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Machine learning approaches for image analysis require extensive training datasets for an accurate analysis. This also applies to the automated analysis of electron microscopy data where training data are usually created by manual annotation. Besides nanoparticle shape and size distribution, their internal crystal structure is a major parameter to assess their nature and their physical properties. The automatic classification of ultrasmall gold nanoparticles (1-3 nm) by their crystallinity is possible after training a neural network with simulated HRTEM data. This avoids a human bias and the necessity to manually classify extensive particle sets as training data. The small size of these particles represents a significant challenge with respect to the question of internal crystallinity. The network was able to assign real particles imaged by HRTEM with high accuracy to the classes monocrystalline, polycrystalline, and amorphous after being trained with simulated datasets. The ability to adjust the simulation parameters opens the possibility to extend this procedure to other experimental setups and other types of nanoparticles.
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Ultrasmall nanoparticles (diameter 2 nm) of silver, platinum, and bimetallic nanoparticles (molar ratio of Ag:Pt 0:100; 20:80; 50:50; 70:30; 100:0), stabilized by the thiolated ligand glutathione, were prepared and characterized by transmission electron microscopy, differential centrifugal sedimentation, X-ray photoelectron spectroscopy, small-angle X-ray scattering, X-ray powder diffraction, and NMR spectroscopy in aqueous dispersion. Gold nanoparticles of the same size were prepared as control. The particles were fluorescently labeled by conjugation of the dye AlexaFluor-647 via copper-catalyzed azide-alkyne cycloaddition after converting amine groups of glutathione into azide groups. All nanoparticles were well taken up by HeLa cells. The cytotoxicity was assessed with an MTT test on HeLa cells and minimal inhibitory concentration (MIC) tests on the bacteria Escherichia coli and Staphylococcus xylosus. Notably, bimetallic AgPt nanoparticles had a higher cytotoxicity against cells and bacteria than monometallic silver nanoparticles or a physical mixture of silver and platinum nanoparticles. However, the measured release of silver ions from monometallic and bimetallic silver nanoparticles in water was very low despite the ultrasmall size and the associated high specific surface area. This is probably due to the surface protection by a dense layer of thiolated ligand glutathione. Thus, the enhanced cytotoxicity of bimetallic AgPt nanoparticles is caused by the biological environment in cell culture media, together with a polarization of silver by platinum.
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Concurrent structural and electronic transformations in VO2 thin films are of 2-fold importance: enabling fine-tuning of the emergent electrical properties in functional devices, yet creating an intricate interfacial domain structure of transitional phases. Despite the importance of understanding the structure of VO2 thin films, a detailed real-space atomic structure analysis in which the oxygen atomic columns are also resolved is lacking. Moreover, intermediate atomic structures have remained elusive due to the lack of robust atomically resolved quantitative analysis. Here, we directly resolve both V and O atomic columns and discover the presence of intermediate monoclinic (M2) phase nanolayers (less than 2 nm thick) in epitaxially grown VO2 films on a TiO2 (001) substrate, where the dominant part of VO2 undergoes a transition from the tetragonal (rutile) phase to the monoclinic M1 phase. Strain analysis suggests that the presence of the M2 phase is related to local strain gradients near the TiO2/VO2 interface. We unfold the crucial role of imaging the spatial configurations of the oxygen anions (in addition to V cations) by utilizing atomic-resolution electron microscopy. Our approach can be used to unravel the structural transitions in a wide range of correlated oxides, offering substantial implications for, e.g., optoelectronics and ferroelectrics.
