ABSTRACT
High-entropy nanomaterials exhibit exceptional mechanical, physical, and chemical properties, finding applications in many industries. Peroxidases are metalloenzymes that accelerate the decomposition of hydrogen peroxide. This study uses the high-entropy approach to generate multimetal oxide-based nanozymes with peroxidase-like activity and explores their application as sensors in ex vivo bioassays. A library of 81 materials was produced using a coprecipitation method for rapid synthesis of up to 100 variants in a single plate. The A and B sites of the magnetite structure, (AA')(BB'B'')2O4, were substituted with up to six different cations (Cu/Fe/Zn/Mg/Mn/Cr). Increasing the compositional complexity improved the catalytic performance; however, substitutions of single elements also caused drastic reductions in the peroxidase-like activity. A generalized linear model was developed describing the relationship between material composition and catalytic activity. Binary interactions between elements that acted synergistically or antagonistically were identified, and a single parameter, the mean interaction effect, was observed to correlate highly with catalytic activity, providing a valuable tool for the design of high-entropy-inspired nanozymes.
Subject(s)
Entropy , Immunoassay/methods , Oxides/chemistry , Catalysis , Nanostructures/chemistry , Structure-Activity Relationship , Computer Simulation , Hydrogen Peroxide/chemistryABSTRACT
CeO2-supported noble metal clusters are attractive catalytic materials for several applications. However, their atomic dispersion under oxidizing reaction conditions often leads to catalyst deactivation. In this study, the noble metal cluster formation threshold is rationally adjusted by using a mixed CeO2-Al2O3 support. The preferential location of Pd on CeO2 islands leads to a high local surface noble metal concentration and promotes the in situ formation of small Pd clusters at a rather low noble metal loading (0.5â wt %), which are shown to be the active species for CO conversion at low temperatures. As elucidated by complementary in situ/operando techniques, the spatial separation of CeO2 islands on Al2O3 confines the mobility of Pd, preventing the full redispersion or the formation of larger noble metal particles and maintaining a high CO oxidation activity at low temperatures. In a broader perspective, this approach to more efficiently use the noble metal can be transferred to further systems and reactions in heterogeneous catalysis.
ABSTRACT
Subnanometer clusters with precise atom numbers hold immense potential for applications in catalysis, as single atoms can significantly impact catalytic properties. Typically, inorganic clusters are produced using batch processes with high dilutions, making the scale-up of these processes time-consuming and its reproducibility challenging. While continuous-flow systems have been employed for organic synthesis and, more recently, nanoparticle preparation, these approaches have only rarely been applied to cluster synthesis. In a flexible, continuous flow synthesis platform, we integrate multiple continuous stirred tank reactors (CSTR) into a cascade to synthesize clusters with a precise number of atoms, demonstrating the potential of this approach for atom precise cluster synthesis and expanding the application of continuous-flow systems beyond organic synthesis.
ABSTRACT
The structure and the chemical composition of individual layers as well as of interfaces belonging to the two heterostructures M1 (BaFe12O19/YbFeO3/YSZ) and M2 (YbFeO3/BaFe12O19/YSZ) grown by pulsed laser deposition on yttria-stabilized zirconia (YSZ) substrates are deeply characterized by using a combination of methods such as high-resolution X-ray diffraction, transmission electron microscopy (TEM), and atomic-resolution scanning TEM with energy-dispersive X-ray spectroscopy. The temperature-dependent magnetic properties demonstrate two distinct heterostructures with different coercivity, anisotropy fields, and first anisotropy constants, which are related to the defect concentrations within the individual layers and to the degree of intermixing at the interface. The heterostructure with the stacking order BaFe12O19/YbFeO3, i.e., M1, exhibits a distinctive interface without any chemical intermixture, while an Fe-rich crystalline phase is observed in M2 both in atomic-resolution EDX maps and in mass density profiles. Additionally, M1 shows high c-axis orientation, which induces a higher anisotropy constant K1 as well as a larger coercivity due to a high number of phase boundaries. Despite the existence of a canted antiferromagnetic/ferromagnetic combination (T < 140 K), both heterostructures M1 and M2 do not reveal any detectable exchange bias at T = 50 K. Additionally, compressive residual strain on the BaM layer is found to be suppressing the ferromagnetism, thus reducing the Curie temperature (Tc) in the case of M1. These findings suggest that M1 (BaFe12O19/YbFeO3/YSZ) is suitable for magnetic storage applications.
