Study on the electrodeposition of uranium in chloride molten salt.

This study focuses on the recovery of UO2 from oxide spent fuel using electrodeposition. U3O8 was used as the initial material and dissolved in NaCl-2CsCl using NH4Cl at high temperatures by means of chlorination reaction. The electrolysis process was conducted using a three-electrode system to investigate the effects of cathode material and diameter, electrolysis temperature, electrolysis time, electrolysis voltage, and uranium concentration in the molten salt on the electrolysis reaction. By optimizing the electrolysis conditions, pure UO2 with a recovery efficiency of 97% was obtained, and the products were characterized using XRD, SEM-EDS, ICP-AES and XPS. It was found that within the scope of this experiment, increasing the cathode diameter, extending the electrolysis time, and increasing the reduction voltage appropriately all led to an improvement in the recovery efficiency of the electrolysis reaction, while other conditions had minimal effect on the reaction. Furthermore, doping of the electrolyte system was performed by adding La, Ce and Nd elements, while the removal of La showed good purification effects, with a maximum decontamination factor of 119. Furthermore, the system showed good purification effects for Nd, with a decontamination factor of 57.

Ion sieving in graphene oxide membrane enables efficient actinides/lanthanides separation.

Separation of actinides from lanthanides is of great importance for the safe management of nuclear waste and sustainable development of nuclear energy, but it represents a huge challenge due to the chemical complexity of these f-elements. Herein, we report an efficient separation strategy based on ion sieving in graphene oxide membrane. In the presence of a strong oxidizing reagent, the actinides (U, Np, Pu, Am) in a nitric acid solution exist in the high valent and linear dioxo form of actinyl ions while the lanthanides (Ce, Nd, Eu, Gd, etc.) remain as trivalent/tetravalent spheric ions. A task-specific graphene oxide membrane with an interlayer nanochannel spacing between the sizes of hydrated actinyl ions and lanthanides ions is tailored and used as an ionic cut-off filter, which blocks the larger and linear actinyl ions but allows the smaller and spheric lanthanides ions to penetrate through, affording lanthanides/actinides separation factors up to ~400. This work realizes the group separation of actinides from lanthanides under highly acidic conditions by a simple ion sieving strategy and highlights the great potential of utilizing graphene oxide membrane for nuclear waste treatment.

Experimentally and Theoretically Revealing the Co-Doping Effects of Ce-Sr in Gd2Zr2O7.

To safely dispose radioactive waste (including, e.g., thorium and radiostrontium), Ce4+ and Sr2+ were chosen as simulated surrogates of α and ß waste and were introduced into the Gd3+ site in Gd2Zr2O7 to maintain the average cationic radius and to compensate for charge. A series of Gd2-xSrx/2Cex/2Zr2O7 (0.00 ≤ x ≤ 0.25) compounds were examined by experimental and theoretical calculations to investigate the co-doping effects of α and ß waste in a Gd2Zr2O7-based matrix. The effects of Ce4+ and Sr2+ content on the phase, unit cell parameters, active modes, mechanical property, and microstructure were studied systematically. Moreover, the limit of incorporation of Ce4+ and Sr2+ in Gd2Zr2O7 pyrochlore and the lattice parameters were also calculated through virtual crystal approximation theory, and the results were found to well agree with experimental results.

Metal-enhanced fluorescence of graphene oxide sheets.

Graphene oxide (GO) is an excellent chemical tunable optical platform for imaging and sensing. The photoluminescence (PL) quantum yield of GO is relatively low, which limited the application of the intrinsic and tunable fluorescence from GO. Here, we report the first case of metal-enhanced fluorescence (MEF) of GO. A significant enhancement (~10-fold) in fluorescence intensity is observed from GO on the Ag substrate as compared to that on the glass. FL, Raman, and SEM images are used to investigate the MEF behavior and are coincident with each other. The influence of the metal particle size of Ag substrate is investigated. The fluorescence is also found to be responsive when adding different metal ions into GO solution. GO contacting directly with metal substrate exhibits strong MEF without quenching, which makes it possible to use GO sheets for three-dimension optical imaging and sensing.

Application of carbon dots and their composite materials for the detection and removal of radioactive ions: A review.

