Confinement Of Atoms Research Articles

Density Functional Tight-Binding Models for Band Structures of Transition-Metal Alloys and Surfaces across the d-Block.

First-principles electronic structure simulations are an invaluable tool for understanding chemical bonding and reactions. While machine-learning models such as interatomic potentials significantly accelerate the exploration of potential energy surfaces, electronic structure information is generally lost. Particularly in the field of heterogeneous catalysis, simulated electron band structures provide fundamental insights into catalytic reactivity. This ab initio knowledge is preserved in semiempirical methods such as density functional tight binding (DFTB), which extend the accessible computational length and time scales beyond first-principles approaches. In this paper we present Shell-Optimized Atomic Confinement (SOAC) DFTB electronic-part-only parametrizations for bulk and surface band structures of all d-block transition metals that enable efficient predictions of electronic descriptors for large structures or high-throughput studies on complex systems outside the computational reach of density functional theory.

Engineering of uniform dispersed Ni nanoparticles supported on carbon nanosheets for reduction of Nitroarenes to Aminoarenes

Facile synthesis of uniform supported metal catalysts is of great significance yet remains challenging for sustainable catalysis. Herein, a nanopore confinement strategy is developed to efficiently anchor metal ions in suitably sized polymer nanopores via strong coordinate bonds and ensure successful fabrication of uniform carbon-supported metal nanoparticles. Specifically, Ni2+-coordinated polydopamine (PDA) mesoporous layer was coated on GO nanosheets for the confinement of the nickel atoms (GO@PDA-Ni-x, x means pore size of PDA layer), resulting Ni@C-x nanosheets catalysts with uniformly dispersed Ni nanoparticles after pyrolysis in H2/Ar atmosphere. Characterization methods including SEM, TEM, and XPS reveal the intrinsic formation mechanism and physicochemical details. In the catalytic reaction of NaBH4-mediated hydrogenation of 4-nitrophenol (4-NP), the obtained Ni/C-10 exhibits exceptional catalytic performance with a rapid rate constant (0.686 min−1), outperforming many previously reported metal catalysts. Moreover, the catalytic activity remains almost unchanged after being recycled five times, proving the prominent stability. This work opens up an innovative avenue for rational design and synthesis of supported catalysts with controllable size for broad catalytic applications.

Miniature atom bottle traps enabled by chiral doughnut light

We highlight what we believe to be a novel optical set-up which enables the confinement of cold atoms in a finite set of sub-wavelength bottle traps. This involves two counter-propagating vortex beams with the same winding number ℓ = ±1 and the same circular polarization (. Strong focusing generates significant longitudinal field components which become responsible for an on-axis standing wave enabling the axial confinement of far blue-detuned atoms. The off-axis radial confinement is provided by the optical potential due to the transverse components of the light. The trap characteristics are illustrated using experimentally accessible parameters and are tunable by changing the power, focusing and ellipticity of the light. Atoms trapped in such a set-up are useful for applications, including quantum simulation and quantum information processing.

Review of: "fluorine molecule can be used for storage in nano supercapacitors and confinement of non-carbon atoms"

Review of: "fluorine molecule can be used for storage in nano supercapacitors and confinement of non-carbon atoms"

Atomic circulation in evanescent of LG 10 mode with active dipole and quadrupole transitions

The total internal reflection of a light with phase singularity, such as Laguerre–Gaussian (LG) light, can generate an evanescent wave. The distribution of this type of light is firmly localized in the vicinity above the dielectric surface and displays a rotational character. Any atom approaching the surface from the vacuum region interacts with evanescent wave and produces interesting rotational effects. Recent studies have established the coupling of LG beams to both electric atomic transitions; dipole and quadrupole according to the selection rules of each, permitted and prohibited. Due to the small magnitude of the quadrupole interaction compared to the dipole interaction, we chose the two counter-propagating beams configuration to generate the doubling Rabi frequencies with more stable surface optical forces. We describe the essential rotational features and discuss how they can be used to influence atoms. Atom confinement and dynamics in the interaction of surface optical vortices with the two different atomic transitions are illustrated using typical experimentally accessible parameters for the case of the Cs atom interacts with the L G 10 mode.

