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DOE OSTI2025

Thermostable Enzyme Variants in the Lower Mevalonate Pathway Improve Isoprenoid Production by Cell-Free Biocatalysis

Cell-free biocatalysis is a rapidly evolving field with great potential for sustainably producing valuable chemicals. Some challenges in cell-free biocatalysis include reaction longevity, enzyme stability, and the cost of the biocatalysts. Here, the challenge of enzyme instability was addressed by employing thermophilic enzymes to improve the productivity of the lower mevalonate pathway, using limonene as an example isoprenoid product. The Classical mesophilic mevalonate pathway was compared to a newly assembled set of thermophilic enzymes comprising the Archaea I mevalonate pathway. The thermophilic pathway enzymes were thermostable to at least 60 °C and exhibited a 6× longer operating lifetime at 22 °C. Thus, despite lower initial activity rates at ambient temperature, the thermophilic pathway was longer-lived and resulted in a more productive cell-free reaction overall, achieving 1.7× higher yield of limonene compared to using enzymes from mesophiles. Moreover, the thermostable pathway retained activity for longer with the challenge of solvent exposure, namely, ethanol and isoprenol, which broadens the scope of accessible substrates and/or products in cell-free reactions employing this pathway. Altogether, we showed significant improvement in the stability and productivity of the lower mevalonate pathway, which will enable more efficient cell-free biosynthesis of isoprenoid products. This represents a valuable strategy to increase the robustness of cell-free systems by carefully sourcing biocatalysts from thermophilic organisms, which have proven to be resilient to challenges unique to cell-free reaction systems.

09 BIOMASS FUELS↗

DOE OSTI2026

Impact of Anode to Cathode Crossover in Lithium‐metal Batteries With High‐Nickel Cathodes

The advancement of high-energy-density lithium-metal batteries (LMBs) is hindered by the chemical instability of both lithium-metal anode and high-nickel layered oxide cathodes. While cathode-to-anode crossover is well-documented, the reverse process of anode-to-cathode crossover remains underexplored. Here, we systematically investigate such crossovers and the degradation pathway in pouch cells with a localized high-concentration electrolyte, comparing NMC622, NMC811, and NMC90 cathodes paired with lithium-metal and graphite anodes. Despite delivering higher initial capacities, LMBs exhibit faster capacity fade under long-term cycling at 45 °C. To isolate cathode-side degradation, galvanostatic electrochemical impedance spectroscopy (GEIS) measurements of cycled cathodes paired with delithiated lithium iron phosphate (LFP) counter electrodes reveal significantly higher charge-transfer resistance in cathodes cycled with lithium-metal. Surface characterization via X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) reveals greater electrolyte decomposition on cathodes cycled with lithium metal, leading to thicker, more organic-rich cathode–electrolyte interphases (CEIs), consistent with the elevated charge-transfer resistance observed in GEIS measurements. Notably, NMC90 shows the most pronounced CEI thickening, linking higher cathode surface reactivity to greater susceptibility to anode-to-cathode crossover. This work presents compelling evidence of crosstalk degradation originating from lithium-metal anodes and underscores the importance of cross-interface stability for the design of durable LMBs.

25 ENERGY STORAGE↗

DOE OSTI2020

Electrochemical Reduction Selectivity of Crotonaldehyde on Copper

Lignocellulosic waste is a potential feedstock for the generation of fuels and commodity chemicals, but existing conversion methods are too cost-intensive to be viable long-term solutions. Electrochemical reductions are promising for decentralized biomass valorization due to their modular scaling and capacity to run intermittently and without high temperatures or pressures. Using crotonaldehyde as a multi-functional model compound for the many partially unsaturated oxygenates found in processed biomass, we here demonstrate the production of butanal, butanol, butene, and butane (variously useful as commodity chemicals and major components of liquified petroleum gas) under ambient conditions by reductive bulk electrolysis with a copper mesh working electrode. We identify an optimum potential for reduced organic production under the reaction conditions and compare product distributions from reductions of intermediate species to further propose branching reaction pathways. Though butanal is typically the most abundant product from crotonaldehyde reduction, most of the butene and butane appear to result from a pathway involving initial reduction of the aldehyde group. We discuss evidence that selectivity is driven by interplay between crotonaldehyde reduction, local pH shifts due to the hydrogen evolution reaction, and changes in site reactivity and availability due to electrode fouling. This demonstration of model electrochemical biomass valorization also serves to inform further exploration into reduction of multi-functional molecules and electrochemical biomass processing in general.

