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At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Surface and bulk characterization of reservoir and cap-rocks: Past, present, and future

Geologic formations provide potentially some of the largest volume capacities for CO 2 storage or sequestration. Potential storage sites can be deep saline aquifers, depleted oil reservoirs, and coal seams, surrounded by sealing layers to prevent CO 2 from leaking. It is therefore critical to understand mechanisms contributing to CO 2 trapping and CO 2 leaks. Both phenomena are governed by reactions at the interfaces of the reservoir and cap-rocks and are controlled by the complex chemistry and pore structures of rocks. Mechanisms at the macroscale are affected by the processes occurring at the nanoscale. This review highlights the necessity of multitechnique, multiscale characterization of rocks and points to the importance of surface analysis and surface science studies. Two shale rocks (seals) from Niobrara and Agardhfjellet formations with complex surface chemistry are used as examples throughout the paper. Typically, evaluation of rocks with x-ray diffraction, thermogravimetric analysis, Rock-Eval pyrolysis, gas adsorption, and electron microscopy combined with energy dispersive x-ray spectroscopy is conducted to provide valuable information about the bulk mineralogy, elemental composition, pore volume, and adsorbed species on the sample surface. These studies are necessary prior to designing surface sensitive experiments with x-ray photoelectron spectroscopy (XPS), guiding both sample preparation and sample analysis. XPS has been widely used to study the surface composition of rocks during the investigations of their fine-scale wettability, and the main findings are highlighted here. This paper also reviews the existing literature on ambient-pressure XPS, which provides new opportunities to study in situ chemical alteration due to interactions with CO 2 and offers recommendations for adapting this technique to study rock-fluid interactions, allowing for the identification of fundamental interactions during CO 2 sequestration and guide selection of formation sites for improved storage.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Automated pipeline processing X-ray diffraction data from dynamic compression experiments on the Extreme Conditions Beamline of PETRA III

Presented and discussed here is the implementation of a software solution that provides prompt X-ray diffraction data analysis during fast dynamic compression experiments conducted within the dynamic diamond anvil cell technique. It includes efficient data collection, streaming of data and metadata to a high-performance cluster (HPC), fast azimuthal data integration on the cluster, and tools for controlling the data processing steps and visualizing the data using the DIOPTAS software package. This data processing pipeline is invaluable for a great number of studies. The potential of the pipeline is illustrated with two examples of data collected on ammonia–water mixtures and multiphase mineral assemblies under high pressure. The pipeline is designed to be generic in nature and could be readily adapted to provide rapid feedback for many other X-ray diffraction techniques, e.g. large-volume press studies, in situ stress/strain studies, phase transformation studies, chemical reactions studied with high-resolution diffraction etc.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2020

Thermal, mechanical, and electrical properties of LSCo/mullite composite contact materials for solid oxide fuel cells

Lanthanum strontium cobaltite (LSCo) is considered as a good candidate cathode contact material for solid oxide fuel cells, due to high electrical conductivity. However, LSCo has a very large coefficient of thermal expansion (CTE) than the cells and metallic interconnects. As a result, poor mechanical stability is expected during thermal cycling. To minimize the CTE mismatch, we investigate a composite approach involving mixing LSCo with an inert material of low CTE, such as mullite at volume fractions from 0.1 to 0.4. Composite’s CTE shows a decreasing trend with increasing mullite volume fractions, and is consistent with model predictions. X-ray powder diffraction analysis of sintered LSCo/mullite composites exhibits no presence of other phases for samples aged for 500h at 800oC, indicating chemical compatibility. Electrical conductivity by a 4-pt method shows a decreasing trend with increasing mullite content. Contact strength of as-sintered and thermally cycled samples show that only the composite with 0.4 volume fraction has a measurable strength; the other composites have no strength. Overall, the composite approach is demonstrated in the LSCo/mullite system to lower the CTE and hence achieve thermal cycle stability. The addition of the inert phase to the LSCo matrix; however, also reduces the electrical conductivity.

