Boosting Activity and Selectivity of CO2 Electroreduction by Pre-Hydridizing Pd Nanocubes
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99 GENERAL AND MISCELLANEOUS↗
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Optimizing Vertical Crystallization for Efficient Perovskite Solar Cells by Buried Composite Layers
Planar-heterojunction perovskite solar cells (PSCs) have experienced rapid evolution in recent years because of the low-temperature processing, suitable alignment, and high mobility of the tin oxide buried contact layer. However, improper SnO 2 surface states and poor crystallinity of the top perovskite films are still the main obstacles for the planar PSCs in which performance always lags behind their mesoporous counterparts. Herein, a new buried contact is reported by introducing graphitic carbon nitride (g-C 3 N 4 ) into the commonly used SnO 2 which performs outstanding transmittance, conductivity, and surface states for a high-quality electron-transporting layer. Moreover, the vertical composition and crystallinity of the top perovskite film are manipulated by rich amino groups on the edge of the g-C 3 N 4 nanosheets which induce the prenucleation of the lead-rich species at the buried interface. Benefiting from the high-quality buried contacts and the optimized perovskite layers, the resultant PSCs achieve a champion efficiency of 21.5% with all photovoltaic parameters enhanced in comparison with their control counterparts (<20%).
planar-heterojunction perovskite solar cells↗
Laser-Induced Photoreduction of Iron(III) Oxide Nanoparticles Enhanced by the Presence of Organic Chromophores
Light-induced electron transfer between chromophoric organic matter and Fe(III)-oxides lies at the heart of aqueous Fe(II) fluxes in the photic zone of natural systems. Understanding this photoreductive dissolution process is also essential for developing water purification techniques based on this class of materials. Previously, optical transient absorption spectroscopy (TAS) measurements revealed that sub-picosecond relaxation times of photo-excited rhodamine B (RhB) dye increased when sorbed onto hematite nanoparticles (HNPs), consistent with electron transfer to the oxide. Here, in the present study, we exploit time-resolved X-ray absorption spectroscopy (XAS) at the Fe K-edge to follow the Fe oxidation state for this same process to (i) confirm that RhB photoexcitation leads to interfacial electron transfer and Fe reduction; and (ii) quantify the lifetime of injected electrons as a function of solution conditions. Regardless of RhB dye availability and pH, direct band gap photoexcitation of HNPs yields an Fe(II)-like small polaronic absorption signature with a lifetime of ~ 1 ns, an order of magnitude longer than previously reported. However, when RhB is present at low pH under conditions where dye favorably interacts with the positively charged hematite surface, a second relaxation process approaching microsecond timescales is observed that likely represents back-reaction with the photoexcited adsorbed dye. At pH above neutral, the efficiency of the interfacial electron transfer is diminished by weaker interaction between sorbed dye and particle surfaces.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Modulation of Tropical Convection-Circulation Interaction by Aerosol Indirect Effects in Convective Self-Aggregation Simulations of a Gray Zone Global Model
Disentangling the response of tropical convective updrafts to enhanced aerosol concentrations has been challenging. Leading theories for explaining the influence of aerosol concentrations on tropical convection are based on the dynamical response of convection to changes in cloud microphysics, neglecting possible changes in the environment. In recent years, global convection-permitting models (GCPM) have been developed to circumvent problems arising from imposing artificial scale separation on physical processes associated with deep convection. Here, we use a global model in the convective gray zone that partially simulates deep convection to investigate how enhanced concentrations of aerosols that act as cloud condensate nuclei (CCN) impact tropical convection features by modulating the convection-circulation interaction. Results from a pair of idealized non-rotating radiative-convective equilibrium simulations show that the enhanced CCN concentration leads to weaker large-scale circulation, the closeness of deep convective systems to the moist cluster edges, and more mid-level cloud water at an equilibrium state in which convective self-aggregation occurred. Correspondingly, the enhanced CCN concentration modulates how the physical processes that support or oppose convective aggregation maintain the aggregated state at equilibrium. Overall, the enhanced CCN concentration facilitates the development of deep convection in a drier environment but reduces mean precipitation. Our results emphasize the importance of allowing atmospheric phenomena to evolve continuously across spatial and temporal scales in simulations when investigating the response of tropical convection to changes in cloud microphysics.
