Transmission Electron Microscopy Investigations Research Articles

Polydopamine functionalized FeTiO3 nanohexagons for selective and simultaneous electrochemical determination of dopamine and uric acid.

Herein we report the simultaneous detection of dopamine (DA) and uric acid (UA) using polydopamine (PDA) functionalized FeTiO3 nanohexagons. The nanohexagons were hydrothermally synthesized and subsequently functionalized with PDA in a Tris-buffer solution. The PDA functionalized nanostructure was characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FTIR), respectively. The SEM and TEM investigations revealed the presence of FeTiO3 nanohexagons along with a peripheral coating of PDA over the nanostructures. The XRD pattern confirmed the formation of the ilmenite structure, while the chemical structure was investigated through XPS and FTIR respectively. Using cyclic voltammetry (CV) the efficacy of FeTiO3-PDA electrode was evaluated toward DA oxidation. The enhanced activity of the functionalized electrode in DA oxidation, as compared to the untreated FeTiO3, may be attributed to the significant presence of hydroxyl, amine, and imine functional groups over the polymer layer. Differential pulse voltammetry (DPV) was utilized for the detection of DA and UA. With a linear range of 50 μM to 250 μM, the detection limits of 0.30 μM and 4.61 μM were determined for DA and UA, respectively. The peak separation of 263 mV between DA and UA demonstrates the sensor's remarkable selectivity. In addition, the study displayed the ability to detect both DA and UA simultaneously, and the validity of the sensor was evaluated in serum samples, respectively.

A study of the spinodal decomposition of ag[sbnd]cu alloy films using in situ transmission electron microscopy

We performed in situ transmission electron microscopy (TEM) investigations to understand spinodal decomposition in AgCu alloy thin films. The decomposition of a homogeneous nanocrystalline morphology into a heterogeneous two-phase structure when annealed in situ from room temperature to 400 °C was investigated with different imaging modes in the TEM. These studies reveal phase transformation proceeds in stages: between 180 and 200 °C, onset of phase separation via spinodal decomposition is observed. Then, prominent phase separation occurs between 200 and 2 50 °C with minimal grain growth. Next, between 2 50 and 300 °C, grain growth primarily occurs via coalescence, with no apparent phase separation. From 300 to 3 50 °C, we observe significant phase separation and Ostwald Ripening. Finally, between 3 50 and 400 °C, further coarsening occurs via coalescence. STEM-HAADF mode reveals the onset of phase separation from domains as small as 5 nm and these results are also supported by electron diffraction and compositional mapping.

Adapting Conductivity and Mechanical Properties through Layer Thickness Variation in Copper Niobium Laminated Metallic Composites

Cu/Nb laminated metallic composites (LMCs) exhibit extraordinary mechanical strength while electrical conductivity is maintained at a high level. In this research, Cu‐based LMCs with varying volume fraction of niobium are produced via accumulative roll bonding (ARB) and additionally cold‐rolled and heat‐treated to identify the role of these heterogeneous phase boundaries on the overall sheet properties. Deformation structures in these layered materials are studied through scanning transmission electron microscopy investigations. The existence of an interface‐affected zone at the phase boundaries and mechanical intermixing is attributed to decreasing electrical and increasing mechanical properties, especially in very thin layered LMCs. Atom probe tomography measurements show that mechanical alloying occurs due to severe plastic deformation during ARB processing of the laminates. An additional subsequent heat treatment leads to chemical demixing at the interfaces of the phase boundaries.

Using In-situ Transmission Electron Microscopy to Study Strong Metal-Support Interactions in Heterogeneous Catalysis.

Precisely controlling the microstructure of supported metal catalysts and regulating metal-support interactions at the atomic level are essential for achieving highly efficient heterogeneous catalysts. Strong metal-support interaction (SMSI) not only stabilizes metal nanoparticles and improves their resistance to sintering but also modulates the electrical interaction between metal species and the support, optimizing the catalytic activity and selectivity. Therefore, understating the formation mechanism of SMSI and its dynamic evolution during the chemical reaction at the atomic scale is crucial for guiding the structural design and performance optimization of supported metal catalysts. Recent advancements in in-situ transmission electron microscopy (TEM) have shed new light on these complex phenomena, providing deeper insights into the SMSI dynamics. Here, the research progress of in-situ TEM investigation on SMSI in heterogeneous catalysis is systematically reviewed, focusing on the formation dynamics, structural evolution during the catalytic reactions, and regulation methods of SMSI. The significant advantages of in-situ TEM technologies for SMSI research are also highlighted. Moreover, the challenges and probable development paths of in-situ TEM studies on the SMSI are also provided.