Contact materials, LSCo, mullite, CTE, electrical ↗
DOE OSTI2022

Tuscaloosa Marine Shale: Seal or Source? Petrophysical Comparative Study of Wells in SE Louisiana and SW Mississippi

The Tuscaloosa Marine Shale (TMS) is a versatile Late Cretaceous shale formation present in central and SE Louisiana and SW Mississippi, which drew attention because of the various roles played within the Tuscaloosa Group. In this paper, it is debated whether the Tuscaloosa Marine Shale can act as a source, reservoir, or seal all throughout the shale play or only in certain areas. Well log and core data from Adams County, Mississippi, are compared to data from East Feliciana Parish in Louisiana. Conclusions were drawn based on the results of well log analysis, X-ray Diffraction (XRD), porosity–permeability measurements, programmed pyrolysis, and fracture analysis. It was shown that the Tuscaloosa Marine Shale interval in SE Louisiana consists of important amounts of calcite, exhibits multiple natural fractures, has porosity values as high as 9.3%, and shows a TOC content of up to 2.8 wt%. On the other hand, samples from a well at the Cranfield field, MS, are characterized by considerably lower TOC values of around 0.88 wt%, porosities between 0.33% and 4%, and no serious fracturing. The formation demonstrates better reservoir and source potential in SE Louisiana and reliable CO2 sealing capacity in SW Mississippi. The analysis presented in this paper represents a holistic approach to the characterization of shale formations, is applicable to other plays around the world, and can be used as an integral part of CO2 sequestration or hydraulic fracturing programs.

04 OIL SHALES AND TAR SANDS↗
DOE OSTI2022

LDRD 226360 Final Project Report: Simulated X-ray Diffraction and Machine Learning for Optimizing Dynamic Experiment Analysis

This report is the final documentation for the one-year LDRD project 226360: Simulated X-ray Diffraction and Machine Learning for Optimizing Dynamic Experiment Analysis. As Sandia has successfully developed in-house X-ray diffraction tools for study of atomic structure in experiments, it has become increasingly important to develop computational analysis methods to support these experiments. When dynamically compressed lattices and orientations are not known a priori, the identification requires a cumbersome and sometimes intractable search of possible final states. These final states can include phase transition, deformation and mixed/evolving states. Our work consists of three parts: (1) development of an XRD simulation tool and use of traditional data science methods to match XRD patterns to experiments; (2) development of ML-based models capable of decomposing and identifying the lattice and orientation components of multicomponent experimental diffraction patterns; and (3) conducting experiments which showcase these new analysis tools in the study of phase transition mechanisms. Our target material has been cadmium sulfide, which exhibits complex orientation-dependent phase transformation mechanisms. In our current one-year LDRD, we have begun the analysis of high-quality c-axis CdS diffraction data from DCS and Thor experiments, which had until recently eluded orientation identification.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2021

Combined effect of NaAlO2 and NaOH on the early age hydration of Portland cement with a high concentration of borate solution

The early age hydration of ordinary Portland cement in 5 M borate solution, with or without the addition of NaAlO{sub 2} and/or NaOH, was investigated. Hydration was measured using calorimetry, X-ray diffraction, thermogravimetric analysis, {sup 11}B and {sup 27}Al magic angle spinning NMR analysis, and scanning transmission electron microscopy. The purpose of this study was to reveal the mechanisms behind the retardation caused by a high concentration borate solution and the restoration of hydration through the combined addition of NaOH and NaAlO{sub 2}. Amorphous ulexite, which formed on the surface of the cement particles and prevented the further dissolution of anhydrous phases, was identified as the retardation product. The mechanism of the combined addition of NaAlO{sub 2} and NaOH in overcoming retardation was to transform amorphous ulexite into B-AFt and gowerite (CaB{sub 6}O{sub 10}·5H{sub 2}O). Formation of gowerite is favorable because of the much higher boron immobilization capacity in weight percentage, comparing to usual boron-containing phases reported previously.

