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At least 415 records · Page 23
All sourcesNASA NTRSDOE OSTI
NASA NTRS2010

Miniaturized Environmental Scanning Electron Microscope for In Situ Planetary Studies

The exploration of remote planetary surfaces calls for the advancement of low power, highly-miniaturized instrumentation. Instruments of this nature that are capable of multiple types of analyses will prove to be particularly useful as we prepare for human return to the moon, and as we continue to explore increasingly remote locations in our Solar System. To this end, our group has been developing a miniaturized Environmental-Scanning Electron Microscope (mESEM) capable of remote investigations of mineralogical samples through in-situ topographical and chemical analysis on a fine scale. The functioning of an SEM is well known: an electron beam is focused to nanometer-scale onto a given sample where resulting emissions such as backscattered and secondary electrons, X-rays, and visible light are registered. Raster scanning the primary electron beam across the sample then gives a fine-scale image of the surface topography (texture), crystalline structure and orientation, with accompanying elemental composition. The flexibility in the types of measurements the mESEM is capable of, makes it ideally suited for a variety of applications. The mESEM is appropriate for use on multiple planetary surfaces, and for a variety of mission goals (from science to non-destructive analysis to ISRU). We will identify potential applications and range of potential uses related to planetary exploration. Over the past few of years we have initiated fabrication and testing of a proof-of-concept assembly, consisting of a cold-field-emission electron gun and custom high-voltage power supply, electrostatic electron-beam focusing column, and scanning-imaging electronics plus backscatter detector. Current project status will be discussed. This effort is funded through the NASA Research Opportunities in Space and Earth Sciences - Planetary Instrument Definition and Development Program.

Gaskin, Jessica↗
DOE OSTI2020

The Bonding Nature and Adhesion of Polyacrylic Acid Coating on Li-Metal for Li Dendrite Prevention

The success of polyacrylic acid (PAA) to suppress Li dendrite growth suggests that the mechanical properties of polymer-based coatings, including the modulus, toughness, and interfacial adhesion are important design criteria. However, the measurement of the adhesion of thin PAA, as well as other polymer coatings to the reactive Li-metal anode surface is limited experimentally and challenging computationally. In this paper, a strategy was proposed to estimate the adhesion and delamination of the PAA(polymer)/Li interface, based on the bonding nature at the simpler PAA (oligomer)/Li interfaces using density functional theory calculations. It has been shown that the carboxylic acid groups in PAA reacted strongly with metallic Li, which significantly enhances the interfacial adhesion through the Li–O bonds formation, Li ionization and its incorporation into PAA, and –H or –OH termination of Li after decomposition of the COOH functional group. During delamination, it was found that the most likely PAA delamination route involved breaking partial Li–O bonds and lifting some ionized Li atoms from the Li-metal, especially for the Li atoms that showed a charge closer to +1 or are bonded with two O atoms from PAA. Based on the average bonding energies from PAA(oligomer)/Li interface delamination calculations, the work of separation, W sep , of the PAA(polymer)/Li interface was estimated to be ~1.0 (J/m 2 ). The high W sep of PAA (polymer)/Li was comparable with the Li 2 O/Li interface and higher than Li 2 CO 3 /Li and LiF/Li interfaces. This order correlated well with the areal density of Li–O bonds, which can serve as a descriptor for the interfacial adhesion. Furthermore, this computational approach can be applied to other interfaces with polymer-based coatings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

First-principle investigation on catalytic hydrogenation of benzaldehyde over Pt-group metals

