Atomic Arrangement Research Articles

Chalcogen-Based Precursors for Transition Metal (Co, Ni) Phosphides: (Di)chalcogenide-to-Phosphide Transformation via Chemical Extraction of Chalcogenides.

The chemical properties of polymorphic compounds are highly dependent on their stoichiometry and atomic arrangements, making certain phases technologically more important. Selective development of these phases is challenging. This study introduces a method where chalcogenide atoms from metal chalcogenides are chemically extracted by trioctylphosphine (TOP) and substituted with phosphide. Using this approach, dithiocarbamate/xanthate complexes of cobalt and nickel were employed for the selective synthesis of pure metal sulfides or phosphides. Optimization yielded either sulfur-deficient phases (Ni3S2, Co9S8) or a complete transformation to phosphides (Ni2P, CoP). Likewise, for the first time, selenobenzoate complexes of Ni and Co were used for the synthesis of transition metal diselenides (NiSe2, CoSe2), which could then be converted to metal phosphides (Ni2P, Co2P). The synthesis used solution-phase thermal decomposition with various precursors, surfactants, and temperatures. With TOP, different phases of metal chalcogenides, metal phosphides, and mixed metal phosphide nanomaterials (NiS, Ni3S2, Co9S8, NiSe2, CoSe2, Ni2P, Ni5P4, Co2P, CoP, and Ni2-xCoxP) were obtained by varying reaction conditions. The formation mechanism of nickel and cobalt phosphide nanoparticles from precursors is proposed, demonstrating that presynthesized metal chalcogenides can be transformed into phosphides, opening a new research avenue for dimensionally controlled metal chalcogenides as templates for metal phosphides.

Contact Geometry-Dependent Excitonic Emission in Mixed-Dimensional van der Waals Heterostructures.

Manipulation of excitonic emission in two-dimensional (2D) materials via the assembly of van der Waals (vdW) heterostructures unlocks numerous opportunities for engineering their photonic and optoelectronic properties. In this work, we introduce a category of mixed-dimensional vdW heterostructures, integrating 2D materials with one-dimensional (1D) semiconductor nanowires composed of vdW layers. This configuration induces spatially distinct localized excitonic emissions through a tailored interfacial heterolayer atomic arrangement. By precisely adjusting both the axial and sidewall facet orientations of bottom-up grown PbI2 vdW nanowires and by transferring them onto 1L WSe2 flakes, we establish vdW heterointerfaces with either perpendicular or parallel interatomic arrangements. The edge-standing heterojunction, featuring perpendicular PbI2 layers atop WSe2, promotes efficient charge transfer through the edges and coupled localized states, leading to an enhanced redshifted excitonic emission. Conversely, the layer-by-layer heterointerface, where PbI2 layers are in parallel contact with WSe2, exhibits substantial quenching due to deep midgap states in a type-II alignment, as evidenced by power-dependent measurements and first-principle calculations. Our results introduce a method for actively manipulating excitonic emissions in 2D transition metal dichalcogenides (TMDs) through edge engineering, highlighting their potential in the development of various quantum devices.

Crystal-Phase- and B-Content-Dependent Electrochemical Behavior of Pd─B Nanocrystals toward Oxygen Reduction Reaction.

The manipulation of crystal phases in metal-nonmetal interstitial alloy nanostructures has attracted considerable attention due to the formation of unique electronic structures and surface atomic arrangements, resulting in unprecedented catalytic performances. However, achieving simultaneous control over crystal phase and nonmetal elements in metal-nonmetal interstitial alloy nanostructures has remained a formidable challenge. Here, a novel synthesis approach is presented for Pd─B interstitial alloy nanocrystals (NCs) that allows investigation of the crystal-phase- and B-content-dependent catalytic performance. Through comparison of the oxygen reduction reaction (ORR) properties of Pd─BX interstitial alloy NCs with different crystal phases and B contents, achieved by precise control of reaction temperature and time, the influences of crystal phase and B contents in the Pd─BX interstitial alloy NCs on ORR are precisely investigated. The hexagonal closed packed (hcp) PdB0.5 NCs exhibit superior catalytic activity, with mass activities reaching 2.58 A mg-1, surpassing Pd/C by 10.3 times, attributed to synergistic effects by the hcp crystal phase and relatively high B contents. This study not only provides a novel approach to fabricate interstitial alloy nanostructures with unconventional crystal phases and finely controlled nonmetal elements but also elucidates the importance of crystal phase and nonmetal element content in optimizing electrocatalytic efficiency.

