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At least 991 records · Page 55

Representing Soil Microbial Dynamics and Organo‐Mineral Interactions in the E3SM Land Model (ELM‐ReSOM)

Explicit representation of soil microbial processes and interactions with biotic and abiotic processes in Earth System Models (ESMs) remains limited, despite their importance in biogeochemical cycles. To address this gap, which hinders prediction of global biogeochemial cycling and responses to atmospheric conditions, we integrated a microbe- and mineral-surface-explicit model, the Reaction-network-based model of soil organic matter and Microbes (ReSOM), into the Energy Exascale ESM (E3SM) land model (ELM). Here, we describe ELM-ReSOM and show a case study at a conifer forest in California. ELM-ReSOM accurately simulated surface CO 2 fluxes and SOM stocks, demonstrating improved representations of microbial and mineral interactions compared to the default ELM. We examined ELM-ReSOM sensitivity to microbial traits, enzyme properties, and organo-mineral interactions. Microbial traits such as the maximum mortality rate, transporter-density scaling factor, and maximum monomer assimilation rate were strong controllers of heterotrophic respiration, while these microbial traits and enzyme-related properties collectively influenced SOM stocks. Mineral surfaces primarily affected SOM stocks by adsorbing enzymes, thereby limiting depolymerization. Synergies among processes led to stronger impacts of parameters when evaluated together versus separately (i.e., most parameters had greater indirect than direct effects). For example, due to interactions of microbial necromass with mineral surface adsorption, the indirect effect of the maximum microbial mortality rate was 33% larger than its direct effect on SOM stock. Thus, microbial and enzyme dynamics and their interactions with mineral surfaces play critical roles in SOM cycling. Tackling the challenges of microbe-explicit models will advance understanding and modeling of SOM dynamics.

Tao, Jing [Lawrence Berkeley National Laboratory (↗

Development of a continuous synthesis process for carbamazepine using validated in-line Raman spectroscopy and kinetic modelling for disturbance simulation

Mitigation of failure modes in the continuous synthesis (CS) of a drug substance (DS) has the potential to widen the adoption of continuous manufacturing (CM) technologies by the pharmaceutical industry. Here, this work demonstrates the development of a robust continuous process for the synthesis of carbamazepine (CBZ), an essential medicine as per the World Health Organization (WHO), facilitated by kinetic modelling and monitored by in-line Raman spectroscopy. Accurate kinetic modelling and the use of validated process analytical technology (PAT) models for quantitative measurement were found to play an important role in developing CS of drug substances. Kinetic data for the formation of CBZ from iminostilbene (ISB) were collected by batch reaction sampling and high-performance liquid chromatography (HPLC) analysis. A non-linear solver and iterative method was applied to determine two sets of Arrhenius parameters simultaneously for the reaction system by minimizing the standard error of the model fit. The start-up and dynamic equilibrium stages for the CS of CBZ using a continuous stirred tank reactor (CSTR) were modelled based on the batch kinetic data and employed to optimize conversion and simulate process disturbances. An in-line Raman spectroscopy method was successfully developed, validated, and integrated to determine the concentrations of CBZ and ISB within the operating range for the CS. The CS kinetic model was evaluated experimentally from startup to dynamic equilibrium over 10 residence times with monitoring by HPLC and in-line Raman spectroscopy. The developed kinetic model in tandem with in-line Raman spectroscopy successfully predicted disturbances due to changes in process variables and can serve as a useful tool in the future design of advanced process control strategies for the continuous synthesis of CBZ.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Northeastern Center for Chemical Energy Storage (NECCES)

The chemical reactions that occur in batteries are complex, spanning a wide range of time and length scales from atomic jumps to the entire battery structure. The NECCES team of experimentalists and theorists made use of, and developed new methodologies to determine how model compound electrodes function in real time, as batteries are cycled. The team determined that kinetic control of intercalation reactions (reactions in which the crystalline structure is maintained) can be achieved by control of the materials morphology and explains and allows for the high rates of many intercalation reactions where the fundamental properties might indicate poor behavior in a battery application. The small overvoltage required for kinetic control is technically effective and economically feasible. A wide range of state-of-the-art operando techniques was developed to study materials under realistic battery conditions, which are now available to the scientific community. The team also investigated the key reaction steps in conversion electrodes, where the crystal structure is destroyed on reaction with lithium and rebuilt on lithium removal. These so-called conversion reactions have in principle much higher capacities, but were found to form very reactive discharge products that reduce the overall energy efficiency on cycling. It was found that by mixing either the anion, as in FeOF, or the cation, as in Cu1-yFeyF2, the capacity on cycling could be improved. The fundamental understanding of the reactions occurring in electrode materials gained in this study will allow for the development of much improved battery systems for energy storage. This will benefit the public in longer lived electronics, higher electric vehicle ranges at lower costs, and improved grid storage that also enables renewable energy supplies such as wind and solar.