36 MATERIALS SCIENCE↗
DOE OSTI2022

HP-PdF2-type FeCl2 as a potential Cl-carrier in the deep Earth

Here, we report for the first time the formation of a HP-PdF 2 -type FeCl 2 phase (space group Pa$\bar{3}$), through high pressure-temperature (P-T) reactions in the hydrous systems (Mg 0.6 Fe 0.4 )SiO 3 –H 2 O–NaCl and FeO2H–NaCl in a laser-heated diamond-anvil cell up to 108 GPa and 2000 K. Applying single-crystal X-ray diffraction (XRD) analysis to individual submicrometer-sized grains, we have successfully determined the crystal structure of the as-synthesized FeCl 2 phase, in agreement with our theoretical structure search results. In situ high P-T XRD data revealed the substitution of Cl for OH(O) in such a cubic Pa$\bar{3}$ structure, demonstrating that this topology is a potential host for both H and Cl in the deep Earth. The chemical analysis of the recovered sample showed that the post-perovskite phase contains considerable amounts of Na 2 O and Fe 2 O 3 . The coexistence of the cubic FeCl 2 phase and post-perovskite suggests that the lowermost mantle could be a potential reservoir of Cl. The possible presence of volatiles such as H and Cl in the deep lower mantle would impact the composition and iron valence state of the post-perovskite phase.

58 GEOSCIENCES↗
DOE OSTI2022

Influence of oxidizing and reducing pretreatment on the catalytic performance of CeO 2 for CO oxidation

Cerium oxide (CeO 2 ) and ceria-based materials have been extensively investigated as catalyst and support materials for various catalytic reactions, due to higher oxygen storage capacity and excellent redox properties. In the current work, we investigated the impact of pretreatment conditions (e.g., oxidation and reduction) on the physical properties of bulk CeO 2 and catalytic activity for CO oxidation as a model reaction. To understand the physical properties of pretreated CeO 2 catalysts, a suite of complementary characterization techniques, including X-ray diffraction (XRD), surface area analysis (BET), X-ray photoemission spectroscopy (XPS), and Raman spectroscopy, were applied. The results showed that a higher pretreatment temperature led to a decreased specific surface area (SSA), a decrease in oxygen vacancy/defect sites, and increased crystallite size, while surface Ce 3+ /Ce 4+ ratio did not show a specific relationship to the treatment conditions. The 700 °C treated CeO 2 samples under oxidizing and reducing conditions showed higher specific oxidation rate (μmolCO/s/m 2 ) compared to other samples at 280 and 300 °C (or < 15% CO conversion). The CO conversion per total mass of catalysts, however, decreased with increasing temperatures, especially at 700 °C under reducing condition, indicating that the catalytic performance was affected by the physical properties (SSA, oxygen vacancy/defect sites, and crystallite size).

36 MATERIALS SCIENCE↗
DOE OSTI2025

Ba 1−x Sr x FeO 3−δ as an improved oxygen storage material for chemical looping air separation: a computational and experimental study

Chemical looping air separation (CLAS) is a promising technology to generate oxygen-rich gas streams to enable efficient carbon dioxide capture during fossil fuel combustion or gasification. CLAS relies on the capture and release of oxygen from the atmosphere using the redox properties of an oxygen-selective solid oxide carrier. This study investigates the redox characteristics of Ba 1−x Sr x FeO 3−δ (0.0 ≤ x ≤ 0.417, 0.0 ≤ δ ≤ 0.5) using a combination of density functional theory (DFT) calculations and experimental verification using X-ray diffraction, thermogravimetric analysis, and oxygen-temperature-programmed desorption. The DFT computed energies of the Ba 1−x Sr x FeO 3−δ perovskites reveal a composition-dependent transition from hexagonal to cubic phases as the Sr-concentration or oxygen vacancy concentration increases. Oxygen vacancy formation energies of the cubic perovskites are found to be lower than those of their hexagonal counterparts. A low oxygen diffusion barrier of ∼1 eV combined with the thermodynamic preference of Ba 1−x Sr x FeO 3−δ compositions that form in a cubic phase suggests them as promising candidates for oxygen storage applications. The experimental results corroborate this finding by identifying Ba 0.75 Sr 0.25 FeO 3−δ in the cubic phase as an optimal composition offering low-temperature oxygen storage capacities comparable to that of the state-of-the-art Sr 0.75 Ca 0.25 FeO 3−δ perovskite oxygen storage material at 325 °C and 350 °C.

