时间为120 s,氧化电压为5.0 V,扩孔时间为50 s。结论通过实验验证,优化后的工艺能够制备出表面较平整、孔隙率较高的纳米孔结构。     

Oxygen Reduction Reaction Performance of [MTBD][beti]‐Encapsulated Nanoporous NiPt Alloy Nanoparticles

Recent advances in oxygen reduction reaction catalysis for proton exchange membrane fuel cells (PEMFCs) include i) the use of electrochemical dealloying to produce high surface area and sometimes nanoporous catalysts with a Pt‐enriched outer surface, and ii) the observation that oxygen reduction in nanoporous materials can be potentially enhanced by confinement effects, particularly if the chemical environment within the pores can bias the reaction toward completion. Here, these advances are combined by incorporating a hydrophobic, protic ionic liquid, [MTBD][beti], into the pores of high surface‐area NiPt alloy nanoporous nanoparticles (np‐NiPt/C + [MTBD][beti]). The high O₂ solubility of the [MTBD][beti], in conjunction with the confined environment within the pores, biases reactant O₂ toward the catalytic surface, consistent with an increased residence time and enhanced attempt frequencies, resulting in improved reaction kinetics. Half‐cell measurements show the np‐NiPt/C+[MTBD][beti] encapsulated catalyst to be nearly an order of magnitude more active than commercial Pt/C, a result that is directly translated into operational PEMFCs.     

改性纳米多孔钴低温催化二氧化碳加氢制甲醇

低温条件下二氧化碳（CO2）加氢制甲醇（CH3OH）被认为是一项重要且仍具挑战性的工作，本文制备了纳米多孔钴（NP-Co）及改性纳米多孔钴NP-CoxM（M=Cr，V，Mo，Mn，Ce，W，x=nCo∶nM）催化剂，评价其在60-140 ℃的温和条件下催化CO2加氢制CH3OH，铬作为改性元素显著提高了催化剂性能。采用N2-物理吸脱附、SEM、TEM、XRD、XPS和CO2-TPD对NP-Co、NP-Co3Cr进行表征，结果显示CrxO作为改性组分显著增强了CO2与活性位点之间的强相互作用、表面羟基的大量增加促进了CO2低温活化，具体表现为采用NP-Co3Cr的表观活化能（59.08 kJ/mol）相比NP-Co（89.12 kJ/mol）显著降低。CH3OH作为主要产物，其60 ℃下的时间收率为106.4 μmol/（gCat.·h）且选择性达92.8%，相同反应条件下的NP-Co则未观察到CH3OH生成。     

Core–Sheath Wet Electrospinning of Nanoporous Polycaprolactone Microtubes to Mimic Fenestrated Capillaries

Formation of capillary vessel structures in scaffolds is critical for engineering various tissues and organs. Various biofabrication techniques are developed in recent years to create scaffolds integrated with perfusion channels. However, rapid fabrication of artificial capillary vessels (<10 µm) still remains challenging. In this study, a novel electrospinning approach is developed to fabricate nanoporous polycaprolactone microtubes as potential functional capillaries. The results show that ambient environment parameters and solution properties affect the pore formation and tube morphology. Porous microbeads, helical fibers, and microtubes were fabricated under different processing conditions. The optimal tubular structure is obtained with consistent viscosities between the core and the sheath solutions. The biomimetic nanoporous microtubes hold great potential for vascularization in tissue engineering.