Exchange Diffusion Research Articles

Investigate of Electrochemical Properties of Nd(II) and Nd(III) in Eutectic LiCl-KCl Molten Salt

Pyroprocessing is one of the promising methods to reprocess the spent nuclear fuel. Neodymium (Nd) constitutes about one third of rare earth in fission products, however, the electrochemical properties of Nd have not been thoroughly understood, especially the exchange current. In the present study, the transit electrochemical methods of cyclic voltammetry and square wave voltammetry were applied to study the properties of Nd in LiCl-KCl system. The reduction of Nd3+ was determined as a two-step reaction with Nd3+/Nd2+ to be a reversible but Nd2+/Nd to be a quasi or irreversible reactions. Additionally, parameters such as the diffusion coefficient, exchange current, and apparent potential were derived from the cyclic voltammetry curves. Their relationship with temperature and concentration was investigated under 723 K, 773 K, 823 K with concentrations of 3 wt%, 6 wt% and 9 wt%. The present study contributes significantly to rich the database of Nd in LiCl-KCl molten salt and to understand the electrochemical behaviors of Nd during electrochemical separation of spent nuclear fuel.

Multiphase flow and reactive transport benchmark for radioactive waste disposal

AbstractCompacted bentonite is part of the multi-barrier system of radioactive waste repositories. The assessment of the long-term performance of the barrier requires using reactive transport models. Here we present a multiphase flow and reactive transport benchmark for radioactive waste disposal. The numerical model deals with a 1D column of unsaturated bentonite through which water, dry air and $${\hbox {CO}_{2{(g)}}}$$ CO 2 ( g ) may flow and with the following reactions; aqueous complexation, calcite and gypsum dissolution/precipitation, cation exchange and gas dissolution. INVERSE-FADES-CORE V2, $$\hbox {DuMu}^X$$ DuMu X , TOUGHREACT and iCP were benchmarked with 6 test cases of increasing complexity, starting with conservative tracer transport under variably unsaturated conditions and ending with water flow, gas diffusion, minerals and cation exchange. The solutions of all codes exhibit similar trends. Small discrepancies are found in conservative tracer transport due to differences in hydrodynamic dispersion. Computed $${\hbox {CO}_{2{(g)}}}$$ CO 2 ( g ) pressures agree when a sufficiently refined grid is used. Small discrepancies in $${\hbox {CO}_{2{(g)}}}$$ CO 2 ( g ) and pH are found near the no-flow boundary at early times which vanish later. Discrepancies are due differences in the formulations used for gas flow at nearly water-saturated conditions. Computed $${\hbox {CO}_{2{(g)}}}$$ CO 2 ( g ) pressures show a fluctuation between $$10^{-4}$$ 10 - 4 and $$10^{-3}$$ 10 - 3 years which slows down the in-diffusion of $${\hbox {CO}_{2{(g)}}}$$ CO 2 ( g ) . This fluctuation is associated with chemical reactions involving $${\hbox {CO}_{2}}$$ CO 2 . There are discrepancies in solute concentrations due to differences in the Debye–Hückel (DH) formulation. They are overcome when all codes use the same DH formulation. The results of this benchmark will contribute to increase the confidence on multiphase reactive transport models for radioactive waste disposal.

129Xe Image Processing Pipeline: An open-source, graphical user interface application for the analysis of hyperpolarized 129Xe MRI.

Hyperpolarized 129Xe MRI presents opportunities to assess regional pulmonary microstructure and function. Ongoing advancements in hardware, sequences, and image processing have helped it become increasingly adopted for both research and clinical use. As the number of applications and users increase, standardization becomes crucial. To that end, this study developed an executable, open-source 129Xe image processing pipeline (XIPline) to provide a user-friendly, graphical user interface-based analysis pipeline to analyze and visualize 129Xe MR data, including scanner calibration, ventilation, diffusion-weighted, and gas exchange images. The customizable XIPline is designed in MATLAB to analyze data from all three major scanner platforms. Calibration data is processed to calculate optimal flip angle and determine129Xe frequency offset. Data processing includes loading, reconstructing, registering, segmenting, and post-processing images. Ventilation analysis incorporates three common algorithms to calculate ventilation defect percentage and novel techniques to assess defect distribution and ventilation texture. Diffusion analysis features ADC mapping, modified linear binning to account for ADC age-dependence, and common diffusion morphometry methods. Gas exchange processing uses a generalized linear binning for data acquired using 1-point Dixon imaging. The XIPline workflow is demonstrated using analysis from representative calibration, ventilation, diffusion, and gas exchange data. The application will reduce redundant effort when implementing new techniques across research sites by providing an open-source framework for developers. In its current form, it offers a robust and adaptable platform for 129Xe MRI analysis to ensure methodological consistency, transparency, and support for collaborative research across multiple sites and MRI manufacturers.

