High‐Yield Synthesis of Crystal‐Phase‐Heterostructured 4H/fcc Au@Pd Core–Shell Nanorods for Electrocatalytic Ethanol Oxidation

Noble‐metal nanomaterials are attracting increasing research interest due to their promising applications in electrochemical catalysis, for example. Although great efforts have been devoted to the size‐, shape‐, and architecture‐controlled synthesis of noble‐metal nanomaterials, their crystal‐phase‐controlled synthesis is still in its infancy. Here, for the first time, this study reports high‐yield synthesis of Au nanorods (NRs) with alternating 4H/face‐centered cubic (fcc) crystal‐phase heterostructures via a one‐pot wet‐chemical method. The coexistence of 4H and fcc phases is relatively stable, and the 4H/fcc Au NRs can serve as templates for crystal‐phase‐controlled epitaxial growth of other metals. As an example, bimetallic 4H/fcc Au@Pd core–shell NRs are synthesized via the epitaxial growth of Pd on 4H/fcc Au NRs. Significantly, the 4H/fcc Au@Pd NRs show superior mass activity toward the ethanol oxidation reaction, i.e., 6.2 and 4.9 times those of commercial Pd black and Pt/C catalysts, respectively. It is believed that this new synthetic strategy can be used to prepare other novel catalysts for various promising applications.     

Size‐Dependent Phase Transformation of Noble Metal Nanomaterials

As an important aspect of crystal phase engineering, controlled crystal phase transformation of noble metal nanomaterials has emerged as an effective strategy to explore novel crystal phases of nanomaterials. In particular, it is of significant importance to observe the transformation pathway and reveal the transformation mechanism in situ. Here, the phase transformation behavior of face‐centered cubic (fcc) Au nanoparticles (fcc‐AuNPs), adhering to the surface of 4H nanodomains in 4H/fcc Au nanorods, referred to as 4H‐AuNDs, during in situ transmission electron microscopy imaging is systematically studied. It is found that the phase transformation is dependent on the ratio of the size of the monocrystalline nanoparticle (NP) to the diameter of 4H‐AuND. Furthermore, molecular dynamics simulation and theoretical modeling are used to explain the experimental results, giving a size‐dependent phase transformation diagram which provides a general guidance to predict the phase transformation pathway between fcc and 4H Au nanomaterials. Impressively, this method is general, which is used to study the phase transformation of other metal NPs, such as Pd, Ag, and PtPdAg, adhering to 4H‐AuNDs. The work opens an avenue for selective phase engineering of nanomaterials which may possess unique physicochemical properties and promising applications.     

Syntheses and Properties of Metal Nanomaterials with Novel Crystal Phases

In recent decades, researchers have devoted tremendous effort into the rational design and controlled synthesis of metal nanomaterials with well‐defined size, morphology, composition, and structure, and great achievements have been reached. However, the crystal‐phase engineering of metal nanomaterials still remains a big challenge. Recent research has revealed that the crystal phase of metal nanomaterials can significantly alter their properties, arising from the distinct atomic arrangement and modified electronic structure. Until now, it has been relatively uncommon to synthesize metal nanomaterials with novel crystal phases in spite of the fact that these nanostructures would be promising for various applications. Here, the research progress regarding the fine control of noble metal (Au, Ag, Ru, Rh, Pd) and non‐noble metal (Fe, Co, Ni) nanomaterials with novel crystal phases is reviewed. First, synthesis strategies and their phase transformations are summarized, while highlighting the peculiar characteristics of each element. The phase‐dependent properties are then discussed by providing representative examples. Finally, the challenges and perspectives in this emerging field are proposed.     

Seed‐Induced Growth of Flower‐Like Au–Ni–ZnO Metal–Semiconductor Hybrid Nanocrystals for Photocatalytic Applications

