Tuning Surface Structure of 3D Nanoporous Gold by Surfactant‐Free Electrochemical Potential Cycling

3D dealloyed nanoporous metals have emerged as a new class of catalysts for various chemical and electrochemical reactions. Similar to other heterogeneous catalysts, the surface atomic structure of the nanoporous metal catalysts plays a crucial role in catalytic activity and selectivity. Through surfactant‐assisted bottom‐up synthesis, the surface‐structure modification has been successfully realized in low‐dimensional particulate catalysts. However, the surface modification by top‐down dealloying has not been well explored for nanoporous metal catalysts. Here, a surfactant‐free approach to tailor the surface structure of nanoporous gold by surface relaxation via electrochemical redox cycling is reported. By controlling the scan rates, nanoporous gold with abundant {111} facets or {100} facets can be designed and fabricated with dramatically improved electrocatalysis toward the ethanol oxidation reaction.     

Dealloying by metallic melt

Dealloying, which commonly involves corrosion processes in aqueous solutions, is a promising technique for preparing functional nanoporous metals. While this technique is ideal for preparing nanoporous noble metals such as of Au, it is not readily applicable to less-noble metals. Here, we propose a novel dealloying method employing a metallic melt, instead of an aqueous solution, as the dealloying liquid for a preparing of nanoporous metals. An atomic interaction among alloy components and metallic melt causes specific component to dissolve out from the alloy solid into the melt with self-organizing nanoporous structure by the remaining component. The dealloying method can be applied for preparation of nanoporous less-noble metal such as of Ti for the development of functional materials such as fluid filters, gas absorption media, and biomaterials.     

Hierarchical Nanoporous Copper Architectures via 3D Printing Technique for Highly Efficient Catalysts

Nanoporous metals represent a class of functional materials with unique bicontinuous open porous structural properties, making them ideal candidates for various catalyst applications. However, the pursuit of nanoporous properties, extremely small pores, and high surface area, results in the restriction of mass transport. Herein, a free‐standing hierarchical nanoporous Cu material, prepared by a selective laser melting 3D printing technique and a one‐step dealloying process, is presented as a highly efficient electrocatalyst for methanol oxidation. It is demonstrated that the digitally controlled hierarchical structure with macro‐ and nano‐scaled pores can be utilized for promoting and directing mass transport as well as for the enhancement of catalytic properties. This work highlights a facile, low‐cost, and alternative strategy for hierarchical nanoporous structure design that can be applied to binary, ternary, and quaternary metal alloys for various functional applications.     

Facile synthesis of metal and alloy nanoparticles by ultrasound-assisted dealloying of metallic glasses

Metal and alloy nanoparticles synthesized by chemical reduction have attracted increasing attention due to their superior physical,chemical,and biological properties.However,most chemical synthesis processes rely on the use of harsh reducing agents and complicated chemical ingredients.Herein,we report a novel reduction-agent-free and surfactant(stabilizer)-free strategy to synthesize Cu,Ag,Au,Cu-Pt,Cu-Au,Cu-Au-Pt-Pd,and Au-Pt-Pd-Cu nanoparticles by ultrasound-assisted dealloying of Mg-based metallic glasses.The formation mechanism of the metal and alloy nanoparticles is revealed by a detailed investigation of sequential intermediate products.We demonstrate that the glass-liquid phase transition of the initially dealloying metallic glasses,together with the synergistic effect of dealloying and ultrasound-driven ligament-breakage of small enough nanoporous intermediates,play key roles in preparing the uniformly dispersed metal and alloy nanoparticles.This approach greatly simplifies the up-scaling synthesis of monometallic and bimetallic nanoparticles,and also provides a general strategy for synthesizing unprecedented multimetallic nanoparticles.     