Selective Sorption of Noble Metals on Polymer Gel Modified with Ionic Liquid.

The solid phase extraction of Au, Ir, Pd, Pt, and Rh on a polymer gel modified with ionic liquid containing methylimidazolium groups (MIA-PG) has been investigated. The positively charged surface of the sorbent is highly suitable for the sorption of stable chlorido complexes of the studied analytes, while the retention of base metals Cu, Fe, Ni, Zn, and Mn is negligible. Optimization experiments performed showed that, at 0.05 M HCl, the degree of sorption of Au, Ir, Pd, and Pt is above 95%, and only for Rh, the maximum degree is 65%; complete elution is achieved in the mixture of thiourea in HCl. The results obtained from the equilibrium adsorption studies are fitted in various adsorption models, such as Langmuir and Freundlich, and the model parameters have been evaluated. The kinetics analysis indicated that the adsorption of Au, Ir, Pd, Pt, and Rh onto the sorbent follows the pseudo-second-order model. Intraparticle diffusion and ion exchange reactions were the rate-limiting steps. Analytical procedures were developed for Pd, Pt, and Rh determination in road dust and soil and for Au determination in copper ore and copper concentrate. The procedures are validated by the analysis of certified reference materials. Analytical figures of merit confirmed their applicability in routine laboratory practice.

Hyperpolarized 129Xe Lung MRI and Spectroscopy in Mechanically Ventilated Mice.

Hyperpolarized (HP) xenon-129 (129Xe) is an inhaled magnetic resonance imaging (MRI) contrast agent with unique spectral and physical properties that can be exploited to quantify pulmonary physiology, including ventilation, restricted diffusion (alveolar-airspace size), and gas exchange. In humans, it has been used to evaluate disease severity and progression in a variety of pulmonary disorders and is approved for clinical use in the United States and United Kingdom. Beyond its clinical applications, the ability of 129Xe MRI to noninvasively assess pulmonary pathophysiology and provide spatially resolved information is valuable for preclinical research. Among animal models, mice are the most widely used due to the accessibility of genetically modified disease models. Here, 129Xe MRI is promising as a minimally invasive, radiation-free, and sensitive technique to longitudinally monitor lung disease progression and therapy response (e.g., in drug discovery). This technique can extend to preclinical applications by incorporating an MRI-triggered, free-breathing apparatus or mechanical ventilator to deliver gas. Here, we describe the steps and provide checklists to ensure robust data collection and analysis, including creating a thermally polarized xenon gas phantom for quality control, optimizing polarization, animal handling (sedation, intubation, ventilation, and care for mice), and protocols for ventilation, restricted diffusion, and gas exchange data. While preclinical 129Xe MRI can be applied in various animal models (e.g., rats, pigs, sheep), this protocol focuses on mice due to the challenges posed by their small anatomy, which are balanced by their affordability and the availability of many disease models.

Assessing tumor microstructure with time-dependent diffusion imaging: Considerations and feasibility on clinical MRI and MRI-Linac.