The combination of metal and semiconductor components in nanoscale to form a hybrid nanocrystal provides an important approach for achieving advanced functional materials with special optical, magnetic and photocatalytic functionalities. Here, a facile solution method is reported for the synthesis of Au–Ni–ZnO metal–semiconductor hybrid nanocrystals with a flower‐like morphology and multifunctional properties. This synthetic strategy uses noble and magnetic metal Au@Ni nanocrystal seeds formed in situ to induce the heteroepitaxial growth of semiconducting ZnO nanopyramids onto the surface of metal cores. Evidence of epitaxial growth of ZnO{0001} facets on Ni {111} facets is observed on the heterojunction, even though there is a large lattice mismatch between the semiconducting and magnetic components. Adjustment of the amount of Au and Ni precursors can control the size and composition of the metal core, and consequently modify the surface plasmon resonance (SPR) and magnetic properties. Room‐temperature superparamagnetic properties can be achieved by tuning the size of Ni core. The as‐prepared Au–Ni–ZnO nanocrystals are strongly photocatalytic and can be separated and re‐cycled by virtue of their magnetic properties. The simultaneous combination of plasmonic, semiconducting and magnetic components within a single hybrid nanocrystal furnishes it multifunctionalities that may find wide potential applications.     

Formation of Heteroepitaxy in Different Shapes of Au–CdSe Metal–Semiconductor Hybrid Nanostructures

Formation of heteroepitaxy and designing different‐shaped heterostructured nanomaterials of metal and semiconductor in solution remains a frontier area of research. However, it is evident that the synthesis of such materials is not straightforward and needs a selective approach to retain both metal and semiconductor identities in the reaction system during heterostructure formation. Herein, the epitaxial growth of semiconductor CdSe on selected facets of metal Au seeds is reported and different shapes (flower, tetrapod, and core/shell) hetero‐nanostructures are designed. These results are achieved by controlling the reaction parameters, and by changing the sequence and timing for introduction of different reactant precursors. Direct evidence of the formation of heteroepitaxy between {111} facets of Au and (0001) of wurtzite CdSe is observed during the formation of these three heterostructures. The mechanism of the evolution of these hetero‐nanostructures and formation of their heteroepitaxy with the planes having minimum lattice mismatch are also discussed. This shape‐control growth mechanism in hetero‐nanostructures should be helpful to provide more information for establishing the fundamental study of heteroepitaxial growth for designing new nanomaterials. Such metal–semiconductor nanostructures may have great potential for nonlinear optical properties, in photovoltaic devices, and as chemical sensors.     

Amorphous/Crystalline Hetero‐Phase Pd Nanosheets: One‐Pot Synthesis and Highly Selective Hydrogenation Reaction

Similar to heterostructures composed of different materials, possessing unique properties due to the synergistic effect between different components, the crystal‐phase heterostructures, one variety of hetero‐phase structures, composed of different crystal phases in monometallic nanomaterials are herein developed, in order to explore crystal‐phase‐based applications. As novel hetero‐phase structures, amorphous/crystalline heterostructures are highly desired, since they often exhibit unique properties, and hold promise in various applications, but these structures have rarely been studied in noble metals. Herein, via a one‐pot wet‐chemical method, a series of amorphous/crystalline hetero‐phase Pd nanosheets is synthesized with different crystallinities for the catalytic 4‐nitrostyrene hydrogenation. The chemoselectivity and activity can be fine‐tuned by controlling the crystallinity of the as‐synthesized Pd nanosheets. This work might pave the way to preparing various hetero‐phase nanostructures for promising applications.     

The synthesis and photocatalytic properties of epitaxial SnO2-ZnS nanocomb heterostructure

A growth of SnO₂-ZnS heterostructure was realized by a rational two-step thermal evaporation method. Starting with Sn powder, the SnO₂ bicrystalline nanoribbons were grown on the silicon wafers. The secondary growth of ZnS on the former SnO₂ nanostructures correspondingly resulted in the SnO₂-ZnS nanocomb structures. We investigated the morphology, detailed structure by X-ray diffraction (XRD), scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). It revealed that the ZnS nanobranches with [001] growth direction are epitaxial grown from the (− 101) crystal plane of the SnO₂ trunks with a good lattice match. The nanocomb exhibited an effective photocatalytic activity.     

Gold Microplates with Well‐Defined Shapes

The synthesis and growth mechanism of well‐defined nanostructures are still challenging. In this study, gold microplates with starlike, shieldlike, and other polygonal shapes are successfully achieved in high yields on the basis of the polyol process. Structural studies demonstrate that these newly shaped Au plates are single‐crystalline, several micrometers in lateral size, and tens of nanometers in thickness. It is believed that the introduction of temperature variation in the early stage of crystal growth is important for these products. The newly discovered Au microplates result from the growth of the {111} plane along the 〈211〉 and other high‐index directions, in addition to the {111}‐close‐packed 〈110〉 directions. Simulations on the multiple‐twin‐induced crystal growth and surface energy are also carried out to explain the experimental observations. This work is valuable for anisotropic growth of newly shaped noble‐metal nanostructures.     

