Jian-Hui Lan

A high efficient sorption of U(VI) from aqueous solution using amino-functionalized SBA-15

Uranium is one of the most hazardous heavy metal due to its long half-life radioactivity, high toxicity and mobility as aqueous uranyl ion (UO22+) under ordinary environmental conditions. Herein, amino functionalized SBA-15 (APSS) was developed as a rapid and efficient sorbent for removal of U(VI) from the environment. The APSS sample was synthesized by grafting method and was characterized by SEM, NMR, SAXS, and N2 sorption/desorption isothermal experiments. The sorption of U(VI) by APSS was investigated under different conditions of pH, contact time, initial U(VI) concentration, ionic strength and solid–liquid ratio. The results show that the sorption of U(VI) by APSS is strongly dependent on pH but independent of ionic strength and solid–liquid ratios (m/V). The sorption is ultrafast with an equilibrium time of less than 30xa0min, and the sorption capacity is as large as 409xa0mg/g at pH 5.3xa0±xa00.1. Besides, the U(VI) sorption by APSS from extremely diluted solution and the desorption of U(VI) from APSS were also studied. It is found that 100xa0mg of APSS can almost completely remove the U(VI) ions from 4xa0L aqueous solution with the U(VI) concentration as low as 4.2xa0ppb and the sorbed U(VI) can be completely desorbed by 0.1xa0mol/L nitric acid. The results strongly reveal the high performance of the APSS material in the removal and preconcentration of U(VI) from the aqueous solution.

Mesoporous silica SBA-15 functionalized with phosphonate and amino groups for uranium uptake

Mesoporous silicas have a very attractive ability of sorption and enrichment of metal ions due to their huge surface area and facile functionalization by organic ligands. In this work, phosphonate-amino bifunctionalized mesoporous silica SBA-15 (PA-SBA-15) as U(VI) sorbent was fabricated through post-grafting method. The obtained mesoporous silica was characterized by SEM, XRD, NMR and nitrogen sorption/desorption experiments, which revealed the existence of ordered mesoporous structure with uniform pore diameter and large surface area. The adsorptivity of PA-SBA-15 for U(VI) from aqueous solution was investigated using batch sorption technique under different experimental conditions. The preliminary results show that the U(VI) sorption by PA-SBA-15 is very quick with equilibrium time of less than 1 h, and the U(VI) uptake is as large as 373 mg/g at pH 5.5 under 95 °C. The sorption isotherm has been successfully modeled by the Langmuir isotherm, suggesting a monolayer homogeneous sorption of U(VI) in PA-SBA-15. The sorption is pH-dependent due to the pH-dependent charge of sorbent in the aqueous solution. The thermodynamics research shows that the sorption is a feasible and endothermic process. Based on these results, PA-SBA-15 could be a promising solid phase sorbent for highly-efficient removal of U(VI) ions from waste water and enrichment of U(VI) from a solution at a very low level.

Nanomaterials and nanotechnologies in nuclear energy chemistry

Abstract With the rapid growth of human demands for nuclear energy and in response to the challenges of nuclear energy development, the world’s major nuclear countries have started research and development work on advanced nuclear energy systems in which new materials and new technologies are considered to play important roles. Nanomaterials and nanotechnologies, which have gained extensive attention in recent years, have shown a wide range of application potentials in future nuclear energy system. In this review, the basic research progress in nanomaterials and nanotechnologies for advanced nuclear fuel fabrication, spent nuclear fuel reprocessing, nuclear waste disposal and nuclear environmental remediation is selectively highlighted, with the emphasis on Chinese research achievements. In addition, the challenges and opportunities of nanomaterials and nanotechnologies in future advanced nuclear energy system are also discussed.

