Atomic Clusters Research Articles

Boosting Electrocatalytic Ammonia Synthesis via Synergistic Effect of Iron-Based Single Atoms and Clusters.

Electrocatalytic reduction of nitrate to ammonia (NO3RR) is gaining attention for low carbon emissions and environmental protection. However, low ammonia production rate and poor selectivity have remained major challenges in this multi-proton coupling process. Herein, we report a facile strategy toward a novel Fe-based hybrid structure composed of Fe single atoms and Fe3C atomic clusters that demonstrates outstanding performance for synergistic electrocatalytic NO3RR. By operando synchrotron Fourier transform infrared spectroscopy and theoretical computation, we clarify that Fe single atoms serve as the active site for NO3RR, while Fe3C clusters facilitate H2O dissociation to provide protons (*H) for continued hydrogenation reactions. As a result, the Fe-based electrocatalyst exhibits ammonia Faradaic efficiency of nearly 100%, with a corresponding production rate of 24768 μg h-1 cm-2 at -0.4 V vs RHE, exceeding most reported metal-based catalysts. This research provides valuable guidance toward multi-step reactions.

A Multilevel Method for Many-Electron Schrödinger Equations Based on the Atomic Cluster Expansion

A Multilevel Method for Many-Electron Schrödinger Equations Based on the Atomic Cluster Expansion

Evaluation of the structural, electronic and magnetic properties of modified 8-16-4 graphyne by 3d transition metals: A DFT-D2 study

A new two-dimensional carbon allotrope called 8-16-4 graphyne (GY) has been recently introduced (in 2021). This allotrope consists of sp. and sp2 hybridized carbon atoms. To investigate the adsorption behavior of single atom of 3d transition metals (TM) on 8-16-4 GY, corrected density functional theory (DFT-D2) was employed. The results reveal that single TM atoms prefer to bind tightly in the center of the 16-carbon ring of GY, and the adsorption energy of TMs decreases from Sc to Zn with a reducible trend from −9.282 to −1.158 eV, respectively. These high adsorption energies show that diffusion of TM atoms and clustering of them are prevented on the surface of the carbon frame. Pristine and 3d TM decorated GY have some Dirac points, zero band gap, and conductivity properties. Also, pristine and all of TM decorated GY except Cr, Mn, and Fe-decorated GY haven't magnetic properties. These findings suggest that 8-16-4 GY is a suitable carbonic substrate to prevent the clustering of TM atoms that is essential for some applications such as effective single-atom catalysts, hydrogen storage, CO2 capture, etcetera.

Phase transition and atomic competition mechanism of in-situ particle reinforced TixAl/Ti5Si3 composite coating prepared by laser cladding Al-xSi-2Nb alloy powder on Ti6Al4V alloy

The in-situ particle reinforced TixAl/Ti5Si3 composite coatings with excellent wear resistance were successfully fabricated by laser cladding Al-xSi-2Nb alloy powder on Ti6Al4V alloy. The microstructure evolution and properties were systematically studied. Meanwhile, the phase transformation and atomic competition of the composite coatings were also investigated based on the Ti-Al-Si phase diagrams and the self-consistent bond length difference (SCBLD) method. The results indicate that a large number of in-situ particle reinforced phases, such as Ti5Si3, α2-Ti3Al and γ-TiAl, exhibit in the composite coatings. Moreover, the morphology and quantity of in-situ particle reinforced phases are significantly affected by laser cladding parameters. The fabricated coatings not only own a good and narrow metallurgical bonding (MB) with the substrate, but also have the excellent wear resistance. The Ti5Si3 atom cluster owns the significant advantage in the atomic competition to form embryo and bulk crystals; while the α2-Ti3Al phase is easier formed than γ-TiAl phase during the decomposition of β solid solutions. Moreover, the V and Nb elements are easier dissolved in α2-Ti3Al phases than that of γ-TiAl phase.