Quantitative imaging biomarkers (QIBs) can characterize tumor heterogeneity and provide information for biological guidance in radiotherapy (RT). Time-dependent diffusion MRI (TDD-MRI) derived parameters are promising QIBs, as they describe tissue microstructure with more specificity than traditional diffusion-weighted MRI (DW-MRI). Specifically, TDD-MRI can provide information about both restricted diffusion and diffusional exchange, which are the two time-dependent effects affecting diffusion in tissue, and relevant in tumors. However, exhaustive modeling of both effects can require long acquisitions and complex model fitting. Furthermore, several introduced TDD-MRI measurements can require high gradient strengths and/or complex gradient waveforms that are possibly not available in RT settings. In this study, we investigated the feasibility of a simple analysis framework for the detection of restricted diffusion and diffusional exchange effects in the TDD-MRI signal. To promote the clinical applicability, we use standard gradient waveforms on a conventional 1.5 T MRI system with moderate gradient strength (Gmax=45 mT/m), and on a hybrid 1.5 T MRI-Linac system with low gradient strength (Gmax=15 mT/m). Restricted diffusion and diffusional exchange were simulated in geometries mimicking tumor microstructure to investigate the DW-MRI signal behavior and to determine optimal experimental parameters. TDD-MRI was implemented using pulsed field gradient spin echo with the optimized parameters on a conventional MRI system and a MRI-Linac. Experiments in green asparagus and 10 patients with brain lesions were performed to evaluate the time-dependent diffusion (TDD) contrast in the source DW-images. Simulations demonstrated how the TDD contrast was able to differentiate only dominating diffusional exchange in smaller cells from dominating restricted diffusion in larger cells. The maximal TDD contrast in simulations with typical cancer cell sizes and in asparagus measurements exceeded 5% on the conventional MRI but remained below 5% on the MRI-Linac. In particular, the simulated TDD contrast in typical cancer cell sizes (r=5-10µm) remained below or around 2% with the MRI-Linac gradient strength. In patients measured with the conventional MRI, we found sub-regions reflecting either dominating restricted diffusion or dominating diffusional exchange in and around brain lesions compared to the noisy appearing white matter. On the conventional MRI system, the TDD contrast maps showed consistent tumor sub-regions indicating different dominating TDD effects, potentially providing information on the spatial tumor heterogeneity. On the MRI-Linac, the available TDD contrast measured in asparagus showed the same trends as with the conventional MRI but remained close to typical measurement noise levels when simulated in common cancer cell sizes. On conventional MRI systems with moderate gradient strengths, the TDD contrast could potentially be used as a tool to identify which time-dependent effects to include when choosing a biophysical model for more specific tumor characterization.

Dilational rheological properties of extended anionic surfactants at decane-water interface

The dynamic interfacial dilational properties of extended surfactants octadecyl-(polypropylene oxide)m-(polyethylene oxide)n-carboxylic sodium (C18POmEOnC) with different numbers of polypropylene oxide (PO) and polyethylene oxide (EO) groups at the decane–water interface were investigated by means of oscillating drop method. The influences of interface ageing time, dilational frequency, bulk concentration and interfacial pressure on the dilational properties were investigated. The experimental results demonstrate that, at low concentrations, the adsorption film is predominantly influenced by diffusion exchange, while intermolecular interactions at the interface play a more significant role at high concentrations. Beyond the critical micelle concentration (CMC), the primary relaxation process in the adsorption film is driven by the formation of micellar structures. Additionally, the weak hydrophobic PO groups exhibit compressibility and extensibility, facilitating the formation of spring-like helical structures at the decane–water interface. As a result, the dilational modulus increases and the phase angle decreases in low concentration with the increase of PO number. With increasing concentration, the weak hydrophilic EO chains gradually transition from a partially flat state to an upright orientation toward the aqueous phase, forming sublayer structures through polar interactions. At this stage, the increase in EO group chain length has a more pronounced impact on the elastic modulus compared to PO groups. These experimental findings suggest the existence of a mechanistic model for the extended surfactant adsorption films.

