Synthesis of Monodisperse Ag?Au Alloy Nanoparticles with Independently Tunable Morphology,Composition, Size,and Surface Chemistry and Their 3‐D Superlattices

Here, a strategy for synthesizing monodisperse Ag? Au alloy nanoparticles whereby particle attributes such as morphology, composition, size, and surface chemistry may be independently controlled, varied, and customized is presented. The synthesis uses a multi‐step procedure to deliver control of morphology, size, and composition in discrete and independent steps. Specifically Ag nanoparticles with the same morphology but different sizes are first prepared by the chemical reduction of Ag ions. A digestive ripening post‐treatment followed by seed‐mediated growth is then applied to narrow the size distribution and to vary the particle size. Monodisperse Ag? Au alloy nanoparticles are then formed by a replacement reaction with HAuCl₄. Both single‐crystalline truncated octahedral (TO) Ag? Au alloy nanoparticles and icosahedral multiply twinned particles can be easily prepared by this procedure. By using truncated octahedrons as the model morphology, the syntheses of nanoparticles with the same size but different compositions, of nanoparticles with the same composition but variable sizes, and of nanoparticles with different surface chemistry are demonstrated and discussed in detail. Because of the shape and size monodispersity, all of the as‐synthesized Ag? Au alloy nanoparticles easily form superlattices on a solid substrate upon slow evaporation of the solvent. The packing pattern of the nanoparticles is strongly dependent on the native morphology of the nanoparticles.     

Atomic‐Level Passivation of Individual Upconversion Nanocrystal for Single Particle Microscopic Imaging

Lanthanide‐doped upconversion nanoparticles (UCNPs) have significant applications for single‐molecule probes and high‐resolution display. However, one of their major hurdles is the weak luminescence, and this remains a grand challenge to achieve at the single‐particle level. Here, 484‐fold luminescence enhancement in LuF₃:Yb³⁺, Er³⁺ rhombic flake UCNPs is achieved, thanks to the Yb³⁺‐mediated local photothermal effect, and their original morphology, size, and good dispersibility are well preserved. These data show that the surface atomic structure of UCNPs as well as transfer from amorphous to ordered crystal structure is modulated by making use of the local photothermal conversion that is generated by the directional absorption of 980 nm light by Yb³⁺ ions. The confocal luminescence images obtained by super‐resolution stimulated emission depletion also show the great enhancement of individual LuF₃:Yb³⁺, Er³⁺ nanoparticles; the high signal‐to‐noise ratio images indicate that the laser treatment technology opens the door for single particle imaging and practical application.     

Citrate Effects on Amorphous Calcium Carbonate (ACC) Structure,Stability, and Crystallization

Understanding the role of citrate in the crystallization kinetics of amorphous calcium carbonate (ACC) is essential to explain the formation mechanisms, stabilities, surface properties, and morphologies of CaCO₃ biominerals. It also contributes to deeper insight into fluid–mineral interactions, both in nature and for industrial processes. In this study, ACC formation and its crystallization are monitored in real time as a function of citrate (CIT) concentration in solution. Additionally, synchrotron radiation pair distribution function analyses combined with solid‐state, spectroscopic, and microscopic techniques are used to determine the effect of CIT on ACC structure, composition, and size. Results show an increase in ACC lifetime coupled with an increase in CIT uptake by ACC and slight changes in ACC atomic structure with an increase in CIT concentration. ACC does not form at concentrations ≥ 75% CIT/Ca and vaterite is absent in all cases where CIT is present. These findings can be explained by CIT binding with Ca ions, thereby forming Ca–CIT complexes in solution and decreasing ACC and calcite saturation levels. The formation of CIT‐bearing ACC with calcitic structure and the absence of vaterite formation suggest that these solution complexes form a calcite‐type atomic arrangement while CIT probably also acts as a growth inhibitor.     

