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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Interaction of Soil Microbes with Organoclays and their Impact on the Immobilization of Hg under Aerobic Conditions

Immobilization of mercury (Hg) leaching from bank soils of East Fork Poplar Creek (EFPC) is considered part of remediation strategies to mitigate the amount of Hg entering the creek. Different approaches are currently being evaluated, such as utilizing engineered sorbents to immobilize Hg species in EFPC bank soils. However, the influence of environmental microbes on the immobilization of Hg by sorbents is unknown. Organocation-modified phyllosilicate clay minerals (organoclays) are widely used as sorbents for the immobilization of contaminants. This study evaluates the interactions of Serratia marcescens and Burkholderia thailandensis with the sorbent Organoclay PM-199 and their impact on the immobilization of Hg under aerobic conditions. We evaluated the competitive binding of Hg between sorbents and selected microorganisms in a series of pure culture studies using bacterial strains identified in EFPC bank soil samples. Our results suggest that Hg sorption by Organoclay PM-199 is not significantly impacted by common soil bacteria present in EFPC, specifically Serratia marcescens and Burkholderia thailandensis, which are known to form biofilms. These findings suggest that sorbent amendments are an effective strategy for the remediation of Hg contamination in natural ecosystems.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Design and Application of Materials for Sequestration and Immobilization of 99 Tc

99 Technetium ( 99 Tc) is a hazardous radionuclide generated by the nuclear industry that poses a serious environmental threat. The wide variation and complex chemistries of nuclear waste streams containing 99 Tc often create unique, site specific challenges when sequestering and immobilizing the waste in a matrix suitable for long-term storage and disposal. Therefore, an effective management plan for 99 Tc containing radioactive waste will likely require a variety of suitable materials/matrices capable of adapting to and addressing these challenges. In this review, we discuss and highlight the key developments for effective removal and immobilization of 99 Tc in inorganic waste forms. Specifically, we review the synthesis, characterization, and application of materials for targeted removal of 99 Tc from (simulated) waste solutions under various experimental conditions. These materials include: i) layered double hydroxides (LDHs), ii) metal-organic frameworks (MOFs), iii) ion-exchange resins (IERs) as well as cationic organic polymers (COPs), and iv) surface modified natural clay materials (SMCMs). Secondly, we discuss some of the major and recent developments towards 99 Tc immobilization in i) glass, ii) cement, and iii) iron mineral waste forms. Finally, we present future challenges that need to be addressed for the design, synthesis, and selection of suitable matrices for the efficient sequestration and immobilization of 99 Tc from targeted wastes. Finally, the purpose of this review is to inspire the researches on the design and application of various suitable materials/matrices for selective removal of 99 Tc present globally in different radioactive wastes and its immobilization in stable/durable waste forms.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Colloidal immobilized protein based on stable colloid of TiO 2 nanoparticles at neutral pH for protein microarray

A stable colloid of titanium dioxide nanoparticles was specially prepared at neutral pH so that horse radish peroxidase as a model protein can interact and be immobilized with colloidal titanium dioxide nanoparticles, while usually titanium dioxide colloid is only stable at acidic condition. Colloidal immobilized peroxidase based on titanium dioxide nanoparticles at neutral pH were highly active and stably dispersible in aqueous solution. The resulting colloidal immobilized peroxidase can be readily printed using a standard microarray printer for facile fabrication of protein microarrays. After printing, the colloidal immobilized protein formed uniform membrane of proteinated nanoparticles with 3-dimensional nanoconfiguration. Finally, the protein microarray sensitivity based on peroxidase-titanium dioxide nanoparticles was nearly 20 times as high as that using conventional technology.