54 ENVIRONMENTAL SCIENCES↗
In Situ Liquid Electron Microscope Cells Strongly Attenuate Electrochemical Behavior
In situ electrochemical Scanning Transmission Electron Microscopy (ec-S/TEM) probes the dynamics of electrochemical processes in real time and at high spatial resolution. This method utilizes microfabricated electrochemical cells, with enclosed dimensions of 800 μm wide, 800 μm long, and 1–2 μm tall, with electron-transparent silicon nitride windows. Working, counter, and reference electrodes in the configuration studied are deposited Pt with a planar surface area of about 1 μm 2 and a height of 50 nm. The cell confines the electrolyte within a 1 μm tall channel, and the microfabricated electrodes have a non-standard geometry, are coplanar, and are not front-facing. As such, standard assumptions of electrochemical experiments do not apply. COMSOL modeling was used to compare and contrast differences in electrochemical behavior between conventional experimental setups and the in situ ec-S/TEM cells. Cell height strongly affected voltammogram measurements: peak magnitudes and shifts correlate directly to cell height. Reactant concentration above the electrode quickly decreases during deposition, leading to a planar diffusion-dominated regime. The concentration gradient prioritizes particle growth along the thin edges of the electrode and not on the planar part of the electrode. Experiments done in the ec-S/TEM ex situ of a TEM verify the model’s accuracy.
Wittman, Reed M. [Oak Ridge National Laboratory (O↗
Plasmons in two-dimensional topological insulators
Here, we analyze collective excitations in models of two-dimensional topological insulators using the random phase approximation. In a two-dimensional extension of the Su-Schrieffer-Heeger model, edge plasmonic excitations with induced charge-density distributions localized at the boundaries of the system are found in the topologically nontrivial phase, dispersing similarly as one-dimensional bulk plasmons in the conventional Su-Schrieffer-Heeger chain. For two-dimensional bulk collective modes, we reveal regimes of enhanced interband wave function correlations, leading to characteristic hardening and softening of inter- and intraband bulk plasmonic branches, respectively. In the two-dimensional Haldane Chern insulator model, chiral, unidirectional edge plasmons in nano-ribbon architectures are observed, which can be characterized by an effective Coulomb interaction cross section. Bulk collective excitations in the two-dimensional Haldane model are shown to be originated by single-particle band structure details in different topological phases.
2-dimensional systems↗
Effect of anisotropic thermal transport on tearing mode stability in negative versus positive triangularity plasmas
The combined effects of anisotropic thermal transport and the plasma shaping, including negative triangularity, on the n = 1 (n is the toroidal mode number) tearing mode (TM) stability are numerically investigated utilizing the MARS-F code [Liu et al., Phys. Plasmas 7, 3681–3690 (2000)]. While varying the plasma boundary triangularity, the TM stability is found to be dictated by the competing effects of the Shafranov shift induced stabilization and the bad-curvature induced destabilization. The negative triangularity shape increases the Shafranov shift (stabilizing) in the plasma core but also enlarges bad-curvature regions (destabilizing) near the plasma edge, with the net effect being largely destabilizing for the TM as compared to the positive triangularity counter-part. Large negative triangularity however can also lead to more stabilization for the plasma core-localized TM. Anisotropic thermal transport reduces the stabilizing effect on the TM associated with the favorable averaged curvature, resulting in more unstable core-localized TMs in both negative and positive triangularity plasmas. But the opposite effect can also take place for the edge-localized TM in finite-pressure plasmas with negative triangularity.
