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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 739 records · Page 41
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Hierarchical reconstruction of 3D well-connected porous media from 2D exemplars using statistics-informed neural network

The relationships between porous microstructures and transport properties are of fundamental importance in various scientific and engineering applications. Due to the intricacy, stochasticity and heterogeneity of porous media, reliable characterization and modeling of transport properties often require a complete dataset of internal microstructure samples. However, it is often an unbearable cost to acquire sufficient 3D digital microstructures by purely using microscopic imaging systems. Herein this paper presents a machine learning-based technique to hierarchically reconstruct 3D well-connected porous microstructures from one isotropic or several anisotropic low-cost 2D exemplar(s). To compactly characterize the large-scale microstructural features, a Gaussian image pyramid is built for each 2D exemplar. Local morphology patterns are collected from the Gaussian image pyramids, and then they serve as the training data to embed the 2D morphological statistics into feed-forward neural networks at multiple length levels. By using a specially-developed morphology integration scheme, the 3D morphological statistics at different levels can be inferred from the statistics-informed neural networks. Gibbs sampling is adopted to hierarchically reconstruct 3D microstructures by using multi-level 3D morphological statistics, where the large-scale, regional and local morphological patterns are statistically generated and successively added to the same 3D random field. The proposed method is tested on a series of porous media with distinct morphologies, and the statistical equivalence between the reconstructed and the real microstructures is systematically evaluated by comparing morphological descriptors and transport properties. The results demonstrate that the proposed 2D-to-3D microstructure reconstruction method is a universal and efficient approach to generating morphologically and physically realistic samples of porous media.

42 ENGINEERING↗
DOE OSTI2022

Power quality disturbances diagnosis: A 2D densely connected convolutional network framework

The fast and accurate diagnosis of power quality disturbances (PQD) aids in avoiding shutdowns and unnecessary procedures, concerning electric energy distribution systems. As such, a number of techniques have been tested and applied in order to reach this objective. Majority of the techniques applied are two-step based. On the first step, power quality disturbances features are extracted. Second step, considering features extracted, disturbance classification is implemented. Recently, relevant literature has presented data-driven signal processing-based approaches, as deep convolutional neural networks (DCNN), which can implement both processing steps while providing automated recognition of patterns and outliers in data. However, not considered by state-of-art, power quality disturbances are evolving in nature, while all possible regularities might not be represented in the dataset. In this work a 2 Dimension Densely Connected Convolutional Network (2D-DenseNet) framework is presented. Further, a case study with synthetic disturbance events are analyzed. Easy-to-implement formulation, built on the 2D-DenseNet, without hard-to-design parameters, highlight potential aspects for real-life implementation.

42 ENGINEERING↗
DOE OSTI2025

Cost-optimized energy storage operation for a grid-connected solar PV system at community and individual scales

This study provides a comparative analysis of grid-connected PV-integrated battery storage at individual and community scales. The paper addresses the challenge of managing energy demand-generation mismatch by using a battery energy storage optimization algorithm, which minimizes operational costs while accounting for battery degradation. Also, this work introduces a broader evaluation basis that includes seasonal variability, grid exchange smoothness, and scalability across different battery capacities. Results show that community-scale storage more effectively dampens grid exchange power fluctuations and reduces system costs, particularly with moderate price differences between electricity buying and selling prices and low battery capacities. The paper also analyzes the impacts of static control versus cost-optimized battery system management. Here, it is shown that the gap in system costs between the cost-optimized and static control scenarios widens as the price difference increases.

25 ENERGY STORAGE↗
DOE OSTI2023

Terahertz EPR spectroscopy using a 36-tesla high-homogeneity series-connected hybrid magnet