biomass↗

DOE OSTI2022

Morphological and crystallographic controls in the replacement of calcite and aragonite by cerussite and otavite

Mineral replacement reactions are essential solid-fluid interactions in natural and industrial processes including metasomatism, diagenesis, and metamorphism, and sequestration of metal toxins from polluted water. In this paper, we explore the morphological evolution of aragonite and calcite (polymorphs of CaCO 3 ) during their replacement by cerussite (PbCO 3 , an isomorph of aragonite) and otavite (CdCO 3 , an isomorph of calcite) in acidic aqueous solutions (with initial pH 3 to 4). Observations using scanning electron and synchrotron-based transmission X-ray microscopies reveal the formation of pseudomorphic shells (~5 to 10 µm thick) of cerussite and otavite when Pb 2+ is reacted with either calcite or aragonite and when Cd 2+ is reacted with aragonite. The formation of pore space at the substrate-precipitate interface and within the precipitate is found to be key in promoting chemical exchange between the dissolving phase and the solution. In contrast, minimal reactivity is observed when Cd 2+ is reacted with calcite. These results demonstrate that the lack of substrate-precipitate epitaxy (either because of inconsistent symmetries or due to large lattice constant mismatch) is a critical factor that enables replacement of primary CaCO 3 minerals by Pb- or Cd-bearing secondary minerals while the presence of epitaxial relationships inhibit those reactions. When calcite and aragonite coexist, the replacement of aragonite by cerussite and otavite occurs preferentially over calcite. We postulate that the relative reactivity of calcite and aragonite to Pb 2+ and Cd 2+ can be determined by interplay between morphological and crystallographic properties of CaCO 3 materials as well as solution chemistry. Our results demonstrate that coupled dissolution-precipitation processes of carbonate minerals play an important role in controlling mobility and bioavailability of lead and cadmium in environments where acidic metal-contaminated water interacts with carbonate-rich rocks and soils.

58 GEOSCIENCES↗

DOE OSTI2025

Excited State Covalency, Dynamics, and Photochemistry of Square Planar Ni-Thiolate Complexes Revealed by Ultrafast X-ray Absorption

Highly covalent Ni bis(dithiolene) and related complexes provide an ideal platform for investigating the effects of metal–ligand orbital hybridization on excited state character and dynamics. In particular, we focus on the ligand field excited states that dominate the photophysics of first-row transition metal complexes. Here, we investigate if they can be significantly delocalized off the metal center, possibly yielding photochemical reactivity more similar to charge transfer excited states than metal-centered ligand field excited states. Here [Ni(mpo) 2 ] (mpo = 2-mercaptopyridine- N-oxide) provides a representative example for the larger chemical class and is an active electro- and photo-catalyst for proton reduction. A detailed characterization of the excited state electronic structure, dynamics, and photochemistry of [Ni(mpo) 2 ] is presented based on ultrafast transient X- ray absorption spectroscopy at the Ni and S 1s core absorption K-edges. By comparing the ultrafast Ni K-edge absorption to ab initio calculations, we identify an excited state relaxation mechanism where an initial ligand-to-metal charge transfer excitation results in both excited state electron transfer (generating a catalytically relevant reduced photoproduct [Ni(mpo) 2 ] − ) and relaxation to a pseudo-tetrahedral triplet ligand field excited state. From the ultrafast S K-edge absorption, the ligand field excited state is found to be highly delocalized onto the thiolate ligands and a tetrahedral structural distortion is shown to substantially influence the degree of delocalization. The results identify a significant structural coordinate to target when aiming to control the excited state covalency in square planar complexes.