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

Application of Fe-doped biochar in Cr(VI) removal from washing wastewater and residual Cr(VI) immobilization in contaminated soil

High-content Cr(VI)-contaminated soils are challenging to remediate using a single remediation technique. This study combined soil washing and immobilization to remediate high-content (3440 mg kg -1 ) Cr(VI)-contaminated soil, which investigated the effects of operating time, temperature, and liquid-solid ratio (LSR) on the Cr(VI) removal efficiency of soil washing and evaluated the potential of Fe-doped biochar (FeBC) in soluble Cr(VI) removal from the washing wastewater and residual Cr(VI) immobilization in the washed soil. The Cr(VI) removal efficiency of soil washing increased with the operating time, temperature, and LSR, but still cannot remove Cr(VI) to achieve the safety content (<100 mg kg -1 ). FeBC showed satisfactory potential in both Cr(VI) removal and immobilization from wastewater and soil, in which the main mechanisms involve ion exchange, redox, and coprecipitation. These results demonstrate applying soil washing & immobilization to remediate high-content Cr(VI)-contaminated soil is a promising alternative method.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Aerosol-Assisted Deposition for TiO 2 Immobilization on Photocatalytic Fibrous Filters for VOC Degradation

Atomization and spraying are well-established methods for the production of submicrometer- and micrometer- sized powders. In addition, they could be of interest to the immobilization of photocatalytic nanoparticles onto supports because they enable the formation of microporous films with photocatalytic activity. Here, we provide a comparison of aerosol-assisted immobilization methods, such as spray-drying (SD), spray atomization (SA), and spray gun (SG), which were used for the deposition of TiO 2 dispersions onto fibrous filter media. The morphology, microstructure, and electronic properties of the structures with deposited TiO 2 were characterized by SEM and TEM, BET and USAXS, and UV-Vis spectrometry, respectively. The photocatalytic performances of the functionalized filters were evaluated and compared to the benchmark dip-coating method. Our results showed that the SG and SA immobilization methods led to the best photocatalytic and operational performance for the degradation of toluene, whereas the SD method showed the lowest degradation efficiency and poor stability of coating. We demonstrated that TiO2 sprays using the SG and SA methods with direct deposition onto filter media involving dispersed colloidal droplets revealed to be promising alternatives to the dip-coating method owing to the ability to uniformly cover the filter fibers. In addition, the SA method allowed for fast and simple control of the coating thickness as the dispersed particles were continuously directed onto the filter media without the need for repetitive coatings, which is common for the SG and dip-coating methods. Our study highlighted the importance of the proper immobilization method for the efficient photocatalytic degradation of VOCs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Low cost immobilized amine regenerable solid sorbents

A method of modifying a chemical interaction between a functional group of an immobilized amine in a solid sorbent composition and a compound that chemically interacts with the functional group to reduce the heat required to desorb the compound from the solid sorbent. A method of inhibiting degradation of an immobilized amine in an immobilized amine solid sorbent. Compositions and methods of use of a low-cost regenerable immobilized amine solid sorbent resistant to degradation.

Chuang, Steven S. C.↗
DOE OSTI2025

Hydrogel-Immobilized Multienzyme Systems for Cell-Free Chemical Bioproduction

Cell-free gene expression systems derived from bacterial lysates enable the expression of biosynthetic pathways from inexpensive and easily prepared DNA templates. These systems hold great promise for modular and on-demand bioproduction of valuable small molecules in resource-limited settings but are constrained in their long-term stability, reusability, and deployability. In this work, we demonstrate that multiple cell-free expressed enzymes can be co-immobilized in biocompatible hydrogels made from poly(ethylene glycol) diacrylate (PEGDA) with added glycerol for enhanced gel integrity. Using small-angle X-ray scattering (SAXS), we show that the mesh size of PEGDA-glycerol hydrogels is comparable to the globular sizes of many proteins and enzymes, which could be used for protein entrapment. We found that the combination between entrapment and chemical ligation of the enzymes was effective to retain proteins. By employing a method for direct fluorescence measurement from hydrogels, we found that proteins can be retained in PEGDA-glycerol for at least a week. By separating the cell-free enzyme expression from the immobilization step, we successfully fabricated enzyme-laden hydrogels with three heterologous cell-free enzymes for the bioconversion of pyruvic acid to malic acid, an industrially valuable and versatile precursor chemical. Both heterologous and endogenous enzymes from the lysate remain functional in photo-cross-linked hydrogels and can be reused for multiple biocatalytic cycles. Moreover, we also found that the immobilized enzymes exhibit up to 1.6-fold higher activity and 2-fold longer lifetimes than free enzymes in liquid reactions. Furthermore, these results could advance the deployment of cell-free synthetic biology because they show that reusable, stable, and durable multienzyme systems can be created using readily available materials and fabrication techniques.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Photoelectrocatalytic reduction of CO 2 to formate using immobilized molecular manganese catalysts on oxidized porous silicon

