Surface Facets Research Articles

Seebeck Coefficient Modulation of Graphene Grown on Faceted Cu Surfaces

The thermoelectric properties of polycrystalline copper (Cu) surfaces partially covered with graphene grown by Joule‐heating chemical vapor deposition using scanning thermoelectric microscopy are investigated. Atomic‐resolution atomic force microscopy topographic images of graphene grown on Cu(100) surfaces showed a 1D stripe pattern of Moiré superlattices, while thermoelectric voltage images clearly distinguish wrinkle defects caused by thermal mismatch between graphene and Cu substrate. Regions of different signs were found in the thermoelectric voltage image of the graphene island, which are attributed to the faceted surface of the Cu substrate. In addition, faceted surfaces consisting of low‐ and high‐index Cu surfaces are formed on the Cu grain to minimize the surface energy. Due to these structural changes, charge transfer and chemical interactions at the interface between the graphene and Cu facets affect the electronic structure of the graphene, which is understood as the observed Seebeck coefficients with different signs in the thermoelectric microscopy measurements, which are sensitive to the local density of states.

Tracking the Early-life of PtNi/C Shape-Controlled Catalysts upon their Integration in PEMFC

Abstract The integration of promising bimetallic electrocatalytic active materials for oxygen reduction reaction (ORR) into practical and functional proton-exchange membrane fuel cell (PEMFC) electrodes remains largely impeded by the poor performances that these exhibit at high current loads. The early life of PtNi/C catalysts presenting either structurally faceted/ordered or defective/disordered surface morphology is compared to that of both spherical PtNi/C and Pt/C catalysts. Different single-cell operating conditions were studied. At low current density, in the kinetically limited region, a good agreement between liquid electrolyte and single-cell configuration is reported and the kinetic benefit of PtNi/C catalysts compared to Pt/C is (at least partially) maintained. However, PtNi/C catalysts show severe limitations in the O2 mass transport limited region. Morphological and compositional changes were monitored at each stage showing that Ni atoms are leached at every step from ink formulation to the first PEMFC test. We show that Ni is already redistributed in the membrane in the fresh membrane electrode assembly (MEA) state. Ni2+ cationic contamination of the ionomer/membrane contributes to the disappointing results obtained in MEA configuration. In addition, for shaped-controlled PtNi/C, the surface faceting loss combined with restructuring via coalescence and crystallite growth further compromise their transfer in technological devices.

A comparative study of the effect of facet tropism on the index-level kinematics and biomechanics after artificial cervical disc replacement (ACDR) with Prestige LP, Prodisc-C vivo, and Mobi-C: a finite element study

IntroductionArtificial cervical disc replacement (ACDR) is a widely accepted surgical procedure in the treatment of cervical radiculopathy and myelopathy. However, some research suggests that ACDR may redistribute more load onto the facet joints, potentially leading to postoperative axial pain in certain patients. Earlier studies have indicated that facet tropism is prevalent in the lower cervical spine and can significantly increase facet joint pressure. The present study aims to investigate the changes in the biomechanical environment of the cervical spine after ACDR using different prosthese when facet tropism is present.MethodsA C2-C7 cervical spine finite element model was created. Symmetrical, moderate asymmetrical (7 degrees tropism), and severe asymmetrical (14 degrees tropism) models were created at the C5/C6 level by adjusting the left-side facet. C5/C6 ACDR with Prestige LP, Prodisc-C vivo, and Mobi-C were simulated in all models. A 75 N follower load and 1 N⋅m moment was applied to initiate flexion, extension, lateral bending, and axial rotation, and the range of motions (ROMs), facet contact forces(FCFs), and facet capsule stress were recorded.ResultsIn the presence of facet tropism, all ACDR models exhibited significantly higher FCFs and facet capsule stress compared to the intact model. In the asymmetric model, FCFs on the right side were significantly increased in neutral position, extension, left bending and right rotation, and on both sides in right bending and left rotation compared to the symmetric model. All ACDR model in the presence of facet tropism, exhibited significantly higher facet capsule stresses at all positions compared to the symmetric model. The stress distribution on the facet surface and the capsule ligament in the asymmetrical models was different from that in the symmetrical model.ConclusionsThe existence of facet tropism could considerably increase FCFs and facet capsule stress after ACDR with Prestige-LP, Prodisc-C Vivo, and Mobi-C. None of the three different designs of implants were able to effectively protect the facet joints in the presence of facet tropism. Research into designing new implants may be needed to improve this situation. Clinical trials are needed to validate the impact of facet tropism.