25 ENERGY STORAGE↗

In situ measurements of heterogeneous reactions on ambient aerosol particles: Impacts on atmospheric chemistry and climate

Aerosol particles play a critical role in the Earth’s energy budget through the absorption and scattering of radiation, and/or through their ability to form clouds and alter cloud lifetime. Heterogeneous and multi-phase reactions alter the climate-relevant properties of aerosol particles and catalyze reaction pathways that are energetically unfavorable in the gas phase. The chemical composition of aerosol particles dictates the kinetics of heterogeneous and multi-phase reactions. At present, the vast majority of the molecular level information on these processes has been determined in laboratory investigations on model aerosol systems. The work described here provides a comprehensive investigation into the reactivity of complex, ambient aerosol particles is proposed to determine: 1) how representative laboratory investigations of heterogeneous and multi-phase processes conducted on model, simple systems are of the real atmosphere, and 2) the impact of heterogeneous and multi-phase processes on ambient particle optical properties and their ability to nucleate clouds. This work has focused on the uptake kinetics for ammonia (NH 3 ) and dinitrogen pentoxide (N 2 O 5 ). The results of these investigations will be used to directly improve the representation of heterogeneous and multi-phase processes in global climate models, by identifying the key mechanistic drivers that control the variability in the observed kinetics.

54 ENVIRONMENTAL SCIENCES↗

Defending the Homeland: Growing Foreign Challenges to the U.S. Missile Defense Posture

The Office of the Secretary of Defense (OSD) for Policy requested that Lawrence Livermore National Laboratory conduct a Congressionally directed study on homeland missile defense, pursuant to Section 1692 of the fiscal year 2020 National Defense Authorization Act. In accordance with the statutory language, this study considers whether the security benefits obtained by deployment of homeland missile defenses of the United States are undermined or counterbalanced by adverse reactions of potential adversaries, and considers the effectiveness of homeland missile defense efforts of the United States to deter the development of ballistic missiles. Almost a half-century has elapsed since the United States and the Soviet Union signed the Anti-Ballistic Missile (ABM) Treaty, and almost two decades since the former withdrew. Since withdrawing, the United States has sought to develop and deploy a layered missile defense system to defend against regional threats to U.S. and allied interests abroad and to counter limited threats to the U.S. homeland. As such, missile defense supports key national defense policy objectives. Protecting the U.S. homeland, forces abroad, allies, and partners. Deterring attacks against the United States, its allies, and partners. Assuring allies an strengthening U.S. diplomatic activities in peacetime and crisis. We offer five key findings: 1. The primary benefit of the Ground-based Midcourse Defense (GMD) system is the protection it provides the U.S. homeland against a limited but evolving rogue-state missile threat. While this system has never been tested in combat, it appears thus far to have effectively paced North Korea’s development and deployment of intercontinental ballistic missiles (ICBMs). In the absence of such a defensive capability, the United States would likely have been more heavily exposed to North Korean actions, would have operated at a much higher-risk posture, and would have had less negotiating room with which to navigate coercive tactics and crises. Its allies would have been more concerned about U.S. willingness in time of crisis and war to run the risks of protecting them. The GMD system also serves as a hedge against Iranian breakout. 2. Potential adversaries continue to develop long-range ballistic missiles despite deployment of a U.S. homeland missile defense system. This includes both rogue states and major power rivals whose long-range missile programs predated the deployment of U.S. missile defenses. While North Korea has continued its long-range missile developments and achieved an intercontinental capability, Iran has not yet reached this threshold. The broader proliferation of long-range missiles anticipated in the late 1990s has not materialized. 3. While Russia has used the existence of a U.S. homeland missile defense system as a justification for its substantial and continuing weapon modernization program, neither Russian force modernization nor the limited U.S. homeland missile defense system has altered the strategic balance. Russia has long considered U.S. missile defenses—both theater and homeland—as directed against its strategic forces and as a capability that could rapidly advance, thereby eroding Russian confidence in its nuclear deterrent. Russia’s political and military actions appear excessive and negatively impact areas such as arms control, but they do not undermine the primary benefit of the U.S. system cited in Key Finding 1. 4. China’s expansion and diversification of nuclear and missile forces has been influenced by its concerns about U.S. homeland missile defense, but those concerns are only one of many factors in China’s force planning. Although China’s actions to preserve and expand its assured retaliation prospects have not fundamentally altered the strategic balance, its buildup and lack of transparency about its force modernization goals are troubling. Taken together, the aggregate pattern of China’s modernization activities over the past two decades strongly suggests a concerted effort to develop a modern military force commensurate with its intended geopolitical status. Whatever China’s legacy concerns over the survivability of its strategic nuclear forces, its ability to overwhelm the GMD system appears intact today and will be further strengthened in the years ahead as it continues its long-term modernization program. China’s political and military actions negatively affect U.S. security interests but do not undermine the primary benefit of the U.S. system cited in Key Finding 1. 5. The basic finding that benefits have not so far been undermined by adverse reactions is a function of circumstances that are increasingly in flux. The existing GMD-centered system is under increasing pressure from the pace and scope of North Korean missile deployments. The proposed “layered” system seeks to mitigate this impending capability gap in the near term and to complement future capabilities, such as the Next Generation Interceptor, when they come online. Given the pace of U.S. missile defense developments since 2000, it is possible that adversary advances in capability will outpace the U.S. system’s ability to adapt. Additionally, because this layered system is in principle more readily scaled, it will almost certainly be viewed skeptically by China and Russia. In a context of growing great-power security competition, the Department of Defense (DoD) should consider undertaking a broader net assessment of the U.S., Russian, and Chinese force balance.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗

