Atomic Environment Research Articles

Long-Range Influence of Cr on the Stacking Fault Energy of Cr-Containing Concentrated Solid-Solution Alloys

Single-phase concentrated solid-solution alloys (CSAs) have exhibited excellent mechanical and radiation tolerance properties, making them potential candidate materials for nuclear applications. These excellent properties are closely related to dislocation movements, which depend on the stacking fault energies (SFEs). In CSAs, SFEs show large fluctuations due to variations in the local atomic environments in the vicinity of the stacking faults. In this work, first-principle calculations were performed to investigate the origin of the fluctuations in the SFEs of the widely studied CSA, NiCoCr, which show a very wide distribution from about −200 mJ/m2 to 60 mJ/m2. Compared to the common understanding that only atoms in close proximity to the stacking fault influence the SFEs in pure metals and dilute alloys, charge redistribution can be observed in several nearby planes of the stacking fault in NiCoCr, indicating that atoms several atomic layers away from stacking fault also contribute to the SFEs. Our analysis shows that Cr plays a major role in the large fluctuation in the SFEs of NiCoCr based on both electronic and magnetic responses. The flexible electronic structure of Cr facilitates easier charge transfer with Cr in several nearby atomic planes near the stacking fault, leading to significant changes in the d-electron number, orbital occupation number, and magnetic moments of Cr.

Machine learned environment-dependent corrections for a spds∗ empirical tight-binding basis

Abstract Empirical tight-binding (ETB) methods have become a common choice to simulate electronic and transport properties for systems composed of thousands of atoms. However, their performance is profoundly dependent on the way the empirical parameters were fitted, and the found parametrizations often exhibit poor transferability. In order to mitigate some of the the criticalities of this method, we introduce a novel Δ-learning scheme, called MLΔTB. After being trained on a custom data set composed of ab-initio band structures, the framework is able to correlate the local atomistic environment to a correction on the on-site ETB parameters, for each atom in the system. The converged algorithm is applied to simulate the electronic properties of random GaAsSb alloys, and displays remarkable agreement both with experimental and ab-initio test data. Some noteworthy characteristics of MLΔTB include the ability to be trained on few instances, to be applied on 3D supercells of arbitrary size, to be rotationally invariant, and to predict physical properties that are not exhibited by the training set.

Precipitation of oxide dispersion strength steels after long-term annealing at temperature of 475 °C

Oxide dispersion strengthened steels are key alloys used in nuclear installations. Steels with chromium content of up to 10 wt % are suitable due to their advantageous properties and these alloys are used for the construction of technological devices in the primary circuit of nuclear power plants. From other studies, it can be concluded that chromium has anti-corrosive properties due to the formation of a passivation layer, which results in reduced activation of the material by thermal neutrons. Macroscopic properties are determined by their microstructure, and therefore, the description of the microstructure is important. Transmission Mössbauer spectroscopy and atom probe tomography were used to characterise the material. This provides information about the physical and/or chemical environment of the resonant atoms can be obtained. Obtained spectral parameters reach saturation values from which the solubility limit of chromium in iron can be determined. In Cr-rich phase, the solubility limit can be estimated from the value of spectral parameters of the single-line in the spectrum annealed for the longest time. The suggested procedures are subsequently applied to the case studies of stainless steels suitable for the construction of various components of the III+/IVth generation of nuclear reactors (including fast and fusion reactors).

Yu–Shiba–Rusinov states induced by single Fe atoms on reconstructed compound superconductor V[formula omitted]Si

Reconstructed surfaces of the A15-compound superconductor V3Si(100) that are possibly induced by the segregation of bulk impurities serve as platforms to study the dependence of Yu–Shiba–Rusinov states induced by a single Fe atom on the adsorption site. Their number, energy and electron–hole asymmetry vary strongly with the atomic environment of the Fe atom. These variations are indicative of different Fe d-orbitals being active in the site-dependent exchange coupling with the substrate Cooper pairs. Spatially resolved spectroscopy gives rise to a short decay length of the Yu–Shiba–Rusinov states and thereby suggests the three-dimensional character of the scattering process underlying the bound states.