Lim, Hyeongtaek [SLAC National Accelerator Laborat↗

DOE OSTI2024

Compositional and temporal division of labor modulates mixed sugar fermentation by an engineered yeast consortium

Abstract Synthetic microbial communities have emerged as an attractive route for chemical bioprocessing. They are argued to be superior to single strains through microbial division of labor (DOL), but the exact mechanism by which DOL confers advantages remains unclear. Here, we utilize a synthetic Saccharomyces cerevisiae consortium along with mathematical modeling to achieve tunable mixed sugar fermentation to overcome the limitations of single-strain fermentation. The consortium involves two strains with each specializing in glucose or xylose utilization for ethanol production. By controlling initial community composition, DOL allows fine tuning of fermentation dynamics and product generation. By altering inoculation delay, DOL provides additional programmability to parallelly regulate fermentation characteristics and product yield. Mathematical models capture observed experimental findings and further offer guidance for subsequent fermentation optimization. This study demonstrates the functional potential of DOL in bioprocessing and provides insight into the rational design of engineered ecosystems for various applications.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2022

Model study of the energy dependence of the correlation between anisotropic flow and the mean transverse momentum in Au + Au collisions

A hybrid model that employs the hadron-string transport model UrQMD and the (3+1)-dimensional relativistic viscous hydrodynamic code vHLLE, is used to investigate the beam energy dependence of the correlation coefficient ρ(v$^{2}_{2}$,[p T ]) between the average transverse momentum [p T ] of hadrons emitted in an event and the square of the anisotropic flow coefficient v$^{2}_{2}$. For Au+Au collisions, the model predicts characteristic patterns for the energy and event-shape dependence of the variances for [p T ] and v$^{2}_{n}$ [Var([p T ] and Var(v$^{2}_{2}$)], and the covariance of v$^{2}_{n}$ and [p T ][cov(v$^{2}_{2}$,[p T ])], consistent with the attenuation effects of the specific shear viscosity η/s. Here in contrast, ρ(v$^{2}_{2}$,[p T ]) is predicted to be insensitive to the beam energy but sensitive to the initial-state geometry of the collisions. These observations suggest that a precise set of measurements for Var([p T ]), Var(v$^{2}_{2}$), cov(v$^{2}_{2}$,[p T ]) and ρ(v$^{2}_{2}$,[p T ]) as a function of beam energy and event shape, could serve to constrain better the eccentricities and their fluctuations over the entire span of beam energies, and consequently aid precision extraction of the temperature and baryon chemical-potential dependence of η/s from the wealth of Au+Au data obtained in the RHIC beam energy scan.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2023

Chemical significance of x-ray photoelectron spectroscopy binding energy shifts: A Perspective

The principal intent of this Perspective is to review the mechanisms that are responsible for the shifts of binding energies, ΔBE, observed in x-ray photoelectron spectroscopy (XPS) measurements and so to relate the shifts to the electronic structure and the chemical bonding in the systems studied. To achieve this goal, several theoretical considerations are necessary beyond just the calculation of XPS BEs. Though briefly discussed here, we are not primarily interested in absolute values of BE or quantitation using relative intensities. Within the molecular orbital (MO) theory framework, it is shown that the analysis of orbital properties is critical for the correct interpretation of XPS. In particular, rigorous definitions are given for the initial state and final state contributions to BEs and to BE shifts, ΔBE. It is first shown how the BEs of core levels are related to the electronic structure by consideration of the BEs for a model atomic system to establish the origins and magnitudes of BE shifts. The mechanisms established for the model system are then applied to a review of XPS measurements and MO theory on a set of real examples. An important focus of the paper is to demonstrate that, in many cases, initial state mechanisms allow for a definitive interpretation of the XPS BE shifts and that an important role of theory is to provide qualitative explanations rather than quantitative agreement with XPS measurements. The mechanisms established are a guide to the interpretation of XPS measurements and consideration of these mechanisms may suggest additional calculations that would be useful. It is concluded that there is still a bright future for the coupling of ab initio MO theory with XPS measurements.