Quasielastic neutron scattering with in situ humidity control: Water dynamics in uranyl fluoride

The structural phase diagram of uranyl fluoride (UO{sub 2}F{sub 2}), while incomplete, contains at least one anhydrous crystal structure and a second, zeolite-like structure with the formula [(UO{sub 2}F{sub 2})(H{sub 2}O)]{sub 7} ⋅ (H{sub 2}O){sub 4} that can be produced by adding water to the anhydrous structure. While traditional diffraction measurements can easily differentiate these crystals, additional aqueous structures (in general of the form UO{sub 2}F{sub 2} + xH{sub 2}O) have been proposed as well. We present results using a novel sample environment setup to intercalate water during a quasielastic neutron scattering measurement over the course of 86 h. Our sample environment allows low-pressure (<2 atm) humid air flow across the sample coupled with a system to control the relative humidity of this air flow between 10% and 70%. The water dynamics in UO{sub 2}F{sub 2} and [(UO{sub 2}F{sub 2})(H{sub 2}O)]{sub 7} ⋅ (H{sub 2}O){sub 4} are sufficiently different to distinguish them, with water in the latter executing a restricted diffusion (D = 2.7 × 10{sup −6} cm{sup 2}/s) within the structure's accessible pores (r = 3.17 Å) such that the dynamics can be used as a fingerprinting tool. We confirm that water vapor pressure is the driving thermodynamic force for the conversion of the anhydrous structure to [(UO{sub 2}F{sub 2})(H{sub 2}O)]{sub 7} ⋅ (H{sub 2}O){sub 4}, and we demonstrate the feasibility of extending this approach to aqueous forms of UO{sub 2}F{sub 2} + xH{sub 2}O. This method has general applicability to systems in which water content itself is a driving variable for structural or dynamical phase transitions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Establishing a geochemical heterogeneity model for a contaminated vadose zone – Aquifer system