Atomistic phase transition mechanism of zero-strain electrode material: Transmission electron microscopy investigation of Li4Ti5O12 spinel lattice upon lithiation

The lithiation mechanism of electrode materials is important for understanding the basic reactions in Li-ion batteries. In particular, zero-strain materials have garnered interest owing to their stable charge–discharge performances. In this study, we investigated the atomistic phase transition mechanism of spinel Li4Ti5O12, a well-known zero-strain material, using high-resolution transmission electron microscopy. A single-crystalline Li4Ti5O12 (100) specimen was prepared and observed in situ at a lattice resolution under electron-beam-assisted lithiation. The lattice fringes originating from the Li plane of the spinel crystal were anisotropically altered during phase transition, suggesting the asymmetrical site shifting of Li atoms during lithiation. This spontaneous symmetry-breaking mechanism for the phase transition is considered essential for the lithiation of spinel lattice.

Effects of aging on the microstructure and mechanical properties of metastable β-type Ti-23.6Nb-5.1Mo-6.7Zr alloy with low elastic modulus

In this study, the influence of thermomechanical treatments on the microstructure and mechanical properties of a new metastable β-titanium Ti-23.6Nb-5.1Mo-6.7Zr alloy was assessed. The objective was to determine if the alloy is a potential candidate for a future fabrication of orthopedic implants, in particular prosthetic hip stems with a functional gradient of mechanical properties. Two thermomechanical processing routes were investigated: (a) 90% cold-rolled, (b) 90% cold-rolled, followed by annealing at 950 °C for 1 h. After these initial processing steps, samples were aged between 300 °C and 500 °C from 0.5 h to 4 h. Microstructural characterization was conducted by optical microscopy, transmission electron microscopy and x-ray diffraction. Young's modulus and microhardness were measured. Young's modulus of the sample annealed after cold rolling is lower than that after the cold rolled one. Aging was effective at increasing hardness but also increasing Young's modulus. The hardening during aging resulted from fine ωiso and α precipitation. The transmission electron microscopy investigations indicated that an aging treatment at 500 °C leads to a fine (α + β) microstructure, avoiding brittle ωiso precipitation. For these reasons, this alloy is a potential candidate for the manufacture of a hybrid hip prosthetic stem by employing localized aging treatment at 500 °C in the neck region, creating a functional strength gradient and maintaining a low Young's modulus in the distal part, which is needed to mitigate the stress shielding of the bone.

Microstructure and mechanical response of as-built and solution-annealed LPBF Hastelloy X under high-temperature fatigue loading

This study investigates the microstructural characteristics and the high-temperature mechanical behavior of Hastelloy X, fabricated via laser powder-bed fusion (LPBF) technology. Hastelloy X, a solid solution-strengthened nickel-based superalloy known for its high strength and oxidation resistance at elevated temperatures, has gained significant interest for the fabrication of complex aerospace components through LPBF technology. The study initially focuses on the impact of solution annealing heat treatment at 1227 °C on the alloy microstructure, based on scanning electron microscopy (SEM) and transmission electron microscopy (TEM) investigations. It then explores the fatigue and cyclic deformation response of the alloy at 750 °C across different strain ranges, comparing the as-built and solution-annealed conditions. To understand the observed differences in the cyclic mechanical response of as-built and solution-annealed LPBF HX, for a particular condition, a set of dedicated tests have been performed and interrupted at selected numbers of cycles in the different stages of the mechanical response. At each interruption point, specimens have been examined by TEM to provide an in-depth understanding of the effect of dislocation microstructural evolution on the high-temperature cyclic mechanical response of the alloy.