Materials Science↗

DOE OSTI2021

Computational Investigation of the Catalytic Hydrodeoxygenation of Propanoic Acid over a Cu(111) Surface

Cu-based alloy catalysts have recently been investigated experimentally for the hydrodeoxygenation (HDO) of biomass-derived organic acids. Here, the HDO of propanoic acid (PAc) has been studied over Cu(111) by mean-field microkinetic modeling based on parameters obtained from first-principles calculations. Models were developed for the gas- and liquid-phase HDO in condensed water and 1,4-dioxane. In agreement with experimental observations, the gas-phase PAc conversion rate is low at 573 K and increases in liquid water by 1 order of magnitude. In all reaction environments, the decarboxylation mechanism is dominant at low hydrogen partial pressures less than 0.1 bar, and the C–COO bond dissociation is the rate-controlling elementary step. This observation contrasts with the rate-controlling step identified over most group VIII metal surfaces, which is the C–OH bond dissociation in the decarbonylation mechanism. At high hydrogen (H 2 ) partial pressures greater than 10 bar, the HDO of PAc produces propionaldehyde that can readsorb and further react through decarbonylation to produce C 2 alkane products, which is conceptually different from the low H 2 partial pressure scenario. At high H 2 partial pressures, the initial hydrogenation at the carbonyl carbon of PAc becomes the rate-controlling elementary step.

Catalysts↗

DOE OSTI2020

Predicting 3D moisture sorption behavior of materials from 1D investigations

Abstract Moisture in materials can be a source of future outgassing and exacerbate unwanted changes in physical and chemical properties. Here, we investigate the effect of sample size and shape on the moisture transport phenomena through a combined experimental and modeling approach. Several different materials varying in size and shape were investigated over a wide range of relative humidities (0–90%) and temperatures ( $$30{-}70^{\,\circ } \hbox {C}$$ 30 - 70 ∘ C ) using gravimetric type dynamic vapor sorption (DVS). A dynamic triple-mode sorption model, developed previously, was employed to describe the experimental results with good success; the model includes absorption, adsorption, pooling (clustering) of species, and molecular diffusion. Here we show that the full triple-mode sorption model is robust enough to predict the dynamic uptake and outgassing of 3-dimensional (3D) samples using parameters derived from quasi-1D samples. This successful demonstration on three different materials (filled polydimethylsiloxane (PDMS), unfilled PDMS, and ceramic inorganic composite) illustrates that the model is robust at describing the scale-independent physics and chemistry of moisture sorption and diffusion materials. This work demonstrates that while sorption mechanisms manifest in testing of all sample sizes, some of these mechanisms were so subtle that they were overlooked in our initial modeling and assessment, illustrating the importance of multi-scale experiments in the development of robust predictive capabilities. Our study also outlines the challenges and viable solutions for global optimization of a multi-parameter model. The ability to quantify moisture sorption and diffusion, independent of scale, using 1D lab-scale experiments enables prediction of long-term bulk materials behavior in real applications.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Preliminary results of neutron and X-ray diffraction data collection on a lytic polysaccharide monooxygenase under reduced and acidic conditions

