Chemical Dealloying Mechanism of Bimetallic Pt–Co Nanoparticles and Enhancement of Catalytic Activity toward Oxygen Reduction

The chemical dealloying mechanism of bimetallic Pt–Co nanoparticles (NPs) and enhancement of their electrocatalytic activity towards the oxygen reduction reaction (ORR) have been investigated on a fundamental level by the combination of X‐ray absorption spectroscopy (XAS) and aberration‐corrected scanning transmission electron microscopy (STEM). Structural parameters, such as coordination numbers, alloy extent, and the unfilled d states of Pt atoms, are derived from the XAS spectra, together with the compositional variation analyzed by line‐scanning energy‐dispersive X‐ray spectroscopy (EDX) on an atomic scale, to gain new insights into the dealloying process of bimetallic Pt–Co NPs. The XAS results on acid‐treated Pt–Co/C NPs reveal that the Co–Co bonding in the bimetallic NPs dissolves first and the remaining morphology gradually transforms to a Pt‐skin structure. From cyclic voltammetry and mass activity measurements, Pt–Co alloy NPs with a Pt‐skin structure significantly enhance the catalytic performance towards the ORR. Further, it is observed that such an imperfect Pt‐skin surface feature will collapse due to the penetration of electrolyte into layers underneath and cause further dissolution of Co and the loss of Pt. The electrocatalytic activity decreases accordingly, if the dealloying process lasts for 4 h. The findings not only demonstrate the importance of appropriate treatment of bimetallic catalysts, but also can be referred to other Pt bimetallic alloys with transition metals.     

Mechanistic study on the replacement reaction between silver nanostructures and chloroauric acid in aqueous medium

The replacement reaction between silver nanostructures and an aqueous HAuCl(4) solution has recently been demonstrated as a versatile method for generating metal nanostructures with hollow interiors. Here we describe the results of a systematic study detailing the morphological, structural, compositional, and spectral changes involved in such a heterogeneous reaction on the nanoscale. Two distinctive steps have been resolved through a combination of microscopic and spectroscopic methods. In the first step, silver nanostructure (i.e., the template) is dissolved to generate gold atoms that are deposited epitaxially on the surface of each template. Silver atoms also diffuse into the gold shell (or sheath) to form a seamless, hollow nanostructure with its wall made of Au-Ag alloys. The second step involves dealloying, a process that selectively removes silver atoms from the alloyed wall, induces morphological reconstruction, and finally leads to the formation of pinholes in the walls. Reaction temperature was found to play an important role in the replacement reaction because the solubility constant of AgCl and the diffusion coefficients of Ag and Au atoms were both strongly dependent on this parameter. This work has enabled us to prepare metal nanostructures with controllable geometric shapes and structures, and thus optical properties (for example, the surface plasmon resonance peaks could be readily shifted from 500 to 1200 nm by controlling the ratio between Ag and HAuCl(4)).     

One‐Step Synthesis of Small‐Sized and Water‐Soluble NaREF4 Upconversion Nanoparticles for In Vitro Cell Imaging and Drug Delivery

Small (2–28 nm) NaREF₄ (rare earth (RE)=Nd–Lu, Y) nanoparticles (NPs) were prepared by an oil/water two‐phase approach. Meanwhile, hydrophilic NPs can be obtained through a successful phase‐transition process by introducing the amphiphilic surfactant sodium dodecylsulfate (SDS) into the same reaction system. Hollow‐structured NaREF₄ (RE=Y, Yb, Lu) NPs can be fabricated in situ by electron‐beam lithography on solid NPs. The MTT assay indicates that these hydrophilic NPs with hollow structures exhibit good biocompatibility. The as‐prepared hollow‐structured NPs can be used as anti‐cancer drug carriers for drug storage/release investigations. Doxorubicin hydrochloride (DOX) was taken as model drug. The release of DOX from hollow α‐NaLuF₄:20 % Yb³⁺, 2 % Er³⁺ exhibits a pH‐sensitive release patterns. Confocal microscopy observations indicate that the NPs can be taken up by HeLa cells and show obvious anti‐cancer efficacy. Furthermore, α‐NaLuF₄:20 % Yb³⁺, 2 % Er³⁺ NPs show bright‐red emission under IR excitation, making both the excitation and emission light fall within the “optical window” of biological tissues. The application of α‐NaLuF₄:20 % Yb³⁺, 2 % Er³⁺ in the luminescence imaging of cells was also investigated, which shows a bright‐red emission without background noise.     