New ion radii for oxides and oxysalts, fluorides, chlorides and nitrides.

Ion radii are derived here from the characteristic (grand mean) bond lengths for (i) 135 ions bonded to oxygen in 459 configurations (on the basis of coordination number) using 177 143 bond lengths extracted from 30 805 ordered coordination polyhedra from 9210 crystal structures; and (ii) 76 ions bonded to nitrogen in 137 configurations using 4048 bond lengths extracted from 875 ordered coordination polyhedra from 434 crystal structures. There are two broad categories of use for ion radii: (1) those methods which use the relative sizes of cation and anion radii to predict local atomic arrangements; (2) those methods which compare the radii of different cations (or the radii of different anions) to predict local atomic arrangements. There is much uncertainty with regard to the relative sizes of cations and anions, giving rise to the common failure of type (1) methods, e.g. Pauling's first rule which purports to relate the coordination adopted by cations to the radius ratio of the constituent cation and anion. Conversely, type (2) methods, which involve comparing the sizes of different cations with each other (or different anions with each other), can give very accurate predictions of site occupancies, physical properties etc. Methods belonging to type (2) can equally well use the characteristic bond lengths themselves (from which the radii are derived) in place of radii to develop correlations and predict crystal properties. Extensive quantum-mechanical calculations of electron density in crystals in the literature indicate that the radii of both cations and anions are quite variable with local arrangement, suggesting significant problems with any use of ion radii. However, the dichotomy between the experimentally derived ion radii and the quantum-mechanical calculations of electron density in crystals is removed by the recognition that ion radii are proxy variables for characteristic bond lengths in type (2) relations.

Molecular dynamics simulation study of Zr interposer promoting Cu-Cu low-temperature hybrid bonding

With the development of the microelectronics industry, microelectronics packaging technology continues to develop towards higher integration and smaller size. To overcome the problem that the micro-bump size of solder cannot meet the fine pitch bonding, Cu-Cu direct bonding has become one of the most promising methods in advanced packaging technology. However, since the temperature required for Cu-Cu direct bonding is approximately 400 °C, currently Cu-Cu direct bonding is mostly achieved through a hot-pressing process. Such high temperatures will lead to reduced alignment accuracy, damage to device performance, and increased equipment requirements. In order to overcome these problems, this study proposed to use active metal Zr as the interposer material to improve the Cu-Cu atomic diffusion ability and reduce the Cu-Cu direct bonding temperature. The research results indicated that the interposer structure of Zr with (111), (11-2), and (1-10) surfaces contribute to promote Cu-Cu diffusion and bonding at low temperatures. Among them, the Zr (11-2) structure had the strongest promoting effect. Due to the tight arrangement of atoms in the densely packed crystal plane, the diffusion ability of atoms is significantly weakened during the bonding process of the densely packed crystal plane. Therefore, the Zr (001) structure can only promote bonding process under specific crystalline surface of Cu, and the bonding ability was very weak. The application of this research result will have a beneficial effect on the reliability and manufacturability of three-dimensional integrated packaging.