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The development of competitive rechargeable Mg batteries is hindered by the poor mobility of divalent Mg ions in cathode host materials. In this work, we explore the dual cation co-intercalation strategy to mitigate the sluggishness of Mg2+ in model TiS2 material. The strategy involves pairing Mg2+ with Li+ or Na+ in dual-salt electrolytes in order to exploit the faster mobility of the latter with the aim to reach better electrochemical performance. A combination of experiments and theoretical calculations details the charge storage and redox mechanism of co-intercalating cationic charge carriers. Comparative evaluation reveals that the redox activity of Mg2+ can be improved significantly with the help of the dual cation co-intercalation strategy, although the ionic radius of the accompanying monovalent ion plays a critical role on the viability of the strategy. More specifically, a significantly higher Mg2+ quantity intercalates with Li+ than with Na+ in TiS2. The reason being the absence of phase transition in the former case, which enables improved Mg2+ storage. Our results highlight dual cation co-intercalation strategy as an alternative approach to improve the electrochemical performance of rechargeable Mg batteries by opening the pathway to a rich playground of advanced cathode materials for multivalent battery applications.
ABSTRACT
Focused ion beam scanning electron microscopy (FIB-SEM) tomography is a serial sectioning technique where an FIB mills off slices from the material sample that is being analysed. After every slicing, an SEM image is taken showing the newly exposed layer of the sample. By combining all slices in a stack, a 3D image of the material is generated. However, specific artefacts caused by the imaging technique distort the images, hampering the morphological analysis of the structure. Typical quality problems in microscopy imaging are noise and lack of contrast or focus. Moreover, specific artefacts are caused by the FIB milling, namely, curtaining and charging artefacts. We propose quality indices for the evaluation of the quality of FIB-SEM data sets. The indices are validated on real and experimental data of different structures and materials.
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The connectivity and thermal stability of pores in heterogeneous, mesoporous metal oxide catalysts are key properties controlling their (long-term) efficacy. In this study, we investigate the influence of pH and temperature during a common hydrothermal aftertreatment step in the synthesis of mesoporous CexZr1-x-y-zYyLazO2-δ oxides obtained from molecular precursors via hydrothermal synthesis. This study has a strong focus on the methodological approach, elucidating whether and how even the smallest changes in morphology and connectivity may be unraveled and related to the underlying chemical processes to uncover key parameters for the ongoing improvement of material properties. Deep insights into the mesopore space were obtained by state-of-the-art physisorption (including hysteresis scanning), electron tomography, and small-angle X-ray scattering (SAXS) analysis. We also provide a simple tool to simulate SAXS curves from electron tomography data that allow direct comparison to experimentally obtained SAXS curves. Furthermore, the impact on surface-bound nitrate groups and the development during calcination were studied in detail by thermogravimetric analysis coupled with mass spectrometry. The key observations indicate a significant increase in thermal stability at temperatures as high as 1050 °C and improved mesopore accessibility with an increase in pH of the aftertreatment solution. The combined observations from the employed methods suggest a pH-dependent removal of surface-bound nitrate groups as well as a dissolution and reprecipitation-based fusing of the primary particles that constitute the mesopore skeleton. This transformation yields a mechanically and thermally stronger mesopore space with the capability to endure high temperatures.
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We have studied the effect of platinum underlayer for two deposited thicknesses on the microstructure, crystalline quality, morphology, chemical composition, and magnetic properties as well as magnetic domain formation of BaFe12O19 (BaM) grown on YSZ(111) by pulsed laser deposition (PLD). We found that PLD platinum deposited with a thickness of 25 nm cannot withstand the dewetting phenomenon occurring during the subsequent BaM layer growth. A smooth and continuous Pt underlayer that possesses a sharp interface and omits the intermixing between the BaM and substrate was successfully achieved for a deposited Pt film thickness of 75 nm. Independent of the thickness of the deposited Pt layer, the c-axis orientation as well as coercivity Hc and the anisotropy HA fields were significantly improved due to a remarkable improvement of lattice mismatch in comparison with the BaM layer grown without a Pt underlayer on YSZ(111). By applying high-resolution X-ray diffraction, scanning and transmission electron microscopy (SEM/TEM), and atomically resolved scanning TEM imaging combined with energy-dispersive X-ray spectroscopy, as well as atomic and magnetic force microscopy, a comprehensive investigation of both structure and chemical composition of the deposited BaM films and their interfacial regions was performed. This study aimed to correlate the enhancement of the overall magnetic properties and of the local spin magnetic domain orientation with the modification of BaM microstructure and chemical composition at the nanometer scale due to the Pt underlayer. Finally, we attempted to understand the mechanisms that control the magnetic properties of these BaM films in order to be able to tailor them.