The reduction of carbon dioxide (CO 2 ) to formate using molecular catalysts immobilized on high surface area porous silicon is described. Manganese complexes of the type ( R bpy)Mn(CO) 3 Br (bpy = 2,2′-bipyridine) were prepared with silatrane groups on the bpy ligand for attachment to oxide-coated porous silicon (SiO x -porSi). SiO x -porSi wafers were formed by heating hydrogen-terminated p-type porous silicon wafers under air, and the manganese complexes were immobilized on SiO x -porSi by heating at 80°C. The resulting hybrid photoelectrodes are photoelectrocatalysts for CO 2 reduction in acetonitrile containing 2.0 M triethylamine and 2.0 M isopropanol, yielding formate with high selectivity (>96%) and current density (∼0.6 mA/cm 2 ), excellent reproducibility, and a photovoltage of 280 mV at −1.75 V (versus ferrocenium/ferrocene) under 1 sun illumination. Here, the applied potential is close to the equilibrium potential for CO 2 reduction to formate. This work presents rare examples of immobilized molecular catalysts for CO 2 reduction to formate and the first on semiconducting silicon.

13 HYDRO ENERGY↗
DOE OSTI2025

Water reactive polyurethane grouting for deep vadose zone contaminant immobilization

Contaminants in the deep vadose zone (DVZ) pose a long-term threat to groundwater, human health, and the environment. Polyurethane grouting is a type of chemical grouting that is potentially advantageous in immobilizing contaminants in DVZs. Polyurethane resin has low viscosity that makes it feasible to penetrate and fill the pore space between fine particles. Here, in this study a series of laboratory pressure grouting and leaching tests were conducted to simulate and assess the effectiveness of polyurethane grouting for immobilizing contaminants in DVZs. Soil with fine particles was prepared with 127 I (as iodide) that served as a non-radioactive surrogate for radioactive 129 I. After grouting and curing, leaching tests were used to measure and compare contaminant diffusivity and leachability index values. Additionally, changes in porosity and saturated hydraulic conductivity of grouted soil were measured. X-Ray Computer Tomography (XCT) results showed that the cured polyurethane was distributed nearly homogeneously and approximately half of the voids were filled with cured polyurethane. Grouting reduced the saturated hydraulic conductivity of soil by 37 %. The effective diffusivity decreased by more than 80 % as compared with the ungrouted soil. The leachability index of the grouted soil was 6.5; meeting the criteria established by the U.S. Nuclear Regulatory Commission (NRC) standard. The results obtained in this study provide a valuable assessment of polyurethane grouting for iodide immobilization in the DVZ and indicate this approach may be a viable method for contaminant remediation in DVZ soils.

Contaminant Diffusion↗
DOE OSTI2024

Statistical analysis of HAADF-STEM images to determine the surface coverage and distribution of immobilized molecular complexes

The surface immobilization of molecular catalysts is attractive because it combines the benefits of homogeneous and heterogeneous catalysis. However, determining the surface coverage and distribution of a molecular catalyst on a solid support is often challenging, inhibiting our ability to design improved catalytic systems. Here, in this work, we demonstrate that the combination of scanning transmission electron microscopy (STEM) and image analysis of the individual positions of heavy atoms in transition metal complexes via a convolutional neural network (CNN) allows statistically robust determination of the surface coverage and distribution of immobilized molecular catalysts. These observations provide information about how changes in the functionalization conditions, attachment group, and structure of the molecular catalyst affect the surface coverage and distribution, providing insight into the chemical mechanism of surface immobilization. The method could be generally valuable for correlating the surface coverage and distribution to the activity, selectivity, and stability of a catalytic system.