Multiscale Confinement Engineering for Boosting Overall Water Splitting by One-Step Stringing of a Single Atom and a Janus Nanoparticle within a Carbon Nanotube.

Enzyme-mimicking confined catalysis has attracted great interest in heterogeneous catalytic systems that can regulate the geometric or electronic structure of the active site and improve its performance. Herein, a liquid-assisted chemical vapor deposition (LCVD) strategy is proposed to simultaneously confine the single-atom Ru sites onto sidewalls and Janus Ni/NiO nanoparticles (NPs) at the apical nanocavities to thoroughly energize the N-doped carbon nanotube arrays (denoted as Ni/NiO@Ru-NC). The bifunctional Ni/NiO@Ru-NC electrocatalyst exhibits overpotentials of 88 and 261 mV for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) at 100 mA cm-2 in alkaline solution, respectively, all ranking the top tier among the carbon-supported metal-based electrocatalysts. Moreover, once integrated into an anion-exchange membrane water electrolysis (AEMWE) system, Ni/NiO@Ru-NC can act as an efficient and robust bifunctional electrocatalyst to operate stably for 50 h under 500 mA cm-2. Theoretical calculations and experimental exploration demonstrate that the confinement of Ru single atoms and Janus Ni/NiO NPs can regulate the electron distribution with strong orbital couplings to activate the NC nanotube from sidewall to top, thus boosting overall water splitting.

Nanoscale one-dimensional close packing of interfacial alkali ions driven by water-mediated attraction.

The permeability and selectivity of biological and artificial ion channels correlate with the specific hydration structure of single ions. However, fundamental understanding of the effect of ion-ion interaction remains elusive. Here, via non-contact atomic force microscopy measurements, we demonstrate that hydrated alkali metal cations (Na+ and K+) at charged surfaces could come into close contact with each other through partial dehydration and water rearrangement processes, forming one-dimensional chain structures. We prove that the interplay at the nanoscale between the water-ion and water-water interaction can lead to an effective ion-ion attraction overcoming the ionic Coulomb repulsion. The tendency for different ions to become closely packed follows the sequence K+ > Na+ > Li+, which is attributed to their different dehydration energies and charge densities. This work highlights the key role of water molecules in prompting close packing and concerted movement of ions at charged surfaces, which may provide new insights into the mechanism of ion transport under atomic confinement.

Atomic Manufacturing of Advanced Nanomaterials.

The quest for cutting-edge materials and devices has necessitated elevated demands for manufacturing methodologies. Atomic manufacturing involves the meticulous design and fabrication of materials and devices at the atomic level, a process that has been facilitated by advancements in comprehending and manipulating atomic behavior. The attainment of atomic manufacturing is dependent on the capacity to precisely manipulate atoms, directing their reactions at will. In this review, five methodologies of atomic fabrication encompassing atomic manipulation, atomic programming, atomic epitaxy, atomic confinement, and atomic assembly are elucidated. Based on this, the utilization of atomic manufacturing in the most advanced domains including energy conversion, energy storage, quantum information technology, and optoelectronic devices is elucidated. Finally, the current challenges and outlook on the forthcoming advancement of atomic manufacturing are presented.

1D selective confinement and diffusion of metal atoms on graphene

The role of moiré graphene superstructures in favoring confined adsorption of different metal atoms is an intriguing problem not yet completely solved. Graphene (G) grown on Ni(100) forms a striped moiré pattern of valleys, where G approaches the nickel substrate and interacts with it rather strongly, and ridges, where G stays far away from the substrate and acts almost free-standing. Combining density functional theory (DFT) calculations and scanning-tunneling microscopy (STM) measurements, we show that this peculiar moiré constitutes a regular nanostructured template on a 2D support, confining in 1D trails single metal atoms and few atoms clusters. DFT calculations show that the confinement is selective and highly dependent on the atomic species, with some species preferring to adsorb on ridges and the other showing preference for valleys. Co and Au adsorbates, for instance, have opposite behavior, as predicted by DFT and observed by STM. The origin of such disparate behavior is traced back to the electrostatic interaction between the charged adsorbate and the nickel surface. Moreover, the selectivity is not restricted to the adsorption process only, but persists as adsorbate starts its diffusion, resulting in unidirectional mass transport on a continuous 2D support. These findings hold great promise for exploiting tailored nanostructured templates in a wide range of potential applications involving mass transport along element-specific routes.

