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At least 181 records · Page 10

Revealing Local Structures through Machine-Learning-Fused Multimodal Spectroscopy

Atomistic structures of materials offer valuable insights into their functionality. Determining these structures remains a fundamental challenge in materials science, especially for systems with defects. While both experimental and computational methods exist, each has limitations in resolving nanoscale structures. Core-level spectroscopies, such as X-ray absorption (XAS) or electron energy-loss spectroscopies (EELS), have been used to determine the local bonding environment and structure of materials. Recently, machine learning (ML) methods have been applied to extract structural and bonding information from XAS/EELS data. However, frameworks relying solely on a single data stream, defined as characterization data derived from a single element using one technique, are often insufficient because multiple local environments can yield similar spectral features, making it challenging to differentiate between competing structural hypotheses. Here, in this work, we address this challenge by integrating multimodal ab initio simulations, experimental data acquisition, and ML techniques for structure characterization. Our goal is to determine local structures and properties using EELS and XAS data from multiple elements and edges. To showcase our approach, we use various lithium nickel manganese cobalt (NMC) oxide compounds which are used for lithium ion batteries, including those with oxygen vacancies and antisite defects, as the sample material system. We successfully inferred local element content, ranging from lithium to transition metals, with quantitative agreement with experimental data. Beyond local element inference, we find that ML model based on multimodal spectroscopic data is able to determine whether local defects such as oxygen vacancy and antisites are present, a task which is impossible for single mode spectra or other experimental techniques. Furthermore, our framework is able to provide physical interpretability, bridging spectroscopy with the local atomic and electronic structures.

battery↗

Thermal Hydroquinone Oxidation on Co/N-doped Carbon Proceeds by a Band-Mediated Electrochemical Mechanism

Molecules catalyze aerobic oxidation reactions via redox cycling at the metal center to effect sequential activation of O 2 and the substrate. Metal surfaces can catalyze the same transformations by coupling independent half-reactions for oxygen reduction and substrate oxidation mediated via the exchange of band-electrons. Metal/nitrogen-doped carbons (MNCs) are promising catalysts for aerobic oxidation that consist of molecule-like active sites embedded in a conductive carbon host. Owing to their combining molecular and metallic features, it remains unclear whether they proceed via the sequential redox cycling pathways of molecules or the band-mediated pathways of metals. Herein, we simultaneously track the potential of the catalyst and the rate of the turnover of aerobic hydroquinone oxidation on a cobalt-based MNC catalyst contacted to a catalytically inactive carbon electrode. By comparing operando measurements of rate and potential with the current-voltage behavior of each constituent half-reaction under identical conditions, we show that these molecular materials can display the band-mediated reaction mechanisms of extended metallic solids. Further, we show that the action of these band-mediated mechanisms explains fractional reaction orders in both oxygen and hydroquinone, the time evolution of catalyst potential and rate, and the dependence of rate on overall reaction free energy. Selective poisoning experiments suggest that oxygen reduction proceeds at cobalt sites, whereas quinone oxidation proceeds at native oxidic defects on the carbon. These findings highlight that molecule-like active sites can take advantage of band-mediated mechanisms when coupled to conductive hosts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electronic parameters in cobalt-based perovskite-type oxides as descriptors for chemocatalytic reactions

Perovskite-type transition metal (TM) oxides are effective catalysts in oxidation and decomposition reactions. Yet, the effect of compositional variation on catalytic efficacy is not well understood. The present analysis of electronic characteristics of B-site substituted LaCoO3 derivatives via in situ X-ray absorption spectroscopy (XAS) establishes correlations of electronic parameters with reaction rates: TM t2g and eg orbital occupancy yield volcano-type or non-linear correlations with NO oxidation, CO oxidation and N2O decomposition rates. Covalent O 2p-TM 3d interaction, in ultra-high vacuum, is a linear descriptor for reaction rates in NO oxidation and CO oxidation, and for N2O decomposition rates in O2 presence. Covalency crucially determines the ability of the catalytically active sites to interact with surface species during the kinetically relevant step of the reaction. The nature of the kinetically relevant step and of surface species involved lead to the vast effect of XAS measurement conditions on the validity of correlations.

