Dark-field Scanning Transmission Electron Microscopy Research Articles

Enhanced N2O decomposition on Rh/ZrO2 catalysts through the promotional effect of palladium

Supported rhodium oxide (RhOx) catalysts have emerged as highly promising for effectively catalytic decomposition of N2O, hence contributing to the mitigation of greenhouse gas emission and combating global warming. Supported RhOx catalysts outperform catalysts employing zeolites and composite metal oxides even under challenging conditions involving O2, H2O, and CO2. This study explores the augmentation of Rh/ZrO2 (RhOx supported on monoclinic ZrO2) catalyst efficiency through the addition of palladium (Pd) to yield RhPd/ZrO2. The augmented catalyst demonstrates notable improvements in N2O decomposition under both N2O-only and more realistic conditions (N2O + O2 + H2O + CO2). Various techniques, including high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption spectroscopy, were employed to investigate the structural characteristics of Rh and Pd species on ZrO2. Kinetic studies further delved into the promotional effect, revealing that the introduction of Pd enhanced the catalytic activity of RhOx catalysts by augmenting their thermal reduction capability. This enhancement proved beneficial in facilitating the efficient progression of the rate-determining step for N2O catalytic decomposition, namely the thermal reduction of the catalyst to produce gaseous O2, particularly at low temperatures. These results highlight the potential of Pd-mediated improvements in Rh/ZrO2 catalysts for sustainable and efficient N2O decomposition.

Single-atom iridium doped ultrathin MoS2 layers as a highly efficient catalyst for the hydrodeoxygenation of 5-hydroxymethylfurfural

The catalytic transformation of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) is of great importance within the context of biomass valorization, but remains a major challenge due to the complicated reaction networks. Herein, single-atom Ir doped ultrathin MoS2 layers were synthesized and used as catalyst for the hydrodeoxygenation of HMF, yielding 96.5% of DMF. The single atomic structure of Ir was determined by X-ray diffraction (XRD), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), X-ray absorption fine structure analysis (XAFS), and X-ray photoelectron spectroscopy (XPS). Furthermore, the Ir doped MoS2 catalyst showed excellent stability and did not deactivate after five reaction cycles. This work expands the applications of single-atom catalysts and introduces a new and highly efficient catalyst for the sustainable production of DMF.

Spontaneous Deposition of Single Platinum Atoms on Anatase TiO2 for Photocatalytic H2 Evolution.

Single-atom (SA) decoration has emerged as a frontier in catalysis due to its unique characteristics. Recently, decorated Pt single atoms on titania have shown promise in photocatalytic hydrogen evolution. In this work, we demonstrate that Pt SAs can spontaneously deposit on the surface, driven by electrostatic forces; the key is to determine the golden pH and surface potential. We conducted a comprehensive investigation into the influence of the pH of the deposition precursor on the spontaneous adsorption of Pt SAs onto TiO2 nanosheets (TiNSs). We introduced a straightforward pH-dependent and charge-dependent strategy for the solid electrostatic anchoring of Pt SAs on TiO2. Furthermore, we established that the level of Pt loading can be controlled by adjusting the precursor pH. X-ray photoelectron spectroscopy (XPS) and high-angle annular dark-field imaging scanning transmission electron microscopy (HAADF-STEM) were used to evaluate the Pt SA-decorated samples. Photocatalytic hydrogen production activity was assessed under ultraviolet (UV) (365 nm) irradiation. Notably, we found that at a pH of 8, slightly below the measured point of zero charge (PZC), a unique mixture of Pt clusters and single atoms was deposited on the surface of TiNSs. This unique composition significantly improved hydrogen production, resulting in ∼3.7 mL of hydrogen generated after 8 h of UV exposure by only 10 mg of the Pt-decorated TiNS (with Pt loadings of 0.12 at. %), which is ∼300 times higher than the undecorated TiNS.

Dynamically Reconstructed Triple-Copper-Vacancy Associates Confined in Cu Nanowires Enabling High-Rate and Selective CO2 Electroreduction to C2+ Products.

