Aberration-corrected Scanning Transmission Electron Microscopy Research Articles

Alkaline hydrogen evolution reaction catalyzed by atomically dispersed ruthenium on phosphorus-nitrogen co-doped porous carbon

Exploring high-efficiency catalyst toward hydrogen evolution reaction (HER) for sustainable hydrogen production is critical for building a forthcoming hydrogen economy. Atomically dispersed catalysts have shown great promises for catalyzing HER yet further fine-tuning the coordination chemical environment to boost the performance is still challenging. Herein, we report the synthesis and electrocatalytic HER application of Ru single atoms dispersed in P, N co-doped porous carbon (Ru SAs@PNC). Spherical aberration corrected scanning transmission electron microscope (AC-STEM) analysis revealed the formation of atomically dispersed Ru single atoms. The as-prepared Ru SAs@PNC catalyst showed excellent HER activity in 1 M KOH, evidenced by a small overpotential of 21 mV @ 10 mA cm−2 and a low Tafel slope of 31 mV dec−1, both of which are comparable to the Pt/C benchmark catalyst. It also exhibited great durability for long-time operation, as demonstrated by negligible overpotential increase in the 50 h E-t test, and outperformed stability in the accelerated durability test. Such excellent HER performance is mainly attributed to the N, P co-doped chemical coordination environment that differs from most widely reported solely nitrogen-coordinated Ru single atoms.

Probing the interaction range of electron beam-induced etching in STEM by a non-contact electron beam

Beside its main purpose as a high-end tool in material analysis reaching the atomic scale for structure, chemical and electronic properties, aberration-corrected scanning transmission electron microscopy (STEM) is increasingly used as a tool to manipulate materials down to that very same scale. In order to obtain exact and reproducible results, it is essential to consider the interaction processes and interaction ranges between the electron beam and the involved materials. Here, we show in situ that electron beam-induced etching in a low-pressure oxygen atmosphere can extend up to a distance of several nm away from the Ångström-size electron beam, usually used for probing the sample. This relatively long-range interaction is related to beam tails and inelastic scattering involved in the etching process. To suppress the influence of surface diffusion, we measure the etching effect indirectly on isolated nm-sized holes in a 2 nm thin amorphous carbon foil that is commonly used as sample support in STEM. During our experiments, the electron beam is placed inside the nanoholes so that most electrons cannot directly participate in the etching process. We characterize the etching process from measuring etching rates at multiple nanoholes with different distances between the hole edge and the electron beam.

Hidden Impurities Generate False Positives in Single Atom Catalyst Imaging.

Single-atom catalysts (SACs) are an emerging class of materials, leveraging maximum atom utilization and distinctive structural and electronic properties to bridge heterogeneous and homogeneous catalysis. Direct imaging methods, such as aberration-corrected high-angle annular dark-field scanning transmission electron microscopy, are commonly applied to confirm the atomic dispersion of active sites. However, interpretations of data from these techniques can be challenging due to simultaneous contributions to intensity from impurities introduced during synthesis processes, as well as any variation in position relative to the focal plane of the electron beam. To address this matter, this paper presents a comprehensive study on two representative SACs containing isolated nickel or copper atoms. Spectroscopic techniques, including X-ray absorption spectroscopy, were employed to prove the high metal dispersion of the catalytic atoms. Employing scanning transmission electron microscopy imaging combined with single-atom-sensitive electron energy loss spectroscopy, we scrutinized thin specimens of the catalysts to provide an unambiguous chemical identification of the observed single-atom species and thereby distinguish impurities from active sites at the single-atom level. Overall, the study underscores the complexity of SACs characterization and establishes the importance of the use of spectroscopy in tandem with imaging at atomic resolution to fully and reliably characterize single-atom catalysts.