A large set of sediment samples from a 1600 m2 experimental plot within a 2.2 km2 vadose zone and groundwater uranium (VI) plume were subject to physical, chemical, and mineralogic characterization. The plot is being used for field experimentation on U(VI) recharge and transport processes within a persistent groundwater plume that exists in the groundwater-river interaction zone of the Columbia River at the U.S. DOE Hanford site. The samples were obtained during the installation of 35 tightly spaced (10 m separation) groundwater monitoring wells. The characterization measurements for each sample included total contaminant concentrations (U and Cu primarily), bicarbonate extractable U(VI), sequential 238U(VI) contaminant desorption Kd, 233U(VI) adsorption Kd, grain size distribution, surface area, extractable poorly crystalline Fe(III) oxides, and mineralogy. The characterization objective was to inform a conceptual model of coupled processes controlling the anomalous longevity of the plume, and to quantify the spatial heterogeneity of the contaminant inventory and the primary properties effecting reactive transport. Correlations were drawn between chemical, physical, and reaction properties, and Gaussian simulation was used to compute multiple 3-D realizations of extractable U(VI), the 233U(VI) adsorption Kd, and the distribution of the reactive < 2 mm fraction. Adsorbed contaminant U(VI) was highest in the vadose zone and the zone of seasonal water table fluctuation lying at its base. Adsorbed U(VI) was measureable, but low, in the groundwater plume region where very high hydraulic conductivities existed. The distribution of adsorbed U(VI) displayed no apparent correlation with sediment physical or chemical properties. Desorption [238U(IV)] and adsorption [233U(VI)] Kd values showed appreciable differences due to mass transfer controlled surface complexation and the effects of long subsurface residence times. The 233U(VI) adsorption Kd, a combined measure of surface complexation strength and site concentration, was relatively uniform throughout the domain, displaying correlation with fines distribution and surface area. The characterization results revealed U(VI) supplied to the groundwater plume through spatially heterogeneous recharge from residual contamination in the zone of seasonal water table fluctuation, and transport of U(VI) controlled by weak, kinetically-controlled surface complexation in the coarse-textured saturated zone. Geostatistical relationships for the adsorbed contaminant U distribution in the characterization domain allow an extrapolation to inventory at the plume scale, a critical unknown for remedial action.

contaminant heterogeniety, uranium groundwater plu↗

Watching the dynamics of electrons and atoms at work in solar energy conversion

The photochemical reactions performed by transition metal complexes have been proposed as viable routes towards solar energy conversion and storage into other forms that can be conveniently used in our everyday applications. In order to develop efficient materials, it is necessary to identify, characterize and optimize the elementary steps of the entire process on the atomic scale. To this end, we have studied the photoinduced electronic and structural dynamics in two heterobimetallic ruthenium–cobalt dyads, which belong to the large family of donor–bridge–acceptor systems. Using a combination of ultrafast optical and X-ray absorption spectroscopies, we can clock the light-driven electron transfer processes with element and spin sensitivity. In addition, the changes in local structure around the two metal centers are monitored. These experiments show that the nature of the connecting bridge is decisive for controlling the forward and the backward electron transfer rates, a result supported by quantum chemistry calculations. More generally, this work illustrates how ultrafast optical and X-ray techniques can disentangle the influence of spin, electronic and nuclear factors on the intramolecular electron transfer process. Finally, some implications for further improving the design of bridged sensitizer-catalysts utilizing the presented methodology are outlined.

14 SOLAR ENERGY↗

Chemistry and kinetics of the pyrophoric plutonium hydride-air reaction

The chemistry and kinetics of the pyrophoric reaction of the plutonium hydride solid solution (PuH x , 1.9 ≤ x ≤ 3) are derived from pressure-time and gas analysis data obtained after exposure of PuH 2.7 to air in a closed system. The reaction is described in this paper by two sequential steps that result in reaction of all O 2 , partial reaction of N 2 , and formation of H 2 . Hydrogen formed by indiscriminate reaction of N 2 and O 2 at their 3.71:1 M ratio in air during the initial step is accommodated as PuH 3 inside a product layer of Pu 2 O 3 and PuN. H 2 is formed by reaction of O 2 and partial reaction of N 2 with PuH 3 during the second step. Both steps of reaction are described by general equations for all values of x. The rate of the first step is proportional to the square of the O 2 pressure, but independent of temperature, x, and N 2 pressure. The second step is a factor of ten slower than step one with its rate controlled by diffusion of O 2 through a boundary layer of product H 2 and unreacted N 2 . Finally, rates and enthalpies of reaction are presented and anticipated effects of reactant configuration on the heat flux are discussed.