Radioactive ions with high-heat release or long half-life could cause long-term influence on environment and they might enter the food chain to damage human body for their toxicity and radioactivity. It is of great importance to develop methods and materials to detect and remove radioactive ions. Carbon dots and their composite materials has been applied widely in many fields due to their plentiful raw materials, facile synthesis and functional process, unique optical property and abundant functional groups. This comprehensive review focuses on the preparation of CDs and composite materials for the detection and adsorption of radioactive ions. Firstly, the recent-developed synthetic methods for CDs were summarized briefly, including hydrothermal/solvothermal, microwave, electrochemistry, microplasma, chemical oxidation methods, focusing on the influence of CDs properties. Secondly, the synthetic methods for CDs composite materials were classified to four categories and summarized generally. Thirdly, the application of CDs for radioactive ions detection and adsorption were explored and concluded including uranium, iodine, europium, strontium, samarium et al. Finally, the detection and adsorption mechanism for radioactive ions were searched and the perspective and outlook of CDs for detection and adsorption radioactive ions have been proposed based on our understanding.

Graphene Oxide Membranes for Tunable Ion Sieving in Acidic Radioactive Waste.

Graphene oxide (GO) membranes with unique nanolayer structure have demonstrated excellent separation capability based on their size-selective effect, but there are few reports on achieving ion-ion separation, because it is difficult to inhibit the swelling effect of GO nano sheets as well as to precisely control the interlayer spacing d to a specific value between the sizes of different metal ions. Here, selective separation of uranium from acidic radioactive waste containing multication is achieved through a precise dual-adjustment strategy on d. It is found that GO swelling is greatly restricted in highly acidic solution due to protonation effect. Then the interlayer spacing is further precisely reduced to below the diameter of uranyl ion by increasing the oxidation degree of GO. Sieving uranyl ions from other nuclide ions is successfully realized in pH =3-3 mol L-1 nitric acid solutions.

Single-strand DNA-scaffolded copper nanoclusters for the determination of inorganic pyrophosphatase activity and screening of its inhibitor.

A fluorescence method for the determination of inorganic pyrophosphatase (PPase) activity has been established based on copper nanoclusters (CuNCs). The polythymine of 40 mer (T40) acts as a template for the reduction reaction from Cu2+ to Cu0 by ascorbic acid (AA). This reaction leads to the formation of fluorescent CuNCs with excitation/emission peaks at 340/640 nm. However, the higher binding affinity between inorganic pyrophosphate (PPi) and Cu2+ hinders the effective formation of CuNCs. This shows low fluorescence intensity. PPase catalyzes the hydrolysis of PPi into Pi during which free Cu2+ ions are produced. This facilitates the formation of fluorescent CuNCs. Thus, the fluorescence intensity was restored. The fluorescence enhancement of the system has a linear relationship with PPase activity in the range 0.3 to 20 mU·mL-1, and the detection limit is0.2 mU·mL-1. The relative intensity (I/I0) at 640 nm for the analytical solution versus system is also employed to screen the inhibitor for PPase with high efficiency. Graphical abstract Schematic representation of a fluorescent assay for the determination of inorganic pyrophosphatase activity and screening its inhibitor based on single-strand polythymine-scaffolded copper nanoclusters.

In situ monitoring of catalytic reaction on single nanoporous gold nanowire with tuneable SERS and catalytic activity.

Single nanoporous gold nanowire was introduced as a tunable one-dimensional nano-sensor platform with both SERS and catalytic activity, and it precisely fit the requirement of materials for in situ SERS monitoring of plasmon-assisted catalytic reaction. The nanoporous gold nanowires exhibited much more "hot spots" on their surface and much better SPR effect than the smooth nanowires. We demonstrated that these nanowires could be used as a SERS substrate assuring the sensitivity and reproducibility of Raman signals. Besides, they could be applied as a kind of heterogeneous catalyst for in situ SERS monitoring of the plasmon-assisted catalytic reaction-reduction of p-nitrothiophenol (p-NTP) to p,p-dimercaptoazobenzene (DMAB) at their surface. The SERS and catalytic activity of the nanowires could be respectively optimized by adjusting their dealloying time, similar to the procedure of catalyst screening.

DNA-scaffold copper nanoclusters integrated into a cerium(III)-triggered Fenton-like reaction for the fluorometric and colorimetric enzymatic determination of glucose.