Control of the Oxygen and Cobalt Atoms Diffusion through Co Nanoparticles Differing by Their Crystalline Structure and Size

The size‐dependent Kirkendall effect is studied by using Co nanoparticles. The sizes of Co nanoparticles differing by their crystal structures called nanocrystallinity, namely amorphous, polycrystalline fcc, single crystalline hcp, and single crystalline ε phase, are modulated from 4 to 10 nm. The nanoparticles self‐assembled in 2D superlattices and differing by their nanocrystallinities are subjected to oxygen at 200 °C for 10 min. With single‐domain nanocrystals differing by their crystalline structure (ε and hcp phases), marked changes in the final structures are observed: upon increasing the nanocrystal size, the ε phase favors formation of a hollow structure whereas a transition from single‐domain hollow to multidomain core/shell structures takes place with the hcp phase. With polycrystalline fcc Co nanocrystals, a transition from a hollow to a yolk/shell structure is observed, whereas with amorphous cobalt, solid CoO nanoparticles are produced at the smaller size and are converted to the core/shell structure at the larger one. These differences in size effect are attributed to the change in the control of the inward flow of oxygen atoms and the outward flow of Co atoms with the crystalline structure of cobalt nanoparticles. Such a diffusion process described here on the Kirkendall effect can be studied for other metal nanocrystals.     

Spray Deposition of Titania Films with Incorporated Crystalline Nanoparticles for All‐Solid‐State Dye‐Sensitized Solar Cells Using P3HT

Spray coating, a simple and low‐cost technique for large‐scale film deposition, is employed to fabricate mesoporous titania films, which are electron‐transporting layers in all‐solid‐state dye‐sensitized solar cells (DSSCs). To optimize solar cell performance, presynthesized crystalline titania nanoparticles are introduced into the mesoporous titania films. The composite film morphology is examined with scanning electron microscopy, grazing incidence small‐angle X‐ray scattering, and nitrogen adsorption–desorption isotherms. The crystal phase and crystallite sizes are verified by X‐ray diffraction measurements. The photovoltaic performance of all‐solid‐state DSSCs is investigated. The findings reveal that an optimal active layer of the all‐solid‐state DSSC is obtained by including 50 wt% titania nanoparticles, showing a foam‐like morphology with an average pore size of 20 nm, featuring an anatase phase, and presenting a surface area of 225.2 m² g^?1. The optimized morphology obtained by adding 50 wt% presynthesized crystalline titania nanoparticles yields, correspondingly, the best solar cell efficiency of 2.7 ± 0.1%.     

Amorphous and Crystalline GeTe Nanocrystals

A facile method for the synthesis of crystalline and amorphous GeTe nanoparticles (NPs) using bis((trimethylsilyl)amido)germanium(II), Ge[N(SiMe₃)₂]₂, and elemental tellurium dispersed in tri‐n‐octylphosphine (TOP) is reported. As synthesized, crystalline particles exhibit narrow dispersity at smaller sizes and tend to grow into anisotropic shapes with increasing reaction time (growth). Furthermore, crystalline GeTe NPs possess rhombohedral symmetry with absorption band energies in near IR region (0.76–0.86 eV). Amorphous GeTe particles prepared at low temperatures are nearly spherical in morphology and display amorphous‐to‐crystalline phase transition at 209–237 °C depending on their primary particle size. Detailed investigation of the local structure of the amorphous GeTe using pair distribution function (PDF) method reveals that it is closely related to that of the pressure‐ and temperature‐stabilized orthorhombic GeTe.     

N,N‐Dimethylformamide as a Reaction Medium for Metal Nanoparticle Synthesis

The versatility of wet chemical methods has rendered them extremely popular for the preparation of metal nanoparticles with tailored size and shape. This Feature Article reviews the use of N,N‐dimethylformamide (DMF) for the reduction of metal salts, mainly Au and Ag, while also acting as a solvent. Apart from describing the ability of DMF to reduce metal salts, the effect of different parameters, such as the concentration of capping agent and metal precursors, the presence of preformed seeds acting as catalysts or their crystalline structure, on particle morphology are analyzed. Published reports on the use of different capping agents are summarized, with particular emphasis on the role of poly(vinylpyrrolidone) to determine the morphology of the particles. Finally, a brief overview is provided on the modulation of the optical response in DMF‐based metal nanoparticle colloids with tunable size and shape.     