Medium-entropy strategy to inhibit the surface Sr segregation and enhance the stability of Sr2Fe1.5Mo0.5O6-δ cathode for CO2 direct electrolysis

Solid oxide electrolysis cell (SOEC) is a promising solid-state electrochemical device that can convert CO2 into CO with high efficiency. However, the poor catalytic activity and Sr segregation of the cathode diminish the electrode reaction, hindering the large-scale application. Herein, a medium-entropy strategy is proposed to suppress the Sr enrichment while enhancing the catalytic activity for CO2. The surface Sr content on Sr2Fe1.2Ni0.1Cu0.1Co0.1Mo0.5O6-δ (SFNCCM) is significantly reduced after the Ni, Cu, and Co co-doping at Fe-site. Moreover, the oxygen surface exchange and bulk diffusion coefficient at 800 °C for SFNCCM oxide reach 2.42 × 10−4 cm2 s−1 and 2.28 × 10−5 cm2 s−1, which are 1.35 and 1.39 times higher than parent Sr2Fe1.5Mo0.5O6-δ(SFM) oxide. At 850 °C and 1.5 V, single with SFNCCM-Sm0.2Ce0.8O6-δ(SDC) composite exhibits a current density of 2.22 A cm−2 with good stability for up to 100 h. The results suggest that the medium-entropy strategy is a promising method to inhibit Sr segregation and enhance the performance of CO2 direct electrolysis.

Waste glass as a source for green synthesis of mesoporous adsorbent for efficient removal of heavy metals

Mesoporous analcime Adsorbent (MaA) was cogently synthesized in a hydrothermal reaction where a waste silica glass powder was mixed into NaOH solution. The satisfactory reaction properties were achieved by regulating the conditioning time (Ct), reaction temperature (Rt), and relative ratio of the reactants (Rr= SiO2:Na2O). XRF, XRD, SEM, BET, FTIR, AFM, TG and TEM analysis formed part of the selected samples. The prepared MaA adsorbent was then applied to treat Pb2+, Cd2+ and Cu2+ ions, thus effectively allowing the physicochemical properties (pH, temperature and contact duration), on the adsorption amount to be examined. Upon completion, the results indicated that the initial pH as well as the contact duration had notable effect on the adsorption amount. Conversely, the temperature change had an insignificant effect on the equilibrium adsorption amount. In addition, a dosage of 0.1 g of MaA, concentration of 1000 mg/L, pH ranging from 6−8, and temperature of about 25°C were found to be the optimum process conditions for the adsorption of the examined heavy metals, whereas difference in contact time was recorded as follows: 1 h for Pb2+ and Cu2+ ions with adsorption amounts of 75.081 mg/g and 74.054 mg/g, respectively; and 3 h for Cd2+ ion with adsorption equal to 75.530 mg/g. In the analysis of the trend, the coefficients of correlation (R2=0.99) of the Langmuir isotherm model were increasingly consistent compared to Freundlich isotherm model (R2 from 0.10 to 0.55), thus indicating that the process to be a homogeneous monomolecular layer adsorption. Moreover, the kinetic aspects were similarly consistent in relation to quasi-secondary kinetic equation, which then further established that the process was primarily controlled by ion exchange, extra-particle, intra-particle, and liquid film diffusion. In addition, research on the potential reusability of MaA adsorbent after being employed to treat heavy metals was also performed. The crystalline phase of the composite after subjected to high temperature indicated wollastonite (CaSiO₃) and gregoryite (Na₂CO₃) as the main mineralogical phases. These minerals are beneficial in the preparation of functional building materials by promoting a sustainable solution for the full recycling of waste glass and contributing to efficient solid waste management and environment protection.

Reversible image hiding algorithm based on adaptive embedding mechanism

A reversible blind image hiding algorithm (ReBIHA) with help of an adaptive embedding mechanism and a compressive sensing technology is presented in this paper, of which can effectively hide the secret image through a natural meaningful carrier image. In the first phase, a new key generation model (KeyGM) is built by combining random numbers and the plaintext, followed by a newly designed four dimensional chaotic map (NewCM) with stronger pseudo-randomness. Then, the generated chaotic sequence is taken to produce a measurement matrix for compressive sensing. In the second phase, the plain image is sparsely processed, confused, encrypted and compressed to get measurements. Afterward, these measurements are subjected to diffusion and binary exchange to achieve a middle cipher image (MCI). In the third stage, a meaningful carrier image is randomly selected, and integer wavelet transform (IWT) is applied to it, getting one low-frequency and three high-frequency coefficients. Then, the pixels of MCI are subjected by splitting and symmetrically shifting transformation for three element matrices. Finally, these matrices are respectively embedded into the high-frequency coefficients through an adaptive mechanism to find replaceable elements, and a final carrier image hiding secrets (CiHS) can be achieved after performing an inverse IWT. The experimental results show that the proposed algorithm can avoid the extra transmission of original carrier image. Moreover, peak signal-to-noise ratio (PSNR) of reconstructed image can surpass 32 dB at compression ratio 0.5. Especially, the proposed adaptive embedding mechanism can not only achieve blind extraction of secrets well, but also ensure the visual quality for the original carrier image.