Physics↗
Expanded Analogs of Three-Dimensional Lead-Halide Hybrid Perovskites
Replacing the Pb-X octahedral building unit of A I PbX 3 perovskites (X=halide) with a pair of edge-sharing Pb-X octahedra affords the expanded perovskite analogs: A II Pb 2 X 6 . We report seven members of this new family of materials. In 3D hybrid perovskites, orbitals from the organic molecules do not participate in the band edges. In contrast, the more spacious inorganic sublattice of the expanded analogs accommodates larger pyrazinium-based cations with low-lying π* orbitals that form the conduction band, substantially decreasing the band gap of the expanded lattice. The molecular nature of the conduction band allows us to electronically dope the materials by reducing the organic molecules. By synthesizing derivatives with AII=pyridinium and ammonium, we can isolate the contributions of the pyrazinium-based orbitals in the band gap transition of A II Pb 2 X 6 . The organic-molecule-based conduction band and the inorganic-ion-based valence band provide an unusual electronic platform with localized states for electrons and more disperse bands for holes upon optical or thermal excitation.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Numerical simulation study of impurity B transport during real-time B powder injection in EAST
To understand the beneficial effects of impurity boron (B) on the plasma, the transport of B species in both atomic and ionic states in the edge plasma and the ensuing evolution of the background plasma are simulated during real-time B powder injection by using two-dimensional fluid code SOLPS-ITER. The initial background plasma profiles for the simulation are reconstructed based on an EAST upper-single null discharge (shot No. 70601). With the injection rate of B atoms, 4.0 × 10 21 atoms/s, the simulation shows that effective charge number is less than 1.1 at the inner boundary R - R sep = -5.2 cm (background plasma density, 5.1 × 10 19 m -3 ) at the outer mid-plane indicating that the B impurity does not have much influence on the energy confinement. The present work finds that the impurity B exhibits very specific features in the edge plasma, mostly present in the narrow region just outside the separatrix. The particular distribution pattern can reduce the heat flux greatly, leading to the divertor detachment. The divertor detachment can be achieved easily under an injection rate of B powder in a reasonable range. This study suggests that the impurity B has a promising potential application in future tokamaks.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Non-Covalent Interactions and Helical Packing in Thiophene-Phenylene Copolymers: Tuning Solid-State Ordering and Charge Transport for Organic Field-Effect Transistors
In this study, we introduce two thiophene-phenylene-thiophene (TPT) polymers designed to leverage noncovalent intramolecular interactions to regulate main-chain conformation and enhance solid-state ordering. By incorporating unsubstituted thiophene (T) or bithiophene (2T) units, we reveal striking divergence in the thermal, morphological, and optoelectronic properties of the resulting films, facilitated by these noncovalent interactions. Using a combination of computational and experimental approaches, we show that annealing yields remarkably different polymer conformations and, consequently, charge transport properties. TPT-T undergoes a significant structural transformation, adopting a more planar backbone conformation and a highly crystalline, edge-on molecular orientation. In contrast, the introduction of a single additional thiophene unit in TPT-2T leads to a more isotropic molecular orientation with a slight preference for face-on alignment, resulting in a heterogeneous film structure that hinders charge transport despite achieving tighter molecular packing. Remarkably, despite being composed of achiral components, TPT-2T develops chirality upon annealing, indicating the formation of a helical conformation. Organic field-effect transistor measurements reveal that the well-ordered alignment in annealed TPT-T films results in higher charge carrier mobility and a narrower distribution of mobility values than in TPT-2T. These findings provide critical insights into the structure−property relationships of conjugated polymers, offering guidance for optimizing molecular design and processing strategies for highperformance organic electronic materials.