Electron Paramagnetic Resonance (EPR) is a powerful technique to study materials and biological samples on an atomic scale. High-field EPR in particular enables extracting very small g-anisotropies in organic radicals and half-filled 3d and 4f metal ions such as Mn II (3d 5 ) or Gd III (4f 7 ), and resolving EPR signals from unpaired spins with very close g-values, both of which provide high-resolution details of the local atomic environment. Before the recent commissioning of the high-homogeneity Series Connected Hybrid magnet (SCH, superconducting + resistive) at the National High Magnetic Field Laboratory (NHMFL), the highest-field, high-resolution EPR spectrometer available was limited to 25 T using a purely resistive “Keck” magnet at the NHMFL. Herein, we report the first EPR experiments performed using the SCH magnet capable of reaching the field of 36 T, corresponding to an EPR frequency of 1 THz for g = 2. The magnet’s intrinsic homogeneity (25 ppm, that is 0.9 mT at 36 T over 1 cm diameter, 1 cm length cylinder) was previously established by NMR. We characterized the magnet’s temporal stability (5 ppm, which is 0.2 mT at 36 T over one-minute, the typical acquisition time) using 2,2-diphenyl-1-picrylhydrazyl (DPPH). This high resolution enables resolving the weak g-anisotropy of 1,3-bis(diphenylene)-2-phenylallyl (BDPA), Δg = 2.5 × 10 –4 obtained from measurements at 932 GHz and 33 T. Subsequently, we recorded EPR spectra at multiple frequencies for two Gd III complexes with potential applications as spin labels. In conclusion, we demonstrated a significant reduction in line broadening in Gd[DTPA], attributed to second order zero field splitting, and a resolution enhancement of g-tensor anisotropy for Gd[sTPATCN]-SL.

47 OTHER INSTRUMENTATION↗
DOE OSTI2022

Optically connected memory for disaggregated data centers

Recent advances in integrated photonics enable the implementation of reconfigurable, high-bandwidth, and low energy-per-bit interconnects in next-generation data centers. We propose and evaluate an Optically Connected Memory (OCM) architecture that disaggregates the main memory from the computation nodes in data centers. OCM is based on micro-ring resonators (MRRs), and it does not require any modification to the DRAM memory modules. We calculate energy consumption from real photonic devices and integrate them into a system simulator to evaluate performance. Here, our results show that (1) OCM is capable of interconnecting four DDR4 memory channels to a computing node using two fibers with 1.02 pJ energy-per-bit consumption and (2) OCM performs up to 5.5× faster than a disaggregated memory with 40G PCIe NIC connectors to computing nodes.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2016

Connecting the irreversible capacity loss in Li-ion batteries with the electronic insulating properties of solid electrolyte interphase (SEI) components.

The formation and continuous growth of a solid electrolyte interphase (SEI) layer are responsible for the irreversible capacity loss of batteries in the initial and subsequent cycles, respectively. In this article, the electron tunneling barriers from Li metal through three insulating SEI components, namely Li 2 CO 3 , LiF and Li 3 PO 4 , are computed by density function theory (DFT) approaches. Based on electron tunneling theory, it is estimated that sufficient to block electron tunneling. It is also found that the band gap decreases under tension while the work function remains the same, and thus the tunneling barrier decreases under tension and increases under compression. A new parameter, η, characterizing the average distances between anions, is proposed to unify the variation of band gap with strain under different loading conditions into a single linear function of η. An analytical model based on the tunneling results is developed to connect the irreversible capacity loss, due to the Li ions consumed in forming these SEI component layers on the surface of negative electrodes. As a result, the agreement between the model predictions and experimental results suggests that only the initial irreversible capacity loss is due to the self-limiting electron tunneling property of the SEI.

25 ENERGY STORAGE↗
DOE OSTI2016

Calcite veins as an indicator of fracture dilatancy and connectivity during strike-slip faulting in Toarcian shale (Tournemire tunnel, Southern France)

The reactivation of faults induced by natural/human induced fluid pressure increases is a major concern to explain subsurface fluid migration and to estimate the risk of losing the integrity of reservoir/seal systems. This study focusses on paleo-fluid migration in a strike slip fault with >100 m long, affecting a Toarcian shale (Causses Basin, France). A high calcite concentration is observed in a 5 cm thick zone at the boundary between the fault core and damage zone. Cumulated displacements in this zone are of millimeter-to-centimeter-scale offsets and different dilatant deformation textures are observed. The zone is affected by thin slip planes containing gouge. Cathodo-luminescence observations indicate that two phases of vein formation occurred. The first phase coincides with the fluid migration along this centimeter thick dilatant zone. The second one is associated to re-shear along the millimeter thick slip planes that results in more localized mineralization, but also in a better hydrologic connection through the shale formation. These results show that in shales fluids may migrate off a slipping surface in centimeter scale dilatant volumes, at first controlled by the intact shale anisotropy related to bedding and then favored by brecciating, structures re-orientation and strengthening processes induced by calcite sealing effects.

