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1.
Nanotechnology ; 2024 Oct 03.
Artigo em Inglês | MEDLINE | ID: mdl-39362237

RESUMO

Fast and accurate detection of light in the near-infrared (NIR) spectral range plays a crucial role in modern society, from alleviating speed and capacity bottlenecks in optical communications to enhancing the control and safety of autonomous vehicles through NIR imaging systems. Several technological platforms are currently under investigation to improve NIR photodetection, aiming to surpass the performance of established III-V semiconductor p-i-n (PIN) junction technology. These platforms include in situ-grown inorganic nanocrystals and nanowire arrays, as well as hybrid organic-inorganic materials such as graphene-perovskite heterostructures. However, challenges remain in nanocrystal and nanowire growth, large-area fabrication of high-quality 2D materials, and the fabrication of devices for practical applications. Here, we explore the potential for tailored semiconductor nanocrystals to enhance the responsivity of planar metal-semiconductor-metal (MSM) photodetectors. MSM technology offers ease of fabrication and fast response times compared to PIN detectors. We observe enhancement of the optical-to-electric conversion efficiency by up to a factor of ~2.5 through the application of plasmonically-active semiconductor nanorods and nanocrystals. We present a protocol for synthesizing and rapidly testing the performance of non-stoichiometric tungsten oxide (WO3-x) nanorods and cesium-doped tungsten oxide (CsyWO3-x) hexagonal nanoprisms prepared in colloidal suspensions and drop-cast onto photodetector surfaces. The results demonstrate the potential for a cost-effective and scalable method exploiting tailored nanocrystals to improve the performance of NIR optoelectronic devices.

2.
Sci Rep ; 14(1): 22948, 2024 Oct 03.
Artigo em Inglês | MEDLINE | ID: mdl-39363057

RESUMO

In order to meet the needs of geologists for the analysis of data characterizing field outcrops (rock sections or formations exposed on the ground surface), this study developed a field digital outcrop visualization platform based on Cesium (a 3D geospatial visualization technology) digital outcrop characterization technology. The platform was developed based on WebGL (a protocol for rendering interactions on web pages), which overcame the shortcomings of traditional software in terms of visualization, cross-device, cross-platform, and ease of use. Firstly, UAV inclined photography is used for data collection, which transforms a large amount of geological data into an intuitive 3D geological model, while the visualization platform provides rich measurement and mapping tools for the identified features, which more intuitively displays the outcrop information, helps geological explorers to understand the geological conditions in the field more quickly and comprehensively, and improves the analysis efficiency and ease-of-use of outcrop characterization data. Combined with the improved VGG19 (a deep convolutional neural network architecture) algorithm model, it has excellent performance in dealing with the fine texture and complex structure of rocks, which significantly improves the accuracy of lithology identification. The synergistic application of this technology provides geologists with a faster and more comprehensive means to understand the geological conditions in the field. The reliability of combining the Cesium digital outcrop characterization technology with the VGG19 lithology identification algorithm in geological exploration is verified through case studies. The synergistic application of this technology will greatly enhance the efficiency and ease of analysis of outcrop characterization in the field, and provide new perspectives for future research in geosciences.

3.
J Environ Manage ; 370: 122746, 2024 Oct 05.
Artigo em Inglês | MEDLINE | ID: mdl-39369522

RESUMO

This review discusses recent advances in the use of alkali-activated materials (AAMs) to host high heat and radiation-emitting cesium (Cs) and strontium (Sr) wastes. It examines the evolution of geopolymerization, mechanical properties, mineralogy, microstructure, and leaching behavior of Cs-and/or Sr-bearing AAMs, considering their chemical interaction with Cs and Sr nuclides and exposure to temperature and gamma radiation induced by Cs and Sr. The literature indicates that Cs and Sr slightly degrade the mechanical properties of AAMs, with Sr having a more pronounced effect. For AAMs with a low SiO2/Al2O3 ratio, decay heat from Cs and Sr can crystallize zeolitic phases, which are beneficial in the short term but detrimental in the long term because of their low stability against gamma radiation. Cs was immobilized via ion exchange within the aluminosilicate phase and Sr mainly by precipitation, but the immobilization of their respective daughter nuclides Ba and Zr was not demonstrated. Gamma radiation exposure does not significantly alter AAM properties, and nitrates in Cs and Sr-bearing wastes reduce gamma-induced water radiolysis. AAMs are promising hosts for Cs and Sr-bearing wastes, but further studies are needed using realistic Cs and Sr waste loading to evaluate the synergistic effects of Cs and Sr chemical behavior, decay heat, and gamma irradiation on the evolution of properties of waste forms, and the ability of AAMs to accommodate daughter nuclides Ba and Zr.