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Ultrasmall gold nanoparticles were functionalized with peptides of two to seven amino acids that contained one cysteine molecule as anchor via a thiol-gold bond and a number of alanine residues as nonbinding amino acid. The cysteine was located either in the center of the molecule or at the end (C-terminus). For comparison, gold nanoparticles were also functionalized with cysteine alone. The particles were characterized by UV spectroscopy, differential centrifugal sedimentation (DCS), high-resolution transmission electron microscopy (HRTEM), and small-angle X-ray scattering (SAXS). This confirmed the uniform metal core (2 nm diameter). The hydrodynamic diameter was probed by 1H-DOSY NMR spectroscopy and showed an increase in thickness of the hydrated peptide layer with increasing peptide size (up to 1.4 nm for heptapeptides; 0.20 nm per amino acid in the peptide). 1H NMR spectroscopy of water-dispersed nanoparticles showed the integrity of the peptides and the effect of the metal core on the peptide. Notably, the NMR signals were very broad near the metal surface and became increasingly narrow in a distance. In particular, the methyl groups of alanine can be used as probe for the resolution of the NMR spectra. The number of peptide ligands on each nanoparticle was determined using quantitative 1H NMR spectroscopy. It decreased with increasing peptide length from about 100 for a dipeptide to about 12 for a heptapeptide, resulting in an increase of the molecular footprint from about 0.1 to 1.1 nm2.
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Ouro , Nanopartículas Metálicas , Peptídeos , Ouro/química , Nanopartículas Metálicas/química , Peptídeos/química , Propriedades de Superfície , Tamanho da PartículaRESUMO
Dealloying of Ag-Au alloy nanoparticles (NPs) strongly differs from the corresponding bulk alloy materials. Here, we have investigated the effects of potentiodynamic and potentiostatic dealloying on structure and distribution of residual Ag atoms for Au rich NPs. Two different sizes of Ag rich alloy NPs, 77 ± 26 nm Ag77Au23 and 12 ± 5 nm Ag86Au14, were prepared. 77 nm Ag77Au23 NPs form a homogeneous alloy, while 12 nm Ag86Au14 NPs show an Ag rich shell-Au rich core arrangement. The two groups of as-prepared NPs were dealloyed either under potentiodynamic (0.2-1.3 VRHE) or potentiostatic (0.9, 1.2, and 1.6 VRHE) conditions in 0.1 M HClO4. For the initial 77 nm Ag77Au23 NPs, both dealloying protocols lead to pore evolution. Interestingly, instead of homogenous Ag distribution, numerous Ag rich regions form and locate near the pores and particle edges. The critical dealloying potential also differs by â¼500 mV depending on the dealloying method. The initial 12 nm Ag86Au14 NPs remain dense and solid, but Ag distribution and thickness of the Au passivation layer vary between both dealloying protocols. When the Au passivation layer is very thin, the residual Ag atoms tend to segregate to the particle surface after dealloying. Due to the size effect, small NPs are less electrochemically stable and show a lower critical dealloying potential. In this systematic study, we demonstrate that the mobility of Au surface atoms and dealloying conditions control the structure and residual Ag distribution within dealloyed NPs.
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Alloyed ultrasmall silver-platinum nanoparticles (molar ratio Ag:Pt = 50:50) were prepared and compared to pure silver, platinum, and gold nanoparticles, all with a metallic core diameter of 2 nm. They were surface-stabilized by a layer of glutathione (GSH). A comprehensive characterization by high-resolution transmission electron microscopy (HRTEM), electron diffraction (ED), X-ray diffraction (XRD), small-angle X-ray scattering (SAXS), differential centrifugal sedimentation (DCS), and UV spectroscopy showed their size both in the dry and in the water-dispersed state (hydrodynamic diameter). Solution NMR spectroscopy (1H, 13C, COSY, HSQC, HMBC, and DOSY) showed the nature of the glutathione shell including the number of GSH ligands on each nanoparticle (about 200 with a molecular footprint of 0.063 nm2 each). It furthermore showed that there are at least two different positions for the GSH ligand on the gold nanoparticle surface. Platinum strongly reduced the resolution of the NMR spectra compared to silver and gold, also in the alloyed nanoparticles. X-ray photoelectron spectroscopy (XPS) showed that silver, platinum, and silver-platinum particles were at least partially oxidized to Ag(+I) and Pt(+II), whereas the gold nanoparticles showed no sign of oxidation. Platinum and gold nanoparticles were well crystalline but twinned (fcc lattice) despite the small particle size. Silver was crystalline in electron diffraction but not in X-ray diffraction. Alloyed silver-platinum nanoparticles were almost fully amorphous by both methods, indicating a considerable internal disorder.