We report that understanding the hydrogenation of organic compounds in the aqueous phase has always been fundamentally important for improving carbon neutral pathways to fuels and value-added chemicals. In this study, we investigated both thermodynamic and kinetic profiles of benzaldehyde hydrogenation over the Pd(111) and Pt(111) metal surfaces using density functional theory (DFT) and ab initio molecular dynamic (AIMD) simulations. The adsorption of H 2 shows the mixed preference of H adsorption sites on the Pt(111), while the fcc adsorption site is dominant for H on the Pd(111). When benzaldehyde is added to the systems, we observe a strong reduction of benzaldehyde on charged Pd (111) surface compared with that on neutral surface. In contrast, charged state of the Pt(111) surface does not change their interaction. Subsequent hydrogenation reaction of benzaldehyde over Pd(111), proceeding via Langmuir-Hinshelwood mechanism, is affected by two major factors: the presence of H 2 O solvent and surface charge. The presence of H 2 O solvent greatly reduces the activation energy of C-H and O-H bond formation during the hydrogenation process. Furthermore, the hydrogenation step via C-H bond formation is preferred thermodynamically and kinetically over O-H bond formation during thermocatalytic hydrogenation, while the opposite trend holds true during electrocatalytic hydrogenation.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2022

Interlayer spacing in pillared and grafted MCM-22 type silicas: density functional theory analysis versus experiment

Pillaring of synthetic layered crystalline silicates and aluminosilicates provides a strategy to enhance their adsorption and separation performance, and can facilitate the understanding of such behavior in more complex natural clays. In this study, we perform the first-principles density functional theory calculations for the pillaring of the pure silica polymorph of an MCM-22 type molecular sieve. Starting with a precursor material MCM-22P with fully hydroxylated layers, a pillaring agent, (EtO) 3 SiR, can react with hydroxyl groups (–OH) on adjacent internal surfaces, 2(–OH) + (EtO) 3 SiR + H 2 O → (–O) 2 SiOHR + 3EtOH, to form a pillar bridging these surfaces, or with a single hydroxyl, –OH + (EtO) 3 SiR + 2H 2 O → (–O)Si(OH) 2 R + 3EtOH, grafting to one surface. For computational efficiency, we replace the experimental organic ligand, R, by a methyl group. We find that the interlayer spacing in MCM-22 is reduced by 2.66 Å relative to weakly bound layers in the precursor MCM-22P. Including (–O) 2 SiR bridges for 50% (100%) of the hydroxyl sites in MCM-22P increases the interlayer spacing relative to MCM-22 by 2.52 Å (2.46 Å). For comparison, we also analyze the system where all –OH groups in MCM-22P are replaced by non-bridging grafted (–O)Si(OH) 2 R which results in a smaller interlayer spacing expansion of 2.17 Å relative to MCM-22. Our results for the interlayer spacing in the pillared materials are compatible with experimental observations for a similar MCM-22 type material with low Al content (Si : Al = 51 : 1) of an expansion relative to MCM-22 of roughly 2.8 Å and 2.5 Å from our x-ray diffraction and scanning transmission electron microscopy analyses, respectively. The latter analysis reveals significant variation in individual layer spacings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1972

Spectrophotometric studies of the photometric function, composition, and distribution of the surface materials of Mars.

Results of a program of mapping the surface of Mars carried out at a spatial resolution of 300 to 500 km during the 1969 opposition at IR (0.60 to 2.27 microns). Spectral albedo curves were obtained for 150 mare and desert areas. These curves fall into two well-defined and fairly uniform color-albedo groups corresponding to mare and desert units. The lack of areas with color and albedo that are distinctively different from those of these groups is interpreted as an indication that the surface of Mars consists of basically only two types of materials. Laboratory comparison data support a model of the Martian regolith that suggests that the general color of these surface units is due to a limonite stain coating the particles of lithic soils. Features in the spectral albedo curves at 1.6 and 2.1 microns are interpreted as being due to the H2O ice on the surface or in the Martian atmosphere.

Binder, A. B.↗
DOE OSTI2020

Interactions of Oxide Surfaces with Water Revealed with Solid-State NMR Spectroscopy