Influence of nickel plating on the welding metallurgical mechanism, microstructure, and shear performance of C101/80Au20Sn/C101 solder joints

Herein, electroplated and electroless plating processes were used to plate nickel (Ni) on the surface of C101 alloy, which is a low-carbon steel with a carbon content of approximately 0.1% and Fe primarily contributing to the rest of the content and which is commonly used in metal packaging, and electroplated Ni and electroless Ni C101/80Au20Sn/C101 solder joints were prepared. The welding metallurgical mechanisms, microstructures, and shear performances of the two types of solder joints were investigated through experimental observation, material characterization, shear testing, and finite-element analysis (FEA). The diffusion of Ni atoms within the two platings was evaluated using first-principles calculation. Results indicated that the atomic arrangement of the electroplated Ni layer was polycrystalline, whereas that of the electroless Ni layer was primarily amorphous. The orientation of Ni grains in the electroplated-Ni joints affected the growth of (Ni,Au)3Sn2 throughout the welding metallurgical process. The [111] orientation suppressed the growth of (Ni,Au)3Sn2, resulting in a discontinuous distribution of (Ni,Au)3Sn2 at the Ni/solder interface and considerable variations in the thickness of (Ni,Au)3Sn2. Amorphous Ni in the electroless Ni layer promoted the growth of (Ni,Au)3Sn2, resulting in a continuous (Ni,Au)3Sn2 layer having a relatively uniform thickness. The shear strength of the electroplated-Ni joints was considerably lower than that of the electroless-Ni joints. FEA results demonstrated that the locations of stress concentration in the electroplated- and electroless-Ni joints were at the (Ni,Au)3Sn2/solder interface and within the solder matrix, respectively. First-principles calculations showed that the diffusion performance of Ni atoms in the electroless Ni layer was considerably superior to that of Ni atoms in the electroplated Ni layer.

Single-Molecule Identification of the Isomers of a Lipidic Antibody Activator.

Molecular structural elucidation can be accomplished by different techniques, such as nuclear magnetic resonance or X-ray diffraction. However, the former does not give information about the three-dimensional atomic arrangement, and the latter needs crystallizable solid samples. An alternative is direct, real-space visualization of the molecules by cryogenic scanning tunneling microscopy (STM). This technique is usually limited to thermally robust molecules because an annealing step is required for sample deposition. A landmark development has been the coupling of STM with electrospray deposition (ESD), which smooths the process and widens the scope of the visualization technique. In this work, we present the on-surface characterization of air-, light-, and temperature-sensitive rhamnopolyene with relevance in molecular biology. Supported by theoretical calculations, we characterize two isomers of this flexible molecule, confirming the potential of the technique to inspect labile, non-crystallizable compounds.

Superior corrosion-resistant Zr-Ti-Ag thin film metallic glasses as potential biomaterials

Low-cost and non-cytotoxic ternary Zr-Ti-Ag thin film metallic glasses (TFMGs) were synthesized by DC magnetron sputtering. Results revealed that Ag addition enhanced the crystallization resistance and thermal stability of TFMGs. An appropriate Ag addition favored the mechanical property and corrosion resistance of TFMGs, while the excessive Ag addition had the opposite effect. Moreover, Ag did not directly form the passive film but altered the passive film stability and anti-corrosion capacity of TFMGs by inducing the disordered atomic arrangement, forming a dense microstructure, and tuning the corrosion-resistant Zr and Ti components. With low Young’s modulus of 116.2 GPa and passive current density of 0.45 × 10−7 A/cm2, the TFMG with an Ag target sputtering power of 11 W exhibited superior corrosion resistance, suggesting its application potential as biomaterials.

Atomic-Layer IrOx Enabling Ligand Effect Boosts Water Oxidation Electrocatalysis.