Incorporating Kappa-carrageenan in Liposomes Facilitates Development of Lipopolysaccharide Hybrid Nanoplatform

Sulfated polysaccharides (kappa-carrageenan) integration in lipids provides diverse structural and physicochemical properties in nanotechnology. Such a lipopolysaccharide hybrid (LPHS) system offers superior applications in the food and pharmaceutical industry. This study investigates the synthesis and characterization of sulfated polysaccharide (kappa-carrageenan: κ-CG) integrated smart liposomes (cubosomes) for establishing cubic tendency in the LPHS system. The κ-CG integrated smart liposomes were prepared using the modified thin film hydration approach. Characterization studies (liposomes and smart liposomes) were performed using dynamic light scattering (DLS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). DLS studies confirmed the nano-range of both delivery systems. The SEM and TEM investigation revealed the formation of classical cubic morphology of the smart liposomes. Sulfated polysaccharide (κ-CG) integrated smart liposomes exhibited an enhanced κ-CG release profile compared to the liposome-free κ-CG alone. This was due to improved entrapment efficiency (68%) and better overall stability established by the κ-CG incorporation.

Synergistic and potential antifungal properties of tailored, one pot multicomponent monoterpenes co-delivered with fluconazole encapsulated nanostructure lipid carrier

Frequent and variant infections are caused by the virtue of opportunistic fungi pathogens. Candidiasis, aspergillosis, and mucormycosis are pathogenic microorganisms that give rise to vast fungal diseases that alternate between moderate to fatal in severity. The use of fluconazole as an antifungal drug was limited due to the acquired resistance in some types of Candida and other fungal species. This study aims to consolidate fluconazole’s biological effectiveness against several pathogenic fungi. Six active monoterpenes (MTs) of carvacrol, linalool, geraniol, α-terpinene, citronellal, and nerolidol were selected and encapsulated in nanostructure lipid carrier (NLC) with (NLC-Flu-MTs) and/without (NLC-MTs) fluconazole in one nanoformulation to determine if they will act synergistically or not? The synthesized nanoformulation NLC-Flu-MTs and NLC-MTs exhibited very good particle size of 144.5 nm and 138.6 nm for size and zeta potential values of (− 23.5 mV) and (− 20.3 mV), respectively. Transmission electron microscope investigation confirmed that the synthesized NLCs have regular and spherical shape. The abundance and concentration of the six released monoterpenes were determined, as a novel approach, using GC–MS with very good results and validity. In-vitro antifungal screening was done before and after nano co-delivery against seven pathogenic, and aggressive fungi of Candida tropicalis, Candida krusei, Candida glabrata, Geotrichum Candidum, Candidaalbicans, Aspergillus Niger, and mucor circinelloides. Inhibition Zone diameter (IZD) and the minimum inhibitory concentration (MIC) were measured. Nanoformulations NLC-Flu-MTs and NLC-MTs manifested potential and unique biological susceptibility against all the tested microorganisms with reduced (MIC) values, especially against Candida Tropicalis (MIC = 0.97 µg/ml) which represents 16-fold of the value shown by NLC-MTs (MIC = 15.6 µg/ml) and 64-fold of fluconazole free before nanoformulation (MIC = 62.5 µg/ml). The efficiency of nanomaterials, particularly NLC-Flu-MTs, has become evident in the diminishing value of MIC which affirmed the synergism between fluconazole and the other six monoterpenes.

Microstructural and elemental analysis of flow lips of heavy haul curved rails affected by deformation driven phase transformation

A combination of optical imaging (OM), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and atom probe tomography (APT) was used to examine the white etching layer (WEL) and brown etching layer (BEL) formed in the flow lip region of a heavy haul curved rail. These flow lips eventually serve as crack initiating regions, leading to reverse detail fractures. OM distinctly identified the WEL/BEL region based on light contrast, while SEM micrographs identified a fine-grained structure within the WEL with intermittent patches of a deformed pearlitic structure. SEM images of the WEL/BEL indicate that the fraction of cementite patches was higher in the BEL region than in the WEL. TEM investigations revealed the presence of martensite/nano-crystalline ferrite along with newly formed austenite and cementite particles in the WEL and the BEL. The ferrite/martensite grain size was much finer in the WEL than in the BEL. The lath morphology of martensite was observed in the BEL, whereas a mixed morphology of lath and twinned martensite was observed in the WEL. APT studies show no Mn/Si partitioning in WEL/BEL along with C-concentrations ranging from 10 to 15 at.% and up to 20 at.% in the WEL and BEL respectively. The synergistic effect of elevated wheel-rail contact temperatures and severe plastic deformation dictated the overall microstructural evolution of the BELs and WELs on the outer rail surface in the flow lip.

