INORGANIC CHEMISTRY
·
2021
·
IF 5.165
Rongzhen Xie,Nannan Shen,Xijian Chen,Jie Li,Yaxing Wang,Chao Zhang,Chengliang Xiao,Zhifang Chai,Shuao Wang
99Tc is one of the most abundant radiotoxic isotopes in used nuclear fuel with a high fission yield and a long half-life. Effective removal of pertechnetate (TcO4–) from an aqueous solution is important for nuclear waste separation and remediation. Herein, we report a series of facilely obtained benzene-linked guanidiniums that could precipitate TcO4– and its nonradioactive surrogate ReO4– from a high-concentration acidic solution through self-assembly crystallization. The resulting perrhenate and pertechnetate solids exhibit exceptionally low aqueous solubility. The benzene-linked guanidiniums hold one of the highest TcO4– removal capacities (1279 mg g–1) among previously reported materials and possess a removal percentage of 59% for ReO4– in the presence of Cl– over 50 times. The crystallization mechanism was clearly illustrated by the single-crystal structures and density functional theory calculations, indicating that TcO4– is captured through a charge-assisted hydrogen bonding interaction and stabilized by π–π stacking layers. In addition, the removal process is easily recycled and no toxic organic reagents are introduced. This work provides a green approach to preliminarily separate TcO4– from high-level nuclear wastes.
研究领域:
化学
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环境科学
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核能工程
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DOI
PubMed
高影响因子
INORGANIC CHEMISTRY
·
2023
·
IF 4.6
Yanqin Hu,Ben Qin,Xiaoyan Li,Fan Yang,Chuan-Pin Lee,Meiying Xie,Liyan Xue
With the development of nuclear energy, the reprocessing of 99TcO4–/ReO4– has become a very difficult problem due to environmental issues such as high output, long life, and easy leakage. In this study, three extraction systems containing carbamic acid were introduced into the reprocessing of 99TcO4–/ReO4– for the first time. The results involving one of the three results show that N-[N,N-di(2-ethylhexyl) aminocarbonylmethyl] glycine (D2EHAG) has ultrahigh selectivity for removal to 99TcO4–/ReO4–. When the extreme concentration ratio of SO42– and Cl– to ReO4– of D2EHAG is 10,000:1, the distribution coefficient of ReO4– still reaches 12.73 and 2.67, respectively. Additionally, the most hydrophilic NO3–, when the extreme concentration ratio of NO3– and ReO4– is 1000:1, still has a distribution coefficient close to 2.33, which is more than the most reported MOF adsorption materials. Moreover, the reaction kinetics, stripping rate, and reuse rate were studied. After five cycles, the removal rate is still 98.12%, with a decrease of less than 0.7%. The system containing carbamic acid is a potential extraction removal system to remove 99TcO4–/ReO4– from nuclear radioactive wastewater.