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We demonstrate the epitaxial coating of GaN NWs with an epitaxial ZnO shell by atomic layer deposition at 300 °C. Scanning transmission electron microscopy proves a sharp and defect-free coherent interface. The strain in the core-shell structure due to the lattice mismatch and different thermal expansion coefficients of GaN and ZnO was analyzed using 4D-STEM strain mapping and Raman spectroscopy and compared to theoretical calculations. The results highlight the outstanding advantages of epitaxial shell growth using atomic layer deposition, e.g., conformal coating and precise thickness control.
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The realization of the broad range of application of MXenes relies on the successful and reproducible synthesis of quality materials of tailored properties. To date, most MXenes have been produced making use of acid-based etching methods, yet an in-depth understanding of etching processes is lacking. Herein, we have engaged in a comprehensive study of the multiple variables involved in the synthesis of V2CTx with focus on the properties of etched materials. Two main sets of experiments were considered, each using a different V2AlC precursor and a range of synthesis variables including reaction time and temperature, mixing rate, and type of acid. Correlations of synthesis conditions-materials properties were investigated using a broad range of characterization techniques including analytical methods, scanning and transmission electron microscopy, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Findings indicated the crucial relevance of properties of the MAX precursor such as elemental composition, particle size, and crystal structure on etching processes and properties of etched materials. Particularly, depending on the MAX precursor, two etching patterns were identified, core-shell and plate-by-plate, the latter describing a more efficient etching. Combined studies of elemental composition, crystal structure, and yield quantification allowed us to evaluate the effectiveness of etching processes. XRD studies revealed key crystal-structure-type of acid correlations showing advantages of using a HF/HCl mix over only HF. Analytical methods XRD and XPS delivered insights into undergoing chemical processes and their influence on bulk and surface chemistry of etched materials. The relevance for reaction kinetics of highly correlated variables such as reaction vessel dimensions, mixing efficiency, and reaction temperature was recognized. For the first time, a MXene synthesis has been investigated comprehensively highlighting its multivariable nature and the high variable intercorrelation, opening up venues for further investigation on MAX and MXene synthesis.
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For decades, scanning/transmission electron microscopy (S/TEM) techniques have been employed to analyze shear bands in metallic glasses and understand their formation in order to improve the mechanical properties of metallic glasses. However, due to a lack of direct information in reciprocal space, conventional S/TEM cannot characterize the local strain and atomic structure of amorphous materials, which are key to describe the deformation of glasses. For this work, 4-dimensional-STEM (4D-STEM) is applied to map and directly correlate the local strain and the atomic structure at the nanometer scale in deformed metallic glasses. Residual strain fields are observed with quadrupolar symmetry concentrated at dilated Eshelby inclusions. The strain fields percolate in a vortex-like manner building up the shear band. This provides a new understanding of the formation of shear bands in metallic glass.
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High entropy oxides (HEOs) with chemically disordered multi-cation structure attract intensive interest as negative electrode materials for battery applications. The outstanding electrochemical performance has been attributed to the high-entropy stabilization and the so-called 'cocktail effect'. However, the configurational entropy of the HEO, which is thermodynamically only metastable at room-temperature, is insufficient to drive the structural reversibility during conversion-type battery reaction, and the 'cocktail effect' has not been explained thus far. This work unveils the multi-cations synergy of the HEO Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O at atomic and nanoscale during electrochemical reaction and explains the 'cocktail effect'. The more electronegative elements form an electrochemically inert 3-dimensional metallic nano-network enabling electron transport. The electrochemical inactive cation stabilizes an oxide nanophase, which is semi-coherent with the metallic phase and accommodates Li+ ions. This self-assembled nanostructure enables stable cycling of micron-sized particles, which bypasses the need for nanoscale pre-modification required for conventional metal oxides in battery applications. This demonstrates elemental diversity is the key for optimizing multi-cation electrode materials.