From ID-TIMS U-Pb dating of single monazite grain to APT-nanogeochronology: application to the UHT granulites of Andriamena (North-Central Madagascar)

Monazite and zircon grains from the ultra-high temperature (UHT) granulite of the Andriamena unit in the centre north of Madagascar, previously investigated using micro-drilled single grain isotopic dissolution geochronology and in-situ electron microprobe chemical dating by Paquette et al. (2004), are reinvestigated using high spatial resolution techniques: atom probe tomography (APT), transmission electron microscopy (TEM), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and secondary ion mass spectrometry (SIMS). The dated grains are located in quartz, garnet belonging to the peak UHT metamorphic assemblage and in retrograde coronitic texture composed of biotite, cordierite and orthoamphibole. Monazite grains show complex discordant trends with several radiogenic Pb (Pb*) loss dispersions, that were previously interpreted as recording at least four geologic episodes occurring from the Archean (~2.7 Ga) to the Proterozoic-Cambrian (~0.5 Ga). Multiscale investigations with SIMS, TEM and APT have been carried out on monazite and LA-ICP-MS on zircon. Zircon grains hosted in garnet and those in quartz record concordant ages at 2758 ±28 Ma and 2609 ±51 Ma, respectively. Monazite grains show age dispersion and a Pb*-loss trend correlated with the grain petrographic position. Grains located in garnet and quartz present less Pb*-loss than those located in the coronitic texture. The discordia indicates a crystallisation age at 2555 ±71 Ma and monazite grains hosted in quartz and garnet record a disturbance event at 1053 ±246 Ma. TEM investigations show that monazite located in quartz and garnet contain numerous Pb-bearing nanophases compared to monazite located in coronitic texture. There is an inverse correlation between the number of Pb-bearing nanophases and the percentage of Pb*-loss in monazite grains. 232Th/208Pb ratio obtained with APT in monazite matrix (i.e. excluding Pb-bearing nanophases) located in quartz and garnet indicated a mean age of 1092 ±127 Ma. This date is interpreted as a hitherto undetected geochronological record in Andriamena unit.

In-situ TEM investigation of recovery mechanisms in ion-irradiated ITER-grade tungsten

The annealing of irradiation defects in tungsten was investigated under in-situ observations conducted using transmission electron microscopy (TEM). ITER-specification tungsten was exposed to heavy-ion irradiation by 10 MeV Au+ ions to 0.5 and 1 dpa at room temperature to generate defects. Subsequently, the thermal stability and recovery mechanisms of the generated defects are investigated by in-situ TEM at 600 °C, 800 °C, 900 °C and 1000 °C. The obtained TEM data are used to visualize and quantify the defect characteristics such as loops and voids as well as for observing the evolution of the microstructure and defect diffusion/recovery mechanisms. Focus is made on specific spatial phenomena such as loop-loop interaction, loop-dislocation and loop-grain boundary decoration, loop pinning, entanglement, formation of raft and transformation of loops into a dislocation network. The obtained results are in line with earlier obtained data for pure recrystallized tungsten, still, present results provide important information such as radiation-induced defect characteristics and recovery mechanisms under high temperature for the ITER-specification tungsten.

Atomic and electronic structures of domain boundaries in LaTiO3 thin films

Domain boundaries in perovskite oxides often exhibit abundant physical properties and phenomena. Here, epitaxial LaTiO3 thin films on (100) SrTiO3 substrates are prepared by pulsed-laser deposition. X-ray diffraction and transmission electron microscopy investigations reveal that the epitaxial LaTiO3 thin films have good crystallinity but a high density of domain boundaries. Atomic-scale scanning transmission electron microscopy observations reveal that two types of domain boundaries are formed in the LaTiO3 thin films. The type I domain boundaries are formed on the {100} crystal planes, while the type II domain boundaries on the {110} crystal planes. Electron energy-loss spectroscopy analyses suggest that the valence states of Ti ions at the type I domain boundaries are +3, while those at the type II domain boundaries are +4. First-principles calculations reveal that the bandgap decreases at both domain boundaries compared to the bulk. The carrier concentration at the type I domain boundaries is significantly higher than that of the bulk, while the carrier concentration at the type II domain boundaries is lower. These findings suggest that domain boundaries play an important role in tailoring the electrical properties of the LaTiO3 thin films, thereby promoting the potential applications and property modulation of related materials and devices.