Electrochemically reconstructed Cu-based catalysts always exhibit enhanced CO2 electroreduction performance; however, it still remains ambiguous whether the reconstructed Cu vacancies have a substantial impact on CO2 -to-C2+ reactivity. Herein, Cu vacancies are first constructed through electrochemical reduction of Cu-based nanowires, in which high-angle annular dark-field scanning transmission electron microscopy image manifests the formation of triple-copper-vacancy associates with different concentrations, confirmed by positron annihilation lifetime spectroscopy. In situ attenuated total reflection-surface enhanced infrared absorption spectroscopy discloses the triple-copper-vacancy associates favor *CO adsorption and fast *CO dimerization. Moreover, density-functional-theory calculations unravel the triple-copper-vacancy associates endow the nearby Cu sites with enriched and disparate local charge density, which enhances the *CO adsorption and reduces the CO-CO coupling barrier, affirmed by the decreased *CO dimerization energy barrier by 0.4eV. As a result, the triple-copper-vacancy associates confined in Cu nanowires achieve a high Faradaic efficiency of over 80% for C2+ products in a wide current density range of 400-800mA cm-2 , outperforming most reported Cu-based electrocatalysts.

Electrocatalysis of ammonia on NiCu nanoclusters with higher activity and stability synthesized by a simplified polyol technique

This work focuses on a simplified polyol process by which to synthesize five different NiCu/C nanoclusters (NCs) electrocatalysts with the variation of mass and atomic ratio. NCs are characterized by X-ray diffractometry (XRD), X-ray photoelectron spectroscopy, transmission electron spectroscopy (TEM), and scanning electron microscopy with energy-dispersive spectroscopy (EDS) for their crystallite and electronic structures, morphological studies, and elemental composition. The high-angle annular dark-field scanning TEM coupled with EDS elemental mapping has confirmed that nanoparticles (NPs) are formed with Ni and Cu, and NPs are subsequently noted to conform into NCs in such a fashion that NiCu NPs are interconnected to each other rather than overlapping considered a unique distribution of NiCu NCs on the carbon support observed in STEM. NPs arrangement in the conformation of NCs has largely increased in the coverage of NiCu-oxyhydroxides working as active sites for ammonia electrocatalysis evidenced in cyclic voltammograms and XPS investigation. NCs were employed for the oxidation of NH4OH, NH4Cl, NH4NO3, and (NH4)2SO4 of which NiCu/C-2 has shown the highest performance over other NiCu/C samples and their individuals. NiCu/C-2 is also found to have higher stability than other mono/bi-metallic electrocatalysts on the stability test preformed in an electrochemical environment. In addition, the sharp drops of the current in the chronoamperometric curves have been investigated during the stability test.

A novel synthesis from instability difference between SiC 3-C and 6-H crystal to form nanoparticles stems by alkali solution and its degrading various environmental pollutants

In this paper, the nano silicon carbide with different sizes was prepared without hydrofluoric acid by using simple milling and related low temperature etching process in normal pressure. Also, it was the first time verified that 3-C dominated crystalline form of polycrystalline silicon carbide is etched, leaving the 6-H silicon carbide crystalline form by the Raman spectra and HAADF-STEM (high-angle-annular dark-field scanning transmission electron microscopy) imaging that. The application of the alkali etching technique could precise control the partial structural transformation of silicon carbide crystals to a certain extent, which further expands the traditional crystal structure transformation process. In addition, this paper demonstrates the silicon carbide composites in photocatalytic removal of various organic pollutants from aqueous solutions. In the photo degradation of MB (Methylene Blue), the removal rate of the modified silicon carbide shown ten times as much as the commercial silicon carbide. The 1-h degradation efficiency was significantly higher in the 50 μL H2O2 system (100.0%, 86.8% and 89.9% removal of MB, Rhodamine B, Methyl Orange and Tetracycline hydrochloride, respectively). Furthermore, the unit spin concentrations of vacancy defects, superoxide radicals and hydroxyl radicals were quantitatively analyzed. The vacancy defects of the etched material were 1000 times higher than before, and the modified silicon carbide had higher transmittance to infrared and visible light. It strongly absorbs ultraviolet light. Conversely, the research on micron-sized silicon carbide loaded with Ag and Pt atoms found that it had a nitrogen fixation effect during the warming up process, in a nitrogen atmosphere.