Exploring the atomic-scale dynamics of Fe3O4(001) at catalytically relevant temperatures using FastSTM

Surfaces and interfaces of functional nanoscale materials are typically highly dynamic when employed at elevated temperatures. Both, lateral surface and vertical bulk exchange diffusion processes set in, which can be relevant for applications such as heterogeneous catalysis. Time-resolved scanning tunneling microscopy (STM) is being pushed to ever faster measurement modes to follow such dynamic phenomena in situ. Here, we present FastSTM movies monitoring a range of atomic-scale dynamics of a prototypical reducible oxide catalyst support, Fe3O4(001), at elevated temperatures. Antiphase domain boundaries between two domains of the reconstructed surface exhibit local mobility from around 350 K, while Fe-rich point defects, in a stable equilibrium with the bulk, appear to diffuse in a peculiar zigzag pattern above 500 K. Finally, exploiting the diffusivity of Fe interstitials, we follow the propagation of step edges in the topmost atomic layer of the Fe3O4(001) surface in an oxygen atmosphere.

Nd Isotopic Equilibration During Channelized Melt Transport Through the Lithosphere: A Feasibility Study Using Idealized Numerical Models

AbstractThis study is motivated by the observed variability in trace element isotopic and chemical compositions of primitive (Si52 wt %) basalts in southwest North America (SWNA) during the Cenozoic transition from subduction to extension. Specifically, we focus on processes that may explain the enigmatic observation that in some localities, basalts with low Ta/Th, consistent with parental melts in a subduction setting, have signatures consistent with continental lithospheric mantle (CLM). In locations with the oldest CLM (Proterozoic and Archean), Cenozoic basalts with low Ta/Th have well below zero. We model channelized magma transport through the CLM using simple 1D transport models to explore the extent to which diffusive and reactive mass exchange can modify Nd isotopic compositions via open system melt‐wallrock interactions. For geologically reasonable channel spacings and volume fractions, we quantify the reactive assimilation rates required for incoming melt with a different than the wall‐rock to undergo a substantial isotopic shift during 10 km channelized melt transport. In the presence of grain boundaries, enhanced diffusion between melt‐rich channels and melt‐poor surrounding rock contributes to isotopic equilibration, however this effect is not enough to explain observations; our models suggest a significant contribution from reactive assimilation of wall‐rock. Additionally our models support the idea that the observed covariability in Ta/Th and in Cenozoic basalts cannot be attributed to transport alone and must also reflect the transition from subduction‐related to extension‐related parental melts in SWNA.

Advanced alginate-based nanofiber aerogels: A synthetic matrix for high-efficiency lysozyme adsorption and controlled release

The development of materials with high lysozyme adsorption is critical for drug delivery and skin wound applications, as it enhances antibacterial properties, stability, and controlled release of therapeutic agents, thereby improving treatment efficacy and safety. Alginate-based nanofiber scaffolds, featuring high surface area and multiple adsorption sites, can efficiently absorb lysozyme and regulate its release through tunable pore channels, offering a promising approach to chronic wound management. In this study, we fabricated poly (vinyl alcohol-co-ethylene) (EVOH) nanofiber-based sodium alginate (ENSA) aerogels using a simple two-step crosslinking procedure. The resulting aerogels, with controllable porosity formed via high-pressure spraying techniques (aerogel film) and molding (aerogel sponge), were evaluated for their high-loading capacity and controllable release of lysozyme. The aerogel film exhibited a remarkable lysozyme adsorption capacity of 1965 ± 36 mg/g, while the aerogel sponge sustained lysozyme release over 14 days. Analysis of the drug-release mechanism through four kinetic models revealed two distinct processes: cation exchange and matrix diffusion. The aerogel's pore structure influenced the diffusion processes, enabling tailored drug release profiles. Additionally, the ENSA aerogels demonstrated good mechanical properties, non-cytotoxicity, and potent antibacterial activity, positioning them as promising materials for skin wound dressings.