An in situ formed IrOx (x ≤ 2) layer driven by anodic bias serves as the essential active site of Ir-based materials for oxygen evolution reaction (OER) electrocatalysis. Once being confined to atomic thickness, such an IrOx layer possesses both a favorable ligand effect and maximized active Ir sites with a lower O-coordination number. However, limited by a poor understanding of surface reconstruction dynamics, obtaining atomic layers of IrOx remains experimentally challenging. Herein, we report an idea of material design using intermetallic IrVMn nanoparticles to induce in situ formation of an ultrathin IrOx layer (O-IrVMn/IrOx) to enable the ligand effect for achieving superior OER electrocatalysis. Theoretical calculations predict that a strong electronic interaction originating from an orderly atomic arrangement can effectively hamper the excessive leaching of transition metals, minimizing vacancies for oxygen coordination. Linear X-ray absorption near edge spectra analysis, extended X-ray absorption fine structure fitting outcomes, and X-ray photoelectron spectroscopy collectively confirm that Ir is present in lower oxidation states in O-IrVMn/IrOx due to the presence of unsaturated O-coordination. Consequently, the O-IrVMn/IrOx delivers excellent acidic OER performances with an overpotential of only 279 mV at 10 mA cm-2 and a high mass activity of 2.3 A mg-1 at 1.53 V (vs RHE), exceeding most Ir-based catalysts reported. Moreover, O-IrVMn/IrOx also showed excellent catalytic stability with only 0.05 at. % Ir dissolution under electrochemical oxidation, much lower than that of disordered D-IrVMn/IrOx (0.20 at. %). Density functional theory calculations unravel that the intensified ligand effect optimizes the adsorption energies of multiple intermediates involved in the OER and stabilizes the as-formed catalytic IrOx layer.

Theoretical study of the effects of surface Cu coordination environment on CO2 hydrogenation to CH3OH

The coordination environment of Cu (the coordination number and arrangement of surface atoms) plays an important role in CO2 hydrogenation to CH3OH. Compared with the extensive studies of the effects of coordination number, the comprehensive effects of coordination number and arrangement of surface atoms were seldom explored in literature. To unravel the effects of surface Cu coordination environment on CO2 hydrogenation to CH3OH, the adsorption and reaction behaviors of H2 and CO2 on Cu(111), (100), (110) and (211) with different coordination numbers and arrangement of surface Cu were systematically calculated by density functional theory (DFT) and kinetic Monte Carlo (kMC) simulation. It was found that the adsorption energies of intermediates in CO2 hydrogenation on Cu surfaces increase with the decrease of coordination number. When the Cu coordination numbers are similar, the charge density on the open surface derived from the different atom arrangement becomes larger and leads to stronger interaction with intermediates than that on the compact one. DFT calculation and kMC simulation indicate that methanol formation pathway follows CO2*→HCOO*→HCOOH*→H2COOH*→H2CO*→CH3O*→CH3OH* on four Cu facets; CO formation is via CO2 direct dissociation on Cu(111), (100) and (110) but COOH* dissociation on (211). The low-coordinated surface Cu with more openness on Cu(211) is the highly active site for CO2 hydrogenation to CH3OH with high turnover of frequency (3.71 × 10−4 s−1) and high selectivity (87.17 %) at 600 K, PCO2 = 7.5 atm and PH2 = 22.5 atm, which is much higher than those on Cu(111), (100) and (110). This work unravels the effects of coordination environment on CO2 hydrogenation at the molecular level and provides an important insight into the design and development of catalysts with high performance in CO2 hydrogenation to CH3OH.

Crystal Symmetry-Inspired Algorithm for Optimal Design of Contemporary Mono Passivated Emitter and Rear Cell Solar Photovoltaic Modules