4.
Int J Radiat Biol ; : 1-19, 2024 Sep 20.
Artigo em Inglês | MEDLINE | ID: mdl-39302823

RESUMO

To quantitatively investigate the effects of chronic low-dose internal exposure to Cesium-137 on DNA damage, carcinogenicity, and offspring over multiple generations. The potential genetic risk in humans was predicted based on next-generation murine mutation rates to confirm the reasonableness of the current Cesium-137 dose limits for food. Cesium-137 (100 Bq/mL) was provided in drinking water to A/J mice, facilitating chronic, low-dose, low-dose-rate internal exposure through sibling mating over 25 generations (G25). The A/J mice were compared with a control strain with the same origin ancestry (no Cesium-137 water) for DNA double-strand breaks (DSBs), oxidative stress, chromosome aberrations, micronucleus test results, whole genome analysis, carcinogenicity, tumor growth rate, and immune competence. Compared to the control group, DNA DSBs and oxidative stress were significantly increased in the Cesium-137 group. However, no significant differences were observed between the groups regarding chromosome aberration, micronuclei, or the whole genome sequence mutation analysis. Although the carcinogenic rate did not differ between the groups, the rate of tumor growth was significantly suppressed in the Cesium-137 group. The anti-tumor cytokine trend in the Cesium-137 group likely contributed to this effect. No pathological or genetic effects were observed in the offspring of mice drinking water containing 100 Bq/mL Cesium-137 after G25. The contribution of low dose-rate radiation to carcinogenicity was not additive but growth-inhibitory. Although the negative data are not conclusive, these findings are deemed highly reliable.

5.
ACS Nano ; 2024 Sep 12.
Artigo em Inglês | MEDLINE | ID: mdl-39265106

RESUMO

Cesium-based two-dimensional (2D) perovskites with attractive phase and environmental stability have broad application prospects in single-junction and tandem perovskite solar cells (PSCs). However, the severe nonradiative recombination and significant energy losses due to disordered phase orientations and phase distributions greatly hinder the carrier transport performance of cesium-based 2D PSCs and severely limit their photovoltaic performance. Here, we employ an asymmetric chiral spacer cation source, (R)-α-phenylethylamine acrylate (R-α-PEAAA), to prepare high-quality 2D cesium-based films with uniform phase distribution and high out-of-plane orientation by air processing, resulting in efficient carrier transport. More importantly, the asymmetric chiral spacer R-α-PEA has a stronger dipole moment than its isomer (PEA), which can regulate the dielectric properties of cesium-based 2D perovskites and promote charge dissociation. In addition, the chiral R-α-PEA can optimize the morphology and out-of-plane orientation of perovskite films, reduce trap density and nonradiative recombination loss, and optimize energy level alignment, thus enhancing carrier transport. As a result, cesium-based 2D PSCs (R-α-PEA2Cs4Pb5I16, n = 5) achieved a record power conversion efficiency of 19.71% and the unencapsulated device maintained over 90% efficiency after 1500 h of continuous light exposure and ambient storage (35 ± 5% relative humidity). This study provides an idea for the development of chiral 2D perovskite with efficient charge carrier transport toward efficient and stable cesium-based 2D PSCs.

6.
Heliyon ; 10(17): e37134, 2024 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-39286105

RESUMO

Radioactive Cs+ and I- ions are major components of nuclear wastewater, typically existing as counter ions. Due to their high water solubility and mobility, these ions can spread through contaminated water and soil into ecosystems, necessitating continuous removal and management. In this study, we synthesized a reusable bifunctional Ni@Pt/K2NiFe(CN)6 composite that can simultaneously remove radioactive Cs+ and I- ions and, for the first time, enable their separate recovery in aqueous solutions. In this material, K2NiFe(CN)6 acted as an electrochemically switched ion exchanger, controlling the adsorption/desorption of Cs+, while Pt enabled the spontaneous adsorption and electrochemical desorption of I-, and the magnetic Ni core allowed for efficient adsorbent recovery. The adsorption isotherms of both Cs+ and I- were best fitted using the Langmuir model, and the corresponding adsorption capacities were comparable to those of conventional adsorbents used for the separate removal of Cs+ and I-. Furthermore, the composite demonstrated stability over 100 sorption cycles, maintaining high recovery efficiencies of 97.9 % for Cs+ and 99.7 % for I-, thereby proving its reusability. Thus, the developed composite holds great promise for radioactive wastewater treatment and environmental restoration.

