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DOE OSTI2022

Advanced adsorption processes for separation of bio-derived products

Disclosed herein are methods for the recovery of target bio-base carboxylic acid products using a sorption-based technology with a mixed elution solvent optimized for minimized downstream distillation energy input. The sorption-based technology includes absorbing the targeted bio-base carboxylic acid products onto a non-ionic resin and eluting the targeted bio-base carboxylic acid products with a mixed elution solvent. The mixed elution solvent includes a first solvent and a second solvent. The first solvent has a boiling point that is lower than the targeted bio-base carboxylic acid products and the second solvent is selected from the group consisting of a phosphine oxide or tertiary amine.

Saboe, Patrick Owen↗

DOE OSTI2024

Copper and bismuth-based sorbent characterization in simulated iodine off-gas streams

The effective capture of volatile radioiodine, a fission product present in used nuclear fuel (UNF), is of paramount importance for development of used fuel reprocessing schemes to prevent release of radioiodine during unit operations and to meet regulatory standards for air emissions. A well-studied method for iodine capture in off-gas streams is the use of silver-functionalized zeolite phases (AgZ), which exploit chemisorption of I to Ag. Advances into other Ag-functionalized materials, including aerogels and metal organic frameworks (MOFs), are underway [1]. Additional metals with the capability to chemisorb iodine, including Cu, Bi, and Sn, [1] are being evaluated as alternatives to Ag for potential applicability to iodine management in off-gas systems. The design of novel functionalized sorbents with Cu and Bi, including composites with metal particles embedded in PAN substrates [2] and composites with metal sulfides embedded in PAN [3], is an ongoing area of study for improved iodine capture. Previously reported work on novel PAN-based metal sorbents has provided the synthesis, characterization, and iodine capture efficiency of this new class of sorbent. Specifically, the metal sulfide PAN composites are found to be easy to produce and reproduce, as well as having a high iodine loading potential under static conditions [3]. Due to the favorable testing previously performed with metal sulfide PAN composites, further testing into the performance of these composites under gas streams containing I2(g) in combination with NO2(g) and H2O(g) is needed. Humid streams of NO2(g) may arise from dissolver off-gas streams, when used fuel is dissolved in HNO3(aq) [4]. NO2(g) has been found to reduce AgZ sorption capacity for I because of oxidation of Ag, the chemisorbing agent, to Ag2O [5]. It follows that performance evaluation of novel sorbents under highly oxidizing conditions such as NO2(g) streams is critical. Therefore, the objective of this study is to determine the effect of flowing NO2(g) and H2O(g) streams on iodine sorption capacity and sorbent performance. This work utilizes custom-built gas handling capabilities for sorbent exposure along with solid-state characterization techniques to assess the physical and chemical properties of sorbents before and after exposure.

copper, bismuth, iodine capture, iodine sorbent, p↗

DOE OSTI2025

Nonadditive CO 2 Uptake of Type II Porous Liquids Based on Imine Cages

Type II porous liquids can potentially exploit the fluidity of liquids and sorption properties of porous sorbents, yet CO 2 uptake in porous liquids is still poorly understood. Molecular simulations and experiments are used to examine CO 2 uptake by a prototypical porous liquid composed of porous organic cages (CC13) in 2′-hydroxyacetophenone (2′-HAP). The simulations are in reasonable agreement with experimental measurements of CO 2 solubility and provide unambiguous information on the partitioning of CO 2 within microenvironments in the liquid. Analysis of CO 2 dynamics is performed using these simulations, including assessing the self-diffusivity of CO 2 in both the neat solvent and porous liquid. This offers insights into the kinetics of CO 2 uptake and transport in type II porous liquids based on imine cages. Experiments with type II porous liquids formed by dissolving CC13 in three different size-excluded solvents show nonadditive CO 2 absorption relative to predictions based on ideal volume additivity. This nonadditive absorption behavior is also observed in simulations. Nonadditive CO 2 uptake is also demonstrated in type II porous liquids based on another imine-based porous cage, CC19.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Manufacturing of Continuous Microporous Polymeric Fibers for Separation Applications