研究领域:
环境科学
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核化学
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放射性废物管理
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产品关联
DOI
PubMed
高影响因子
Toxics
·
2022
·Vol. 10
·期 10
·630
·
IF 4.472
Ben Qin,Yanqin Hu,Meiying Xie,Liyan Xue,Chunfa Liao,Fan Yang
The treatment of radioactive wastewater is one of the major problems in the current research. With the development of nuclear energy, the efficient removal of99TcO4−in radioactive wastewater has attracted the attention of countries all over the world. In this study, a novel functional polyamide polymer p-(Amide)-PAM was synthesized by the two-step method. The experimental results show that p-(Amide)-PAM has good adsorptive properties for99TcO4−/ReO4−and has good selectivity in the nitric acid system. The kinetics of the reaction of p-(Amide)-PAM with99TcO4−/ReO4−was studied. The results show that p-(Amide)-PAM has a fast adsorption rate for99TcO4−/ReO4−, the saturated adsorption capacity reaches 346.02 mg/g, and the material has good reusability. This new polyamide-functionalized polyacrylamide polymer material has good application prospects in the removal of99TcO4−from radioactive wastewater.Keywords:polyacrylamide;polyamidation;99TcO4−/ReO4−removal;polymer adsorption material
研究领域:
环境科学
·
核化学与放射化学
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产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Yalin Huang,Mu Ding,Jie Ding,Jinyang Kang,Zijun Yan,Pengwei Zhao,Xiaoyuan Zhou,Yongdong Jin,Shanyong Chen,Chuanqin Xia
Efficient removal of 99 TcO 4 − from nuclear wastewater is of great significance for the safe development of nuclear energy. In this work, a viologen-based cationic porous aromatic framework (TZ-PAF) was prepared as a novel sorbent for TcO 4 − . With 4,4′-bipyridine as the linker units, tetraphenylmethane was selected as the knot units to construct the diamond-like topology structure of TZ-PAF, which was benefit to its outstanding structural stability (thermal stability and acid resistance). The batch sorption experiments showed that TZ-PAF possessed fast sorption kinetics, higher sorption capacity (982 mg g −1 for ReO 4 − ) and a highest removal depth ( K d for TcO 4 − was 5.02 × 10 6 mL g −1 ), which could be attributed to the low-density skeleton of TZ-PAF resulting in the high density of sorption sites. XPS and SEM analyses revealed that the mechanism of TcO 4 − /ReO 4 − capture was attributed to an anion-exchanged process in which Cl − of TZ-PAF was replaced by ReO 4 − . And more, the excellent reusability to capture ReO 4 − from a highly acidic solution (64.6%) and a simulated nuclear wastewater (77.6%) were obtained. In general, this work exhibited a new sorbent for the highly efficient and deep removal of TcO 4 − form nuclear wastewater, and would provide a valuable insight into designing novel high-stability sorbents for wastewater treatment.
研究领域:
环境科学
·
材料科学
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产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Minsi Shi,Dingyang Chen,Xinyue Zhao,Yuyang Tian,Rui Zhao
High-efficiency capture of 99 TcO 4 − from radioactive wastewater and natural aqueous environment is urgently in demand. In this study, nonporous cationic polymeric networks (CPN-n) were employed as the building units to construct the cationic porous aromatic frameworks (iPAF-10) through a molecular expansion strategy. This process was simple and efficient, in which iPAF-10 with fast mass transfer channels and high adsorption site utilization was achieved. In addition, this strategy could also improve the materials’ stability in highly acidic and alkaline conditions. Remarkably, compared with CPN-n, iPAF-10 exhibited rapid kinetics (3 min) and a high adsorption capacity of 1287 mg g −1 toward ReO 4 − (a safe alternative to 99 TcO 4 − ), ranking iPAF-10 among the top in existing advanced 99 TcO 4 − /ReO 4 − adsorbents. iPAF-10 also maintained the stable removal of ReO 4 − from excess competition anions (NO 3 − and SO 4 2− ), high acid/alkali (1 M HNO 3 and 2 M NaOH) and radiation condition (200 kGy). As a result, iPAF-10 showed satisfying ReO 4 − elimination performance from simulated Hanford and Savannah River Site waste streams. The anion exchange mechanism during adsorption and desorption processes was clearly elucidated through experimental and computational analysis. This work demonstrated the synthesis of new cationic porous aromatic frameworks, which showed great potential for 99 TcO 4 − /ReO 4 − removal from wastewater.