Instrument Optimization of a High-Energy Electron Energy-loss Spectrometry System in an Aberration-Corrected Scanning Transmission Electron Microscope

Instrument Optimization of a High-Energy Electron Energy-loss Spectrometry System in an Aberration-Corrected Scanning Transmission Electron Microscope

Spectroscopic and modeling approaches of arsenic (III/V) adsorption onto Illite

Illite plays an essential role in arsenic (As) transportation in the subsurface. Despite extensive investigations into As adsorption onto illite, debates persist due to the absence of direct evidence revealing the underlying processes. In this research, we conducted batch experiments and employed spherical aberration-corrected scanning transmission electron microscope, X-ray absorption spectroscopy, and density functional theory-based calculations to elucidate the mechanisms for the adsorption of two major inorganic As species (As(III) and As(V)) onto illite. Experimental results indicate adsorption capacities of 0.251 and 0.667 μmol/g for As(III) and As(V) onto illite, respectively. As(III) adsorption occurs within 300 min, whereas As(V) is rapidly adsorbed within 500 min, after which it tends to stabilize. Both As species can adsorbed onto the basal surface via electrostatic forces, where cations act as a bridge, leading to specific-cation effects. Conversely, As adsorption onto the edge surface can be ascribed to inner-sphere complexes via As-O-Al bonds, causing a negatively shifted isoelectric point of illite. These mechanisms collectively account for the partially reversible adsorption and two-stage kinetics pattern. Finally, a process-based surface complexation model was developed to predict As adsorption onto illite, which includes the inner/outer-sphere complexation and monodentate/bidentate complexes.

Structure and exfoliation mechanism of two-dimensional boron nanosheets

Exfoliation of two-dimensional (2D) nanosheets from three-dimensional (3D) non-layered, non-van der Waals crystals represents an emerging strategy for materials engineering that could significantly increase the library of 2D materials. Yet, the exfoliation mechanism in which nanosheets are derived from crystals that are not intrinsically layered remains unclear. Here, we show that planar defects in the starting 3D boron material promote the exfoliation of 2D boron sheets—by combining liquid-phase exfoliation, aberration-corrected scanning transmission electron microscopy, Raman spectroscopy, and density functional theory calculations. We demonstrate that 2D boron nanosheets consist of a planar arrangement of icosahedral sub-units cleaved along the {001} planes of β-rhombohedral boron. Correspondingly, intrinsic stacking faults in 3D boron form parallel layers of faulted planes in the same orientation as the exfoliated nanosheets, reducing the {001} cleavage energy. Planar defects represent a potential engineerable pathway for exfoliating 2D sheets from 3D boron and, more broadly, the other covalently bonded materials.

Elemental distribution and site occupancy in a Co-Ni-Al-Ti-Ta-W superalloy

γ'-precipitate strengthened cobalt-based superalloys show promise for higher temperature-capability over nickel-based superalloys due to higher melting temperatures. This study investigates a multicomponent CoNi-based superalloy with composition of 54Co-30Ni-9Al-1Ta-4Ti-2-W (at.%) in terms of elemental partitioning and site occupancy. Atom probe tomography (APT) reveals preferential partitioning of Ni, Al, Ti, Ta and W to the γ'-precipitate and Co to the γ-matrix. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and energy dispersive spectrometer (EDS) along the [001] zone axis of γ'-precipitate with L12 structure indicate that Co, Ni substitute at A-sites, whereas Al, Ti, Ta, W prefer the B-sites. Density functional theory (DFT) calculations further confirm the results of partitioning behaviors and site preferences. Clarifying elemental partitioning and site occupancy provides valuable insights into alloy design principles for advanced CoNi-based superalloys.

Low-coordinated Mn–N2 sites in graphene oxide induce peroxydisulfate activation for tetracycline degradation: Process optimization and theoretical calculation