36 MATERIALS SCIENCE↗
Sulfurized Polyacrylonitrile for High-Performance Lithium–Sulfur Batteries: In-Depth Computational Approach Revealing Multiple Sulfur’s Reduction Pathways and Hidden Li + Storage Mechanisms for Extra Discharge Capacity
Like no other sulfur host material, polyacrylonitrile-derived sulfurized carbon (SPAN) promises improved electrochemical performance for lithium–sulfur batteries, based on its compatibility with carbonate solvents and ability to prevent self-discharge and shuttle effect. However, a complete understanding of the SPAN’s lithiation mechanism is still missing because its structural features vary widely with synthesis conditions, and its electrochemical performance deviates from elemental sulfur. This study continues our research on the elucidation of the SPAN’s structural characteristics and lithiation mechanisms via computational approaches. Here, our models reproduce most experimental data regarding carbon’s graphitization level and conjugated ordering, sulfur–carbon covalent bonding, sulfur loading, and elemental composition. Our simulations emulate the discharge voltage observed in experiments for the first discharge, which reveals that sulfur follows multiple reduction pathways based on its interaction with the carbon backbone. Sulfur reduction takes place above 1.0 V vs Li/Li + mostly in the SPAN-like material, with no long-chain lithium polysulfide formation. Below 1.0 V vs Li/Li + , the backbone’s electrochemical activity occurs via multiple C–Li and N–Li interactions, mostly with edge carbon atoms and pyridinic nitrogen. Moreover, we identify Li + binding sites throughout the graphitized backbone that might lead to prohibited energy costs for Li + deintercalation, which may explain the irreversible capacity loss between the first and second discharges. This work improves understanding of lithiation mechanisms in sulfurized carbon, which is useful for rationally designing SPAN synthesis pathways tailored to increase sulfur loading and enhanced electrochemical performance.
25 ENERGY STORAGE↗
Fractional magnetic charges and channeling of Faraday lines by disclinations in artificial spin ice
We have studied the magnetic moments of artificial spin ice arrays of nanomagnets in both undistorted square arrays and in arrays with a topological defect induced by a single disclination. We confirm that the disclination induces global, macroscopic changes in the low-energy collective states of the nanomagnet moment configuration. Specifically, the disclination leads to Faraday lines of effective magnetic flux that run from the center all the way to the edge of the arrays. Moreover, the geometric deformation, induced by the topological defect, curves the geometry such that these Faraday lines are channeled preferentially by the arrays’ curved geometry. Our results demonstrate how the intentional combination of topology and geometry can be designed to control magnetic charges and the flow of local magnetization and thus manipulate associated collective excitations.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
A model investigation of the impact of lower hybrid wave scattering angle on current drive profile in EAST and Alcator C-Mod
Lower hybrid current drive (LHCD) is beneficial for developing a steady-state operation scenario in a tokamak. This paper conducts a modeling investigation to identify an optimum rotation angle of the initial lower hybrid perpendicular (to the background magnetic field $\overrightarrow{B}$) wavevector for best matching the experimental RF current profile. It is hypothesized that central RF power deposition widely observed in the present-day LHCD experiments arises from wave scattering by turbulence. In a standard model without considering such interactions, the predicted power deposition profile is generally broad with off-axis peaking, not in agreement with experimental observations. A heuristic approach is adopted by introducing a spectral broadening mechanism by modifying the initial orientation of the perpendicular wavevector. The ray-tracing/Fokker–Planck solver GENRAY/CQL3D is utilized within the python-based π-scope framework. A focus is given to identify the perpendicular wavenumber orientation angle with respect to the magnetic surface normal vector at the initial ray location. Our modeling study shows that rotating the perpendicular wavevector in such a way as to increase the initial poloidal component is effective in reproducing the centrally peaked current profile observed in normal