Enhanced adsorption of radioactive strontium ions from aqueous solution by H2O2-modified attapulgite

Effective adsorption of Sr(II) onto H₂O₂-modified attapulgite in aqueous solution was investigated about kinetics and isothermal equilibrium adsorption. The adsorption equilibrium process of Sr(II) on adsorbents reached about 8 h at 40 °C. The adsorption kinetics followed the pseudo-second order equation and the isothermal adsorption data were fit well with the Langmuir isotherm model. The enhanced adsorption mechanism of H₂O₂-modified attapulgite for Sr(II) in aqueous solution was expatiated in detail. The H₂O₂ treatment for attapulgite is effective and as-made adsorbents can be applied for removal of Sr(II) in radioactive waste water.

     

Evaluation of CO2 adsorption capacity of solid sorbents

The CO₂ adsorption capacity of the low-cost solid sorbents of waste tire char (TC) and chicken waste char (CW) was compared with commercial active carbon (AC) and 5 ? zeolite (ZA) using thermogravimetric analysis (TG), pressurized TG, and differential scanning calorimetry (DSC). The sorbents were degassed in a TG up to 150 °C to release all gases on the surface of the sample, then cooled down to the designed temperature for adsorption. TG results indicated that the CO₂ adsorption capacity of TC was higher than that of CW, but lower than those of AC and ZA. The maximum adsorption rate of TC at 50 °C was 0.61% min⁻¹, lower than that of AC, but higher than that of CW, 0.44% min⁻¹. The maximum adsorption rate of ZA at 50 °C was 3.1% min⁻¹. When the pressure was over 4 bar, the adsorption rate of ZA was lower than that of TC and AC. At 30 bar, the total CO₂ uptake of TC was 20 wt%, higher than that of CW and ZA but lower than that of AC. The temperature, nitrogen concentration, and water content also influenced the CO₂ adsorption capacity of sorbents to some extent. DSC results showed that adsorption was an exothermic process. The heat of CO₂ adsorption per mole of CO₂ of TC at 50 °C was 24 kJ mol⁻¹ while the ZA had the largest heat of adsorption at 38 kJ mol⁻¹. Comparing the characteristics of TC and CW, TC may be a promising sorbent for removal of CO₂.     

<Superscript>99m</Superscript>Tc production via the (<Emphasis Type="Italic">γ, n</Emphasis>) reaction on natural Mo

In this paper, cheap liquorice residue was used to prepare activated carbon (AC), thioacetamide (TAA) was used to modify the AC, and the adsorption experiments were conducted in the simulated acid radioactive wastewater with low uranium concentration to study the adsorption behavior and mechanism for uranium by TAA modified AC (TAA–AC). The removal efficiency by TAA–AC was 92.1–98.2% from the 1 mg L^?1 uranium solution at pH 2–6. The adsorption equilibrium data were well fitted by Dubinin–Radushkevich model, and the maximum adsorption capacity was estimated to be 340 mg g^?1. TAA–AC showed an enhanced selectivity for uranium in the presence of competitive ions. Furthermore, the adsorption experiments were conducted in the actual acid radioactive wastewater with low uranium concentration from an in situ leach uranium mine. The high adsorption rate (98.3%) and selectivity (K_d?=?3.78×10⁴ mL g^?1) for uranium were observed in the actual acid radioactive wastewater, and the adsorption rate was found to maintain 96.2% over six cycles of adsorption–desorption.     

Study of the 137Cs adsorption performance of ion-eroded cement

For this study, ion-eroded cement was prepared from the cement required for construction of middle- and low-level radioactive waste repositories in caves. The properties for adsorption of ¹³⁷Cs on cement before and after ion erosion were investigated. XRF, XRD, SEM–EDS and BET were used to analyse various cement materials. The effects of reaction time, solid–liquid ratio, initial radioactivity and different ions on adsorption were studied by static batch experiments. When the initial radioactivity was 1114.5 Bq L^?1 and the solid–liquid ratio was 5 g L^?1, the adsorption equilibrium time was 12 h. Adsorption of ¹³⁷Cs on ion-eroded cement was more effective than that on untreated cement. The adsorption process was consistent with the pseudosecond-order kinetic model and the Freundlich isotherm model, and the process involved multilayer chemisorption. This study provides basic research data for construction of a disposal repository.

