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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Influence of NaCl on shape deformation of polymersomes

Polymersomes frequently appear in the literature as promising candidates for a wide range of applications from targeted drug delivery to nanoreactors. From a cell mimetic point of view, it is important to understand the size and shape changes of the vesicles in the physiological environment since that can influence the drug delivery mechanism. In this work we studied the structural features of polymersomes consisting of poly(ethylene glycol)–poly(dimethylsiloxane)–poly(ethylene glycol) at the nanoscopic length scale in the presence of NaCl, which is a very common molecule in the biotic aqueous environment. Here, we used dynamic light scattering (DLS), cryo-TEM, small angle neutron scattering (SANS) and small angle X-ray scattering (SAXS). We observed transformation of polymersomes from spherical to elongated vesicles at low salt concentration and into multivesicular structures at high salt concentration. Model fitting analysis of SANS data indicated a reduction of vesicle radius up to 47% and from the SAXS data we observed an increase in membrane thickness up to 8% and an increase of the PDMS hydrophobic segment up to 11% indicating stretching of the membrane due to osmotic imbalance. Also, from the increase in the interlamellar repeat distance up to 98% under high salt concentrations, we concluded that the shape and structural changes observed in the polymersomes are a combined result of osmotic pressure change and ion–membrane interactions.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Electrochemical Reactivity of Hydrogen Storage Materials: Exploring Borohydride and Hydrazinium Salt Mixtures

Electrochemical characterization of hydrogen storage materials was conducted in a non-aqueous environment to investigate the direct electrochemical release and consumption of hydrogen and the potential for regeneration. We first address the challenge of minimal solubility of the synthetic precursors, sodium borohydride (NaBH 4 ) and hydrazinium bromide (N 2 H 5 Br), in both organic and inorganic solvents. We next determine and calibrate a reference electrode formulation compatible with our non-aqueous media and analytes that demonstrates a stable reference potential. We employ cyclic voltammetry (CV) to characterize the precursors and mixtures thereof. Each CV peak is assigned to a corresponding electrochemical reaction. Using the rate-dependent CV method and Randles–Ševčík equation, we calculate the diffusion coefficient of each chemical (NaBH 4 and N 2 H 5 Br). Analysis of the CVs, coupled with 11B NMR analysis, reveals a room temperature chemical transformation of NaBH 4 and N 2 H 5 Br mixtures into hydrazine borane (N 2 H 4 BH 3 ). These results are particularly significant, considering the limited information available on the electrochemical characterization of metal borohydride and hydrazinium salt in non-aqueous media. This work establishes a foundation for adapting a non-aqueous electrochemical system to further study the borohydride family of chemistries and to design and develop electrochemical devices for direct electrical and chemical energy interconversion with hydrogen storage materials.

08 HYDROGEN↗
DOE OSTI2021

Compartmentalization and Photo-Regulating Pathways for Incompatible Tandem Catalysis

This contribution describes an advanced compartmentalized micellar nanoreactor that possesses a reversible photoresponsive feature and its application towards photo-regulating reaction pathways for incompatible tandem catalysis under aqueous conditions. The smart nanoreactor is based on multi-functional amphiphilic poly(2-oxazoline)s and covalently crosslinked with spiropyran upon micelle formation in water. It responds to light irradiation in a wavelength-selective manner switching its morphology as confirmed by dynamic light scattering and cryo-transition electron microscopy. The compartmental structure renders distinct nanoconfinements for two incompatible enantioselective transformations: a rhodium-diene complex-catalyzed asymmetric 1,4-addition occurs in the hydrophilic corona while a Rh-TsDPEN-catalyzed asymmetric transfer hydrogenation proceeds in the hydrophobic core. Control experiments and kinetic studies showed that the gated behavior induced by the photo-triggered reversible spiropyran to merocyanine transition in the cross-linking layer is key to discriminate among substrates/reagents during the catalysis. Here, the smart nanoreactor realized photo-regulation to direct the reaction pathway to give a multi-chiral product with high conversions and perfect enantioselectivities in aqueous media. Our SCM catalytic system, on a basic level, mimics the concepts of compartmentalization and responsiveness Nature uses to coordinate thousands of incompatible chemical transformations into streamlined metabolic processes.