Modification of palladium–copper thin film by reduced graphene oxide or platinum as catalyst for Suzuki–Miyaura reactions

This study describes the synthesis of PdCu, PdCu/reduced graphene oxide and PtPdCu nanoparticle thin films via a simple reduction of organometallic precursors including [PtCl₂(cod)] and [PdCl₂(cod)] (cod = cis ,cis ‐1,5‐cyclooctadiene) complexes, in the presence of [Cu(acac)₂] (acac = acetylacetonate) complex at toluene–water interface. The structure and morphology of the thin films were characterized using energy‐dispersive analysis of X‐rays, X‐ray diffraction and transmission electron microscopy techniques. Our studies show that all of these nanoparticles are suitable for the Suzuki–Miyaura coupling (SMC) reaction in water. PtPdCu and PdCu thin films showed higher catalytic activity compared to Pd thin film in the SMC reaction due to the appropriate interaction among palladium, platinum and copper metals.     

Defect‐Rich Copper‐doped Ruthenium Hollow Nanoparticles for Efficient Hydrogen Evolution Electrocatalysis in Alkaline Electrolyte

It is of great importance to develop highly e?cient and stable Pt‐free catalysts for electrochemical hydrogen generation from water electrolysis. Here, monodisperse 7.5 nm copper‐doped ruthenium hollow nanoparticles (NPs) with abundant defects and amorphous/crystalline hetero‐phases were prepared and employed as efficient hydrogen evolution electrocatalysts in alkaline electrolyte. Specifically, these NPs only require a low overpotential of 25 mV to achieve a current density of 10 mA cm^?2 in 1.0 M KOH and show acceptable stability after 2000 potential cycles, which represents one of the best Ru‐based electrocatalysts for hydrogen evolution. Mechanism analysis indicates that Cu incorporation can modify the electronic structure of Ru shell, thereby optimizing the energy barrier for water adsorption and dissociation processes or H adsorption/desorption. Cu doping paired with the defect‐rich and highly open hollow structure of the NPs greatly enhances hydrogen evolution activity.     

Highly active nanoreactors: nanomaterial encapsulation based on confined catalysis

It happens inside: highly active nanoreactors are prepared by encapsulating dendritic Pt nanoparticles (NPs) grown on a polystyrene template inside hollow porous silica capsules. The catalytic activity of these Pt NPs is preserved after encapsulation and template removal. Different metals, such as Ni, can thus be reduced inside the capsules, thereby leading to the formation of composites with tunable magnetic properties.     

CoPt纳米空心球甲醇电催化氧化和原位电化学傅里叶变换红外光谱研究

采用化学还原和电位置换法制备了CoPt 纳米空心球, 该催化剂对甲醇氧化表现出较好的电催化活性.透射电镜(TEM)、能量散射光谱(EDS)和电化学循环伏安实验结果表明, 在0.1 mol·L^-1 H₂SO₄+0.1 mol·L^-1CH₃OH中进行测试时, CoPt 纳米空心球发生了去合金化过程, 催化剂表面Co元素溶解, 形成了富Pt 表面, 表现出更好的电催化活性, 同时表现出较好的结构稳定性. 采用原位电化学红外光谱在分子水平研究了CoPt 纳米空心球上甲醇氧化过程, 发现甲醇在CoPt 纳米空心球氧化中间产物主要为CO, 且CO表现出异常红外效应, 与CO为探针分子在CoPt纳米空心球上得到的红外光谱结果一致. 研究结果表明, 去合金化方法是一种有效调节催化剂表面组成和性能的手段, 原位电化学红外光谱是潜在的原位研究有机小分子氧化机理的方法, 在燃料电池中将得到广泛的应用.     