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

Trickier than It Looks: Isomerization between Five- and Six-Coordinated Zinc in Heterometallic Li 2 Zn 2 Molecule

This report describes the synthesis and characterization of two hetero bi metallic Li–Zn coordination isomers [Li 2 Zn 2 (tbaoac) 6 ] (tbaoac = tert -butyl acetoacetato) that have been isolated separately by the same stoichiometric reaction run in different organic solvents. The 6-coordinated zinc isomer ( 6-Zn ) was synthesized in acetone with high yield, while the 5-coordinated one ( 5-Zn ) was readily obtained from ethanol. The 5-Zn isomer has a low solubility in organic solvents such as alkanes and haloalkanes, while its 6-Zn counterpart exhibits a good solubility in almost all common solvents. Two isomeric molecules feature similar centrosymmetric tetranuclear cyclic assemblies, which are different in their arrangement of tbaoac ligands. While all ligands act as μ 2 -type in the structure of 5-Zn , the two tbaoac groups chelating Li appear as μ 3 -type in 6-Zn , thus providing an additional coordination for Zn ions. However, the real structural transformation between these isomers was shown to be more complex than simply making or breaking a couple of Zn–O bonds. X-ray single-crystal structure analysis, powder X-ray diffraction, multinuclear NMR, DART mass spectrometry, ICP-OES analysis, and TGA have been employed for the characterization of the isomers. The combination of powder X-ray diffraction and 1 H NMR investigation revealed that 6-Zn isomer can be quantitatively transformed to 5-Zn in ethanol, while the reverse conversion instantly takes place in acetone.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

High Strain Response and Dielectric Properties of Bi 1/2 (Na 0.78 K 0.22 ) 1/2 TiO 3 Ceramics Doped with (Fe 1/2 Nb 1/2 ) 4+

Environmentally friendly piezoceramics Bi 1/2 (Na 0.78 K 0.22 ) 1/2 Ti 1-x (Fe 1/2 Nb 1/2 ) x O 3 (BNKT-FN) with FeNb (FN) ratios 0, 0.01, 0.02, 0.03 and 0.04 were synthesized via conventional solid-state reaction (CSSR). X-ray diffraction (XRD) analysis revealed that the FN complexes were completely dissolved in BNKT perovskite and the structural transition occurred from ferroelectric to relaxor state. The average grain sizes for x = 0, 0.01, 0.02, 0.03 and 0.04 were found to be 0.34 μm, 0.35 μm, 0.38 μm, 0.32 μm and 0.39 μm, respectively. It is observed that the grain size increased with the addition of FN, except for x = 0.03. Here, the coercive field (E c ) and remnant polarization (P r ) of the system were decreased with increasing FN concentration and the highest E c of 21.1 kV/cm and P r of 29.2 μC/cm 2 were noted for the base pure sample. In addition, the increase of FN content steadily broadened the dielectric anomaly at maximum dielectric constant temperature (T m ) in the BNKT-FN system. Consequently, unipolar normalized strain (S max /E max ) was found to be enhanced monotonically achieving the highest value of around 654 pm/V (x = 0.02). These properties suggest that the investigated system could be a promising eco-friendly candidate for piezoelectric actuators and many other applications requiring high piezoelectric induced strain.

25 ENERGY STORAGE↗
DOE OSTI2022

Caution on Using Tetrahydrofuran for Processing Crystalline Silica Samples From Engineered Stone for XRD Analysis

Abstract We conducted laboratory experiments to investigate a suspected effect of tetrahydrofuran (THF) on quantifying crystalline silica in samples collected from working with engineered stone when THF is used to process samples prior to the X-ray diffraction (XRD) analysis. Two groups of samples from grinding either engineered stone or granite were simultaneously taken from a laboratory testing system, with one group of samples using THF for processing and another group using muffle furnace for ashing. For each stone type, we also tested four levels of respirable dust loading on the samples by varying the grinding time from 1 to 8 min. Statistical analysis of the experimental results on crystalline silica contents of the two groups of samples showed that the difference between the two methods was not significant (P ≥ 0.05) for the granite at all four levels of respirable dust loading and for the engineered stone at the two levels of respirable dust loading greater than 0.5 mg. However, the crystalline silica content from using THF processing was significantly lower (P = 0.001) than that from using muffle furnace ashing for engineered stone when the respirable dust loading levels were less than 0.5 mg. For the engineered stone dust samples with grinding times of 1 and 2 min, the average respirable dust loading was about 0.19 and 0.34 mg, respectively; while the crystalline silica content from using THF processing was 30.9 and 21.5% lower than that from using muffle furnace ashing, respectively. Since most full-shift samples from field assessments in this industry are expected to have respirable dust loading less than 0.5 mg, muffle furnace or radio frequency plasma ashing should be specified as the preferred sample processing method instead of the THF processing method for quantification of crystalline silica when engineered stone is expected to present to avoid artificially reduced silica content values, which are likely caused by the reactions between THF and the resins in engineered stone.