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Metallic nanoparticles were analysed with respect to size and shape by a machine learning approach. This involved a separation of particles from the background (segmentation), a separation of overlapping particles, and the identification of individual particles. An algorithm to separate overlapping particles, based on ultimate erosion of convex shapes (UECS), was implemented. Finally, particle properties like size, circularity, equivalent diameter, and Feret diameter were computed for each particle of the whole particle population. Thus, particle size distributions can be easily created based on the various parameters. However, strongly overlapping particles are difficult and sometimes impossible to separate because of an a priori unknown shape of a particle that is partially lying in the shadow of another particle. The program is able to extract information from a sequence of images of the same sample, thereby increasing the number of analysed nanoparticles to several thousands. The machine learning approach is well-suited to identify particles at only limited particle-to-background contrast as is demonstrated for ultrasmall gold nanoparticles (2 nm).
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The chemical selectivity and faradaic efficiency of high-index Cu facets for the CO2 reduction reaction (CO2 RR) is investigated. More specifically, shape-controlled nanoparticles enclosed by Cu {hk0} facets are fabricated using Cu multilayer deposition at three distinct layer thicknesses on the surface facets of Au truncated ditetragonal nanoprisms (Au DTPs). Au DTPs are shapes enclosed by 12 high-index {310} facets. Facet angle analysis confirms DTP geometry. Elemental mapping analysis shows Cu surface layers are uniformly distributed on the Au {310} facets of the DTPs. The 7â nm Au@Cu DTPs high-index {hk0} facets exhibit a CH4 : CO product ratio of almost 10 : 1 compared to a 1 : 1 ratio for the reference 7â nm Au@Cu nanoparticles (NPs). Operando Fourier transform infrared spectroscopy spectra disclose reactive adsorbed *CO as the main intermediate, whereas CO stripping experiments reveal the high-index facets enhance the *CO formation followed by rapid desorption or hydrogenation.
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Liquid methanol has the potential to be the hydrogen energy carrier and storage medium for the future green economy. However, there are still many challenges before zero-emission, affordable molecular H2 can be extracted from methanol with high performance. Here, we present noble-metal-free Cu-WC/W plasmonic nanohybrids which exhibit unsurpassed solar H2 extraction efficiency from pure methanol of 2,176.7 µmol g-1 h-1 at room temperature and normal pressure. Macro-to-micro experiments and simulations unveil that local reaction microenvironments are generated by the coperturbation of WC/W's lattice strain and infrared-plasmonic electric field. It enables spontaneous but selective zero-emission reaction pathways. Such microenvironments are found to be highly cooperative with solar-broadband-plasmon-excited charge carriers flowing from Cu to WC surfaces for efficient stable CH3OH plasmonic reforming with C3-dominated liquid products and 100% selective gaseous H2. Such high efficiency, without any COx emission, can be sustained for over a thousand-hour operation without obvious degradation.
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Azide-terminated ultrasmall gold nanoparticles (2 nm gold core) were covalently functionalized with alkyne-terminated small-interfering siRNA duplexes by copper-catalyzed azide-alkyne cycloaddition (CuAAC; click chemistry). The nanoparticle core was visualized by transmission electron microscopy. The number of attached siRNA molecules per nanoparticle was determined by a combination of atomic absorption spectroscopy (AAS; for gold) and UV-Vis spectroscopy (for siRNA). Each nanoparticle carried between 6 and 10 siRNA duplex molecules which corresponds to a weight ratio of siRNA to gold of about 2.2 : 1. Different kinds of siRNA were conjugated to the nanoparticles, depending on the gene to be silenced. In general, the nanoparticles were readily taken up by cells and highly efficient in gene silencing, in contrast to free siRNA. This was demonstrated in HeLa-eGFP cells (silencing of eGFP) and in LPS-stimulated macrophages (silencing of NF-κB). Furthermore, we demonstrated that nanoparticles carrying antiviral siRNA potently inhibited the replication of Herpes simplex virus 2 (HSV-2) in vitro. This highlights the strong potential of siRNA-functionalized ultrasmall gold nanoparticles in a broad spectrum of applications, including gene silencing and treatment of viral infections, combined with a minimal dose of gold.