A Facile Process for the Preparation of Three‐Dimensional Hollow Zn(OH)2 Nanoflowers at Room Temperature

A facile strategy has been developed to synthesize double‐shelled Zn(OH)₂ nanoflowers (DNFs) at room temperature. The nanoflowers were generated via conversion of Cu₂O nanoparticles (NPs) using ZnCl₂ and Na₂S₂O₃ by a simple process. Outward diffusion of the Cu²⁺, produced by an oxidation process on the surface of NPs, and the inward diffusion of Zn²⁺ by coordination and migration, eventually lead to a hollow cavity in the inner NPs with a double‐shelled 3D hollow flower shapes. The thickness of the inner and outer shells is estimated to be about 20 nm, and the thickness of nanopetals is about 7 nm. The nanoflowers have large surface areas and excellent adsorption properties. As a proof of potential applications, the DNFs exhibited an excellent ability to remove organic molecules from aqueous solutions.     

Bioorthogonal oxime ligation mediated in vivo cancer targeting

Current cancer targeting relying on specific biological interaction between the cell surface antigen and respective antibody or its analogue has proven to be effective in the treatment of different cancers; however, this strategy has its own limitations, such as the heterogeneity of cancer cells and immunogenicity of the biomacromolecule binding ligands. Bioorthogonal chemical conjugation has emerged as an attractive alternative to biological interaction for in vivo cancer targeting. Here, we report an in vivo cancer targeting strategy mediated by bioorthogonal oxime ligation. An oxyamine group, the artificial target, is introduced onto 4T1 murine breast cancer cells through liposome delivery and fusion. Poly(ethylene glycol)-polylactide (PEG-PLA) nanoparticles (NPs) are surface-functionalized with aldehyde groups as targeting ligands. The improved in vivo cancer targeting of PEG-PLA NPs is achieved through specific and efficient chemical reaction between the oxyamine and aldehyde groups.     

One-Pot Fabrication of Pd Nanoparticles@Covalent-Organic-Framework-Derived Hollow Polyamine Spheres as a Synergistic Catalyst for Tandem Catalysis

Facile fabrication of nanocatalysts consisting of metal nanoparticles (NPs) anchored on a functional support is highly desirable, yet remains challenging. Covalent organic frameworks (COFs) provide an emerging materials platform for structural control and functional design. Here, a facile one-pot in situ reduction approach is demonstrated for the encapsulation of small Pd NPs into the shell of COF-derived hollow polyamine spheres (Pd@H-PPA). In the one-pot synthetic process, the nucleation and growth of Pd NPs in the cavities of the porous shell take place simultaneously with the reduction of imine linkages to secondary amine groups. Pd@H-PPA shows a significantly enhanced catalytic activity and recyclability in the tandem dehydrogenation of ammonia borane and selective hydrogenation of nitroarenes through an adsorption–activation–reaction mechanism. The strong interactions of the secondary amine linkage with borane and nitroarene molecules afford a positive synergy to promote the catalytic reaction. Moreover, the hierarchical structure of Pd@H-PPA allows the accessibility of active Pd NPs to reactants.     

Region‐Selective Deposition of Core–Shell Nanoparticles for 3 D Hierarchical Assemblies by the Huisgen 1,3‐Dipolar Cycloaddition

A method for the region‐selective deposition of nanoparticles (NPs) by the Huisgen 1,3‐dipolar cycloaddition is presented. The approach enables defined stacking of various oxide NPs in any order with control over layer thickness. Thereby the reaction is performed between a substrate, functionalized with a self‐assembled monolayer of an azide‐bearing phosphonic acid (PA) and aluminum oxide (AlO_x) NPs functionalized with an alkyne bearing PA. The layer of alkyne functionalized AlO_x NPs is then used as substrate for the deposition of azide‐functionalized indium tin oxide (ITO) NPs to provide a binary stack. This progression is then conducted with alkyne‐functionalized CeO₂ NPs, yielding a ternary stack of NPs with three different NP cores. The stacks are characterized by AFM and SEM, defining the region‐selectivity of the deposition technique. Finally, these assemblies have been tested in devices as a dielectric to form a capacitor resulting in a dramatic increase in the measured capacitance.     