7.
Heliyon ; 10(14): e34447, 2024 Jul 30.
Artigo em Inglês | MEDLINE | ID: mdl-39130465

RESUMO

Timely decontamination will reduce the consequences of a radiological contamination event. For this purpose, pressure washing can be rapidly deployed, but its effectiveness will change if the interactions between the surface and radionuclides changes as the contamination "ages" under the influence of time and precipitation. While effects of this aging have been reported for dissolved cesium, they have not been studied for radionuclides present as particulate, e.g., fallout. This work studied the effects of aging on decontamination with low (<280 kPa/40 psi) and mild (14,000 kPa/2000 psi) pressure washing, on concrete contaminated with surrogate fallout consisting of soluble Cs-137, 0.5 µm silica particles, and 2 µm silica particles. The samples were aged up to 59 days (time between contamination and decontamination) with and without simulated precipitation. The percent removal following decontamination of the soluble cesium decreased over the first ten days of aging until the removals were less than 10 % for both low and mild pressure washing. The particle decontamination was independent of aging time but decontaminating via mild pressure washing (>80 % particle removal) significantly outperformed decontaminating by low pressure washing by flowing solution across (parallel to) the contaminated surface (<25 % particle removal). The observed changes in decontamination efficacy are explained via measurements of the penetration depth of contaminants. For soluble cesium, the results compared favorably with prior studies and theoretical treatment of cesium penetration, and they yielded additional insight into the effect of washing pressures on decontamination. There are no comparable studies for particulate contamination, so this study resulted in several novel observations which are operationally important for timely decontamination of surfaces following a radiological incident. It also suggests an evidence-based pressure washing procedure for timely decontamination of soluble and insoluble radionuclides which can be used throughout the emergency phase and into the early recovery phase.

8.
Sci Total Environ ; 950: 175368, 2024 Nov 10.
Artigo em Inglês | MEDLINE | ID: mdl-39122022

RESUMO

Considering the widespread and indispensable nature of nuclear energy for future power generation, there is a concurrent increase in the discharge of radioactive Cs into water streams. Recent studies have demonstrated that adsorption is crucial in removing Cs from wastewater for environmental remediation. However, the existing literature lacks comprehensive studies on various adsorption methods, the capacities or efficiencies of adsorbents, influencing factors, isotherm and kinetic models of the Cs adsorption process. A bibliometric and comprehensive analysis was conducted using 1179 publications from the Web of Science Core Collection spanning from 2014 to 2023. It reviews and summarizes current publication trends, active countries, adsorption methods, adsorption capacities or efficiencies of adsorbents, tested water sources, influencing factors, isotherm, and kinetic models of Cs adsorption. The selection of suitable adsorbents and operating parameters is identified as a crucial factor. Over the past decade, due to their notable capacity for Cs adsorption, considerable research has focused on novel adsorbents, such as Prussian blue, graphene oxide, hydrogel, and nanoadsorbents (NA). However, there remains a need for further development of application-oriented laboratory-scale experiments. Future research directions should encompass exploring adsorption mechanisms, developing new adsorbents or their combinations, practical applications of lab-scale studies, and recycling radioactive Cs from wastewater. Drawing upon this literature review, we present the most recent research patterns concerning adsorbents to remove Cs, outline potential avenues for future research, and delineate the obstacles hindering effective adsorption. This comprehensive bibliometric review provides valuable insights into prevalent research focal points and emerging trends, serving as a helpful resource for researchers and policymakers seeking to understand the dynamics of adsorbents for Cs removal from water.

