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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 955 records · Page 53
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

On-demand nanoengineering of in-plane ferroelectric topologies

Hierarchical assemblies of ferroelectric nanodomains, so-called super-domains, can exhibit exotic morphologies that lead to distinct behaviours. Controlling these super-domains reliably is critical for realizing states with desired functional properties. Here we reveal the super-switching mechanism by using a biased atomic force microscopy tip, that is, the switching of the in-plane super-domains, of a model ferroelectric Pb 0.6 Sr 0.4 TiO 3 . We demonstrate that the writing process is dominated by a super-domain nucleation and stabilization process. A complex scanning-probe trajectory enables on-demand formation of intricate centre-divergent, centre-convergent and flux-closure polar structures. Correlative piezoresponse force microscopy and optical spectroscopy confirm the topological nature and tunability of the emergent structures. The precise and versatile nanolithography in a ferroic material and the stability of the generated structures, also validated by phase-field modelling, suggests potential for reliable multi-state nanodevice architectures and, thereby, an alternative route for the creation of tunable topological structures for applications in neuromorphic circuits.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

Controlling structural phases of Sn through lattice engineering

Topology and superconductivity, two distinct phenomena, offer unique insight into quantum properties and their applications in quantum technologies, spintronics, and sustainable energy technologies. Tin (Sn) plays a pivotal role here as an element because of its two structural phases, α-Sn exhibiting topological characteristics and β-Sn showing superconductivity. Here, we demonstrate precise control of these phases in Sn thin films using molecular beam epitaxy with systematically varied lattice parameters of the buffer layer. The Sn films exhibit either β-Sn or α-Sn phases as the buffer layer's lattice constant varies from 6.10 Å to 6.48 Å, spanning the range from GaSb (like InAs) to InSb. Further, the crystal structures of α- and β-Sn films are characterized by x-ray diffraction and confirmed by Raman spectroscopy and scanning transmission electron microscopy. Atomic force microscopy validates the smooth, continuous surface morphology. Electrical transport measurements further verify the phases: resistance drop near 3.7 K for β-Sn superconductivity and Shubnikov-de Haas oscillations for α-Sn topological characteristics. Density functional theory shows that α-Sn is stable under tensile strain and β-Sn under compressive strain, aligning well with experimental findings. Hence, this study introduces a platform controlling Sn phases through lattice engineering, enabling innovative applications in quantum technologies and beyond.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Characterization and Optimization of a Spectral Window for Direct Gaseous Uranium Hexafluoride Enrichment Assay Using Laser-Induced Breakdown Spectroscopy

Through a systematic scanning of 235 U and 238 U emission lines between 280 nm and 745 nm, the optimal emission line for direct gaseous uranium hexafluoride (UF 6 ) enrichment assay using laser-induced breakdown spectroscopy (LIBS) was found. Screening for spectral features that are potentially useful for U isotopic analysis was gauged from the magnitude of the 235 U– 238 U isotopic shift and the signal-to-background ratio of the emission line through a parameter termed ΔSBR 235U–238U . The ΔSBR spectrum shows peaks at wavelength positions where there are strong lines with significant 235 U– 238 U shifts. The screening identified 13 spectral-window candidates, which were down selected based on their overall accuracy in predicting the 235 U enrichment of three UF 6 samples of natural (0.720 atom% 235 U) and low-enriched (4.675 atom% and 9.157 atom% 235 U) grades. The U(I) 646.498 nm emission line, with a determined 235 U– 238 U isotopic shift of -17.7 pm, was found to be the optimal spectral window for direct UF 6 enrichment assay. The root mean square error for enrichment assays on the three natural and low-enriched UF 6 samples, with each sample measured in six replicates, was 0.31% in absolute 235 U content. Each measurement comprised LIBS signals accumulated from 3000 laser shots. In conclusion, the analytical bias and precision were better than 0.5% and 0.3%, respectively, in absolute [ 235 U/( 235 U + 238 U)] ratios. Specific for the two low-enriched UF 6 samples, the relative standard deviations from six replicated measurements were around 2%.