Non-collinear magnetic atomic cluster expansion for iron

The Atomic Cluster Expansion (ACE) provides a formally complete basis for the local atomic environment. ACE is not limited to representing energies as a function of atomic positions and chemical species, but can be generalized to vectorial or tensorial properties and to incorporate further degrees of freedom (DOF). This is crucial for magnetic materials with potential energy surfaces that depend on atomic positions and atomic magnetic moments simultaneously. In this work, we employ the ACE formalism to develop a non-collinear magnetic ACE parametrization for the prototypical magnetic element Fe. The model is trained on a broad range of collinear and non-collinear magnetic structures calculated using spin density functional theory. We demonstrate that the non-collinear magnetic ACE is able to reproduce not only ground state properties of various magnetic phases of Fe but also the magnetic and lattice excitations that are essential for a correct description of finite temperature behavior and properties of crystal defects.

Disentangling the Activity‐Stability Trade‐Off of Pyrrolic N‐Coordinated Fe─N4 Catalytic Sites for Long‐Life Oxygen Reduction Reaction in Acidic Medium

AbstractFe─N─C materials with Fe─N4 sites are considered as most promising non‐precious metal‐based electrocatalysts for low‐cost proton‐exchange‐membrane fuel cells (PEMFCs). Breaking the trade‐off between activity and stability has been a long‐standing challenge in the field of acidic oxygen reduction reaction (ORR). Herein, a “top‐down” thermally‐driven strategy is developed to achieve highly active pyrrolic N‐coordinated Fe sites in a high spin state with Fe atomic cluster (Fen@Fe─Npyrr─C) and discover that the neighboring Fen cluster can synergistically stabilize such vulnerable Fe─N4 sites by inhibiting their protonation. Consequently, the Fen@Fe─Npyrr─C catalysts exhibit much enhanced ORR activity and stability, endowing PEMFCs with a high power density of 804.6 mW cm−2 (testing conditions: 80 °C, 100% RH, 2.0 bar) and over 100 h durability (at 0.5 V). These findings open up opportunities for the exploration of durable Fe─N─C ORR electrocatalysts for non‐precious metal‐based PEMFCs and other applications.

Robust additive manufacturable Ni superalloys designed by the integrated optimization of local elemental segregation and cracking susceptibility criteria

To achieve an effective design of additively manufacturable Ni superalloys with decent service performance, a hybrid computational design model has been developed, where the strategy to tailor local elemental segregations was integrated within a scheme of minimizing the cracking susceptibility. More specifically, the phase boundary of primary NbC / γ matrix was introduced into the design routine to tune the spatial distribution of critical solutes at an atomic scale, thereby inhibiting the formation of borides and segregation-induced cracking. Based on the output of the design, new grades of Ni superalloy have been developed with excellent additive manufacturability, as confirmed by the robustness of printing parameters in fabricating low-defect-density samples. The capability of the phase boundaries to evenly distribute boron atoms was validated experimentally, and the cracking induced by uncontrolled boron segregation at grain boundaries was effectively prevented. The newly designed alloys showed good tensile properties and decent oxidation resistance at different service temperatures, which are comparable to those of conventionally produced superalloys. The finding that phase boundaries can be employed to prevent undesirable clustering of boron atoms can be extended to manipulate the distributions of other critical elements, which provides a new path for designing novel Ni superalloys with balanced printability and mechanical properties.

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.

Recent advances in atomic cluster synthesis: a perspective from chemical elements.

Despite its potential significance, "cluster chemistry" remains a somewhat marginalized topic within the chemistry field. However, atomic clusters with their unusual and unique structures and properties represent a novel material group situated between molecules and nanoparticles or solid matter, judging from both scientific standpoints and historical backgrounds. Surveying an entire material group, including all substances that can be regarded as a cluster, is essential for establishing cluster chemistry as a more prominent chemistry field. This review aims to provide a comprehensive understanding by categorizing, summarizing, and reviewing clusters, focusing on their constituent elements in the periodic table. However, because numerous disparate synthetic processes have been individually developed to date, their straightforward and uniform classification is a challenging task. As such, comprehensively reviewing this field from a chemical composition viewpoint presents significant obstacles. It should be therefore noted that despite adopting a synthetic method-based classification in this review, the discussions presented herein could entail inaccuracies. Nevertheless, this unorthodox viewpoint unfolds a new scientific perspective which accentuates the common ground between different development processes by emphasizing the lack of a definitive border between their synthetic methods and material groups, thus opening new avenues for cementing cluster chemistry as an attractive chemistry field.