First Principles Unveiling Equilibrium Shapes for Understanding Morphological Growth Mechanisms in Alumina Polymorphs

Understanding the morphological evolution of crystals is crucial for industrial applications and surface engineering. This study employs a multifaceted analytical approach to comprehensively analyze gibbsite, boehmite, η, γ, δ, θ, κ, and α-Al2O3. Density Functional Theory (DFT) surface energy calculations provide essential viewpoints into facet exposure and stability, enriching our comprehension of growth patterns. Using the Bravais–Friedel–Donnay–Harker (BFDH) method, a meticulous investigation into morphological properties reveals equilibrium shapes for each structure. Crucially, our models unveil the inaugural equilibrium shapes for structures previously undocumented in the literature (e.g., η, δ, θ, and κ-Al2O3). The study explores morphological growth process during phase transitions from gibbsite and boehmite to alpha alumina, emphasizing nucleation and dissolution preferences for specific facets. A grain analysis, considering bulk energy, surface area, and volume, designates α-Al2O3 as the most stable phase, offering valuable standpoints on thermodynamics and indicating a direct correlation between facet area and volume. Additionally, a comprehensive 3D surface energy mapping offers intricate visualization of facet interactions, providing valuable viewpoints into the complex relationships between surface energy, facet area, and interplanar distance. Comparisons of Fourier-transform infrared spectroscopy (FTIR) spectra, exclusively within the 200–400 cm-1 range, underscore close agreement between theoretical and experimental spectra, consistent with the expected reduction in specific surface area during polymorphic transformation.

Dynamics of phase separation of metastable crystal surfaces by surface diffusion: A phase-field study.

A new phase-field approach is designed to model surface diffusion of crystals with strongly anisotropic surface energy. The model can be shown to asymptotically converge toward the sharp-interface equationfor surface diffusion in the limit of vanishing interface width. It is employed to investigate the dynamical evolution of a thermodynamically metastable crystal surface. We find that nucleation and growth by surface diffusion of the newly formed surface induce the formation of additional stable surfaces at its wake. This induced nucleation mechanism is found to produce domains composed of several stable surfaces of prescribed width. The domains propagate on the crystal surface and then coalesce to form a hill-and-valley structure. The resulting morphology is more regular than the typical hill-and-valley surface produced by random thermal nucleation, i.e., when motion-by-curvature controls the phase separation dynamics. Moreover, the induced nucleation mechanism is found to be peculiar to surface diffusion and to dominate the phase separation at high degree of metastability. Once the hill-and-valley structure is formed, coarsening operates by motion and elimination of facet junctions, points where two facets merge to form one and we find the following scaling law L∼t^{1/6}, for the growth in time t of the characteristic length scale L during this coarsening stage. The density of junctions is found to exhibit a t^{-2/3} regime. Our results elucidate the role of the induced nucleation mechanism on the dynamics of interfacial phase separation and corroborate surface faceting experiments on ceramics.

Facet-Engineered BiVO4 Photocatalysts for Water Oxidation: Lifetime Gain Versus Energetic Loss.