Research of surface diffusion and growth of Ni-Pd nanoparticles

ABSTRACT Building upon the foundation of embedded atom method potential, this study employs the Nudged Elastic Band method to computationally investigate the diffusion and structural behaviour of Ni-Pd bimetallic nanoparticles on Wulff surfaces. The results reveal that, whether Ni or Pd serves as the substrate, the energy barrier is significantly lower when adatom exchange occurs with two adjacent (111) interfacet atoms compared to the interfacet of (111) and (100). The optimal diffusion path is identified as the centre-positive diagonal exchange (CPDE). Furthermore, it is observed that the energy of the system decreases after the exchange diffusion with the substrate surface atoms. However, successful exchange diffusion requires overcoming specific energy barriers (>0.43 eV), enabling the deposition of NicorePdshell and PdcoreNishell nanoparticles at low temperatures. In Ni-Pd nanoparticles, surface energy plays a predominant role when the size is very small (Natom≦55), leading to the stable configuration of NicorePdshell nanoclusters. However, as the size increases, the impact of bond energy becomes more pronounced, resulting in an alloyed structure as the stable configuration. Furthermore, in cases where the proportion of Pd atoms is small, all Pd atoms are situated on the surface, displaying a discrete distribution morphology.

Comparison of non-reactive solute transport models for the evaluation of fluid flow in packed beds with implications for heap leaching practice

This study investigated the effects of mean particle size fraction, bottom particle size, particle porosity and wettability on solution scale preferential flow behaviour via step input tracer tests in drip irrigated, narrowly and mixed-sized beds under steady state fluid flux. Nine solute transport models were used to quantify this behaviour reflected in the residence time distribution (RTD) profiles. Four were empirical models: three compartmental model configurations (CM-1, CM-2, CM-3) and tanks-in-series (TIS) model. The remainder five models were semi-empirical: advection dispersion (AD), piston exchange (PE), piston exchange - diffusion variant (PE-D), piston dispersion and exchange (PDE) and piston dispersion and exchange - diffusion variant (PDED). The model fit results showed that the mono-porosity TIS, AD and CM-2 models were the worst performers, while the dual porosity PDE and novel PDE-D models achieved the lowest average error values across the various systems. Higher levels of particle wettability coupled with capillary effects produced peculiar RTD curves that were relatively more difficult for the mono-porosity models to simulate. The model parameters investigated included the longitudinal dispersion coefficient (Dds), dead to total volume fraction (VD/VT), dynamic to total saturation fraction (βd/βT), overall mass transfer coefficient (Kma) and maximum diffusional pore length (X). The results showed that an increase in the average particle size within the beds led to higher VD/VT, Dds and X values, but lower βd/βT and Kma values. These indicate an overall increase in solution scale preferential flow behaviour. Decreased capillary suction and connectivity between particle pores and inter-particle voids were deemed responsible for the results. Higher levels of particle porosity acted as a buffer against these effects. Overall, the results highlight the benefit of the addition of fines (0.1–1 mm particles) during the agglomeration process in heaps to help reduce solution scale preferential flow behaviour and increase liquid hold-up. This is more necessary when the ore has low to moderate levels of porosity (surface area: <2 m2/g) and will also increase the modelling options available as most models performed better fitting data from such beds.