Lytic polysaccharide monooxygenases (LPMOs) are copper-center enzymes that are involved in the oxidative cleavage of the glycosidic bond in crystalline cellulose and other polysaccharides. The LPMO reaction is initiated by the addition of a reductant and oxygen to ultimately form an unknown activated copper–oxygen species that is responsible for polysaccharide-substrate H-atom abstraction. Given the sensitivity of metalloproteins to radiation damage, neutron protein crystallography provides a nondestructive technique for structural characterization while also informing on the positions of H atoms. Neutron cryo-crystallography permits the trapping of catalytic intermediates, thereby providing insight into the protonation states and chemical nature of otherwise short-lived species in the reaction mechanism. Here, to characterize the reaction-mechanism intermediates of LPMO9D from Neurospora crassa, a cryo-neutron diffraction data set was collected from an ascorbate-reduced crystal. A second neutron diffraction data set was collected at room temperature from an LPMO9D crystal exposed to low-pH conditions to probe the protonation states of ionizable groups involved in catalysis under acidic conditions.

Neurospora crassa↗

DOE OSTI2023

Long-Term Stability of Ferri-/Ferrocyanide as an Electroactive Component for Redox Flow Battery Applications: On the Origin of Apparent Capacity Fade

We assess the suitability of potassium ferri-/ferrocyanide as an electroactive species for long-term utilization in aqueous organic redox flow batteries. A series of electrochemical and chemical characterization experiments was performed to distinguish between structural decomposition and apparent capacity fade of ferri-/ferrocyanide solutions used in the capacity-limiting side of a flow battery. Our results indicate that, in contrast with previous reports, no structural decomposition of ferri-/ferrocyanide occurs at tested pH values as high as 14 in the dark or in diffuse indoor light. Instead, an apparent capacity fade takes place due to a chemical reduction of ferricyanide to ferrocyanide, via chemical oxygen evolution reaction. We find that this parasitic process can be further exacerbated by carbon electrodes, with apparent capacity fade rates at pH 14 increasing with an increased ratio of carbon electrode surface area to ferricyanide in solution. Based on these results, we report a set of operating conditions that enables the long-duration cycling of alkaline ferri-/ferrocyanide electrolytes and demonstrate how apparent capacity fade rates can be engineered by the initial system setup. If protected from direct exposure to light, the structural stability of ferri-/ferrocyanide anions allows for their practical deployment as electroactive species in long duration energy storage applications.

25 ENERGY STORAGE↗

DOE OSTI2024

Strategies to overcome electron-beam issues in liquid phase TEM: Study of chemical processes

Abstract Liquid phase (or liquid cell) transmission electron microscopy (TEM) has become a powerful platform for in situ investigation of various chemical processes at the nanometer or atomic level. The electron beam for imaging can also induce perturbation to the chemical processes. Thus, it has been a concern that the observed phenomena in a liquid cell could deviate from the real-world processes. Strategies have been developed to overcome the electron-beam-induced issues. This article provides an overview of the electron-beam effects, and discusses various strategies in liquid cell TEM study of nucleation, growth, and self-assembly of nanoscale materials, where an electron beam is often used to initiate the reactions, and highly electron-beam-sensitive electrochemical reactions. Graphical abstract

Zheng, Wenjing↗

DOE OSTI2023

Bottom-up synthesis of mesoscale nanomeshes of graphene nanoribbons on germanium

The synthesis of functional graphene nanostructures on Ge(001) provides an attractive route toward integrating graphene-based electronic devices onto complementary metal oxide semiconductor-compatible platforms. In this study, we leverage the phenomenon of the anisotropic growth of graphene nanoribbons from rationally placed graphene nanoseeds and their rotational self-alignment during chemical vapor deposition to synthesize mesoscale graphene nanomeshes over areas spanning several hundred square micrometers. Lithographically patterned nanoseeds are defined on a Ge(001) surface at pitches ranging from 50 to 100 nm, which serve as starting sites for subsequent nanoribbon growth. Rotational self-alignment of the nanoseeds followed by anisotropic growth kinetics causes the resulting nanoribbons to be oriented along each of the equivalent, orthogonal Ge < 110 > directions with equal probability. As the nanoribbons grow, they fuse, creating a continuous nanomesh. In contrast to nanomesh synthesis via top-down approaches, this technique yields nanomeshes with atomically faceted edges and covalently bonded junctions, which are important for maximizing charge transport properties. Additionally, we simulate the electrical characteristics of nanomeshes synthesized from different initial nanoseed-sizes, size-polydispersities, pitches, and device channel lengths to identify a parameter-space for acceptable on/off ratios and on-conductance in semiconductor electronics. The simulations show that decreasing seed diameter and pitch are critical to increasing nanomesh on/off ratio and on-conductance, respectively. With further refinements in lithography, nanomeshes obtained via seeded synthesis and anisotropic growth are likely to have superior electronic properties with tremendous potential in a multitude of applications, such as radio frequency communications, sensing, thin-film electronics, and plasmonics.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2022