Hedgehog‐Like Upconversion Crystals: Controlled Growth and Molecular Sensing at Single‐Particle Level

Topological control of nanostructures plays a crucial role in understanding the crystal growth process at the nanometer length scale. Here, the scalable synthesis of upconversion materials with distinct hedgehog‐like morphologies by a seed‐mediated synthetic procedure is reported. It is demonstrated that a close match in the crystal lattice between the core and shell components is essential for synthesizing such hierarchical nanostructures. These optical nanomaterials also enable the development of a single‐particle‐based platform for high‐sensitivity molecular sensing.     

Functionalized Cluster‐Assembled Magnetic Nanostructures for Applications to high Integration‐Density Devices

This paper presents recent results on the preparation and characterization of original magnetic nanostructures from nanoclusters preformed in the gas phase. Magnetic binary‐clusters (i.e. Co‐Sm, Co‐Pt, Co‐Ag) with rather well controlled sizes, structures and compositions, are prepared in the gas phase using a combined laser vaporization‐rare gas condensation source and subsequently deposited at low energy (LECBD : Low Energy Cluster Beam Deposition) on various functionalized substrates to grow cluster‐assembled magnetic nanostructures exhibiting specific magnetic properties. Especially a high magnetic anisotropy and consequently a high magnetic blocking temperature compatible with future applications to high density memory devices and spin electronics are expected. In this context of applications, 2D‐organized arrays of functionalized binary‐cluster assembled dots are prepared by LECBD on FIB‐functionalized substrates (FIB: Focussed Ion Beam) with the ultimate objective to reach areal densities in the range of the Tbits/in².     

Postsynthesis of h‐BN/Graphene Heterostructures Inside a STEM

Combinations of 2D materials with different physical properties can form heterostructures with modified electrical, mechanical, magnetic, and optical properties. The direct observation of a lateral heterostructure synthesis is reported by epitaxial in‐plane graphene growth from the step‐edge of hexagonal BN (h‐BN) within a scanning transmission electron microscope chamber. Residual hydrocarbon in the chamber is the carbon source. The growth interface between h‐BN and graphene is atomically identified as largely N–C bonds. This postgrowth method can form graphene nanoribbons connecting two h‐BN domains with different twisting angles, as well as isolated carbon islands with arbitrary shapes embedded in the h‐BN layer. The electronic properties of the vertically stacked h‐BN/graphene heterostructures are investigated by electron energy‐loss spectroscopy (EELS). Low‐loss EELS analysis of the dielectric response suggests a robust coupling effect between the graphene and h‐BN layers.     

Self‐Aligned Anisotropic Plasmonic Nanostructures

Great opportunities emerge not only in the generation of anisotropic plasmonic nanostructures but also in controlling their orientation relative to incident light. Herein, a stepwise seeded growth method is reported for the synthesis of rod‐shaped plasmon nanostructures which are vertically self‐aligned with respect to the surface of colloidal substrates. Anisotropic growth of metal nanostructure is achieved by depositing metal seeds onto the surface of colloidal substrates and then selectively passivating the seed surface to induce symmetry breaking in the subsequent seed‐mediated growth process. The versatility of this method is demonstrated by producing nanoparticle dimers and linear trimers of Au, Au–Ag, Au–Pd, and Au–Cu₂O. Further, this unique method enables the automatic vertical alignment of the resulting plasmonic nanostructures to the surface of the colloidal substrate, thereby making it possible to design magnetic/plasmonic nanocomposites that allow the dynamic tuning of the plasmon excitation by controlling their orientation using an external magnetic field. The controlled anisotropic growth of colloidal plasmonic nanostructures and their dynamic modulation of plasmon excitation further allow them to be conveniently fixed in a thin polymer film with a well‐controlled orientation to display polarization‐dependent patterns that may find important applications in information encryption.     