     

Experimental and theoretical insights into copper phthalocyanine-based covalent organic frameworks for highly efficient radioactive iodine capture

Exploring efficient materials for capturing radioactive iodine in nuclear waste is of great significance for the progress of nuclear energy as well as the protection of ecological environment. Covalent organic frameworks (COFs) have emerged as promising adsorbents because of their predesignable and functionalizable skeleton structures. However, it remains a grand challenge to achieve large scale preparation of COFs. In this work, we developed a mild and efficient microwave irradiation method instead of the traditional solvothermal method to prepare copper phthalocyanine-based covalent organic frameworks (Cu_xPc-COFs) within only 15 min. The nitrogen-rich 1,2,4,5-tetracarbonitrilebenzene (TCNB) was selected as the solely organic ligand to construct copper phthalocyanine-based 2D conjugated COFs. The resultant Cu_xPc-COFs exhibited excellent iodine enrichment with 2.99 g/g for volatile iodine and 492.27 mg/g for iodine-cyclohexane solution, respectively, outperforming that of many porous materials. As indicated by spectroscopic analysis and DFT calculations, this impressive adsorption performance can be attributed to the charge transfer arising from nitrogen-rich phthalocyanine structures and electron-rich π-conjugated systems with iodine molecules. Moreover, the strong electrostatic interaction between Cu(II) on chelate centers and polyiodide anions (I_x^?) also play an important role in the firmly trapping radioactive iodine. Therefore, this study provides a facile and intelligent approach to implement metal-based COFs for the remediation of toxic radioactive iodine.     

Probing defect-originated properties,actinide-lanthanide doping,and gamma irradiation effect in Lu2Hf2O7 pyrochlore nanocrystals for phosphor and nuclear applications

Multifunctional materials are in high demand these days by virtue of their efficacy to perform more than one role and are expected to ease the high global materials crunch. This work is directed towards probing defect emission in undoped and doping of uranium (U), plutonium (Pu), curium (Cm), cerium (Ce), and samarium (Sm) Lu₂Hf₂O₇ (LuHO) pyrochlore nanocrystals (NCs) for photoluminescence and radioactive waste immobilization. Density of state calculations shows abundant defects in the undoped LuHO NCs. Multiple visible luminescence spanning violet to red in the undoped LuHO pyrochlore NCs upon ultraviolet irradiation was ascribed to the presence of neutral and ionized oxygen vacancies. The doped LuHO NCs show typical blue (Ce³⁺), orange-red (Sm³⁺), and green (U⁶⁺) emissions endowed by 4f→5d, 4f→4f, and charge transfer transitions, respectively. Moreover, uranium is stabilized as UO₆^6? ion (octahedral uranate) in the LuHO pyrochlore lattice. Luminescence lifetime spectroscopy and density functional theory (DFT) calculated defect formation energies suggest that Ce, Sm, Cm, and Pu ared stabilized at Lu³⁺ site whereas U is stabilized at Hf⁴⁺ site in the LuHO NCs. The LuHO pyrochlore NCs also demonstrate high radiation stability on gamma exposure retaining the crystallinity and undergoing structural phase transition from defect fluorite to ideal pyrochlore structure. Considering the significant health hazard posed by radioactive elements present in the spent fuel, these LuHO NCs possess high potential to immobilize U, Pu, Cm, Ce, and Sm. This work poses high significance for immobilizing radioactive nuclear waste and designing tunable luminescent solid-state NCs.     

Comparative study of raw and HNO3-modified porous carbon from waste printed circuit boards for sulfadiazine adsorption: Experiment and DFT study