Single‐Crystal Germanium Growth on Amorphous Silicon

Growing single‐crystal semiconductors directly on an amorphous substrate without epitaxy or wafer bonding has long been a significant fundamental challenge in materials science. Such technology is especially important for semiconductor devices that require cost‐effective, high‐throughput fabrication, including thin‐film solar cells and transistors on glass substrates as well as large‐scale active photonic circuits on Si using back‐end‐of‐line CMOS technology. This work demonstrates a CMOS‐compatible method of fabricating high‐quality germanium single crystals on amorphous silicon at low temperatures of <450 °C. Grain orientation selection by geometric confinement of polycrystalline germanium films selectively grown on amorphous silicon by chemical vapor deposition is presented, where the confinement selects the fast‐growing grains for extended growth and eventually leads to single crystalline material. Germanium crystals grown using this method exhibit (110) texture and twin‐mediated growth. A model of confined growth is developed to predict the optimal confining channel dimensions for consistent, single‐crystal growth. Germanium films grown from one‐dimensional confinement exhibit a 200% grain size increase at 1 μm film thickness compared to unconfined films, while 2D confinement growth achieved single crystal Ge. The area of single crystalline Ge on amorphous layers is only limited by the growth time. Significant enhancement in room temperature photoluminescence and reduction in residual carrier density have been achieved using confined growth, demonstrating excellent optoelectronic properties. This growth method is readily extensible to any materials system capable of selective non‐epitaxial deposition, thus allowing for the fabrication of devices from high‐quality single crystal material when only an amorphous substrate is available.     

Nanostructured Alkaline‐Cation‐Containing δ‐MnO2 for Photocatalytic Water Oxidation

Oxygen evolution from water is one of the key reactions for solar fuel production. Here, two nanostructured K‐containing δ‐MnO₂ are synthesized: K‐δ‐MnO₂ nanosheets and K‐δ‐MnO₂ nanoparticles, both of which exhibit high catalytic activity in visible‐light‐driven water oxidation. The role of alkaline cations in oxygen evolution is first explored by replacing the K⁺ ions in the δ‐MnO₂ structure with H⁺ ions through proton ion exchange. H‐δ‐MnO₂ catalysts with a similar morphology and crystal structure exhibit activities per surface site approximately one order of magnitude lower than that of K‐δ‐MnO₂, although both nanostructured H‐δ‐MnO₂ catalysts have much larger Brunauer–Emmett–Teller (BET) surface areas. Such a low turnover frequency (TOF) per surface Mn atom might be due to the fact that the Ru²⁺(bpy)₃ sensitizer is too large to access the additional surface area created during proton exchange. Also, a prepared Na‐containing δ‐MnO₂ material with an identical crystal structure exhibits a TOF similar to that of the K‐containing δ‐MnO₂, suggesting that the alkaline cations are not directly involved in catalytic water oxidation, but instead stabilize the layered structure of the δ‐MnO₂.     

Insight into Doping Effects in Apatite Silicate Ionic Conductors

Novel apatite‐type silicates are attracting considerable interest as a new family of oxide‐ion conductors with potential use in fuel cells and ceramic membranes. Combined computer modeling and X‐ray absorption (EXAFS) techniques have been used to gain fresh insight, at the atomic level, into the site selectivity and local structures of a wide range of dopants in these apatite materials. The results indicate that an unusually broad range of dopant ions (in terms of size and charge state) can substitute for La in the La_9.33Si₆O₂₆ apatite, in accord with current experimental data. The range is much wider than that observed for doping on a single cation site in most other oxide‐ion conductors, such as the perovskite LaGaO₃. In addition, our local structural investigation demonstrates that this dopant behavior is related to the flexibility of the silicate substructure, which allows relatively large local distortion and alteration of the site volumes. This could be a key factor in the high oxide‐ion conductivity exhibited by these apatite silicates. Indeed, the breadth of possible doping regimes in these novel materials provides new opportunities to design and optimize the conduction properties for fuel cell electrolytes.     