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Supported nanocatalysts exhibit different performances in batch and fixed bed reactors for a wide range of liquid phase catalytic reactions due to differences in metal leaching. To investigate this leaching process and its influence on the catalytic performance, a quantitative 3D characterization of the particle size and the particle distribution is important to follow the structural evolution of the active metal catalysts supported on porous materials during the reaction. In this work, electron tomography has been applied to uncover leaching and redeposition of a Pd@CMK3 catalyst during formic acid decomposition in batch and fixed bed reactors. The 3D distribution of Pd NPs on the mesoporous carbon CMK3 has been determined by a quantitative tomographic analysis and the determined structural changes are correlated with the observed differences in activity and stability of formic acid decomposition using batch and fixed bed reactors.
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Performing reliable preparation of transmission electron microscopy (TEM) samples is the necessary basis for a meaningful investigation by ex situ and even more so by in situ TEM techniques, but it is challenging using materials that are sensitive to electron beam irradiation. Focused ion beam is currently the most commonly employed technique for a targeted preparation, but the structural modifications induced during focused ion beam preparation are not fully understood for a number of materials. Here, we have investigated the impact of both the electron and the Ga+ ion beam on insulating solid-state electrolytes (lithium phosphorus oxynitride, Na-ß"-alumina solid electrolyte and Na3.4Si2.4Zr2P0.6O12 (NaSICON)) and observed significant lithium/sodium whisker growth induced by both the electron and ion beam already at fairly low dose, leading to a significant change in the chemical composition. The metal whisker growth is presumably mainly due to surface charging, which can be reduced by coating with a gold layer or preparation under cryogenic conditions as efficient approaches to stabilize the solid electrolyte for scanning electron microscopy imaging and TEM sample preparation. Details on the different preparation approaches, the acceleration voltage dependence and the induced chemical and morphological changes are reported.
ABSTRACT
Pore size and pore connectivity control diffusion-based transport in mesopores, a crucial property governing the performance of heterogeneous catalysts. In many cases, transition-metal oxide catalyst materials are prepared from molecular precursors involving hydrothermal treatment followed by heat treatment. Here, we investigate the effects of such a hydrothermal aftertreatment step, using an aqueous ammonia solution, on the disordered mesopore network of CexZr1-x-y-zYyLazO2-δ mixed oxides. This procedure is a common synthesis step in the preparation of such ceria-based oxygen storage materials applied in three-way catalysis, employed to improve the materials' thermal stability. We perform state-of-the-art Ar-physisorption analysis, especially advanced hysteresis scanning, to paint a detailed picture of the alterations in mesopore space caused by the hydrothermal aftertreatment and subsequent aging at 1050 °C. Furthermore, we investigate the network characteristics by electron tomography in combination with suitable statistical analysis, enabling a consistent interpretation of the desorption scans (physisorption). The results indicate that the hydrothermal aftertreatment enhances the mesopore connectivity of the continuous 3D network by widening pores and especially necks, hence facilitating accessibility to the particles' internal surface area and the ability to better withstand high temperatures.
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Electron tomography (ET) has attracted significant attention for a quantitative analysis of mesoporous materials, especially for complex disordered pore structures, as no priori assumption on the pore shape is needed, which is normally inevitable when using traditional bulk characterization techniques. However, a reliable quantification of such pore structures from ET critically depends on the fidelity of the segmented reconstruction, which can be significantly affected, e.g. by the raw data quality, the limited tilting range, artifacts introduced during alignment and further depends on the reconstruction algorithm. Therefore, we systematically investigated the reconstruction reliability of three main-stream algorithms including simultaneous iterative reconstruction technique (SIRT), total variation minimization (TVM) and discrete algebraic reconstruction technique (DART) for mesoporous materials using different imperfect (realistic) tilt-series based on a set of phantom simulations. We found that DART outperforms the other two methods in reliably revealing small pores and narrow channels, especially when the number of projections is strongly constrained. The accurately segmented reconstruction from DART makes it possible to achieve reliable quantification of the pores structure, which in turn leads to reliable evaluation of effective diffusion coefficients. We discuss the influence of different acquisition and reconstruction parameters on the reconstructed 3D volume and the quantitative analysis of pore features. We aim to provide a practical guideline for optimizing acquisition and reconstruction parameters and how to evaluate the accuracy when describing the mesoporous structure.
