Novel phosphate functionalized sodium alginate hydrogel for efficient adsorption and separation of Nd and Dy from Co.

The recovery of rare earth elements (REEs) including neodymium (Nd) and dysprosium (Dy) from NdFeB permanent magnets has become one of the main ways to solve the increased demand for rare earth. Herein, n-dodecyl phosphate (DPPA) was used for the first time as the adsorption functional group donor, sodium alginate as the substrate, and calcium chloride solution as the reactive solvent, a hybrid hydrogel adsorbent DPPA/CaALG was synthesized by sol-gel method for application in the adsorption and separation of Nd and Dy from the Co-Nd-Dy ternary system. SEM-EDS, and N2 adsorption-desorption analysis showed the successful preparation of DDPA/CaALG with mesoporous structure. Batch experiments showed the superiority of the hybrid hydrogel for the good selective adsorption of Nd and Dy, such as large adsorption capacity (Nd: 162.5 mg/g, Dy: 183.5 mg/g), and no adsorption for Co. FT-IR, XPS showed that PO and P-O groups are involved in the adsorption process of Nd and Dy as electron acceptors, where the ion exchange of P-OH is dominant. Furthermore, the chemical properties of ligands and complexes were analyzed by Density Functional Theory (DFT) calculations and revealed their adsorption behaviors as well as the competition between different metal ions.

In Situ Interfacial Engineering of CeO2 /Bi2 WO6 Heterojunction with Improved Photodegradation of Tetracycline and Organic Dyes: Mechanism Insight and Toxicity Assessment.

The construction of heterojunction photocatalysts is an auspicious approach for enhancing the photocatalytic performance of wastewater treatment. Here, a novel CeO2 /Bi2 WO6 heterojunction is synthesized using an in situ liquid-phase method. The optimal 15% CeO2 /Bi2 WO6 (CBW-15) is found to have the highest photocatalytic activity, achieving a degradation efficiency of 99.21% for tetracycline (TC), 98.43% for Rhodamine B (RhB), and 94.03% for methylene blue (MB). The TC removal rate remained at 95.38% even after five cycles. Through active species capture experiments, •O2 - , h+ , and •OH are the main active substances for TC, RhB, and MB, respectively. The possible degradation pathways for TC are analyzed using liquid chromatography-mass spectrometry (LC-MS). The photoinduced charge transfer and possible degradation mechanisms are proposed through experimentation and density functional theory (DFT) calculations. Toxicity assessment experiments show a significant reduction in toxicity during the TC degradation process. This study uncovers the mechanism of photocatalytic degradation in CeO2 /Bi2 WO6 and provides new insights into toxicity assessment.

Highly efficient removal of strontium from contaminated wastewater by a porous zirconium phosphate material.

Effective and efficient disposal of radioactive pollution has been crucial for responding to unexpected nuclear accidents and guaranteeing the sustainable development of nuclear energy. In this study, a kind of porous zirconium phosphate was synthesized with a sol-gel process followed by a post-synthesis modification to remove the radioactive Sr2+ from wastewater. The prepared materials were characterized by different technologies including FT-IR, SEM-EDS, XRD and XPS, and then the adsorption performance was evaluated in batch and column modes. Experimental results suggested that the porous zirconium phosphate adsorbent was successfully prepared with Na+ dispersed in the channels for exchange. It inherited the excellent properties of zirconium dioxide aerogel and exhibited mesoporous structure and large specific surface area. Compared with traditional zirconium phosphate, the adsorption kinetics and the adsorption capacity were improved simultaneously. Especially, it showed excellent selectivity towards Sr2+ among different cations, and even could remove the low-level Sr2+ from natural seawater efficiently, which powerfully demonstrated that the prepared material could be applied in the treatment of practical wastewater. Spectra studies uncovered that the adsorption activities were dominated by the ion exchange mechanism between external Sr2+ and interlaminar Na+ or H+. In conclusion, this paper not only reports a novel synthesis strategy for the acquisition of porous zirconium phosphate, but also presents a promising adsorbent for the Sr2+ removal.

Theoretical Study on the Reduction Mechanism of Np(VI) by Hydrazine Derivatives.