Science & Technology - Other Topics↗

Balancing elementary steps enables coke-free dry reforming of methane

Balancing kinetics, a crucial priority in catalysis, is frequently achieved by sacrificing activity of elementary steps to suppress side reactions and enhance catalyst stability. Dry reforming of methane (DRM), a process operated at high temperature, usually involves fast C-H activation but sluggish carbon removal, resulting in coke deposition and catalyst deactivation. Studies focused solely on catalyst innovation are insufficient in addressing coke formation efficiently. Herein, we develop coke-free catalysts that balance kinetics of elementary steps for overall thermodynamics optimization. Beginning from a highly active cobalt aluminum oxide (CoAl 2 O 4 ) catalyst that is susceptible to severe coke formation, we substitute aluminum (Al) with gallium (Ga), reporting a CoAl 0.5 Ga 1.5 O 4 -R catalyst that performs DRM stably over 1000 hours without observable coke deposition. We find that Ga enhances DRM stability by suppressing C-H activation to balance carbon removal. A series of coke-free DRM catalysts are developed herein by partially substituting Al from CoAl 2 O 4 with other metals.

36 MATERIALS SCIENCE↗

Axon-like active signal transmission

Any electrical signal propagating in a metallic conductor loses amplitude due to the natural resistance of the metal. Compensating for such losses presently requires repeatedly breaking the conductor and interposing amplifiers that consume and regenerate the signal. This century-old primitive severely constrains the design and performance of modern interconnect-dense chips. Here we present a fundamentally different primitive based on semi-stable edge of chaos (EOC), a long-theorized but experimentally elusive regime that underlies active (self-amplifying) transmission in biological axons. By electrically accessing the spin crossover in LaCoO 3 , we isolate semi-stable EOC, characterized by small-signal negative resistance and amplification of perturbations. In a metallic line atop a medium biased at EOC, a signal input at one end exits the other end amplified, without passing through a separate amplifying component. While superficially resembling superconductivity, active transmission offers controllably amplified time-varying small-signal propagation at normal temperature and pressure, but requires an electrically energized EOC medium. Operando thermal mapping reveals the mechanism of amplification—bias energy of the EOC medium, instead of fully dissipating as heat, is partly used to amplify signals in the metallic line, thereby enabling spatially continuous active transmission, which could transform the design and performance of complex electronic chips.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Electronic properties of single-layer CoO 2 /Au(111)

Here we report direct measurements via angle-resolved photoemission spectroscopy (ARPES) of the electronic dispersion of single-layer (SL) CoO 2 . The Fermi contour consists of a large hole pocket centered at the $\overline{\Gamma}$ point. To interpret the ARPES results, we use density functional theory (DFT) in combination with the multi-orbital Gutzwiller Approximation (DFT+GA), basing our calculations on crystalline structure parameters derived from x-ray photoelectron diffraction and low-energy electron diffraction. Our calculations are in good agreement with the measured dispersion. We conclude that the material is a moderately correlated metal. We also discuss substrate effects, and the influence of hydroxylation on the CoO 2 SL electronic structure.

36 MATERIALS SCIENCE↗

Controlled synthesis and ordered assembly of Co 3 O 4 nanowires using genetically engineered bacterial flagella as biotemplates (Final Technical Report)

The major goals of the project are to gain a fundamental understanding on the influence of the displayed peptides and other processing parameters on the flagella assembly and the resulting biomimetic control over the synthesis and assembly of Co 3 O 4 nanoparticles (NPs) and nanowires (NWs). To pursue these goals, we designed two specific aims: Aim 1: Understanding the self-assembly of genetically engineered flagella and its outcome for site-specific nucleation and growth of Co 3 O 4 NPs and NWs. Aim 2: Understanding controllable alignment of 1D Co 3 O 4 -flagella NWs into highly ordered 2D and 3D structures.

59 BASIC BIOLOGICAL SCIENCES↗

Task 12 PV Sustainability - Environmental Life Cycle Assessment of Residential PV and Battery Storage Systems