Ultrasmall Metal Nanoparticles Confined within Crystalline Nanoporous Materials: A Fascinating Class of Nanocatalysts

Crystalline nanoporous materials with uniform porous structures, such as zeolites and metal–organic frameworks (MOFs), have proven to be ideal supports to encapsulate ultrasmall metal nanoparticles (MNPs) inside their void nanospaces to generate high‐efficiency nanocatalysts. The nanopore‐encaged metal catalysts exhibit superior catalytic performance as well as high stability and catalytic shape selectivity endowed by the nanoporous matrix. In addition, the synergistic effect of confined MNPs and nanoporous frameworks with active sites can further promote the catalytic activities of the composite catalysts. Herein, recent progress in nanopore‐encaged metal nanocatalysts is reviewed, with a special focus on advances in synthetic strategies for ultrasmall MNPs (<5 nm), clusters, and even single atoms confined within zeolites and MOFs for various heterogeneous catalytic reactions. In addition, some advanced characterization methods to elucidate the atomic‐scale structures of the nanocatalysts are presented, and the current limitations of and future opportunities for these fantastic nanocatalysts are also highlighted and discussed. The aim is to provide some guidance for the rational synthesis of nanopore‐encaged metal catalysts and to inspire their further applications to meet the emerging demands in catalytic fields.     

脱合金法制备纳米多孔镍材料研究进展

纳米多孔金属镍材料的研制成功,开拓了多孔金属新的应用领域。综述了脱合金法从Ni—Al合金中制备纳米多孔镍材料的必要条件,并十分析了脱元素法和脱相法各自的特点。脱元素法获得的纳米多孔镍的结构是三维无序内部互连通孔结构,而脱相法会产生原有的γ相或γ’相与多孔结构互相交织的网状结构,其中互通孔道大多为几百纳米宽。脱相法是个电化学控制的过程,脱元素法不需要加电压。同时,指出了纳米多孔镍基材料的应用领域及今后的研究方向。     

纳米多孔金属力学性能的若干研究进展

纳米多孔金属是近年来发展起来的一类具有纳米级双连续孔洞和高表面积的新型功能材料,具备如化学性能、力学性能、表面拉曼散射性能等多方面的优异特性,在催化、传感、新能源、生物医学等诸多领域拥有广阔的应用前景。围绕纳米多孔金属的制备、力学性能和尺度特性等,展开细述了相关的研究工作,并重点针对力学性能方面的研究进展,如尺度方程、破坏机理、表面效应和表面应力,以及脱合金制备方法和制备过程中的力学问题进行了讨论,并对将来的研究方向进行了展望。     

Hierarchical nanoporous metals as a path toward the ultimate three-dimensional functionality

Abstract

Nanoporous metals prepared via dealloying or selective leaching of solid solution alloys and compounds represent an emerging class of materials. They possess a three-dimensional (3D) structure of randomly interpenetrating ligaments/nanopores with sizes between 5 nm and several tens of micrometers, which can be tuned by varying their preparation conditions (such as dealloying time and temperature) or additional thermal coarsening. As compared to other nanostructured materials, nanoporous metals have many advantages, including their bicontinuous structure, tunable pore sizes, bulk form, good electrical conductivity, and high structural stability. Therefore, nanoporous metals represent ideal 3D materials with versatile functionality, which can be utilized in various fields. In this review, we describe the recent applications of nanoporous metals in molecular detection, catalysis, 3D graphene synthesis, hierarchical pore formation, and additive manufacturing (3D printing) together with our own achievements in these areas. Finally, we discuss possible ways of realizing the ultimate 3D functionality beyond the scope of nanoporous metals.     

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.     