9.
Chemosphere ; 364: 143051, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39127191

RESUMO

In this study, acid-modified activated carbon fibers (ACF-Ps) were synthesized by phosphorylation. Three different types of ACF-based adsorbents functionalized with PO43-, P2O74-, or P3O105- ions, namely, ACF-P1, ACF-P2, and ACF-P3, were prepared by phosphorylating ACF with trisodium phosphate (Na3PO4), sodium dihydrogen pyrophosphate (Na2H2P2O5), and sodium tripolyphosphate (Na5P3O10), respectively, and utilized as adsorbents to remove cesium ions (Cs+) from aqueous solutions. Among the tested adsorbents, ACF-P3 exhibited the highest Cs+ adsorption capacity of 37.59 mg g-1 at 25 °C and pH 7 which is higher than that of ACF (5.634 mg g-1), ACF-P1 (19.38 mg g-1), and ACF-P2 (30.12 mg g-1) under the same experimental conditions. More importantly, the Cs+ removal efficiencies of ACF-P3 (82.90%), ACF-P2 (66.2%), ACF-P1 (34.2%) were 29.3-, 23.4-, and 12.11-fold higher than that of un-treated ACF (2.83%). The results suggested that the phosphorylation with Na5P3O10 is highly suitable for Cs+ adsorption which effectively functionalizes ACF with a greater number of phosphate functional groups. Adsorption and kinetic data well-fitted the Langmuir isotherm and pseudo-second-order model, respectively, which indicated the monolayer adsorption of Cs+ onto ACF-P1, ACF-P2, and ACF-P3 which were largely controlled by chemisorption. Overall, phosphoric acids containing different phosphate-based polyanions (PO43-, P2O74-, or P3O105-) enriched -OH and/or -COOH surface functional groups of ACF in addition to P-containing surface groups (PO, C-P-O, C-O-P, and P-O) and facilitated the Cs+ adsorption through surface complexation and electrostatic interactions.


Assuntos
Césio , Ácidos Fosfóricos , Poluentes Químicos da Água , Ácidos Fosfóricos/química , Adsorção , Césio/química , Poluentes Químicos da Água/química , Fibra de Carbono/química , Carvão Vegetal/química , Cinética , Íons/química , Purificação da Água/métodos , Concentração de Íons de Hidrogênio
10.
J Environ Radioact ; 279: 107514, 2024 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-39142005

RESUMO

The Saltstone Disposal Facility on the Savannah River Site in South Carolina disposes of Low-Level Waste in a reducing-grout waste form. Reducing grout is presently being evaluated as a subsurface disposal waste form at several other locations in the United States, as well as in Europe and Asia. The objective of this study was to collect core samples directly from the Saltstone Disposal Facility and measure desorption distribution coefficients (Kd; radionuclide concentration ratio of saltstone:liquid; (Bq/kg)/Bq/L)) and desorption apparent solubility values (ksp; radionuclide aqueous concentration (moles/L)). An important attribute of this study was that these tests were conducted with actual aged, grout waste form materials, not small-volume simulants prepared in a laboratory. The reducing grout is comprised of blast furnace slag, Class F fly ash, ordinary portland cement, and a radioactive salt waste solution generated during nuclear processing. The grout sample used in this study underwent hydrolyzation in the disposal facility for 30 months prior to measuring radionuclide leaching. Leaching experiments were conducted either in an inert (no oxygen) atmosphere to simulate conditions within the saltstone monolith prior to aging (becoming oxidized) or they were exposed to atmosphere conditions to simulate conditions of an aged saltstone. Importantly, these experiments were designed not to be diffusion limited, that is, the saltstone was ground finely and the suspensions were under constant agitation during the equilibration period. Under oxidized conditions, measured Tc Kd values were 10 mL/g, which was appreciably greater than the historical best-estimate value of 0.8 mL/g. This difference is likely the result of a fraction of the Tc remaining in the less soluble Tc(IV) form, even after extensive oxidation during the experiment. Under oxidized and reducing conditions, the measured Ba and Sr (both divalent alkaline earth metals) Kd value were more than an order of magnitude greater than historical best-estimate values of 100 mL/g. The unexpectedly high Ba and Sr Kd values were attributed to these radionuclides having sufficient time to age (form strong bonds) in the sulfur-rich saltstone sample. Apparent ksp values under reducing conditions were 10-9 mol/L Tc and 10-13 mol/L Pu, consistent with values measured with surrogate materials. Measured apparent Ba, Sr, and Th ksp values were significantly greater than historical best-estimates. The implications of the generally greater Kd values and lower ksp values in these measurements is that these cementitious waste forms have greater radionuclide retention than was previously estimated based on laboratory studies using surrogate materials. This work represents the first leaching study performed with an actual aged, reducing-grout sample and as such provides an important comparison to studies conducted with surrogate materials, and provides high pedigree data for other programs around the world evaluating reducing grouts as a wasteform for subsurface nuclear waste disposal.