The key to effective separation of neptunium from the spent fuel reprocessing process is to adjust and control its valence state. Hydrazine and its derivatives have been experimentally confirmed to be effective salt-free reductants for reducing Np(VI) to Np(V). We theoretically studied the reduction reactions of Np(VI) with three hydrazine derivatives (2-hydroxyethyl hydrazine (HOC2H4N2H3), methyl hydrazine (CH3N2H3), and formyl hydrazide (CHON2H3)) and obtained the free radical ion mechanism and the free radical mechanism. Their potential energy profiles (PEPs) suggest that the free radical mechanism is the most probable reaction. Based on the energy barrier of the free radical ion mechanism, the trend of the reduction ability of the three hydrazine derivatives is HOC2H4N2H3 > CH3N2H3 > CHON2H3, which is in excellent agreement with the experimental results. Lastly, the analyses of natural bond orbitals (NBOs), quantum theory of atoms-in-molecules (QTAIM), and electron localization function (ELF) have been carried out to explore the bonding evolution of the structures along the reaction pathways. This work provides an insight into the reduction mechanism of Np(VI) with hydrazine derivatives from the theoretical perspective and helps to design more effective reductants for the separation of U/Np and Np/Pu in spent fuel reprocessing.

Efficient Uranium Removal from Aqueous Solutions Using Silica-Based Adsorbents Functionalized with Various Polyamines.

With the rapid development of nuclear energy, the contamination of environmental water systems by uranium has become a significant threat to human health. To efficiently remove uranium from these systems, three types of silica-based polyamine resins-SiPMA-DETA (SiPMA: silica/poly methyl acrylate; DETA: diethylenetriamine), SiPMA-TETA (TETA: triethylenetetramine), and SiPMA-TEPA (TEPA: tetraethylenepentamine)-were successfully prepared, characterized, and evaluated in batch experiments. Characterization results showed that the silica-based polyamine resins were successfully prepared, and they exhibited a uniform shape and high specific surface area. SiPMA-DETA, SiPMA-TETA, and SiPMA-TEPA had nitrogen contents of 4.08%, 3.72%, and 4.26%, respectively. Batch experiments indicated that these adsorbents could efficiently remove uranium from aqueous solutions with a pH of 5-9. The adsorption kinetics of U(VI) were consistent with the pseudo-second-order model, indicating that the adsorption process was chemisorption and that adsorption equilibrium was achieved within 10 min. SiPMA-TEPA, with the longest polyamine chain, exhibited the highest adsorption capacity (>198.95 mg/g), while SiPMA-DETA, with the shortest polyamine chain, demonstrated the highest U(VI) adsorption efficiency (83%) with 100 mM Na2SO4. SiPMA-TEPA still removed over 90% of U(VI) from river water and tap water. The spectral analysis revealed that the N-containing functional groups on the ligand were bound to anionic uranium-carbonate species and possibly contributed to the adsorption efficiency. In general, this work presents three effective adsorbents for removing uranium from environmental water systems and thus significantly contributes to the field of environmental protection.

Mastering Surface Sulfidation of MnP-MnO2 Heterostructure to Facilitate Efficient Polysulfide Conversion in Li─S Batteries.

The development of lithium-sulfur (Li─S) batteries has been hampered by the shuttling effect of lithium polysulfides (LiPSs). An effective method to address this issue is to use an electrocatalyst to accelerate the catalytic conversion of LiPSs. In this study, heterogeneous MnP-MnO2 nanoparticles are uniformly synthesized and embedded in porous carbon (MnP-MnO2/C) as core catalysts to improve the reaction kinetics of LiPSs. In situ characterization and density functional theory (DFT) calculations confirm that the MnP-MnO2 heterostructure undergo surface sulfidation during the charge/discharge process, forming the MnS2 phase. Surface sulfidation of the MnP-MnO2 heterostructure catalyst significantly accelerated the SRR and Li2S activation, effectively inhibiting the LiPSs shuttling effect. Consequently, the MnP-MnO2/C@S cathode achieves outstanding rate performance (10 C, 500 mAh g-1) and ultrahigh cycling stability (0.017% decay rate per cycle for 2000 cycles at 5 C). A pouch cell with MnP-MnO2/C@S cathode delivers a high energy density of 429 Wh kg-1. This study may provide a new approach to investigating the surface sulfidation of electrocatalysts, which is valuable for advancing high-energy-density Li-S batteries.