Public, Environmental & Occupational Health↗
DOE OSTI2023

Superconductivity and magnetic and transport properties of single-crystalline CaK ( Fe 1 – x Cr x ) 4 As 4

Members of the CaK (Fe 1–x Cr x ) 4 As 4 series have been synthesized by high-temperature solution growth in single-crystalline form and characterized by x-ray diffraction, elemental analysis, and magnetic and transport measurements. The effects of Cr substitution on the superconducting and magnetic ground states of CaKFe 4 As 4 (T c = 35 K) have been studied. These measurements show that the superconducting transition temperature decreases monotonically and is finally suppressed below 1.8 K as x is increased from 0 to 0.038. For x-values greater than 0.012, signatures of a magnetic transition can be detected in magnetic measurements with the associated features in the transport measurements becoming detectable for x ≥ 0.038. The magnetic transition temperature increases in a roughly linear manner as Cr substitution increases. A temperature-composition (T – x) phase diagram is constructed, revealing a half-dome of superconductivity with the magnetic transition temperature, T*, appearing near 22 K for x ~ 0.017 and rising slowly up to 60 K for x ~ 0.077. The T – x phase diagrams for CaK (Fe 1–x T x ) 4 As 4 for T = Cr and Mn are essentially the same despite the nominally different band filling; this is in marked contrast to T = Co and Ni series for which the T – x diagrams scale by a factor of 2, consistent with the different changes in band filling Co and Ni would produce when replacing Fe. Superconductivity of CaK (Fe 1–x Cr x ) 4 As 4 is also studied as a function of magnetic field. A clear change in $H^{'}_{c2}$ (T)/T c , where $H^{'}_{c2}$ (T) is dH c2 (T)/dT, at x ~ 0.012 is observed and probably is related to a change of the Fermi surface due to magnetic order. Further, coherence length and the London penetration depths are also calculated based on H c1 and H c2 data. Both of them as a function of x show changes near x = 0.012, again consistent with Fermi surface changes associated with the magnetic ordering seen for higher x-values.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Reentrant polar phase induced by the ferroionic coupling in B⁢i 1−𝑥 ⁢S⁢m 𝑥 ⁢Fe⁢O 3 nanoparticles

Using the model of four sublattices, the Landau-Ginzburg-Devonshire-Kittel phenomenological approach and the Stephenson-Highland ionic adsorption model for the description of coupled polar and antipolar long-range orders in ferroics, we analytically calculated the phase diagrams and polar properties of B⁢i 1−𝑥 ⁢S⁢m 𝑥⁢ Fe⁢O 3 nanoparticles covered by surface ions with dependence on their size, surface ions density, samarium content 𝑥 , and temperature. The size effects and ferroionic coupling govern the appearance and stability conditions of the long-range ordered ferroelectric, reentrant ferrielectric, and antiferroelectric phases in B⁢i 1−𝑥 ⁢S⁢m 𝑥 ⁢Fe⁢O 3 nanoparticles. Calculated phase diagrams are in qualitative agreement with the x-ray diffraction phase analysis, electron paramagnetic resonance, infrared spectroscopy, and electrophysical measurements of B⁢i 1−𝑥 ⁢S⁢m 𝑥 ⁢Fe⁢O 3 nanopowders sintered by the solution combustion method. The combined theoretical-experimental approach allows us to explain the influence of the ferroionic coupling and size effects in B⁢i 1−𝑥 ⁢S⁢m 𝑥 ⁢Fe⁢O 3 nanoparticles on their polar properties.

antiferroelectricity↗
DOE OSTI2024

Dielectric and magnetic properties of microwave-absorbing FeAl x O y catalysts fabricated via solution combustion synthesis