HAADF-STEM↗
DOE OSTI2024

Kinetic Analysis of Proton-Coupled Electron Transfer at an Electrode-Immobilized Complex

An alkyne-terminated cobalt complex, [Co(Cp)(dppe ≡H )(Cl)] + (Cp = cyclopentadienyl; dppe ≡H = 1,2-bis-(di-(4-ethynyl-phenyl)phosphino)ethane), (Co ≡H ) was immobilized onto a glassy carbon electrode using two attachment strategies: Cu(I) catalyzed azide–alkyne click chemistry and reductive electropolymerization. The modified electrodes prepared through reductive electropolymerization exhibit current densities and peak resolutions for the electrochemical reduction of the cobalt species, which are amenable to electroanalytical quantification of coupled chemical reactions. Through peak shift analysis of cyclic voltammograms recorded in the presence of 4-chloroanilinium tetrafluoroborate, we quantified the proton transfer rate constant for the stepwise proton-coupled electron transfer reaction that reduces the electrode-immobilized [Co(Cp)(dppe ≡H )(Cl)] + to [H–Co(Cp)(dppe ≡H )] + (k PT app = (9.3 ± 1.8) × 10 5 M –1 s –1 ). In conclusion, the extraction of kinetic parameters for an elementary proton-coupled electron transfer reaction of an electrode-immobilized complex represents the first experimental measurement of its type and lays crucial groundwork for kinetic analyses of hybrid catalyst–electrode architectures.

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

Cell Free and Immobilization Technologies (CFIT)

Today, several key factors negatively impact the production of fuels and chemicals from renewable sources. Common hindrances in the biological production of biochemicals are: (1) end-product or intermediate toxicity to the microbial biocatalyst, (2) the diversion of carbon to biomass formation, and (3) co-production of undesired byproducts. A particularly attractive alternative is to eliminate the biocatalyst entirely and instead operate the desired metabolic pathways in isolation, thus circumventing the roadblocks of biological toxicity, lower yields, and lack of specificity. However, cell-free enzyme systems still suffer from low productivities owing in part to the effects of free diffusion of intermediates, lack of long term enzyme stability, cofactor cost or inefficient recycling rates, and finally, the cost of enzyme production/purification. This project represents a new effort to propose innovative and cost competitive routes to producing biochemicals from a variety of feedstocks using cell free approaches. These routes will help reduce the current risk and cost associated with classical cell free production. Cell free technologies show promise for application to the production of toxic/inhibitory products or products difficult to separate from microbial growth media and can help reduce the production barriers in multiple areas of biological conversion of feedstocks to biochemicals. More specifically, we are developing new technologies and routes that could be used to produce high value biochemicals such as 2,3 BDO and terpenes (among many others) from biomass derived C5/C6 sugars or lignin but also from waste byproducts such as glycerol. This project will lead to significant innovation and also lead to new concepts and rational design of pathways and enzymes. Within this project, we will develop new metabolic enzyme cascades that will represent natural or artificial combinations of enzymes to produce the desired biochemicals from a variety of feedstocks. We are also developing basic design principals for constructing synthetic metabolons, using fusion proteins and synthetic protein scaffolds, to promote substrate channeling and stability while conserving peak activity. Additionally, our efforts include a techno economic analysis (TEA) of cell free approaches to provide the sensitivities of the process to enzyme loading, activity, pH, reactor volumes, cofactor recycling rates. Finally, we are focusing on further increasing stability, operating lifetime and efficiency of the pathway enzymes by immobilization on support surfaces. We are also focus on immobilizing pathway enzymes or combinations of enzymes on several different conducting polymers and evaluate the effect on stability and operating lifetime. As more combinations become available we will conduct a more systematic study of the means of immobilizing these enzymes. This preliminary work will enable the in-depth study of cofactor recycling at these interfaces using mediators for electron transfer. Taken together, these approaches will enable process intensification, continuous operation, lower capital and separations costs and end-product flexibility, and thus has the potential to contribute significantly to BETO's goals of cost competitive biofuels and bioproducts. To date we have demonstrated 1) the conversion of pyruvate to 2,3 BDO (4 enzymes with cofactor recycling, no additional cofactors needed) at >100g/L (>3g/L/h) using our enzyme tethering approach, 2) Generated mutants of a key redox enzyme with >180- fold improvement in NADH utilization over WT to >85% of NADPH utilization. 3) Produced mevalonate at >10g/L from glucose, limonene at >10g/L from mevalonate and more than >5g/L from glucose with crude enzyme preparations and complete cofactor recycling. 4) successfully generated fully active cross-linked aggregates (CLEAs) of NOX, a cofactor-regenerating water-forming oxidase that is key to our process with increased stability 5) Engineered and identified enzymes able to use the biomimetic cofactor NMN and synthesized new synthetic cofactors.