Atom-dispersed low-coordinated transition metal-Nx catalysts exhibit excellent efficiency in activating peroxydisulfate (PDS) for environmental remediation. However, their catalytic performance is limited due to metal-N coordination number and single-atom loading amount. In this study, low-coordinated nitrogen-doped graphene oxide (GO) confined single-atom Mn catalyst (Mn-SA/NGO) was synthesized by molten salt-assisted pyrolysis and coupled to PDS for degradation of tetracycline (TC) in water. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (AC-HAADF-STEM) and X-ray absorption fine structure spectroscopy (XAFS) analysis showed the successful doping of single-atom Mn (weight percentage 1.6%) onto GO and the formation of low-coordinated Mn–N2 sites. The optimized parameters obtained by Box-Behnken Design achieved 100% TC removal in both prediction and experimental results. The Mn-SA/NGO + PDS system had strong anti-interference ability for TC removal in the presence of anions. Besides, Mn-SA/NGO possessed good reusability and stability. O2•−, •OH, and 1O2 were the main active species for TC degradation, and the TC mineralization reached 85.1%. Density functional theory (DFT) calculations confirmed that the introduction of single atoms Mn could effectively enhance adsorption and activation of PDS. The findings provide a reference for the synthesis of high-performance single-atom catalysts for effective removal of antibiotics.

Surface reconstructed layer with bulk high-valence Mo doping to achieve long-life LiMn2O4 cathode material

Mo doping plays a striking role in the stability enhancement of LiMn2O4 cathode materials. However, the underlying microscopic mechanism is still unclear. Here, we elucidate that the relationship between the atomic position of Mo doping in LiMn2O4 and the stability enhancement of Mo-doped LiMn2O4 by utilizing the spherical aberration-corrected scanning transmission electron microscopy (Cs-STEM). It exhibits that the part of Mo6+ ions occupy empty Mn 16c site to form a surface reconstructed layer of rock-salt like phase on the outermost surface and other Mo6+ ions dope into the Mn octahedral 16d sites to form LiMoxMn2-xO4 in bulk, which is beneficial for inhibiting the parasitic side reactions. Concomitantly, this dual modification of bulk structure and surface can significantly enhance electrode reversibility and Li+ diffusion. As a result, excellent long cycling stability of the as-designed optimal LiMo0.01Mn1.99O4 after 1500 cycles with 61.61 % capacity retention at 10 C (1 C = 148 mAh g−1) is presented, with an initial discharge capacity of 88.30 mAh g−1. Our research provides a clever approach for regulating the surface structure/bulk architecture in LiMn2O4 cathode materials.

Unraveling Mechanism for Microstructure Engineering toward High-Capacity Nickel-Rich Cathode Materials.

Microstructural engineering on nickel-rich layered oxide (NRLO) cathode materials is considered a promising approach to increase both the capacity and lifespan of lithium-ion batteries by introducing high valence-state elements. However, rational regulation on NRLO microstructures based on a deep understanding of its capacity enhancement mechanism remains challenging. Herein for the first time, it is demonstrated that an increase of 14mAhg-1 in reversible capacity at the first cycle can be achieved via tailoring the micro and nano structure of NRLO through introducing tungsten. Aberration-corrected scanning transmission electron microscopy (STEM) characterization reveals that the formation of a modified microstructure featured as coherent spinel twin boundaries. Theoretical modeling and electrochemical investigations further demonstrate that the capacity increase mechanism is related to such coherent spinel twin boundaries, which can lower the Li+ diffusion barrier and thus allow more Li+ to participate in deeper phase transitions. Meanwhile, the surface and grain boundaries of NRLOs are found to be modified by generating a dense and uniform LiWxOy phase, which further extends its cycle life by reducing side reactions with electrolytes. This work enables a comprehensive understanding of the capacity-increased mechanism and endows the remarkable potential of microstructural engineering for capacity- and lifespan-increased NRLOs.

Lattice strain induced by trace Pt single atoms in nickel for accelerating industrial hydrogen evolution

Strategically designing the electrocatalytic system and cleverly inducing strain is an effective approach to balance the cost and activity of Pt-based electrocatalysts for industrial-scale hydrogen production. Herein, we present a unipolar pulsed electrodeposition (UPED) strategy to induce strain in the Ni lattice by introducing trace amounts of Pt single atoms (SAs) (0.22 wt%). The overpotential decreased by 183 mV at 10 mA cm−2 in 1.0 M KOH after introducing trace amounts of PtSAs. The industrial electrolyzer, assembled with PtSAsNi cathode and a commercial NiFeOx anode, requires a cell voltage of 1.90 V to attain 1 A cm−2 of current density and remains stable for 280 h, demonstrating significant potential for practical applications. Spherical aberration corrected scanning transmission electron microscopy (AC-STEM), X-ray absorption (XAS), and geometric phase analysis (GPA) indicate that the introduction of trace amounts of Pt SAs induces tensile strain in the Ni lattice, thereby altering the local electronic structure and coordination environment around cubic Ni for enhancing the water decomposition kinetics and fundamentally changing the reaction pathway. The doping-strain strategy showcases conformational relationships that could offer new ideas to construct efficient hydrogen evolution reaction (HER) electrocatalysts for industrial hydrogen production in the future.