Geochemistry of pallasite olivine and the origin of pallasites

I have done major element analyses by electron microprobe, in-situ trace element analyses by laser ablation inductively coupled plasma mass spectrometry, and instrumental neutron activation analyses on bulk samples of olivine grains separated from main-group and Eagle-Station pallasites. Most main-group pallasite olivines have homogeneous Fe/Mg yet have varying Fe/Mn. Those few with anomalously ferroan olivine have Fe/Mn within the range of other main-group pallasites. High-temperature redox process coupled with diffusional exchange resulted in the homogeneous compositions of most main-group pallasites; simple diffusional exchange alone is insufficient. The Eagle-Station pallasites have Fe/Mn twice that of main-group pallasites with similar Fe/Mg, a result of having roughly half the Mn content. The Ni/Co ratio of main-group pallasite olivines is relatively constant and was imposed by the same high-temperature redox/diffusion process that established Fe/Mg-Fe/Mn relationships. Variability in trace lithophile element contents within individual pallasites and within individual olivine grains, coupled with very low contents for some that are inconsistent with formation from a magma, indicate that the current mm-sized olivine grains were recrystallized from a fragmental olivine breccia; grain fragments from different portions of an original dunitic mantle were juxtaposed in the breccia. Main-group pallasites are dimict breccias formed of fragmented and mixed monomict dunite breccia and metallic breccia that were formed in the walls and floor of a large basin that penetrated the mantle of their parent asteroid. Limited data indicate that Eagle-Station pallasites may have been formed by a similar process. Given that Eagle-Station and main-group pallasites were formed in distinct regions of the early Solar System, the pallasite forming process likely was common in early Solar System history.

Elucidating the impact of non-spherical morphology on kinetic behavior of graphite using single-particle microelectrode

The precise assessment of the kinetic properties of graphite is crucial for the design of the material and the development of electrochemical models for lithium-ion batteries. However, conventional evaluation methods using composite electrodes fall short in excluding the influence of its porous structure and evaluating the influence of particle shape on kinetic behavior. In this work, we elucidate the impact of non-spherical morphology on kinetic behavior of single artificial graphite particle, employing the single-particle microelectrode technique. Three single artificial graphite particles with different sizes are pre-cycled and exhibit outstanding rate capability, maintaining a maximum capacity retention of 78.1 % at 200 C. Further, exchange current density and diffusion coefficients are determined through Tafel plots and the potentiostatic intermittent titration technique (PITT), respectively. It is found that the particle with a higher exposure of edge planes present elevated exchange current density and diffusion coefficients. Considering that the graphite particles typically feature an ellipsoidal rather than spherical shape, we propose an approach based on an ellipsoidal diffusion model for extracting diffusion coefficients. This model takes into account the non-spherical morphology of graphite, addressing the limitations inherent in the geometric assumptions of previous methods. The average relative error between the diffusion coefficients derived from the ellipsoidal diffusion model and the previous method using spherical assumptions is 215 %, indicating that accurately depicting the shape of ellipsoidal graphite particles in the model is crucial for obtaining correct estimates of kinetic parameters. This study offers direct experimental evidence of superior kinetic behavior of edge planes over basal planes. To leverage this characteristic, it is recommended to employ an out-of-plane aligned architecture for composite electrodes using novel techniques, e.g., 3D printing or magnetic alignment techniques.

The Diffusion Exchange Ratio (DEXR): A minimal sampling of diffusion exchange spectroscopy to probe exchange, restriction, and time-dependence.

Water exchange is increasingly recognized as an important biological process that can affect the study of biological tissue using diffusion MR. Methods to measure exchange, however, remain immature as opposed to those used to characterize restriction, with no consensus on the optimal pulse sequence(s) or signal model(s). In general, the trend has been towards data-intensive fitting of highly parameterized models. We take the opposite approach and show that a judicious sub-sample of diffusion exchange spectroscopy (DEXSY) data can be used to robustly quantify exchange, as well as restriction, in a data-efficient manner. This sampling produces a ratio of two points per mixing time: (i) one point with equal diffusion weighting in both encoding periods, which gives maximal exchange contrast, and (ii) one point with the same total diffusion weighting in just the first encoding period, for normalization. We call this quotient the Diffusion EXchange Ratio (DEXR). Furthermore, we show that it can be used to probe time-dependent diffusion by estimating the velocity autocorrelation function (VACF) over intermediate to long times (~ 2-500 ms). We provide a comprehensive theoretical framework for the design of DEXR experiments in the case of static or constant gradients. Data from Monte Carlo simulations and experiments acquired in fixed and viable ex vivo neonatal mouse spinal cord using a permanent magnet system are presented to test and validate this approach. In viable spinal cord, we report the following apparent parameters from just 6 data points: , , , and , which correspond to the exchange time, restricted or non-Gaussian signal fraction, an effective spherical radius, and permeability, respectively. For the VACF, we report a long-time, power-law scaling with , which is approximately consistent with disordered domains in 3-D. Overall, the DEXR method is shown to be highly efficient, capable of providing valuable quantitative diffusion metrics using minimal MR data.