shear plasmas on both EAST and C-Mod. These waves can readily be absorbed to the central plasma, which reduces the sensitivity of the power deposition profile to a slight change of the plasma condition. The same approach is also found to help broaden the off-axis power deposition profile in a reverse-shear EAST plasma, leading to a better agreement with the experiment. The results presented here suggest that spectral modification arising from edge density fluctuations in a tokamak may need to be considered in understanding wave propagation and absorption. A further experimental and theoretical/modeling study is vital as a reverse approach is adopted in this study. Finally, our work suggests that mitigation or control measures are critical for parasitic effects occurring on the first pass in a reactor regime.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Using Particle Image Velocimetry to Determine Turbulence Model Parameters
The primary parameter of a standard k-ϵ model, C μ , was calculated from stereoscopic particle image velocimetry (PIV) data for a supersonic jet exhausting into a transonic crossflow. This required the determination of turbulent kinetic energy, turbulent eddy viscosity, and turbulent energy dissipation rate. Image interrogation was optimized, with different procedures used for mean strain rates and Reynolds stresses, to produce useful turbulent eddy viscosity fields. The eddy viscosity was calculated by a least-squares fit to all components of the three-dimensional strain-rate tensor that were available from the PIV data. This eliminated artifacts and noise observed when using a single strain component. Local dissipation rates were determined via Kolmogorov’s similarity hypotheses and the second-order structure function. The eddy viscosity and dissipation rates were then combined to determine C μ . Considerable spatial variation was observed in C μ , with the highest values found in regions where turbulent kinetic energy was relatively low but where turbulent mixing was important, e.g., along the high-strain jet edges and in the wake region. This suggests that use of a constant C μ in modeling may lead to poor Reynolds stress predictions at mixing interfaces. A data-driven modeling approach that can predict this spatial variation of C μ based on known state variables may lead to improved simulation results without the need for calibration.
42 ENGINEERING↗
The effectiveness of D 2 pellet and gas injection in reducing intra-ELM tungsten erosion and heat flux in the DIII-D small angle slot divertor
Edge localized modes (ELMs) in H-mode plasmas can melt and erode plasma-facing components (PFCs) and lead to impurities in the core, reducing confinement. This study analyzes the use of D 2 pellet and gas injection for ELM mitigation on the DIII-D tokamak during the 2022 Small Angle Slot V-shaped Tungsten (W) (SAS-VW) divertor campaign, reducing W erosion and heat flux during ELMs. D α (656 nm) and WI (400.9 nm) filterscopes and Langmuir probes provide photon emission and electron density/temperature to estimate W atom erosion using the S/XB method, while surface eroding thermocouples measured ELM peak heat flux at the outer strike point (OSP). Thomson Scattering measurements of pedestal T e and n e provided input to predict W divertor erosion and heat flux during ELMs via the Free-Streaming plus Recycling Model (FSRM). While a greater D 2 mass injection rate decreased the ELM peak heat flux, the impact on W erosion was not monotonic. The average ‘large’ intra-ELM W erosion was lower for plasma shots with D 2 mass injection compared to the plasma shots without any D 2 mass injection in the SAS-VW divertor. However, plasma shots did not see significant changes in ‘large’ intra-ELM W divertor erosion as the D 2 mass injection rate increased. On average, the FSRM overestimated SAS-VW experimental intra-ELM W erosion by a factor of 6.9, but the overestimation is reduced to a factor of 3.6 with the implication of C deposition effects. Generally, experimentally measured and predicted quantities were worse for plasma shots with a lower D 2 mass injection rate and corresponding higher plasma carbon (C) impurity percentage (f C ). The discrepancies are postulated to be due to C/W material mixing, for which a simple analytic mixed-material model is presented. These results highlight the importance of incorporating and improving the robustness of a mixed-material layer model in the analysis of PFC erosion on present and future tokamak devices.