58 GEOSCIENCES↗
DOE OSTI2016

Initiation and strain compatibility of connected extension twins in AZ31 magnesium alloy at high temperature

Uniaxial compression tests were carried out at 350 °C and a strain rate of 0.3 s{sup −1} on as-extruded AZ31 magnesium alloy samples. At a true strain of − 0.1, extension twin pairs in a grain and twin chains across adjacent grains were detected. The orientation of selected twins and their host grains were determined by electron backscattered diffraction (EBSD) techniques. The Schmid factors (SFs), accommodation strains and geometric compatibility factors (m{sup ′}) were calculated. Analysis of the data indicated that the formation of twin pair and twin chain was related to the SF and m{sup ′}. Regarding to twin chain across adjacent grains, accommodation strain was also involved. The selection of twin variants in twin chain was generally determined by m{sup ′}. When the twins required the operation of pyramidal slip or twinning in adjacent grain, the corresponding connected twins with a relative high m{sup ′} were selected in this adjacent grain. - Highlights: •The formation of paired twins is studied during high temperature deformation. •The initiation of twinning in twin pair and twin chain obeys the Schmid law. •The twin variants' selection in twin chain is related to the geometric compatibility factor. •The accommodation strain plays an important role on the formation of twin chain.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Grain boundary inter-connections in polycrystalline aluminum with random orientation

Highlights: • The GBICs in a pure aluminum are not random, showing remarkable preference on the planes of low Miller index. • {1 1 1}/{1 1 1} is the most frequent GBIC in pure aluminum. • {1 1 1}/{1 1 1} GBIC is mainly coming from the GBs formed by rotations around , and axes. • {1 1 1}/{1 1 1} GBIC possesses higher PCSD and definite dislocation structures compared to the general GBs. • To pursue {1 1 1}/{1 1 1} GBIC is a pint-cut for the GBE research in high stacking fault energy FCC materials. - Abstract: Grain boundary inter-connection (GBIC) is the matching of two crystallographic planes from two abutting grains ending on the grain boundary (GB) position in polycrystalline materials, which can be expressed as {h_1k_1l_1}/{h_2k_2l_2}. GBIC is the critical parameter that intrinsically defines the character and properties of a GB. In current work, a zone-melted polycrystalline aluminum bar with a purity higher than 99.99% (mass fraction) was subjected to a multi-directional forging (MDF) with a true strain of 4 followed by a recrystallization annealing at 360 °C. Such process repeated at least 4 times until an equiaxed-grain microstructure with random orientation and averaged grain size approximate 30 μm was achieved. Then the GBICs were determined by electron backscatter diffraction (EBSD) measurement and stereology-based five-parameter analysis (FPA) coupled with crystallographic analysis after the grain boundaries (GBs) were filtered according to their misorientations (e.g. angle/axis pair). The results revealed that the GBICs for any group of GBs with a given misorientation are not random, showing remarkable preference on the planes of low Miller index forming mixed and twist GBs. The work also demonstrated that among the high angle boundaries (HABs), {1 1 1}/{1 1 1}, including coherent ∑3 boundaries, is the most frequent GBIC, mainly due to the GBs formed by rotations around <1 1 1>, <1 2 2> and <1 1 2> axes. Near coincidence site (NCS) and O-lattice theory analyses indicate that the {1 1 1}/{1 1 1} GBICs usually possess higher planar coincidence site density (PCSD) and definite dislocation structures compared to the general GBs, implying their more structural stability when only crystallography is taken into account. This result agrees very well with the recent results obtained by molecular dynamic simulations. It is significant to the grain boundary engineering (GBE) in the high stacking fault energy (SFE) face-centered cubic (FCC) materials such as aluminum and its alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Metabolic and functional connections between cytoplasmic and chloroplast triacylglycerol storage