Resolving heterogeneous particle mobility in deeply quenched liquid iron: an ultra-fast assembly-free two-step nucleation mechanism.

Despite intensive research, little is known about the intermediate state of phase transforming materials, which may form the missing link between e.g. liquids and solids on the nanoscale. The unraveling of the nanoscale interplay between the structure and dynamics of the intermediate state of phase transformations (through which e.g. crystal nucleation proceeds) is one of the biggest challenges and unsolved problems of materials science. Here we show using unbiased molecular dynamics simulations and spatially resolved atomic displacement maps (d-maps) that upon deep quenching the solidification of undercooled liquid iron proceeds through the formation of metastable pre-nucleation clusters (PNCs). We also reveal that the hitherto hidden PNCs are nearly immobile (dynamically arrested) and the related heterogeneity in atomic mobilities becomes clearly visible on atomic displacement-maps (d-maps) when atomic jumps are referenced to the final crystalline positions. However, this is in contrast to PNCs found in molecular solutions, in which PNCs tend to aggregate, move and crystallize via an activated process. Coordination filtered d-maps resolved in real space directly demonstrate that previously unseen highly ramified intermediate atomic clusters with a short lifetime emerge after incubation of undercooled liquid iron. The supercooled liquid iron is neither a spinodal system nor a liquid and undergoes a transition into a specific state called a quasi-liquid state within the temperature regime of 700-1250 K (0.5Tm > 0.7Tm, where the melting point is Tm ≈ 1811 K). Below 700 K the supercooled system is spinodal-like and above 1300 K it behaves like an ordinary liquid with long incubation times. A two-step process is proposed to explain the anomalous drop in the incubation time in the temperature regime of 700-1250 K. The 1st step is activated aggregation of small atomic clusters followed by assembly-free nearly barrierless ultrafast growth of early ramified prenucleation clusters called germs. The display and characterization of the hidden PNCs in computer simulations could provide new perspectives on the deeper understanding of the long-standing problem of precursor development during crystal nucleation following deep quenching.

Frame-by-frame observations of structure fluctuations in single mass-selected Au clusters using aberration-corrected electron microscopy.

The multi-dimensional potential energy surface (PES) of a nanoparticle, such as a bare cluster of metal atoms, controls both the structure and dynamic behaviour of the particle. These properties are the subject of numerous theoretical simulations. However, quantitative experimental measurements of critical PES parameters are needed to regulate the models employed in the theoretical work. Experimental measurements of parameters are currently few in number, while model parameters taken from bulk systems may not be suitable for nanosystems. Here we describe a new measurement methodology, in which the isomer structures of a single deposited nanocluster are obtained frame-by-frame in an aberration-corrected scanning transmission electron microscope (ac-STEM) in high angle annular dark field (HAADF) mode. Several gold clusters containing 309 ± 15 atoms were analysed individually after deposition from a mass-selected cluster source onto an amorphous carbon film. The main isomers identified are icosahedral (Ih), decahedral (Dh) and face-centred-cubic (fcc) (the bulk structure), alongside many amorphous (glassy) structures. The results, which are broadly consistent with static ac-STEM measurements of an ensemble of such clusters, open the way to dynamic measurements of many different nanoparticles of diverse sizes, shapes and compositions.

Atomic Ru clusters supported on CeO2(110) for effectively catalyzing the electrochemical N2 reduction reaction: insights from density functional theory

The electrochemical nitrogen reduction reaction on Ru3/CeO2(110).

Gold nanostructures/quantum dots for the enhanced efficiency of organic solar cells.

