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At least 343 records · Page 19

Synthesis of dysprosium oxychloride (DyOCl)

Dysprosium oxychloride, DyOCl, was synthesized using a simple dehydration method with DyCl3·6H2O. X-ray powder diffraction data was used to determine the crystal structure. The DyOCl compound is isostructural to the matlockite (PbFCl) crystal structure and crystallizes in the tetragonal P4/nmm (#129) space group. The crystal structure contains the alternating cationic layers of (DyO)n and anionic layers of nCl– along the c-axis. The structural data including unit cell, volume, and density of DyOCl were compared to other REOCl data from Inorganic Crystal Structure Database (ICSD) and our previous study on TbOCl. Fourier-transform infrared spectroscopy (FTIR) was performed, and the vibrations of DyOCl possibly from Dy–O and Dy–Cl were observed at 543 and 744 cm-1. Scanning electron microscopy analysis (SEM) showed irregularly shaped crystals.

Chong, Saehwa↗

Optical Characterization of the Keck Array and BICEP3 CMB Polarimeters from 2016 to 2019

The BICEP/Keck experiment (BK) is a series of small-aperture refracting telescopes observing degree-scale cosmic microwave background (CMB) polarization from the South Pole in search of a primordial B-mode signature. This B-mode signal arises from primordial gravitational waves interacting with the CMB and has amplitude parametrized by the tensor-to-scalar ratio r. Since 2016, BICEP3 and the Keck Array have been observing with 4800 total antenna-coupled transition-edge sensor detectors, with frequency bands spanning 95, 150, 220, and 270 GHz. Here we present the optical performance of these receivers from 2016 to 2019, including far-field beams measured in situ with an improved chopped thermal source and instrument spectral response measured with a field-deployable Fourier transform spectrometer. As a pair differencing experiment, an important systematic that must be controlled is the differential beam response between the co-located, orthogonally polarized detectors. We generate per-detector far-field beam maps and the corresponding differential beam mismatch that is used to estimate the temperature-to-polarization leakage in our CMB maps and to give feedback on detector and optics fabrication. The differential beam parameters presented here were estimated using improved low-level beam map analysis techniques, including efficient removal of non-Gaussian noise as well as improved spatial masking. These techniques help minimize systematic uncertainty in the beam analysis, with the goal of constraining the bias on r induced by temperature-to-polarization leakage to be subdominant to the statistical uncertainty. This is essential as we progress to higher detector counts in the next generation of CMB experiments.

79 ASTRONOMY AND ASTROPHYSICS↗

Hierarchical Phased-Array Antennas Coupled to Al KIDs: A Scalable Architecture for Multi-band Millimeter/Submillimeter Focal Planes

We present the optical characterization of two-scale hierarchical phased-array antenna kinetic inductance detectors (KIDs) for millimeter/submillimeter wavelengths. Our KIDs have a lumped-element architecture with parallel plate capacitors and aluminum inductors. The incoming light is received with a hierarchical phased array of slot dipole antennas, split into 4 frequency bands (between 125 GHz and 365 GHz) with on-chip lumped-element band-pass filters, and routed to different KIDs using microstriplines. Individual pixels detect light for the 3 higher-frequency bands (190–365 GHz), and the signals from four individual pixels are coherently summed to create a larger pixel detecting light for the lowest frequency band (125–175 GHz). The spectral response of the band-pass filters was measured using Fourier transform spectroscopy (FTS), the far-field beam pattern of the phased-array antennas was obtained using an infrared source mounted on a 2-axis translating stage, and the optical efficiency of the KIDs was characterized by observing loads at 294 K and 77 K. We report on the results of these three measurements.