Polyolefin plastic waste, particularly polypropylene, is one of the most prevalent components in the plastic waste stream generated globally. However, only a small fraction of this waste is recycled and reintegrated into second applications. These materials have significant embedded energy that could be used for additional productivity if recycled properly. Therefore, there is a critical need to develop scalable processing techniques with high throughput to effectively recycle it. We report the continuous manufacturing of microporous fibers using waste polypropylene plastic and melt-processable lignin, a plant biomass constituent produced as a byproduct in paper mills or biorefineries, as a template to create pores. Further, these filaments with hierarchical porosity─created by controlled microphase separation during high-speed extensional flow followed by removal of lignin─exhibit exceptional capillary action for hydrophobic liquids. The resulting porous fibers can be used for various separation applications. For example, the oil uptake of the fibers is 9.59 ± 0.82 g/g for applications in oil recovery in bodies of water. In addition, polyethylenimine infiltration within these nanoporous fibers introduces cyclic room temperature sorption and thermal desorption potential of acidic gases such as CO 2 in a bench-scale experiment. The fibers exhibit multiple cycles of CO 2 absorption, with a range of 0.15 to 0.17 mmol/g. Thus, these polyethylenimine-infiltered nanoporous polypropylene fibers can also be used in removing acidic gases from a gas mixture.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Covalent Organic Frameworks for Water Treatment

Covalent organic frameworks (COFs) are an emerging type of porous crystalline material with highly ordered aperture size and tunable structures with designer properties. COFs have been proposed as promising materials for water treatment because of their notable intrinsic properties like excellent chemostability, high surface area, abundant functional sites, and uniform adjustable aperture size. This review focuses on fundamental COF design principles for water treatment (stability, aperture size, and surface functionalization) and the state-of-the-art application of COFs in desalination, organic contaminant sorption, and ion capture. Additional potential promising applications of COFs for water treatment, including solar steam generation, photocatalysis for degradation of organic contaminants, and capacitive deionization are also presented along with an outlook toward future opportunities in the field.

36 MATERIALS SCIENCE↗

DOE OSTI2022

New Insights into Physical Aging-Induced Structure Evolution in Carbon Molecular Sieve Membranes

Carbon molecular sieve (CMS) membranes offer the best available combination of scalable economical processability with excellent separation performance. Physical aging of CMS membranes causes pore structure changes over time that affect CMS membrane performance. To provide fundamental insights into the structure evolution in CMS membranes during physical aging, a combined dual-mode sorption and transport model is used in this study to characterize the diffusion coefficients of gas molecules in fresh and 7-day vacuum aged CMS membranes. Further, the results show physical aging of CMS membrane is primarily “diffusion related” and such aging behavior simultaneously causes ultramicropore changes in the continuous phase and Langmuir phase of CMS membrane. The new insights offered in this study suggest strategies to control the physical aging of CMS membranes and even use it as a valuable tool to tune the separation performance of CMS membranes for demanding gas separations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Cerium oxide impact on fresh and hardened properties of cementitious materials

Cements used in global nuclear waste treatment, storage, and disposal require thorough testing of fresh and cured properties to demonstrate regulatory compliance. Using actual radioactive wastes is often cost-prohibitive during early scoping tests necessitating the use of non-radiological surrogates. Cerium (Ce) is often used as a surrogate for actinides uranium (U) and plutonium (Pu) in spent nuclear fuel, yet few studies have explored how Ce impacts the properties used to qualify a cement for use. Here, this work compares the fresh and cured properties of three classes of cements – ordinary portland cements, ultra-high performance cement composites, and magnesium phosphate cements – each with and without ceria (CeO 2 ). Due to CeO 2 sorption of water (54 vol%) that effectively decreases the water available to hydrate and form binding cement phases, variations in key cement properties were detected that suggest surrogate CeO 2 –cementitious matrices may not be representative of matrix behaviors when using U and Pu sources.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Specific molecular design of polycarboxylate polymers exhibiting optimal compatibility with clay contaminants in concrete