Incorporating gold nanoparticles (AuNPs) into organic solar cell (OSC) structures provides an effective means to manipulate light-matter interactions. AuNPs have been used as plasmonic-enhancement and light-trapping materials in OSCs and exhibit diverse single and mixed morphologies. Substantial near-field enhancement from metal periodic structures has consistently demonstrated high enhancement in solar cell efficiency. Additionally, coupling with atomic gold clusters in the form of gold quantum dots holds promise for light harvesting through fluorescence phenomena. The configured devices optimize light utilization in OSCs by considering factors such as the morphology, position, and hybridization of localized surface plasmon resonance, propagating surface plasmon resonance, and fluorescence phenomena. This optimization enhances light absorption, scattering, and efficient trapping facilitated by gold nanostructures/quantum dots. The configured setup exhibits multiple effects, concurrently improving plasmonic and fluorescence responses under solar irradiation, thereby enhancing energy conversion performance. Integrating plasmonic nanostructures with OSCs can address fundamental issues, providing opportunities to enhance the light-absorption intensity and charge transfer efficiency at intra and intermolecular levels. This comprehensive review demonstrates that the greatest improvement in solar cell efficiency exceeded 30% compared with the reference cells.

Theoretical investigation of Cu5/silicates deposited on rutile TiO2 as a photocatalyst.

Titanium dioxide (TiO2) is an exceptional compound with unique optical properties, which have been intensively used for applications in photocatalysis. Recent studies show that Cu5 atomic quantum clusters (AQCs) could facilitate visible light absorption and enhance the photocatalytic properties of rutile TiO2 by creating mid-gap states. In this work, to move the theory of these catalysts closer to the experiment, we investigate the electronic structures of Cu5 adsorbed on a perfect and reduced rutile TiO2 surface in the absence and presence of silicate SiO32- ions, which are introduced for the purification of Cu5 AQCs. Encouragingly, our DFT simulations predict that the presence of SiO32- does not reduce the gap states of the Cu5@TiO2 composite and could even enhance them by shifting more states into the band gap. Our results also demonstrate that the polarons created by oxygen vacancies (Ov) and Cu5 coexist within the band gap of TiO2. Indeed an Ov behaves like a negative gate on the electronic states located on the AQCs, thereby shifting states out of the valence band into the band gap, which could lead to enhanced photocatalytic performance.

Support effects on conical intersections of Jahn-Teller fluxional metal clusters on the sub-nanoscale.

The concept of fluxionality has been invoked to explain the enhanced catalytic properties of atomically precise metal clusters of subnanometer size. Cu3 isolated in the gas phase is a classical case of a fluxional metal cluster where a conical intersection leads to a Jahn-Teller (JT) distortion resulting in a potential energy landscape with close-lying multiminima and, ultimately, fluxional behavior. In spite of the role of conical intersections in the (photo)stability and (photo)catalytic properties of surface-supported atomic metal clusters, they have been largely unexplored. In this work, by applying a high-level multi-reference ab initio method aided with dispersion corrections, we analyze support effects on the conical intersection of Cu3 considering benzene as a model support molecule of carbon-based surfaces. We verify that the region around the conical intersection and the associated Jahn-Teller (JT) distortion is very slightly perturbed by the support when the Cu3 cluster approaches it in a parallel orientation: Two electronic states remain degenerate for a structure with C3 symmetry consistent with the D3h symmetry of unsupported Cu3 at the conical intersection. It extends over a one-dimensional seam that characterizes a physisorption minimum of the Cu3-benzene complex. The fluxionality of the Cu3 cluster, reflected in large fluctuations of relaxed Cu-Cu distances as a function of the active JT mode, is kept unperturbed upon complexation with benzene as well. In stark contrast, for the energetically favored perpendicular orientation of the Cu3 plane to the benzene ring plane, the conical intersection (CI) is located 12 100 cm-1 (∼1.5 eV) above the chemisorption minimum, with the fluxionality being kept at the CI's nearby and lost at the chemisorption well. The first excited state at the perpendicular orientation has a deep well (>4000 cm-1), being energetically closer to the CI. The transition dipole moment between ground and excited states has a significant magnitude, suggesting that the excited state can be observed through direct photo-excitation from the ground state. Besides demonstrating that the identity of an isolated Jahn-Teller metal cluster can be preserved against support effects at a physisorption state and lifted out at a chemisorption state, our results indicate that a correlation exists between conical intersection topography and fluxionality in the metal cluster's Cu-Cu motifs.