Pb/Pb3O4 Metal-Semiconductor Nanocomposite Obtained on 4A Zeolite-Optical and Structural Properties.

This work describes a controlled and low-cost synthesis method to obtain Pb/Pb3O4 nanocomposites using synthetic zeolite 4A. The nanostructures obtained have a core-shell configuration with 5-25 nm diameters. High-resolution transmission electron microscopy (HRTEM), BF, high-angle annular dark-field annular scanning transmission electron microscopy (HAADF-STEM), energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and ultraviolet-visible (UV-vis) characterization techniques were used. Crystallographic planes (111), (200), and (220) for the core and planes (110) and (211) for the shell, corresponding to FCC and tetragonal structures for Pb and Pb3O4, respectively, were determined using HRTEM. The HAADF-STEM images allowed the analysis of intensity contrast images proportional to the number of atoms. XPS spectral analysis showed a 4.8 eV difference in binding energy between Pb 4f7/2 and Pb 4f5/2 for lead and lead oxide. EDS elemental mapping, XPS, and UV-vis spectroscopy analyses revealed the simultaneous presence of lead and lead oxide in the same structure. The band gap obtained for the shell was determined to be 4.50 eV. Consequently, Pb/Pb3O4 nanocomposites show a higher response to high-energy photons, making them suitable for UV photocatalysis applications.

Effect of Solution Temperature and Quench Delay on the Microstructure and Mechanical Properties of an Extruded Al-Mg-Si-Cu-Mn alloy

The effect of solution temperature and quench delay on the microstructure and mechanical properties of an extruded Al-Mg-Si-Cu-Mn alloy was investigated by employing differential scanning calorimetry, transmission electron microscopy, hardness test, and tensile test. The extruded specimens were held at 500 and 540 <sup>o</sup>C, respectively, for 80 min for solutionizing and then immediately quenched in water or exposed to air for 30 sec before water quenching. Each specimen was further heat treated at 180 <sup>o</sup>C for 6 hr for artificial aging. Quantitative analysis of the precipitates in the artificially aged specimens was performed using high-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM) and fast Fourier transforms (FFT) analysis. Solution treatment at 540 <sup>o</sup>C led to higher number density of precipitates and higher strengths after artificial aging, compared with solution treatment at 500 <sup>o</sup>C. Quench delay resulted in a lower number density of precipitates and lower strengths after artificial aging. The specimen solution treated at 540 <sup>o</sup>C with no quench delay showed the largest peak area of precipitate formation in the differential scanning calorimetry, and concurrently exhibited the highest strengths after artificial aging. Strength reduction by quench delay was higher in the specimen solution treated at 500 <sup>o</sup>C than that treated at 540 <sup>o</sup>C; this was consistent with the results of higher reduction in the number density of precipitates.

Catalytic propane dehydrogenation by anatase supported Ni single-atom catalysts

With the increasing production of propane from shale gas and the growing demand for propylene, propane dehydrogenation (PDH) has gained significant attention as a promising route for the on-purpose production of propylene. As a cheap yet efficient catalyst, Ni-based catalysts have attracted interest because of its ability to activate alkane. Single-atom catalysts (SACs) can maximize the metal atom utilization. Here, we demonstrate that anatase TiO2 supported Ni SAC (Ni1/A-TiO2) exhibits not only superior intrinsic activity and propylene selectivity but also much better stability than the corresponding Ni nanoparticle (NP) catalyst (NiNP/A-TiO2) in PDH reaction at 580 °C. The rate of propylene production on Ni1/A-TiO2 is about 1.96 molC3H6 gNi−1 h−1, about 65 times higher than that of NiNP/A-TiO2 sample (0.03 molC3H6 gNi−1 h−1). In combination of high-angle annular dark-field scanning transmission electron microscopy, in-situ diffuse reflectance infrared Fourier transform spectra, in-situ X-ray photoelectron spectroscopy and X-ray absorption spectroscopy characterizations, we confirm that the Ni SAC mainly contains individual Ni atom singly dispersed on the support in positive Ni (II) valence state. In addition, as a result of strong metal-support interaction (SMSI) between Ni NP and TiO2 carrier under reduced conditions, the Ni NPs sites are encapsulated by TiOx overlayer (~2 nm thick) thus display poor reaction performance.