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Recently proposed bimetallic octahedral Pt-Ni electrocatalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cell (PEMFC) cathodes suffer from particle instabilities in the form of Ni corrosion and shape degradation. Advanced trimetallic Pt-based electrocatalysts have contributed to their catalytic performance and stability. In this work, we propose and analyse a novel quaternary octahedral (oh-)Pt nanoalloy concept with two distinct metals serving as stabilizing surface dopants. An efficient solvothermal one-pot strategy was developed for the preparation of shape-controlled oh-PtNi catalysts doped with Rh and Mo in its surface. The as-prepared quaternary octahedral PtNi(RhMo) catalysts showed exceptionally high ORR performance accompanied by improved activity and shape integrity after stability tests compared to previously reported bi- and tri-metallic systems. Synthesis, performance characteristics and degradation behaviour are investigated targeting deeper understanding for catalyst system improvement strategies. A number of different operando and on-line analysis techniques were employed to monitor the structural and elemental evolution, including identical location scanning transmission electron microscopy and energy dispersive X-ray analysis (IL-STEM-EDX), operando wide angle X-ray spectroscopy (WAXS), and on-line scanning flow cell inductively coupled plasma mass spectrometry (SFC-ICP-MS). Our studies show that doping PtNi octahedral catalysts with small amounts of Rh and Mo suppresses detrimental Pt diffusion and thus offers an attractive new family of shaped Pt alloy catalysts for deployment in PEMFC cathode layers.
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We report and analyze a synthetic strategy toward low-Pt platinum-nickel (Pt-Ni) alloy nanoparticle (NP) cathode catalysts for the catalytic electroreduction of molecular oxygen to water. The synthesis involves the pyrolysis and leaching of Ni-organic polymers, subsequent Pt NP deposition, followed by thermal alloying, resulting in single Ni atom site (NiNC)-supported PtNi alloy NPs at low Pt weight loadings of only 3-5â wt %. Despite low Pt weight loading, the catalysts exhibit more favorable Pt-mass activities compared to conventional 20-30â wt % benchmark PtNi catalysts. Using in situ microscopic techniques, we track and unravel the key stages of the PtNi alloy formation process directly at the atomic scale. Surprisingly, we find that carbon-encapsulated metallic Ni@C structures, rather than NiNx sites, act as the Ni source during alloy formation. Our materials concepts offer a pathway to further decrease the overall Pt content in hydrogen fuel cell cathodes.
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Over the past decade, advances in the colloidal syntheses of octahedral-shaped Pt-Ni alloy nanocatalysts for use in fuel cell cathodes have raised our atomic-scale control of particle morphology and surface composition, which, in turn, helped raise their catalytic activity far above that of benchmark Pt catalysts. Future fuel cell deployment in heavy-duty vehicles caused the scientific priorities to shift from alloy particle activity to stability. Larger particles generally offer enhanced thermodynamic stability, yet synthetic approaches toward larger octahedral Pt-Ni alloy nanoparticles have remained elusive. In this study, we show how a simple manipulation of solvothermal synthesis reaction kinetics involving depressurization of the gas phase at different stages of the reaction allows tuning the size of the resulting octahedral nanocatalysts to previously unachieved scales. We then link the underlying mechanism of our approach to the classical "LaMer" model of nucleation and growth. We focus on large, annealed Mo-doped Pt-Ni octahedra and investigate their synthesis, post-synthesis treatments, and elemental distribution using advanced electron microscopy. We evaluate the electrocatalytic ORR performance and stability and succeed to obtain a deeper understanding of the enhanced stability of a new class of relatively large, active, and long-lived Mo-doped Pt-Ni octahedral catalysts for the cathode of PEMFCs.
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Ultrasmall nanoparticles of platinum group metal oxides (core diameter of about 1.8 nm) were prepared by alkaline hydrolysis of metal precursors in the presence of NaBH4 and by colloidal stabilization with tripeptide glutathione. We obtained water-dispersed nanoparticles of Rh2O3, PdO, RuO2, IrO2, Os/OsO2, and Pt/PtO. Their size was probed using high-resolution transmission electron microscopy, differential centrifugal sedimentation, small-angle X-ray scattering, and diffusion-ordered 1H NMR spectroscopy (1H DOSY). Their oxidation state was clearly determined using X-ray photoelectron spectroscopy, X-ray powder diffraction, and electron diffraction. The chemical composition of the nanoparticles, that is, the ratio of the metal oxide core and glutathione capping agent, was quantitatively determined by a combination of these methods.