A huge amount of waste printed circuit boards (WPCBs) was produced while the electronic manufacturing industry developed rapidly. WPCBs mainly consist of organic compounds, which makes it possible to prepare them into porous carbon as valuable adsorbent. However, WPCBs are also rich in valuable metals. Cu makes up the most of these metals. It is worth studying whether the residual metal will affect the application of carbon materials. In this study, the porous active carbon (AC) was prepared from WPCBs as an adsorbent. Sulfadiazine (SD), a widely detected antibiotic contaminant, was used as a target pollutant. Nitric acid (HNO₃) was used to modify AC (AC-HNO₃) to remove the residual Cu. The experiment results showed that the adsorption kinetics of SD by AC (k = 0.0025) and AC-HNO₃ (k = 0.0029) can be described better using a pseudo-second-order kinetic equation. The adsorption isotherms of AC and AC-HNO₃ on SD could be fitted by the Langmuir model. AC had a larger adsorption capacity than AC-HNO₃. Density functional theory (DFT) calculation results suggested that the −OH group and Cu on the surface of AC could be the adsorption sites and promote the SD adsorption. This work provides practical methods to recycle WPCBs into wealth and realized waste control by waste.     

Synthesis and characterization of ammonium molybdophosphate–silica nano-composite (AMP–SiO2) as a prospective sorbent for the separation of 137Cs from nuclear waste

The ammonium molybdophosphate–silica (AMP–SiO₂) nano-composites were prepared by sol–gel method. The material synthesized was nanocrystalline, with average crystallite size of primary particles in the range of 10–25 nm. Small angle X-ray scattering showed presence of mass fractal aggregates made of small particles with rough pore boundaries. To realize the scope of using AMP–SiO₂ nano-composites sorbent for removal of ¹³⁷Cs from nuclear waste solutions, its adsorption characteristics for cesium were evaluated. It was found that the AMP–SiO₂ nanocomposites were amenable for column operation, have high affinity for Cs, and possess very high adsorption capacity for Cs. From the perspective of separation of ¹³⁷Cs from acidic radioactive waste solution, AMP–SiO₂ nanocomposite holds significant promise.     

Investigation of the stability of glass-ceramic composites containing CeTi2O6 and CaZrTi2O7 after ion implantation

Glass-ceramic composite materials have been investigated for nuclear waste sequestration applications due to their ability to incorporate large amounts of radioactive waste elements. A key property that needs to be understood when developing nuclear waste sequestration materials is how the structure of the material responds to radioactive decay of nuclear waste elements, which can be simulated by high energy ion implantation. Borosilicate glass-ceramic composites containing brannerite-type (CeTi₂O₆) or zirconolite-type (CaZrTi₂O₇) oxides were synthesized at different annealing temperatures and investigated after being implanted with high-energy Au ions to mimic radiation induced structural damage. Backscattered electron (BSE) images were collected to investigate the interaction of the brannerite crystallites with the glass matrix before and after implantation and showed that the morphology of the crystallites in the composite materials were not affected by radiation damage. Surface sensitive Ti K-edge glancing angle XANES spectra collected from the implanted composite materials showed that the structures of the CeTi₂O₆ and CaZrTi₂O₇ ceramics were damaged as a result of implantation; however, analysis of Si L_2,3-edge XANES spectra indicated that the glass matrix was not affected by ion implantation.     

Effects of activation conditions on the structural and adsorption characteristics of pinecones derived activated carbons

This study was conducted to understand and optimize the activation process for the production of a low-cost activated carbon (AC) using a renewable and plentiful biomass waste, pinecones. This was achieved by tracking the changes in porous structure, surface chemistry and adsorption properties of the AC produced using different activating agents, activation temperatures, holding times and heating rates. Generally, produced ACs were predominantly microporous with small external surface area and were different in terms of H/C and O/C ratios. Study of Pb²⁺ cations adsorption on these samples proved the high affinity of the pinecones derived ACs to this cation. The best adsorption behaviour was recognized in sample prepared by impregnation with H₃PO₄ at weight ratio of 2, then heating at 400?°C for 2?h at 5?°C/min heating rate. This sample possessed the highest BET surface area (1335 m²/g). The adsorption process obeyed the pseudo-first-order and Freundlich model slightly better than the pseudo-second-order kinetics and Langmuir model. The high Langmuir maximum adsorption capacity of 418?mg/g supports the applicability of the produced AC for the removal of Pb²⁺ cations from wastewater.     