47 OTHER INSTRUMENTATION↗

Exploration of fibers produced from petroleum based-mesophase pitch and pet blends for carbon fiber production

Petroleum-derived mesophase pitch and polyethylene terephthalate (PET) were blended and melt-extruded to create precursor fibers. The raw blends, heat treated bulk materials, and fibers were all examined to determine compatibility between petroleum-derived mesophase pitch and PET. Thermal investigation of the raw blends showed the presence of both the pitch and PET in separate phases suggesting no interactions had occurred during mixing. Here, the heat-treated bulk material also showed multiple phases under polarized light while Fourier-transform infrared spectroscopy indicated that the two materials did not fully separate during extrusion. Elemental scans of the precursor fibers showed areas of high oxygen concentrations averaging 11.7% as compared to a 2% oxygen concentration across the majority of the cross-section. Tensile tests of the precursor fibers showed a decrease in average modulus as compared to pure pitch fibers; however, the depressed modulus of the blended fibers was found to be independent of the PET weight percentage. Fibers created from 5 wt.% PET had a strength value within 10% of pure pitch and a 200% increase in modulus and were therefore found to be the most promising for carbon fiber production. Pure pitch and the 5 wt.% PET fibers were stabilized and carbonized to 1000 °C. Both types of fibers were tensile tested to determine their strength and stiffness. Pure pitch carbon fibers maintained a higher strength while the carbon fibers produced from 5 wt.% PET possessed a stiffer modulus which can be attributed to their radial microstructure.

36 MATERIALS SCIENCE↗

Micromechanical Fields Associated with Irregular Deformation Twins in Magnesium

Understanding and controlling the development of deformation twins is paramount for engineering strong and stable hexagonal close-packed (HCP) Mg alloys. Actual twins are often irregular in boundary morphology and twin crystallography, deviating from the classical picture commonly used in theory and simulation. In this work, the elastic strains and stresses around irregular twins are examined both experimentally and computationally to gain insight into how twins develop and the microstructural features that influence their development. A nanoprecession electron diffraction (N-PED) technique is used to measure the elastic strains within and around a $\left\{ {10\overline{1}2} \right\}$ tensile twin in AZ31B Mg alloy with nm scale resolution. A full-field elasto-viscoplastic fast Fourier transform (EVP-FFT) crystal plasticity model of the same sub-grain and irregular twin structure is employed to understand and interpret the measured elastic strain fields. The calculations predict spatially resolved elastic strain fields in good agreement with the measurement, as well as all the stress components and the dislocation density fields generated by the twin, which are not easily obtainable from the experiment. The model calculations find that neighboring twins, several twin thicknesses apart, have little influence on the twin-tip micromechanical fields. Furthermore, this work reveals that irregularity in the twin-tip shape has a negligible effect on the development of the elastic strains around and inside the twin. Importantly, the major contributor to these micromechanical fields is the alignment of the twinning shear direction with the twin boundary.

36 MATERIALS SCIENCE↗

Applying Improved Optical Recognition with Machine Learning on Sorting Cu Impurities in Steel Scrap