Assuntos
Monitoramento de Radiação , Resíduos Radioativos , Resíduos Radioativos/análise , Monitoramento de Radiação/métodos , South Carolina , Eliminação de Resíduos/métodos , Instalações de Eliminação de Resíduos , Radioisótopos/análise
11.
Cancers (Basel) ; 16(15)2024 Jul 31.
Artigo em Inglês | MEDLINE | ID: mdl-39123451

RESUMO

Brain metastases pose a significant therapeutic challenge in the field of oncology, necessitating treatments that effectively control disease progression while preserving neurological and cognitive functions. Among various interventions, brachytherapy, which involves the direct placement of radioactive sources into or near tumors or into the resected cavity, can play an important role in treatment. Current literature describes brachytherapy's capacity to deliver targeted, high-dose radiation while minimizing damage to adjacent healthy tissues-a crucial consideration in the choice of treatment modality. Furthermore, advancements in implantation techniques as well as in the development of different isotopes have expanded its efficacy and safety profile. This review delineates the contemporary applications of brachytherapy in managing brain metastases, examining its advantages, constraints, and associated clinical outcomes, and provides a comprehensive understanding of advances in the use of brachytherapy for brain metastasis treatment, with implications for improved patient outcomes and enhanced quality of life.

12.
Brachytherapy ; 2024 Aug 03.
Artigo em Inglês | MEDLINE | ID: mdl-39098499

RESUMO

PURPOSE: Surgically targeted radiation therapy (STaRT) with Cesium-131 seeds embedded in a collagen tile is a promising treatment for recurrent brain metastasis. In this study, the biological effective doses (BED) for normal and target tissues from STaRT plans were compared with those of external beam radiotherapy (EBRT) modalities. METHODS: Nine patients (n = 9) with 12 resection cavities (RCs) who underwent STaRT (cumulative physical dose of 60 Gy to a depth of 5 mm from the RC edge) were replanned with CyberKnifeⓇ (CK), Gamma KnifeⓇ (GK), and intensity modulated proton therapy (IMPT) using an SRT approach (30 Gy in 5 fractions). Statistical significance comparing D95% and D90% in BED10Gy (BED10Gy95% and BED10Gy90%) and to RC + 0 to + 5 mm expansion margins, and parameters associated with radiation necrosis risk (V83Gy, V103Gy, V123Gy and V243Gy) to the normal brain were evaluated by a Wilcoxon-signed rank test. RESULTS: For RC + 0 mm, median BED10Gy 90% for STaRT (90.1 Gy10, range: 64.1-140.9 Gy10) was significantly higher than CK (74.3 Gy10, range:59.3-80.4 Gy10, p = 0.04), GK (69.4 Gy10, range: 59.8-77.1 Gy10, p = 0.005), and IMPT (49.3 Gy10, range: 49.0-49.7 Gy10, p = 0.003), respectively. However, for the RC + 5 mm, the median BED10Gy 90% for STaRT (34.1 Gy10, range: 22.2-59.7 Gy10) was significantly lower than CK (44.3 Gy10, range: 37.8-52.4 Gy10), and IMPT (46.6 Gy10, range: 45.1-48.5 Gy10), respectively, but not significantly different from GK (34.1 Gy10, range: 22.8-47.0 Gy10). The median V243Gy was significantly higher in CK (11.7 cc, range: 4.7-20.1 cc), GK(6.2 cc, range: 2.3-11.9 cc) and IMPT (19.9 cc, range: 11.1-36.6 cc) compared to STaRT (1.1 cc, range: 0.0-7.8 cc) (p < 0.01). CONCLUSIONS: This comparative analysis suggests a STaRT approach may treat recurrent brain tumors effectively via delivery of higher radiation doses with equivalent or greater BED up to at least 3 mm from the RC edge as compared to EBRT approaches.