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

Labile Fe(III) supersaturation controls nucleation and properties of product phases from Fe(II)-catalyzed ferrihydrite transformation

We report Fe(II)-catalyzed ferrihydrite (Fh) transformation to more crystalline iron (oxyhydr)oxide phases is a widely occurring geochemical process which has been extensively studied as a function of Fe(II)/Fh ratios at fixed Fh loadings. However, recent isolation of an intermediate Fe(III) species resulting from Fe(II)-Fh contact that facilitates transformation by dissolution/reprecipitation suggests that the kinetics and properties of product phases will instead depend mostly on its rate of accumulation to a critical concentration, consistent with principles in the classical nucleation theory (CNT). This suggests a dependence both on the loading of Fe(II) on the surface, which controls the rate of labile Fe(III) formation, as well as the available volume of solution, which also impacts how fast it can achieve its critical concentration to nucleate product phases. To specifically examine the latter effect, here we studied transformation of 15 mg Fh in 1 mM FeSO 4 solutions at pH 7.2 in batch suspensions of 30 mL, 150 mL, and 450 mL volumes. Time-dependent concentrations of aqueous Fe(II), surface-associated Fe(II), and resulting labile Fe(III) were monitored along with bulk solids characterization as a function of time. Transmission electron microscopy (TEM) was used to visualize the evolution of phases at identical locations on TEM grids. The collective results show that the rates of Fh loss and emergence of product lepidocrocite (Lp) and goethite (Gt) as well as their phase proportions, nucleation mode and morphological properties depend directly on the rate of accumulation of the labile Fe(III) precursor to its critical concentration, which in our experiments was controlled simply by varying the available volume of solution into which it enters. Statistical analyses of TEM image data suggest that while both heterogeneous and homogeneous nucleation occurred in all experiments, the former was increasingly favored at lower Fh/solution ratio due to its lower nucleation barrier being more favorable at attendant lower supersaturations of Fe(III).

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

Influence of soluble oligomeric aluminum on precipitation in the Al-KOH-H2O system

The role of oligomeric aluminate (Al(OH)4-) species in the precipitation of aluminum phases such as gibbsite (a-Al(OH)3) from aqueous hydroxide solutions remains unclear and difficult to probe directly, despite its importance to developing accurate predictions of Al solubility in highly alkaline systems. Precipitation in this system entails a transition from predominantly tetrahedrally coordinated Al species in solution to octahedrally coordinated Al in gibbsite. Here we report a quantitative study of dissolved Al in the Al-KOH-H2O system using a combination of molecular spectroscopies. We established a relationship between changes in 27Al NMR chemical shifts and the relative intensity of Raman vibrational bands, indicative of variations in the ensemble speciation of Al in solution, and the formation of unique contact ion pair interactions with the aluminate dimer, Al2O(OH)62 . A strong correlation between the extent of Al oligomerization and the amount of solvated Al was demonstrated by systematically varying the KOH:Al molar ratio. The concentration of dissolved oligomeric Al in solution also directly impacted the particle size and morphology of gibbsite; high concentrations of dimeric Al2O(OH)62-, yielded smaller and more numerous anhedral to subhedral gibbsite particles, while low concentrations yielded fewer and larger euhedral gibbsite platelets. The collective observations suggest a key role of the Al2O(OH)62- dimer in promoting gibbsite precipitation from solution, where the potassium ion-paired dimer possibly catalyzes a more rapid transformation of Al coordination from tetrahedral in solution to octahedral in gibbsite.

Dembowski, Mateusz↗
DOE OSTI2022

Ni-H-Beta Catalysts for Ethylene Oligomerization: Impact of Parent Cation on Ni Loading, Speciation, and Siting