Precise Design and Modification Engineering of Single-Atom Catalytic Materials for Oxygen Reduction.

Due to their unique electronic and structural properties, single-atom catalytic materials (SACMs) hold great promise for the oxygen reduction reaction (ORR). Coordinating environmental and engineering strategies is the key to improving the ORR performance of SACMs. This review summarizes the latest research progress and breakthroughs of SACMs in the field of ORR catalysis. First, the research progress on the catalytic mechanism of SACMs acting on ORR is reviewed, including the latest research results on the origin of SACMs activity and the analysis of pre-adsorption mechanism. The study of the pre-adsorption mechanism is an important breakthrough direction to explore the origin of the high activity of SACMs and the practical and theoretical understanding of the catalytic process. Precise coordination environment modification, including in-plane, axial, and adjacent site modifications, can enhance the intrinsic catalytic activity of SACMs and promote the ORR process. Additionally, several engineering strategies are discussed, including multiple SACMs, high loading, and atomic site confinement. Multiple SACMs synergistically enhance catalytic activity and selectivity, while high loading can provide more active sites for catalytic reactions. Overall, this review provides important insights into the design of advanced catalysts for ORR.

Photocatalytic splitting of water on g-C3N4-based single-atom Pt catalysts with stable “sandwich” structure: a combined first principles and semi-empirical investigation

Solar-to-hydrogen energy conversion is a promising strategy to solve environmental pollution and energy crisis by utilizing photocatalytic water splitting. In this work, a “sandwich” structure of g-C3N4-based single-atom platinum (Pt) catalyst for photocatalytic water splitting is proposed and investigated using a combined first principles and semi-empirical study method. The calculation results indicate that, without any co-catalyst, the photogenerated holes in the valence band of BL-g-C3N4 cannot oxidize H2O to O2, and its oxygen evolution reaction (OER) performance is not better than that of the pristine monolayer g-C3N4. Significantly, the photogenerated holes in the valence band of the “sandwich”-structured photocatalyst g-C3N4–Pt1–g-C3N4 can oxidize H2O to O2 without any co-catalyst. That is, the OER performance of g-C3N4–Pt1–g-C3N4 is better than that of the pristine g-C3N4 and the pristine bilayer-g-C3N4 (BL-g-C3N4). However, it can be found that the introduction of single Pt atom confinement in the BL-g-C3N4 cannot effectively reduce hydrogen evolution reaction (HER) energy barrier or improve the hydrogen evolution kinetics of BL-g-C3N4. In other words, the introduction of the confined single Pt atom in the BL-g-C3N4 not only fails to improve HER performance of BL-g-C3N4, but deteriorates HER catalytic performance of BL-g-C3N4. These findings provide some theoretical insights for engineers to prepare photocatalysts with higher activity and stability.

Confinement of Fe atoms between MoS2 interlayers drives phase transition for improved reactivity in Fenton-like reactions

Confinement of Fe atoms between MoS2 interlayers drives phase transition for improved reactivity in Fenton-like reactions

Ultrahigh Performance H2 O2 Generation by Single-Atom Fe Catalysts with N/O Bidentate Ligand via Oxalic Acid and Oxygen Molecules Activation.