Hydrous materials are ubiquitous in the natural environment and efforts have previously been made to investigate the structures and dynamics of hydrated surfaces for their key roles in various chemical and physical applications, with the help of theoretical modeling and microscopy techniques. However, an overall atomic-scale understanding of the water–solid interface, including the effect of water on surface ions, is still lacking. Herein, we employ ceria nanorods with different amounts of water as an example and demonstrate a new approach to explore the water–surface interactions by using solid-state NMR in combination with density functional theory. NMR shifts and relaxation time analysis provide detailed information on the local structure of oxygen ions and the nature of water motion on the surface: the amount of molecularly adsorbed water decreases rapidly with increasing temperature (from room temperature to 150 °C), whereas hydroxyl groups are stable up to 150 °C, and dynamic water molecules are found to instantaneously coordinate to the surface oxygen ions. Additionally, the applicability of dynamic nuclear polarization for selective detection of surface oxygen species is also compared to conventional NMR with surface selective isotopic-labeling: the optimal method depends on the feasibility of enrichment and the concentration of protons in the sample. These results provide new insight into the interfacial structure of hydrated oxide nanostructures, which is important to improve performance for various applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

The Role of Protons and Hydrides in the Catalytic Hydrogenolysis of Guaiacol at the Ruthenium Nanoparticle-water Interface

The mechanistic roles of free hydronium ions, surface hydrides, and interfacial protons during guaiacol hydrodeoxygenation (HDO) on ruthenium nanoparticles are established. As guaiacol adsorbs on Ru, it loses its strong aromaticity and undergoes a rapid H-shift from its hydroxyl to meta carbons (in relation to its hydroxyl group), leading enol and keto surface isomers to exist in chemical equilibrium. HDO occurs via a hydridic H-adatom (H*) attack to the enol, followed by a kinetically relevant C-O bond rupture step, during which water shuttles the hydroxyl proton, enabling its intramolecular attack to the methoxy, evolving a high charged [Ru(s)-(C6H5O-)…(H+)…OCH3]† transition state. The competing HYD begins with a rapid H* attack to the keto, before a second, kinetically relevant H* attack, without proton involvement. Water, despite shifting the thermodynamics towards the more polar surface keto, promotes HDO to a much greater extent than HYD, because of its dual catalytic roles—it mobilizes hydroxyl proton (Brønsted acid) to cleave the strong C-O bond, synchronizing with the Ru metal surface (base) function that stabilizes the resulting [Ru(s)-(C6H5O-)…(H+)…OCH3]† transition state, and the water layers solvate this charged transition state, further reducing its free energy. Free hydronium ions do catalyze a separate homogeneous enol-keto isomerization, but this reaction is kinetically unrelated to HDO catalysis. This mechanistic picture explains the strong effects of polar protic solvent in hydrodeoxygenation, highlighting (i) the requirements of surface hydrides and interfacial protons acting in tandem to complete a HDO turnover and (ii) the cooperative role of protic solvent and metal surface in breaking the aromaticity and stabilizing charged reactive precursors and transition states.

Shangguan, Junnan↗
DOE OSTI2023

Impact of hydrogen bonding pendant groups in polymer grafted nanoparticles on interlayer adhesion and mechanical properties in material extrusion printing

The addition of nanoparticles or copolymer grafted nanoparticles (CPGNPs) to polymeric matrices greatly improves thermomechanical properties of the resulting nanocomposite, but corresponding studies of nanocomposite systems created by 3D printing are few, especially in the realm of functional polymeric materials. Here we describe how silica nanoparticle-grafted, random copolymers of poly(methyl methacrylate-random-2-uriedo-[1H]-pyrimidinone methacrylate) (P(MMA-r-UPyMA) dramatically increases the mechanical properties of poly(methyl methacrylate) (PMMA) based nanocomposite specimens created by melt extrusion printing. Most notably, when these novel CPGNPs are combined with PMMA matrix chains via a solution-based process, printed specimens containing only 0.5 wt% additive show significant increases in Young’s modulus (90%), storage modulus (93%), tensile modulus (148%) and ultimate tensile strength (110%). These improvements are ascribed to strengthening of adhesion across interfaces due to multi-point hydrogen bonding between UPyMA groups, the reinforcement effect of the P(MMA-r-UPyMA)-grafted silica nanoparticles, as well as hydrogen bonding interactions and entanglements between graft and matrix chains. Imaging of fracture surfaces after tensile testing reveals that in comparison to nanocomposites created by simple mechanical mixing of solids, the solution-casting process improves the dispersion of nanoparticles and reduces the void spaces between printed roads. These studies demonstrate that introducing functionality into polymer grafts, such as hydrogen bonding interactions, and intimate mixing of polymer-modified nanomaterials can greatly improve interlayer adhesion and mechanical properties, thereby advancing this method of polymer additive manufacturing