Annually, 20–55 million tons of electronic waste (e-waste) is produced worldwide (5% of all municipal solid waste). Although e-waste embodies only 2% of America’s municipal waste, it accounts for a significantly larger proportion of the heavy metals and flame retardants present in the waste stream. Currently, less than 20% of all e-waste is recycled in the United States because the heterogeneity of the feedstock limits the opportunity for reuse in high value products and processing of the waste itself is often too costly to justify handling. To address this concern, the aims of this study are: 1) to identify the major plastic and metal compositions within electronic shredder residue (ESR), 2) to formulate solvents and processing conditions to separate 90% of the plastics targeted from consumer shred ESR, and 3) to develop a process design model to estimate the cost and energy efficiency of the proposed solvent-based processing. In this study, a pre-sorted heterogeneous ESR feedstock (one where aluminum, magnetic components, and hazardous battery materials removed by an e-waste recycling facility) was used, with the major compositions of the ESR characterized. It was found that 25 wt.% of the feedstock was composed of plastics, 6 wt.% rubber, 27 wt.% printed circuit boards, 23% wire, and the remainder metals and capacitors. Within the plastic portion, polystyrene (PS, 40 wt.%), acrylonitrile butadiene styrene (ABS, 25 wt.%), and styrene-acrylonitrile (SAN, 9wt.%) were identified to compose the majority of the screened plastics using Fourier transform infrared spectroscopy (FTIR). Next, selective solvents were screened using Hansen Solubility Parameter Theory (HSP) for dissolving PS and ABS. The pre-screening results show that methylene chloride (dichloromethane, DCM) and tetrahydrofuran (THF) are capable of dissolving the most PS and ABS, while methanol (MeOH) and ethylene glycol (EG) are capable of precipitating the most PS and ABS. These solvents were subsequently used to recover polymers and remove. flame retardants within the ESR feedstock. By optimizing the dissolution time and the solvents used, the highest polymer dissolution yield (99 wt.%%) was achieved using DCM for 48 hr. Both pre-screened anti-solvents (MeOH and EG) showed the highest polymer precipitation yield (71 wt.%). In terms of flame retardant removal rate, EG was found to have a high phosphorus-containing flame retardant removal rate (up to 98%). Characterization shows that the proposed solvent-based processing can preserve a high molecular weight fraction of the polymers and effectively remove flame retardants. Cost analysis indicates that the amount of the solvent/anti-solvent recovered after the reaction would play a critical role in reducing the operating costs. The energy analysis shows that the proposed solvent-based processes can save up to 60% of the embodied energy used to manufacture plastics used in electronics (PS and ABS were used for calculations). The results from this project prove the potential of solvent-based processing to produce secondary materials (plastics and metals) from e-waste for cross-industry reuse.

36 MATERIALS SCIENCE↗

Investigation of twin growth mechanisms in precipitate hardened AZ91

Here, in this work, an elasto-viscoplastic fast-Fourier-transform (EVP-FFT) model with a dislocation-density (DD) based hardening law is employed to study the growth of a {10$\bar{1}$2} tensile twin that is blocked by basal-precipitates in precipitate-hardened AZ91 magnesium alloy. It is frequently reported that twin growth is hindered in precipitate-hardened Mg alloys; however, thick twin domains are often observed experimentally in these material systems. Detailed numerical investigation of deformation twinning starting from an early propagation stage, before twin growth, reveals that the stress fields that result from two sequentially propagated twins co-impinging on a precipitate relaxes the twin back stress locally and promotes twin growth at the twin-precipitate junction. Based on these findings, a two-step growth mechanism is proposed for twins arrested by precipitates. In the first step, the interaction of a twin tip with a precipitate develops a stress concentration on the other side of the precipitate, prompting the formation of a second twin. Subsequently, the back stresses associated with the first twin are relaxed by the formation of the second twin, allowing the first twin to grow at the twin-precipitate junction and eventually engulf the precipitate. This mechanism suggests that twin growth can be achieved locally with minimal additional external forces, explaining how relatively large twin domains can develop even in the presence of arrays of precipitates.

36 MATERIALS SCIENCE↗

Multi-modal characterization of the B2 phase in the Ta-Re binary system

The energy and transportation industries demand materials that retain their mechanical property at high temperatures. Refractory complex concentrated alloys (RCCAs) with a BCC + B2 microstructure offer a potential solution, where maintaining the high temperature mechanical properties can be achieved by precipitation strengthening. This depends on the B2 phase in RCCAs being thermodynamically stable with a high solvus temperature. Recently, we predicted the high temperature stability of the B2 structure in the Ta-Re binary system, using density functional theory. Here, in this study, we provide experimental evidence for the existence of this phase for the first time, using a Ta 65 Re 35 alloy. Despite Ta-Re binary phase diagrams predicting a single-phase BCC microstructure for Ta 65 Re 35 , we show that a high Z nanoscale secondary phase appears after heat treatment at 1550 °C and 1100 °C. Scanning transmission electron microscopy (STEM) revealed that this phase has a cubic structure and is equiatomic TaRe though B2 superlattice reflections were absent in fast Fourier transforms (FFT) and diffraction patterns (DPs). DP simulations indicate that the B2 TaRe superlattice reflections are up to two orders of magnitude weaker than their fundamental reflections, making their detection challenging via electron microscopy. Neutron diffraction confirmed the second phase had a B2 structure. This study identified a previously unobserved high temperature stable B2 phase in the Ta-Re system, enabling the development of new high temperature BCC + B2 RCCAs.