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Intermetallic nanoparticles (NPs) are highly interesting materials in catalysis due to their geometrically ordered structures and altered electronic properties, but the synthesis of defined intermetallic NPs remains a challenge. Here, we report a novel and facile approach for the synthesis of intermetallic Pd-In NPs in ionic liquids (ILs) at moderate temperatures. Depending on the molar ratio of the metal precursors and the reaction temperature, single-phase Pd3In, PdIn and Pd3In7 NPs were obtained, which was confirmed, e.g. by powder X-ray diffraction, electron microscopy, and optical emission spectroscopy with inductively coupled plasma. The Pd-In NPs stabilized in ILs were used as catalysts in the liquid-phase semi-hydrogenation of diphenylacetylene (DPA). Highly ordered PdIn NPs with a CsCl type structure revealed both high activity and selectivity to cis-stilbene even at full DPA conversion. Intermetallic compounds such as PdIn can be used to isolate contiguous Pd atoms with another base metal into single Pd sites, thereby increasing the catalytic selectivity of Pd while stabilizing the individual sites in the intermetallic structures. This work may provide new pathways for the synthesis of single-phase intermetallic NPs and future insights into a more rational design of bimetallic catalysts with specific catalytic properties.
ABSTRACT
The reactive hydride composite (RHC) LiBH4-MgH2 is regarded as one of the most promising materials for hydrogen storage. Its extensive application is so far limited by its poor dehydrogenation kinetics, due to the hampered nucleation and growth process of MgB2. Nevertheless, the poor kinetics can be improved by additives. This work studied the growth process of MgB2 with varying contents of 3TiCl3·AlCl3 as an additive, and combined kinetic measurements, X-ray diffraction (XRD), and advanced transmission electron microscopy (TEM) to develop a structural understanding. It was found that the formation of MgB2 preferentially occurs on TiB2 nanoparticles. The major reason for this is that the elastic strain energy density can be reduced to ~4.7 × 107 J/m3 by creating an interface between MgB2 and TiB2, as opposed to ~2.9 × 108 J/m3 at the original interface between MgB2 and Mg. The kinetics of the MgB2 growth was modeled by the Johnson-Mehl-Avrami-Kolmogorov (JMAK) equation, describing the kinetics better than other kinetic models. It is suggested that the MgB2 growth rate-controlling step is changed from interface- to diffusion-controlled when the nucleation center changes from Mg to TiB2. This transition is also reflected in the change of the MgB2 morphology from bar- to platelet-like. Based on our observations, we suggest that an additive content between 2.5 and 5 mol% 3TiCl3·AlCl3 results in the best enhancement of the dehydrogenation kinetics.
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Electron tomography (ET) has gained increasing attention for the 3D characterization of nanoparticles. However, the missing wedge problem due to a limited tilt angle range is still the main challenge for accurate reconstruction in most experimental TEM setups. Advanced algorithms could in-paint or compensate to some extent the missing wedge artifacts, but cannot recover the missing structural information completely. 360° ET provides an option to solve this problem by tilting a needle-shaped specimen over the full tilt range and thus filling the missing information. However, sample preparation especially for fine powders to perform full-range ET is still challenging, thus limiting its application. In this work, we propose a new universal sample preparation method that enables the transfer of selected individual nanoparticle or a few separated nanoparticles by cutting a piece of carbon film supporting the specimen particles and mounting them onto the full-range tomography holder tip with the help of an easily prepared sharp tungsten tip. This method is demonstrated by 360° ET of Pt@TiO2 hollow cage catalyst showing high quality reconstruction without missing wedge.
ABSTRACT
The hampered kinetics of reactive hydride composites (RHCs) in hydrogen storage and release, which limits their use for extensive applications in hydrogen storage S1and energy conversion, can be improved using additives. However, the mechanism of the kinetic restriction and the additive effect on promoting the kinetics have remained unclear. These uncertainties are addressed by utilizing versatile transmission electron microscopy (TEM) on the LiBH4-MgH2 composite under the influence of the 3TiCl3·AlCl3 additives. The formation of the MgB2 phase, as the rate-limiting step, is emphatically studied. According to the observations, the heterogeneous nucleation of MgB2 relies on different nucleation centers (Mg or TiB2 and AlB2). The varied nucleation and growth of MgB2 are related to the in-plane strain energy density at the interface, resulting from the atomic misfit between MgB2 and its nucleation centers. This leads to distinct MgB2 morphologies (bars and platelets) and different performances in the dehydrogenation kinetics of LiBH4-MgH2. It was found that the formation of numerous MgB2 platelets is regarded as the origin of the kinetic improvement. Therefore, to promote dehydrogenation kinetics in comparable RHC systems for hydrogen storage, it is suggested to select additives delivering a small atomic misfit.