Selective hydrodeoxygenation of guaiacol to phenol over CoFe/reduced graphene oxide

A reduced graphene oxide (rGO)-supported CoFe bimetallic catalyst (CoFe/rGO) was synthesized and used for hydrodeoxygenation of guaiacol to phenol (Ph). The CoFe/rGO catalyst without reduction pretreatment showed excellent catalytic performance, achieving 94.0 mol% conversion and 70.8 mol% selectivity to Ph at mild reaction temperature and low H2 pressure. The microstructure and chemical composition of the CoFe/rGO catalyst were characterized by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Raman spectroscopy, and H2 temperature-programmed reduction (H2-TPR) characterization analysis. Co and Fe are supported on rGO in forms of the isolated metal atoms embedded in the rGO matrix and the CoFe oxide nanoparticles attached on rGO surface. Fe as a promoter weakens the hydrogenation activity of Co to benzene ring and dramatically improves the selectivity to Ph. The unique of rGO on constructing catalytic active sites and the synergistic effect of Co and Fe bimetals make CoFe/rGO an excellent catalyst.

Artifactual atomic displacements on surfaces using annular dark-field images with image simulation.

We investigated artifactual atomic displacements on a Pt (111) surface using annular dark-field (ADF) scanning transmission electron microscopy images under ideal conditions with multi-slice image simulation. Pt atomic columns on the surface exhibited artifact displacement. The bright spots shifted slightly toward the interior of the crystal, indicating that ADF imaging underestimates atomic distance measurements on the crystal surface. Multiple peak fitting is an effective method for determining the positions of bright spots and obtaining more accurate atomic positions while reducing the impact of surface-related artifacts. This is important for the measurement of interatomic distances on crystal surfaces, particularly for catalyst particles.

Fe-nanocluster embedded biomass-derived carbon for efficient photo-Fenton-like activity in water purification

Single-atom catalysts (SACs) as photo-Fenton-like catalysts have attracted widespread attention in water purification. However, the development of SACs with renewability, cleanliness, high mass loading, and raw material abundance is a formidable challenge to achieve efficient pollutant removal. In this study, we fabricated high-performance Fe-nanocluster embedded biomass-derived carbon (Fe/Bio-C) from Ficus altissima wastes for quinolone antibiotics degradation. The high-angle annular dark-field scanning transmission electron microscopy with aberration correction (AC-HAADF-STEM) and X-ray absorption fine structure spectroscopy (XAFS) revealed that the Fe/Bio-C exhibited a porous structure with abundant Fe-N4 active sites. The Fe/Bio-C catalysts achieved an exceptional efficiency of 98.6 % for the removal of the representative quinolone antibiotic, namely lomefloxacin (LOM), within 30 min. Furthermore, an in-depth exploration was conducted to assess the influence of reaction parameters on degradation performance, kinetics, toxicity, and mechanism. The free radical quenching experiments and electron paramagnetic resonance (EPR) spectra demonstrated the existence of ·O2−, 1O2, ·OH, SO4·− in the reaction system and the ·O2− radicals played a relatively important role in the degradation progress. This work broaden the avenue for constructing metal-nanocluster photocatalysts with the high reactivity, low metal leaching, and universality to various pollutants.