Effect of oxidative breakers on organic matter degradation, contaminant mobility and critical mineral release during shale-fracturing fluid interactions in the Marcellus Shale

Oil and gas production from organic-rich shale formations has become viable through advancements in multistage hydraulic fracturing. However, fluctuations in oil and gas prices, coupled with the sharp decline in gas production after the initial days of fracturing operations, drive operators to devise strategies for enhancing hydrocarbon production. The use of highly reactive fracturing fluids that include strong oxidizing agents, also known as breakers, can potentially increase well productivity. The oxidative breakers are used to reduce the viscosity of gel-based fluids after the proppant is transported into fracture zones of the target formation. These breakers can also degrade the organic matter, enhancing the release of hydrocarbons. However, chemical byproducts generated by the interaction of oxidative breakers with the shale matrix have not been extensively studied. Here, this study investigated the fluid-rock interactions between Marcellus Shale and synthetic hydraulic fracturing fluid (HFF) solutions comprising three different oxidative breakers, i.e., ammonium persulfate, sodium bromate, and sodium hypochlorite, commonly used in the Appalachian Basin, USA. Our results demonstrate that the type of oxidizing breakers used in the HFF controlled the type and amount of volatile organic compounds (VOCs) and semi-volatile organic compounds (SVOCs) produced. In all HFF reacted effluents, we observed the transformation of VOCs and the presence of organic acids in variable amounts. However, effluents from HFF containing sodium bromate and sodium hypochlorite breakers showed the presence of several halogenated organic compounds. Changes in major ions and mineralogy indicate that carbonate dissolution and barite precipitation were ubiquitous in all shale reacted effluents. Our results also demonstrate that the addition of oxidative breakers increased the concentration of several major and trace elements in the effluents. These elements fall under the critical mineral (CM) or critical element category due to their high demand in emerging technologies and susceptibility to supply chain disruption due to variety of factors. However, before oxidative breakers can be used at a larger field scale to enhance the release and recovery of CM and hydrocarbons, a better understanding is required of the potential environmental impacts associated with the generation and transformation of contaminants during breaker-fluid-rock interaction.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

PGM-Free Oxygen-Reduction Catalyst Development for Proton-Exchange Membrane Fuel Cells: Challenges, Solutions, and Promises