New Three-Fold Interpenetrated Uranyl Organic Framework Constructed by Terephthalic Acid and Imidazole Derivative

A new 3-fold interpenetrated uranyl organic framework, UO2(bdc)(dmpi), was hydrothermally synthesized using 1,4-benzenedicarboxylic acid (H2bdc) and 1-(4-(1H-imidazol-1-yl)-2,5-dimethylphenyl)-1H-imidazole (dmpi). This framework, which was determined by synchrotron radiation X-ray, exhibited a new 3-fold interpenetrated (2,4)-connected topology with the Schläfli symbol of (12(6))(12)2. Additionally, large incurvation happened to the bond angle of [O=U=O](2+), which was always arranged in a rigorous line. Computational results based on density functional theory (DFT) indicated that the bent geometry of uranyl in UO2(bdc)(dmpi) was mainly due to the higher charge populations in the valence 6d shells of uranium, rendered by the electronegative imidazoles.

Orbital symmetry induced conductance switching in a graphene nanoribbon heterojunction with different edge hydrogenations

First principles calculations are performed to investigate the electron transport through a zigzag-edged graphene nanoribbon (ZGNR) heterojunction constructed by connecting a monohydrogenated ZGNR and a dihydrogenated ZGNR and its response to external magnetic fields. It is found that the heterojunction can be switched between a conducting state and an insulating state by tuning the magnetic fields. It arises from the matching or mismatching between the π or π* states of the two ribbons under different magnetic fields. This mechanism of conductance switching by tuning the orbital symmetry can be considered in the future design of graphene based electronic devices.

Adsorption of uranyl species on hydroxylated titanium carbide nanosheet: A first-principles study.

In this work, hydroxylated titanium carbide Ti3C2(OH)2, a representative of the two-dimensional transition metal carbides, has been predicted to be an effective adsorbent for uranyl ions in aqueous environments for the first time using density functional theory simulations. The calculations revealed that the uranyl ion can strongly bind with Ti3C2(OH)2 nanosheet in aqueous solution regardless of the presence of anionic ligands such as OH(-), Cl(-) and NO3(-). The bidentate coordination of uranyl to the surface is energetically more favorable than other adsorption configurations, and the uranyl ion prefers to bind with the deprotonated O adsorption site rather than the protonated one on the hydroxylated surface. During the adsorption process, the chemical adsorption as well as the formation of hydrogen bonds is the dominant factor.

Adsorption behavior of actinides and some typical fission products by silica/polymer-based isoHex-BTP adsorbent from nitric acid solution

The silica/polymer-based isoHex-BTP adsorbent (isoHex-BTP/SiO2-P) was prepared for partitioning Am(III) and Cm(III) from HLLW. Batch adsorption results showed that isoHex-BTP/SiO2-P exhibited high affinity and selectivity for Am(III) and Pu(IV) over U(VI), Ln(III) and other typical fission products in 3xa0molxa0dm−3 nitric acid. The effects of contact time, initial Dy(III) concentration and temperature on the adsorption of Dy(III) [as a simulated element of MA(III) and a representative element of Ln(III)] by isoHex-BTP/SiO2-P in 3xa0molxa0dm−3 nitric acid were investigated. The adsorption of Dy(III) fitted well to the pseudo-second-order kinetic model and the Langmuir isotherm model. The adsorption thermodynamic parameters revealed that the adsorption was a spontaneous, endothermic and entropy-driving process.

Theoretical studies on the complexation of Eu(III) and Am(III) with HDEHP: structure, bonding nature and stability