47 OTHER INSTRUMENTATION↗
DOE OSTI2023

Toward precision Fermi-liquid theory in two dimensions

The ultracold and weakly coupled Fermi gas in two spatial dimensions is studied in an effective field theory framework. It has long been observed that universal corrections to the energy density to two orders in the interaction strength do not agree with Monte Carlo simulations in the weak-coupling regime. Here, universal corrections to three orders in the interaction strength are obtained, and are shown to provide agreement between theory and simulation. Special consideration is given to the scale ambiguity associated with the nontrivial renormalization of the singular contact interactions. Further, the isotropic superfluid gap is obtained to next-to-leading order, and nonuniversal contributions to the energy density due to effective range effects, p -wave interactions, and three-body forces are computed. Results are compared with precise Monte Carlo simulations of the energy density and the contact in the weakly coupled attractive and repulsive Fermi-liquid regimes. In addition, the known all-orders sum of ladder and ring diagrams is compared with Monte Carlo simulations at weak coupling and beyond.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Project 8: Measuring the tritium beta-decay spectrum using Cyclotron Radiation Emission Spectroscopy

Abstract. The goal of the Project 8 experiment is to measure the absolute neutrino mass using tritium beta decays and a new spectroscopic technique, Cyclotron Radiation Emission Spectroscopy (CRES). The first phase of Project 8 demonstrated that CRES could be used to detect single-electron cyclotron radiation and perform precision electron spectroscopy. We are in Phase II of the experiment, performing a 100-day measurement of the endpoint of the tritium spectrum. We will demonstrate the ability to measure the last ~2 keV of the beta-decay spectrum and explore the background rate at energies just above the endpoint; CRES has the potential for extremely low backgrounds. In Phase III we will demonstrate the ability to scale up the volume of the experiment. In Phase IV we will switch the source from molecular tritium to atomic tritium, which will avoid systematic uncertainties from the final states of the molecule. I will present the current status of Project 8 Phase II and the plans for Phases III and IV.

Oblath, Noah↗
DOE OSTI2022

Molecular insights into the structure-property relationships of 3D printed polyamide reverse-osmosis membrane for desalination

3D-printing is an emerging method for manufacturing polyamide (PA) reserve osmosis (RO) membranes for water treatment and desalination, which can precisely control membrane structural properties, such as thickness, roughness, and resolution. However, the synthesis-structure (i.e., degree of cross-linking (DC), m-phenylenediamine/trimesoyl chloride (MPD/TMC) ratio, and membrane thickness) to property (permeability and water-salt selectivity) relationships for these membranes has not been well understood. At the same time, a microscopic understanding of the physical mechanism of water and salt transport is needed to guide the design of high-performance 3D-printed membranes and improve the printing efficiency. Furthermore, the atomic-scale transport features and energetics of water and salt ions are studied at high pressure for the 3D-printed PA RO membranes with the different DCs and MPD/TMC ratios through non-equilibrium molecular dynamics (NEMD) simulations. Factoring in membrane structure properties, rejection ratio of salt ions and pressure-dependent water flux, 3D-printed PA membranes having an MPD/TMC ratio of 3.0:2.0 and a DC between 80%~90% attains ideal performance: high water flux, high rejection of salt ions, and excellent structural integrity. Mechanistically, water permeability for highly cross-linked PA RO membranes depends on the temporary on-and-off channels that allow water molecules to jump from one cavity to another at high pressure. In addition, higher pressures cause rapid compaction of PA membranes’ free volume and membrane thickness. Membrane failure at high pressure is determined by the DC and MPD/TMC ratios-dependent compressive yield strength. In short, these findings provide physical insights for optimizing existing PA membranes and designing next-generation desalination membranes at the molecular level.

3D-printed PA RO membrane↗
DOE OSTI2023

Shadow Molecular Dynamics and Atomic Cluster Expansions for Flexible Charge Models