Dual electron microregion with oxygen vacancy of Fe0.8La/MCM-48 in bridging peracetic acid and ozonation: taking the pathway of free radical or nonradical generation?

Efficient tetracycline hydrochloride (TCH) degradation and interface reaction mechanism were investigated by constructing nonradical pathways in heterogeneous peracetic acid coupling with ozonation (O3/PAA) process. Ball-milling assisted Fe–La anchoring MCM-48 catalysts with dual electron microregion was designed to trigger 1O2-dominated non-radical for strong immunity to environment interference. Results exhibited that 83.4% degradation efficiency of TCH was achieved by Fe0.8La/MCM-48/O3/PAA system in only 2min and 94% TCH was degraded in a 12-hour continuous flow experiment. La with oxygen vacancy regulated the local atomic environment and electron structure of Fe sites, which could initiate peracetic acid activation to promote 1O2 production by surface adsorbed atomic oxygen (*Oad) reaction and this process overcame a lower reaction energy barrier than the binding of surface *Oad to O3. This work offers a reasonable interpretation for Fe–La synergy for inducing non-free radical route, which furnishes theoretical support and practical application for heterogeneous O3/PAA.

Controllable Regulation of the Oxygen Redox Process in Lithium-Oxygen Batteries by High-Configuration-Entropy Spinel with an Asymmetric Octahedral Structure.

Designing bifunctional electrocatalysts to boost oxygen redox reactions is critical for high-performance lithium-oxygen batteries (LOBs). In this work, high-entropy spinel (Co0.2Mn0.2Ni0.2Fe0.2Cr0.2)3O4 (HEOS) is fabricated by modulating the internal configuration entropy of spinel and studied as the oxygen electrode catalyst in LOBs. Under the high-entropy atomic environment, the Co-O octahedron in spinel undergoes asymmetric deformation, and the reconfiguration of the electron structure around the Co sites leads to the upward shift of the d-orbital centers of the Co sites toward the Fermi level, which is conducive to the strong adsorption of redox intermediate LiO2 on the surface of the HEOS, ultimately forming a layer of a highly dispersed Li2O2 thin film. Thin-film Li2O2 is beneficial for ion diffusion and electron transfer at the electrode-electrolyte interface, which makes the product easy to decompose during the charge process, ultimately accelerating the kinetics of oxygen redox reactions in LOBs. Based on the above advantages, HEOS-based LOBs deliver high discharge/charge capacity (12.61/11.72 mAh cm-2) and excellent cyclability (424 cycles). This work broadens the way for the design of cathode catalysts to improve oxygen redox kinetics in LOBs.

From Local Atomic Environments to Molecular Information Entropy.

The similarity of local atomic environments is an important concept in many machine learning techniques, which find applications in computational chemistry and material science. Here, we present and discuss a connection between the information entropy and the similarity matrix of a molecule. The resulting entropy can be used as a measure of the complexity of a molecule. Exemplarily, we introduce and evaluate two specific choices for defining the similarity: one is based on a SMILES representation of local substructures, and the other is based on the SOAP kernel. By tuning the sensitivity of the latter, we can achieve good agreement between the respective entropies. Finally, we consider the entropy of two molecules in a mixture. The gain of entropy due to the mixing can be used as a similarity measure of the molecules. We compare this measure to the average and best-match kernel. The results indicate a connection between the different approaches and demonstrate the usefulness and broad applicability of the similarity-based entropy approach.

Surface Coordination Environment Engineering on PtxCu1-x Alloy Catalysts for the Efficient Photocatalytic Reduction of CO2 to CH4.