Neutral lipids in the form of triacylglycerol (TAG) have emerged as critical regulators of cellular energy balance, lipid homeostasis, growth, development and stress response in organisms ranging from plants to yeast. Although TAGs are mostly recognized as the main storage component in cytoplasmic lipid droplets (LDs), TAG-rich LDs with similar structural and functional characteristics to those found in the cytoplasm also exist in chloroplasts of microalgae and higher plants. Chloroplasts contain up to 70% of total lipids in photosynthetic cells, yet how organisms maintain chloroplast lipid homeostasis remains an under-investigated area of research. In this work, we summarize the current state of knowledge about the metabolism of TAG and its function in chloroplasts, with a focus on the enzymes catalyzing the final steps of TAG assembly and the role of TAG synthesis in protection against lipotoxicity. We also discuss emerging data regarding connections between cytoplasmic and chloroplast TAG metabolism and the role of autophagy in the degradation of chloroplast storage lipids.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Modeling interconnections of safety and financial performance of nuclear power plants, part 3: Spatiotemporal probabilistic physics-of-failure analysis and its connection to safety and financial performance

Here, this paper is a byproduct of a line of research by the authors to analyze interrelationships of safety and financial performance of nuclear power plants (NPPs). The result of this line of research is summarized in three parts: Part 1 covers a categorical review of relevant literature and the theoretical bases that support the methodological developments in Part 2. Part 2 introduces an Integrated Enterprise Risk Management (I-ERM) methodological framework to quantify the interconnections of safety and financial performance with a focus on operation and maintenance (O&M) of NPPs. Part 2 has also demonstrated the applicability and values of the I-ERM methodology through an NPP case study. This paper is Part 3, where detailed development and implementation of one of the I-ERM modules, i.e., probabilistic physics-of-failure (PPoF) analysis, and its connection with safety and financial performance is reported. In this article, the physical failure modeling for hardware components is advanced by incorporating finite element analysis (FEA) into PPoF analysis and coupling the FEA-based PPoF with the maintenance performance through a renewal process model. This article covers two scientific contributions: (i) first-of-its-kind incorporation of FEA into the PPoF model of thermal fatigue for NPP components; and (ii) advancing the interface between the PPoF analysis and the renewal process model in order to deal with spatiotemporal FEA outputs and to efficiently estimate the physical transition rates even when the PPoF outputs are dominated by success data. Through the incorporation of FEA, the resolution of the PPoF analysis is enhanced as spatiotemporal conditions such as stress and temperature can be considered explicitly instead of relying on simplified assumptions or analytical models with reduced spatiotemporal dimensions. To demonstrate an application of the FEA-based PPoF analysis and its coupling with maintenance through the renewal process model, a case study is conducted using excess letdown elbow piping in the chemical and volume control system of a Pressurized Water Reactor.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2024

Connecting radiation-driven changes in structural, thermal, and mechanical properties in several medical device polymers

Stemming from security threats and shortages in supply, a recent push has emerged to develop alternatives to radioisotope Cobalt-60 gamma radiation for sterilization of polymeric medical products, including electron beam (e-beam) and X-ray machine-based sources. However, before large-scale implementation, the effects of these non-isotope-based methods must be thoroughly investigated from several perspectives, involving their potential detrimental effects on the structural, thermal, and mechanical properties of polymers in medical devices. This paper investigates such effects in commonly used medical device polymers, including polypropylene homopolymer (PPH), polyolefin elastomer (POE), low-density polyethylene (LDPE), acrylonitrile butadiene styrene (ABS), and chlorobutyl rubber (CIIR). To connect radiation-driven changes in polymer structural and thermal properties and corresponding changes in mechanical properties, several characterization techniques were utilized, including gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FTIR), dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). We found that the tensile strength of X-ray irradiated PPH, as well as X-ray, e-beam, and gamma irradiated CIIR decreases due to chain scission, which is corroborated by GPC and DMA. The GPC results of LDPE suggest chain scission, but interestingly without a corresponding decline in tensile strength. By comparison, POE and ABS appear to undergo further crosslinking with increasing irradiation dose, which generally strengthens them. Importantly, in the vast majority of the cases, there were small to no changes in properties upon changing radiation technologies (at a given dose), i.e., no radiation source dependence. However, in a few specific cases, radiation method dependencies did arise, for instance, in terms of the molecular weight of PPH being significantly increased upon X-ray irradiation, while the melting temperature, glass transition temperature, and elongation at break reduced compared to gamma. Overall, this study provides valuable insight into radiation-driven chemical and structural changes in polymers that produce changes in physical and functional properties.