A limiting factor to the efficiency of water Oxygen Evolution Reaction (OER) in metal oxide nanoparticle photocatalysts is the rapid recombination of holes and electrons. Facet-engineering can effectively improve charge separation and, consequently, OER efficiency. However, the kinetics behind this improvement remain poorly understood. This study utilizes photoinduced absorption spectroscopy to investigate the charge yield and kinetics in facet-engineered BiVO4 (F-BiVO4) compared to a non-faceted sample (NF-BiVO4) under operando conditions. A significant influence of preillumination on hole accumulation is observed, linked to the saturation and, thus, passivation of deep and inactive hole traps on the BiVO4 surface. In DI-water, F-BiVO4 shows a 10-fold increase in charge accumulation (∼5 mΔOD) compared to NF-BiVO4 (∼0.5 mΔOD), indicating improved charge separation and stabilization. With the addition of Fe(NO3)3, an efficient electron acceptor, F-BiVO4 demonstrates a 30-fold increase in the accumulation of long-lived holes (∼45 mΔOD), compared to NF-BiVO4 (∼1.5 mΔOD) and an increased half-time, from 2 to 10 s. Based on a simple kinetic model, this increase in hole accumulation suggests that facet-engineering causes at least a 50-100 meV increase in band bending in BiVO4 particles, thereby stabilizing surface holes. This energetic stabilization/loss results in a retardation of OER relative to NF-BiVO4. This slower catalysis is, however, offset by the observed increase in density and lifetime of photoaccumulated holes. Overall, this work quantifies how surface faceting can impact the kinetics of long-lived charge accumulation on metal oxide photocatalysts, highlighting the trade-off between lifetime gain and energetic loss critical to optimizing photocatalytic efficiency.

Interfacial Robustness and Improved Kinetics of Single-Crystal Ni-Rich Co-Free Cathodes Enabled by Surface Crystal-Facet Modulation.

The elimination of Co from Ni-rich layered cathodes is critical to reduce the production cost and increase the energy density for sustainable development. Herein, a delicate strategy of crystal-facet modulation is designed and explored, which is achieved by simultaneous Al/W-doping into the precursors, while the surface role of the crystal-facet is intensively revealed. Unlike traditional studies on crystal structure growth along a certain direction, this work modulates the crystal-facet at the nanoscale based on the effect of W-doping dynamic migration with surface energy, successfully constructing the core-shell (003)/(104) facet surface. Compared to the (003) plane, the induced (104) facet at the surface can provide more space for Li+-activity, enabling lower interfacial polarization and higher Li+-transport rate. Additionally, bulk Al-doping is beneficial for enhancing the Li+-diffusion from the exterior surface to the interior lattice. With improved interfacial stability and restrained surface erosion, the product exhibits superior capacity retention and boosted rate performance under the elevated temperature.

Surface Facets Reconstruction in Copper-Based Materials for Enhanced Electrochemical CO2 Reduction.

The unavoidable and unpredictable surface reconstruction of metallic copper (Cu) during the electrocatalytic carbon dioxide (CO2) reduction process is a double-edged sword affecting the production of high-value-added hydrocarbon products. It is crucial to control the surface facet reconstruction and regulate the targeted facets/facet interfaces, and further understand the mechanism between activity/selectivity and the reconstructed structure of Cu for CO2 reduction. Based on the current catalyst design methods, a facile strategy combining chemical reduction and electro-reduction is proposed to achieve specified Cu(111) facets and the Cu(110)/(111) interfaces in reconstructed Cu derived from cuprous oxide (Cu2O). The surface facet reconstruction significantly boosted the electrocatalytic conversion of CO2 into multi-carbon (C2+) products comparing to the unmodified catalyst. Theoretical and experimental analyses show that the Cu(110)/(111)s interface between Cu(110) and a small amount of Cu(111) can tailor the reaction routes and lower the reaction energy barrier of C-C coupling to ethylene (C2H4). The work will guide the surface facets reconstruction strategy for Cu-based CO2 electrocatalysts, providing a promising paradigm to understand the structural variation in catalysts.

Facet deflection and strain are dependent on axial compression and distraction in C5-C7 spinal segments under constrained flexion.