36 MATERIALS SCIENCE↗

An algorithmic approach to predicting mechanical draft cooling tower fan speeds from infrasound signals

Mechanical draft cooling towers (MDCTs) serve a critical heat management role in a variety of industries. For nuclear reactors in particular, the consistent, predictable operation of MDCTs is required to avoid damage to infrastructure and reduce the potential for catastrophic failure. Accurate, reliable measurement of MDCT fan speed is therefore an important maintenance and safety requirement. To that end, we have developed an algorithm for automatically predicting the rotational speeds of multiple, simultaneously operating fan rotors using contactless, infrasound measurements. The algorithm is based on identifying the blade passing frequencies (BPFs), their harmonics, as well as the motor frequencies (MFs) for each fan in operation. Using the algorithm, these frequencies can be automatically identified in the acoustic waveform’s short-time Fourier transform spectrogram. Attribution is aided by a set of filters that rely on the unique spectral and temporal characteristics of fan operation, as well as the intrinsic frequency ratios of the BPF harmonics and the BPF/MF signals. The algorithm was tested against infrasound data acquired from infrasound sensors deployed at two research reactors: the Advanced Test Reactor (ATR) located at Idaho National Laboratory (INL) and the High Flux Isotope Reactor (HFIR) located at Oak Ridge National Laboratory (ORNL). After manually identifying the MDCT gearbox ratio, the algorithm was able to quickly yield fan speeds at both reactors in good agreement with ground truth. Ultimately, this work demonstrates the ease by which MDCT fans may be monitored in order to optimize operational conditions and avoid infrastructure damage.

42 ENGINEERING↗

Effect of pretreatment conditions on acidity and dehydration activity of CeO 2 -MeO x catalysts

A series of MeOx-modified CeO 2 (CeO 2 -MnO x , CeO 2 -ZnO, CeO 2 -MgO, CeO 2 -CaO, and CeO 2 -Na 2 O) catalysts were prepared by the impregnation of CeO 2 with corresponding metal nitrates. Acidity and oxidation state of cerium were investigated on both oxidized and reduced catalysts by employing Fourier Transform Infrared spectroscopy (FTIR) on adsorbed pyridine and in situ H 2 -Temperature Programmed Reduction/X-ray Absorption Spectroscopy (H 2 -TPR/XAS) techniques, respectively. Metal oxide addition tended to alter both type and number of acid sites on ceria. EXAFS data showed a significant difference in N Ce-O between unmodified and CeO 2 -MeO x , suggesting that added MeO x interferes with vacancy formation on ceria during reduction. Here, in comparison with air-pretreated samples, H 2 -pretreated ones under similar conversion of 1,5 pentanediol exhibited a higher selectivity towards linear alcohols. Alcohol conversion found to correlate with total acidity (i.e., Brønsted and Lewis). CeO 2 benefited from the addition of alkali (Na) or alkaline earth metals (Mg, Ca) by producing unsaturated alcohols.

1,5-Pentanediol↗

Systematic investigations on iron cycling in phosphorus/siderophore systems: Synergism or antagonism?