Highlights: • Allyl ether-based PCEs with short side chain length and low side chain density presented superior clay resistance. • PCEs with medium side chain density exhibited best clay robustness when compared at the absolute dosed quantities. • The proportion of PCE being intercalated into the layered structure of clay was quantified. It is widely recognized that the dispersing ability of polycarboxylate superplasticizers (PCEs) could be hindered due to the presence of clay contaminants in concrete. In this study, a series of allyl ether-based polycarboxylate superplasticizers possessing short polyethylene glycol side chains was successfully synthesized and probed for their clay tolerance. The resulting PCE polymers were characterized via Size Exclusion Chromatography (SEC) to obtain their molecular properties. Thereafter, their dispersing ability was probed in the absence and presence of sodium bentonite. Allyl ether-based polycarboxylate (APEG) polymers possessing short side chains were found to exhibit enhanced clay resistance as compared to that of conventional MPEG PCEs holding long pendant chains. The mode of interaction between APEG PCEs and bentonite was investigated via sorption and XRD measurements. The data revealed that APEG PCEs possessing a lower side chain density intercalate less into the interlayer space of bentonite than those exhibiting higher side chain density.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Dynamic in situ imaging of methane hydrate formation in coal media

Fast 3D X-ray imaging has proved to provide crucial insights into multi-phase dynamic processes in various geomaterials. In particular, many in situ imaging experiments have been made to study gas-hydrate formation in porous sandy samples. Such imaging is challenging for the methane gas-hydrate formation in coal samples because of the coal micro-porosity structure and lower X-ray contrast. Here we present results of the first dynamic in situ micro-computed tomography experiment of methane-hydrate formation in coal samples. Synchrotron phase-contrast tomography techniques allowed to achieve necessary contrast levels to separate all the materials of interest (gas, water, coal, and gas hydrate) in reconstructed images with high spatial and temporal resolution. The imaging results are compared to the ones from a similar tomographic experiment with sand samples. Methane-hydrate formation is accompanied by the water movements caused by cryogenic water suction that happens in sequences of short fast movements with longer equilibrium states in between. Only one type of the hydrate formation was observed in coal (growth as shells on grain boundaries) as opposed to three types in sand (shells, growth into gas pockets, and inside water volumes). In particular, this leads to a slower hydrateformation speed in coal. For the coal sample, we also observed water extraction from grains, and interpreted it as competitive sorption of methane. Lastly, we visualized the dynamic behavior of this water extraction via microchannels inside the coal grains, and performed nano-tomography imaging of these channels for a better understanding of this phenomenon.

58 GEOSCIENCES↗

DOE OSTI2023

Application of community data to surface complexation modeling framework development: Iron oxide protolysis

This study presents a comprehensive community data-driven surface complexation modeling framework for simulating potentiometric titration of mineral surfaces. Compiled community data for ferrihydrite, goethite, hematite, and magnetite are fit to produce representative protolysis constants that can reproduce potentiometric titration data collected from multiple literature sources. Using this framework, the impact of surface complexation model type and surface site density (SSD) on the fit quality and protolysis constants can be readily evaluated. For example, the non-electrostatic model yielded a poor data fit compared to diffuse double layer model and constant capacitance models due to the absence of known surface charge effects. Regardless of the choice of iron oxide mineral, pK a1 decreased with increasing SSD while the opposite tendency was observed for pK a2 . This newly developed framework demonstrates a method to reconcile community data-wide potentiometric titration data using Findable, Accessible, Interoperable, Reusable data principles to produce mineral protolysis constants that improve robustness of surface complexation models for applications in metal sorption and reactive transport modeling. The framework is readily expandable (as community data increase) and extensible (as the number of minerals increase). The framework provides a path forward for developing self-consistent, comprehensive, and updateable surface complexation databases for surface complexation and reactive transport modeling.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2024