Adsorption characteristics and mechanisms of bisphenol A on novel nitrogen-modified biochar derived from waste masks and biomass.

Resource utilization of waste masks has become an urgent scientific issue. In this work, with sustainably, waste masks and biomass were co-pyrolysis with oxygen limitation to prepare mask-based biochar (MB). Then, urea was introduced to prepare novel nitrogen modified mask-based biochar (NMB) via a one-step hydrothermal synthesis method. The adsorption characteristics of NMB on the emerging environmental pollutant, bisphenol A (BPA), were evaluated via batch adsorption tests. Moreover, the physicochemical properties of the materials were characterized with various advanced techniques. Also, the roles of waste masks and nitrogen modification were explored. The adsorption mechanisms of NMB on BPA were revealed as well as the performance differences between different adsorbents. The results showed that waste masks participated in thermochemical reactions, shaped the microsphere structure of biochar, and increased the types of surface functional groups. The nitrogen modification enriched the surface elemental composition and activated the specific surface area via the mesopore. These would enhance the adsorption performance. The maximum adsorption of BPA by NMB was 62.63mg·g-1, which was approximately 2.35-5.58 times higher than that of the control materials. Temkin model and pseudo-second-order model optimally simulate the isothermal and kinetic adsorption, respectively. The adsorption mechanisms are jointly by physical and chemical adsorption, which mainly includes π-π interaction, hydrogen bonding, intraparticle diffusion, surface adsorption, and ion exchange. After discussion and evaluation, NMB has lower preparation process cost (7.21 USD·kg-1) and safety, with potential for environmental applications. This study aims to expand new ideas for the comprehensive utilization of waste masks and the preparation of eco-friendly materials. Moreover, it provides a theoretical basis for the removal of BPA.

Nanoclustering in non-ideal ethanol/heptane solutions alters solvation dynamics.

Alcohol/alkane solutions widely used in chemical synthesis and as transportation fuels are highly non-ideal due to the nanoscale clustering of the amphiphilic alcohol molecules within the nonpolar alkanes. Besides impacting reactivity, such as combustion, non-ideal solutions are likely to exhibit unusual solvation dynamics on ultrafast time scales arising from the structurally heterogeneous nature of molecular-scale association. Using a convenient transition metal carbonyl vibrational probe [(C5H5)Mn(CO)3, CMT], linear absorption and nonlinear two-dimensional infrared (2D-IR) spectroscopy reveal composition-dependent solvation dynamics as reported by the frequency fluctuation correlation function in a series of ethanol/heptane solutions. Slow spectral diffusion with dilute ethanol indicates preferential solvation of the polar solute by the alcohol with a mechanism largely dominated by solvent exchange. Comparison with an ethanol/acetonitrile solution series yields no substantial preferential solvation or solvent exchange signatures in the linear or 2D-IR spectra. In ethanol/heptane solutions, increasing the ethanol concentration speeds up the solvation dynamics, which is largely consistent with a model that includes solvent exchange and single-solvent spectral diffusion. Detailed analysis of the deviation from the experimental time constants from the model's optimal parameters yields a remarkable resemblance of the concentration-weighted Kirkwood-Buff integrals for ethanol/heptane solutions. This trend indicates that solution non-ideality alters the spectral diffusion dynamics of the probe solute. Given that nanoscale clustering drives the non-ideality, these experiments reveal a dynamical consequence of nanoscale heterogeneity on the ultrafast dynamics of the solution. Refined understanding of the structural and dynamical aspects of mixed solvents will be necessary for predictive solution strategies in chemistry.