研究领域:
环境科学
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材料科学
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产品关联
DOI
高影响因子
Journal of Environmental Chemical Engineering
·
2024
·
IF 7.4
Long Li,Xuanhao Huang,Xiaoyang Hu,Xingyue Liu,Rui Li,Hang Zhou,Fengfeng Li,Fangxiang Luo,Qingjiang Pan,Songdong Ding
Efficient and selective extraction of pertechnetate (TcO 4 − ) from nitric acid medium has become a significant challenge, especially in the presence of a large excess of interfering anions. By employing a combined strategy involving H-bonding and electrostatic interaction, a highly selective extraction of TcO 4 − can be achieved. The present work reports three homologous amine-diamide ligands with different alkyl chain lengths on the amine N atom of 2,2′-(metylimino)bis( N , N -dioctylacetamide) (MIDOA), 2,2′-(butylimino)bis( N , N -dioctylacetamide) (BIDOA) and 2,2′-(octylimino)bis( N , N -dioctylacetamide) (OIDOA), and their extraction behaviors for TcO 4 − /ReO 4 − in HNO 3 solution are also investigated by using n -dodecane as a diluent. It has been shown that all of them exhibit excellent extractability and high selectivity to TcO 4 − /ReO 4 − . Their extractability and phase disengagement follow the order of OIDOA > BIDOA > MIDOA, revealing a greater extractability and rapider phase disengagement for the amine-diamide ligand with longer chain substituents on the amine N atom. Both slope analysis and loading capacity test indicate the formation of 1:1 metal/ligand extracted complex, which is also confirmed by the analyses of single-crystal X-ray diffraction (SC-XRD), electrospray ionization mass (ESI-MS), Fourier transform infrared (FT-IR), and X-ray photoelectron spectroscopy (XPS). The extraction of TcO 4 − /ReO 4 − by the amine-diamide ligand follows the anion exchange extraction model and is a spontaneous and endothermic process. Furthermore, a competing extraction test was also conducted and demonstrates excellent extractability and high selectivity to TcO 4 − /ReO 4 − .
研究领域:
化学
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核化学与放射化学
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环境科学
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产品关联
DOI
高影响因子
Environmental Chemistry Letters
·
2020
·Vol. 18
·期 4
·1379-1388
·
IF 5.922
Zhang Hao,Yang Fan,Lu Chuan,Du Chang,Bai Ruixi,Zeng Xian,Zhao Zhigang,Cai Chunqing,Li Jianguo
Treatment and recycling of radioactive waste are major challenges for the nuclear energy sector. Pertechnetate anions, 99 TcO 4 − , occur in nuclear waste and are formed mainly during nuclear fission. 99 TcO 4 − is a very hazardous contaminant due to its long half-life and high solubility and mobility in water. The effective capture of 99 Tc contamination at legacy nuclear sites remains a serious and unsolved environmental issue. In this work, 99 TcO 4 − /ReO 4 − was adsorbed by compressible graphene–chitosan sponges with grafted tertiary amine groups. Moreover, the hydrophobic branched chains strongly reduced the interference of competitive anions during adsorption. Results show that 99 TcO 4 − /ReO 4 − can be effectively removed even under highly acidic conditions and in the presence of competing anions. More than 98% of 99 TcO 4 − /ReO 4 − was removed using simulated nuclear wastes.
研究领域:
环境科学
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核能工程
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
Chemical Science
·
2019
·Vol. 10
·期 15
·4293-4305
·
IF 9.556
Linwei He,Shengtang Liu,Long Chen,Xing Dai,Jie Li,Mingxing Zhang,Fuyin Ma,Chao Zhang,Zaixing Yang,Ruhong Zhou,Zhifang Chai,Shuao Wang
99Tc is one of the most problematic fission products in the nuclear fuel cycle owing to its large inventory in used nuclear fuel, long half-life, potential radiation hazard, high environmental mobility of its major species 99TcO4−, and its redox-active nature. Ideally, 99TcO4− should be removed at the first stage, when the used fuel rods are dissolved in highly concentrated nitric acid solution, which can substantially reduce its interference with the solvent extraction process through catalytic redox reactions with the key actinides and diminish the chance of discharge into the environment as the volatile species during the waste vitrification process. However, this task cannot be achieved by any of the reported anion-scavenging materials including traditional polymeric anion-exchange resins, inorganic cationic framework materials, and recently developed cationic metal–organic framework materials, because they either are not stable under the extreme conditions of the combined high acidity and strong radiation field or do not possess the required uptake selectivity towards 99TcO4− in the presence of a huge excess of competing anions such as NO3− and SO42−. Herein, we present the first study of 99TcO4− removal under extreme conditions by a two-dimensional conjugated cationic covalent organic framework material, SCU-COF-1. This material exhibits ultrahigh acid stability, great resistance towards both large-dose β and γ irradiation and unprecedented 99TcO4− uptake capabilities including extremely fast sorption kinetics (sorption equilibrium can be reached within 1 min), ultrahigh uptake capacity (702.4 mg g−1 for the surrogate ReO4− at a slightly elevated temperature), and good anion-exchange selectivity towards 99TcO4−. These excellent features endow SCU-COF-1 with the practical capabilities of separating 99TcO4− from both simulant highly acidic fuel reprocessing solutions (3 M nitric acid) and low-activity waste streams at the US legacy nuclear site. The anion-exchange mechanism and the 99TcO4− uptake selectivity are further demonstrated and clearly visualized by the molecular dynamics simulation investigations.