Three-Dimensional Reconstruction of Interface Roughness and Alloy Disorder in Ge/GeSi Asymmetric Coupled Quantum Wells Using Electron Tomography.

Interfaces play an essential role in the performance of ever-shrinking semiconductor devices, making comprehensive determination of their three-dimensional (3D) structural properties increasingly important. This becomes even more relevant in compositional interfaces, as is the case for Ge/GeSi heterostructures, where chemical intermixing is pronounced in addition to their morphology. We use the electron tomography method to reconstruct buried interfaces and layers of asymmetric coupled Ge/Ge0.8Si0.2 multiquantum wells, which are considered a potential building block in THz quantum cascade lasers. The three-dimensional reconstruction is based on a series of high-angle annular dark-field scanning transmission electron microscopy images. It allows chemically sensitive investigation of a relatively large interfacial area of about (80 × 80) nm2 with subnanometer resolution as well as the analysis of several interfaces within the multiquantum well stack. Representing the interfaces as iso-concentration surfaces in the tomogram and converting them to topographic height maps allows the determination of their morphological roughness as well as layer thicknesses, reflecting low variations in either case. Simulation of the reconstructed tomogram intensities using a sigmoidal function provides in-plane-resolved maps of the chemical interface widths showing a relatively large spatial variation. The more detailed analysis of the intermixed region using thin slices from the reconstruction and additional iso-concentration surfaces provides an accurate picture of the chemical disorder of the alloy at the interface. Our comprehensive three-dimensional image of Ge/Ge0.8Si0.2 interfaces reveals that in the case of morphologically very smooth interfaces─depending on the scale considered─the interface alloy disorder itself determines the overall characteristics, a result that is fundamental for highly miscible material systems.

Arrayed Pt Single Atoms via Phosphotungstic Acids Intercalated in Silicate Nanochannels for Efficient Hydrogen Evolution Reactions.

Single-atom catalysts, known for their high activity, have garnered significant interest. Currently, single-atom catalysts were prepared mainly on 2D substrates with random distribution. Here, we report a strategy for preparing arrayed single Pt (Pt1) atoms, which are templated through coordination with phosphotungstic acids (PTA) intercalated inside hexagonally packed silicate nanochannels for a high single Pt-atom loading of ca. 3.0 wt %. X-ray absorption spectroscopy, high-angle annular dark-field scanning transmission electron microscopy, and energy-dispersive X-ray spectroscopy, in conjunction with the density-functional theory calculation, collectively indicate that the Pt single atoms are stabilized via a four-oxygen coordination on the PTA within the nanochannels' inner walls. The critical reduction in the Pt-adsorption energy to nearly the cohesive energy of Pt clustering is attributed to the interaction between PTA and the silicate substrate. Consequently, the transition from single-atom dispersion to clustering of Pt atoms can be controlled by adjusting the number density of PTA intercalated within the silicate nanochannels, specifically when the number ratio of Pt atoms to PTA changes from 3.7 to 18. The 3D organized Pt1-PTA pairs, facilitated by the arrayed silicate nanochannels, demonstrate high and stable efficiency with a hydrogen production rate of ca. 300 mmol/h/gPt─approximately twice that of the best-reported Pt efficiency in polyoxometalate-based photocatalytic systems.

Unravelling co-catalyst integration methods in Ti-based metal-organic gels for photocatalytic H2 production.