Understanding and Mitigating Lattice Collapse Degradation in Layered Oxide Materials for Sodium-Ion Battery Anode.

Na2Ti3O7 has attracted significant attention due to its ecofriendliness and cost-effectiveness for sodium-ion batteries. However, their limited cycling stability hampers their practical applications. Herein, we elucidate a mechanism of structural degradation caused by the heterogeneous phase transition in the Na2Ti3O7 anode using aberration-corrected (scanning) transmission electron microscopy (S)TEM and in situ TEM. It is found that the unevenly distributed phase transition results in the accumulation of strain, which promotes the growth of microcracks and eventually leads to structural decomposition and electrochemical failure. Motivated by this degradation mechanism, nanowires were proposed, and the structural stability is thus improved with the lattice strain effectively released. These findings deepen our understanding of ion transport and degradation mechanisms in intercalated layered electrode materials while emphasizing the significance of the material structure engineered for improving electrode performance.

Engineering Oxide Epitaxy beyond Substrate Constraint.

Orientation engineering is a crucial aspect of thin film growth, and it is rather challenging to engineer film epitaxy beyond the substrate constraint. Guided by density functional theory calculations, we use SrRuO3 (SRO) as a buffer layer and successfully deposit [111]-oriented CoFe2O4 (CFO) on [001]-, [110]-, and [111]-oriented SrTiO3 (STO) substrates. This enables subsequent growth of [111]-oriented functional oxides, such as PbTiO3 (PTO), overcoming the constraint of the substrate. This strategy is quite general and applicable to lanthanum aluminate and yttria-stabilized zirconia substrates as well. X-ray Φ scans and atomic resolution aberration-corrected scanning transmission electron microscopy (AC-STEM) reveal detailed epitaxial relations in each of the cases, with four variants of [111]-CFO found on [001]-STO and two variants found on [110]-STO, formed to mitigate the large lattice misfit strain between the film and substrate. Our strategy thus provides a general pathway for orientation engineering of oxide epitaxy beyond substrate constraint.

RhRu Bimetallic Oxide Cluster Catalysts for Cross-Dehydrogenative Coupling of Arenes and Carboxylic Acids.

Noble-metal-based bimetallic oxide clusters are promising novel catalysts. In this study, we developed carbon-supported RhRu bimetallic oxide clusters (RhRuOx/C) with a mean diameter of 1.2 nm, which showed remarkable catalytic activity for the cross-dehydrogenative coupling (CDC) of arenes and carboxylic acids with O2 as the sole oxidant. RhRu bimetallic oxide cluster formation was confirmed by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy with energy-dispersive X-ray spectroscopy and synchrotron X-ray absorption spectroscopy. Kinetic isotope and substituent effects indicated that arene C-H bond cleavage was the rate-determining step and proceeded via electrophilic concerted metalation-deprotonation mechanism, with a carboxylate as an internal base. Density functional theory calculations supported the proposed mechanism and indicated that the active center for C-H bond activation was Rh(V) rather than Rh(III), while Ru enhanced the electrophilicity of the Rh(V) site by decreasing the negative charge of the surrounding oxygen atoms. Electron-rich arenes showed relatively high reactivity for the RhRuOx/C-catalyzed CDC reaction, and both aliphatic and aromatic carboxylic acids were applicable to the reaction. The RhRuOx/C catalyst is promising for the CDC reaction of arenes and carboxylic acids to produce aryl esters. This work promotes the development of noble-metal-based bimetallic oxide clusters for C-H bond activation reactions.