13.
J Hazard Mater ; 477: 135410, 2024 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-39098200

RESUMO

The widespread use of nuclear energy has raised concerns about nuclear safety and radioactive waste management, particularly due to the release of radioactive cesium. This study investigates the use of t-BAMBP (4-tert-butyl-2-(α-methylbenzyl) phenol) for the extraction and separation of cesium from simulate high concentration cesium containing wastewater, focusing on the selection of suitable diluents to enhance the efficiency of the process. We performed a systematic study using density functional theory (DFT) calculations to evaluate the intrinsic properties and interactions of various common diluents with t-BAMBP. The diluents studied include aromatic hydrocarbons (benzene, toluene, xylene), alkanes (cyclohexane, hexane, heptane), and alcohols (hexanol, octanol). Our computational results revealed that cyclohexane is the most suitable diluent due to its moderate solvation-free energy, high nonpolarity, and optimal balance between solubility and reactivity. Experimental validation confirmed the computational findings. The cyclohexane-diluted t-BAMBP system achieved the highest cesium extraction efficiency of over 94 %, with a separation factor (ßCs/K) of 767.67. Cyclohexane demonstrated the lowest toxicity and cost among the diluents evaluated, making it a safer and more economical choice for practical applications. The results of this study provide a comprehensive theoretical and experimental basis for the selection of diluents in the t-BAMBP extraction system, offering insights for the sustainable utilization of cesium resources and effective management of radioactive waste.

14.
Environ Geochem Health ; 46(8): 270, 2024 Jul 02.
Artigo em Inglês | MEDLINE | ID: mdl-38954122

RESUMO

Radioactive nuclides cesium (Cs) and strontium (Sr) possess long half-lives, with 135Cs at approximately 2.3 million years and 87Sr at about 49 billion years. Their persistent accumulation can result in long-lasting radioactive contamination of soil ecosystems. This study employed geo-accumulation index (Igeo), pollution load index (PLI), potential ecological risk index (PEPI), health risk assessment model (HRA), and Monte Carlo simulation to evaluate the pollution and health risks of Cs and Sr in the surface soil of different functional areas in a typical mining city in China. Positive matrix factorization (PMF) model was used to elucidate the potential sources of Cs and Sr and the respective contribution rates of natural and anthropogenic sources. The findings indicate that soils in the mining area exhibited significantly higher levels of Cs and Sr pollution compared to smelting factory area, agricultural area, and urban residential area. Strontium did not pose a potential ecological risk in any studied functional area. The non-carcinogenic health risk of Sr to the human body in the study area was relatively low. Because of the lack of parameters for Cs, the potential ecological and human health risks of Cs was not calculated. The primary source of Cs in the soil was identified as the parent material from which the soil developed, while Sr mainly originated from associated contamination caused by mining activities. This research provides data for the control of Cs and Sr pollution in the surface soil of mining city.


Assuntos
Radioisótopos de Césio , Mineração , Poluentes Radioativos do Solo , Medição de Risco , China , Poluentes Radioativos do Solo/análise , Radioisótopos de Césio/análise , Humanos , Radioisótopos de Estrôncio/análise , Césio/análise , Cidades , Solo/química , Método de Monte Carlo , Monitoramento de Radiação
15.
Sci Total Environ ; 949: 175012, 2024 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-39053525

RESUMO

The frayed edge site (FES) of micas, a partially weathered interlayer site, selectively adsorbs Cs radioisotopes. Despite extensive research on Cs+ adsorption, the interactive dynamics of FES elements remain unclear. This study employs experimental and computational methods to examine how interlayer cations at the FES affect Cs stability. We measured the solid-liquid distribution coefficients of Cs+ for partially expanded K- and Rb-fixed biotite using chemical extraction and adsorption methods. We evaluated the standard Gibbs free energy for the Cs exchange reaction between the FESs of K- and Rb-fixed muscovite models and bulk water, expanding the d001 spacing from collapsed to fully expanded conditions. Our results reveal that the interlayer cation significantly influences Cs+ affinity for FES, with the substitution of K+ with Rb+ largely reducing Cs+ stability. The computational approach further disclosed that the K+ to Rb+ replacement only at the wedge-shaped part of the FES contributed to the decrease in Cs+ stability whereas the replacement at other interlayer sites caused little impact. Our studies offer microscopic structural insights into FES, highlighting the critical role of the wedge-shaped part of FES in Cs+ stability.