Here, a shadow molecular dynamics scheme for flexible charge models is presented where the shadow Born–Oppenheimer potential is derived from a coarse-grained approximation of range-separated density functional theory. The interatomic potential, including the atomic electronegativities and the charge-independent short-range part of the potential and force terms, is modeled by the linear atomic cluster expansion (ACE), which provides a computationally efficient alternative to many machine learning methods. The shadow molecular dynamics scheme is based on extended Lagrangian (XL) Born–Oppenheimer molecular dynamics (BOMD). XL-BOMD provides stable dynamics while avoiding the costly computational overhead associated with solving an all-to-all system of equations, which normally is required to determine the relaxed electronic ground state prior to each force evaluation. To demonstrate the proposed shadow molecular dynamics scheme for flexible charge models using atomic cluster expansion, we emulate the dynamics generated from self-consistent charge density functional tight-binding (SCC-DFTB) theory using a second-order charge equilibration (QEq) model. The charge-independent potentials and electronegativities of the QEq model are trained for a supercell of uranium oxide (UO 2 ) and a molecular system of liquid water. The combined ACE+XL-QEq molecular dynamics simulations are stable over a wide range of temperatures both for the oxide and for the molecular systems and provide a precise sampling of the Born–Oppenheimer potential energy surfaces. Accurate ground Coulomb energies are produced by the ACE-based electronegativity model during an NVE simulation of UO 2 , predicted to be within 1 meV of those from SCC-DFTB on average during comparable simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Formation of the oxyl’s potential energy surface by the spectral kinetics of a vibrational mode

One of the most reactive intermediates for oxidative reactions is the oxyl radical, an electron-deficient oxygen atom. The discovery of a new vibration upon photoexcitation of the oxygen evolution catalysis detected the oxyl radical at the SrTiO3 surface. The vibration was assigned to a motion of the sub-surface oxygen underneath the titanium oxyl (Ti–O●−) created upon hole transfer to (or electron extraction from) a hydroxylated surface site. Evidence for such an interfacial mode is derived from its spectral shape, which exhibited a Fano resonance—a coupling of a sharp normal mode to continuum excitations. Here, this Fano resonance is utilized to derive precise formation kinetics of the oxyl radical and its associated potential energy surface (PES). From the Fano lineshape, the formation kinetics are obtained from the anti-resonance (the kinetics of the coupling factor), the resonance (the kinetics of the coupled continuum excitations), and the frequency integrated spectrum (the kinetics of the normal mode’s cross-section). All three perspectives yield logistic function growth with a half-rise of 2.3 ± 0.3 ps and a time constant of 0.48 ± 0.09 ps. A non-equilibrium transient associated with photoexcitation is separated from the rise of the equilibrated PES. The logistic function characterizes the oxyl coverage at the very initial stages (t ∼ 0) to have an exponential growth rate that quickly decreases toward zero as a limiting coverage is reached. Such time-dependent reaction kinetics identify a dynamic activation barrier associated with the formation of a PES and quantify it for oxyl radical coverage.

Chemistry↗
DOE OSTI2025

Diverse Manifestations of Electron-Phonon Coupling in a Kagome Superconductor

Recent angle-resolved photoemission spectroscopy (ARPES) experiments on the kagome metal CsV_{3}Sb_{5} revealed distinct multimodal dispersion kinks and nodeless superconducting gaps across multiple electron bands. The prominent photoemission kinks suggest a definitive coupling between electrons and certain collective modes, yet the precise nature of this interaction and its connection to superconductivity remain to be established. Here, employing the state-of-the-art ab initio many-body perturbation theory computation, we present direct evidence that electron-phonon (e-ph) coupling induces the multimodal photoemission kinks in CsV_{3}Sb_{5}, and profoundly, drives the nodeless s-wave superconductivity, showcasing the diverse manifestations of the e-ph coupling. Our calculations well capture the experimentally measured kinks and their fine structures, and reveal that vibrations from different atomic species dictate the multimodal behavior. Results from anisotropic GW-Eliashberg equations predict a phonon-mediated superconductivity with nodeless s-wave gaps, in excellent agreement with various ARPES and scanning tunneling spectroscopy measurements. Despite the universal origin of the e-ph coupling, the contributions of several characteristic phonon vibrations vary in different phenomena, highlighting a versatile role of e-ph coupling in shaping the low-energy excitations of kagome metals.