Synergisms between microbial exudates on Fe (hydr)oxide dissolution as an effective Fe acquisition pathway have been recently addressed and vigorously debated. However, Fe liberation mechanisms and where siderophores and phosphorus (P) coexist received little attentions. Current study systematically investigated ferrihydrite dissolution in the presence of desferrioxamine B (DFOB) (a kind of fungally-derived siderophores) and inorganic/organic phosphorus (orthophosphate, Pi; myo-inositol hexaphosphate, IHP), as a function of solute pH, reaction time and reagent content. Reacted solids were characterized by N 2 -BET adsorption, zeta (ζ) potential analysis, sequential extraction analysis (SEDEX), field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), micro Raman spectroscopy and attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR). Our results indicate that upon reaction with P-only or (DFOB + P) systems, interfacial complexation partially switched from monolayer bidentate-binuclear surface complexes to ternary complexes, or laterally transformed into amorphous Fe–P precipitates. The Fe-Pi complex precipitated more readily under acidic conditions, and Fe-IHP complex preferentially nucleated in neutral-alkaline environments. Phosphorus slightly promoted Fe release from minerals and fixation to the leached layer or interfacial liquid zone initially, but subsequently prevented further attacks from protons and DFOB. The co-effects of P and DFOB likely correspond to two successive scenarios: 1) DFOB is preferentially attracted toward ferrihydrite surfaces by negative electrical fields induced by adsorbed phosphorus and can act synergistically with labile P–Fe complexes, resulting in intensive temporal dissolution of Fh; 2) subsequent Fe shuttling to DFOB can be prohibited by stabilized, passive P/Fe–P layers. Finally, our results emphasize the antagonism between P compounds and siderophores (i.e., DFOB here) on ferrihydrite dissolution to improve understanding of the biologically-mediated Fe cycling in natural systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Vapor-phase grafting of a model aminosilane compound to Al 2 O 3 , ZnO, and TiO 2 surfaces prepared by atomic layer deposition

Atomic layer deposition (ALD) is a highly versatile surface functionalization technique that can conformally coat both planar and porous substrates. Here we use ALD metal oxide layers to establish a well-defined starting surface for vapor-phase surface organic modification. Vapor-phase (3-aminopropyl)triethoxysilane (APTES) surface silanization of ALD Al 2 O 3 , ZnO and TiO 2 surfaces were studied at 100 °C, 150 °C and 200 °C. In situ quartz crystal microbalance (QCM) and Fourier-transform infrared (FTIR) spectroscopy measurements, and ex situ atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) measurements showed uniform monolayer silane formation through self-limiting APTES reaction. We observed a higher surface density of grafted APTES species following silanization at 100 °C compared to 200 °C, and we attribute this to the temperature-dependent reactivity of the surface hydroxyls and changes in the mode of APTES reaction. The FTIR and XPS measurements revealed that APTES reacts with Al 2 O 3 and ZnO exclusively through metal siloxy bond formation. However, APTES reacts with TiO 2 through both siloxy bond formation and ammonium salt formation via the amine group.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modification of LiMn 2 O 4 surfaces by controlling the Acid–Base surface chemistry of atomic layer deposition

In this combined theoretical and experimental study, we report the effects of Al precursor selection on the growth chemistry, interfacial structure, and electrochemistry of Al 2 O 3 coatings on spinel LiMn 2 O 4 (LMO) surfaces by atomic layer deposition (ALD). Five Al precursors, exhibiting a range of Lewis acid-base properties, were used to establish trends in the ALD Al 2 O 3 growth chemistry on LMO powders in comparison to redox-inactive planar silicon substrates. We show that the Lewis acid-base properties of the Al precursor ligands can be used to tune both the Mn oxidation states and the Al 2 O 3 coverage on the LMO surface. Density functional theory calculations are used to examine the reaction mechanism of each precursor on LMO surfaces, elucidating a correlation between the Lewis acidity of the ligands and the decomposition thermochemistry. In-depth X-ray photoelectron spectroscopy and in situ Fourier transform infrared spectroscopy measurements support these theoretical predictions and further reveal how different Al precursors modify the atomic and electronic structure near the LMO surface during ALD. While the Mn oxidation state is strongly influenced by the Lewis acidity of the precursor ligand, the surface coverage and thickness of the Al 2 O 3 coating are a more representative descriptor of the electrochemical performance measured in coin cell experiments. Finally, we show how the ligand acid-base properties of ALD precursors can be used to rationally tailor atomic layer growth mechanisms, which may enable atomic level control over the structure of functionalized interfaces for various applications related to catalysis, semiconductors, and energy storage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Online data-enabled predictive control