36 MATERIALS SCIENCE↗
DOE OSTI2020

Electron beam injection from a hollow cathode plasma into a downstream reactive environment: Characterization of secondary plasma production and Si 3 N 4 and Si etching

A material etching system was developed by combining beam electron injection from a direct current (DC) hollow-cathode (HC) electron source with the downstream reactive environment of a remote CF 4 /O 2 low temperature plasma. The energy of the injected beam electrons is controlled using an acceleration electrode biased positively relative to the HC Argon discharge. For an acceleration voltage greater than the ionization potential of Ar, the extracted primary electrons can produce a secondary plasma in the process chamber. We characterized the properties of the secondary plasma by performing Langmuir probe measurements of the electron energy probability function (EEPF) 2.5 cm below the extraction ring. The data indicate the existence of two major groups of electrons, including electrons with a primary beam electron energy which varies as the acceleration voltage is varied, along with low energy electrons produced by ionization of the Ar gas atoms in the process chamber by the injected beam electrons. When combining the HC Ar beam electron with a remote CF 4 /O 2 electron cyclotron wave resonance (ECWR) plasma, the EEPF of both the low energy plasma electron and beam electron components decreases. Additionally, we studied surface etching of Si3N4 and poly-crystalline Si (poly-Si) thin films as a function of process parameters, including the acceleration voltage (0-70 V), discharge current of the HC discharge (1-2 A), pressure (2- 100 mTorr), source to substrate distance (2.5 to 5 cm), and feed gas composition (with or without CF 4 /O 2 ). The direction of the incident beam electrons was perpendicular to the surface. Si 3 N 4 and poly-crystalline silicon etching are seen and indicate an electronneutral synergy effect. No/little remote plasma spontaneous etching was observed for the conditions used in this study, and the etching is confined to the substrate area irradiated by the injected beam electrons. The electron etched Si 3 N 4 surface etching rate profile distribution is confined within a ~30 mm diameter circle, which is slightly broader than the area for which poly-Si etching is seen, and coincides closely with the spatial profile of beam electrons as determined by the Langmuir probe measurements. The magnitude of poly-Si etching rate is by a factor of two times smaller than the Si 3 N 4 etching rate. In this paper, we discuss possible explanations of the data and the role of surface charging.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2026

Probing Interfacial Reaction Pathways in Atomic Layer Deposition on Sulfide Superionic Conductors

Sulfide superionic conductors (e.g., argyrodite Li 6 PS 5 Cl, LPSCl) are extremely promising for all solid-state batteries, but poor atmospheric stability and high interfacial reactivity limit widespread adoption. Coating LPSCl powders with ultrathin coatings using atomic layer deposition (ALD) mitigates these problems, protecting against atmospheric degradation and reducing reactivity with Li metal, yielding more stable cycling. Despite significant promise, the ALD mechanism is unknown, hampering the development of new coating chemistries. In this study, we elucidate the mechanism for Al 2 O 3 ALD on LPSCl using trimethyl aluminum (TMA) and H 2 O by combining in situ Fourier transform infrared spectroscopy, ex situ solid-state magic angle spinning nuclear magnetic resonance, UV Raman spectroscopy, X-ray photoelectron spectroscopy, and density functional theory calculations. We determine that ALD Al 2 O 3 nucleates promptly via TMA reaction with native —OH, —SH, and PS 3 -OH groups to form transient C–Al–O(S) species that are rapidly hydrolyzed during the subsequent H 2 O exposure. This reversible transformation maintains surface nucleophilicity and prevents sulfide decomposition. The resulting layer-by-layer growth leads to highly conformal Al 2 O 3 coatings on LPSCl that are readily scalable to ≥ 50 g quantities using a rotating drum fixture. This detailed understanding of ALD surface reactions provides critical insights guiding the selection of future ALD chemistries with improved performance.