Electron-phonon coupling↗
DOE OSTI2024

Reductive quantum phase estimation

Estimating a quantum phase is a necessary task in a wide range of fields of quantum science. To accomplish this task, two well-known methods have been developed in distinct contexts, namely, Ramsey interferometry (RI) in atomic and molecular physics and quantum phase estimation (QPE) in quantum computing. We demonstrate that these canonical examples are instances of a larger class of phase estimation protocols, which we call reductive quantum phase estimation (RQPE) circuits. Here, we present an explicit algorithm that allows one to create an RQPE circuit. This circuit distinguishes an arbitrary set of phases with a smaller number of qubits and unitary applications, thereby solving a general class of quantum hypothesis testing to which RI and QPE belong. We further demonstrate a tradeoff between measurement precision and phase distinguishability, which allows one to tune the circuit to be optimal for a specific application. Published by the American Physical Society 2024

Papadopoulos, Nicholas J. C. (ORCID:00000002635700↗
DOE OSTI2022

On-Demand Designing of Cathode Internal Surface Architecture for Dramatic Enhancement of SOFC Performance and Durability

This project is aimed to design and modify the internal surfaces of porous composite cathode from currently commercially viable Solid Oxide Fuel Cells (SOFCs), using additive manufacturing process of Atomic Layer Deposition (ALD). The material systems being investigated are commercial composite electrodes complex three-dimensional topographies. In term of the chemistry of the ALD layer applied on the internal surface of the porous cathode, this project has employed commercially relevant electrolyte, electrocatalyst and noble metal materials set. Such materials are fully compatible with the commercial fuel cells, and this project has developed special nanostructure on the surface of the commercial composite cathodes. The formation of the designed nanoarchitecture on the surface of SOFC cathode has been achieved through precise control of ALD parameters and their effect on overall cell performance and resultant electrochemical reaction mechanism of cathodes has been investigated through full cell electrochemical performance testing and nanostructure characterization by transmission electron microscopy (TEM). Under the support of this award, following has been achieved: (1). For cathode materials in solid oxide fuel cells (SOFCs), such as perovskite mixed conductor La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-x (LSCF), cation surface segregation and consequently losing conductivity and active sites for the oxygen reduction reaction (ORR) are problematic. To mitigate the cation segregation and enhance SOFC durability, further decorating the internal backbone surface using the desired electrocatalysts could be a promoting approach. Commonly, the cation segregation such as Sr is very volatile, so the effective surface decoration is ideally conformal. Nevertheless, the conformal surface coating would inevitably alter the ORR pathways that initially take place on the surface of the backbone. To reveal the impact of the conformal coating on both the catalytic activity and the conductivity of the cathode, the unary electrocatalyst of Pt or CoO x , was applied to the LSCF/SDC composite electrode of inherently functional SOFCs, respectively. Both ALD coating layers evolve strong interaction with the LSCF composite cathode. Upon operations, the Pt coating layer remains conformal on LSCF grain surfaces but turns into discrete particles on SDC grain surfaces. Meanwhile, CoO x conformal coating grows to be the discrete nanograins on both the LSCF and SDC grains. ALD coating of the cathode alone reduces the ohmic resistance up to 28 % for the entire cells. The increased conductivity induced by the ALD coating of Pt or CoO x is ascribed to different mechanisms. For the inherent functional SOFCs, the present study presents a novel and feasible approach to apply a conformal, dense coating layer on the surface of a mixed conductor, simultaneously increasing the conductivity and durability of the SOFC cathode. (2). High resistance of the oxygen electrode still significantly hinders the state-of-the-art Solid Oxide Fuel Cells (SOFCs). In particular, for an oxygen electrode consisting of mixed electronic and ionic conductors, such as perovskite lanthanum strontium cobalt ferrite (LSCF), it deteriorates due to its low chemical stability of the grain surface. Such degradation is often associated with the segregation of cations. To prevent the cation surface segregation and its resultant perovskite phase decomposition, we demonstrate a conformal ultra-thin (7-10 nm) surface heterogeneous coating layer consisting of subjacent discrete Pt nanoparticles capped with a superjacent fully dense conformal CoO x layer. The performance studies indicate the ALD coating reduces the cell series resistance by up to 40 %. The conformal CoO x layer consists of randomly orientated but single-layered nanograins, with high-density intergranular and surface grain boundaries serving as the electrochemical reaction sites and facilitating mass transport. The conformal coating layer appears to have successfully suppressed the Sr outward diffusion and confined the Sr enriched layer to a ~ 2 nm interface perovskite phase between the coating layer and the LSCF grain surface. Moreover, this ultra-thin Sr enriched perovskite layer presumably possesses high oxygen vacancy and high ionic conductivity and further imposes tensile strain to the LSCF grain surfaces. With the combination of a conformal CoO x nanoionics, Sr enriched layer, and its strained interface, the ALD coating induced surface layer is estimated to have a conductivity of ~ 1.27x10 4 S/cm, which is over two orders magnitude of that from LSCF at 750 ºC.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2025