Using a life cycle assessment (LCA), the environmental impacts from generating 1 kWh of electricity for self-consumption via a photovoltaic-battery system are determined. The system includes a 10 kWp multicrystalline-silicon photovoltaic (PV) system (solar irradiation about 1350 kWh/m2/year and annual yield 1000 kWh/kWp), an iron phosphate lithium-ion (LiFePO4) battery, and other components such as the control system, battery housing, and two inverters (one for the PV system and one for the battery system). Three options for the AC-coupled system with changing battery capacities (5, 10, or 20 kWh nominal capacity) are investigated. The environmental impacts are assessed using the indicators greenhouse gas emissions and cumulative energy demand (separated into total and non-renewable cumulative energy demand). In addition, the four most important impact categories for PV electricity - respiratory inorganics (particulate matter), acidification, energy carrier resource use, and minerals and metals resource use - are assessed according to the environmental footprint (EF) method. Data are drawn from the DETEC data DQRv2:2018, recent literature, and product details provided by manufacturers. The results show larger environmental impacts of PV-battery systems with increasing battery capacity; for capacities of 5, 10, and 20 kWh, the cumulative greenhouse gas emissions from 1 kWh of electricity generation for self-consumption via a PV-battery system are 80, 84, and 88 g CO 2- eq/kWh, respectively. The cumulative greenhouse gas emissions of PV electricity consumed directly or fed into the grid are 54 g CO 2 -eq/kWh. The corresponding total cumulative energy demands are 5.27, 5.40, and 5.50 MJ oil-eq/kWh, with non-renewable energy carriers contributing 1.16, 1.22, and 1.29 MJ oil-eq/kWh. In the investigated EF impact categories, we similarly observe a larger environmental burden with increasing battery capacity, except in the use of minerals and metals. Our sensitivity analyses show that using a nickel cobalt manganese oxide (NCM) lithium-ion battery, instead of an LiFePO 4 battery, leads to a comparable environmental impact in terms of greenhouse gas emissions and cumulative energy demand. However, the NCM battery increases the impact in the EF categories of acidification and respiratory inorganics by 7 and 10%, respectively, whereas energy carrier resource use decreases by 4% and minerals and metals resource use decrease by 1%. Using a copper indium selenium (CIS) PV panel instead of a multicrystalline-silicon decreases greenhouse gas emissions by 24%, non-renewable cumulative energy demand by 13%, and particulate matter emissions by 60% (the largest decrease). Furthermore, the calculated environmental impacts are sensitive to the assumed battery lifetime. A decrease from 5000 to 3000 charge cycles increases non-renewable cumulative energy demand by 24% and greenhouse gas emissions by 16%. Increasing from 5000 to 7000 charge cycles decreases the environmental impacts by 6% and 7% in terms of non-renewable cumulative energy demand and greenhouse gas emissions, respectively. A utility-scale battery system case study shows that using batteries to store PV electricity overproduction reduces greenhouse gas emissions compared to using natural gas backup electricity generation.

14 SOLAR ENERGY↗

The Transport Properties of Quasi–One-Dimensional Ba 3 Co 2 O 6 (CO 3 ) 0.7

We have performed combined elastic neutron diffuse, electrical transport, specific heat, and thermal conductivity measurements on the quasi–one-dimensional Ba 3 Co 2 O 6 (CO 3 ) 0.7 single crystal to characterize its transport properties. A modulated superstructure of polyatomic CO 3 2- is formed, which not only interferes the electronic properties of this compound, but also reduces the thermal conductivity along the c-axis. Furthermore, a large magnetic entropy is observed to be contributed to the heat conduction. Our investigations reveal the influence of both structural and magnetic effects on its transport properties and suggest a theoretical improvement on the thermoelectric materials by building up superlattice with conducting ionic group.

36 MATERIALS SCIENCE↗

Atomic Layer Deposition for Preparing Isolated Co Sites on SiO 2 for Ethane Dehydrogenation Catalysis

Unlike Co clusters, isolated Co atoms have been shown to be selective for catalytic dehydrogenation of ethane to ethylene; however, preparation of isolated Co sites requires special preparation procedures. Here, we demonstrate that Atomic Layer Deposition (ALD) of tris(2,2,6,6-tetramethyl-3,5-heptanedionato)cobalt(III) (Co(TMHD) 3 ) on silica and other supports is effective in producing these isolated species. Silica-supported catalysts prepared with one ALD cycle showed ethylene selectivities greater than 96% at 923 K and were stable when CO 2 was co-fed with the ethane. Co catalysts prepared by impregnation formed clusters that were significantly less active, selective, and stable. Rates and selectivities also decreased for catalysts with multiple ALD cycles. Isolated Co catalysts prepared on Al 2 O 3 and MgAl 2 O 4 showed reasonable selectivity for ethane dehydrogenation but were not as effective as their silica counterpart.

36 MATERIALS SCIENCE↗

Dual conductor surface modified SOFC cathode particles and methods of making same

A novel method to produce ALD films disposed on powders is disclosed. Examples include the formation of a cobalt doped zirconia (CDZ), hafnia, and cobalt doped hafnia (CDH) films on lanthanum strontium cobalt iron oxide (LSCF) powder for solid oxide fuel cell cathodes. The coated powders are sintered into porous cathodes that have utility for preventing the migration of cations in the powder to the surface of the sintered cathode and/or other performance enhancing attributes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Cobalt promotion of the InO x –TiO 2 heterojunction for dual photothermal reduction of CO 2