Exploring viral particle, soil, and extraction buffer physicochemical characteristics and their impacts on extractable viral communities

Viruses are expected to be pivotal members of soil ecosystems, and recent advances in viral size fraction metagenomic (viromic) approaches have improved our ability to interrogate soil viral ecology. However, viromics relies on extraction buffers to effectively desorb viral particles from the soil matrix for downstream analysis, and viral extraction efficiency could be affected by the interplay between viral particles, soils, and extraction buffer chemistry. Here, we investigated whether extraction buffer chemistry affected extractable viral community composition measured by viromics from different soil types, for both biological (samples collected 1 m apart) and technical (subsamples from the same soil homogenate) replicates. We investigated pH manipulation of protein-supplemented phosphate-buffered saline buffer (PPBS, pHs 4.5, 5.5, 6.5, and 7.5) on forest, grassland and wetland soils that exhibited different soil edaphic properties, and we tested different buffer chemistries (PPBS, Carbonated Buffer, Glycine, and Saline Magnesium) on just the wetland soil. Spatial distance (i.e., biological replicate) was the primary driver of extractable viral community composition across all buffers and soils tested. Differences in viral community composition according to extraction buffer properties were only observed in the grassland technical replicates at PPBS buffer pH 4.5, and in both the wetland technical and biological replicates treated with different buffer chemistries, but the effects of buffer chemistry were secondary to spatial distance in the biological replicates. The lack of buffering capacity in the grassland soil technical replicates likely increased sorption of viral particles at pH 4.5, but neither protein composition nor isoelectric point explained this phenomenon. In conclusion, given that most soil viral ecological studies to date include sample collection over distances much farther apart than the 1-m distances considered here, results suggest that extraction buffer chemistry is likely of much lower importance than ecological considerations, such as spatial distance, in the design of future soil viral ecological investigations.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2023

Porous Semiconducting K–Sn–Mo–S Aerogel: Synthesis, Local Structure, and Ion-Exchange Properties

Chalcogenide-based aerogels are emerging porous semiconducting nanomaterials that appeal to applications in clean energy and the environment. Here, we report a novel gel, potassium–tin–molybdenum–sulfides (KTMS), that integrates the electrostatically bound K + ions in the covalent network of Sn–Mo–S. Its gelation requires a concurrent reduction of Mo 6+ → Mo 4+/5+ and the oxidation of S 2– → Sn – (n ≈ 1) and Sn 2+ → Sn 4+ . KTMS is an amorphous semiconductor showing quantum confinement effects on band gap energies, 2.1 → 1.4 → 0.9 eV for its wet- → aero- → xerogels. Synchrotron X-ray pair distribution function (PDF) and extended X-ray absorption fine structure (EXAFS) revealed a complex local structure of KTMS consisting of molecular Mo 2 (S 2 ) 6 and Mo 3 S(S 2 ) 6 clusters. In addition, the Sn–S coordination is related to crystalline Na4Sn3S8 and SnS2. KTMS also demonstrated the removal of the radionuclides of Cs + , Sr 2+ , and UO 2 2+ from ppm to ppb levels with distribution constants (Kd) up to ≥104 mL/g. Notably, despite the lack of atomic periodicity in the amorphous KTMS, the K+ ion is ion-exchangeable with chemically diverse Sr 2+ , Cs + , and UO 2 2+ in aqueous solutions; especially the ion-exchange properties of Sr 2+ and UO 2 2+ ≡(O=U=O) 2+ is not known to any chalcogels known to date. The sequestration of Cs + and Sr 2+ was achieved by the exchange of K + in the amorphous KTMS, and the removal of [O=U 6+ =O] 2+ synergistically involves surface sorption via -S····U 6+ =O 2 2+ covalent interactions and ion-exchange via the hard–soft Lewis acid–base paradigm. Overall, cooperative roles played by the diverse bonding motifs, surface-exposed Lewis basic frameworks, and polarizability of the (poly)sulfides make it an exceptional adsorbent for chemically diverse radioactive species. This finding will guide the design of superior sorbents for chemically distinct metal ion separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Synthesis and Characterization of Macrocyclic Ionic Liquids for CO 2 Separation