Importance of Micropore–Mesopore Interfaces in Carbon Dioxide Capture by Carbon‐Based Materials

Mesoporous carbonaceous materials (Starbons®) derived from low‐value/waste bio‐resources separate CO₂ from CO₂/N₂ mixtures. Compared to Norit activated charcoal (AC), Starbons® have much lower microporosities (8–32 % versus 73 %) yet adsorb up to 65 % more CO₂. The presence of interconnected micropores and mesopores is responsible for the enhanced CO₂ adsorption. The Starbons® also showed three–four times higher selectivity for CO₂ adsorption rather than N₂ adsorption compared to AC.     

Atenolol sequestration using activated carbon derived from gasified Glyricidia sepium

Activated carbon (AC) derived from gasified Glyricidia sepium woodchip (GGSWAC) was prepared using KOH and CO₂ activation via microwave radiation technique to remove atenolol (ATN) from aqueous solution. The surface area (S_BET) and total pore volume (TPV) of GGSWAC were 483.07 m²/g and 0.255 cm³, respectively. The n-BET model fits well with the isothermal data indicating a multilayer adsorption with the saturation capacity of 121, 143 and 163 mg/g at 30, 45 and 60 °C, respectively. The kinetic study showed that ATN adsorption followed Avrami model equation (R² ≅ 0.99). Based on the thermodynamic parameters, the adsorption of ATN onto GGSWAC was endothermic (ΔH_S = 234.17 kJ/mol) in the first layer of adsorption and exothermic in the subsequent layer (ΔH_L = −165.62 kJ/mol). The ATN adsorption was controlled by both diffusion and chemisorption. In continuous operation, the Thomas (R² = 0.9822) and Yoon–Nelson (R² = 0.9817) models successfully predicted the ATN adsorption.     

Comparative study of cesium adsorption on dioctahedral and trioctahedral smectites

Bentonites which are characterized by good rheological, mineralogical and chemical stability is considered used as sealing barriers in multibarrier Slovak system of deep geological repository for high-level radioactive waste and spent nuclear fuel. In Slovak Republic there are several significant deposits of bentonite, which are characterized by appropriate adsorption properties and meet the geotechnical requirements for this type of barriers. Study of adsorption properties of bentonites and other smectites is an essential step for developing the migration model long-lived corrosion and activation products, and fission products of uranium. Nuclear wastes contain the most important nuclear fission products, radioisotopes ¹³⁴Cs and ¹³⁷Cs. The present paper investigates and compares the cesium adsorption properties of Slovak and North America bentonites composed mainly of dioctahedral smectite montmorillonite (J, L, SAz-1 and STx-1) and trioctahedral smectites saponite (SapCa-2) and hectorite (SHCa-1).     

Spinel structure of activated carbon supported MFe2O4 composites as an economic and efficient electrocatalyst for oxygen reduction reaction in neutral media

For more sustainability and marketing of microbial fuel cells (MFCs) in wastewater treatment, the sluggish kinetics of cathode oxygen reduction reaction (ORR) and platinum scarcity (with its high cost) should be swept away. So, this work aimed to synthesize metal ferrite (MFe₂O₄; M = Mn, Cu, and Ni) -based activated carbon composites as inexpensive ORR cathode catalysts. The composites were synthesized using a facile modified co-precipitation approach with low-thermal treatment and labeled as MnFe₂O₄/AC, CuFe₂O₄/AC, and NiFe₂O₄/AC. The as-synthesized catalysts are physicochemically characterized by X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared microscopy (FTIR), Barrett-Joyner-Halenda (BJH), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), and electron spin resonance (ESR). The electrochemical catalytic performance toward ORR was studied in a phosphate buffer solution (PBS) at neutral media via cyclic voltammetry (CV) and linear sweep voltammetry (LSV). MnFe₂O₄/AC has the highest onset potential (E_onset) value of − 0.223 V compared to CuFe₂O₄/AC (− 0.280 V) and NiFe₂O₄/AC (− 0.270 V). MnFe₂O₄/AC also has the highest kinetic current density (j_K) and lowest Tafel slope (− 5 mA cm⁻² and − 330 mV dec⁻¹) compared to CuFe₂O₄/AC (− 3.05 mA cm⁻² and − 577 mV dec⁻¹) and NiFe₂O₄/AC (− 2.67 mA cm⁻² and − 414 mV dec⁻¹). The ORR catalyzed by MnFe₂O₄/AC at pH = 7 proceeds via a 4e⁻ -kinetic pathway. The ESR is in good agreement with the electrochemical analysis due to the highest ∆H_ppvalue for MnFe₂O₄/AC compared to CuFe₂O₄/AC and NiFe₂O₄/AC. Thus, MnFe₂O₄/AC is suggested as a promising alternative to Pt- electrocatalyst cathode for MFCs at neutral conditions.