We develop an online data-enabled predictive (ODeePC) control method for optimal control of unknown systems, building on the recently proposed DeePC (Coulson et al., 2019). Our proposed ODeePC method leverages a primal-dual algorithm with real-time measurement feedback to iteratively compute the corresponding real-time optimal control policy as system conditions change. The proposed ODeePC conceptual-wise resembles standard adaptive system identification and model predictive control (MPC), but it provides a new alternative for the standard methods. ODeePC is enabled by computationally efficient methods that exploit the special structure of the Hankel matrices in the context of DeePC with Fast Fourier Transform (FFT) and primal-dual algorithm We provide theoretical guarantees regarding the asymptotic behavior of ODeePC, and we demonstrate its performance through numerical examples.

97 MATHEMATICS AND COMPUTING↗

A high throughput assay to detect enzymatic polyethylene oxidation

Biological plastics deconstruction and upcycling have emerged as sustainable alternatives to traditional recycling technologies for plastics waste. The discovery and engineering of efficient thermostable poly(ethylene terephthalate) (PET) hydrolases have made biological PET recycling possible at scale; however, enzymes for non-PET plastics, which account for approximately 70% of all plastics produced, remain largely undiscovered. To accelerate the discovery of such enzymes, we develop a high-throughput screen to detect initial polymer oxidation, specifically that of the C-H bond to an aldehyde. We test 4-hydrazino-7-nitro-2,1,3-benxoxadiozole hydrazine (NBD-H), which reacts with generated aldehydes to form a fluorescent hydrazone on plasma oxidized low-density polyethylene (LDPE) films. Hydrazone generation correlated well with the area of aldehyde peaks as measured by Fourier Transform Infrared Spectroscopy (FTIR) (R2 = 0.92). Moreover, we demonstrate that the probe reliably identifies LDPE-active dye decolorizing peroxidases (DyPs) that generate aldehydes on LDPE films (1.7 – 3.0 fold change relative to background), serving as an effective screen as demonstrated by receiver operating characteristic area under the curve of 0.95. Furthermore, this assay offers an LDPE oxidation screening platform that can be readily parallelized and automated for accelerated discovery of enzymes involved in polyolefin deconstruction.

biocatalysis↗

Unlocking the secret of lignin-enzyme interactions: Recent advances in developing state-of-the-art analytical techniques

Bioconversion of renewable lignocellulosics to produce liquid fuels and chemicals is one of the most effective ways to solve the problem of fossil resource shortage, energy security, and environmental challenges. Among the many biorefinery pathways, hydrolysis of lignocellulosics to fermentable monosaccharides by cellulase is arguably the most critical step of lignocellulose bioconversion. In the process of enzymatic hydrolysis, the direct physical contact between enzymes and cellulose is an essential prerequisite for the hydrolysis to occur. However, lignin is considered one of the most recalcitrant factors hindering the accessibility of cellulose by binding to cellulase unproductively, which reduces the saccharification rate and yield of sugars. This results in high costs for the saccharification of carbohydrates. The various interactions between enzymes and lignin have been explored from different perspectives in literature, and a basic lignin inhibition mechanism has been proposed. However, the exact interaction between lignin and enzyme as well as the recently reported promotion of some types of lignin on enzymatic hydrolysis is still unclear at the molecular level. Multiple analytical techniques have been developed, and fully unlocking the secret of lignin-enzyme interactions would require a continuous improvement of the currently available analytical techniques. This review summarizes the current commonly used advanced research analytical techniques for investigating the interaction between lignin and enzyme, including quartz crystal microbalance with dissipation (QCM-D), surface plasmon resonance (SPR), attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy, atomic force microscopy (AFM), nuclear magnetic resonance (NMR) spectroscopy, fluorescence spectroscopy (FLS), and molecular dynamics (MD) simulations. Interdisciplinary integration of these analytical methods is pursued to provide new insight into the interactions between lignin and enzymes. Finally, this review will serve as a resource for future research seeking to develop new methodologies for a better understanding of the basic mechanism of lignin-enzyme binding during the critical hydrolysis process.