Strategies for Improving the Functionality of Zeolitic Imidazolate Frameworks: Tailoring Nanoarchitectures for Functional Applications

Zeolitic imidazolate frameworks (ZIFs), a subclass of metal–organic frameworks (MOFs) built with tetrahedral metal ions and imidazolates, offer permanent porosity and high thermal and chemical stabilities. While ZIFs possess some attractive physical and chemical properties, it remains important to enhance their functionality for practical application. Here, an overview of the extensive strategies which have been developed to improve the functionality of ZIFs is provided, including linker modifications, functional hybridization of ZIFs via the encapsulation of guest species (such as metal and metal oxide nanoparticles and biomolecules) into ZIFs, and hybridization with polymeric matrices to form mixed matrix membranes for industrial gas and liquid separations. Furthermore, the developed strategies for achieving size and shape control of ZIF nanocrystals are considered, which are important for optimizing the textural characteristics as well as the functional performance of ZIFs and their derived materials/hybrids. Moreover, the recent trends of using ZIFs as templates for the derivation of nanoporous hybrid materials, including carbon/metal, carbon/oxide, carbon/sulfide, and carbon/phosphide hybrids, are discussed. Finally, some perspectives on the potential future research directions and applications for ZIFs and ZIF‐derived materials are offered.     

Hydrogen Isotope Separation in Confined Nanospaces: Carbons,Zeolites, Metal–Organic Frameworks,and Covalent Organic Frameworks

One of the greatest challenges of modern separation technology is separating isotope mixtures in high purity. The separation of hydrogen isotopes can create immense economic value by producing valuable deuterium (D) and tritium (T), which are irreplaceable for various industrial and scientific applications. However, current separation methods suffer from low separation efficiency owing to the similar chemical properties of isotopes; thus, high‐purity isotopes are not easily achieved. Recently, nanoporous materials have been proposed as promising candidates and are supported by a newly proposed separation mechanism, i.e., quantum effects. Herein, the fundamentals of the quantum sieving effect of hydrogen isotopes in nanoporous materials are discussed, which are mainly kinetic quantum sieving and chemical‐affinity quantum sieving, including the recent advances in the analytical techniques. As examples of nanoporous materials, carbons, zeolites, metal–organic frameworks, and covalent organic frameworks are addressed from computational and experimental standpoints. Understanding the quantum sieving effect in nanospaces and the tailoring of porous materials based on it will open up new opportunities to develop a highly efficient and advanced isotope separation systems.     

Nanopore-Supported Metal Nanocatalysts for Efficient Hydrogen Generation from Liquid-Phase Chemical Hydrogen Storage Materials

Hydrogen has emerged as an environmentally attractive fuel and a promising energy carrier for future applications to meet the ever-increasing energy challenges. The safe and efficient storage and release of hydrogen remain a bottleneck for realizing the upcoming hydrogen economy. Hydrogen storage based on liquid-phase chemical hydrogen storage materials is one of the most promising hydrogen storage techniques, which offers considerable potential for large-scale practical applications for its excellent safety, great convenience, and high efficiency. Recently, nanopore-supported metal nanocatalysts have stood out remarkably in boosting the field of liquid-phase chemical hydrogen storage. Herein, the latest research progress in catalytic hydrogen production is summarized, from liquid-phase chemical hydrogen storage materials, such as formic acid, ammonia borane, hydrous hydrazine, and sodium borohydride, by using metal nanocatalysts confined within diverse nanoporous materials, such as metal–organic frameworks, porous carbons, zeolites, mesoporous silica, and porous organic polymers. The state-of-the-art synthetic strategies and advanced characterizations for these nanocatalysts, as well as their catalytic performances in hydrogen generation, are presented. The limitation of each hydrogen storage system and future challenges and opportunities on this subject are also discussed. References in related fields are provided, and more developments and applications to achieve hydrogen energy will be inspired.     