The synthesis, characterization and photocatalytic hydrogen evolution reaction (HER) performance of a series of metal-organic gels (MOGs) constructed from titanium(IV)-oxo clusters and dicarboxylato linkers (benzene-1,4-dicarboxylato and 2-aminobenzene-1,4-dicarboxylato) are described. All the MOGs exhibit a microstructure comprised of metal-organic nanoparticles intertwined into a highly meso-/macroporous structure, as demonstrated by cryogenic transmission electron microscopy and gas adsorption isotherms. Comprehensive chemical characterization enabled the estimation of the complex formula for these defective materials, which exhibit low crystallinity and linker vacancies. To gain deeper insights into the local structure, X-ray absorption fine structure (XAFS) spectroscopy experiments were performed and compared to that of the analogous crystalline metal-organic framework. Additionally, the ultraviolet-visible absorption properties and optical band gaps were determined from diffuse reflectance spectroscopy data. The MOGs were studied as light absorbers for the sacrificial photocatalytic HER under simulated solar light irradiation using a platinum co-catalyst by either (1) in situ photodeposition or (2) ex situ doping process, through a post-synthetic metalation of the MOG structure. The chemical analysis of the metalation, along with high-angle annular dark-field scanning transmission electron microscopy, revealed that although the in situ addition of the co-catalyst led to greater HER rates (227 vs. 110 μmolH2 gMOG-1 h-1 for in situ and ex situ, respectively), the ex situ modification provided a finer distribution of platinum nanoparticles along the porous microstructure and, as a result, it led to a more efficient utilization of the co-catalyst (45 vs. 110 mmolH2 gPt-1 h-1).

Carbon-supported Au25 cluster catalysts partially decorated with dendron thiolates: enhanced loading weight and durability for hydrogen evolution reaction.

In order to establish a design principle for efficient Au electrocatalysis, it is desirable to synthesize a highly loaded, robust, and atomically precise Au cluster catalyst on a conductive carbon support. In this work, heterogeneous Au25 catalysts were prepared by calcining 5.0 wt% of mixed ligated [Au25(D2S)x(PET)18-x]0 (D2S = second generation Fréchet-type dendron thiolate, PET = 2-phenylethanethiolate) on a carbon support. X-ray absorption fine structure analysis, powder X-ray diffraction, and aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (AC-HAADF-STEM) revealed the successful synthesis of carbon-supported partially thiolated Au25 clusters by calcining [Au25(D2S)10.7(PET)7.3]0 at 425 °C for ≥12 h, whereas calcination of [Au25(PET)18]0 under the same conditions resulted in thermally induced aggregation into larger Au nanoparticles. The D2S-modified Au25 catalyst showed better durability than PET-modified Au25 in electrocatalytic hydrogen evolution reaction. The higher durability was attributed to the suppression of aggregation of Au25 clusters during the reaction, as confirmed by AC-HAADF-STEM. These results indicate that the residual D2S ligands on Au25 enhance the stability against aggregation more than the residual PET due to stronger non-covalent interactions with carbon supports and/or greater steric hindrance of dendritic structure. This work demonstrates that the stability of Au catalysts can be improved by partial decoration with designed ligands.

First synthesis of RuSn solid-solution alloy nanoparticles and their enhanced hydrogen evolution reaction activity.

Solid-solution alloys based on platinum group metals and p-block metals have attracted much attention due to their promising potential as materials with a continuously fine-tunable electronic structure. Here, we report on the first synthesis of novel solid-solution RuSn alloy nanoparticles (NPs) by electrochemical cyclic voltammetry sweeping of RuSn@SnOx NPs. High-angle annular dark-field scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy maps confirmed the random and homogeneous distribution of Ru and Sn elements in the alloy NPs. Compared with monometallic Ru NPs, the RuSn alloy NPs showed improved hydrogen evolution reaction (HER) performance. The overpotentials of Ru0.94Sn0.06 NPs/C and Ru0.87Sn0.13 NPs/C to achieve a current density of 10 mA cm-2 were 43.41 and 33.19 mV, respectively, which are lower than those of monometallic Ru NPs/C (53.53 mV) and commercial Pt NPs/C (55.77 mV). The valence-band structures of the NPs investigated by hard X-ray photoelectron spectroscopy demonstrated that the d-band centre of RuSn NPs shifted downward compared with that of Ru NPs. X-ray photoelectron spectroscopy and X-ray absorption near-edge structure analyses indicated that in the RuSn alloy NPs, charge transfer occurs from Sn to Ru, which was considered to result in a downward shift of the d-band centre in RuSn NPs and to regulate the adsorption energy of intermediate Hads effectively, and thus enable the RuSn solid-solution alloy NPs to exhibit excellent HER catalytic properties.