36 MATERIALS SCIENCE↗

Optical Dedoping Mechanism for P3HT:F4TCNQ Mixtures

Doping-induced solubility control (DISC) is a recently introduced photolithographic technique for semiconducting polymers, which utilizes reversible changes in polymer solubility upon doping to allow the polymer to function as its own photoresist. Central to this process is a wavelength sensitive optical dedoping reaction, which is poorly understood but generates subdiffraction-limited topographic features and provides optical control of the polymer doping level. In this work, we examine the mechanism of optical dedoping in the semiconducting polymer poly-3-hexylthiophene (P3HT) doped by 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), via a combination of ultrafast and steady-state spectroscopy, ab initio calculations, and multidimensional NMR. A simple photoinduced back electron transfer mechanism from reduced F4TCNQ to oxidized P3HT does not explain the observed photophysics. Instead, photoexcited F4TCNQ* reacts with THF solvent molecules to form a neutral, nondoping, and highly soluble F4TCNQ-THF complex. Hence, ionized F4TCNQ is removed from the P3HT indirectly by depletion of the neutral F4TCNQ. Because the reaction involves only the dopant and similar photoreactivity would expected for most other dopant molecules, we expect optical DISC patterning should be generalizable to a wide range of polymer:dopant systems.

36 MATERIALS SCIENCE↗

Multiple Mechanisms Mapped in Aryl Alkyl Ether Cleavage via Aqueous Electrocatalytic Hydrogenation over Skeletal Nickel

We present here detailed mechanistic studies of electrocatalytic hydrogenation (ECH) in aqueous solution over skeletal nickel cathodes to probe the various paths of reductive catalytic C–O bond cleavage among functionalized aryl ethers relevant to energy science. Heterogeneous catalytic hydrogenolysis of aryl ethers is important both in hydrodeoxygenation of fossil fuels and in upgrading of lignin from biomass. The presence or absence of simple functionalities such as carbonyl, hydroxyl, methyl, or methoxyl groups is known to cause dramatic shifts in reactivity and cleavage selectivity between sp3 C–O and sp2 C–O bonds. Specifically, reported hydrogenolysis studies with Ni and other catalysts have hinted at different cleavage mechanisms for the C–O ether bonds in α-keto and α-hydroxy β-O-4 type aryl ether linkages of lignin. Our new rate, selectivity, and isotopic labeling results from ECH reactions confirm that these aryl ethers undergo C–O cleavage via distinct paths. For the simple 2-phenoxy-1-phenylethane or its alcohol congener, 2-phenoxy-1-phenylethanol, the benzylic site is activated via Ni C–H insertion, followed by beta elimination of the phenoxide leaving group. But in the case of the ketone, 2-phenoxyacetophenone, the polarized carbonyl π system apparently binds directly with the electron rich Ni cathode surface without breaking the aromaticity of the neighboring phenyl ring, leading to rapid cleavage. Substituent steric and electronic perturbations across a broad range of β-O-4 type ethers create a hierarchy of cleavage rates that supports these mechanistic ideas while offering guidance to allow rational design of the catalytic method. Furthermore, on the basis of the new insights, the usage of cosolvent acetone is shown to enable control of product selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding and Strategies for Controlled Interfacial Phenomena in Lithium-Ion Batteries and Beyond

Electrolyte chemistry and properties and electrode structure and chemical properties particularly at the interfaces are crucial for the development of advanced battery components. This project focused on elucidating the roles of the electrolyte and electrode on the formation and evolution of the SEI layer and cell electrochemical performance on silicon and on Li metal anodes. For Si nano/microstructures we evaluated lithiation, volume changes, reactivity, and chemo-mechanical transformations as functions of nanoparticle size, shape, presence of coatings, electrolyte composition, electron leakage to the electrolyte, and cycling. For Li metal anodes we provided detailed analyses of the electrode and electrolyte effects on interfacial reactivity and as a function of microstructural evolution and underlying stochasticity as dendrites nucleate and grow. We thoroughly investigated and simulated how the chemistry of the various components of the electrolyte and the electrode architecture may affect the electrochemical reactions as well as cell degradation. A multiscale modeling approach was utilized, where atomistic simulations informed about the microscopic behavior of the system, and intermediate time and length scales were investigated with mesoscopic models. Results were also tested against selected experiments from our collaborators. The combined theoretical-experimental strategy saves costs by utilizing predictions from computational analyses to guide experimentation.