General synthesis of sponge-like ultrafine nanoporous metals by dealloying in citric acid

A general method is proposed to synthesize ultrafine nanoporous Cu,Ag,and Ni with novel sponge-like morphologies,high porosities,and large surface areas.The materials are produced by dealloying Mg65M25Y10 (M =Cu,Ag,and Ni) metallic glasses in citric acid.Citric acid played a key role due to its capping effect,which reduced the surface diffusion of metals.A structural model consistent with the sponge-like morphology was constructed to calculate the porosity and the surface area.The mechanism of the dealloying process in dtric add,involving ligament formation and coarsening,was illustrated.The mechanism was capable of explaining the experimental trends of dealloying,especially the morphology.A glucose sensor,which can be further developed into a high-precision real-time glucose monitor for medical use,was constructed using sponge-like nanoporous copper.Our findings are not only relevant to understanding the dealloying mechanism of metallic glasses,but also provide promising materials for multiple applications.     

Photodegradation of methyl orange under visible light by micro-nano hierarchical Cu2O structure fabricated by hybrid laser processing and chemical dealloying

Micro-nano hierarchical structure on the substrate was fabricated by a hybrid approach including laser deposition, laser ablation and chemical dealloying. The structure consists of micro bumps with a width of 50 μm and a height of 100 μm, and nanoporous structures with a size of 70-150 nm on the micro bumps. XRD and XPS results confirm that these hierarchical structures were made of Cu(2)O. For use in comparison, three additional structures with feature size in milliscale, microscale, and nanoscale were also prepared respectively by the proposed methods. Under visible light, the micro-nano structure exhibited the best performance of photodegradation. It is the result of the large specific surface and the catalytic reaction driven by the cuprous oxides.     

Facile fabrication of ultrathin freestanding nanoporous Cu and Cu-Ag films with high SERS sensitivity by dealloying Mg-Cu(Ag)-Gd metallic glasses

Nanoporous metals prepared by dealloying have attracted increasing attention due to their interesting size-dependent physical,chemical,and biological properties.However,facile fabrication of metallic ultra-thin freestanding nanoporous films(UF-NPFs)by dealloying is still challenging.Herein,we report a novel strategy of facile preparation of flexible Cu,Cu3Ag,and CuAg UF-NPFs by dealloying thick Mg-Cu(Ag)-Gd metallic glass ribbons.During dealloying,the local reaction latent heat-induced glass transition of the precursor ribbons leads to the formation of a solid/liquid interface between the initially dealloyed nanoporous layer and the underlying supercooled liquid layer.Due to the bulging effect of in situ gen-erated H2 on the solid/liquid interface,Cu,Cu3Ag,and CuAg UF-NPFs with thicknesses of～200 nm can self-peel off from the outer surface of the dealloying ribbons.Moreover,it was found that the surface-enhanced Raman scattering(SERS)detection limit of Rhodamine 6G(R6G)on the Cu and CuAg UF-NPF substrates are 10-6 M and 10-11 M,respectively,which are lower than most of the Cu and Cu-Ag sub-strates prepared by other methods.This work presents a reliable simple strategy to synthesize a variety of cost effective and flexible metallic UF-NPFs for functional applications.     

Fabrication of nanoporous Cu-Pt(Pd) core/shell structure by galvanic replacement and its application in electrocatalysis

We describe a general strategy to fabricate a new type of nanoporous core/shell structured bimetallic nanocomposites with controllable metal components. Nanoporous copper (NPC) obtained by dealloying Cu/Al alloy is used as both reducing agent and three-dimensional substrate. Electron microscope and X-ray diffraction characterizations demonstrated that a simply galvanic-replacement reaction with H(2)PtCl(6) aqueous solution can easily generate nanoporous core/shell structure with a thin Pt/Cu alloy shell and Cu (or Pt/Cu alloy) core. The morphology and crystal structure evolution of the nanocomposites are studied and discussed in detail. The as-prepared bimetallic PtCu nanocomposites show greatly enhanced catalytic activity and stability toward methanol electro-oxidation as compared with commercial Pt/C catalyst. This facile in situ preparation strategy is also suitable for large-scale production of this novel and inexpensive catalyst.     