研究领域:
核化学与放射化学
·
材料科学
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环境科学
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产品关联
DOI
PubMed
高影响因子
ACS Applied Polymer Materials
·
2024
·
IF 4.4
Jiang Liu,Zhaoheng Zhu,Yukun Huang,Long Wang,Kai Jia
There is a critical need to develop cost-effective and efficient adsorption materials for the removal of technetium-99 (99Tc) from contaminated water sources. This research presents the synthesis of amino-modified cellulose microspheres (CM-APTS) through the addition of 3-amino-propyl triethoxysilane (APTS) to regenerated cellulose microspheres (CM), followed by a subsequent reaction with ethylene dibromide (EDB) to produce halogen-modified amino cellulose microspheres (CM-APTS-EDB). These are engineered for the effective absorption of ReO4–, serving as a chemical surrogate for TcO4–. By altering the amount of ethylene dibromide used, two variations of bromine-modified cellulose microspheres, CM-APTS-EDBs and CM-APTS-EDBe, are synthesized. Among these, CM-APTS-EDBe exhibits robust adsorption capabilities for ReO4– across a pH spectrum of 2.5–10, attaining a peak capacity of 281 mg·g–1, and demonstrates selective adsorption of ReO4– even in the presence of competing anions such as NO3–, Cl–, and SO42–. Characterization through X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FTIR) indicates that the adsorption mechanism predominantly involves interactions between ReO4– and N+, hydrogen bonding with amino hydrogen, and σ-hole-anion interactions between Re–O and C–Br. After eight adsorption–desorption cycles, CM-APTS-EDBe retains notable stability and reusability. Additionally, the material efficiently captures ReO4– from simulated Hanford Low Activity Waste (LAW) wastewater, achieving an adsorption efficiency of 77.26% at a solid–liquid ratio of 40 g·L–1. This investigation underlines the potential of halogenated regenerated cellulose microspheres in designing advanced adsorbents for the removal of radioactive pollutants like TcO4–/ReO4–, offering a strategy for environmental remediation efforts.
研究领域:
环境科学
·
放射化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
DESALINATION
·
2026
·
IF 9.9
Xiangjun Liao,Huining Zhang,Yuxiao Tian,Guangtai Zheng,Shijian Pan,Jing Chen,Yuri A. Ustynyuk,Valentin G. Nenajdenko,Yuan Liao,Cheng-peng Li
The sustainable and efficient treatment of high-salinity radioactive wastewater containing 99 TcO 4 − represents a critical challenge, driven by the severe environmental risks of 99 TcO 4 − and the inadequacy of existing treatment technologies. Here, we introduced membrane distillation (MD) as a novel approach for such wastewater and developed a robust superhydrophobic membrane (# PVDF-PN ) that simultaneously resisted wetting and scaling while overcoming the conventional selectivity-permeability trade-off. The # PVDF-PN was fabricated through in situ hydrolysis and polymerization of trichloromethylsilane (TCMS) on hydroxylated polyvinylidene fluoride (PVDF), yielding a surface densely covered with low-surface-energy polysiloxane nanofilaments. This unique nanofilament architecture significantly enhanced the gas-liquid interfacial area for vapor evaporation, without compromising pore integrity or permeability due to surface modification. When tested with challenging feeds containing surfactants or supersaturated gypsum, # PVDF-PN maintained a stable flux of ∼33.0 kg·m −2 ·h −1 and near-complete salt rejection (>99.99%), outperforming both unmodified # PVDF and fluorinated silica-coated # PVDF-FS . Its exceptional performance was attributed to a high liquid entry pressure, an elevated energy barrier for crystal nucleation, and reduced liquid-solid contact area and interaction time. Importantly, in long-term MD treatment of simulated 99 TcO 4 − /ReO 4 − -laden high-salinity wastewater, # PVDF-PN achieved non-detectable effluent concentrations of target oxyanions, demonstrating its potential as a reliable and efficient solution for radioactive wastewater management and emergency response.