Ni-H-Beta catalysts for ethylene oligomerization (EO) were prepared by ion exchange of NH 4 -Beta and H-Beta zeolites with aqueous Ni(NO 3 ) 2 and characterized by H 2 -temperature-programmed reduction (TPR), NH 3 -temperature-programmed desorption (TPD), and diffuse-reflectance infrared Fourier-transform spectroscopy (DRIFTS). Quadruple exchange of NH 4 -Beta at 70 °C resulted in 2.5 wt.% Ni loading corresponding to a Ni 2+ /framework aluminum (FAl) molar ratio of 0.52. [NiOH] + and H + are the primary charge-compensating cations in the uncalcined catalyst, as evidenced by TPR and DRIFTS. Subsequent calcination at 550 °C in air yielded a Ni-H-Beta catalyst containing primarily bare Ni 2+ ions bonded to framework oxygens. Quadruple exchange of H-Beta at 70 °C gave 2.0 wt.% Ni loading (Ni 2+ /FAl = 0.41). After calcination at 550 °C, the resulting Ni-H-Beta catalyst comprises a mixture of bare Ni 2+ ions: [NiOH] + and NiO species. The relative abundance of [NiOH] + increases with the number of exchanges. In situ pretreatment at 500 °C in flowing He converted the [NiOH] + species to bare Ni 2+ ions via dehydration. The bare Ni 2+ ions interact strongly with the Beta framework as evidenced by a perturbed antisymmetric T-O-T vibration at 945 cm -1 . DRIFT spectra of CO adsorbed at 20 °C indicate that the Ni 2+ ions occupy two distinct exchange positions. The results of EO testing at 225 °C and 11 bar (ethylene) suggested that the specific Ni 2+ species initially presented (e.g., bare Ni 2+ , [NiOH] + ) did not significantly affect the catalytic performance.

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

Integrated atomic force microscopy and x-ray irradiation for in situ characterization of radiation-induced processes

Understanding radiation-induced chemical and physical transformations at material interfaces is important across diverse fields, but experimental approaches are often limited to either ex situ observations or in situ electron microscopy or synchrotron-based methods in which cases the radiation type and dose are inextricably tied to the imaging basis itself. In this work we overcome this limitation by demonstrating integration of an X-ray source with an atomic force microscope to directly monitor radiolytically-driven interfacial chemistry at the nanoscale. We illustrate the value of in situ observations by examining effects of radiolysis on material adhesion forces in aqueous solution, as well as examining the production of alkali nitrates at the interface between an alkali halide crystal surface and air. For the examined salt-air interface, direct visualization under flexible experimental conditions greatly extends prior observations by enabling the transformation process to be followed comprehensively from source-to-sink with mass balance quantitation. Overall, our novel rad-AFM opens doors into understanding the dynamics of radiolytically-driven mass transfer and surface alteration at the nanoscale in real-time.

47 OTHER INSTRUMENTATION↗
DOE OSTI2020

First-Principles Modeling of Sodium Ion and Water Intercalation into Titanium Disulfide Interlayers for Water Desalination

Recent experiments revealed the possibility of using titanium disulfide (TiS 2 ) as the cathode material in capacitive deionization (CDI) devices for water desalination. Although it performed stably up to 70 cycles with a salt removal capacity of 14 mg/g (corresponding to a sodium ion removal capacity of 35.8 mg/g) at high molar concentration (600 mM NaCl), the maximum capacity of TiS 2 as a CDI electrode was much lower (~70 mAh/g) than as a supercapacitor (239 mAh/g). Understanding why the ion capacities of these two configurations of the same material differ will entail elucidating detailed charge/discharge mechanisms at the atomic scale. Here, we present density functional theory simulations of sodium intercalation into TiS 2 interlayers in order to gain such understanding. We systematically investigated TiS 2 stacking patterns and ion intercalation sites, energetics of the intercalated compounds, and phase transformation during sodium intercalation. The calculated structural evolution and capacitance–voltage curve agree quite well with previous measurements. We conclude that the different maximum capacities of TiS 2 measured in aqueous and dry environments originate from weaker interlayer interactions with respect to shear strain after ~33% intercalation of Na + –H 2 O pairs, which is detrimental to the mechanical stability of TiS 2 . In conclusion, this study sheds light on the underlying mechanisms of ion intercalation into layered materials and contributes to understanding requirements for future design and optimization of CDI electrode materials for water desalination.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Elucidating the Solvation Structures and Dynamics in Iron-Based TFSI – Aqueous Systems

This study investigates the solvation structures and dynamics of bis(trifluoromethanesulfonyl)imide (TFSI – )-based aqueous electrolytes, focusing on Fe(TFSI) 2 and Fe(TFSI) 3 . Using advanced characterization techniques, including small-angle X-ray scattering, molecular dynamics simulations, Raman spectroscopy, Fourier-transform infrared spectroscopy, and nuclear magnetic resonance, we elucidate how the electrolyte concentration influences ion association, solvation structures, and transport properties. Furthermore, our findings show that higher electrolyte concentrations promote the formation of contact ion pairs and anion networks, leading to reduced ion mobility and altered hydrogen-bonding dynamics. These insights provide a deeper understanding of solvation phenomena in TFSI-based electrolytes and contribute to the development of efficient and environmentally friendly iron electrodeposition processes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Silicate coprecipitation reduces green rust crystal size and limits dissolution-precipitation during air oxidation