Single-atom catalysts (SACs) for photocatalytic hydrogen peroxide (H2 O2 ) generation are researched but it is still challenging to obtain high H2 O2 yields. Herein, graphite carbon nitride (FeSA /CN) confined single Fe atoms with N/O coordination is prepared, and FeSA /CN shows high H2 O2 production via oxalic acid and O2 activation. Under visible light illumination, the concentration of H2 O2 generated by FeSA /CN can achieve 40.19mM g-1 h-1 , which is 10.44 times higher than that of g-C3 N4 . The enhanced H2 O2 generation can be attributed to the formation of metal-organic complexes and rapid electron transfer. Moreover, the O2 activation of photocatalysts is revealed by 3,3',5,5'-tetramethylbenzidine oxidation. The results display that the O2 activation capacity of FeSA /CN is higher than that of g-C3 N4 , which facilitates the formation of H2 O2 . Finally, density functional theory calculation demonstrates that O2 is chemically adsorbed on Fe atomic sites. The adsorption energy of O2 is enhanced from -0.555 to -1.497eV, and the bond length of OO is extended from 1.235 to 1.292 Å. These results exhibit that the confinement of single Fe atoms can promote O2 adsorption and activation. Finally, the photocatalytic mechanism is elaborated, which provides a deep understanding for SACs-catalyzed H2 O2 generation.

Hellmann–Feynman theorem and internal pressure for atoms, molecules and plasmas under pressure

Since the beginning of the twentieth century, confinement of atoms, molecules and plasma inside impenetrable sharp (hard) and smooth (soft) cavities has been studied with utmost interest. Physically, such situations introduce the trapping of a quantum system under high pressure. The internal pressure () of the system under multi-megabar external pressure has not yet been explored. Also, there is a lack of Hellmann–Feynman theorem (HFT) in such a scenario, which is essential to derive a concrete analytical expression of under stressed condition. Here using a scaling concept we provide a general HFT in terms of expectation values of total energy, potential and kinetic energy of a given confined system. A change in boundary condition (from smooth to sharp and vice versa) does not affect this. Applying this proposed HFT, a closed-form expression of and has been obtained for confined and shell-confined quantum systems. Based on this , several virial-like equations are also modeled. This HFT and are demonstrated for one- and many-electron atoms, plasmas and molecules using both analytical and numerical methods. Their applicability in several other confined systems is discussed from simple arguments.

Suppression of laser beam’s polarization and intensity fluctuation via a Mach–Zehnder interferometer with proper feedback

Long ground-Rydberg coherence lifetime is interesting for implementing high-fidelity quantum logic gates, many-body physics, and other quantum information protocols. However, the potential well formed by a conventional far-off-resonance red-detuned optical-dipole trap that is attractive for ground-state cold atoms is usually repulsive for Rydberg atoms, which will result in the rapid loss of atoms and low repetition rate of the experimental sequence. Moreover, the coherence time will be sharply shortened due to the residual thermal motion of cold atoms. These issues can be addressed by a one-dimensional magic lattice trap, which can form a deeper potential trap than the traveling wave optical dipole trap when the output power is limited. In addition, these common techniques for atomic confinement generally have certain requirements for the polarization and intensity stability of the laser. Here, we demonstrated a method to suppress both the polarization drift and power fluctuation only based on the phase management of the Mach–Zehnder interferometer for a one-dimensional magic lattice trap. With the combination of three wave plates and the interferometer, we used the instrument to collect data in the time domain, analyzed the fluctuation of laser intensity, and calculated the noise power spectral density. We found that the total intensity fluctuation comprising laser power fluctuation and polarization drift was significantly suppressed, and the noise power spectral density after closed-loop locking with a typical bandwidth of 1–3000 Hz was significantly lower than that under the free running of the laser system. Typically, at 1000 Hz, the noise power spectral density after locking was about 10 dB lower than that under the free running of a master oscillator power amplifier system. The intensity–polarization control technique provides potential applications for atomic confinement protocols that demand fixed polarization and intensity.

Principles of tractor atom interferometry

We present principles and possible design concepts for a tractor atom interferometer (TAI) based on three-dimensional confinement and transport of ultracold atoms. The confinement reduces device size and wave-packet dispersion, enables arbitrary holding times, and facilitates control to create complex trajectories that allow for optimization to enable fast splitting and recombination, to suppress detrimental nonadiabatic excitation, and to cancel unwanted sensitivity. Thus, the design allows for further advancement of compact, high-sensitivity, quantum sensing technology. In particular, we focus on the implementation of quantum-enhanced accelerometers and gyroscopes. We discuss TAI protocols for both spin-dependent and scalar trapping potentials. Using optimal control theory, we demonstrate the splitting of the wave function on a time scale two orders of magnitude shorter than a previous proposal using adiabatic dynamics, thus maximizing the time spent at full separation, where the interferometric phase is accumulated. The performance estimates for TAI give a promising perspective for atom-interferometry-based sensing, significantly exceeding the sensitivities of current state-of-the-art devices.