On‐Surface Synthesis of 8‐ and 10‐Armchair Graphene Nanoribbons

Armchair graphene nanoribbons (AGNRs) with 8 and 10 carbon atoms in width (8‐ and 10‐AGNRs) are synthesized on Au (111) surfaces via lateral fusion of nanoribbons that belong to different subfamilies. Poly‐para‐phenylene (3‐AGNR) chains are pre‐synthesized as ladder ribbons on Au (111). Subsequently, synthesized 5‐ and 7‐AGNRs can laterally fuse with 3‐AGNRs upon annealing at higher temperature, producing 8‐ and 10‐AGNRs, respectively. The synthetic process, and their geometric and electronic structures are characterized by scanning tunneling microscopy/spectroscopy (STM/STS). STS investigations reveal the band gap of 10‐AGNR (2.0 ± 0.1 eV) and a large apparent band gap of 8‐AGNRs (2.3 ± 0.1 eV) on Au (111) surface.     

Aligned Growth of Millimeter‐Size Hexagonal Boron Nitride Single‐Crystal Domains on Epitaxial Nickel Thin Film

Atomically thin hexagonal boron nitride (h‐BN) is gaining significant attention for many applications such as a dielectric layer or substrate for graphene‐based devices. For these applications, synthesis of high‐quality and large‐area h‐BN layers with few defects is strongly desirable. In this work, the aligned growth of millimeter‐size single‐crystal h‐BN domains on epitaxial Ni (111)/sapphire substrates by ion beam sputtering deposition is demonstrated. Under the optimized growth conditions, single‐crystal h‐BN domains up to 0.6 mm in edge length are obtained, the largest reported to date. The formation of large‐size h‐BN domains results mainly from the reduced Ni‐grain boundaries and the improved crystallinity of Ni film. Furthermore, the h‐BN domains show well‐aligned orientation and excellent dielectric properties. In addition, the sapphire substrates can be repeatedly used with almost no limit. This work provides an effective approach for synthesizing large‐scale high‐quality h‐BN layers for electronic applications.     

Identifying Phase‐Dependent Electrochemical Stripping Performance of FeOOH Nanorod: Evidence from Kinetic Simulation and Analyte–Material Interactions

Metal hydroxide nanomaterials are widely applied in the energy and environment fields. The electrochemical performance of such materials is strongly dependent on their crystal phases. However, as there are always multiple factors relating to the phase‐dependent electrochemistry, it is still difficult to identify the determining one. The well‐defined crystal phases of α‐ and β‐FeOOH nanorods are characterized through the transmission electron microscopy by a series of rotation toward one rod, where the cross‐section shape and the growth direction along the [001] crystalline are first verified for 1D FeOOH nanostructures. The electrosensitivity of the two materials toward Pb(II) is tested, where α‐FeOOH performs an outstanding sensitivity whilst it is only modest for β‐FeOOH. Experiments via Fourier transform infrared spectroscopy, X‐ray absorption fine structure (XAFS), etc., show that α‐FeOOH presents a larger Pb(II) adsorption capacity due to more surficial hydroxyl groups and weaker Pb? O bond strength. The reaction kinetics are simulated and the adsorption capacity is found to be the determining factor for the distinct Pb(II) sensitivities. Combining experiment with simulation, this work reveals the physical insights of the phase‐dependent electrochemistry for FeOOH and provides guidelines for the functional application of metal hydroxide nanomaterials.     

Improving Defect‐Based Quantum Emitters in Silicon Carbide via Inorganic Passivation

Defect‐based color centers in wide‐bandgap crystalline solids are actively being explored for quantum information science, sensing, and imaging. Unfortunately, the luminescent properties of these emitters are frequently degraded by blinking and photobleaching that arise from poorly passivated host crystal surfaces. Here, a new method for stabilizing the photoluminescence and charge state of color centers based on epitaxial growth of an inorganic passivation layer is presented. Specifically, carbon antisite‐vacancy pairs (CAV centers) in 4H‐SiC, which serve as single‐photon emitters at visible wavelengths, are used as a model system to demonstrate the power of this inorganic passivation scheme. Analysis of CAV centers with scanning confocal microscopy indicates a dramatic improvement in photostability and an enhancement in emission after growth of an epitaxial AlN passivation layer. Permanent, spatially selective control of the defect charge state can also be achieved by exploiting the mismatch in spontaneous polarization at the AlN/SiC interface. These results demonstrate that epitaxial inorganic passivation of defect‐based quantum emitters provides a new method for enhancing photostability, emission, and charge state stability of these color centers.     