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Nanopartículas Metálicas , Óxidos , Nanopartículas Metálicas/química , Óxidos/química , Platina/química , Água/química , Difração de Raios XRESUMO
The shuttling behavior and sluggish conversion kinetics of the intermediate lithium polysulfides (LiPS) represent the main obstructions to the practical application of lithium-sulfur batteries (LSBs). Herein, a 1D π-d conjugated metal-organic framework (MOF), Ni-MOF-1D, is presented as an efficient sulfur host to overcome these limitations. Experimental results and density functional theory calculations demonstrate that Ni-MOF-1D is characterized by a remarkable binding strength for trapping soluble LiPS species. Ni-MOF-1D also acts as an effective catalyst for S reduction during the discharge process and Li2 S oxidation during the charging process. In addition, the delocalization of electrons in the π-d system of Ni-MOF-1D provides a superior electrical conductivity to improve electron transfer. Thus, cathodes based on Ni-MOF-1D enable LSBs with excellent performance, for example, impressive cycling stability with over 82% capacity retention over 1000 cycles at 3 C, superior rate performance of 575 mAh g-1 at 8 C, and a high areal capacity of 6.63 mAh cm-2 under raised sulfur loading of 6.7 mg cm-2 . The strategies and advantages here demonstrated can be extended to a broader range of π-d conjugated MOFs materials, which the authors believe have a high potential as sulfur hosts in LSBs.
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Using a combination of in situ bulk and surface characterization techniques, we provide atomic-scale insight into the complex surface and bulk dynamics of a LaNiO3 perovskite material during heating in vacuo. Driven by the outstanding activity LaNiO3 in the methane dry reforming reaction (DRM), attributable to the decomposition of LaNiO3 during DRM operation into a Ni//La2O3 composite, we reveal the Ni exsolution dynamics both on a local and global scale by in situ electron microscopy, in situ X-ray diffraction and in situ X-ray photoelectron spectroscopy. To reduce the complexity and disentangle thermal from self-activation and reaction-induced effects, we embarked on a heating experiment in vacuo under comparable experimental conditions in all methods. Associated with the Ni exsolution, the remaining perovskite grains suffer a drastic shrinkage of the grain volume and compression of the structure. Ni particles mainly evolve at grain boundaries and stacking faults. Sophisticated structure analysis of the elemental composition by electron-energy loss mapping allows us to disentangle the distribution of the different structures resulting from LaNiO3 decomposition on a local scale. Important for explaining the DRM activity, our results indicate that most of the Ni moieties are oxidized and that the formation of NiO occurs preferentially at grain edges, resulting from the reaction of the exsolved Ni particles with oxygen released from the perovskite lattice during decomposition via a spillover process from the perovskite to the Ni particles. Correlating electron microscopy and X-ray diffraction data allows us to establish a sequential two-step process in the decomposition of LaNiO3 via a Ruddlesden-Popper La2NiO4 intermediate structure. Exemplified for the archetypical LaNiO3 perovskite material, our results underscore the importance of focusing on both surface and bulk characterization for a thorough understanding of the catalyst dynamics and set the stage for a generalized concept in the understanding of state-of-the art catalyst materials on an atomic level.
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Core-shell particles with thin noble metal shells represent an attractive material class with potential for various applications ranging from catalysis to biomedical and pharmaceutical applications to optical crystals. The synthesis of well-defined core-shell architectures remains, however, highly challenging. Here, we demonstrate that atomically-thin and homogeneous platinum shells can be grown via a colloidal synthesis method on a variety of gold nanostructures ranging from spherical nanoparticles to nanorods and nanocubes. The synthesis is based on the exchange of low binding citrate ligands on gold, the reduction of platinum and the subsequent kinetically hindered growth by carbon monoxide as strong binding ligand. The prerequisites for homogeneous growth are low core-binding ligands with moderate fast ligand exchange in solution, a mild reducing agent to mitigate homonucleation and a strong affinity of a second ligand system that can bind to the shell's surface. The simplicity of the described synthetic route can potentially be adapted to various other material libraries to obtain atomically smooth core-shell systems.