biocatalysis↗
DOE OSTI2022

Cs 3 Bi 2 I 9 -hydroxyapatite composite waste forms for cesium and iodine immobilization

Perovskite-based ceramic composites were developed as potential waste form materials for immobilizing cesium (Cs) and iodine (I) with high waste loadings and chemical durability. The perovskite Cs 3 Bi 2 I 9 has high Cs (22 wt%) and I (58 wt%) content, and thus can be used as a potential host phase to immobilize these critical radionuclides. In this work, the perovskite Cs 3 Bi 2 I 9 phase was synthesized by a cost effective solution-based approach, and was embedded into a highly durable hydroxyapatite matrix by spark plasma sintering to form dense ceramic composite waste forms. The chemical durabilities of the monolithic Cs 3 Bi 2 I 9 and Cs 3 Bi 2 I 9 -hydroxyapatite composite pellets were investigated by static and semi-dynamic leaching tests, respectively. Cs and I are incongruently released from the matrix for both pure Cs 3 Bi 2 I 9 and composite structures. The normalized Cs release rate is faster than that of I, which can be explained by the difference in the strengths between Cs-I and Bi-I bonds as well as the formation of insoluble micrometer-sized BiOI precipitates. The activation energies of elemental releases based on dissolution and diffusion-controlled mechanisms are determined with significantly higher energy barriers for dissolution from the composite versus that of the monolithic Cs 3 Bi 2 I 9 . The ceramic-based composite waste forms exhibit excellent chemical durabilities and waste loadings, commensurate with the state-of-the-art glass-bonded perovskite composites for I and Cs immobilization.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Presence of aromatic-rich organic matter and its characterization in grout materials: Implications for radionuclide immobilization

Grout materials are commonly used to immobilize low-level radioactive waste. Organic moieties can be unintentionally present in common ingredients used to make these grout waste forms, which may result in the formation of organo-radionuclide species. These species can positively or negatively affect the immobilization efficiency. However, the presence of organic carbon compounds is rarely considered in models or characterized chemically. Here, we quantify the organic pool of grout formulations with and without slag, as well as the individual dry ingredients used to make the grout samples (ordinary Portland cement (OPC), slag and fly ash), including total organic carbon (TOC) and black carbon, followed by aromaticity evaluation and molecular characterization via Electro Spray Ionization Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (ESI-FTICRMS). All dry grout ingredients contained significant amounts of organic carbon, ranging from 550 mg/kg to 6250 mg/kg for the TOC pool, with an averaged abundance of 2933 ± 2537 mg/kg, of which 60 ± 29% was composed of black carbon. The significant abundance of a black carbon pool implies the presence of the aromatic-like compounds, which was further identified by both phosphate buffer-assisted aromaticity evaluation (e.g., >1000 mg-C/kg as aromatic-like carbon in the OPC) and dichloromethane (DCM) extraction with ESIFTICRMS analysis. Besides aromatic-like compounds, other organic moieties were also detected in the OPC, such as carboxyl-containing aliphatic molecules. While the organic compound only consists of minor fractions of the grout materials investigated, our observations of the presence of various radionuclide-binding organic moieties suggests the potential formation of organo-radionuclides, such as radioiodine, which might be present at lower molar concentrations than TOC. Here, evaluating the role of organic carbon complexation in controlling the disposed radionuclides, especially for those radionuclides with strong association with organic carbon, has important implications for the long-term immobilization of radioactive waste in grout systems.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Immobilizing Pertechnetate in Ettringite via Sulfate Substitution