Facet fractures are frequently associated with clinically observed cervical facet dislocations (CFDs); however, to date there has only been one experimental study, using functional spinal units (FSUs), which has systematically produced CFD with concomitant facet fracture. The role of axial compression and distraction on the mechanical response of the cervical facets under intervertebral motions associated with CFD in FSUs has previously been shown. The same has not been demonstrated in multi-segment lower cervical spine specimens under flexion loading (postulated to be the local injury vector associated with CFD). This study investigated the mechanical response of the bilateral inferior C6 facets of thirteen C5-C7 specimens (67±13 yr, 6 male) during non-destructive constrained flexion, superimposed with each of five axial conditions: (1) 50 N compression (simulating weight of the head); (2-4) 300, 500, and 1000 N compression (simulating the spectrum of intervertebral compression resulting from neck muscle bracing prior to head-first impact and/or externally applied compressive forces); and, (5) 2 mm of C6/C7 distraction (simulating the intervertebral distraction present during inertial loading of the cervical spine by the weight of the head). Linear mixed-effects models (α = 0.05) assessed the effect of axial condition. Increasing amounts of intervertebral compression superimposed on flexion rotations, resulted in increased facet surface strains (range of estimated mean difference relative to Neutral: maximum principal = 77 to 110 με, minimum principal = 126 to 293 με, maximum shear = 203 to 375 με) and angular deflection of the bilateral inferior C6 facets relative to the C6 vertebral body (range of estimated mean difference relative to Neutral = 0.59° to 1.47°). These findings suggest increased facet engagement and higher load transfer through the facet joint, and potentially a higher likelihood of facet fracture under the compressed axial conditions.

Interfacial inhomogeneous plastic deformation during rotary friction welding of dissimilar AA2219-SS321 joint combination with AA6061 interlayer

This research investigates the inherent radial non-uniformity within the rotary friction welding process, particularly concerning microstructure attributes like grain size, grain boundaries, misorientation angles, and interlayer presence along the radial axis. SS321-AA2219 rotary friction welding was carried out with and without an AA6061 interlayer. The numerical thermal model suggests increase in temperatures from the center to the periphery, due to non-uniform heat generation. Also, dissimilar material across the interface resulted in an asymmetric temperature profile along axial direction. Plastic deformation on the Aluminum side suggests dynamic recrystallization and grain refinement, whereas pronounced low-angle grain boundary (LAGB) formation near the SS side interface validates dynamic recovery. A radial non-uniformity in microstructure is observed, with metrics such as average grain size, LAGB fraction, and misorientation showing an increase from the center towards the periphery. The insertion of an interlayer alters process dynamics, manifesting in reduced temperatures and heightened forces, resulting in a more consolidated joint by enhancing the strength by 31 %. Interdiffusion of elements across the interface formed Fe-Al intermetallic compounds (IMC) confirmed with X ray diffraction. Fractography analysis elucidates the presence of rubbing marks and facet surfaces in interlayer-less joints, while joints with interlayer display sticking and dimples.

Water-Etched Porous Ti: Surface Manipulation of Ti Foam Fabricated by Liquid Metal Dealloying Technique.

The liquid metal dealloying (LMD) process enables the fabrication of porous metals with various chemical compositions. Despite its advantages, LMD still faces key challenges such as maintaining the high-temperature molten metal bath for a prolonged time, avoiding the use of toxic etchants, and so on. To overcome these challenges, the study develops a water-leachable and oxidation-resistant alloy melt (AM) in Ca-Mg binary system. Specifically, Ca72Mg28 eutectic AM is designed, which exhibits higher oxidation resistance and lower melting temperature compared to pure Mg, allowing LMD to be conducted in atmospheric conditions as well as temperatures >200K lower. The AM also enables an innovative process to fabricate Ti foams with a hexagonal faceted surface structure by carefully manipulating the etching rate during the water etching process. This approach allows for the creation of foam with a surface area over 13% larger than that of foams with smooth surfaces via normal acid etching, potentially enhancing efficiency in applications such as electrodes for electrochemical systems or biomedical materials where increased cell adhesion can be beneficial. This study paves the way for efficiently manipulating the LMD process to fabricate metal foams with customized compositions and enhanced surface properties.