Alloy catalysts have been reported to be robust in catalyzing various heterogeneous reactions due to the synergistic effect between different metal atoms. In this work, aimed at understanding the effect of the coordination environment of surface atoms on the catalytic performance of alloy catalysts, a series of PtxCu1-x alloy model catalysts supported on anatase-phase TiO2 (PtxCu1-x/Ti, x = 0.4, 0.5, 0.6, 0.8) were developed and applied in the classic photocatalytic CO2 reduction reaction. According to the results of catalytic performance evaluation, it was found that the photocatalytic CO2 reduction activity on PtxCu1-x/Ti showed a volcanic change as a function of the Pt/Cu ratio, the highest CO2 conversion was achieved on Pt0.5Cu0.5/Ti, with CH4 as the main product. Further systematic characterizations and theoretical calculations revealed that the equimolar amounts of Pt and Cu in Pt0.5Cu0.5/Ti facilitated the generation of more Cu-Pt-paired sites (i.e., the higher coordination number of Pt-Cu), which would favor a bridge adsorption configuration of CO2 and facilitate the electron transfer, thus resulting in the highest photocatalytic CO2 reduction efficiency on Pt0.5Cu0.5/Ti. This work provided new insights into the design of excellent CO2 reduction photocatalysts with high CH4 selectivity from the perspective of surface coordination environment engineering on alloy catalysts.

JEDI: A versatile code for strain analysis of molecular and periodic systems under deformation.

Stretching or compression can induce significant energetic, geometric, and spectroscopic changes in materials. To fully exploit these effects in the design of mechano- or piezo-chromic materials, self-healing polymers, and other mechanoresponsive devices, a detailed knowledge about the distribution of mechanical strain in the material is essential. Within the past decade, Judgement of Energy DIstribution (JEDI) analysis has emerged as a useful tool for this purpose. Based on the harmonic approximation, the strain energy in each bond length, bond angle, and dihedral angle of the deformed system is calculated using quantum chemical methods. This allows the identification of the force-bearing scaffold of the system, leading to an understanding of mechanochemical processes at the most fundamental level. Here, we present a publicly available code that generalizes the JEDI analysis, which has previously only been available for isolated molecules. Now, the code has been extended to two- and three-dimensional periodic systems, supramolecular clusters, and substructures of chemical systems under various types of deformation. Due to the implementation of JEDI into the Atomic Simulation Environment, the JEDI analysis can be interfaced with a plethora of program packages that allow the calculation of electronic energies for molecular systems and systems with periodic boundary conditions. The automated generation of a color-coded three-dimensional structure via the Visual Molecular Dynamics program allows insightful visual analyses of the force-bearing scaffold of the strained system.

Robust Activity and Stability of P-Doped Fe-Carbon Composites Derived from MOF for Bromate Reduction.

Iron-based materials are effective for the reductive removal of the disinfection byproduct bromate in water, while the construction of highly stable and active Fe-based materials with wide pH adaptability remains greatly challenging. In this study, highly dispersed iron phosphide-decorated porous carbon (Fe2P(x)@P(z)NC-y) was prepared via the thermal hydrolysis of Fe@ZIF-8, followed by phosphorus doping (P-doping) and pyrolysis. The reduction performances of Fe2P(x)@P(z)NC-y for bromate reduction were evaluated. Characterization results showed that the Fe, P, and N elements were homogeneously distributed in the carbonaceous matrix. P-doping regulated the coordination environment of Fe atoms and enhanced the conductivity, porosity, and wettability of the carbonaceous matrix. As a result, Fe2P(x)@P(1.0)NC-950 exhibited enhanced reactivity and stability with an intrinsic reduction kinetic constant (kint) 1.53-1.85 times higher than Fe(x)@NC-950 without P-doping. Furthermore, Fe2P(0.125)@P(1.0)NC-950 displayed superior reduction efficiency and prominent stability with very low Fe leaching (4.53-22.98 μg L-1) in a wide pH range of 4.0-10.0. The used Fe2P(0.125)@P(1.0)NC-950 could be regenerated by phosphating, and the regenerated Fe2P(0.125)@P(1.0)NC-950 maintained 85% of its primary reduction activity after five reuse cycles. The study clearly demonstrates that Fe2P-decorated porous carbon can be applied as a robust and stable Fe-based material in aqueous bromate reduction.

Axially Modified Square-Pyramidal CoN4-F1 Sites Enabling High-Performance Zn-Air Batteries.