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Two ways to deliver ultrasmall gold nanoparticles and gold-bovine serum albumin (BSA) nanoclusters to the colon were developed. First, oral administration is possible by incorporation into gelatin capsules that were coated with an enteric polymer. These permit the transfer across the stomach whose acidic environment damages many drugs. The enteric coating dissolves due to the neutral pH of the colon and releases the capsule's cargo. Second, rectal administration is possible by incorporation into hard-fat suppositories that melt in the colon and then release the nanocarriers. The feasibility of the two concepts was demonstrated by in-vitro release studies and cell culture studies that showed the easy redispersibility after dissolution of the respective transport system. This clears a pathway for therapeutic applications of drug-loaded nanoparticles to address colon diseases, such as chronic inflammation and cancer.
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Colo/efeitos dos fármacos , Sistemas de Liberação de Medicamentos , Nanopartículas Metálicas/química , Polímeros/farmacologia , Administração Oral , Cápsulas/química , Cápsulas/farmacologia , Gelatina/química , Gelatina/farmacologia , Ouro/química , Ouro/farmacologia , Humanos , Polímeros/química , Soroalbumina Bovina/química , Soroalbumina Bovina/farmacologia , Supositórios/química , Supositórios/farmacologiaRESUMO
The adaption of the sol-gel autocombustion method to the Cu/ZrO2 system opens new pathways for the specific optimisation of the activity, long-term stability and CO2 selectivity of methanol steam reforming (MSR) catalysts. Calcination of the same post-combustion precursor at 400 °C, 600 °C or 800 °C allows accessing Cu/ZrO2 interfaces of metallic Cu with either amorphous, tetragonal or monoclinic ZrO2, influencing the CO2 selectivity and the MSR activity distinctly different. While the CO2 selectivity is less affected, the impact of the post-combustion calcination temperature on the Cu and ZrO2 catalyst morphology is more pronounced. A porous and largely amorphous ZrO2 structure in the sample, characteristic for sol-gel autocombustion processes, is obtained at 400 °C. This directly translates into superior activity and long-term stability in MSR compared to Cu/tetragonal ZrO2 and Cu/monoclinic ZrO2 obtained by calcination at 600 °C and 800 °C. The morphology of the latter Cu/ZrO2 catalysts consists of much larger, agglomerated and non-porous crystalline particles. Based on aberration-corrected electron microscopy, we attribute the beneficial catalytic properties of the Cu/amorphous ZrO2 material partially to the enhanced sintering resistance of copper particles provided by the porous support morphology.
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Ultrasmall silver nanoparticles were prepared by reduction with NaBH4 and surface-terminated with glutathione (GSH). The particles had a solid core diameter of 2 nm as shown by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS). NMR-DOSY gave a hydrodynamic diameter of 2 to 2.8 nm. X-ray photoelectron spectroscopy (XPS) showed that silver is bound to the thiol group of the central cysteine in glutathione under partial oxidation to silver(+I). In turn, the thiol group is deprotonated to thiolate. X-ray powder diffraction (XRD) together with Rietveld refinement confirmed a twinned (polycrystalline) fcc structure of ultrasmall silver nanoparticles with a lattice compression of about 0.9% compared to bulk silver metal. By NMR spectroscopy, the interaction between the glutathione ligand and the silver surface was analyzed, also with 13C-labeled glutathione. The adsorbed glutathione is fully intact and binds to the silver surface via cysteine. In situ 1H NMR spectroscopy up to 85 °C in dispersion showed that the glutathione ligand did not detach from the surface of the silver nanoparticle, i.e. the silver-sulfur bond is remarkably strong. The ultrasmall nanoparticles had a higher cytotoxicity than bigger particles in in vitro cell culture with HeLa cells with a cytotoxic concentration of about 1 µg mL-1 after 24 h incubation. The overall stoichiometry of the nanoparticles was about Agâ¼250GSHâ¼155.