Charge-driven flocculation of poly(L-lysine)-gold nanoparticle assemblies leading to hollow microspheres

An unusual aggregation phenomenon that involves positively charged poly(L-lysine) (PLL) and negatively charged gold nanoparticles (Au NPs) is reported. Discrete, submicrometer-sized spherical aggregates are found to form immediately upon combining a PLL solution with gold sol (diameter approximately 14 nm). These PLL-Au NP assemblies grow in size with time, according to light scattering experiments, which indicates a dynamic flocculation process. Water-filled, silica hollow microspheres (outer diameter approximately microns) are obtained upon the addition of negatively charged SiO2 NPs (diameter approximately 13 nm) to a suspension of the PLL-Au NP assemblies, around which the SiO2 NPs form a shell. Structural analysis through confocal microscopy indicates the PLL (tagged with a fluorescent dye) is located in the interior of the hollow sphere, and mostly within the silica shell wall. The hollow spheres are theorized to form through flocculation, in which the charge-driven aggregation of Au NPs by PLL provides the critical first step in the two-step synthesis process ("flocculation assembly"). The SiO2 shell can be removed and re-formed by decreasing and increasing the suspension pH about the point-of-zero charge of SiO2, respectively.     

Formation of hollow Ni2p nanoparticles based on the nanoscale Kirkendall effect

Colloidal hollow nanoparticles (NPs) of Ni2P have been prepared by a one-pot reaction from a mixture of nickel acetate, oleylamine, trioctylphosphine (TOP), and 1-octadecene. The mechanism to the hollow structure is related to the nanoscale Kirkendall effect. The process contains two important steps. First, oleylamine-stabilized Ni NPs were formed, which can protect them from TOP etching and slow down the inward diffusion of P atoms. Second, the solid-state reaction between the Ni NPs occurred when the TOP concentration and the reaction temperature were correctly adjusted.     

Sandwich‐Structured Graphene–Nickel Silicate–Nickel Ternary Composites as Superior Anode Materials for Lithium‐Ion Batteries

We report the synthesis of sandwich‐structured graphene–nickel silicate–Ni ternary composites by using the solvothermal method followed by a simple in situ reduction procedure. The composites show an interesting structure with graphene sandwiched between two layers of well‐dispersed Ni nanoparticles (NPs) anchored on ultrathin nickel silicate nanosheets. These ternary composites exhibit enhanced performance as anode materials owing to the synergistic effect between the graphene matrix and electrochemically inert Ni nanoparticles, an effect that holds promise for the design and fabrication of other advanced electrode materials.     

Amplification of Lipid Peroxidation by Regulating Cell Membrane Unsaturation To Enhance Chemodynamic Therapy

Lipid peroxidation (LPO) is one of the most damaging processes in chemodynamic therapy (CDT). Although it is well known that polyunsaturated fatty acids (PUFAs) are much more susceptible than saturated or monounsaturated ones to LPO, there is no study exploring the effect of cell membrane unsaturation degree on CDT. Here, we report a self-reinforcing CDT agent (denoted as OA@Fe-SAC@EM NPs), consisting of oleanolic acid (OA)-loaded iron single-atom catalyst (Fe-SAC)-embedded hollow carbon nanospheres encapsulated by an erythrocyte membrane (EM), which promotes LPO to improve chemodynamic efficacy via modulating the degree of membrane unsaturation. Upon uptake of OA@Fe-SAC@EM NPs by cancer cells, Fe-SAC-catalyzed conversion of endogenous hydrogen peroxide into hydroxyl radicals, in addition to initiating the chemodynamic therapeutic process, causes the dissociation of the EM shell and the ensuing release of OA that can enrich cellular membranes with PUFAs, enabling LPO amplification-enhanced CDT.     

Dealloying technique in the synthesis of lithium-ion battery anode materials

In the last decade, dealloying has become a popular and effective strategy to fabricate nanoporous metals used in electrochemical applications such as electrocatalysis and energy storage. This review article summarizes the recent literature on dealloyed non-noble metals and oxides evaluated as lithium-ion battery anode materials. The importance of dealloying parameters to achieve desired pore and ligament sizes is emphasized. A future research roadmap is also provided.     

Quantitative energy dispersive X-ray microanalysis of electron beam-sensitive alloyed nanoparticles.