16.
J Chromatogr A ; 1730: 465091, 2024 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-38964159

RESUMO

An extraction chromatography resin, prepared by the impregnation of bis-octyloxy-calix[4]arene-mono-crown-6 (BOCMC)onto an acrylic ester based polymeric support material, gave excellent uptake data for the removal of radio-cesium (Cs-137) from nitric acid feed solutions. The weight distribution coefficient (Kd) value of >300 obtained during the present study at 3 M HNO3 was the highest reported so far while using a calix-crown-6 based extraction chromatographic resin material. Analogous resin reported previously has yielded a Kd value <100 at comparable feed conditions. The sorbed metal ions could be efficiently desorbed with de-ionized water. Kinetic modeling of the uptake data indicated that both the film and the intra-particle diffusion mechanism are simultaneously operating in the sorption of Cs+ion onto the BOCMC resin. The metal ion sorption data were fitted to the sorption isotherm models and did not conform to the chemisorptions of physisorption models and indicated a pi-pi interaction between the benzene rings of the calix-crown-6 ligand and the Cs+ ion. The reusability of the resins was quite satisfactory after 5 cycles and the radiation stability of the resin material was very good upto an absorbed dose of 500 kGy. The results of column studies were quite encouraging with 15 mL (9 bed volumes) as the breakthrough volume while the elution was complete in about 12 bed volumes of de-ionized water.


Assuntos
Calixarenos , Calixarenos/química , Adsorção , Éteres de Coroa/química , Fenóis/química , Fenóis/isolamento & purificação , Cinética , Resinas Sintéticas/química , Ligantes , Ácido Nítrico/química
17.
Chemosphere ; 363: 142870, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39019175

RESUMO

Retention or trapping of cesium, one of the radiologically important fission products, in the nuclear reactor becomes a great concern as the occurrence may affect radioactivity in the long term or its environmental fate. Herein the chemical compound of cesium that had been largely trapped on the nuclear reactor structural material of (calcium silicate) thermal insulator in a simulated nuclear accident condition was investigated. A combined pre- and post-water dissolution analysis through infrared (IR) spectroscopy and optical emission spectroscopy (OES) was explored to resolve the characterization difficulty encountered in conventional X-ray diffraction analysis reported in the previous works. This method allowed us to identify for the first time the related large amount of water-soluble cesium in the calcium silicate material after a high-temperature chemical reaction as cesium metasilicate (Cs2SiO3). It was evidenced by similar vibrational characteristics of the material to that in the synthesized Cs2SiO3 as well as based on the dissolved Cs and Si in the leaching water having a molar ratio of 2.16 ± 0.33. The corresponding 79-98% of the retained cesium in calcium silicate materials in the case study of 700 and 800 °C reactions was of this compound, emphasizing its significance once formed. Thermodynamic considerations further corroborated the higher stability of Cs2SiO3 in the cesium-calcium silicate reaction than other cesium silicates such as Cs2Si4O9, Cs2Si2O5, or Cs6Si2O7. This clearly poses a high environmental risk due to the volatility of cesium metasilicate as it may spread out further through the water leak path from a damaged nuclear reactor.


Assuntos
Compostos de Cálcio , Césio , Silicatos , Silicatos/química , Compostos de Cálcio/química , Césio/química , Césio/análise , Difração de Raios X , Radioisótopos de Césio/análise , Radioisótopos de Césio/química , Liberação Nociva de Radioativos
18.
Heliyon ; 10(11): e31697, 2024 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-38832275