Kinetics of Mg-Ni saponite crystallization from precursor mixtures

Abstract Smectite growth is of importance across various fields due to its abundance on the surface of both Earth and Mars. However, the impact of the crystallinity of initial materials on smectite growth processes remains poorly understood. In this study, the kinetic processes of smectite growth were examined via experimental synthesis of trioctahedral Mg-Ni saponites. Mg-Ni saponites were synthesized using mixed precursors, specifically end-member Mg-saponite and Ni-saponite, which exhibit different crystallinities. The crystal chemistry and morphology of samples were analyzed using X-ray diffraction, Fourier-transform infrared spectroscopy, and high-angle annular dark-field scanning transmission electron microscopy. The experimental results converge towards these main conclusions: (i) the formation of Mg-Ni saponite solid solutions are promoted when the precursors are small particles, whereas large-particle precursors limit their own dissolution and do not yield Mg-Ni saponite solid solutions under the experimental conditions; (ii) because Ni exhibits a greater stability within the saponite structure compared to Mg, the Mg-Ni-saponite solid solutions formed more easily from the mixture of Ni-saponite germs and well-crystallized Mg-saponite precursors than from the mixture of Mg-saponite germs and well-crystallized Ni-saponite precursors; (iii) the dissolution extent (DE) of precursor mixtures increases with longer synthesis time, higher synthesis temperature, and larger gap between synthesis temperature of precursors and of samples, and stabilizes once it reaches a certain value. Thus DE can be used to estimate the kinetics of Mg-Ni saponite crystallization from precursor mixtures. These results obtained from the experimental Mg-Ni saponite system are useful for predicting the evolution processes of smectite in natural systems.

Visualization of the structural transformation of NiO/YSZ/BZY nanocomposite particles using in situ gas environmental transmission electron microscopy.

This study focused on investigating the dynamic structural transformations of spherical NiO/YSZ/BZY triple-phase nanocomposite particles, commonly employed for cermet anodes, during the hydrogen reduction reaction. We utilized both spherical aberration (Cs) corrected transmission electron microscopy (TEM) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) observation modes under a controlled gaseous environment. The environmental gas pressure was set to 1 atm (760 Torr), mirroring real-world conditions. To elucidate pre- and post-hydrogen reduction compositional alterations, we conducted elemental mapping using energy-dispersive X-ray spectroscopy (EDS). Our findings indicated that NiO nanoparticles underwent reduction to Ni particles upon heat treatments in an environment containing H2 gas. Significantly, this reduction of NiO led to the migration of Ni along the external surface of each composite particle, ultimately resulting in the agglomeration at the interparticle spaces among the three NiO/YSZ/BZY nanocomposite particles.

Colloidal 2D Mo1-xWxS2 nanosheets: an atomic- to ensemble-level spectroscopic study.

Composition dependent tuning of electronic and optical properties in semiconducting two-dimensional (2D) transition metal dichalcogenide (TMDC) alloys is promising for tailoring the materials for optoelectronics. Here, we report a solution-based synthesis suitable to obtain predominantly monolayered 2D semiconducting Mo1-xWxS2 nanosheets (NSs) with controlled composition as substrate-free colloidal inks. Atomic-level structural analysis by high-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) coupled with energy dispersive X-ray spectroscopy (EDXS) depicts the distribution of individual atoms within the Mo1-xWxS2 NSs and reveals the tendency for domain formation, especially at low molar tungsten fractions. These domains cause a broadening in the associated ensemble-level Raman spectra, confirming the extrapolation of the structural information from the microscopic scale to the properties of the entire sample. A characterization of the Mo1-xWxS2 NSs by steady-state optical spectroscopy shows that a band gap tuning in the range of 1.89-2.02 eV (614-655 nm) and a spin-orbit coupling-related exciton splitting of 0.16-0.38 eV can be achieved, which renders colloidal methods viable for upscaling low cost synthetic approaches toward application-taylored colloidal TMDCs.