Green Triplet Self-Trapped Exciton Emission in Layered Rb3Cd2Cl7:Sb3+ Perovskite: Comparison with RbCdCl3:Sb3.

Metal halide materials have recently sparked intense research because of their excellent photophysical properties and chemical stability. For example, RbCdCl3:Sb3+ exhibits broad emission at about 600 nm with a high photoluminescence quantum yield (PLQY) over 91% and double emission bands with bright white color. Herein, we obtained a novel Rb and Cd layered perovskite Rb3Cd2Cl7 doped with Sb3+, which gives luminescence at 525 nm with a large Stokes shift of 200 nm, originating from a self-trapped exciton (STE). Its PLQY is 57.47%, but its low-temperature PLQY becomes much higher at the same wavelength. When Rb3Cd2Cl7:Sb3+ and RbCdCl3:Sb3+ were compared, the two classes of quantum confinement effects by Rb and Cd ions in the lattice were identified to describe their electronic states and different optical properties. These results suggest that properties of Sb-doped cadmium halides could be modified by the structure type and local atomic confinement to find applications as promising luminescent materials for optoelectronic devices.

Introducing Spontaneously Phase‐Separated Heterogeneous Interfaces Enables Low Power Consumption and High Reliability for Phase Change Memory

AbstractPhase‐change memory is one of the most promising candidates for the next generation nonvolatile memory, but their high power consumption and low reliability remain bottleneck problems that limit the data storage density and its storage‐class memory application. Here, an innovative phase change material with embedded self‐precipitated interfaces, where the nanoscale grains of phase change material are cut into interconnecting “crystal islands” by thermally stable self‐precipitated material with low thermal conductivity, is proposed. The precipitated material provides both thermal and atomic migration confinements in three dimensions. The thermal confinement enables low power consumption, and the atomic migration confinement enables high device reliability. The devices based on spontaneously phase‐separated O‐doped Sb2Te3 verify the material design, where Sb oxide acts as the precipitated heterogeneous phase and Sb–Te alloy as the phase change material. O‐doped Sb2Te3 device with 250 nm hole diameter shows an ultralow power consumption, down to a few hundreds of femtojoule, which is comparable with those of phase change nanowires. Besides, good thermal stability and low resistivity drift (drift coefficient 0.005) as well as excellent cycle endurance up to 108 times are also obtained at the same time. The doping fabrication process is quite compatible with current semiconductor industry.

Spatial confinement of copper single atoms into covalent triazine-based frameworks for highly efficient and selective photocatalytic CO2 reduction

Spatial confinement of copper single atoms into covalent triazine-based frameworks for highly efficient and selective photocatalytic CO2 reduction

Atomic Isolation and Anchoring of Commercial Pt/C Nanoparticles, a Promising Pathway for Durable PEMFCs.

This study examines the atomic confinement of commercial Pt/C electrocatalysts. While a high electrocatalytic activity for the oxygen reduction reaction is important for proton-exchange membrane fuel cell (PEMFC) performance, the high stability of the electrocatalyst is essential for real applications under harsh operating conditions. The demands necessitate the development of advanced electrocatalysts that are resistant to corrosion. A combination of diazonium chemistry with Cu electrodeposition permits the selective protection of the carbon surface of the commercial Pt/C to prevent corrosion while improving wettability and ionic transfer. The resulting electrocatalysts exhibit an exceptional ORR stability after accelerated stress testing (AST) with a 250% improvement in comparison with unprotected commercial Pt/C. This novel electrochemical pathway provides a much-needed boost to carbon-based catalytic supports, which still face several stability challenges in energy applications in a harsh environment.