Cobalt-nitrogen-carbon (Co-N-C) catalysts with a CoN4 structure exhibit great potential for oxygen reduction reaction (ORR), but the imperfect adsorption energy toward oxygen species greatly limits their reduction efficiency and practical application potential. Here, F-coordinated Co-N-C catalysts with square-pyramidal CoN4-F1 configuration are successfully synthesized using F atoms to regulate the axial coordination of Co centers via hydrothermal and chemical vapor deposition methods. During the synthesis process, the geometry structure of the Co atom converts from six-coordinated Co-F6 to square-pyramidal CoN4-F1 in the coordinatively unsaturated state, which provides an open binding site for the O2. The introduction of axial F atoms into the CoN4 plane alters the local atomic environment around Co, significantly improving the ORR activity and Zn-air batteries performance. In situ spectroscopy proves that CoN4-F1 sites strongly combine with the OOH* intermediate and facilitate the splitting of O-O bond, making OOH* readily decompose into O* and OH* via a dissociative pathway. Theoretical calculations confirm that the axial F atom effectively reduces the electronic density of the Co centers and facilitates the desorption of the OH* intermediate, efficiently accelerating the overall ORR kinetics. This work advances a feasible synthesis mechanism of axial ligands and provides a route to construct efficient high-coordination catalysts.

Breaking Continuously Packed Bimetallic Sites to Singly Dispersed on Nonmetallic Support for Efficient Hydrogen Production.

We have synthesized Pt1Zn3/ZnO, also termed 0.01 wt %Pt/ZnO-O2-H2, as a catalyst containing singly dispersed single-atom bimetallic sites, also called a catalyst of singly dispersed bimetallic sites or a catalyst of isolated single-atom bimetallic sites. Its catalytic activity in partial oxidation of methanol to hydrogen at 290 °C is found to be 2-3 orders of magnitude higher than that of Pt-Zn bimetallic nanoparticles supported on ZnO, 5.0 wt %Pt/ZnO-N2-H2. Selectivity for H2 on Pt1Zn3/ZnO reaches 96%-100% at 290-330 °C, arising from the uniform coordination environment of single-atom Pt1 in singly dispersed single-atom bimetallic sites, Pt1Zn3 on 0.01 wt %Pt/ZnO-O2-H2, which is sharply different from various coordination environments of Pt atoms in coexisting PtxZny (x ≥ 0, y ≥ 0) sites on Pt-Zn bimetallic nanoparticles. Computational simulations attribute the extraordinary catalytic performance of Pt1Zn3/ZnO to the stronger adsorption of methanol and the lower activation barriers in O-H dissociation of CH3OH, C-H dissociations of CH2O to CO, and coupling of intermediate CO with atomic oxygen to form CO2 on Pt1Zn3/ZnO as compared to those on Pt-Zn bimetallic nanoparticles. It demonstrates that anchoring uniform, isolated single-atom bimetallic sites, also called singly dispersed bimetallic sites on a nonmetallic support can create new catalysts for certain types of reactions with much higher activity and selectivity in contrast to bimetallic nanoparticle catalysts with coexisting, various metallic sites MxAy (x ≥ 0, y ≥ 0). As these single-atom bimetallic sites are cationic and anchored on a nonmetallic support, the catalyst of singly dispersed single-atom bimetallic sites is different from a single-atom alloy nanoparticle catalyst. The critical role of the 0.01 wt %Pt in the extraordinary catalytic performance calls on fundamental studies of the profound role of a trace amount of a metal in heterogeneous catalysis.

Fabricating highly active Pt atomically dispersed catalysts with the co-existence of Pt-O1Ni1 single atoms and Pt sub-nanoclusters for improved hydrogen evolution

Atomically dispersed catalysts (ADCs), including single atoms and sub-nanoclusters, simultaneously, are considered as the most promising candidate to boost the reaction kinetics of hydrogen evolution reaction (HER). However, the correlation between the coordination environment of single atoms and catalytic activity has not been clearly discussed in ADCs system. Herein, Pt ADCs with the different coordination structures were fabricated by a facile sulfurate route coupling deposition strategy. Importantly, Pt ADCs, including Pt-O1Ni1 single atoms and Pt sub-nanoclusters (Pt1+n/Ni3S2), show good basic HER activity, which just need 17 mV at 10 mA cm−2. Meanwhile, the turnover frequency for Pt1+n/Ni3S2 is 0.49 H2 s−1 under the overpotential of 100 mV, which is 8.6 times higher than Pt/C. Besides, the assembled RuO2 || Pt1+n/Ni3S2 system could get 100 mA cm−2 current density under 1.7 V cell voltage in alkaline water electrolyzer. Notably, in-situ Raman and attenuated total reflection-surface enhanced infrared absorption spectroscopy reveal that Pt-O1Ni1 coordination is conducive to promoting the fracture of H-O-H bond, realizing the rapid transform of Pt-H* intermediates. Further, density functional theory calculations confirm Pt single atoms with Pt-O1Ni1 coordination environment in Pt1+n/Ni3S2 serves as the main role for HER because Pt-O1Ni1 are more likely to accelerate the production of Pt-H* at the Pt sites, extremely achieving the rapid HER progress. This work discloses the structure-activity relationship in ADCs system, which is essential for the development of highly active electrocatalysts.