Controlling the Edge Length of Gold Nanoprisms via a Seed‐Mediated Approach

A straightforward method is investigated for controlling and reinitiating the growth of single‐crystalline Au nanoprisms. This work is based on seeding methodology, and depends on the slow reduction of metal ions onto the surface of a growing nanoprism. In this manner, we can tailor the edge length of Au nanoprisms between 100 and 300 nm without changing their thickness or crystallinity. Each nanoprism size has been characterized by UV‐vis‐NIR (NIR: near‐IR) spectroscopy, transmission electron microscopy (TEM) techniques, and statistical analysis. Based on this work and existing silver halide crystal‐growth theories, a preliminary mechanism is proposed which comments on the interplay between crystal growth and surface chemistry that ultimately dictates the morphology of the resulting nanostructure.     

In Situ Thermolysis of a Ni Salt on Amorphous Carbon and Graphene Oxide Substrates

Understanding the thermal decomposition of metal salt precursors on carbon structures is essential for the controlled synthesis of metal-decorated carbon nanomaterials. Here, the thermolysis of a Ni precursor salt, NiCl₂·6H₂O, on amorphous carbon (a-C) and graphene oxide (GO) substrates is explored using in situ transmission electron microscopy. Thermal decomposition of NiCl₂·6H₂O on GO occurs at higher temperatures and slower kinetics than on a-C substrate. This is correlated to a higher activation barrier for Cl₂ removal calculated by the density functional theory, strong Ni-GO interaction, high-density oxygen functional groups, defects, and weak van der Waals using GO substrate. The thermolysis of NiCl₂·6H₂O proceeds via multistep decomposition stages into the formation of Ni nanoparticles with significant differences in their size and distribution depending on the substrate. Using GO substrates leads to nanoparticles with 500% smaller average sizes and higher thermal stability than a-C substrate. Ni nanoparticles showcase the fcc crystal structure, and no size effect on the stability of the crystal structure is observed. These findings demonstrate the significant role of carbon substrate on nanoparticle formation and growth during the thermolysis of carbon–metal heterostructures. This opens new venues to engineer stable, supported catalysts and new carbon-based sensors and filtering devices.     

Biogenic Calcium Carbonate: Calcite Crystals of Variable Morphology by the Reaction of Aqueous Ca2+ Ions with Fungi

The biological synthesis of CaCO₃ crystals of variable morphology by challenging non‐calcareous microorganisms such as fungi with aqueous Ca²⁺ ions has been described. Many fungi are known to produce reasonable amounts of CO₂ during growth. We show here that CO₂ and characteristic proteins released from the fungi Fusarium oxysporum and Trichothecium sp. may be reacted with aqueous Ca²⁺ ions to produce truly biogenic CaCO₃ crystals. While calcite crystals are obtained with both fungi, significant differences in the morphology of the crystals is observed, indicating that the proteins secreted by the fungi play a crucial role in directing the morphology of the calcite crystals. The action of specific proteins secreted by the microorganisms in directing calcite crystal morphology as well as the more complex issue of synergistic action of mixtures of proteins in directing crystal structure and morphology has been addressed.     

A Cooperative Copper Metal–Organic Framework‐Hydrogel System Improves Wound Healing in Diabetes

Chronic nonhealing wounds remain a major clinical challenge that would benefit from the development of advanced, regenerative dressings that promote wound closure within a clinically relevant time frame. The use of copper ions has shown promise in wound healing applications, possibly by promoting angiogenesis. However, reported treatments that use copper ions require multiple applications of copper salts or oxides to the wound bed, exposing the patient to potentially toxic levels of copper ions and resulting in variable outcomes. Herein the authors set out to assess whether copper metal organic framework nanoparticles (HKUST‐1 NPs) embedded within an antioxidant thermoresponsive citrate‐based hydrogel would decrease copper ion toxicity and accelerate wound healing in diabetic mice. HKUST‐1 and poly‐(polyethyleneglycol citrate‐co‐N‐isopropylacrylamide) (PPCN) are synthesized and characterized. HKUST‐1 NP stability in a protein solution with and without embedding them in PPCN hydrogel is determined. Copper ion release, cytotoxicity, apoptosis, and in vitro migration processes are measured. Wound closure rates and wound blood perfusion are assessed in vivo using the splinted excisional dermal wound diabetic mouse model. HKUST‐1 NPs disintegrated in protein solution while HKUST‐1 NPs embedded in PPCN (H‐HKUST‐1) are protected from degradation and copper ions are slowly released. Cytotoxicity and apoptosis due to copper ion release are significantly reduced while dermal cell migration in vitro and wound closure rates in vivo are significantly enhanced. In vivo, H‐HKUST‐1 induced angiogenesis, collagen deposition, and re‐epithelialization during wound healing in diabetic mice. These results suggest that a cooperatively stabilized, copper ion‐releasing H‐HKUST‐1 hydrogel is a promising innovative dressing for the treatment of chronic wounds.     