Green rusts (GR) are mixed-valence iron (Fe) hydroxides which form in reducing redox environments like riparian and wetland soils and shallow groundwater. In these environments, silicon (Si) can influence Fe oxides’ chemical and physical properties but its role in GR formation and subsequent oxidative transformation have not been studied starting at initial nucleation. Green rust sulfate [GR(SO 4 )] and green rust carbonate [GR(CO 3 )] were both coprecipitated from salts by base titration in increasing % mol Si (0, 1, 10, and 50). The minerals were characterized before and after rapid (24 h) aqueous air-oxidation by x-ray diffraction (XRD), scanning electron microscopy (SEM), Fe extended x-ray absorption fine structure spectroscopy (EXAFS), and N 2 -BET surface area. Results showed that only GR(SO4) or GR(CO3) was formed at every tested Si concentration. Increasing % mol Si caused decreased plate size and increased surface area in GR(CO3) but not GR(SO4). GR plate basal thickness was not changed at any condition indicating a lack of Si interlayering. Air oxidation of GR(SO4) at all % mol Si contents transformed by dissolution and reprecipitation into lepidocrocite and goethite, favoring ferrihydrite with higher % Si content. Air oxidation of GR(CO3) transformed into magnetite and goethite but increasing Si caused GR to oxidize while retaining its hexagonal plate structure via solid-state oxidation. Our results indicate that Si has the potential to cause GR to form in smaller particles and upon air oxidation, Si can either stabilize the plate structure or alter transformation to ferrihydrite.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Ions Tune Interfacial Water Structure and Modulate Hydrophobic Interactions at Silica Surfaces

The structure and ultrafast dynamics of the electric double layer (EDL) are central to chemical reactivity and physical properties at solid/aqueous interfaces. While the Gouy–Chapman–Stern model is widely used to describe EDLs, it is solely based on the macroscopic electrostatic attraction of electrolytes for the charged surfaces. Structure and dynamics in the Stern layer are, however, more complex because of competing effects due to the localized surface charge distribution, surface–solvent–ion correlations, and the interfacial hydrogen bonding environment. Here, we report combined time-resolved vibrational sum frequency generation (TR-vSFG) spectroscopy with ab initio DFT-based molecular dynamics simulations (AIMD/DFT-MD) to get direct access to the molecular-level understanding of how ions change the structure and dynamics of the EDL. We show that innersphere adsorbed ions tune the hydrophobicity of the silica–aqueous interface by shifting the structural makeup in the Stern layer from dominant water–surface interactions to water–water interactions. This drives an initially inhomogeneous interfacial water coordination landscape observed at the neat interface toward a homogeneous, highly interconnected in-plane 2D hydrogen bonding (2D-HB) network at the ionic interface, reminiscent of the canonical, hydrophobic air–water interface. This ion-induced transformation results in a characteristic decrease of the vibrational lifetime (T 1 ) of excited interfacial O–H stretching modes from T 1 ~ 600 fs to T 1 ~ 250 fs. Hence, we propose that the T 1 determined by TR-vSFG in combination with DFT-MD simulations can be widely used for a quantitative spectroscopic probe of the ion kosmotropic/chaotropic effect at aqueous interfaces as well as of the ion-induced surface hydrophobicity.

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

Coupled Interfacial and Bulk Kinetics Govern the Timescales of Multiphase Ozonolysis Reactions