Structural, bandgap tailoring, photoluminescence and electrochemical characteristics of Sm3+-doped ZnS quantum dots prepared in Ar-atmosphere

Sm3+-doped ZnS quantum dots were prepared by a cost-effective, simple co-precipitation technique under an argon atmosphere. The prepared Sm3+-doped QDs exhibited a cubic structure with an average particle size of ∼ 2 nm, as confirmed through X-ray diffraction and high-resolution transmission electron microscopic investigations. The crystallite was reduced and strain produced due to the larger ionic radius of Sm3+ ions. The Sm (at. 2 %)-doped ZnS exhibited a blue shift, and the optical transmittance was enhanced. A highly intense red emission was obtained in photoluminescence investigations, and this is due to the transfer of photons from 4G5/2 → 6H11/2 for f-f transitions of the Sm3+ in the 4f5 configuration. The obtained photoluminescence emissions lead to red phosphor applications. The cyclic voltammogram analysis showed that adding Sm to ZnS QDs made their specific capacitance value higher and it found potential applications in supercapacitors.

Interplay of heat treatment and deformation temperature on the microstructural evolution and mechanical behavior of SLM AlSi10Mg alloy

This study conducts a comprehensive examination of the microstructural and dislocation dynamics of AlSi10Mg alloys under various thermal conditions, utilizing quasi in-situ Electron Backscatter Diffraction (EBSD) and Transmission Electron Microscopy (TEM) analyses. The research focuses on comparing the microstructural response of as-built and T6 heat-treated samples to mechanical stress at both ambient (298 K) and cryogenic (77 K) temperatures. EBSD analysis underscores the grain stability under applied strain, while TEM investigations expose notable variations in dislocation mobility influenced by temperature, with a particular emphasis on the interaction between dislocations and silicon particles at cryogenic temperatures. An observed increase in Geometrically Necessary Dislocation (GND) density at 77 K points to enhanced resistance to plastic deformation, suggesting mechanisms of cryogenic strengthening. The findings illuminate the impact of heat treatment in augmenting the mechanical properties of the alloy, shedding light on its potential applications in aerospace and cryogenic environments.

Creep anisotropy of additively manufactured Inconel-738LC: Combined experiments and microstructure-based modeling

The current lack of quantitative knowledge on processing-microstructure–property relationships is one of the major bottlenecks in today’s rapidly expanding field of additive manufacturing. This is centrally rooted in the nature of the processing, leading to complex microstructural features. Experimentally-guided modeling can offer reliable solutions for the safe application of additively manufactured materials. In this work, we combine a set of systematic experiments and modeling to address creep anisotropy and its correlation with microstructural characteristics in laser-based powder bed fusion (PBF-LB/M) additively manufactured Inconel-738LC (IN738LC). Three sample orientations (with the tensile axis parallel, perpendicular, and 45° tilted, relative to the building direction) are crept at 850 °C, accompanied by electron backscatter secondary diffraction (EBSD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) investigations. A crystal plasticity (CP) model for Ni-base superalloys, capable of modeling different types of slip systems, is developed and combined with various polycrystalline representative volume elements (RVEs) built on the experimental measurements. Besides our experiments, we verify our modeling framework on electron beam powder bed fusion (PBF-EB/M) additively manufactured Inconel-738LC. The results of our simulations show that while the crystallographic texture alone cannot explain the observed creep anisotropy, the superlattice extrinsic stacking faults (SESF) and related microtwinning slip systems play major roles as active deformation mechanisms. We confirm this using TEM investigations, revealing evidence of SESFs in crept specimens. We also show that the elongated grain morphology can result in higher creep rates, especially in the specimens with a tilted tensile axis.

Comparative study between oxide/soft ferrite, oxide/hard ferrite, and soft/hard ferrite nanocomposites: structural, electrical, and magnetic properties