25 ENERGY STORAGE↗

Validation of FSP Reactor Design with Sensitivity Studies of Beryllium-Reflected Critical Assemblies

The baseline design for space nuclear power is a fission surface power (FSP) system: sodium-potassium (NaK) cooled, fast spectrum reactor with highly-enriched-uranium (HEU)-O 2 fuel, stainless steel (SS) cladding, and beryllium reflectors with B4C control drums. Previous studies were performed to evaluate modeling capabilities and quantify uncertainties and biases associated with analysis methods and nuclear data. Comparison of Zero Power Plutonium Reactor (ZPPR)-20 benchmark experiments with the FSP design indicated that further reduction of the total design model uncertainty requires the reduction in uncertainties pertaining to beryllium and uranium cross-section data. Further comparison with three beryllium-reflected HEU-metal benchmark experiments performed at the Oak Ridge Critical Experiments Facility (ORCEF) concluded the requirement that experimental validation data have similar cross section sensitivities to those found in the FSP design. A series of critical experiments was performed at ORCEF in the 1960s to support the Medium Power Reactor Experiment (MPRE) space reactor design. The small, compact critical assembly (SCCA) experiments were graphite- or beryllium-reflected assemblies of SS-clad, HEU-O 2 fuel on a vertical lift machine. All five configurations were evaluated as benchmarks. Two of the five configurations were beryllium reflected, and further evaluated using the sensitivity and uncertainty analysis capabilities of SCALE 6.1. Validation of the example FSP design model was successful in reducing the primary uncertainty constituent, the Be(n,n) reaction, from 0.28 %$\delta$k/k to 0.0004 %$\delta$k/k. Further assessment of additional reactor physics measurements performed on the SCCA experiments may serve to further validate FSP design and operation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Rotating Disk Slurry Au Electrodeposition at Unsupported Carbon Vulcan XC-72 and Ce 3+ Impregnation for Ethanol Oxidation in Alkaline Media

A robust electrodeposition method consisting of the rotating disk slurry electrode (RoDSE) technique to obtain Au nanoparticles highly dispersed on a conductive carbonaceous support, i.e., Vulcan XC-72R, for ethanol electrooxidation reaction in alkaline media was developed. Ceria was used as a cocatalyst using a Ce(III)-EDTA impregnation method in order to enhance the catalytic activity and improve the catalyst’s overall stability. Furthermore, the RoDSE method used to obtain highly dispersed Au nanoparticles does not require the use of a reducing agent or stabilizing agent, and the noble-metal loading was controlled by the addition and tuning of the metal precursor concentration. Inductively coupled plasma and thermogravimetric analysis indicated that the Au loading in the catalyst was 9 %. We determined the particle size and characteristic Au fcc crystal facets by X-ray diffraction. The morphology of the catalyst was also investigated using electron microscopy techniques. In addition, X-ray absorption spectroscopy was used to corroborate the presence and identify the oxidation state of Ce in the system and to observe if there are any electronic interactions within the 8 % Au/CeO x /C system. Cyclic voltammetry of electrodeposited 9 % Au/C and Ce-promoted 8 % Au/C showed a higher catalytic current density for ethanol oxidation when compared with commercially available catalysts (20 % Au/C) of a higher precious metal loading. Additionally, we report a higher stability toward the ethanol electrooxidation process, which was corroborated by 1 mV/s linear sweep voltammetry and chronoamperometric studies.

36 MATERIALS SCIENCE↗

Shape-persistent phthalocyanine cages

Phthalocyanine (Pc), an electro-redox active moiety, has many attractive properties stemming from its large aromatic system and ability to act as a catalyst in electrochemical reactions, such as the CO 2 reduction reaction (CO 2 RR). However, due to the synthetic challenge related to geometric requirements and poor solubility (strong aggregation), discrete shape-persistent cages consisting of site-isolated, readily accessible Pc moieties have not been available. Here, we report the synthesis of Zn- and Ni-metallated Pc-based molecular cages via one-step dynamic spiroborate linkage formation in high yields. The ZnPc cage structure is unambiguously elucidated at the atomic level by single-crystal X-ray diffraction. Moreover, owing to the site-isolated redox-active metal centers, readily accessible intrinsic cavity, and shape-persistent backbone, the Ni-metallated Pc (NiPc) cage exhibits high catalytic efficiency, selectivity, and stability, superior to the non-caged control molecules in electrocatalytic CO 2 RR.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Discovery and Characterization of a Metastable Cubic Interstitial Nickel–Carbon System with an Expanded Lattice