Chemical transformations in aerosols impact the lifetime of particle phase species, the fate of atmospheric pollutants, and both climate- and health-relevant aerosol properties. Timescales for multiphase reactions of ozone in atmospheric aqueous phases are governed by coupled kinetic processes between the gas phase, the particle interface, and its bulk, which respond dynamically to reactive consumption of O 3 . However, models of atmospheric aerosol reactivity often do not account for the coupled nature of multiphase processes. Herein, to examine these dynamics, we use new and prior experimental observations of aqueous droplet reaction kinetics, including three systems with a range of surface affinities and ozonolysis rate coefficients ( trans -aconitic acid (C 6 H 6 O 6 ), maleic acid (C 4 H 4 O 4 ), and sodium nitrite (NaNO 2 )). Using literature rate coefficients and thermodynamic properties, we constrain a simple two-compartment stochastic kinetic model which resolves the interface from the particle bulk and represents O 3 partitioning, diffusion, and reaction as a coupled kinetic system. Our kinetic model accurately predicts decay kinetics across all three systems, demonstrating that both the thermodynamic properties of O 3 and the coupled kinetic and diffusion processes are key to making accurate predictions. An enhanced concentration of adsorbed O 3 , compared to gas and bulk phases is rapidly maintained and remains constant even as O 3 is consumed by reaction. Multiphase systems dynamically seek to achieve equilibrium in response to reactive O 3 loss, but this is hampered at solute concentrations relevant to aqueous aerosol by the rate of O 3 arrival in the bulk by diffusion. As a result, bulk-phase O 3 becomes depleted from its Henry's law solubility. This bulk-phase O 3 depletion limits reaction timescales for relatively slow-reacting organic solutes with low interfacial affinity (i.e., trans-aconitic and maleic acids, with k rxn ≈ 10 3 -10 4 M -1 s -1 ), which is in contrast to fast-reacting solutes with higher surface affinity (i.e., nitrite, with k rxn ≈ 10 5 M -1 s -1 ) where surface reactions strongly impact the observed decay kinetics.

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

A Reduced-Temperature Process for Preparing Atomically Clean Si(100) and SiGe(100) Surfaces with Vapor HF

Silicon processing techniques such as atomic precision advanced manufacturing (APAM) and epitaxial growth require surface preparations that activate oxide desorption (typically >1000 °C) and promote surface reconstruction toward atomically clean, flat, and ordered Si(100)-2 × 1. Here, in this study, we compare the aqueous and vapor phase cleaning of Si and Si/SiGe surfaces to prepare APAM-ready and epitaxy-ready surfaces at lower temperatures. Angle resolved X-ray photoelectron spectroscopy (ARXPS) and Fourier transform infrared (FTIR) spectroscopy indicate that vapor hydrogen fluoride (VHF) cleans dramatically reduce carbon surface contamination and allow the chemically prepared surface to reconstruct at lower temperatures, 600 °C for Si and 580 °C for a Si/Si 0.7 Ge 0.3 heterostructure, into an ordered atomic terrace structure indicated by scanning tunneling microscopy (STM). After thermal treatment and vacuum hydrogen termination, we demonstrate STM hydrogen desorption lithography (HDL) on VHF-treated Si samples, creating reactive zones that enable area-selective chemistry by using a thermal budget similar to CMOS process flows. We anticipate that these results will establish new pathways to integrate APAM with Si foundry processing.

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

Understanding the Adsorption of Rare-Earth Elements in Oligo-Grafted Mesoporous Carbon

Rare-earth elements (REEs) are 17 elements of the periodic table primarily consisting of lanthanides. In modern society, the usage of REEs is ubiquitous in almost all modern gadgets and therefore efficient recovery and separation of REEs are of high importance. Selective adsorption and chelation of REEs in solid sorbents is a unique and sustainable process for their recovery. In this work, single-stranded oligos with 100 units of thymine were grafted onto carboxylated mesoporous carbon to synthesize a sorbent with phosphorus and oxygen functionalities. Additionally, the sorbent was characterized by X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, and scanning electron microscopy-energy-dispersive X-ray spectroscopy. Three different REEs with varying atomic radii and densities, Lu, Dy, and La, were adsorbed onto the carbon from aqueous solutions. It was observed that the adsorbed amounts increased with the increase in the atomic radius or decrease in the atomic density. Calculation of the distribution coefficients for all the equilibrium adsorption amounts suggested that adsorption is more effective in the lower concentration region. The L 3 -edge X-ray absorption near-edge structure confirmed a 3+ oxidation state of REEs in the adsorbed phase. Extended X-ray absorption fine structure (EXAFS) confirmed the binding of REEs with oxygen functionalities in the adsorbed phase. The radial distribution functions calculated from the EXAFS data suggest a longer RE–O distance for La compared to those for Lu and Dy. The coordination numbers and Debye–Waller factors have typical values of about 8–9 atoms and 0.01–0.02 Å 2 , respectively.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Directing the adsorption and assembly of laponite nano-discs at oil–water interfaces