atomic layer deposition↗
DOE OSTI2021

Nitrogen-doped char as a catalyst for wet oxidation of phenol-contaminated water

Catalytic wet oxidation (CWO) of aqueous effluents rich in organic compounds is a very promising technology for the treatment of liquid wastes from biomass conversion processes. CWO reactions occur through the formation of free radical species, produced in the presence of an oxidant, which act on organic contaminates in the effluent. Although the reaction is well known, there exists a lack of affordable catalysts to conduct this process at the lower temperatures and pressures in novel bioenergy processes. Here, this study assessed the catalytic effect of nitrogen-doped chars as such an option. Phenol in aqueous solution was used as a model waste effluent. Treatment was conducted at moderate temperatures (190 to 260 °C), oxygen partial pressure of 1 MPa, and reaction times of 15, 30, and 45 min in stainless steel and glass-lined tube reactors. High pressure liquid chromatography (HPLC) analyses of the products quantified phenol and by-product concentrations used in the calculation of reaction activation energy. The char catalyst was studied by X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and scanning electron microscopy (SEM) in order to gain insight into its structure and surface composition. The results indicate that nitrogen-doped char catalysts accelerate the oxidation of phenol by decreasing its reaction activation energy from 82.2 kJ/mol (non-catalyzed) to 40.4 kJ/mol (catalyzed). An analysis from first principles using density functional theory (DFT) was conducted to ascertain which N functional group has the most significant impact on free radical formation in the presence of oxygen. Among all the N functional groups studied, the dipyridinic functional groups showed the most promising characteristics to facilitate the formation of hydroxyl free radicals.

Advanced Oxidation Processes for Organic Pollutant↗
DOE OSTI2021

Janus Nanocages of Platinum-Group Metals and Their Use as Effective Dual-Electrocatalysts

Janus nanocages with distinctive platinum-group metals on the outer and inner surfaces can naturally catalyze at least two different reactions. In this work, we report a general method based on successive deposition and then selective etching for the facile synthesis of such nanocages. Herein, we have fabricated 11 different types of Janus nanocages characterized by a uniform size and well-defined {100} facets, together with porous, ultrathin, asymmetric walls up to 1.6 nm thick. When tested as dual-electrocatalysts toward oxygen reduction and evolution reactions, the Janus nanocages based on Pt and Ir exhibited superior activities depending on the thickness and relative position of the metal layer. Density functional theory studies suggest that the alloy composition and surface structure of the nanocages both play important roles in enhancing the electrocatalytic activities by modulating the stability of key reaction intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Explicit entropic proofs of irreversibility theorems for holographic RG flows

We revisit the existence of monotonic quantities along renormalization group flows using only the Null Energy Condition and the Ryu-Takayanagi formula for the entanglement entropy of field theories with anti-de Sitter gravity duals. In particular, we consider flows within the same dimension and holographically reprove the c-, F -, and a-theorems in dimensions two, three, and four. We focus on the family of maximally spherical entangling surfaces, define a quasi-constant of motion corresponding to the breaking of conformal invariance, and use a properly defined distance between minimal surfaces to construct a holographic c-function that is monotonic along the flow. We then apply our method to the case of flows across dimensions: there, we reprove the monotonicity of flows from AdS D+1 to AdS 3 and prove the novel case of flows from AdS 5 to AdS 4 .

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
NASA NTRSDate not supplied

Remote Sensing of Lineage Functional Types for Modeling and Monitoring Biodiversity