Transfer Hydrogenation of Nitro Compounds Catalyzed by Co Atom Cluster Confined in Metal-Organic Frameworks Derived Nitrogen Doped Carbon

Transfer Hydrogenation of Nitro Compounds Catalyzed by Co Atom Cluster Confined in Metal-Organic Frameworks Derived Nitrogen Doped Carbon

Selecting dual atomic clusters supported on two-dimensional biphenylene with significantly optimized capability to reduce carbon monoxide

Four dual-atomic clusters supported on two-dimensional biphenylene were identified from 28 TM2@BPN candidates, which can surpass the activity benchmarks for metals and achieve efficient CORR.

Research on microstructure and mechanical properties of hot extruded Mg-Gd-Y-Sm-Zr alloy at room and high temperatures

In this study, the age hardening behavior of hot extruded Mg-8Gd-4Y-1Sm-0.5Zr (GWS841) alloy, mechanical properties and microstructural evolution of hot extruded GWS841 alloy during elevated temperature tensile processes were mainly investigated. The results show that the hot extrusion aged GWS841 alloy possess excellent mechanical properties at room and high temperature, which are 397 MPa, 386 MPa, 376 MPa, and 312 MPa at 25 °C, 200 °C, 250 °C, and 300 °C, respectively. After aging for 200 °C × 96 h, the hot extruded GWS841 alloy reaches its maximum hardness and room temperature tensile strength, and strengthening precipitation phase, being nano β′ phase, approximately 12 nm × 20 nm in size, precipitates simultaneously in three prismatic planes, (1‾21‾0)α、 (1‾1‾20)α and (21‾1‾0)α planes, which present precipitation strengthening behavior. During tensile testing at 200 °C, the strengthening precipitate remains β′ phase. During elevated tensile processes at 250 °C and 300 °C, strengthening precipitation phase undergoes significant transformation at grain boundary, β′ phase → β phase, and additionally, nano precipitation zone formed by rare earth atoms aggregation along grain boundary, which strengthen the grain boundary. During elevated tensile deformation at 300 °C, β′ phase completely disappeared and transformed into nano rare earth atom cluster region uniformly distributing inner grain.

Size limits and fission channels of doubly charged noble gas clusters.

Small, highly charged liquid droplets are unstable with respect to spontaneous charge separation when their size drops below the Rayleigh limit or, in other words, their fissility parameter X exceeds the value 1. The absence of small doubly charged atomic cluster ions in mass spectra below an element-specific appearance size na has sometimes been attributed to the onset of barrierless fission at X = 1. However, more realistic models suggest that na marks the size below which the rate of fission surpasses that of competing dissociative channels, and the Rayleigh limit of doubly charged van der Waals clusters has remained unchartered. Here we explore a novel approach to form small dicationic clusters, namely by Penning ionization of singly charged noble gas (Ng) clusters that are embedded in helium nanodroplets; the dications are then gently extracted from the nanodroplets by low-energy collisions with helium gas. We observe Ngn2+ ions that are about 40% smaller than previously reported for xenon and krypton and about 20% for argon. These findings suggest that fission barriers have been underestimated in previous theoretical work. Furthermore, we measure the size distributions of fragment ions that are produced by collisional excitation of mass-selected dications. At lowest collision gas pressure, dicationic Kr and Xe clusters that are smaller than previously observed are found to evaporate an atom before they undergo highly symmetric fission. The distribution of fragments resulting from fission of small dicationic Ar clusters is bimodal.

Atomically dispersed metal cocatalysts for solar energy conversion

This review explores the role of atomic metal site cocatalysts in photocatalysis for solar energy conversion, focusing on the recent advances in single-atom and atomic cluster cocatalysts, their structure–activity relationships, and key applications.