Iron-based alumina (FeAl x O y ) nanocomposites are microwave-absorbers and catalysts, which makes them promising for emerging microwave-assisted thermocatalytic technologies. Solution combustion synthesis (SCS) has been used to synthesize FeAl x O y powders, and prior work has demonstrated that adjusting SCS parameters significantly changes phase composition and specific surface area of the products. However, it is unclear how synthesis parameters affect their microwave-absorbing properties, which are essential for optimizing microwave-assisted technologies. To address this challenge, in the present work, twelve different FeAl x O y products were synthesized at different combinations of the SCS parameters such as two fuels (citric acid and glycine), two heating modes (hotplate and muffle furnace), and three Fe:Al molar ratios (2:1, 1:1, 1:2). Dielectric and magnetic properties of the products were characterized using a network analyzer and a vibrating sample magnetometer. Based on the measured permittivity and permeability, penetration depth and reflection loss were calculated as a function of frequency and bed thickness. The products were heated by microwaves at 2.45 GHz and then examined with X-ray diffraction (XRD) analysis. For all products, the magnetic saturation was lower than for bulk iron oxides because of the small crystallite size and aluminum substitution. The use of glycine induced high dielectric losses and enabled fast microwave-heating rates compared to citric acid. Higher Fe:Al ratio also led to higher dielectric and magnetic losses. With glycine fuel, SCS in a furnace induced larger penetration depth and lower microwave absorption than SCS on a hotplate. The minimization of reflected power was more sensitive to the thickness of the product bed than to the frequency of the electromagnetic field. Post-heating XRD analysis revealed different phase transformations in the FeAl x O y powders depending on the SCS parameters. As a result, an FeAl x O y material, synthesized via incipient wetness impregnation, lacked magnetic losses and did not heat well as compared to the SCS products.

Combustion synthesis↗
DOE OSTI2025

Uptake and binding of La 3+ and Cr 3+ ions by alkali metal substituted alpha-zirconium phosphate

The conversion of alpha-zirconium phosphate, Zr(HPO 4 ) 2 ·H 2 O, to the K-, Rb-, and Cs-phases and the subsequent ion exchange behavior of these alkali metal phases, A-ZrP, with La 3+ and Cr 3+ have been investigated. The conversion to the A-ZrP phases was achieved by reaction with metal chloride, metal hydroxide solution, and confirmed through various techniques, including X-ray powder diffraction, thermogravimetry analysis, IR spectroscopy, scanning and transmission electron microscopy, and X-ray photoelectron spectroscopy. The effect of material hydration, which increased the interlayer distance, was also examined. The ion exchange behavior of the A-ZrP showed strong affinity for both La 3+ , a representative for trivalent lanthanide metals, and Cr 3+ , a representative for the trivalent transition metals, with a rapid, near quantitative removal of the M 3+ ions at a pH of 3 when the ion concentration was ≤25% of the ion exchange capacity of the materials. Additionally, the ion affinity was shown to be pH and concentration-dependent, decreasing with a decrease in pH or an increase in ion concentration. Lastly, the binding strength of La- and Cr-loaded ZrP materials was examined through a series of leaching experiments in a carbonate buffer, phosphate buffer, HEPES buffer, and a series of EDTA solutions at various concentrations. No observable leaching occurred in the carbonate buffer, phosphate buffer, HEPES buffer, or when the EDTA concentration was below 0.1 mM. These results highlight the potential for the A-ZrP materials to provide a platform for trivalent transition metal and trivalent lanthanide radionuclide capture for various applications.

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

Laboratory-Scale Coal-Derived Graphene Process (Final Report)