Separation of trivalent lanthanides (Ln(III)) and actinides (An(III)) is a key issue in the advanced spent nuclear fuel reprocessing. In the well-known trivalent actinide lanthanide separation by phosphorus reagent extraction from aqueous komplexes (TALSPEAK) process, the organophosphorus ligand HDEHP (di-(2-ethylhexyl) phosphoric acid) has been used as an efficient reagent for the partitioning of Ln(III) from An(III) with the combination of a holdback reagent in aqueous lactate buffer solution. In this work, the structural and electronic properties of Eu3+ and Am3+ complexes with HDEHP in nitric acid solution have been systematically explored by using scalar-relativistic density functional theory (DFT). It was found that HDEHP can coordinate with M(III) (M=Eu, Am) cations in the form of hydrogen-bonded dimers HL2- (L=DEHP), and the metal ions prefer to coordinate with the phosphoryl oxygen atom of the ligand. For all the extraction complexes, the metal-ligand bonds are mainly ionic in nature. Although Eu(III) complexes have higher interaction energies, the HL2- dimer shows comparable affinity for Eu(III) and Am(III) according to thermodynamic analysis, which may be attributed to the higher stabilities of Eu(III) nonahydrate. It is expected that this work could provide insightful information on the complexation of An(III) and Ln(III) with HDEHP at the molecular level.

Paving the way for the synthesis of a series of divalent actinide complexes: a theoretical perspective

Recently, the +2 formal oxidation state in soluble molecular complexes for lanthanides (La-Nd, Sm-Lu) and actinides (Th and U) has been discovered [W. J. Evans, et al., J. Am. Chem. Soc., 2011, 133, 15914; J. Am. Chem. Soc., 2012, 134, 8420; J. Am. Chem. Soc., 2013, 135, 13310; Chem. Sci., 2015, 6, 517]. To explore the nature of the bonding and stabilities of the low-valent actinide complexes, a series of divalent actinide species, [AnCp3](-) (An[double bond, length as m-dash]Th-Am, Cp = [η(5)-C5H4(SiMe3)](-)) have been investigated in THF solution using scalar relativistic density functional theory. The electronic structures and electron affinity properties were systematically studied to identify the interactions between the +2 actinide ions and Cp ligands. The ground state electron configurations for the [AnCp3](-) species are [ThCp3](-) 6d(2), [PaCp3](-) 5f(2)6d(1), [UCp3](-) 5f(3)6d(1), [NpCp3](-) 5f(5), [PuCp3](-) 5f(6), and [AmCp3](-) 5f(7), respectively, according to the MO analysis. The total bonding energy decreases from the Th- to the Am-complex and the electrostatic interactions mainly dominate the bonding between the actinide atom and ligands. The electron affinity analysis suggests that the reduction reaction of AnCp3→ [AnCp3](-) should become increasingly facile across the actinide series from Th to Am, in accord with the known An(iii/ii) reduction potentials. This work expands the knowledge on the low oxidation state chemistry of actinides, and further motivates and guides the synthesis of related low oxidation state compounds of 5f elements.

Theoretical insights into the separation of Am(III) over Eu(III) with PhenBHPPA

Due to the similar chemical properties of actinides An(iii) and lanthanides Ln(iii), their separation in spent nuclear fuel reprocessing is extremely challenging. A 1,10-phenanthroline dipicolinamide-based ligand (PhenBHPPA) has been identified to possess a selectivity for Am(iii) over Eu(iii) and could potentially be used for group actinide extraction. In this study, quasi-relativistic density functional theoretical calculations have been used to disclose the interaction mechanisms of Am(iii) and Eu(iii) complexes with PhenBHPPA. The electronic structures, bonding nature, QTAIM (Quantum Theory of Atoms in Molecules) analyses and thermodynamic behaviors of the Am(iii) and Eu(iii) complexes with PhenBHPPA have been explored in detail. According to the Wiberg bond indices (WBIs) and QTAIM analyses, interactions between the ligand and metal cations (Am(iii) and Eu(iii)) exhibit a weakly covalent character. Thermodynamic analyses show that the charged complexes [ML(NO3)2](+) appear to be the most stable species in the complexation processes. Moreover, it is more energetically favorable for PhenBHPPA to bind to Am(iii) compared to Eu(iii). Our study could render new insights into understanding the selectivity of the ligand towards minor actinides and the separation of An(iii) from Ln(iii) via liquid-liquid extraction.