Biomimetic Hydroxyapatite Crystallization in Gelatin Nanoparticles Synthesized Using a Miniemulsion Process

Here, we report a novel biomimetic strategy to synthesize hydroxyapatite (HAP) inside of crosslinked gelatin nanoparticles, which serve as a nanoenvironment for crystal growth in the aqueous phase. The synthesis of gelatin nanoparticles with the inverse miniemulsion technique is very intriguing because of the flexibility offered by the technique in tailoring the properties of the gelatin nanoparticles. It can be shown that the nanoenvironment promotes a different growth environment for the crystal because of the confinement inside the particle. The formation of HAP inside the particles follows Ostwald's rule of stages. At first an amorphous phase is formed, which itself has a great potential to be used as a resorbable bone substitute. This further transforms into single crystalline HAP via an octacalcium phosphate intermediate. The solution‐mediated transformation into the HAP phase without any calcination step is studied in detail using transmission electron microscopy (TEM) and X‐ray diffraction (XRD) measurements.     

Positive and Negative Lattice Shielding Effects Co‐existing in Gd (III) Ion Doped Bifunctional Upconversion Nanoprobes

Gadolinium (Gd) doped upconversion nanoparticles (UCNPs) have been well documented as T₁‐MR and fluorescent imaging agents. However, the performance of Gd³⁺ ions located differently in the crystal lattice still remains debatable. Here, a well‐designed model was built based on a seed‐mediated growth technique to systematically probe the longitudinal relaxivity of Gd³⁺ ions within the crystal lattice and at the surface of UCNPs. We found, for the first time, a nearly 100% loss of relaxivity of Gd³⁺ ions buried deeply within crystal lattices (> 4 nm), which we named a “negative lattice shielding effect” (n‐LSE) as compared to the “positive lattice shielding effect” (p‐LSE) for the enhanced upconversion fluorescent intensity. As‐observed n‐LSE was further found to be shell thickness dependent. By suppressing the n‐LSE as far as possible, we optimized the UCNPs' structure design and achieved the highest r₁ value (6.18 mM^?1s^?1 per Gd³⁺ ion) among previously reported counterparts. The potential bimodal imaging application both in vitro and in vivo of as‐designed nano‐probes was also demonstrated. This study clears the debate over the role of bulk and surface Gd³⁺ ions in MRI contrast imaging and paves the way for modulation of other Gd‐doped nanostructures for highly efficient T₁‐MR and upconversion fluorescent bimodal imaging.     

Versatile Amorphous Structures of Phosphonate Metal−Organic Framework/Alginate Composite for Tunable Sieving of Ions

Versatile amorphous structures of phosphonate metal–organic framework (pMOF)/alginate composite are proposed to selectively separate alkaline and alkaline earth metal ions. Initially, the gelation of alginate by Al³⁺ ions provides preconfined Al³⁺ coordination. The phosphonate organic ligand is subsequently coordinated with Al³⁺ ions to make pMOF based on the preconfined Al³⁺ coordination. Al³⁺?phosphonate organic ligand complexes of pMOF are simultaneously intertwined with Al³⁺?alginate crosslinks with the aid of partial hydrolysis. Amorphous structures of Al³⁺‐based pMOF/alginate composite are largely modulated, as the reaction temperature and intertwinement degree of alginate networks vary. In addition, partial hydrolysis plays an important role for amorphization, which gives rise to versatile amorphous structures. The Al³⁺‐based pMOF/alginate composite is found to have tunable sieving of alkaline and alkaline earth metal ions with varying the degrees of intertwinement of amorphous structures and Al³⁺?phosphonate organic ligand complexes. In particular, a certain type of amorphous structure can effectively reject Li⁺ ions with small hydration energy through dehydration. Benefiting from amorphous structures, this work will provide a variety of separation opportunities accompanying unique properties and allow efficient separation of ions and similar‐sized molecules.     