A series of cobalt-promoted indium–titanium composite oxides was synthesized using a microemulsion method. Their functional properties were investigated for the photothermal reduction of carbon dioxide. In this series, the indium content varied between 2.5 and 20%, while the cobalt percentage was kept constant at 4% throughout the series. In all cases, carbon monoxide formation occurred selectively through the reverse water gas shift reaction. The sample with 2.5% In maximized the synergistic use of the two energy sources, while the sample with 10% In showed the highest catalytic activity under both thermal and dual photo-thermo conditions. A physicochemical characterization was performed for all samples. The use of microscopy and X-ray absorption spectroscopy demonstrated that sub-nanometric indium entities, in combination with atomically dispersed cobalt oxide entities, achieved a balance between high thermal activity and significant synergy between light and heat in a catalytic process. The system with 10% indium is thus able to improve the thermal catalytic process through the use of light, providing an intensification procedure for the classic process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of a chemical-free process utilizing ozone oxidative precipitation for the recovery of cobalt and manganese from acid mine drainage

Acid mine drainage (AMD) has been identified as a viable secondary resource of Co, and Mn. However, recovery of these elements while treating AMD is challenging due to the unfavorable pH and Eh conditions for Co-Mn precipitation. This study investigated the effects of various ligands (hydroxide, carbonate, ammonium, sulfate, and phosphate) and oxidizers (sodium persulfate, potassium permanganate, and ozone) on the precipitation of Co-Mn from AMD through experimental and solution chemistry studies. Ozone was found to be the most effective agent for the recovery of these elements. Based on the results, an AMD treatment process was formulated for selective recovery of multiple critical elements, including Al, REEs, Co, and Mn. More than 95 % of Co and Mn were recovered through the proposed process utilizing chemical-less ozone oxidative precipitation. In conclusion, a precipitate containing 0.9 % Co and 54.6 % Mn was obtained from an AMD source containing 0.9 ppm Co and 41.8 ppm Mn.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Role of Co-ZSM-5 Catalysts in Aerobic Oxidation of Ethylbenzene

Various forms of cobalt catalysts have been studied extensively for selective aerobic oxidation of hydrocarbons. However, it remains unclear whether cobalt can directly activate molecular oxygen under mild reaction conditions. Here we investigated the catalytic roles of cobalt in ethylbenzene oxidation with and without a hydroperoxide initiator. The contribution of different cobalt species was studied by varying the metal loading on Co-impregnated ZSM-5 samples. Quantitative EPR was used to determine the impact of cobalt catalysts on the free radical concentrations. Furthermore, this work provided strong evidence that cobalt, in several different forms, catalyzes hydrocarbon oxidation by facilitating peroxy bond cleavage, instead of direct oxygen activation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Concealed Cathode Degradation in Lithium-Ion Cells with a Ni-Rich Oxide

Difficulties with sourcing cobalt and the interest in increasing cell energy have motivated the development of Ni-rich oxide materials for lithium-ion battery cathodes. Despite the intense research on the topic, there is limited information available on the long-term performance of novel cathode formulations. Here, we evaluate the stability of LiNi 0.9 Mn 0.05 Co 0.05 O 2 in full-cells tested for over five months, assessing how cycling, voltage and electrolyte additives impact cathode aging. We use differential voltage analysis to extract insights about the cathode from the full-cell data and identify the isolation of cathode particles in the delithiated (charged) state as a relevant mode of aging. Importantly, this particular mechanism of cathode aging does not cause immediate cell capacity fade, causing the simple analysis of cell capacity retention to overestimate the cathode stability under the investigated conditions. So, our observations serve as cautionary tale indicating that careful analysis of data from extended testing may be required for assessing the performance of Ni-rich cathodes and for evaluating how these materials are affected by electrolyte additives.

25 ENERGY STORAGE↗

Cobalt-substituted perovskite compounds for solid oxide electrochemical cells

Oxygen electrodes are provided, comprising a perovskite compound having Formula (I), Sr(Ti 1-x Fe x-y Co y )O 3-δ wherein 0.90 ≥ x ≥ 0.40 and 0.02 ≥ y ≥ 0.30. Electrochemical devices comprising such oxygen electrodes are also provided, comprising a counter electrode in electrical communication with the oxygen electrode, and a solid oxide electrolyte between the oxygen electrode and the counter electrode. Methods of using such electrochemical devices are also provided, comprising exposing the oxygen electrode to a fluid comprising O 2 under conditions to induce the reaction O 2 +4e − →2O 2− , or to a fluid comprising O 2− under conditions to induce the reaction 2O 2− →O 2 +4e − .

Zhang, Shan-Lin↗