The Energy & Environmental Research Center (EERC) conducted a laboratory-scale coal-derived graphene (CDG) project focused on developing a technological process for making graphene from four U.S. domestic coal or coal wastes, including lignite from North Dakota, subbituminous coal from Wyoming, bituminous coal from Utah, and anthracite from Pennsylvania. The project was divided into two performance or budget periods (BPs), with BP1 comprising the up-front laboratory experiments to make graphene materials from coal beginning on May 1, 2020, to April 30, 2022. BP2 was conducted from May 1, 2022, to April 30, 2023, and was focused on analyzing the CDG process economic feasibility and the technical gaps for technological scale-up and commercialization. During this project, a few different coal-derived high-value products have been demonstrated, including graphite, graphene oxide (GO), reduced graphene oxide (rGO), and graphene quantum dots (GQDs). A new graphite microstructure was discovered and named “croissant graphite” because of the exterior morphological and textural resemblance to croissant food items sold in commercial groceries stores. The new graphite structure and the associated preparation from coal or coal waste feedstocks has been the subject of a U.S. patent application. The systematic experimental processes involving coal cleaning, upgrading, and conversion to high-value carbon products culminated into a developed upgraded coal-to-products (UCP) technology that is being pursued for potential fast-track commercialization, if funding is available. It is envisioned that commercialization of the UCP technology would increase consumption of U.S. domestic coals or coal wastes to make environmentally sustainable high-value products for the electronics industry, high-energy-storage applications, and clean energy technologies such as electric vehicle (EV) lithium-ion batteries (LIBs), for which graphite has become a critical mineral commodity. Croissant graphite microstructures, when observed by field emission scanning electron microscopy (FESEM), display wavy surface morphology and often grow from a base that is made of graphitized particles with honeycomb-like layers, which are believed to be graphene layers. While more studies are needed to fully ascertain the mechanisms of the croissant graphite microstructure formation, it is postulated that their growth may begin from curling of the graphene sheets into ribbon-like structures, and continuous growth and densification of the ribbon-like structures forms croissant microstructures. Additional studies are ongoing to evaluate the electrochemical performance of croissant graphite for LIB applications and to determine the experimental conditions necessary to tune on/off croissant formation so that it can be either optimized or suppressed depending on performance evaluation results. In addition to the discovery of croissant graphite, the graphitization process from the four coal ranks in general was successful. X-ray diffraction (XRD) analysis showed that the degree of graphitization (DoG) ranged from 12% to 80% in an early sample set, and further optimization on lignite coal produces a DoG of about 92%, which was spectacular to see as lignite is the lowest-rank coal. Thus, it is expected that the graphitization performance for higher-rank coals will be similar or better when optimized as well. The coal-derived graphite was used to make GO and rGO. Analytical characterization, e.g., by methods such as Raman spectroscopy, XRD, Fourier transform infrared (FTIR) spectroscopy and FESEM, showed that the sequence of converting the coal to graphite, exfoliating it to GO, and then chemically reducing the GO to rGO was successful. Although coal naturally contains aromatic compounds and some relatively small-sized condensed aromatic units, it does not contain graphene sheets. In the UCP process, the aromatic domains in the coals, particularly low-rank coals, are concentrated and condensed further into graphene sheets, which are ordered into a 3D stack during graphitization. The synthesized graphite is then unpacked by methods such as exfoliation to various graphene products. GQDs were synthesized from all four coal types, and their optical properties were demonstrated to be tunable by the coal precursor preprocessing treatments. In all four coal types, enhanced optical properties were observed for the produced GDQs with incremental improvements made to the coal precursors. GQDs produced from raw coal samples displayed lower ultraviolet–visible (UV–Vis) spectroscopy absorbance intensity compared to those obtained from cleaned and upgraded coal residues. The photoluminescence (PL) intensities also varied with pretreatment conditions and with the concentration of GQDs in aqueous solutions. GQDs obtained from anthracite show longer emission wavelengths and can be excited by visible light as opposed to GQDs derived from the other coal ranks. UV fluorescence 3D maps and spectra revealed that the emission wavelength at which the GQDs solutions display the highest intensity was slightly redshifted based on the coal precursor pretreatments. In low-rank coal (lignite and subbituminous) samples, two clusters were observed in the maps for GQDs, which may suggest that there are potentially two types of fluorophores in solution or two main size populations. The ability to tune the properties of GQDs based on processing methods can be exploited to make GQDs for various optical display or optoelectronics applications. The results also highlight the importance of removing coal-borne impurities to improve the quality of the coal precursor for preparation of graphene products. Coal and/or coal wastes preprocessing methods were developed and applied to clean and upgrade the coal precursors prior to graphitization and subsequent conversion to graphene products. The preprocessing methods involve high specific-gravity