Study of the Adsorption and Separation Behavior of Scandium and Zirconium by Trialkyl Phosphine Oxide-Modified Resins in Sulfuric and Hydrochloric Acid Media.

Zirconium is recognized as one of the main impurities of the rare earth element scandium during purification. It presents significant challenges due to its similar chemical properties, making separating it difficult. This study used trialkyl phosphine oxide (TRPO) as a functional ligand, and the effects of carrier type and acidity on adsorption performance were first investigated. Among these, the novel extraction resin SiO2-P as a carrier for TRPO demonstrated more prominent separation performance in 0.2 M H2SO4 and 5 M HCl solutions. The kinetic and isotherm data were consistent with the pseudo-secondary kinetics and Langmuir model, respectively, and the adsorption process could be regarded as homogeneous monolayer adsorption subject to the dual effects of chemisorption and internal diffusion. In addition, thermodynamic analysis showed that the adsorption process of zirconium under the experimental conditions was a spontaneous endothermic process. Combined with the results of SEM-EDS, FT-IR, and XPS analyses, scandium and zirconium were successfully adsorbed by the resin and uniformly distributed on its surface, and the greater affinity of the P=O groups on the resin for zirconium was the critical factor contributing to the separation of scandium and zirconium. Finally, scandium and zirconium in sulfuric acid and hydrochloric acid media were extracted and separated by column experiments, and the purity of scandium could reach 99.8% and 99.99%, respectively.

A new strategy to construct MOF-on-MOF derivatives for the removal of tetracycline hydrochloride from water by activation of peroxymonosulfate.

A MOF-on-MOF composite derivative material named ZIF-67@Ce-MOF-600 was designed and synthesized. The preparation of ZIF-67@Ce-MOF-600 was optimized from the aspects of the ratio of metal and ligand, heat-treatment temperature. It was demonstrated by XRD, FT-IR, SEM-EDS and TEM. The optimum conditions for the activation of PMS by ZIF-67@Ce-MOF-600 for the degradation of tetracycline (TC) were investigated by adjusting the catalyst dosage, TC, pH, peoxymonosulfate (PMS) concentration, and different kinds of water, co-existing anions and pollution. Under optimal conditions (20 mg catalysts and 50 mg PMS added) in 100 mL of tetracyclines (TC) solvent (20 mg TC/L), the removal rate could reach up to 99.2% and after five cycles was 70.5%. The EPR results indicated the presence of free radicals and non-free radical, among which free radicals intended to play a major role in the degradation process. Its possible degradation pathways and attack sites were analyzed by liquid-phase mass spectrometry and DFT analysis.

Constructing Ce-OH groups on CeO2 for enhancing removal and recovery of uranium from wastewater and seawater.

Efficient recovery of uranium from wastewater and seawater provides an important guarantee for the sustainable growth of nuclear energy. Herein, we skillfully use the alkali etching method to construct CeO2 hollow spheres rich in Ce-OH groups for the removal and recovery of uranium from water matrixes. It is found that the CeO2 exhibits fast adsorption kinetics (equilibrium time within 10 min) and moderate adsorption capacity (143.1 mg/g), and the removal efficiency of low concentration uranium (0.1 g/L and 1 g/L) reaches 100% within 1 min of adsorption. Moreover, the adsorption of uranium by CeO2 is almost unaffected by common anions and cations in the environment, even if the concentration of anions is 1000 times that of uranium. More importantly, the CeO2 can enrich uranium concentration in seawater by 167.9 times and the recovery rate reaches 83.9%. Mechanistic studies reveal that the adsorption of uranium by CeO2 is mainly attributed to the rich Ce-OH groups on the surface of CeO2, resulting in the rapid adsorption of U(VI) and mainly forms a single-bridge model. The findings of this study provide a green and efficient path for the removal and recovery of uranium from wastewater and seawater.

Adsorption and Desorption Behavior and Mechanism of Ruthenium in Nitrite-Nitric Acid System.