Achieving tunable controls on the adsorption and self-assembly of nanoscale building blocks at immiscible fluid interfaces is essential for synthesizing advanced materials, stabilizing emulsions, and the sustainable storage and recovery of fluids. Although extensive efforts have been directed toward resolving the assembly of spherical nanoparticles at water–hydrocarbon interfaces, 2D nanoparticles have received far less attention. In this study, we developed novel controls to direct the adsorption and assembly of 2D laponite nano-discs (diameter = ∼30 nm and thickness = ∼1 nm) at water–heptane interfaces using traces of sodium dodecyl sulfate (SDS) surfactant, demonstrated by advanced in situ small-angle X-ray scattering, atomic force microscopy, spinning drop tensiometer measurements and molecular dynamics simulations. The results show that SDS surfactant displaces the adsorbed laponite nano-discs from the interface toward the aqueous phase. The extent of this displacement increases with SDS concentration such that high SDS concentrations convert laponite-rich interfaces to SDS-rich interfaces free of laponite nano-discs. This transformation is associated with significant alterations in the rheological and nanomechanical properties of the host interface. In this context, reduction in interfacial tension and interfacial stiffness and an increase in the interfacial deformation is observed on increasing the SDS concentration from 0 to 0.1 wt%. The displacement of laponite nano-discs from the interface is driven by strong electrostatic interactions between the hydrophilic SDS group and interfacial water molecules. These studies unlock new insights into the adsorption and assembly of 2D nanoscale particles at water–hydrocarbons interfaces that are relevant for various applications related to energy and environmental science and engineering.

interfacial tension↗
DOE OSTI2022

Efficient Removal of Lead Ions from Aqueous Media Using Sustainable Sources Based on Marine Algae

The goal of this project is to explore a new method to efficiently remove Pb(II) ions from water by processing Undaria pinnatifida into immobilized beads using sodium alginate and calcium chloride. The resulting biosorbent was characterized by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDS). Using immobilized U. pinnatifida, we investigated the effect of various factors on Pb(II) ion removal efficiency such as temperature, pH, ionic strength, time, and underlying biosorption mechanisms. For Pb(II) ion biosorption studies, Pb(II) ion biosorption data were obtained and analyzed using Langmuir and Freundlich adsorption models. It is found that the maximum Pb(II) ion adsorption capacity (X m ) of U. pinnatifida was estimated to be ~5 times greater than that of activated carbon, indicating the superior Pb(II) ion removal capability of U. pinnatifida compared to activated carbon. In addition, a thermodynamic study indicates that biosorption processes are found to be endothermic and an increase in the Pb(II) ion solution temperature provides a more preferential reaction toward Pb(II) ion biosorption.

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

Aqueous buffer solution-induced crystallization competes with enzymatic depolymerization of pre-treated post-consumer poly (ethylene terephthalate) waste

In this paper, the complex relationship between kinetics and substrate morphology during enzymatic depolymerization of melt processed poly(ethylene terephthalate) (PET) is explored and the effects of competing transformations are analyzed. Extruded PET substrates from post-consumer recycled PET (RPET) bottles flakes subjected to enzymatic depolymerization are examined to reveal increases in crystallinity from ~10% post-extrusion to >30% after 3 days of depolymerization as well as increases in glass transition temperature (T g ) from ~66°C to > 80°C. Further investigation into this behavior shows that post-extrusion RPET substrates do not exhibit changes in crystallinity when subjected to dry annealing at 65°C in an oven over 7 days, but they do experience annealing in depolymerization buffer solution with no enzymes at 65°C within 3 days. This difference may be attributed to plasticization of PET in the presence of water, also known as solvent induced crystallization. The impact of this plasticized annealing behavior is demonstrated by subjecting RPET substrates to increasing enzyme-to-substrate loads. As enzyme load increases, overall conversion of substrates increases despite crystallinity also increasing to similar levels regardless of the initial enzyme loading. The competition between depolymerization and crystallization suggests that the rate at which PET substrates are depolymerized at the operational temperature is integral to achieving high conversion to monomeric product. This, in turn, also suggests that savings from lowered enzyme loadings may be more detrimental than helpful in pursuing the most cost-effective recycling systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