Effects of surface anisotropy on the surface morphological response of plasma-facing tungsten

Surface free energy has been hypothesized as the cause behind the experimental evidence (Parish et al., 2014) of a strong correlation between crystallographic orientation and surface morphology changes in helium ion-irradiated tungsten at the early stages of ‘fuzz’ growth in fusion plasma-facing tungsten. Here, this hypothesis is tested through self-consistent dynamical simulation based on an atomistically informed model of surface evolution in plasma-irradiated tungsten. Low-energy helium plasma irradiation of a tungsten surface, even when the ion energy is below the sputtering threshold, generates surface vacancy-adatom pairs in addition to adatoms from the flux of self-interstitial atoms to the surface resulting from the growth of high-pressure helium bubbles. Along with the stress-driven surface morphological instability as the primary driving force, preferential diffusion of these surface adatoms modulated by the associated Ehrlich–Schwoebel (ES) barriers, combined with the surface free energy anisotropy drive the anisotropic surface nanostructure growth. Simulation results for helium irradiation on W(100) show growth of pyramidal surface features, akin to experimental observations. This work confirms the hypothesis on the effect of tungsten surface crystallographic orientation on helium-ion-induced surface morphology changes, where surface mound formation is the outcome of a stress-driven surface morphological instability, while the anisotropic growth of the mounds is controlled by the ES-barrier-modulated anisotropic surface adatom diffusion and faceting of the mounds is controlled by the surface free energy anisotropy.

Study on the Erosion Resistance of Different TiN Crystal Planes by Molecular Dynamics.

In this study, we innovatively combined the Fe-Ti-N potential function file to construct simulation models of different crystal facets of TiN/Fe ((001), (110), and (111)), which had not been previously explored. Employing molecular dynamics (MD) simulations, the research investigates the microscale differences in erosion resistance and surface properties of various TiN crystal planes under continuous impacts at varying velocities and angles. The results indicate that both surface wear and internal defects of the model increase with the impact velocity. Both TiN(110) and TiN(111) exhibit damage on their surfaces and interiors, with a larger wear range. In contrast, TiN(001), due to its superior elastic recovery capability, maintains a better surface condition, showing significantly less wear compared to TiN(110) and TiN(111). This disparity in performance among different crystal planes is attributed to variations in molecular gaps between planes, bonding points within the lattice, types of forces, and modes of action. Further research revealed that the wear volume increased with the rise in impact angle, reaching its peak at 90°. Regardless of the impact angle, TiN(001) consistently outperformed TiN(110) and TiN(111). The aim of the research is to compare the surface and internal defects of different crystal facets at the microscopic level, thereby selecting superior crystal facets and providing theoretical reference for the application of TiN materials in practical fracturing environments.

(Invited) Charge Separation and Stabilisation in Photocatalyst Materials for Solar Driven Water Splitting

In photocatalytic systems for solar energy conversion, a key challenge for efficient operation is the efficient separation and stabilisation of photogenerated charges, and thereby the minimisation of undesired recombination losses. This challenge is particularly great for photocatalytic systems because of the long charge lifetimes required to drive catalysis A further consideration is to minimise the energy losses required to drive this charge separation. My talk will cover examples of recent work from my group addressing aspects of this challenge. I will start by considering the role of polaron localisation / relaxation in driving charge separation in metal oxides, and quantification of the energetic loss associated with this polaron formation. Kinetic competion between polaron formation and ligand field state mediated charge recombination will be highlighted as the key challenge limiting the performance of many visible light absorbing metal oxides. The roles of metal oxide dielectric constant, surface facet energies, traps, ‘photocharging’ and heterojunctions in aiding charge separation in metal oxides will be discussed, drawing on examples from BiVO4 and SrTiO3. I will then go on to discuss charge separation and stabilisation in alternative photocatalyst materials, including organic semiconductor nanoparticles and metal-organic frameworks, highlighting the observation of remarkably long lived charge photogeneration in both systems and their relevance to the efficiency photocatalytic performance.