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产品关联
DOI
高影响因子
CHINESE JOURNAL OF CHEMICAL ENGINEERING
·
2025
·
IF 3.7
Tangzheng Lu,Jiayi Feng,Yong Kang
The design of highly stable and efficient porous materials is crucial for physisorption-based separation of radioactive species ( 99 TcO 4 - /ReO 4 - ), serving as an alternative to current concentrate-storage-solidification treatment technologies. Herein, employing a covalent-ionic dual-crosslinking strategy with economical ionic compounds as reactive monomers, a novel cationic organic polymer (TJU-COP-1) was synthesized for the first time via facile radical polymerization for 99 TcO 4 - /ReO 4 - sequestration. TJU-COP-1 demonstrates exceptional adsorption capacity, kinetics and selectivity ( K d ) for 99 TcO 4 - /ReO 4 - (861.87 mg·g –1 , K d = 5.0 × 10 5 ml·g -1 ), achieving adsorption equilibrium within merely 1 min. Notably, TJU-COP-1 maintains adsorption efficiency as high as 96.25% after five adsorption-desorption cycles. The TJU-COP-1 showed high stability after acid (3 mol·L –1 HNO 3 ), alkali (3 mol·L –1 NaOH) and radiation (200 kGy 60 Co γ) treatment. More significantly, TJU-COP-1 demonstrated robust and promising removal performance in complex solution, achieving 98.55% efficiency for 99 TcO 4 - /ReO 4 - amid high concentrations of competing anions and an excellent 72.11% removal in simulated Hanford LAW waste solution. Combined experimental characterization and density functional theory theoretical validation confirmed that the adsorption mechanism involves a synergistic combination of electrostatic interactions and anion exchange. This study illustrates that TJU-COP-1 has great potential for practical application in the capture of 99 TcO 4 - /ReO 4 - , and provides a new approach to the design of high-performance adsorbents for the treatment of nuclear wastewater.
研究领域:
环境科学
·
材料化学
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核化学
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吸附技术
·
聚合物化学
✓ 已验证
产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2025
·
IF 9
Yinshan Zhang,Yingcai Wang,Guolin Huang,Zhibin Zhang,Yunhai Liu
Technetium-99 ( 99 Tc), predominantly exists as the form of hypermobile 99 TcO 4 − anion, poses dual issues in separation interference and environmental pollution risks in nuclear wastewater. This study engineered a hydrospongel adsorbent through emulsion-templated polymerization and a new concept of swelling-induced pore reconfiguration (SIPR) was defined. The long-standing trade-off between adsorption rate and capacity get to reconcile driven by SIPR strategy. Interconnected pore construction effectively minimized trans -scale mass transfer resistance while the specific recognition sites anchored in internal get fully exposure, enabling record 99 TcO 4 − uptake kinetics (equilibrium within 5 min) and exceptional saturation capacity (884.95 mg g −1 ) in shapeable adsorbents. Integrating experiments and density functional theory (DFT) reveal dual mechanism of molecular electrostatic-chelating assisted ion exchange trapping 99 TcO 4 − . This adaptive design overcame the dual restrictions of spatial-scale and steric hindrance of adsorption sites in traditional adsorbents, establishing a paradigm for interconnected pore polymer adsorbents expand into engineering applications in nuclear wastewater remediation.
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DOI
高影响因子
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