Three binary nanocomposites (NCs): (0.5NiO/0.5Ni0.5Zn0.5Fe2O4), (0.5NiO/0.5BaFe12O19), and (0.5Ni0.5Zn0.5Fe2O4/0.5BaFe12O19) were prepared using the co-precipitation method followed by the wet ball-milling technique. X-ray diffraction analysis showed the production of NiO and Ni0.5Zn0.5Fe2O4 single phases, while the α-Fe2O3 secondary phase appeared in the BaFe12O19 and the 0.5Ni0.5Zn0.5Fe2O4/0.5BaFe12O19 nanocomposite. The transmission electron microscopy investigation and the selected area electron diffraction demonstrated the presence of the nanocomposites’ constituent phases. x-ray photoelectron spectroscopy identified the oxidation states found in the prepared samples (Ba2+, Ni2+, Ni3+, Zn2+, Fe3+, and O2−). The bandgap values (Eg) of the nanocomposites are in the range between 2.79 and 3.66 eV, which indicates their semiconductor nature. The DC conductivity experiment confirmed the semiconducting nature of all samples, and the activation energies ( EaH ) and ( EaL ) at high and low-temperature regions, respectively, were calculated from the Arrhenius equation. According to the vibrating sample magnetometer, the NCs exhibited ferromagnetic (FM) as showed by the M-H loops. In the oxide/soft ferrite NC, the dM/dH curve indicated strong exchange coupling interactions, while the hard and the soft magnetic phases in the oxide/hard ferrite and the soft/hard ferrite NCs were weakly exchanged coupled. Significant uses had been found for each of the three nanocomposites according to their constituent phases and properties.

In situ high-temperature transmission electron microscopy investigation of dynamic element migration for Sm-Co-Fe-Cu-Zr sintered magnets

The investigation delved into the dynamic migration of elements and the evolution of interface structures within the Sm(CobalFe0.09Cu0.09Zr0.03)7.2 magnet as temperature increased, employing high-temperature transmission electron microscopy. Notably, the Cu distribution exhibited temperature susceptibility. Elevating the temperature from room temperature (RT) to 400 °C led to a notable expansion in the distribution width of Cu, ranging from 28.5 to 50.8 nm. Simultaneously, the average Cu content at the cell boundaries decreased from 14.4 to 11.6 at.%. According to the high-temperature in-situ experimental results of the transmission electron microscopy thin-film samples, the derived diffusion coefficients, D300°Cand D400°C, were determined as 0.0525 nm2/s and 1.414 nm2/s, respectively. The significantly higher D400°C compared to D300°C underscores the considerable influence of temperature on Cu element diffusion behavior. The simulation results demonstrate that the trend of magnetic properties variation at different temperatures closely aligns with the observed trend. Subsequent calculation of the temperature coefficient of intrinsic coercivity (β) reveals that |β300–400°C| is notably higher than |βRT-300°C|. This suggests a substantial impact of Cu diffusion-induced deterioration on the β. Moreover, micromagnetic simulation results delineated the reverse magnetization process for magnets at varying temperatures, revealing that the presence of the Cu diffusion region diminished the pinning effect of the cell boundary phase. Furthermore, a wider Cu diffusion region facilitated easier magnetic moment reversal at the cell boundary phase, resulting in a marked deterioration of intrinsic coercivity. This elucidates that the formation of the Cu diffusion region stands as one of the primary reasons for the sharp decline in magnetic properties of Sm2Co17-type magnets under high-temperature conditions.

Stacking fault energy, thermal expansion behavior, and elastic coefficients of a single-crystalline CrFeNi medium-entropy alloy

The equiatomic CrFeNi alloy is considered to be a model single-phase face-centered cubic medium-entropy alloy. The Bridgman technique was employed to grow a single crystal of this alloy and its dilatation behavior and elastic properties were measured in the temperature range: 100 K–673 K. Based on transmission electron microscopy investigations, plastic deformation is initially caused by the glide of dissociated dislocations (Shockley pairs bounded by a stacking fault ribbon). From their dissociated widths, a stacking fault energy of 36 mJ∙m-2 was determined.

Structural Evolution of GaOx-Shell and Intermetallic Phases in Ga-Pt Supported Catalytically Active Liquid Metal Solutions.

We present a comprehensive scale-bridging characterization approach for supported catalytically active liquid metal solutions (SCALMS) which combines lab-based X-ray microscopy, nano X-ray computed tomography (nano-CT), and correlative analytical transmission electron microscopy. SCALMS catalysts consist of low-melting alloy particles and have demonstrated high catalytic activity, selectivity, and long-term stability in propane dehydrogenation (PDH). We established an identical-location nano-CT workflow which allows us to reveal site-specific changes of Ga-Pt SCALMS before and after PDH. These observations are complemented by analytical transmission electron microscopy investigations providing information on the structure, chemical composition, and phase distribution of individual SCALMS particles. Key findings of this combined microscopic approach include (i) structural evolution of the SCALMS particles' GaOx shell, (ii) Pt segregation toward the oxide shell leading to the formation of Ga-Pt intermetallic phases, and (iii) cracking of the oxide shell accompanied by the release of liquid Ga-Pt toward the porous support.