Graphical Abstract

     

Effect of gamma-irradiation on adsorption properties of Slovak bentonites

One of the basic prerequisites for the use of bentonite as engineering barrier in deep geological repositories for radioactive waste and spent nuclear fuel is their stability against ionizing radiation stemming from radionuclides present in radioactive waste and spent nuclear fuel. The aim of this study was to compare the changes in the adsorption properties of selected Slovak bentonites in relation to uranium fission products (¹³⁷Cs and ⁹⁰Sr), prior to and after irradiation of bentonites with a ⁶⁰Co γ-source and specifying the changes in the structure of Slovak bentonites induced by γ-radiation. The changes in irradiated natural forms of Slovak bentonites and the changes in their natrified analogues and fractions with different grain sizes were studied from five Slovak deposits: Jelšovy potok, Kopernica, Lastovce, Lieskovec and Dolná Ves. The EPR spectra of bentonites from deposits Jelšovy potok and Lieskovec with absorbed doses of 10⁴ and 10⁵ Gy γ-rays showed no changes in the structure of the studied Slovak bentonites. The changes, which in terms of structure destabilization can be considered insignificant, occurred only in bentonites with absorbed doses of γ-radiation as much as 1 MGy. The absorbed dose of 1 MGy γ-radiation did not have an effect on the adsorption of cesium on every studied bentonite. Changes that can also be regarded as insignificant occurred only during strontium adsorption, especially on Fe–bentonite from deposit Lieskovec and Ca–Mg–bentonite from deposit Jelšovy potok, when an increase in the adsorption capacity occurred. Attention should be paid in further research of this topic which would require carrying out experiments on bentonite samples with absorbed doses higher by several orders of magnitude.     

Adsorption of cesium on domestic bentonites

Bentonite is a natural clay and one of the most promising candidates for use as a buffer material in the geological disposal systems for spent nuclear fuel and high-level nuclear waste. It is intended to isolate metal canisters with highly radioactive waste products from the surrounding rocks because of its ability to retard the movement of radionuclides by adsorption. Slovak Republic avails of many significant deposits of bentonites. Adsorption of Cs on five Slovak bentonites of deposits (Jelšovy potok, Kopernica, Lieskovec, Lastovce and Dolná Ves) has been studied with the use of batch technique. In the case of Dolná Ves deposit, the mixed-layer illite–smectite has been identified as the main clay component. Natural and irradiated samples, in two different kinds of grain size: 45 and 250 μm have been used in the experiments. The adsorptions of Cs on bentonite under various experimental conditions, such as contact time, adsorbent and adsorbate concentrations have been studied. The Cation Exchange Capacity values for particular deposits drop in the following order: Jelšovy potok > Kopernica > Lieskovec > Lastovce > Dolná Ves. Bentonites irradiated samples with 390 kGy have shown higher specific surface and higher values of the adsorption capacity. Distribution coefficients have been determined for bentonite-cesium solution system as a function of contact time and adsorbate and adsorbent concentration. The data have been interpreted in terms of Langmuir isotherm. The uptake of Cs has been rapid and the adsorption of cesium has increased with increasing metal concentrations. The adsorption percentage has decreased with increasing of metal concentrations. Adsorption of Cs has been suppressed by presence of Ca²⁺ more than Na⁺ cation. Sorption experiments carried out show that the most suitable materials intended for use as barriers surrounding a canister of spent nuclear fuel are bentonites of the Jelšovy potok and Kopernica deposits.     

Determination of <Superscript>129</Superscript>I using volatilization method and liquid scintillation spectrometry

A simple and rapid separation method for ¹²⁹I determination in radioactive waste samples was developed. Suitable conditions for iodine volatilization were tested. Iodine was trapped in 1.5 mol L^?1 NaOH and precipitated as PdI₂·H₂O by addition of PdCl₂ with recoveries higher than 80%. The method was applied for analysis of contaminated soil, radioactive sludge, evaporator concentrate and heterogeneous waste samples from nuclear power plants in Slovak Republic. ¹²⁹I was measured on liquid scintillation counter TRI CARB 2900 TR using Ultima Gold AB scintillation cocktail.     

