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.

Monte Carlo modelling of cyclotron and radioisotope center (CYRIC) at Tohoku University: a radiation protection study.

Protection against ionizing radiations is important in laboratories with radioactive materials and high energy cyclotron beams. The Cyclotron and Radioisotope Center (CYRIC) located in Tohoku University in Miyagi prefecture, Japan and is a well-known nuclear science laboratory with cyclotron beams and substantial number of high activity radioactive materials. Considering this, it is important to perform complete radiation transport computations to ensure the safety of non-occupational and occupational workers. In the present work, we have developed a complete 3-dimensional model of the main cyclotron building and radiation labs using Monte Carlo method. We have found that the dispersed photons and neutrons inside and in the surrounding of the CYRIC building pose no significant risk to occupational and non-occupational workers. The present work and the developed models would be useful in the field of radiation protection.

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.

Enhanced adsorption dynamics and thermal stability of radioactive Sr(II) by lamellar Nb-doped sodium vanadosilicate via self-assembly and conditional natroxalate intercalation.

To promote the environmentally friendly and sustainable development of nuclear energy, it is imperative to address the treatment of wastewater generated by the nuclear industry. This necessitates the enhancement of fission product reclamation efficiency post-treatment. This study aims to combine defect control and confined self-assembly strategies for the precise design of interlayer spacing (14.6 Å to 15.1 Å), leading to the fabrication of conditional natroxalate-functionalized vanadosilicate, and its potential application in the efficient adsorption and reclamation of 90Sr. Na0.03Natroxalate2.47Si1.44Nb0.08V1.92O5·1.2 H2O (Nb4-NxSiVO), with a layer spacing of 14.9 Å, exhibits the highest Sr(II) adsorption capacity (248.76 mg/g), enabling effective separation with Cs+. The natroxalate embedded within the confined interlayers demonstrates excellent stability, offering rapid (within 10 min) and stable adsorption sites for Sr(II). Furthermore, Nb4-NxSiVO exhibits a wide band gap and exceptional thermal stability before and after adsorption, rendering hard desorption of 90Sr. The findings highlight the potential of Nb4-NxSiVO as a promising adsorbent for rapid and selective purification of 90Sr-containing wastewater and further application in nuclear batteries.

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.

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.

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.

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.

Novel Adsorbents and Adsorption Methods for Pollutant Removal.

Over the past few decades, with the rapid growth of the global population and economy, the increasing levels of various pollutants such as heavy metals, radionuclides, and organic/inorganic/biological toxins from various industries and human activities, which diffuse into aspects of the environment such as the atmosphere, soil, and natural water, have posed a serious threat to human health and the environment [...].