A metaheuristic algorithm named the Crystal Structure Algorithm (CrSA), which is inspired by the symmetric arrangement of atoms, molecules, or ions in crystalline minerals, has been used for the accurate modeling of Mono Passivated Emitter and Rear Cell (PERC) WSMD-545 and CS7L-590 MS solar photovoltaic (PV) modules. The suggested algorithm is a concise and parameter-free approach that does not need the identification of any intrinsic parameter during the optimization stage. It is based on crystal structure generation by combining the basis and lattice point. The proposed algorithm is adopted to minimize the sum of the squares of the errors at the maximum power point, as well as the short circuit and open circuit points. Several runs are carried out to examine the V-I characteristics of the PV panels under consideration and the nature of the derived parameters. The parameters generated by the proposed technique offer the lowest error over several executions, indicating that it should be implemented in the present scenario. To validate the performance of the proposed approach, convergence curves of Mono PERC WSMD-545 and CS7L-590 MS PV modules obtained using the CrSA are compared with the convergence curves obtained using the recent optimization algorithms (OAs) in the literature. It has been observed that the proposed approach exhibited the fastest rate of convergence on each of the PV panels.

Identification of a Ternary Nitride Ti10Cu3N4 with a Unique Structure Type.

This study presents the synthesis and detailed structural analysis of the ternary nitride Ti10Cu3N4. Initially identified as Ti3CuN within the Ti-Cu-N ternary phase diagram, its crystal structure remained unresolved and was characterized solely as belonging to the tetragonal crystal system. Through a comprehensive structural analysis, this study proposes a revised stoichiometry as Ti10Cu3N4; its crystal structure represents a previously unreported structure type within the P4 2 /mnm space group. Its atomic arrangement was elucidated through a combination of X-ray powder diffraction profile analysis and density functional theory calculations, corroborated by neutron diffraction studies. Furthermore, the hydrogen storage properties of Ti10Cu3N4 were characterized, demonstrating a hydrogen absorption capacity of approximately 0.6 wt % with desorption occurring in the temperature range of 200-550 °C.

Atomic arrangement and mechanical properties of high-entropy nonoxide ceramics simulated via location preference-based disordered random structure

The cell structures and mechanical properties (i.e., hardness, Young's modulus, shear modulus, and Poisson's ratio) of (Hf0.2Zr0.2Ti0.2Nb0.2Ta0.2)C (HEC) and (Hf0.2Zr0.2Ti0.2Nb0.2Ta0.2)N (HEN) high-entropy ceramics were simulated by special quasi-random structure (SQS) and general random structure (GRS) with atomic occupation preference based on the first-principles density functional theory. The results show that compared to SQS, the cell structure constructed by GRS is more realistic, which is verified via scanning electron microscopy, high resolution transmission electron microscopy and energy dispersive spectroscopy. The mechanical properties simulated by GRS were also determined by microhardness and dynamic elastic modulus testers. The hardness, Young's modulus，shear modulus and Poisson's ratio predicted by GRS are 23.07 GPa, 449.71 GPa, 183.28 and 0.227 for HEC and 22.96 GPa, 413.71 GPa, 162.47 and 0.241 for HEN, which are in a reasonable agreement with the measured results (i.e., 22.05 ± 0.32 GPa, 433 ± 12 GPa, 172 ± 18 GPa, 0.21 for HEC and 22.12 ± 0.13 GPa, 372 ± 23 GPa, 158 ± 11 GPa, 0.23 for HEN). This work can provide a promising reference for preparing high-entropy non-oxide ceramics via the prediction.

Investigating the impact of atomic positional variations on crystal magnetism: Insights from B2 crystal structure

Grounded in research on B2 crystal structures, this study systematically substitutes the central 8 atoms with non-metallic Si atoms and metallic Fe atoms, exploring the resulting impacts on stress, magnetism, and energy across the entire crystal lattice. The positional permutations of these atoms are meticulously examined to elucidate their influence. Additionally, alterations in crystal parameters are analyzed through the lenses of energy band distribution and electronic density of states. Findings underscore that substituting non-metallic Si atoms with metallic Fe counterparts significantly increases stress, magnetism, and energy levels throughout the crystal lattice. Moreover, a positive correlation emerges between the quantity of replacements and the resulting stress levels, magnetic intensity, and energy. The arrangement of atoms demonstrates a substantial influence on material magnetism, with denser distributions yielding more pronounced effects on the overall system; individual arrangements are capable of increasing magnetism by approximately 23%. These insights are further validated by changes in energy band distribution and electronic state density, which show a continuous enhancement of metallic properties and reactivity as Si atoms are successively replaced by Fe atoms. This study introduces an innovative idea for enhancing material performance.