Until recently, a nuclear waste form did not exist for the immobilization and long-term storage of the anionic form of radionuclide technetium-99 (99Tc), pertechnetate (TcO 4 - ). Across international nuclear waste sites, the inability to capture TcO 4 - poses a threat to the local environment due to the anion’s long half-life and environmental mobility under environmentally oxic conditions. To combat this challenge, most waste forms would capture 99Tc using materials that reduce TcO 4 - to Tc(IV) species, e.g. 99Tc oxides or 99Tc sulfides. However, this is a short-lived solution unless reducing capacities can be regenerated to last over the long life expectancy of some nuclear waste forms (~10,000 years). In light of recent experimental observations gained from the development of cementitious waste forms and unconfirmed hypotheses from the literature, this work explores how ettringite, a common mineral formed in cementitious materials with demonstrated success in incorporating oxyanions, may be used to immobilize TcO 4 - directly and over the life-time of the waste form. Using batch precipitation experiments, solid phase characterization techniques, and ab initio molecular dynamics simulations, we demonstrate herein successful incorporation of TcO 4 - into ettringite via substitution for SO 4 2- within the ettringite crystal structure. Here, these results are first of their kind and confirm the hypothesis that ettringite acts as an immobilizing mineral within cementitious waste forms for the highly mobile TcO 4 - oxyanion, enhancing the overall performance of these waste forms over time.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Cambered Bipyridyl Ligand with Extended Aryl System Enables Electrochemical Reduction of Carbon Dioxide and Bicarbonate by Mn(bpy)(CO) 3 Br-type Catalyst Immobilized on Carbon Nanotubes

Heterogeneous materials containing molecular catalytic sites show promise for electrocatalytic reduction of CO 2 to energy-enriched carbon products. Interactions between the catalyst and the heterogeneous support increasingly are recognized as important in governing product selectivity and rate. Recent work on Mn(R-bpy)(CO) 3 Br type catalysts immobilized on multiwalled carbon nanotubes (MWCNT) demonstrated control of electrocatalytic behavior with steric modification of the molecular catalyst. Phenyl groups installed in the 4,4' positions of the bipyridine ligand (ph-bpy) maximized performance through π–π interactions with the MWCNT support. Herein we report the outcome of extending the ligand π system with Mn(nap-bpy)(CO) 3 Br (nap-bpy = 4,4'-di(naphthalen-1-yl)-2,2'-bipyridine) and Mn(pyr-bpy)(CO) 3 Br (pyr-bpy = 4,4'-di(pyren-1-yl)-2,2'-bipyridine) immobilized on MWCNT. We demonstrate exceptional electrocatalysis with Mn(nap-bpy)(CO) 3 Br/MWCNT (FE CO > 92%; J CO = 16.5 mA/cm 2 ) and find that this catalyst electrochemically reduces bicarbonate in the absence of deliberately added CO 2 at a remarkable overall selectivity of >80% for carbon products (FE HCOO – = 52% and FE CO = 29%). We show diminishing returns to simply adding aromatic character to the bipyridyl ligand with Mn(pyr-bpy)(CO) 3 Br/MWCNT and observe a unique cambering of the Mn(nap-bpy)(CO) 3 Br bipyridyl ligand that we believe enables selective catalysis. Mechanistic studies were carried out on Mn(nap-bpy)(CO) 3 Br/MWCNT using a novel thin-film infrared spectroelectrochemical (IR-SEC) technique. These experiments observe the immobilized Mn(nap-bpy)(CO) 3 Br undergo single electron reduction to a Mn-centered radical that binds CO 2 in a reduction-coupled process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Unlocking liquid chemisorption in solid matrices: immobilized deep eutectic solvent-ZIF-8 composites for next-generation CO 2 capture