Synergistic role of Sn-doping on the thermal and electrical properties of sinnerite Cu6As4S9

Sinnerite Cu6As4S9 has been identified as a promising material for optoelectronic applications, with potential for other energy-related applications; however, knowledge of the electrical and thermal properties as well as the mechanisms underlying transport in sinnerite is lacking. We present an investigation of the synthesis, structural, thermal and electrical transport properties of stoichiometric and Sn-doped Cu6As4S9. Sinnerite has a triclinic lattice structure, with highly distorted local atomic coordination environments that, in part, results in its complex structure and bonding. Our results and analyses indicate As 4s2 lone pair-induced distortions and strong lattice anharmonicity that leads to a relatively short phonon mean free path, resulting in intrinsically very low thermal conductivity. The electrical resistivity for both compositions, Cu6As4-xSnxS9 (x = 0, 0.2), are relatively high and varies little with temperature, typical of degenerate semiconductors. An increase in mobility and electrical conductivity was obtained by Sn doping in Cu6As3.8Sn0.2S9. This work demonstrates an effective route to synthesize bulk sinnerite as well as advances the knowledge of the properties of sinnerite, as this and other ternary chalcogenides continue to be of interest for potential technologically significant applications.

Influence of non-stoichiometry and local atomic environments on carrier transport in GaAs1−x−yNxBiy alloys

We have investigated the influence of non-stoichiometry and local atomic environments on carrier transport in GaAs(N)Bi alloy films using local-electrode atom probe tomography (LEAP) in conjunction with time-resolved terahertz photoconductivity measurements. The local concentrations of N, Bi, and excess As, as well as Bi pair correlations, are quantified using LEAP. Using time-resolved THz photoconductivity measurements, we show that carrier transport is primarily limited by excess As, with the highest carrier mobilities for layers with yBi > 0.035.

Structure and complexation mechanism of aqueous Zn(II)-acetate complex studied by XAFS and Raman spectroscopies.

In this work, the structure of Zn acetate has been determined by a combination of X-ray absorption fine structure and Raman spectroscopy. We have analyzed the local atomic environment and the main vibrational bands of the acetate and Zn acetate at different pH. The results suggest that Zn acetate complex acquires a bidentate structure that modifies its first coordination shell. Meanwhile, the coordination shell of the hydrated Zn cation is formed by 6 hydroxides at a mean distance of 2.06Å, the coordination shell of the Zn cation in the complex is formed by 2 hydroxides and 2 oxygens from the carboxyl group of the acetate, at a mean Zn-O distance of 1.96Å. The structure of the Zn acetate complex is compared to those of Zn malonate and Zn citrate, none of which present a reduction in the coordination shell neither a shrinkage of the Zn-O shell distance.

Activating the Ni‐Contenting Carbon Nanotube by Covalent Triazine Frameworks to Form Atomically Dispersed Ni Sites with Curvature Effect for Electrocatalytic CO2 Reduction