Total Third-Degree Variation for Noise Reduction in Atomic-Resolution STEM Images.

Scanning Transmission Electron Microscopy (STEM) enables direct determination of atomic arrangements in materials and devices. However, materials such as battery components are weak for electron beam irradiation and low electron doses are required to prevent beam-induced damages. Noise removal is thus essential for precise structural analysis of electron beam sensitive materials at atomic resolution. Total square variation (TSV) regularization is an algorithm that exhibits high noise removal performance. However, the use of the TSV regularization term leads to significant image blurring and intensity reduction. To address these problems, we here propose a new approach adopting L2 norm regularization based on higher-order total variation. An atomic-resolution STEM image can be approximated as a set of smooth curves represented by quadratic functions. Since the third-degree derivative of any quadratic function is 0, total third-degree variation (TTDV) is suitable for a regularization term. The application of TTDV for denoising the atomic-resolution STEM image of CaF2 observed along the [001] zone axis is shown, where we can clearly see the Ca and F atomic columns without compromising image quality.

Enhanced low-temperature CO oxidation activity through crystal facet engineering of Pd/CeO2 catalysts

Cerium dioxide (CeO2) supported palladium (Pd) catalysts have found widespread application in CO oxidation reaction owing to their exceptional catalytic performance. The morphology of the CeO2 support dictates the exposed crystal plane, exerting a profound influence on surface structure and redox properties. This is crucial as the atomic arrangement at the surface directly impacts catalytic activity. In this study, a range of CeO2 supports with diverse morphologies (e.g. nano-octahedra, nano-cubes, nano-particles, nano-spheres, and nano-rods) were successfully synthesized through hydrothermal methods and subsequently supported with Pd for CO oxidation. The spherical 1Pd/CeO2–S catalyst, revealing exposed (111) + (100) crystal planes, exhibited significantly higher CO catalytic oxidation activity compared to the catalysts with other morphological CeO2 supports. The results indicated a positive correlation between the content of PdxCe1-xO2-y species and catalytic activity. Notably, this species was most abundantly formed in the spherical 1Pd/CeO2–S catalyst with exposed (111) + (100) crystal planes. The presence of this active species facilitated the formation of surface defects, increased oxygen vacancy concentration, and enhanced metal-support interaction, consequently greatly improving the CO low-temperature catalytic oxidation activity. Consequently, the oxidation state of Pd in the Pd/CeO2 catalyst could be effectively regulated by controlling the exposure of (111) + (100) crystalline surfaces of the CeO2 support, further optimizing the catalytic performance of the Pd/CeO2 catalytic system.

Design and synthesis of 7-membered lactam fused hydroxypyridinones as potent metal binding pharmacophores (MBPs) for inhibiting influenza virus PAN endonuclease

Since influenza virus RNA polymerase subunit PAN is a dinuclear Mn2+ dependent endonuclease, metal-binding pharmacophores (MBPs) with Mn2+ coordination has been elucidated as a promising strategy to develop PAN inhibitors for influenza treatment. However, few attentions have been paid to the relationship between the optimal arrangement of the donor atoms in MBPs and anti-influenza A virus (IAV) efficacy. Given that, the privileged hydroxypyridinones fusing a seven-membered lactam ring with diverse side chains, chiral centers or cyclic systems were designed and synthesized. A structure-activity relationship study resulted in a hit compound 16l (IC50 = 2.868 ± 0.063 μM against IAV polymerase), the seven-membered lactam ring of which was fused a pyrrolidine ring. Further optimization of the hydrophobic binding groups on 16l afforded a lead compound (R, S)-16s, which exhibited a 64-fold more potent inhibitory activity (IC50 = 0.045 ± 0.002 μM) toward IAV polymerase. Moreover, (R, S)-16s demonstrated a potent anti-IAV efficacy (EC50 = 0.134 ± 0.093 μM) and weak cytotoxicity (CC50 = 15.35 μM), indicating the high selectivity of (R, S)-16s. Although the lead compound (R, S)-16s exhibited a little weaker activity than baloxavir, these findings illustrated the utility of a metal coordination-based strategy in generating novel MBPs with potent anti-influenza activity.