硼基材料在锂硫电池中的研究进展

锂硫电池因其高能量密度和低成本等优势成为新一代电化学储能技术的重要发展方向.然而,其较低的转换反应动力学和可逆性导致电池的实际容量、库仑效率和循环稳定性等仍难以满足实用化发展需求.对此,合理设计和开发具有导电、吸附、催化特性的功能材料是稳定和促进硫电化学反应的关键途径.得益于硼独特的原子和电子结构,硼基材料具有丰富且可...     

Fabrication of nanoporous silver and microstructural change during dealloying of melt-spun Al–20 at.%Ag in hydrochloric acid

Ag nanoporous structure has been fabricated by dealloying of Al–20 at.%Ag in 2 M HCl at room temperature. We describe the changes of phase constitution and microstructural morphology during the dealloying. The bi-phase structure of α-Al and γ-Ag₂Al was obtained using melt-spinning, and considerable amount of γ-Ag₂Al was suppressed. According to the phase quantitative analysis, 5.6 % γ-Ag₂Al was precipitated at the grain boundary and inside the grain. At the early stage of dealloying process, the deep channel occurred at the interface of α-Al and γ-Ag₂Al due to concentration gradient of Ag; and then, α-Al was preferentially dealloyed with comparison to γ-Ag₂Al and formed 3-dimensional nanoporous structure which showed the open-pore/ligament bi-continuous structure. After 720 min, γ-Ag₂Al was dealloyed and formed 2-dimensional pored-wall structure. At the end of dealloying reaction, the initial grain/intermetallic wall structure was maintained. The Ag nanoporous structure was gradually coarsened with the increase of dealloying time, from 25 ± 5 nm at 20 min to 113 ± 22 nm at 720 min. The calculated coefficient of surface diffusion of Ag was 2.34 × 10^?17 m²/s. The surface diffusivity of Ag obtained in this study showed two orders of magnitude higher than the Au dealloyed from Au–Ag precursor at the similar temperature.     

脱合金化制备纳米多孔Ni-Fe合金及其电催化性能

采用真空熔炼与固溶相结合的方法获得原子分数为Ni_30-xFe_xMn₇₀(x=0,10,20)的前驱体合金,通过脱合金化方法制备纳米多孔Ni及Ni-Fe合金,采用X射线衍射(XRD)、扫描电子显微镜(SEM)分析合金相组成和微观结构,运用线性扫描伏安法、交流阻抗、方波电位法及计时电位法研究电极的析氢电催化性能。结果表明:加入Fe获得了片状结构的纳米多孔Ni-Fe合金,提高了纳米多孔Ni的表面积,且Fe与Ni产生协同效应,能够有效提高合金的析氢电催化活性。当Fe含量为10%(原子分数)时,脱合金化得到的纳米多孔Ni-Fe合金表面积最大,析氢电催化性能最好,在0.1A/cm^2电流密度下,析氢过电位仅56mV,经10h连续电解,表现出良好的电催化活性和电化学稳定性。     

Casting Nanoporous Platinum in Metal–Organic Frameworks

Nanocasting based on porous templates is a powerful strategy in accessing materials and structures that are difficult to form by bottom‐up syntheses in a controlled fashion. A facile synthetic strategy for casting ordered, nanoporous platinum (NP‐Pt) networks with a high degree of control by using metal–organic frameworks (MOFs) as templates is reported here. The Pt precursor is first infiltrated into zirconium‐based MOFs and subsequently transformed to 3D metallic networks via a chemical reduction process. It is demonstrated that the dimensions and topologies of the cast NP‐Pt networks can be accurately controlled by using different MOFs as templates. The Brunauer–Emmett–Teller surface areas of the NP‐Pt networks are estimated to be >100 m² g^?1 and they exhibit excellent catalytic activities in the methanol electrooxidation reaction (MEOR). This new methodology presents an attractive route to prepare well‐defined nanoporous materials for diverse applications ranging from energy to sensing and biotechnology.