Ruthenium is required to separate from high-level liquid waste (HLLW) because Ru is a valuable resource and is negatively influential on the vitrification process of HLLW. However, the separation of Ru is very challenging due to its complicated complexation properties. In this study, the adsorption and desorption characteristics of ruthenium on a synthesized SiPyR-N3 (weak-base anion exchange resin with pyridine functional groups) composite were investigated in nitric acid and nitrite-nitric acid systems, respectively, and the adsorption mechanism was explored. The experimental results showed that SiPyR-N3 has a significantly better adsorption effect on Ru in the nitrite-nitric acid system than in the nitric acid system, with an increase in the adsorption capacity of approximately three times. The maximum adsorption capacity of Ru is 45.6 mg/g in the nitrite-nitric acid system. The SiPyR-N3 possesses good adsorption selectivity (SFRu/other metal ions is around 100) in 0.1 M NO2--0.1 M HNO3 solution. The adsorption processes of Ru in the two different systems are fitted with the pseudo-second-order kinetic model and Langmuir model for uptake kinetics and adsorption isotherms, respectively. The results obtained from the FT-IR, XPS, and UV absorption spectrometry indicate that NO2- was involved in the adsorption process either as a complexing species with the metal ions or as free NO2- from the solution. A 0.1 M HNO3 + 1 M thiourea mixed solution shows effective desorption performance, and the desorption efficiency can reach 92% at 328 K.

Precise stepwise recovery of platinum group metals from high-level liquid wastes based on SDB polymer-modified SiO2.

Accurate separation and efficient recovery of platinum group metals (PGMs, mainly Ru, Rh and Pd) from high level liquid waste (HLLW) is a good choice for clean production and sustainable development of nuclear energy. Herein a novel SDB polymer modified silica-based amine-functionalized composite (dNbpy/SiO2-P) was synthesized for the separation and recovery of PGMs. Laser particle size analysis and BET results clarified the regular spherical and highly interconnected mesoporous structure of dNbpy/SiO2-P which is critical for the separation of PGMs. The removal percent of PGMs were over 99% on the optimized conditions. In addition, dNbpy/SiO2-P showed excellent selectivity (SFPd/M > 3805, SFRu/M > 1705, SFRh/M > 336) and repeatability (≥5). Interestingly, based on the different adsorption and desorption kinetics of PGMs, a double-column strategy is designed to solve the challenge of separating and recovering PGMs from HLLW. The enrichment factors of Pd(II), Ru(III) and Rh(III) reached 36.7, 8.2, and 1.2. The adsorption of PGMs was coordination mechanism and required the involvement of NO3- to maintain charge balance. The specific distribution of elements within the adsorbents and the changes in valence state were analyzed using depth-profiling XPS. Both depth-profiling XPS results and slope analysis revealed that the complex of dNbpy and PGMs is a 1 : 1 coordination structure. Overall, this work fills the gap that PGMs cannot be effectively separated and enriched from HLLW.

Precise recognition and efficient recovery of Pd(II) from high-level liquid waste by a novel aminothiazole-functionalized silica-based adsorbent.

Efficient recognition, separation and recovery of palladium from high-level liquid waste (HLLW) not only helps the safe, green and environmentally friendly disposal of nuclear waste, but also is an essential important supplement to overcome the growing shortage of natural palladium resources. Herein, a novel silica-based functional adsorbent named 2AT-SiAaC was prepared by a two-step method, i.e., grafting of 2-aminothiazole (2AT) via the amidated reaction after in-situ polymerization of acrylic monomers on porous silica. SEM, EDS, TG-DSC, BET and PXRD all proved the successful preparation of 2AT-SiAaC, and it exhibited ultrahigh adsorption selectivity for Pd(II) (Kd (distribution coefficient) ≥ 10,344.2 mL/g, SFPd/M (separation factor) ≥ 613.7), fast adsorption kinetics with short equilibrium time (t ≤ 1 h) and good adsorption capacity (Q ≥ 62.1 mg Pd/g). The dynamic column experiments shows that 2AT-SiAaC achieved efficiently separation of Pd(II) from simulated HLLW, and the enrichment coefficients (C/C0) of Pd(II) was as high as about 14 with the recovery rate nearly 99.9% and basically kept the same performance in three adsorption-desorption column cycle experiments. The adsorption mechanism was analyzed by FT-IR, XPS and DFT calculations, and the ultrahigh selectivity of 2AT-SiAaC was attributed to the preferred affinity of the soft N-donor atoms in 2AT for Pd(II). NO3- ions participated in the adsorption reaction to keep charge balance, and the frontier orbital electron density distribution diagram shows the charge transfer in the process of material preparation and adsorption. To sum up, 2AT-SiAaC adsorbent provided a new insight for precise recognition and efficient separation of Pd(II) from HLLW.