RESUMO

A complete model for estimating the electric conductivity of combustion product gases, with added cesium (Cs) or potassium (K) vapor for ionization, is presented. Neutral carrier gases serve as the bulk fluid that carries the seed material, as well as the electrons generated by the partial thermal (equilibrium) ionization of the seed alkali metal. The model accounts for electron-neutral scattering, as well as electron-ion and electron-electron scattering. The model is tested through comparison with published data. The model is aimed at being utilized for the plasma within magnetohydrodynamic (MHD) channels, where direct power extraction from passing electrically conducting plasma gas enables electric power generation. The thermal ionization model is then used to estimate the electric conductivity of seeded combustion gases under complete combustion of three selected fuels, namely: hydrogen (H2), methane (CH4), and carbon (C). For each of these three fuels, two options for the oxidizer were applied, namely: air (21 % molecular oxygen, 79 % molecular nitrogen by mole), and pure oxygen (oxy-combustion). Two types of seeds (with 1 % mole fraction, based on the composition before ionization) were also applied for each of the six combinations of (fuel-oxidizer), leading to a total of 12 different MHD plasma cases. For each of these cases, the electric conductivity was computed for a range of temperatures from 2000 K to 3000 K. The smallest estimated electric conductivity was 0.35 S/m for oxy-hydrogen combustion at 2000 K, with potassium seeding. The largest estimated electric conductivity was 180.30 S/m for oxy-carbon combustion at 3000 K, with cesium seeding. At 2000 K, replacing potassium with cesium causes a gain in the electric conductivity by a multiplicative gain factor of about 3.6 regardless of the fuel and oxidizer. This gain factor declines to between 1.77 and 2.07 at 3000 K. Based on the findings of this research study, the four analyzed factors to increase the electric conductivity of MHD plasma can be listed by their significance (descending order) as (1) type of additive seed type (cesium is better than potassium), (2) temperature (the higher the better), (3) carbon-to-hydrogen ratio of the fuel (the higher the better), and finally (4) the oxidizer type (air is generally better than pure oxygen). The relative size of the two electric conductivity components (due to neutrals scattering and Coulomb scattering) at various plasma conditions are discussed, and a threshold of 10-5 (0.001 %) electrons mole fraction is suggested to safely neglect Coulomb scattering.

19.
Adv Mater ; 36(35): e2405035, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38936842

RESUMO

Integration of solar cells and electrochromic windows offers crucial contributions to green buildings. Solar-charging zinc anode-based electrochromic devices (ZECDs) present opportunities for addressing the solar intermittency issue. However, the limited energy storage capacity of ZECDs results in wasted harnessing of solar energy as well as overcharging. Herein, spectral-selective dual-band ZECDs that continuously transport solar energy to indoor appliances by remotely controlling the repeated bleached-tinted cycles during the daytime, are reported. Hexagonal phase cesium-doped tungsten bronze (h-Cs0.32WO3, CWO) nanocrystals are adopted for dual-band ZECDs due to their independent control ability of near-infrared (NIR) and visible (VIS) light transmittance (∆T = 73.0%, 700 nm; ∆T = 83.7%, 1200 nm) and excellent cycling stability (0.8% optical contrast decay at 1200 nm after 10 000 cycles). The prototype device (i.e., CWO//Zn//CWO) delivers extraordinary thermal insulation capability, displaying a 10 °C difference between "bright" and "dark" modes. Furthermore, an Internet of Things (IoT) controller to control the NIR and VIS lights of the CWO//Zn//CWO window wirelessly with a smartphone, empowering the continuous discharging of the solar-charged window during the daytime remotely, is developed. Such windows represent an intriguing potential technology whose future impact on green buildings may be substantial.

20.
ACS Appl Mater Interfaces ; 16(25): 32220-32231, 2024 Jun 26.
Artigo em Inglês | MEDLINE | ID: mdl-38863140

RESUMO

Cesium (Cs) incorporation and sulfurization on copper indium gallium selenide solar cells are the keys to improving the device quality. In this study, we explore the impact of Cs modulation on sulfur-containing Cu(In, Ga)(S, Se)2 (CIGSSe) absorbers, resulting in a performance increase of over 2%, reaching 18.11%. The improvement stems from a widened surface bandgap, grain boundary (GB) passivation, and a moderate injection blocking layer. The surface bandgap widens from 1.44 to 2.63 eV after Cs incorporation, confirmed by ultraviolet photoelectron spectroscopy (UPS) and low-energy inverse photoemission spectroscopy (LEIPS) analysis. Cs presence and S depletion in GBs suggest a new phase that might mitigate carrier recombination. Heightened Cs incorporation introduces interface issues, including an augmented injection blocking layer and interface defects. Our study offers insights into interface challenges and GB engineering strategies in Cs-treated CIGSSe solar cells, illuminating the multifaceted impact of heavy alkali metal ion Cs in CIGS-based photovoltaics.

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