An energy dispersive X-ray spectrometry (EDXS) method is developed to evaluate the composition of alloyed nanoparticles (NPs) where one of the alloying elements is removed under the electron beam during microanalysis with a transmission electron microscope (TEM). The method is demonstrated for alloyed Au-Ag NPs of a diameter ranging from 6 to 20 nm produced by laser evaporation of a water-suspended Ag-Au powder mixture of varying composition. Series of EDXS spectra are recorded for 30 NPs from samples with five different Ag:Au ratios revealing Ag depletion from NPs during electron irradiation. By studying the evolution of NPs composition as a function of dose, the initial Ag content for each NP is extrapolated. The rate of Ag depletion is discussed in terms of sputtering and knock-on damage. On average, approximately one Ag atom is lost from the NP for each Ag L X-ray detected. To assess the limitations of microanalysis in these sensitive nanoscale structures, the concept of detectability limit is adapted to our method. This benchmark is then evaluated for Ag in Au-Ag NPs of various sizes and acquisition times. This study should be regarded as a guide for the design of analytical TEM measurements of beam-sensitive NPs.     

Function‐Led Design of Aerogels: Self‐Assembly of Alloyed PdNi Hollow Nanospheres for Efficient Electrocatalysis

One plausible approach to endow aerogels with specific properties while preserving their other attributes is to fine‐tune the building blocks. However, the preparation of metallic aerogels with designated properties, for example catalytically beneficial morphologies and transition‐metal doping, still remains a challenge. Here, we report on the first aerogel electrocatalyst composed entirely of alloyed PdNi hollow nanospheres (HNSs) with controllable chemical composition and shell thickness. The combination of transition‐metal doping, hollow building blocks, and the three‐dimensional network structure make the PdNi HNS aerogels promising electrocatalysts for ethanol oxidation. The mass activity of the Pd₈₃Ni₁₇ HNS aerogel is 5.6‐fold higher than that of the commercial Pd/C catalyst. This work expands the exploitation of the electrocatalysis properties of aerogels through the morphology and composition control of its building blocks.     

Synthesis of Hollow Mesoporous TiO2 Microspheres with Single and Double Au Nanoparticle Layers for Enhanced Visible‐Light Photocatalysis

A facile method was used to prepare hollow mesoporous TiO₂ and Au@TiO₂ spheres using polystyrene (PS) templates. Au nanoparticles (NPs) were simultaneously synthesized and attached on the surface of PS spheres by reducing AuCl₄^? ions using sodium citrate which resulted in the uniform deposition of Au NPs. The outer coating of titania via sol‐gel produced PS@Au@TiO₂ core–shell spheres. Removing the templates from these core–shell spheres through calcination produced hollow mesoporous and crystalline Au@TiO₂ spheres with Au NPs inside the TiO₂ shell in a single step. Anatase spheres with double Au NPs layers, one inside and another outside of TiO₂ shell, were also prepared. Different characterization techniques indicated the hollow mesoporous and crystalline morphology of the prepared spheres with Au NPs. Hollow anatase spheres with Au NPs indicated enhanced harvesting of visible light and therefore demonstrated efficient catalytic activity toward the degradation of organic dyes under the irradiation of visible light as compared to bare TiO₂ spheres.     

Facile synthesis of hollow Ti<Subscript>2</Subscript>Nb<Subscript>10</Subscript>O<Subscript>29</Subscript> microspheres for high-rate anode of Li-ion batteries

Titanium niobium oxides emerge as promising anode materials with potential for applications in lithium ion batteries with high safety and high energy density. However, the innate low electronic conductivity of such a composite oxide seriously limits its practical capacity, which becomes a serious concern especially when a high rate charge/discharge capability is expected. Here, using a modified template-assisted synthesis protocol, which features an in-situ entrapment of both titanium and niobium species during the formation of polymeric microsphere followed by a pyrolysis process, we succeed in preparing hollow microspheres of titanium niobium oxide with high efficiency in structural control. When used as an anode material, the structurally-controlled hollow sample delivers high reversible capacity (103.7 mA h g^?1 at 50 C) and extraordinary cycling capability especially at high charge/discharge currents (164.7 mA h g^?1 after 500 cycles at 10 C).