separations, mineral acid cleaning (no hydrofluoric acid), and subsequent upgrading by reducing the coal-borne heteroatom (nitrogen, sulfur, and oxygen) content using proprietary chemical agents. Analytical characterization revealed that the preprocessing steps were successful, with ash reductions that range from 38% to 80% and residual ash content that was below the 5 wt% initial target. Based on proximate and ultimate analysis, the heteroatom reduction reactions produced upgraded coal residues with the oxygen content reduced by 8% to 24%, with additional reductions in the nitrogen and sulfur contents. An initial assessment of the waste streams from the UCP process shows very small to negligible environmental impact due to CO 2 , NO x , and SO x because most process steps are performed under inert atmosphere with argon. Consequently, reactive oxygen environments that tend to create these species are avoided. The inorganic and potentially hazardous species are released into aqueous waste streams that are easy to handle for proper disposal. The liquid waste streams were found to contain low-level concentrations of rare-earth elements (REEs), which could be concentrated and recovered as value-added by-products. Additionally, the volatile and gaseous fractions from carbonization and heat treatment contain useful organic compounds that can also be recovered as potential valuable by-products. Thus, the UCP technology is considered an environmentally sustainable and promising emerging technology for making high-value products from coal and coal wastes, with potential additional value-added by-products. Analysis of potential markets for the coal-derived carbon products shows a strong demand in both niche market sectors and across a wide variety of other industrial sectors. Graphite is currently considered a critical mineral commodity that has a large and growing demand in the LIB industry for EV applications. Based on data from Fortune Business Insights (2022) and Marketwatch (2023) reports, the average global graphite market is projected to reach about 33 billion by 2028, growing at a compound annual growth rate (CAGR) of about 7%, with much of this growth expected to be in the LIB industry. GO and rGO have strong market potentials in various application areas, such as coatings for anticorrosion, anti-icing, and antimicrobial protection, thermal barriers, wear resistance, sensors, additive manufacturing such as 3D inks, and others. GQDs are the emerging key player in the bioimaging, photovoltaics, and light-emitting diodes (LEDs) applications, with the potential to replace traditional semiconductor quantum dots (SQDs), which are based on metallic systems that are more toxic and more expensive. Biomedical applications of GQDs are becoming more attractive because of low to no toxicity and extremely low cost compared to SQDs. The major challenges for scale-up and commercialization of coal-derived carbon products such as graphene vary from the inherent attributes of graphene itself to reluctance to accept graphene in new manufacturing processes because of the uncertainty of the unknown. The 2D nature of graphene materials with a thickness of one atom presents significant challenges to proper handling/processing, and process scale-up becomes difficult because it requires high-end, expensive equipment, even for routine handling and analysis for quality assurance and control. Pristine graphene can also be extremely difficult to work into other matrices, thus hindering downstream processibility, especially at large scale. Currently, the cost of graphene and graphene products is still high and presents an economic risk that tends to slow down investment in scaling up emerging technologies. The lack of a standard for graphene materials for quality assurance and quality control poses a great challenge not only for the markets but also for commercialization efforts. A first-look economic feasibility analysis of the UCP technology provided valuable information that suggests the UCP process would be feasible, especially when it is scaled to a pilot scale and could be more competitive at the full scale. Graphitization was found to be the most energy-consuming and most capital-intensive step in the overall process. In small laboratory- and bench-scale experiments, labor is a significant contributor to the total process costs. Although these energy, capital, and labor constraints contribute to a higher selling price for the product, a preliminary economic model suggests that the process would be feasible at large scale when the process is fully integrated, optimized, and automated.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2025

A Phenazine‐Based Two‐Dimensional Covalent Organic Framework for Photochemical CO 2 Reduction with Increased Selectivity for Two‐Carbon Products

Abstract The reduction of carbon dioxide (CO₂) into valuable products will contribute to sustainable carbon use. Here we report the photocatalytic reduction of CO₂ to carbon monoxide, formate, and oxalate ions using a redox‐active phenazine‐based 2D covalent organic framework (Phen‐COF) and its phenazine monomer. Under similar irradiation conditions,Phen‐COFproduced 2.9 times more CO, 11 times more formate, and 13 times more oxalate compared to equimolar amounts of the monomeric phenazine, demonstrating that the COF architecture enhances catalytic performance (TOF COF : 10 −7 s −1 CO, 10 −8 s −1 formate, and 10 −11 s −1 oxalate). Structural analysis, including X‐ray diffraction and N₂ porosimetry, confirmed the COF's long‐range order and porosity. Mechanistic studies suggest a sequential formate‐to‐oxalate pathway, with CO and formate acting as intermediates. These results demonstrate the potential of the COF architecture to improve the performance of metal‐free, redox‐active aromatic systems such as phenazines to facilitate efficient and selective CO₂ conversion under mild conditions.

Chemistry↗