59 BASIC BIOLOGICAL SCIENCES↗

Characteristics of graphene oxide-like materials prepared from different deashed-devolatilized coal chars and comparison with graphite-based graphene oxide, with or without the ultrasonication treatment

Deashed-devolatilized coal chars were prepared from anthracite, bituminous, subbituminous, and lignite coals, then oxidized to prepare graphene oxide (GO)-like materials that were extensively characterized and compared with a pristine graphite-based GO sample (CGO). Coal-based GO-like materials and CGO were then subjected to ultrasonication treatment for delamination, which also impacted their physicochemical properties. The surface oxygen contents of CGO and coal-based samples were ~32 % and ~26–35 %, respectively, that were reduced to ~27 % and ~21–24 %, respectively, after ultrasonication. The Fourier transform infrared and X-ray photoelectron spectroscopy spectra of all samples showed different profiles before and after the ultrasonication, suggesting a change in chemical functionalities. The Raman spectra of CGO and coal-based samples exhibited similar D and G bands with D/G intensity ratios (I D /I G ) of 0.93 and 0.88–0.92, respectively. The I D /I G ratio of CGO and most of the coal-based samples increased after the ultrasonication due to creation of more defects. The main X-ray diffraction (XRD) peak for CGO and coal-based samples were observed at ~11° and ~22–24°, respectively. Ultrasonication of the samples resulted in a reduction of crystallite size and number of layers for all CGO and coal-based samples, confirming both splitting and delamination of carbon layers. Additionally, different coal-based samples exhibited almost overlapping XRD profiles after the ultrasonication.

36 MATERIALS SCIENCE↗

Diethylenetriamine-functionalized graphene oxide: Insights into ion adsorption and applications in rare earth element separation

The growing demand for critical minerals and materials requires atom- and energy-efficient, selective separations to overcome the challenges posed by the similar chemical and physical properties of the rare earth elements (REEs) and their low concentrations in unconventional domestic feedstocks. Here, in this study, we developed diethylenetriamine-functionalized graphene oxide (DETA-GO) as a membrane material for REE adsorption and separation. Synthesis conditions were optimized to maximize nitrogen incorporation while also preserving GO dispersibility for facile membrane fabrication. We investigated the mechanism of amine functionalization, the nitrogen-bonding configurations, the organization of the interlayer transport channels, and the resulting effects on ion and water transport for REE separations. Neat-GO and DETA-GO multilayer laminate membranes were fabricated by vacuum filtration onto polymer supports. To investigate the effects of amine functionalization, the membranes were characterized using scanning electron microscopy, Raman, Fourier transform infrared, and X-ray photoelectron spectroscopy, as well as grazing-incidence X-ray diffraction measurements. Ion permeation experiments with representative lanthanum (La 3+ ) and ytterbium (Yb 3+ ) solutions revealed enhanced ion adsorption and water transport through DETA-GO membranes compared to neat-GO. The strong affinity of the membranes for multivalent REEs was also validated with conductivity and inductively coupled plasma mass spectrometry measurements. Atomistic insight into the role of amine functionalization in modulating nanochannel architecture and long-term stability, optimizing adsorption sites, and regulating REE and water transport was obtained using classical molecular dynamics simulations. Collectively, our joint experimental and theoretical study demonstrates the potential of DETA-GO membranes for selective REE separations, offering insights into ion-binding mechanisms, water-transport properties, and nanochannel optimization for the recovery of critical materials from aqueous feedstocks.

Adsorbent↗