In this work, a series of ionic liquids with symmetric, macrocyclic cations composed of N-heterocycles connected by alkyl or ether linkages coupled with bis(trifluoromethylsulfonyl)imide or bis(pentafluoroethanesulfonyl)amide anions were synthesized to explore their application in CO 2 separation. These novel ionic liquids showed selective physical absorption of CO 2 compared to N 2 making them potential candidates for carbon capture. We examined the effect of cation structure on the physicochemical and separations properties of the ionic liquid and showed that these ionic liquids exhibit an inverse relationship between molar volume and CO 2 sorption capacity following the trend predicted by models based on regular solution theory. The fractional free volumes of the ionic liquids were lower than typical alkyl-imidazolium ionic liquids despite the cyclic structure of the cations which could be related to the flexibility of the alkyl and ether linkages. These results provide added insight into our understanding of structure–property relationships in CO 2 solubility in ionic liquids and afford a path toward enhancing the separations properties based on structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Performance Degradation of Amine-Infused Fiber Sorbents for Direct Air Capture: Mechanisms and Solutions

Sorbent stability poses significant impacts on longterm performance of direct air capture (DAC) of CO 2 and levelized cost of capture (LCOC). We report the DAC performance degradation of amine-infused fiber sorbents based on poly(ethylenimine) (PEI), mesoporous SiO 2 , and cellulose acetate (CA) over CO 2 cyclic sorption cycles in a nonoxidative environment. Infrared and nuclear magnetic resonance spectra indicate that the aminolysis reactions between CA ester moieties and PEI amine sites lead to the formation of acetamides and hence lower CO 2 affinities of the sorbents. This stability issue can be remedied by hydrolysis treatment of the CA fiber sorbents before PEI impregnation or replacing CA with poly(ether sulfone). This study underscores the importance of selecting proper support or additive materials of DAC contactors that are compatible with active species of CO 2 capture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Unraveling pH-Dependent Changes in Adsorption Structure of Uranyl on Alumina (012)

Mitigating uranium transport in groundwater is imperative for ensuring access to clean water across the globe. Here, in situ resonant anomalous X-ray reflectivity is used to investigate the adsorption of uranyl on alumina (012) in acidic aqueous solutions, representing typical U VI concentrations of contaminated water near mining sites. The analyses reveal that U VI adsorbs at two distinct heights of 2.4-3.2 and 5-5.3 angstrom from the surface terminal oxygens. The former is interpreted as the mixture of inner-sphere and outer-sphere complexes that adsorb closest to the surface. The latter is interpreted as an outer-sphere complex that shares one equatorial H 2 O with the terminal surface oxygen. With increasing pH, we observe an increasing prevalence of these outer-sphere complexes, indicating the enhanced role of the hydrogen bond that stabilizes adsorbed uranyl species. Finally, the presented work provides a molecular-scale understanding of sorption of uranyl on Al-based-oxide surfaces that has implications for environmental chemistry and materials science.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Structure–Property Correlation of Hierarchically Porous Carbons for Fluorocarbon Adsorption