Achieving net-zero emissions by 2050 requires scalable and durable CO 2 capture solutions, with direct air capture (DAC) gaining increasing prominence. Deep eutectic solvents (DESs) have emerged as promising candidates due to their strong chemisorptive properties, but their liquid-phase nature limits integration into solid systems. In this study, we introduce a solid–liquid hybrid approach by immobilizing [TEAB][TEPA] 2 , a highly CO 2 -reactive DES, onto various supports via non-covalent immobilization. This strategy induces solid-like behavior while retaining molecular-level reactivity of the DES. Among the supports including ZIF-8, zeolite Y, zirconia, and alumina, the [TEAB][TEPA] 2 @ZIF-8-56% composite demonstrated promising CO 2 uptake capacity of 2.00 mmol g −1 adsorbent at 1 bar, 1.48 at 0.15 bar, 0.96 at 0.01 bar, and 0.59 at 0.4 mbar. Particularly, we can observe that the chemisorption capacity under 400 ppm conditions is successfully introduced into ZIF-8, whereas pristine ZIF-8 showed negligible uptake under these same conditions. Breakthrough experiments confirmed robust capture behavior under humid conditions. The composite exhibited excellent cycling stability over 100 capture-release cycles, supported by thermogravimetric analysis. In situ DRIFTS verified that the chemisorptive nature of the DES remained intact after immobilization. Additional characterization studies, including FTIR, PXRD, N 2 physisorption, and XPS depth profiling, revealed partial DES infiltration and strong interfacial interactions. Comparative results using alumina-based composites underscored the importance of microporosity in stability. Finally, these findings suggest that DES-MOF composites hold promise as carbon capture materials, bridging liquid-phase functionality and solid-state robustness.

Yoo, Yunsung [Northwestern Univ., Evanston, IL (Un↗
DOE OSTI2020

Development and Characterization of Cementitious Waste Forms for Immobilization of Granular Activated Carbon, Silver Mordenite, and HEPA Filter Media Solid Secondary Waste

At the Department of Energy’s Hanford site, over 53 million gallons of chemically complex and radioactive wastes have been stored in 177 underground tanks. The Hanford Tank Waste Treatment and Immobilization Plant (WTP) is under construction and is designed to treat and immobilize these wastes. During operations of WTP, solid secondary wastes (SSWs) will be generated as a result of waste treatment, vitrification, off-gas management, and supporting process activities. SSW treatment processes and resulting disposal pathways for the final disposition form of the SSW are needed to support direct feed low activity waste (DFLAW) operations and facilitate continued operation of WTP. The SSWs produced through WTP operations are expected to include used process equipment, contaminated tools and instruments, decontamination wastes, high-efficiency particulate air (HEPA) filters, carbon absorption beds (granular activated carbon, GAC), silver mordenite (AgM) and spent ion-exchange resins. These waste streams are planned to be immobilized in a cementitious waste form and disposed of either as stabilized/blended (non-debris) or encapsulated (debris) in a cementitious waste form. Accordingly, cementitious waste forms from these streams were included in the 2017 Integrated Disposal Facility (IDF) Performance Assessment (PA). The input data used to represent these SSW forms in the 2017 IDF PA involved many assumptions and associated uncertainties. This data limitation was due to the lack of material- and site-specific data available for representative SSW materials in cementitious matrices. To verify the assumed values used in the IDF PA and fill this limitation in available data, Washington River Protection Solutions, LLC (WRPS), has initiated a program targeted toward gathering site specific data relevant to Hanford SSW disposal. The work within this report is a continuation of this ongoing program.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