Carbon (C)↗
Dependence of the boundary heat flux width on core and edge profiles in Alcator C-Mod
This work presents new evidence that the heat flux width, λ q , in the Alcator C-Mod tokamak scales with the edge electron pressure, as observed in the ASDEX Upgrade (AUG) tokamak, but the scaling with volume-averaged pressure, $\bar{p}$, from the plasma stored energy, is a better predictor of λ q in Alcator C-Mod than the edge electron pressure. These previous studies, which find that λ q decreases with increasing plasma pressure, imply that a high performance core at high pressure will lead to challenging heat and particle exhaust due to very small λ q . This concern has led to our significant enlargement of the C-Mod database with the electron density, temperature, and pressure profile data from the Thomson scattering and electron cyclotron emission diagnostics. Using the C-Mod database augmented with new profile data, we find that λ q decreases with increasing edge electron pressure as ${\lambda }_{q}\propto {p}_{\mathrm{e},95}^{-0.26}$, similar to results from AUG, and showing the strength of cross-machine comparisons. We also find that ${\lambda }_{q}\propto {p}_{\mathrm{e},\mathrm{c}\mathrm{o}\mathrm{r}\mathrm{e}}^{-0.56}$, consistent with the original finding from C-Mod that the heat flux width scales as ${\bar{p}}^{-0.48}$. The scalings of λ q with separatrix pressure and gradient scale length are found to match the AUG results qualitatively. The C-Mod scalings with edge plasma quantities have more scatter than the $\bar{p}$ scaling, and, importantly, show different trends for H-modes relative to L- and I-mode. Furthermore, investigating the source of this discrepancy presents an opportunity for further study that may improve our ability to predict the heat flux width in different confinement scenarios in the pursuit of optimizing core-edge performance in future reactors.
Alcator C-Mod↗
Spatial Control of Substitutional Dopants in Hexagonal Monolayer WS 2 : The Effect of Edge Termination
The ability to control the density and spatial distribution of substitutional dopants in semiconductors is crucial for achieving desired physicochemical properties. Substitutional doping with adjustable doping levels has been previously demonstrated in 2D transition metal dichalcogenides (TMDs); however, the spatial control of dopant distribution remains an open field. In this work, edge termination is demonstrated as an important characteristic of 2D TMD monocrystals that affects the distribution of substitutional dopants. Particularly, in chemical vapor deposition (CVD)-grown monolayer WS 2 , it is found that a higher density of transition metal dopants is always incorporated in sulfur-terminated domains when compared to tungsten-terminated domains. Here two representative examples demonstrate this spatial distribution control, including hexagonal iron- and vanadium-doped WS 2 monolayers. Density functional theory (DFT) calculations are further performed, indicating that the edge-dependent dopant distribution is due to a strong binding of tungsten atoms at tungsten-zigzag edges, resulting in the formation of open sites at sulfur-zigzag edges that enable preferential dopant incorporation. Based on these results, it is envisioned that edge termination in crystalline TMD monolayers can be utilized as a novel and effective knob for engineering the spatial distribution of substitutional dopants, leading to in-plane hetero-/multi-junctions that display fascinating electronic, optoelectronic, and magnetic properties.
2D transition metal dichalcogenides↗
Edge supercurrent reveals competition between condensates in a Weyl superconductor
In topological materials, the edge states are readily distinguished from the bulk states. The situation where a topological semimetal becomes superconducting so that Cooper pairs occupy both the bulk and the edge states is not well understood. In particular, we do not know if we can force their pairing symmetries to be different. Here we show that, when supercurrent is injected into the superconducting Weyl semimetal MoTe 2 from Nb contacts, the invasive s-wave pairing potential from Nb is incompatible with the intrinsic Cooper pair condensate in MoTe 2 . This incompatibility leads to strong stochasticity in the switching current and an unusual anti-hysteretic behaviour in the current–voltage loops. There is also an asymmetry in the edge oscillations where, as the magnetic field crosses zero, the phase noise switches from one with a noisy spectrum to one that is noise free. Furthermore, using the noise spectrum as a guide, we track the anomalous features to field-induced switching of the device gap function between s-wave symmetry and the unconventional symmetry intrinsic to MoTe 2 . We infer that the behaviour of the gap function along the edges is different from that in the bulk.
Superconducting properties and materials↗