Unraveling the Harmonious Coexistence of Ruthenium States on a Self‐Standing Electrode for Enhanced Hydrogen Evolution Reaction

The development of cost‐effective, highly efficient, and durable electrocatalysts has been a paramount pursuit for advancing the hydrogen evolution reaction (HER). Herein, a simplified synthesis protocol was designed to achieve a self‐standing electrode, composed of activated carbon paper embedded with Ru single‐atom catalysts and Ru nanoclusters (ACP/RuSAC+C) via acid activation, immersion, and high‐temperature pyrolysis. Ab initio molecular dynamics (AIMD) calculations are employed to gain a more profound understanding of the impact of acid activation on carbon paper. Furthermore, the coexistence states of the Ru atoms are confirmed via aberration‐corrected scanning transmission electron microscopy (AC‐STEM), X‐ray photoelectron spectroscopy (XPS), and X‐ray absorption spectroscopy (XAS). Experimental measurements and theoretical calculations reveal that introducing a Ru single‐atom site adjacent to the Ru nanoclusters induces a synergistic effect, tuning the electronic structure and thereby significantly enhancing their catalytic performance. Notably, the ACP/RuSAC+C exhibits a remarkable turnover frequency (TOF) of 18 s−1 and an exceptional mass activity (MA) of 2.2 A mg−1, surpassing the performance of conventional Pt electrodes. The self‐standing electrode, featuring harmoniously coexisting Ru states, stands out as a prospective choice for advancing HER catalysts, enhancing energy efficiency, productivity, and selectivity.

Single−atom Co anchored on covalent organic framework for remarkable photocatalytic hydrogen evolution efficiency

Single-atom catalysts (SACs) have attracted extensive attention because of their high atomic utilization and superior catalytic activity. Herein, single-atom Co has anchored on the β-ketoenamine-linked covalent organic framework (Tp-Tta COF) pores and used for remarkable photocatalytic hydrogen(H2) production under Ultraviolet–Visible light (UV–Vis light) irradiation. The single-atom Co is visualized by the aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (AC HAADF-STEM), and the C3–Co–N1 coordination structure is demonstrated by X-ray absorption fine structure (XAFS) measurements. The modified Co0.4-SAC/Tp-Tta COF shows a high photocatalytic H2 production of 1798.5 μmol g−1 h−1 and the Apparent quantum yield(AQY) is 3.02% at 420 nm. The improvement of the activity and stability of the photocatalyst is mainly attributed to the incorporation of Co single-atom that boosts the separation efficiency of photogenerated electron-hole pair and provides well-dispersed active sites. This study provides valuable insights into the development of UV–Vis light-responsive photocatalysts at the atomic level.

Atomic-Resolution Interfacial Reaction Mechanism between Bi2Te3-Based Alloys and Ni Electrodes.

Interdiffusion and solid-solid phase reaction at the interface between thermoelectric (TE) materials and the electrode critically influence interfacial transport properties and the overall energy conversion efficiency during service. Here, the microstructural evolution and diffusion mechanisms at the interfaces between the most widely used Bi2Te3-based TE materials, n-type Bi2Te2.7Se0.3 (BTS) and p-type Bi0.5Sb1.5Te3 (BST), and Ni electrodes were investigated at atomic resolution using spherical aberration-corrected scanning transmission electron microscopy (STEM). The BTS(0001)/Ni and BST(0001)/Ni interfaces were constructed by depositing Ni nanoparticles on mechanically exfoliated BTS and BST bulk materials and subsequent annealing. The interfacial reaction is initially dominated by Ni diffusion into the TE matrix to form NiAs-type NiM intermetallics, while Ni trans-quintuple-layer diffusion only occurs in Sb-rich BST. The Bi-rich BTS is more influenced by the Ni-Te preferential reaction, resulting in NiM abnormal grain growth and the formation of tilted and rotated interfaces. Bi diffusion into the BTS matrix forms a Bi double layer at the interface or Bi2[Bi2(Te,Se)3] as the annealing temperature increases, while Bi diffusion into the Ni thin film greatly accelerates the interfacial reaction rate, as elucidated by in situ heating STEM. The results provide essential structural details to understand and prevent the degradation of TE device performance.