Hyperspectral remote sensing has the potential to continuously scale plant function and plant diversity information from landscape to global extents. Numerous studies have indicated that VSWIR (400-2500 nm) reflectance properties of vegetation capture evolutionarily conserved biochemical, structural, and other functional attributes of plant species. Spectral properties conserved in plants provide the opportunity to both 1) aggregate species into lineages with improved classification accuracy and 2) link those lineages directly to plant traits. Full realization of this goal will enable parameterization of Land Surface Models (LSMs) with remotely sensed information, e.g., canopy nitrogen, and better representations of biodiversity and functional diversity in biogeographic studies. In this study, we use hyperspectral AVIRIS data from the 2013 HyspIRI campaign over the Southern Sierra Nevada, California flight box to investigate the potential for incorporating evolutionary thinking into landcover classification. We link the airborne hyperspectral data with vegetation plot data from roughly 1372 surveys and a phylogeny representing 1361 species. We aggregate species into lineages ranging from species level groups down to similar number of Plant Functional Types as often used in LSMs. We assessed the ability of Random Forest and Partial Least Squares Discriminant Analysis to discriminate across these different phylogenetic scales and determine the optimal number of lineages to classify. Although there are some temporal and spatial differences in our training data, our best approaches achieved moderate classification accuracy (Kappa > 0.65). Given an optimal number of lineages, we explored approaches to improve classifications including machine learning and unmixing approaches. This work suggests that lineage-based methods may be a promising way to leverage the huge amounts of data that will come from high resolution and high return interval hyperspectral data planned for the Surface Biology and Geology mission with sparsely sampled existing ground-based ecological data.

Hyperspectral↗
DOE OSTI2026

Altered morphology and diffusivity of water confined in MXenes: Machine learning–accelerated computations combined with experiments

Nanoconfined water exhibits unique properties compared to bulk water due to limited quantities, frustrated hydrogen bonding, and surface interactions, which are fundamental for energy storage and transport applications. We integrate machine learning–accelerated ab initio molecular dynamics with x-ray diffraction (XRD) and inelastic neutron scattering (INS) to systematically analyze the thermodynamic and dynamic behavior of water confined between functionalized (-F, -O, and -OH) two-dimensional (2D) Ti 3 C 2 T x MXene layers. As water intercalates between layers, the interlayer spacing exhibits layer-dependent staging characteristics. The water polarization can be flipped by the count and morphology of intercalated molecules interacting with MXene surface groups, resulting in varying electrostatic potential profiles. On the basis of interfacial electrostatic potential, hydrogen bond lifetime, and molecular orientation, we establish a linear combination of exponential model describing water diffusivity. These computational insights align well with experimental x-ray and neutron measurements, suggesting strategies for tuning water morphology and transport by tailoring MXene surface chemistry and water content for electrochemical energy storage and nanofluidic applications.

Tang, Jiawei [Southeast Univ., Nanjing (China)] (O↗
DOE OSTI2023

Development of a molecularly informed biogeochemical framework for reactive transport modeling of subsurface carbon inventories, transformations and fluxes (Final Report)

The overall objective of the project was to combine new molecular-level characterization strategies with soil carbon flux measurements to develop and evaluate model representations of subsurface carbon cycling. We expanded on existing studies in the East River watershed, Colorado, in collaboration with the Berkeley Lab Watershed Function Scientific Focus Area (SFA), SLAC Groundwater Quality SFA, and Rocky Mountain Biological Laboratory (RMBL) to develop an elevation and vegetation gradient that is now the subject of long-term monitoring by the USGS. To achieve the overall objective, we combined field studies of soil respiration with laboratory analyses, ranging from spectroscopy to incubation studies. This combination of techniques enabled us to develop a new understanding of the drivers of high-elevation soil respiration. In the process, we developed three new modeling approaches that improve our ability to conceptualize and ultimately to represent soil respiration in numerical models. The first approach is a plot-scale transient inverse model that can be used to determine in situ CO 2 production rates from measured concentration profiles and surface fluxes. Application of this method revealed the importance of plant phenology and deep CO 2 production in moderating CO 2 fluxes to the atmosphere. The second modeling approach is a molecular-scale tool that enables spectroscopic and elemental data for carbon speciation to be transformed into functional group abundances, or the ‘SOC-fga model’. This method uniquely enables carbon speciation to be tracked within a reactive transport framework to partition carbon among different pathways and storage zones within the soil. The third modeling tool builds strongly on the previous approaches and captures the microbial processes driving heterotrophic respiration. This ‘dormancy model’ allows the native soil microbial population to respond transiently to the presence or absence of water in order to catalyze carbon respiration. This approach was also compared to the simpler and more widely used first-order model using two experimental datasets with different temporal and spatial resolutions. Our results illustrate that the simpler first order model provides a robust and efficient representation of deep (>1 meter) soil respiration, but that shallow soils, where most respiration occurs, require explicit representation of moisture-dependent activation and dormancy rates. By assessing soil organic carbon turnover at multiple scales, we see a complex array of controls emerge. Atte scale of a hillslope, spatial heterogeneity in soil respiration rates dominates and is uncorrelated with instantaneous soil moisture and plant community. At the profile scale, the balance between plant inputs and water availability is the dominant control. At the microbial to molecular scale, physiological processes associated with carbon use and carbon speciation are important controls. These scale-dependent controls emphasize the need for new modeling approaches that examine their interactions and hierarchies.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Creation of discrete active site domains via mesoporous silica poly(styrene) composite materials for incompatible acid–base cascade reactions