Proton-exchange membrane fuel cells (PEMFCs) are efficient and clean hydrogen energy technologies for transportation and stationary applications. Highly active and durable low-cost cathode catalysts for the oxygen-reduction reaction (ORR) under challenging acidic environments are desperately needed to address the cost and durability issues of PEMFCs. The most promising platinum group metal (PGM)-free catalysts for the ORR in acidic media are atomically dispersed and nitrogen-coordinated metal site catalysts denoted as M–N–C, M = Fe, Co, or Mn. Due to significant efforts in the past few decades, these catalysts have demonstrated much-improved ORR activity and promising initial fuel cell performance approaching traditional Pt/C catalysts. However, the insufficient long-term stability (up to 5000 h) under PEMFC operation represents a primary technical barrier to making current PGM-free catalysts less viable yet in PEMFCs. In this Account, we highlight recent advances in synthesizing efficient PGM-free catalysts for the ORR in PEMFCs, emphasizing effective strategies to improve mass and intrinsic activity and the possible degradation mechanisms. In particular, a chemical doping method based on the zeolitic imidazolate framework (ZIF)-8 represents the key to developing efficient M–N–C catalysts containing atomically dispersed and nitrogen-coordinated single metal active sites (i.e., MN 4 ). The newly acquired understanding of the formation mechanism of MN 4 active sites during the thermal activation and its correlation to catalytic properties guide the rational catalyst design rather than relying on current trial-and-error approaches. Considerable efforts have further been invested in increasing the active site density and enhancing intrinsic activity by regulating carbon-phase structures and the local coordination environment. Furthermore, these highly active catalysts usually suffer from significant activity loss during the ORR. Therefore, breaking the activity–stability trade-off is the key to simultaneously achieving activity and stability in one catalyst, which is discussed on the basis of our recent successes in regulating local carbon structures surrounding active single metal sites. Significant research efforts toward understanding the degradation mechanisms and improving the lifetime of PGM-free catalysts are still crucial for viable applications in the future. Novel electrode designing strategies are needed to translate the PGM-free catalysts’ ORR activity to solid-state electrolyte-based membrane electrode assemblies (MEAs) with robust three-phase (i.e., gas–liquid–solid) interfaces for efficient charge and mass transports for performance improvement. On the basis of our effort at the University at Buffalo supported by ElectroCat Consortium associated with U.S. DOE’s Hydrogen and Fuel Cell Technologies Office, we provide a perspective on PGM-free cathode catalysts concerning remaining bottlenecks and future opportunities, aiming to inspire the community in both mechanistic understanding and technological development.

08 HYDROGEN↗

DOE OSTI2025

Mechanism of Mesoscale Woodpile Development via Photoelectrochemical Deposition of Se–Te

A combination of experiments and optical modeling provided insight into the mechanism of mesoscale woodpile formation in response to an orthogonal shift in polarization during photoelectrochemical deposition of Se–Te. Cathodic deposition of semiconducting Se–Te using spatially uniform, linearly polarized illumination produced arrays of lamellae that were aligned parallel to the optical E-field oscillation. Continued deposition in conjunction with an orthogonal shift in the polarization direction then produced aligned bridging features that spanned the void space between, and were orthogonal to, the preexisting lamellae. The height and pitch, respectively, in each layer of the woodpile were a function of the charge density and illumination wavelength during deposition. A Monte Carlo model, in which material addition was scaled by the absorption magnitude obtained from electromagnetic simulations, produced morphologies that were nominally identical to those observed experimentally. Here, the formation of mesoscale woodpiles is consistent with a mechanism that involves a series of spontaneously initiated, concerted light–matter interactions during the photoelectrochemical deposition process.

absorption↗

DOE OSTI2025

Effects of Temperature Fluctuations on Surface Mobility of Atomic Steps and Oxidation Dynamics in High-Temperature Alloys

In contrast to the traditional perspective that thermal fluctuations are insignificant in surface dynamics, here we report their influence on surface reaction dynamics. Using real-time low-energy electron microscopy imaging of NiAl(100) under both vacuum and O 2 atmospheres, we demonstrate that transient temperature variations substantially alter the direction of atom diffusion between the surface and bulk, leading to markedly different oxidation outcomes. During heating, substantial outward diffusion of atoms from the bulk to the surface results in step growth. Conversely, cooling induces considerable inward diffusion of adatoms, producing a distinct oxide morphology. In both scenarios, initially formed oxide islands impede local atomic step mobility, thereby increasing step length due to mass transfer between the surface and bulk, with atomic steps acting as adatom sinks during heating and sources during cooling. Furthermore, we show that this pinning effect on atomic step mobility can be mitigated by applying persistent temperature fluctuations. As a result, understanding these nuances is vital for accurately predicting and dynamically manipulating the performance of active materials in various chemical processes under transient thermal conditions.

36 MATERIALS SCIENCE↗