An emerging quaternary semiconductor nanoribbon with gate-tunable anisotropic conductance

Two-dimensional noble transition metal chalcogenide (NTMC) semiconductors represent compelling building blocks for fabricating flexible electronic and optoelectronic devices. While binary and ternary compounds have been reported, the existence of quaternary NTMCs with a greater elemental degree of freedom remains largely unexplored. This study presents the pioneering experimental realization of a novel semiconducting quaternary NTMC material, AuPdNaS2, synthesized directly on Au foils through chemical vapor deposition. The ribbon-shaped morphology of the AuPdNaS2 crystal can be finely tuned to a thickness as low as 9.2 nm. Scanning transmission electron microscopy reveals the atomic arrangement, showcasing robust anisotropic features; thus, AuPdNaS2 exhibits distinct anisotropic phonon vibrations and electrical properties. The field-effect transistor constructed from AuPdNaS2 crystal demonstrates a pronounced anisotropic conductance (σmax/σmin = 3.20) under gate voltage control. This investigation significantly expands the repertoire of NTMC materials and underscores the potential applications of AuPdNaS2 in nano-electronic devices.

Ion Selectivity, Current, and Water Flow Regulation in Ti3C2 MXene Nanopores.

Recent years have seen a growing interest in zero-dimensional (0D) transport phenomena occurring across two-dimensional (2D) materials for their potential applications to nanopore technology such as ion separation and molecular sensing. Herein, we investigate ion transport through 1 nm-wide nanopores in Ti3C2 MXene using molecular dynamics simulations. The high polarity and fish-bone arrangement of the Ti3C2 MXene offer a built-in potential and an atomic-scale distortion to the nanopore, causing an adsorption preference for cations. Our observation of variable cation-specific ion selectivity and Coulomb blockade highlights the complex interplay between adsorption affinity and cation size. The cation-specific ion selectivity can induce both the ion current and electro-osmotic water transmission, which can be regulated by tailoring the ions' preferential pathways through electric field tilting. Our finding underscores the pivotal role of the atomic arrangement of MXenes in 0D ion transport and provides fundamental insight into the application of 2D material in nanopores-based technologies.

Nanoporous copper titanium tin (np-Cu2TiSn) Heusler alloy prepared by dealloying-induced phase transformation for electrocatalytic nitrate reduction to ammonia

Heusler alloys are a series of well-established intermetallic compounds with abundant structure and elemental substitutions, which are considered as potentially valuable catalysts for integrating multiple reactions owing to the features of ordered atomic arrangement and optimized electronic structure. Herein, a nanoporous copper titanium tin (np-Cu2TiSn) Heusler alloy is successfully prepared by the (electro)chemical dealloying transformation method, which exhibits high nitrate (NO3–) reduction performance with an NH3 Faradaic efficiency of 77.14 %, an NH3 yield rate of 11.90 mg h−1 mg−1cat, and a stability for 100 h under neutral condition. Significantly, we also convert NO3− to high-purity ammonium phosphomolybdate with NH4+ collection efficiency of 83.8 %, which suggests a practical approach to convert wastewater nitrate into value-added ammonia products. Experiments and theoretical calculations reveal that the electronic structure of Cu sites is modulated by the ligand effect of surrounding Ti and Sn atoms, which can simultaneously enhance the activation of NO3−, facilitate the desorption of NH3, and reduce the energy barriers, thereby boosting the electrochemical nitrate reduction reaction.