High-precision mass measurement of 103 Sn restores smoothness of the mass surface

As a step towards the ultimate goal of a high-precision mass measurement of doubly magic 100 Sn, the mass of 103 Sn was measured at the Low Energy Beam and Ion Trap (LEBIT) located at the Facility for Rare Isotope Beams (FRIB). Utilizing the time-of-flight ion cyclotron resonance technique, a mass uncertainty of 3.7 keV was achieved, an improvement by more than an order of magnitude compared to a recent measurement performed in 2023 at the Cooler Storage Ring (CSRe) in Lanzhou. Although the LEBIT and CSRe mass measurements of 103 Sn are in agreement, they diverge from the experimental mass value reported in the 2016 version of the Atomic Mass Evaluation (AME2016), which was derived from the measured 𝑄 𝛽 + value and the mass of 103 In. In AME2020, this indirectly measured 103 Sn mass was classified as a “seriously irregular mass” and replaced with an extrapolated value, which aligns with the most recent measured values from CSRe and LEBIT. As such, the smoothness of the mass surface is confidently reestablished for 103 Sn. Here, LEBIT's mass measurement of 103 Sn enabled a significant reduction in the mass uncertainties of five parent isotopes which are now dominated by uncertainties in their respective 𝑄 values.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2021

Direct Chemical Vapor Deposition Synthesis of Porous Single-Layer Graphene Membranes with High Gas Permeances and Selectivities

Single-layer graphene containing molecular-sized in-plane pores is regarded as a promising membrane material for high-performance gas separations due to its atomic thickness and low gas transport resistance. However, typical etching-based pore generation methods cannot decouple pore nucleation and pore growth, resulting in a trade-off between high areal pore density and high selectivity. In contrast, intrinsic pores in graphene formed during chemical vapor deposition are not created by etching. Therefore, intrinsically porous graphene can exhibit high pore density while maintaining its gas selectivity. Here in this work, the density of intrinsic graphene pores is systematically controlled for the first time, while appropriate pore sizes for gas sieving are precisely maintained. As a result, single-layer graphene membranes with the highest H 2 /CH 4 separation performances recorded to date (H 2 permeance > 4000 GPU and H 2 /CH 4 selectivity > 2000) are fabricated by manipulating growth temperature, precursor concentration, and non-covalent decoration of the graphene surface. Moreover, it is identified that nanoscale molecular fouling of the graphene surface during gas separation where graphene pores are partially blocked by hydrocarbon contaminants under experimental conditions, controls both selectivity and temperature dependent permeance. Overall, the direct synthesis of porous single-layer graphene exploits its tremendous potential as high-performance gas-sieving membranes.

chemical vapor deposition↗
DOE OSTI2022

Molecular-Level Control over Ionic Conduction and Ionic Current Direction by Designing Macrocycle-Based Ionomers

Poor ionic conductivity of the catalyst-binding, submicrometer- thick ionomer layers in energy conversion and storage devices is a huge challenge. However, ionomers are rarely designed keeping in mind the specific issues associated with nanoconfinement. Here, we designed nature-inspired ionomers (calix-2) having hollow, macrocyclic, calix[4]arene-based repeat units with precise, sub-nanometer diameter. In ≤100 nm-thick films, the in-plane proton conductivity of calix-2 was up to 8 times higher than the current benchmark ionomer Nafion at 85% relative humidity (RH), while it was 1-2 orders of magnitude higher than Nafion at 20-25% RH. Confocal laser scanning microscopy and other synthetic techniques allowed us to demonstrate the role of macrocyclic cavities in boosting the proton conductivity. The systematic self-assembly of calix-2 chains into ellipsoids in thin films was evidenced from atomic force microscopy and grazing incidence small-angle X-ray scattering measurements. Moreover, the likelihood of alignment and stacking of macrocyclic units, the presence of one-dimensional water wires across this macrocycle stacks, and thus the formation of long-range proton conduction pathways were suggested by atomistic simulations. We not only did see an unprecedented improvement in thin-film proton conductivity but also saw an improvement in proton conductivity of bulk membranes when calix-2 was added to the Nafion matrices. Nafion-calix-2 composite membranes also took advantage of the asymmetric charge distribution across calix[4]arene repeat units collectively and exhibited voltage-gating behavior. The inclusion of molecular macrocyclic cavities into the ionomer chemical structure can thus emerge as a promising design concept for highly efficient ion-conducting and ion-permselective materials for sustainable energy applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