36 MATERIALS SCIENCE↗
DOE OSTI2020

The global energy footprint of information and communication technology electronics in connected Internet-of-Things devices

Information and communication technology (ICT) has been critical to the emergence of a new Internet-of-Things (IoT) era, as a rapidly increasing number and variety of IoT electronic devices in a wide range of end-use sectors require massive data communication in terms of volume, velocity/speed, and variety. Additionally, semiconductor technology advancements have played a key role in ICT and unlike the past ICT energy footprint analysis, which focused on the final electronic product, an attempt has been made to examine the global energy impacts for the period 2016–2025 based on the market forecasts of three major IoT IC types, i.e., sensors and actuators, connectivity, and processor ICs distributed among four major IoT device components.Total global IoT semiconductor primary energy demand is projected to increase from 2 EJ in 2016 to 35 EJ by 2025, resulting mainly from a substantial projected increase energy needed in the manufacturing of ICs, with growth in the use of sensors and energy-intensive next fab generation manufacturing. Unlike the trend in manufacturing energy, total global operational energy use is projected to decrease significantly with the development of smaller transistor size, low-power devices, and faster wireless data communication technology. Total operational energy is projected to significantly decrease from 118 TWh/year (1,2 EJ/year) to less than 1 TWh/year (0.003 EJ/year) in spite of a significantly higher anticipated growth in its market size during the 2016–2025 forecast period. Its annual share of total primary energy use is projected to reach an insignificant level of 0.01% by the end of 2025, consistent with the past limited electronic product life cycle analyses besides the analysis focus here limited to ICs in IoT devices.

24 POWER TRANSMISSION AND DISTRIBUTION↗
DOE OSTI2026

Optimization-based approaches to control of connected and automated vehicles: Principles, complexities, applications, challenges, and outlook

Safe and optimal motion control for connected and automated vehicles (CAVs) poses a fundamental optimization challenge at the intersection of system complexity, environmental uncertainty, and stringent real-time constraints. Existing surveys address this challenge in isolation – focusing either on specific control techniques or individual uncertainty sources – without providing a unified framework that characterizes the trade-offs among computational tractability, performance verifiability, and adaptive generalization across paradigms. This review addresses that gap by presenting a cohesive analytical framework concentrated on the decision-making and trajectory optimization layers of the CAV autonomy stack. We systematically analyze three major optimization paradigms – first-principles model-based optimization, data-driven methods, and hybrid synergistic architectures – evaluating each against four core complexity axes: problem formulation, constraint handling, optimality guarantees, and robustness. Key applications including platooning, trajectory planning, collision avoidance, and cooperative control are examined to reveal recurring methodological patterns and critical operational constraints that limit real-world performance. Our synthesis identifies verifiable hybrid architectures, incentive-aligned multi-agent cooperation, and hardware-algorithm co-design as the defining research frontiers, and distills a targeted agenda for developing CAV control systems that are simultaneously safe, computationally efficient, and deployable in the full complexity of real-world traffic environments.

Muzahid, Abu Jafar Md [University of Tennessee, Kn↗
DOE OSTI2018

Tuft cells: Distribution and connections with nerves and endocrine cells in mouse intestine

Highlights: • Tuft cells are found in villi/surface epithelia and crypts throughout the intestine. • Tuft cell number decrease in a proximal to distal manner. • Contacts between tuft cells and satiety associated endocrine cells are described. • Tuft cells display numerous contacts with mucosal nerve fibers. Tuft cells are gastrointestinal (GI) sensory cells recognized by their characteristic shape and their microvilli “tuft”. Aims of the present study were to elucidate their regional distribution and spatial connections with satiety associated endocrine cells and nerve fibers throughout the intestinal tract. C57BL/6 J mice were used in the experiments. The small intestine was divided into five segments, and the large intestine was kept undivided. The segments were coiled into “Swiss rolls”. Numbers and topographic distribution of tuft cells and possible contacts with endocrine cells and nerve fibers were estimated in the different segments, using immunocytochemistry. Tuft cells were found throughout the intestines; the highest number was in proximal small intestine. Five percent of tuft cells were found in close proximity to cholecystokinin-immunoreactive (IR) endocrine cells and up to 10% were in contact with peptide YY- and glucagon-like peptide-1-IR endocrine cells. Sixty percent of tuft cells in the small intestine and 40% in the large intestine were found in contact with nerve fibers. Calcitonin gene-related peptide-IR fibers constituted one-third of the fiber-contacts in the small intestine and two-thirds in the large intestine. These observations highlight the possibility of tuft cells as modulators of GI activities in response to luminal signaling.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2025