N‐coordinated Ni sites (NiNx) are effective catalysts for the electrochemical reduction of CO2 to CO. In most researches, modulating the coordination environment of Ni atoms is focused on to improve electrochemical CO2 reduction (ECR) performance. However, the influence of the carbon substrate's structure on the intrinsic activity of NiNx is seldom investigated. The highly curved surface of carbon nanotubes (CNT) may provide a unique curvature effect on NiNx. It is found that the Ni residues in CNT can be atomized to form NiNx sites on the surface of CNT (Ni‐N/CNT@covalent triazine framework [CTF]) through high‐temperature pyrolysis, using a soluble CTF nanosheet as N precursor. The π‐conjugated and ultrathin 2D structure of CTF enables closer interfacial contact between CTF and CNT, which avoids the formation of a thick carbon layer to maximize the curvature effect. Theoretical data reveal that the NiN3 configuration may act as a highly active ECR site, and the curvature effect from CNT can further tune the electronic structure of NiN3, thus improving the ECR kinetics. The Ni‐N/CNT@CTF‐based flow‐cell electrolyzer exhibits a jCO of 201 mA cm−2 at −0.9 V with a high FECO of 98%.

Effect of Al doping on magnetocaloric effect and mechanical properties of La(FeSi)13-based alloys

La(Fe,Si)13 is a candidate room temperature magnetic refrigeration material owing to its large magnetocaloric effect and an adjustable Curie temperature. The structure, magnetocaloric effect, and mechanical properties of La(Fe,Si)13 strongly depend on its microscopic atomic environment. Proportional doping of magnetic or ductile elements can improve its magnetocaloric and mechanical properties. Here, magnetocaloric effect, and mechanical properties of Al-doped La(Fe,Si)13 alloys were studied through density functional theory calculations and experiments. The experimental results show that the doping of Al can increase the Curie temperature of the alloy, broaden the full width at half maximum (FWHM) and improve the mechanical properties of the alloy. The density functional theory describes the magnetic transition and mechanical behavior of the alloy, which is consistent with the experimental results. Therefore, the appropriate doping of Al in La(FeSi)13 alloy can obtain good integrated refrigeration capacity, which is helpful to realize multi-stage refrigeration application in a wide temperature range.

Neural network molecular dynamics study of LiGe2(PO4)3: Investigation of structure

Machine learning interatomic potential for LiGe2(PO4)3 in a form of a set of neural networks (DeePMD-model) was trained on DFT data. DFT simulations in GGA PBE approximation were performed for ordered and disordered LiGe2(PO4)3 supercell with 432 atoms which allowed the developed potential to describe crystalline, molten and glassy states. The developed DeePMD-potential was verified using literature and our experimental data demonstrating good agreement with it. Neural network molecular dynamic simulations indicate that P atoms have tetrahedral oxygen environment in both crystalline and glassy state. Coordination environment of Ge atoms is more complex. They have octahedral oxygen environment in crystalline state and mixed environment in glassy state: 4-, 5- and 6-coordinated Ge atoms were found. It was shown by calculation of orientational order parameters that in glassy LiGe2(PO4)3 4-coordinated Ge atoms have tetrahedral oxygen environment, while 6-coordinated Ge atoms have octahedral oxygen environment. Analysis of O-Ge-O angle distribution for 5-coordinated Ge atoms in glassy LiGe2(PO4)3 demonstrates that the environment of Ge atoms in this case is represented by various structures: square pyramids, trigonal bipyramids and transitional structures from 5-coordinated Ge atoms to tetrahedrons.

Best practices in the characterization of bulk catalyst properties

Bulk characterization of a solid provides us with a spatially-averaged description of its physical and chemical properties. These properties are not site-specific, but they are critical for categorizing materials and understanding their catalytic performance. Important bulk chemical properties include elemental composition, crystal structure, atomic coordination environment, and the oxidation states of elements comprising the catalyst. Significant physical properties include accessible surface area, pore volume, pore diameter, and particle size distributions that exist at the various length scales of catalysis. Each physicochemical property is sensitive to the conditions employed for catalyst synthesis, storage, pre-treatment, activation, and characterization. Thus, it is imperative that authors fully describe materials and methods in publications as this metadata provides context for observed phenomena and allows others to recreate the exact conditions that are essential for reproducibility. Such protocols are necessary for a meaningful interpretation of differences in catalyst performance observed across laboratories. This perspective article defines bulk characterization, provides guidance on bulk characterization methods, and emphasizes important considerations and best practices. Our aim is to build a more nuanced understanding of catalyst characterization. We hope that awareness and application of the principles outlined herein will improve rigor and reproducibility in catalysis science.