Optimizing adsorptive removal of malachite green and methyl orange dyes from simulated wastewater by Mn‐doped CuO‐Nanoparticles loaded on activated carbon using CCD‐RSM: Mechanism,regeneration, isotherm,kinetic, and thermodynamic studies

In the present work, Mn‐doped CuO‐NPs‐AC was prepared by a simple method, characterized using various techniques such as FESEM, EDX, XRD, PSD, and pH_pzc and finally used for the adsorption of malachite green (MG) and methyl orange (MO) in a number of single and binary solutions. A series of adsorption experiments were conducted to investigate and optimize the influence of various factors (such as different pH, concentration of MG and MO, adsorbent mass, and sonication time) on the simultaneous adsorption of MG and MO using response surface methodology. Under optimal conditions of pH 10, adsorbent dose of 0.02 g, MG concentration of 30 mg L^?1, MO concentration of 30 mg L^?1, and sonication time of 4.5 min at room temperature, the maximum predicted adsorption was observed to be 100.0%, for both MG and MO, showing that there is a favorable harmony between the experimental data and model predictions. The adsorption isotherm of MO and MG by Mn‐doped CuO‐NPs‐AC could be well clarified by the Langmuir model with maximum adsorption capacity of 320.69 mg g^?1 and 290.11 mg g^?1 in the single solution and 233.02 mg g^?1 and 205.53 mg g^?1 in the binary solution by 0.005 g of adsorbent mass for MG and MO, respectively. Kinetic studies also revealed that both MG and MO adsorption were better defined by the pseudo‐second order model for both solutions. In addition, the thermodynamic constant studies disclosed that the adsorption of MG and MO was likely to be influenced by a physisorption mechanism. Eventually, the reusability of the Mn‐doped CuO‐NPs‐AC after six times showed a reduction in the adsorption percentage of MG and MO.     

Adsorption of cadmium(II) in wastewater by magnesium oxide modified biochar

A new MgO-AC (magnesium oxide modified activated carbon) adsorbent was successfully synthesized under microwave irradiation. XRD, FT-IR, XPS, SEM and N₂ adsorption were used to characterize the properties of MgO-AC. It was found that MgO-AC was highly crystalline under the preparation process, and the doping of MgO (Magnesium oxide) did not cause the gap blockage of AC (activated carbon), but the micropore area and average pore size of modified AC increased significantly. Multiple conditional parameters were studied to determine the optimal adsorption effect, such as roasting temperature, holding time, MgO doping amount, contact time, adsorption temperature, system pH, and initial concentration of Cd(II) (divalent cadmium ion). The results show that the optimal parameter conditions are as follows: the insulation temperature is 800 °C, holding time of 40 min, the doping amount of MgO is 1/20 of AC, and the maximum adsorption capacity is 649.9 mg·g^?1 at pH = 7. In addition, thermodynamic studies show that the adsorption process is spontaneous and endothermic, and kinetic and adsorption isotherm models show that the pseudo-second-order kinetic model and Langmuir model are well fitted for the adsorption process.     

The effect of calcination temperature on the texture of silica gel waste

In this work, the effect of temperature on the texture of silica gel waste is presented and water vapour adsorption in a different humidity is highlighted. It was found that silica gel waste is a mesoporous material with the parallel plates pores. Its specific surface area is equal to 4.61 m² g^?1, and the calculated total pore volume is equal to 9.01 × 10^?3 cm³ g^?1. The texture of silica gel waste changed during calcination in a 188–550 °C temperature interval: S_BET and ΣV_P increased to 11.32 m² g^?1 and 30.06 × 10^?3 cm³ g^?1, respectively. It was determined that the water vapour pressure influenced the mineralogical composition and the quantity of adsorbed water in the samples. The obtained results were confirmed by the differential scanning microcalorimetry, X-ray diffraction, BET and water vapour adsorption analysis data.