Electroreduction-Driven Formation and Connectivity of Polyoxometalate Coordination Networks

We present the synthesis of metal oxide coordination networks based on Preyssler-type polyoxoanions ([NaP 5 W 30 O 110 ] 14– and [NaP 5 MoW 29 O 110 ] 14– ) bridged with metal–aquo complexes ([M(H 2 O) n ] m+ , M m+ = Co 2+ , Ni 2+ , Zn 2+ , Y 3+ ), induced by electrochemical reduction. Networks bridged with first-row transition metals are isostructural with a previously reported Co-bridged structure, while the Y 3+ -bridged structure is new. All networks feature an uncommon binding motif of the metal cation to the oxygen atoms at cap positions, which we hypothesize is due to increased electron density at the cap upon reduction. Oxidation of a Zn 2+ -bridged network resulted in a new structure in which Zn 2+ –O cap bonds are lost, indicating the importance of reduction in the connectivity of these polyoxometalate-based coordination networks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Møller–Plesset and Density-Fixed Adiabatic Connections for a Model Diatomic System at Different Correlation Regimes

In recent years, adiabatic connection (AC) interpolations developed within density functional theory (DFT) have been found to provide good performances in the calculation of interaction energies when used with Hartree–Fock (HF) ingredients. The physical and mathematical reasons for such unanticipated performance have been clarified, to some extent, by studying the strong-interaction limit of the Møller–Plesset (MP) AC. In this work, we calculate both the MP and the DFT AC integrand for the asymmetric Hubbard dimer, which allows for a systematic investigation of different correlation regimes by varying two simple parameters in the Hamiltonian: the external potential, Δv, and the interaction strength, U. Notably, we find that, while the DFT AC integrand appears to be convex in the full parameter space, the MP integrand may change curvature twice. Furthermore, we discuss different aspects of the second-order expansion of the correlation energy in each AC, and we demonstrate why the derivative of the λ-dependent density in the MP AC at λ = 0 (i.e., at the HF density) is zero in the model. Concerning the strong-interaction limit of both ACs in the Hubbard dimer setting, we show that the asymptotic value of the MP AC, W ∞ HF , is lower than (or equal to) its DFT analogue, W ∞ KS , if the two are compared at a given density, just like in real space. Furthermore, we also show that this is not always the case if the two quantities are compared at a given external potential.

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

Probing Pore Size and Connectivity in Porous Silicas Using 13C MAS NMR Spectroscopy of Supercritical Methane

Measuring the pore size and pore-size distributions and exploring the fluid-exchange dynamics between different types of pores in porous materials remains a significant experimental challenge but is critical to understanding catalysis, chromatography, nutrient cycling, and a whole range of geochemical phenomena, including shale gas and tight gas extraction. Here, we present the results of 1D 13 C NMR and 2D exchange spectroscopy (EXSY) NMR investigations of a porous silica using supercritical methane (scCH 4 ) as a direct probe of pore size and fluid exchange between pore types. The results show that the 13 C chemical shift of scCH 4 adsorbed in nanometer-scale silica pores becomes more negative with increasing pore diameter, in agreement with trends reported for gas hydrates, zeolites, MOFs, and clays and other microporous (<10 nm pores) geochemical materials. These 13 C chemical shifts follow a natural log–linear trend with pore size in the vacuum-dried porous silicas studied here, allowing one to predict pore size based on the 13 C chemical shift in dry silica nanopores. The EXSY and 1D 13 C NMR results both show that CH 4 exchanges between pore and bulk fluid environments over rate scales from 0.01 to 1 kHz in vacuum-dried samples and that exchange dynamics must be considered when interpreting 13 C NMR of pore-adsorbed CH 4 . Introducing H 2 O to the system causes the 13 C chemical shift to become more negative with increasing H 2 O content as a result of H 2 O preferentially filling small pores, forcing CH 4 to occupy larger pores that are better connected to the bulk environment. Likewise, the 1D 13 C data show a decreased distribution of exchange rates between pore-adsorbed and bulk CH 4 in the presence of H 2 O.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