Direct Fabrication of Atomically Defined Pores in MXenes Using Feedback-Driven STEM.

Controlled fabrication of nanopores in 2D materials offer the means to create robust membranes needed for ion transport and nanofiltration. Techniques for creating nanopores have relied upon either plasma etching or direct irradiation; however, aberration-corrected scanning transmission electron microscopy (STEM) offers the advantage of combining a sub-Å sized electron beam for atomic manipulation along with atomic resolution imaging. Here, a method for automated nanopore fabrication is utilized with real-time atomic visualization to enhance the mechanistic understanding of beam-induced transformations. Additionally, an electron beam simulation technique, Electron-Beam Simulator (E-BeamSim) is developed to observe the atomic movements and interactions resulting from electron beam irradiation. Using the MXene Ti3C2Tx, the influence of temperature on nanopore fabrication is explored by tracking atomic transformations and find that at room temperature the electron beam irradiation induces random displacement and results in titanium pileups at the nanopore edge, which is confirmed by E-BeamSim. At elevated temperatures, after removal of the surface functional groups and with the increased mobility of atoms results in atomic transformations that lead to the selective removal of atoms layer by layer. This work can lead to the development of defect engineering techniques within functionalized MXene layers and other 2D materials.

Complementary nanodomain structures in topologically close-packed precipitates of Al-Zn-Mg-Cu alloy

High-strength aluminium alloys attract continuous research interest, owing to their wide use in aerospace and terrestrial transportation industries. The performance of the alloys is essentially determined by nanoscale precipitates, thus understanding the structure and formation mechanism of the precipitates during thermal processing is of great importance. Here, we reveal complementary domain structures in precipitates in a high-strength Al-Zn-Mg-Cu alloy using a combination of aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and energy dispersive X-ray spectroscopy. Through the transfer of fivefold symmetry polyhedra at domain boundaries, the intermediate precipitates develop two sets of highly ordered and structurally complementary nanoscale domains in their nucleation and growth. This new type of atom packing maintains the topologically close-packed structure inside the precipitates while reducing the lattice misfit with the Al matrix and the barrier of structural transformations on two interfaces, demonstrating good thermal stability. Our discoveries lead to insight into the precipitate evolution in the Al-Zn-Mg-Cu alloy system and can help understand other precipitation processes of complex structured phases. Furthermore, the evolution process demonstrates an advanced mode of building metastable architectures with nanoscale interlocking pieces in alloy matrixes, which may inspire strategies to obtain high-strength, lightweight and thermostable alloys.

Oxidation behavior and atomic structural transition of size-selected coalescence-resistant tantalum nanoclusters

Herein a series of size-selected Ta N (N = 147, 309, 561, 923, 1415, 2057, 6525, 10 000, 20 000) clusters are generated using a gas-phase condensation cluster beam source equipped with a lateral time-of-flight mass-selector. Aberration-corrected scanning transmission electron microscopy (AC-STEM) imaging reveals good thermal stability of Ta N clusters in this study. The oxidation-induced amorphization is observed from AC-STEM imaging and further demonstrated through x-ray photoelectron spectroscopy and energy-dispersive spectroscopy. The oxidized Ta predominantly exists in the +5 oxidation state and the maximum spontaneous oxidation depth of the Ta cluster is observed to be 5 nm under prolonged atmosphere exposure. Furthermore, the size-dependent sintering and crystallization processes of oxidized Ta N clusters are observed with an in situ heating technique, and eventually, ordered structures are restored. As the temperature reaches 1300 °C, a fraction of oxidized Ta309 clusters exhibit decahedral and icosahedral structures. However, the five-fold symmetry structures are absent in larger clusters, instead, these clusters exhibit ordered structures resembling those of the crystalline Ta2O5 films. Notably, the sintering and crystallization process occurs at temperatures significantly lower than the melting point of Ta and Ta2O5, and the ordered structures resulting from annealing remain well-preserved after six months of exposure to ambient conditions.