3-center and 4-center 2-particle Gaussian AO integrals on modern accelerated processors

We report an implementation of the McMurchie–Davidson (MD) algorithm for 3-center and 4-center 2-particle integrals over Gaussian atomic orbitals (AOs) with low and high angular momenta l and varying degrees of contraction for graphical processing units (GPUs). This work builds upon our recent implementation of a matrix form of the MD algorithm that is efficient for GPU evaluation of 4-center 2-particle integrals over Gaussian AOs of high angular momenta (l ≥ 4) [A. Asadchev and E. F. Valeev, J. Phys. Chem. A 127, 10889–10895 (2023)]. The use of unconventional data layouts and three variants of the MD algorithm allow for the evaluation of integrals with double precision and sustained performance between 25% and 70% of the theoretical hardware peak. Performance assessment includes integrals over AOs with l ≤ 6 (a higher l is supported). Preliminary implementation of the Hartree–Fock exchange operator is presented and assessed for computations with up to a quadruple-zeta basis and more than 20 000 AOs. The corresponding C++ code is part of the experimental open-source LibintX library available at https://github.com/ValeevGroup/libintx.

Chemistry↗
DOE OSTI2020

Electron correlation effects in attosecond photoionization of CO 2

A technique for measuring photoionization time delays with attosecond precision is combined with calculations of photoionization matrix elements to demonstrate how multielectron dynamics affect photoionization time delays in carbon dioxide. Electron correlation is observed to affect the time delays through two mechanisms: autoionization of molecular Rydberg states and accelerated escape from a continuum shape resonance.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Lattice Strain Measurement of Core@Shell Electrocatalysts with 4D Scanning Transmission Electron Microscopy Nanobeam Electron Diffraction

Strain engineering enables the direct modification of atomic bonding and is currently an active area of research aimed at improving electrocatalytic activity. However, directly measuring the lattice strain of individual catalyst nanoparticles is challenging, especially at the scale of a single unit cell. In this study, we quantitatively map the strain present in rhodium@platinum (core@shell) nanocube electrocatalysts using conventional aberration-corrected scanning transmission electron microscopy (STEM) and the recently developed technique of 4D-STEM nanobeam electron diffraction. We demonstrate that 4D-STEM combined with data preconditioning allows for quantitative lattice strain mapping with subpicometer precision and without the influence of scan distortions. When combined with multivariate curve resolution, 4D-STEM allows us to distinguish the nanocube core from the shell and to quantify the unit cell size as a function of distance from the core–shell interface. Our results demonstrate that 4D-STEM has significant precision and accuracy advantages in strain metrology of catalyst materials compared to aberration-corrected STEM imaging and is beneficial for extracting information about the evolution of strain in catalyst nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Constructing a square-like copper cluster to boost C–C coupling for CO 2 electroreduction to ethylene

The CO 2 electroreduction reaction (CO 2 ER) to ethylene (C 2 H 4 ) offers the dual promise of lowering CO 2 emission while storing energy from renewable electricity, for which the development of highly efficient electrocatalysts is of great significance. Herein, by means of density functional theory (DFT) computations, we designed an electrocatalyst for CO 2 -to-C 2 H 4 conversion by anchoring a Cu 5 cluster supported on a MoS 2 monolayer with an S monovacancy (Cu 5 @MoS 2 ). Our results revealed that one Cu atom of the Cu 5 cluster was embedded into the framework of the defective MoS 2 monolayer, while the other four Cu atoms form a square-like island over the substrate surface. Interestingly, the C–C coupling between two *CO species can easily occur on the unique square-like active site with a low kinetic barrier of 0.56 eV to form the key *C 2 O 2 intermediate, which can then be hydrogenated to the C 2 H 4 product with a very low limiting potential (–0.32 eV). Significantly, alkaline conditions (pH = 13) are beneficial to further promote C 2 H 4 synthesis. Finally, our work may offer a new avenue to precisely modulate the structures of Cu clusters for converting CO 2 into high-value target products.

30 DIRECT ENERGY CONVERSION↗