Phosphination of amino-modified mesoporous silica for the selective separation of strontium.

Radioactive strontium (90Sr) is considered as one of the most dangerous radionuclides due to its high biochemical toxicity. For the efficient and selective separation of Sr from acidic environments, a novel functional adsorbent CEPA@SBA-15-APTES was prepared in this work through the phosphorylation of amino-modified mesoporous silica with organic content of approximately 20 wt%. CEPA@SBA-15-APTES was characterized by TEM, SEM, EDS, TG-DSC, BET, FTIR, and XPS techniques, revealing its characteristics of an ordered hexagonal lattice-like structure and rich functional groups. The experimental results demonstrated that the adsorbent exhibited good adsorption capacity for Sr over a wide acidity range (i.e., from 10-10 M to 4 M HNO3). The adsorption equilibriums of Sr by CEPA@SBA-15-APTES in 10-6 M and 3 M HNO3 solutions were reached within 30 and 5 min, respectively, and the adsorption capacities at 318 K were 112.6 and 71.8 mg/g, respectively. Furthermore, by combining the experimental and characterization results, we found that the adsorption mechanism consisted of ion exchange between Sr(II) and H+ (in P-OH) in the 10-6 M HNO3 solution and coordination between the Sr(II) and oxygen-containing (CO and P = O) functional groups in the 3 M HNO3 solution.

Phosphonation of Alginate-Polyethyleneimine Beads for the Enhanced Removal of Cs(I) and Sr(II) from Aqueous Solutions.

Although Cs(I) and Sr(II) are not strategic and hazardous metal ions, their recovery from aqueous solutions is of great concern for the nuclear industry. The objective of this work consists of designing a new sorbent for the simultaneous recovery of these metals with selectivity against other metals. The strategy is based on the functionalization of algal/polyethyleneimine hydrogel beads by phosphonation. The materials are characterized by textural, thermo-degradation, FTIR, elemental, titration, and SEM-EDX analyses to confirm the chemical modification. To evaluate the validity of this modification, the sorption of Cs(I) and Sr(II) is compared with pristine support under different operating conditions: the pH effect, kinetics, and isotherms are investigated in mono-component and binary solutions, before investigating the selectivity (against competitor metals) and the possibility to reuse the sorbent. The functionalized sorbent shows a preference for Sr(II), enhanced sorption capacities, a higher stability at recycling, and greater selectivity against alkali, alkaline-earth, and heavy metal ions. Finally, the sorption properties are compared for Cs(I) and Sr(II) removal in a complex solution (seawater sample). The combination of these results confirms the superiority of phosphonated sorbent over pristine support with promising performances to be further evaluated with effluents containing radionuclides.

Synthesis and fabrication of segregative and durable MnO2@chitosan composite aerogel beads for uranium(VI) removal from wastewater.

To address the imperative need for efficient removal of uranium-containing wastewater and mitigate radioactive contamination risks associated with nuclear energy, the development of materials with high removal efficiency and facile separation is crucial. This study designed and synthesised MnO2@chitosan (CTS) composite aerogel beads by in-situ growing δ-MnO2 on porous CTS aerogel beads. This approach not only mitigates the agglomeration of MnO2 nanospheres but also significantly enhances the porous structure and surface area of MnO2@CTS. These cost-effective and eco-friendly millimeter-scale spherical aerogels exhibited convenient separation properties after adsorption. These characteristics help mitigate the risk of equipment seam blockage and secondary pollution that are often associated with powdered adsorbents. Additionally, MnO2@CTS exhibited remarkable mechanical strength (stress approximately 0.55 MPa at 60 % strain), enabling rapid separation and easy regeneration while maintaining high adsorption performance even after five cycles. Significantly, MnO2@CTS exhibited a maximum adsorption capacity of 410.7 mg/g at pH 6 and 298 K, surpassing reported values for most CTS/MnO2-based adsorbents. The chemisorption process of U(VI) on MnO2@CTS followed the pseudo-second-order kinetic and Dubinin-Radushkevish models. X-ray photoelectron spectroscopy analysis further confirmed the reduction of U(VI) to U(V/IV). These findings highlight the substantial potential of MnO2@CTS aerogel beads for U(VI) removal from aqueous solutions, positioning them as a promising solution for addressing U(VI) contamination in wastewater.