Although traditional commercially available porous carbon-fluorocarbon working pairs have shown promising applicability for adsorption cooling, advancements in synthetic carbons may further improve performance. Moreover, insights into structure-property relationships that target higher sorption capacities within these synthesized carbons may guide such materials' future design. We utilized hierarchically porous synthetic carbons (HPCs) with colossal microporous and mesoporous characterized by high surface areas (up to 2689 m 2 /g) and pore volumes (up to 10.31 cm 3 /g) towards fluorocarbon R134a adsorption. This unique pore topology leads to exceptional R134a uptake, ~250 wt.%, outperforming the highest uptake carbon material to date, Maxsorb III (~220 wt.%). Additionally, material characterizations reveal that the outstanding R134a capacity may be attributed to textural properties and oxygen-terminated functional groups more than graphitization of the material. Most importantly, HPCs are efficiently utilized in a two-bed model chiller device, where the performance shows excellent working capacity (105 wt%, ~1.5 times the value of reported carbon materials/R134a). Fluorocarbons adsorption on HPCs also displays fast kinetics (equilibrium time: ~2 min) mainly driven by physical adsorption (Qst: ~27 kJ/mol), characteristic of swiftly reversible behavior adsorption-desorption behaviors. This work provides a fundamental understanding of the applicability of HPCs/R134a working pair for adsorption cooling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Removal of Antibiotics from Swine Wastewater Using an Environmentally Friendly Biochar: Performance and Mechanisms

Antibiotics used in the swine industry to treat diseases and improve animal growth are poorly absorbed by swine and have been classified as micropollutants due to their occurrence in surface water, wastewater, and soil. This study investigated the capacity of biochar produced from eastern red cedar to remove target antibiotics that have been extensively used in the swine industry. Biochar was produced by pyrolysis from eastern red cedar at 450 °C. The sorption tests were performed by mixing biochar and a solution (1:10 ratio) containing each antibiotic in 100, 300, 600, and 900 μg L –1 concentrations. The results indicate that red cedar biochar was able to effectively remove up to 99.93% tetracycline, 96.23% oxytetracycline, 98.28% chlortetracycline, 76.4% sulfadiazine, and 78.6% sulfamethazine at the lowest concentrations. The removal efficiencies at higher concentrations declined up to 83.52, 47.23, 64.16, 69.8, and 58.4% for tetracycline, oxytetracycline, chlortetracycline, sulfadiazine, and sulfamethazine, respectively. The biochar exhibited stronger adsorption capacity for chlortetracycline and sulfamethazine compared to the other antibiotics. The likely adsorption mechanisms driving the removal of tetracyclines and sulfonamides are hydrogen-bonding and π–π electron-donor–acceptor, supported by FTIR analyses of the biochar itself. Overall, the results highlighted the potential utilization of eastern red cedar biochar for practical applications, mitigating antibiotic residues from swine wastewater in a cost-effective and environmentally friendly manner due to its relatively low pyrolysis temperature (450 °C) and sustainable repurposing of an invasive tree species.

09 BIOMASS FUELS↗

DOE OSTI2023

Cyclobutanedicarboxylate Metal–Organic Frameworks as a Platform for Dramatic Amplification of Pore Partition Effect

Ultrafine tuning of MOF structures at sub-angstrom or picometer levels can help improve separation selectivity for gases with subtle differences. However, for MOFs with large-enough pore size, the effect from ultrafine tuning on sorption can be muted. Here we show an integrative strategy that couples together extreme pore compression with ultrafine pore tuning. Furthermore, this strategy is made possible by unique combination of two features of the pacs platform (pacs = partitioned acs): multi-modular framework and exceptional tolerance towards isoreticular replacement. Specifically, we use one module (Ligand 1, L1) to shrink pore size to an extreme minimum on pacs. A compression ratio of about 30% was achieved (based on unit-cell c/a ratio) from prototypical 1,4-benzenedicarboxylate-pacs to trans-1,3-cyclobutanedicarboxylate-pacs. This is followed by using another module (Ligand 2, L2) for ultrafine pore tuning (< 3% compression). This L1-L2 strategy increases C 2 H 2 /CO 2 selectivity from 2.6 to 20.8 and gives rise to excellent experi-mental breakthrough performance. Being the shortest cyclic dicarboxylate that mimics para-benzene-based moieties us-ing bioisosteric (BIS) strategy on pacs, trans-1,3-cyclobutanedicarboxylate-based MOF chemistry offers new opportuni-ties in MOF chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