A fluorometric and colorimetric method are described for the determination of hydrogen peroxide and glucose by integrating copper nanoclusters (CuNCs) into a Fenton-like reaction. The mechanism mainly depends on the fast formation of long-strand DNA-templated CuNCs with strong red fluorescence (with excitation/emission maxima at 340/640 nm) in the absence of H2O2. The DNA can be cleaved into short-oligonucleotide fragments by hydroxy radicals as formed in the Ce(III)-triggered Fenton-like reaction in the presence of H2O2. As a result, short-strand DNA loses the ability as a template for the formation of CuNCs. This leads to a decrease of fluorescence. The colorimetric assay, in turn, is based on the oxidation of colorless Ce(III) ions to the distinctly yellow Ce(IV) ions (with an absorption maximum at 400 nm) by H2O2. Compared with those assays based on the use of enzyme mimics, this method does not require any chromogenic substrates such as ABTS and TMB. Based on the dual-signal readout platform, we successfully achieved the detection of H2O2 and glucose. LODs are as low as 0.266 µM and 2.92 µM. The methods were applied to the sensitive determination of glucose by using glucose oxidase (GOx) which catalyzes the oxidization of glucose to produce H2O2. The practical application was demonstrated by determination of glucose in human serum, with apparent recoveries of 98.4-101.9% and 99.1-105.6%, respectively. The concentration of glucose ranges from 1 to 500 µM and 50 to 600 µM based on the dual-signal readout platform, respectively. This fluorometric and colorimetric dual-mode strategy will pave a new avenue for constructing effective assays for H2O2-related analytes in biochemical and clinical applications. Graphical abstractSchematic representation of a fluorometric and colorimetric dual-readout strategy for the sensitive determination of hydrogen peroxide and glucose. The assay has been designed by integrating copper nanoclusters into a Ce(III)-triggered Fenton-like reaction.

Iodide-assisted silver nanoplates for colorimetric determination of chromium(III) and copper(II) via an aggregation/fusion/oxidation etching strategy.

The authors have studied the role of different ligands on the surfaces of silver nanoplates for regulating their analytical applications. Citrate-capped silver nanoplates are applied for the detection of chromium ions (Cr3+) based on aggregation of silver nanoplates. Cr3+ can cause aggregation through high affinity between Cr3+ and carboxylate groups of citrates, resulting in a color change from dark yellow to purple and at last colorless. The detection limit is 8.0 nM. This system shows excellent selectivity in the presence of a variety of other metal ions. Further, silver nanoplates coupled with iodide ions are employed for the colorimetric determination of copper ions (Cu2+) based on a new strategy of fusion/oxidation etching nanoplates. When Cu2+ is introduced into this silver nanoplate system, Cu2+ can oxidize I- to iodine (I2), which can further oxidize silver to form silver iodide (AgI). Simultaneously, the solution color changes from dark yellow to colorless. The lower limit detection is 0.27 µM. This assay exhibits excellent selectivity for Cu2+ over other environmental metal ions. It is perceived that this design concept will open up a fresh insight of simple, rapid and reliable detection of other heavy metal ions in drinking water and environmental samples. Graphical abstract Iodide-assisted silver nanoplates can be used for the colorimetric and visual ldetermination of Cr3+ and Cu2+ based on an aggregation/fusion/oxidation etching mechanism. These systems allows selective and sensitive determination of the ions in real samples.

Cyclodextrin functionalized 3D-graphene for the removal of Cr(VI) with the easy and rapid separation strategy.

As a useful heavy metal ion, chromium has seen its applications in various fields. While it is also a toxic contaminant in water and may cause serious threats to the environment and human health. To develop a novel material with good adsorption capacity and easy solid-liquid separation strategy was necessary and significant. In this paper, the ß-cyclodextrin (ß-CD) functionalized three-dimensional structured graphene foam (CDGF) was successfully synthesized with the facile and one-step hydrothermal method. The SEM, BET, XRD, FT-IR and XPS analysis were carried out and the results confirmed the successfully grafting of ß-CD onto GF. The batch adsorption of Cr(VI) was also taken out and the CDGF possessed good selectivity compared with other metal ions at pH = 3. The adsorption capacity reduced gradually as the initial pH of the Cr(VI) solution grew higher, which was because the anionic species of Cr(VI) were partial to the positively charged surface of CDGF. The easy separation strategy of the CDGF was also demonstrated and the CDGF could be taken out easily with a tweezer after the adsorption of Cr(VI), which significantly simplified the separation procedure and reduced time. By comparing the FT-IR and XPD analysis results, the adsorption mechanism was explored and the hydroxyl groups on CDGF played the main role in the adsorption process. This work brings a novel material for the adsorption of Cr(VI) from water and provides an innovative direction for the easy and fast solid-liquid separation strategy in the adsorption and other application fields.