Preparation of VCo-MOF@MXene composite catalyst and study on its removal of ciprofloxacin by catalytically activating peroxymonosulfate: Construction of ternary system and superoxide radical pathway.

The synergistic effect between transition metal active centers and the generation of multiple removal pathways has a significant impact on the catalytic activation efficiency of peroxymonosulfate. In this work, a kind of composite catalyst was prepared by growing VCo-metal-organic frameworks (VCo-MOF) in-situ on the surface of Ti3C2Tx by a solvothermal method. The morphology and structure are characterized by Transmission Electron Microscope (TEM), Energy Dispersion Spectrum (EDS), Atomic Force Microscope (AFM), etc. Response surface methodology was used to optimize the experimental conditions. Only 5 mg catalyst can be used to effectively activate PMS and remove 96.14 % ciprofloxacin (CIP, 20 mg/L) within 30 min. The removal effect of catalyst on CIP in different actual water environment was explored. In addition, the fluorescence spectrum test also verified the effective removal of ciprofloxacin. V-Co-Ti ternary system provides a wealth of active sites for CIP removal. Cyclic voltammetry (CV) and lear sweep voltammetry (LSV) tests showed the existence of the electron transfer pathway. The results of density functional theory (DFT) calculation show that VCo-MOF@Ti3C2Tx has excellent adsorption and activation ability for PMS. At the same time, the hydrophilicity of the catalyst makes PMS more inclined to react with water molecules, which promotes the formation of a unique superoxide radical path.

Novel NbCo-MOF as an advanced peroxymonosulfate catalyst for organic pollutants removal: Growth, performance and mechanism study.

Multivariate metal-organic frameworks (MTV-MOFs) are expected as catalyst to apply to the advanced oxidation processes (AOPs) based on sulfate radical (SO4·-) to treat wastewater containing organic pollutants. Mixing metals de novo method was combined with stringent solvothermal conditions to synthesize macaroon-like NbCo-MOF catalyst. NbCo-MOF catalyst prepared with different atom ratios and growth time presented various morphology, structure, performance, and distinctive MTV-MOFs growth law which were confirmed by SEM, TEM, EDS, XRD, FTIR, raman spectra and UV-vis spectra. Besides, optimum peroxymonosulfate (PMS) catalytic activation conditions were studied. Furthermore, the effects of anions (Cl-, NO3-, HCO3-, and C2O42-) on NbCo-MOF catalytic activation were explored which were proved very limited. Particularly, the Co2+/Co3+ cycle combining with the Nb4+/Nb5+ cycle for PMS activation were verified by XPS. EPR and quenching experiment results indicated exists non-radical pathway (1O2), but radical pathways are dominant (SO4·- O2·-, and ·OH). Moreover, the TC removal rate exhibited no significant reduce after three times run. Furthermore, NbCo-MOF exhibited excellent decomposing ability towards methylene blue, tylosin tartrate, rhodamine B, and tetracycline with the removal rate reaching to 100%, 98.4%, 99.7%, and 99.7% in 30 min respectively and also maintained good performance in actual water environment.

Layered ammonium vanadate nanobelt as efficient adsorbents for removal of Sr2+ and Cs+ from contaminated water.