Metastable, i.e., kinetically favored but thermodynamically not stable, interstitial solid solutions of carbon in iron are well-understood. Carbon can occupy the interstitial atoms of the host metal, altering its properties. Alloying of the host metal results in the stabilization of the FeC x phases, widening its application. Pure nickel finds niche applications, mainly focusing on catalysis, while nickel alloys are widely applied, e.g., in gas turbines, reactors, and seawater piping. Nickel carbide (Ni 3 C) is the well-known stable Ni–C system displaying a rhombohedral (R3̅c) crystal structure. Some reports describe an elusive cubic Ni–C system, observed during certain catalytic reactions occurring on nickel and formed by the occupation of the interstitials of the metal with carbon: to date, the stabilization and characterization of this phase have not been accomplished. Hereby, we report on the synthesis of a cubic metastable NiC x phase using chemical vapor deposition of methane on supported nickel nanoparticles. The structure was predicted by DFT/ReaxFF, synthesized and monitored with in situ time-resolved synchrotron XRD, and experimentally confirmed by Rietveld refinement and (S)TEM-EELS under ambient conditions. The results show an Fm3̅m phase with a lattice parameter of a = 3.749 ± 0.037 Å at room temperature, with the highest ever reported atomic percentage of carbon occupying the octahedral interstices of 23.1%, resulting in a NiC 0.3 phase. The degree of occupation of the interstitial voids by carbon can be controlled, enabling the tuning of the host metal’s d-spacing and composition, highlighting the applicability of this synthesis route for catalytic nanoparticle preparation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Single-molecule electronics: Cooling individual vibrational modes by the tunneling current

Electronic devices composed of single molecules constitute the ultimate limit in the continued downscaling of electronic components. A key challenge for single-molecule electronics is to control the temperature of these junctions. Controlling heating and cooling effects in individual vibrational modes can, in principle, be utilized to increase stability of single-molecule junctions under bias, to pump energy into particular vibrational modes to perform current-induced reactions, or to increase the resolution in inelastic electron tunneling spectroscopy by controlling the life-times of phonons in a molecule by suppressing absorption and external dissipation processes. Under bias the current and the molecule exchange energy, which typically results in heating of the molecule. However, the opposite process is also possible, where energy is extracted from the molecule by the tunneling current. Designing a molecular “heat sink” where a particular vibrational mode funnels heat out of the molecule and into the leads would be very desirable. It is even possible to imagine how the vibrational energy of the other vibrational modes could be funneled into the “cooling mode,” given the right molecular design. Previous efforts to understand heating and cooling mechanisms in single molecule junctions have primarily been concerned with small models, where it is unclear which molecular systems they correspond to. In this paper, our focus is on suppressing heating and obtaining current-induced cooling in certain vibrational modes. Strategies for cooling vibrational modes in single-molecule junctions are presented, together with atomistic calculations based on those strategies. Cooling and reduced heating are observed for two different cooling schemes in calculations of atomistic single-molecule junctions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Predicting and Controlling Corrosion (Abbreviated Final Report)

Corrosion accumulates significant replacement costs in the transportation, utility, manufacturing, and infrastructure sectors. It also underpins several of LLNL’s core missions in stockpile stewardship, defense, and energy security. Whereas most corrosion and aging models are empirically parameterized to describe well-defined conditions late in the reaction, the factors that determine the early stages of corrosion—during which mitigation could be most impactful— are poorly understood. This project addressed the critical need for new approaches to predict the kinetics of corrosion initiation based on firm physical and chemical understanding. The activities encompassed degradation of relevant metals in both hydrogen-rich and environmental corrosion scenarios. The team integrated state-of-the-art multiscale simulation, in situ characterization, and data science within three technical thrusts: hydriding of Ti alloys; aqueous corrosion of Al and Ni-Cr alloys; and degradation of additively manufactured 316L stainless steel. In each case, novel capabilities were developed to identify and track the impacts of key atomistic, compositional, and microstructural features on the metal systems. For hydriding, protocols were developed to tightly integrate multiscale models, advanced multimodal characterization, and machine learning to determine how hydrogen interacts with native passivating surface oxides and nucleates new undesired phases, shedding new light on the critical role of grain boundaries, interfaces, and atomically disordered regions. For aqueous corrosion, the project demonstrated methods to predict dissolution rates of metal surfaces in corrosive solutions, to measure and understand microstructural and grain orientation effects on corrosion susceptibility, and to investigate competing growth and dissolution kinetics of surface oxides. For additively manufactured metals, analysis using state-of-the-art microscopy techniques revealed the role of specific heterogeneities invoked during laser processing, including cellular structure, dislocations, and precipitates, on corrosion susceptibility. In addition to new capabilities and understanding, the project provided an avenue for workforce development, as well as key partnerships with stakeholders in corrosion science.

08 HYDROGEN↗