The Heterogeneity of Turn-over Number in Electrocatalysis

Chemical catalysts dominate the multi-billion global revenue of the chemical industry because they accelerate the time it takes a particular reaction to reach equilibrium without altering the equilibrium constant. Electrocatalysis can provide significant benefits compared to other methods, as it has minimal purification and separation costs, is operational at low temperatures and pressures, replaces hazardous and toxic chemical sources with electric current, and can be integrated with renewable energy sources. From a techno-economical point of view, some considerations are critical during a catalyst design: cost, activity, and durability. One useful metric to quantify catalyst durability is turn-over number (TON), which represents the maximum yield of products attainable from a catalytic center. Mathematically speaking, the TON is defined as: TON = ∫0 ∞ TOF(t) dt, where TOF is the turn-over frequency, which is the rate of turn-overs (N) per active site. Currently, without any exception, the TON is given as a fixed number describing the total amount of substrate converted until the catalysts fully degrade. Our approach studies electrocatalytic deactivation processes at the single catalyst level using a technique entitled single-entity electrochemistry for freely diffusing catalysts. The hydrogen evolution reaction (HER) is investigated with platinum nanoparticles as the model catalyst because it deactivates at the nanoscale when the catalytic activity decreases over time. At specific applied potentials, the current measured when a single platinum nanoparticle impacts the electrode creates a transient spike and decay back to the baseline current. TON is quantified by fitting the current decay response and integrating above the fit to find the charge transferred to catalyze the reaction. Our results show that electrocatalyst degradation and TON have a distribution, where some catalysts are more stable than others, and depends on the applied potential and size of the nanoparticles. In order to study how the surface facets of platinum affect the TON, SECCM was coupled with scanning electron microscopy (SEM) to compare the deactivation of a polycrystalline platinum surface in the macro scale with immobilized platinum nanoparticles on a glassy carbon surface. Combining local structural, electrochemical activity, and durability will bridge our fundamental understanding of macro and nanoscale catalyst deactivation processes to assist in the bottom-up approach of material development and design of large-scale industrial electrocatalysts.

Tailoring Co‐Free LiNi0.5Mn1.5O4 Material for High‐Voltage Lithium‐Ion Batteries: Particle Design & Grain Boundary Engineering

AbstractCobalt‐free LiNi0.5Mn1.5O4 (LNMO) is a promising cathode material for high‐energy and power‐density lithium‐ion batteries (LIBs). However, its commercial adoption is hindered by rapid capacity degradation due to the unstable LNMO/electrolyte interface caused by LNMO's high operating voltage. Structural degradation from Jahn–Teller distortion and metal‐ion dissolution also contributes to poor cycling stability. Additionally, producing industrial‐grade LNMO with high tap density, low surface area and reduced metal‐ion dissolution is challenging. This study addresses these challenges through a rational material design approach, synthesizing LNMO with large spherical secondary particles (>14.0 µm) and high tap density (>2.0 g cm−3). The primary particles (1.5–6.0 µm) exhibit a truncated‐octahedral shaped morphology that predominantly exposes (111) surface facets, with fewer (100) surfaces, stabilizing the LNMO/electrolyte interface, reducing metal dissolution, and enhancing lithium‐ion kinetics. Silicon infusion into grain boundaries further improves structural integrity by forming a silicon‐rich phase. The tailored LNMO demonstrates exceptional rate capability, cycling stability, and improved interfacial kinetics, significantly advancing the potential for cobalt‐free LNMO in high‐voltage LIBs. This work highlights the importance of tailored cathode material design for achieving the performance and stability required for emerging high‐voltage LIBs applications.

Facet-dependent electrocatalytic oxygen evolution of porous network structure Ni-Fe-O materials

Constructing unique crystal facets can increase active sites and enhance electronic structure for electrocatalysts towards the oxygen evolution reaction (OER). Here, we successfully achieved the transformation between the (311) and (222) facets of the NiFe2O4 catalysts by adjusting the ratio of Ni and Fe elements, and it was found that the activity in OER is enhanced with the exposure of (311) facet. The optimal catalyst shows a lower overpotential of 238 mV at 100 mA/cm2 current density and a small Tafel slope of 26.4 mV/dec. Furthermore, benefiting from the porous network structure, the unique super hydrophilic surface and the low-coordination Fe3+ atoms characteristic, the catalyst has an efficient mass transfer channel and fast charge transfer in the electrocatalytic OER process. More metal-O clusters were exposed on the (311) facet surface as the active site, which further improved the catalytic activity. This work presents a successful approach to creating highly active spinel catalysts through facet-engineering for electrocatalytic water splitting.