In this study, a layered ammonium vanadate (NH4V4O10) nanobelt adsorbent was synthesized by a facile hydrothermal method to remove Sr2+ and Cs+ from contaminated water. The NH4V4O10 nanobelt was texturally and morphologically characterized by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), Raman, thermogravimetric differential thermal analyzer (TG-DSC), Brunauer- Emmett-Teller (BET), and X-ray photoelectron spectroscopy (XPS) both before and after adsorbing Sr2+ and Cs+. The results showed that the NH4V4O10 nanobelt exhibited the optimal morphological structure with a 2:1 ratio of NH4VO3:dipropylamine. In the lattice of the adsorbent, the horizontal distance between oxygen atoms was 0.55 nm, the vertical distance between vanadium was 0.35 nm, and the layer distance of the adsorbent was 0.931 nm. The structure characterization indicated the VO6 octahedron formed a basic framework through sharing connected vertices. Adsorption mechanism studies indicated that ion exchange was the main adsorption mechanism for removing Sr2+ and Cs+. Batch experiments revealed that the adsorption capacity for Sr2+ was 192.52 mg/g under a pH of 2. Similarly, the adsorption capacity for Cs+ was 251.09 mg/g when the pH was 5. The adsorption kinetics and adsorption isotherms data were in accordance with the pseudo-second-order kinetic model and Langmuir model, respectively. Adsorption isotherms results also indicated that the adsorption of Sr2+ and Cs+ was endothermic (ΔHSr0 = 3.6 kJ/mol, ΔHCs0 = 29.1 kJ/mol) and increased entropy (ΔSSr0 = 29.15 J/molK, ΔSCs0 = 160.38 J/molK). Finally, the structure of the adsorbent, the adsorption performance and mechanism, and the interpretation of selective adsorption were also calculated by DFT method at the molecular level and the results were consistent with the experimental data.

Separation of Minor Actinides from High-Level Liquid Waste Using Novel Silica-Based Butyl-BTP Adsorbents.

To separate the long-lived minor actinides (MA = Am, Cm) from high-level liquid waste (HLLW), we have been studying an advanced separation process via selective adsorption that uses minimal amounts of organic solvent and compact equipment. The process consists of two separation columns packed with a CMPO (octyl(phenyl)-N,N-diisobutylcarbamoyl-methyl phosphine oxide) adsorbent for elemental group separation and a soft-donor named the R-BTP (2,6-bis-(5,6-dialkyl-1,2,4-triazine-3-yl) pyridine) adsorbent for the isolation of MA from lanthanides (Ln). In this work, the effects of nitrate ion (NO3-) on the adsorption behavior of Am(III) and a typical fission product Ln(III) onto the isoBu-BTP/SiO2-P adsorbent were studied experimentally. Then, the desorption properties of the adsorbed element were examined using different eluting agents. A hot test for the separation of MA from the fission product Ln in a genuine MA containing effluent from the irradiated MOX-fuel treatment process was carried out using a nBu-BTP/SiO2-P packed column. It was found that the separation factor between Am(III) and Ln(III)-FP is over 100 in the measured 0.5-4 M NO3-. The adsorbed elements could be effectively eluted off using a complexing agent such as DTPA or pure water. Complete separation between MA and Ln was achieved in the column results, indicating that the proposed MA separation process is feasible in principle.

Leaching of indium and tin from waste LCD by a time-efficient method assisted planetary high energy ball milling.

The phenomenon of the long leaching time and low leaching rate is presented in the acid leaching process under the conventional conditions of low reaction temperature and acid concentration. In order to promote leaching rates of indium and tin in waste liquid crystal display, an optimized process combining rapid milling and acid leaching has been proposed, which is more time and energy-efficient, environmentally sound compared with the traditional acid leaching process. Leaching mechanism analysis was conducted to uncover the different leaching behavior of indium and tin. And the external factors affecting the leaching rates of indium and tin were studied to optimize. In this process, the fine powder with a weight ratio of 97.6%, which particle size less than 0.075 mm, was obtained with the optimal milling time of 30 min by rapid grinding in the planetary high energy ball milling. About -0.003 l/s of grinding rate constant was performed in the grinding size fraction from 3 mm to 0.075 mm. The research results indicated that the particle size less than 0.035 mm was agglomerated, and the addition of H2O2 reduced the leaching rate for the particle size less than 0.075 mm. Moreover, 86.3% and 76.1% of indium and tin were leached in a short leaching time of 10 min by using 3 M H2SO4 at 85 °C for particle size range from 0.075 to 0.035 mm, while 96.9% and 85.6%, respectively in 90 min.