This work highlights the design and synthesis of bifunctional mesoporous silicate – polymer composite dual acid–base supported cascade catalysts. Compartmentalization of the two incompatible active sites is sought by segregating acid sites on the silica surface, and base sites within polymer chains and/or polymer domains. The ability to isolate and segregate active sites via control of the mesoporous silica pore size and polymer molecular weight is probed with silica samples functionalized by a grafting-to process. Supplemental activator and reducing agent (SARA) atom transfer radical polymerization is used to synthesize random copolymers containing protected primary amines. Thiol–ene ‘click’ chemistry facilitates silica functionalization via a convergent approach, with the ene-functionalized polymer end group and silica-grafted thiols forming SBA/MCM-SH-poly(styrene-co-2-(4-vinylbenzyl)isoindoline-1,3-dione). Polymer deprotection and thiol oxidation produces primary amine/sulfonic acid containing composite catalysts. With the polymer supported Lewis base and silica grafted Brønsted acid, the two-step deacetalization – Knoevenagel condensation cascade is explored to assess the ability of these polymer/silica hybrids to segregate active sites, allowing both acid and base site accessibility. Six composite catalysts are synthesized and tested in individual and cascade reactions with kinetic results demonstrating that lower molecular weight SBA-15-P1 and MCM-41-P1 catalysts outperform (higher turnover frequencies and initial rates) their higher molecular weight analogues, as well as a polymer-free system containing molecular active sites dispersed on the silica surface. Higher molecular weight composite catalysts perform more poorly due to limited chain solubility, mass transfer limitations, and poor catalyst accessibility. In many cases, the polymer chains effectively thread into the mesopores, with higher molecular weight polymers leading to pore blockage and inhibited mass transfer.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Functionalized Silicon Particles for Enhanced Half- and Full-Cell Cycling of Si-Based Li-Ion Batteries

Vinylene carbonate (VC) and polyethylene oxide (PEO) have been investigated as functional agents that mimic the solid electrolyte interphase (SEI) chemistry of silicon (Si). VC and PEO are known to contribute to the stability of Si-based lithium-ion batteries as an electrolyte additive and as a SEI component, respectively. In this work, covalent surface functionalization was achieved via a facile route, which involves ball-milling the Si particles with sacrificial VC and PEO. Thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy indicate that the additives are strongly bound to Si. In particular, MAS NMR shows Si–R or Si–O–R groups, which confirm functionalization of the Si after milling in VC or PEO. Particle size analysis by dynamic light scattering reveals that the additives facilitate particle size reduction and that the functionalized particles result in more stable dispersions based on zeta potential measurements. Raman mapping of the electrodes fabricated from the VC and PEO-coated active material with a polyacrylic acid (PAA) binder reveals a more homogenous distribution of Si and the carbon conductive additive compared to the electrodes prepared from the neat Si. Furthermore, the VC-milled Si strikingly exhibited the highest capacity in both half- and full-cell configurations, with more than 200 mAh g –1 measured capacity compared to the neat Si in the half-cell format. This is linked to an improved electrode processing based on the Raman and zeta potential measurements as well as a thinner SEI (with more organic components for the functionalized Si relative to the neat Si) based on XPS analysis of the cycled electrodes. In conclusion, the effect of binder was also investigated by comparing PAA with P84 (polyimide type), where an increased capacity is observed in the latter case.

25 ENERGY STORAGE↗