A Simple and Effective Route for the Synthesis of Crystalline Silver Nanorods and Nanowires

A simple and effective approach to the aqueous‐phase synthesis of crystalline silver nanorods and nanowires is demonstrated, using which their diameters and aspect ratios can be effectively controlled. The synthesis involves a template‐less and non‐seed process to high‐quality nanoparticles, which is low‐cost and proceeds at moderate temperatures. The nanorods and nanowires were synthesized by the reduction of silver nitrate with tri‐sodium citrate in the presence of sodium dodecylsulfonate. The concentration of tri‐sodium citrate plays a critical role while sodium dodecylsulfonate, as a capping agent, only plays an assistant role in controlling the diameters and aspect ratios of the products. High‐resolution transmission electron microscopy (HRTEM) and selected‐area electron diffraction (SAED) investigations show that the silver nanocrystals are generated with a twinned crystalline structure. We also put forward a primary experimental model to shed light on their growth mechanisms.     

Insights into the In Vitro Formation of Apatite from Mg-Stabilized Amorphous Calcium Carbonate

A protein-free formation of bone-like apatite from amorphous precursors through ball-milling is reported. Mg²⁺ ions are crucial to achieve full amorphization of CaCO₃. Mg²⁺ incorporation generates defects which strongly retard a recrystallization of ball-milled Mg-doped amorphous calcium carbonate (BM-aMCC), which promotes the growth of osteoblastic and endothelial cells in simulated body fluid and has no effect on endothelial cell gene expression. Ex situ snapshots of the processes revealed the reaction mechanisms. For low Mg contents (<30%) a two phase system consisting of Mg-doped amorphous calcium carbonate (ACC) and calcite “impurities” was formed. For high (>40%) Mg²⁺ contents, BM-aMCC follows a different crystallization path via magnesian calcite and monohydrocalcite to aragonite. While pure ACC crystallizes rapidly to calcite in aqueous media, Mg-doped ACC forms in the presence of phosphate ions bone-like hydroxycarbonate apatite (dahllite), a carbonate apatite with carbonate substitution in both type A (OH⁻) and type B (PO₄³⁻) sites, which grows on calcite “impurities” via heterogeneous nucleation. This process produces an endotoxin-free material and makes BM-aMCC an excellent “ion storage buffer” that promotes cell growth by stimulating cell viability and metabolism with promising applications in the treatment of bone defects and bone degenerative diseases.     

Ultrafast Melting of Metal–Organic Frameworks for Advanced Nanophotonics

The conversion of metal–organic frameworks (MOFs) into derivatives with a well‐defined shape and composition is considered a reliable way to produce efficient catalysts and energy capacitors at the nanometer scale. Yet, approaches based on conventional melting of MOFs provide the derivatives such as amorphous carbon, metal oxides, or metallic nanoclusters with an appropriate morphology. Here ultrafast melting of MOFs is utilized by femtosecond laser pulses to produce a new generation of derivatives with complex morphology and enhanced nonlinear optical response. It is revealed that such a nonequilibrium process allows conversion of interpenetrated 3D MOFs comprising flexible ligands into well‐organized spheres with a metal oxide dendrite core and amorphous organic shell. The ability to produce such derivatives with a complex morphology is directly dependent on the electronic structure, crystal density, ligand flexibility, and morphology of initial MOFs. An enhanced second harmonic generation and three‐photon luminescence are also demonstrated due to the resonant interaction of 100–1000 nm spherical derivatives with light. The results obtained are in the favor of new approaches for melting special types of MOFs for nonlinear nanophotonics.