Native MicroRNA Targets Trigger Self‐Assembly of Nanozyme‐Patterned Hollowed Nanocuboids with Optimal Interparticle Gaps for Plasmonic‐Activated Cancer Detection

The modernized use of nucleic acid (NA) sequences to drive nanostructure self‐assembly has given rise to a new class of designed nanomaterials with controllable plasmonic functionalities for broad surface‐enhanced Raman scattering (SERS)‐based bioanalysis applications. Herein, dual usage of microRNAs (miRNAs) as both valuable cancer biomarkers and direct self‐assembly triggers is identified and capitalized upon for custom‐designed plasmonic nanostructures. Through strict NA hybridization of miRNA targets, Au nanospheres selectively self‐assemble onto hollowed Au/Ag alloy nanocuboids with ideal interparticle distances (≈2.3 nm) for optimal SERS signaling. The intrinsic material properties of the self‐assembled nanostructures further elevate miRNA detection performance via nanozyme catalytic SERS signaling cascades. This enables fM‐level miR‐107 detection limit within a clinically‐relevant range without any molecular target amplification. The miRNA‐triggered nanostructure self‐assembly approach is further applied in clinical patient samples, and showcases the potential of miR‐107 as a non‐invasive prostate cancer diagnostic biomarker. The use of miRNA targets to drive nanostructure self‐assembly holds great promise as a practical tool for miRNA detection in disease applications.     

2D Binary Plasmonic Nanoassemblies with Semiconductor n/p‐Doping‐Like Properties

The electronic, optical, thermal, and magnetic properties of an extrinsic bulk semiconductor can be finely tuned by adjusting its dopant concentration. Here, it is demonstrated that such a doping concept can be extended to plasmonic nanomaterials. Using two‐dimensional (2D) assemblies of Au@Ag and Au nanocubes (NCs) as a model system, detailed experimental and theoretical studies are carried out, which reveal collective semiconductor n/p‐doping‐like plasmonic properties. A threshold doping concentration of Au@Ag NCs is observed, below which p‐doping dominates and above which n‐doping prevails. Furthermore, Au@Ag NC dopants can be converted into corresponding Au seed “voids” dopants by selectively removing Ag without changing the overall structural integrity. The results show that the plasmonic doping concept may serve as a general design principle guiding synthesis and assembly of plasmonic metamaterials for programmable optoelectronic devices.     

Plasmon‐Driven Rapid In Situ Formation of Luminescence Single Crystal Nanoparticle

Single crystal nanomaterials are very important for the fundamental investigation and application of luminescence. However, a very critical growth condition or high temperature treatment is always required for their preparation. Here, an easy and rapid in situ achievement of a single crystal luminescent material is realized by taking advantage of plasmon‐induced thermal and catalysis effects. With the assistance of localized surface plasmon resonance of Au nanoparticles, polycrystalline NaYF₄ transforms to single crystal Y₂O₃ in tens of milliseconds, resulting in remarkable improvement of luminescence emission. It is important to point out that the single crystal transformation is also achieved even at a very low temperature, which is impossible with conventional approaches. Such a convenient and efficient plasmon assisted scheme provides a new technology for the rapid achievement of single crystal materials and extends the application of surface plasmon to a much broader field.     

Structure and Microscopic Magnetism of Epitaxial Ni–Mn–Ga Films

We report on the structural and magnetic properties of epitaxial thin films of the ferromagnetic shape memory material Ni–Mn–Ga prepared by DC magnetron sputter deposition. Different substrate materials, i.e., MgO(100) and Al₂O₃(11?20) allow for a tailored epitaxial growth. Using a sacrificial chromium buffer layer freestanding epitaxial films are obtained. In combination with photolithography partially freestanding structures such as microbridges are fabricated. The complex martensite crystal structure in substrate‐constrained and freestanding films is studied by means of X‐ray diffraction. The identified asymmetric twin variant configuration is associated with a macroscopic surface pattern observed by optical microscopy. The absence of magnetic‐field induced strain in the (100) oriented samples is explained on basis of the detected twin variant configuration using a simplified model. Taking advantage of the thin film geometry spectroscopic methods are applied to the samples. The measurements provide the first experimental test for changes in the electronic structure of the involved 3d metals during a martensitic transition. Exploiting the X‐ray magnetic circular dichroism quantitative information on the element‐specific spin and orbital magnetic moments are accessed. In addition, angular‐dependent experiments allow us to trace the microscopic origin of the magnetic anisotropy in Ni₂MnGa improving the fundamental understanding of this material.