Crystal facet‐controlled CeO2 as surface decoration on nanosheet‐type SnO2 for sensing ultralow concentration gases

AbstractImproving the gas‐sensing properties of sensors is important for the detection of ultralow‐concentration gases. As sensor signals are generated from the reactions on the surface of the sensor material, improving the surface structure of the sensor material can enhance the sensing properties. In this study, nanosheet‐type tin oxide with a metastable (101) crystal facet surface was used as the gas sensor material. To enhance the sensing properties, crystal facet‐controlled cerium oxide with superior oxygen storage capacity at moderate temperatures was decorated on the surface of the nanosheet‐type tin oxide material. An investigation of the sensor properties revealed that the decorated sensor exhibited improved gas selectivity and enhanced sensitivity to all tested gases. Prior to decoration, selectivity was observed for acetone and ethanol, whereas the decorated sensor exhibited high selectivity for acetaldehyde. The limits of detection of the decorated sensors were 245, 459, and 934 ppt for acetone, ethanol, and acetaldehyde, respectively. Thus, the proposed material can effectively enhance the sensing of extremely low‐concentration gases.

Effect of humidity interference on NO2 gas sensing of In2O3 nanoneedles at moderate operating temperature

This study employs both experimental and computational methodologies to examine the gas-sensing performance of needle-like In2O3 nanosensors towards a model NO2 gas in dry (10 % RH) and wet (99 % RH) environments. The single crystalline nanoneedles exhibit distinct surface facets, primarily (110) or (111) crystalline planes, spanning a wide aspect-ratio range of 3.9–7.0. At a relatively low operating temperature of 50 °C and NO2 gas concentration of 10 ppm, the experimental assessment yields sensing-response ratios (i.e., Swet/Sdry) of 0.19 ± 0.18 and 0.23 ± 0.07 for In2O3 nanoneedles featuring (110) and (111) surfaces, respectively. Notably, density-functional theory computations reveal that the adsorption energies of NO2 molecules on both In2O3 (110) and (111) surfaces significantly weaken under moist conditions. A relatively stronger adsorption affinity is observed on the (110) surface than the (111) counterpart. Our calculated electronic band structures reveal conspicuous changes in conductivity upon the adsorption of NO2 and water vapor on the In2O3 surfaces. The observed variations in conductivity, in conjunction with the adsorption-energy calculations, offer valuable insights into the structural mechanisms underlying the experimentally observed sensing-response alterations in humid environments.

Benchmarking of machine learning interatomic potentials for reactive hydrogen dynamics at metal surfaces

Simulations of chemical reaction probabilities in gas surface dynamics require the calculation of ensemble averages over many tens of thousands of reaction events to predict dynamical observables that can be compared to experiments. At the same time, the energy landscapes need to be accurately mapped, as small errors in barriers can lead to large deviations in reaction probabilities. This brings a particularly interesting challenge for machine learning interatomic potentials, which are becoming well-established tools to accelerate molecular dynamics simulations. We compare state-of-the-art machine learning interatomic potentials with a particular focus on their inference performance on CPUs and suitability for high throughput simulation of reactive chemistry at surfaces. The considered models include polarizable atom interaction neural networks (PaiNN), recursively embedded atom neural networks (REANN), the MACE equivariant graph neural network, and atomic cluster expansion potentials (ACE). The models are applied to a dataset on reactive molecular hydrogen scattering on low-index surface facets of copper. All models are assessed for their accuracy, time-to-solution, and ability to simulate reactive sticking probabilities as a function of the rovibrational initial state and kinetic incidence energy of the molecule. REANN and MACE models provide the best balance between accuracy and time-to-solution and can be considered the current state-of-the-art in gas-surface dynamics. PaiNN models require many features for the best accuracy, which causes significant losses in computational efficiency. ACE models provide the fastest time-to-solution, however, models trained on the existing dataset were not able to achieve sufficiently accurate predictions in all cases.