Quantitative Analysis of Surface Sites on Carbon Dots and Their Interaction with Metal Ions by a Potentiometric Titration Method.

Carbon dots (CDs) possess abundant functional groups on their surface which are related to their application in various fields such as sensing, imaging, and catalysis. Understanding the amount and properties of these functional groups and their interaction with metal ions is essential but has posed longstanding challenges because of the diverse and complex structures of CDs. In this work, potentiometric titration is demonstrated as an effective method to figure out the categories and amounts of functional groups. Surface complexation modeling with the FITEQL program was applied to the quantification of the surface sites on CDs with the titration data. Then with the obtained molar concentrations of the surface sites, the pKas of these surface sites were calculated with the Hyperquad program. Finally, titration experiments of CDs with and without Fe(III) were carried out and the stability constants of Fe(III) and ArgCDs were simulated on the Hyperquad program. By utilizing the stability constants, the distribution of Fe(III) species at different pHs and the concentrations of Fe(III) and CDs were also investigated. This potential method might be used for characterizing the surface sites on other CDs or even other soluble nanoparticles as well as for investigating the interactions of the surface sites with different metal ions.

Localized Surface Plasmon Resonance Meets Controlled/Living Radical Polymerization: An Adaptable Strategy for Broadband Light-Regulated Macromolecular Synthesis.

The photophysical process of localized surface plasmon resonance (LSPR) is, for the first time, exploited for broadband photon harvesting in photo-regulated controlled/living radical polymerization. Efficient macromolecular synthesis was achieved under illumination with light wavelengths extending from the visible to the near-infrared regions. Plasmonic Ag nanostructures were in situ generated on Ag3 PO4 photocatalysts in a reversible addition-fragmentation chain transfer (RAFT) system, thereby promoting polymerization of various monomers following a LSPR-mediated electron transfer mechanism. Owing to the LSPR-enhanced broadband photon harvesting, high monomer conversion (>99 %) was achieved under natural sunlight within 0.8 h. The deep penetration of NIR light enabled successful polymerization with reaction vessels screened by opaque barriers. Moreover, by trapping active oxygen species generated in the photocatalytic process, polymerization could be implemented without pre-deoxygenation.

DNA-templated copper nanoclusters as a fluorescent probe for fluoride by using aluminum ions as a bridge.

A selective fluorescent on-off-on probe has have designed for the detection of fluoride (F-) ions based on DNA-templated copper nanocluster (CuNCs) and by using aluminum(III) ions as a bridge. A 40-mer polythymine acts as a template for the reduction of Cu(II) to Cu(0) by ascorbic acid. This result is the formation of red fluorescent CuNCs, with excitation/emission peaks at 340/640 nm. After addition of Al3+ ions, the fluorescence of CuNCs is quenched because the interaction of Al3+ and DNA disturbs the formation of DNA-templated CuNCs. Fluorescence is restored on addition of fluoride to the system. This is due to the desorption of Al3+ from the DNA and the formation of the Al(OH)3F- complex. This system displays a fast fluorometric response to fluoride, with high selectivity over other anions. Fluorescence increases linearly in the 2 to 150 µM F- concentration range, and the detection limit is 1.0 µM. This probe has been successfully used for the detection of F- ions in four brands of toothpaste. The method is rapid, cost-effective, selective, and does not require toxic solvents and reagents. Graphical abstract Schematic presentation of a method for fluorometric determination of fluoride by using DNA-templated copper nanoclusters (CuNCs) and using aluminum(III) as a bridge. The red fluorescence of the CuNCs is quenched in the presence of Al(III) ions but restored after addition of fluoride.

Microplasma Anode Meeting Molten Salt Electrochemistry: Charge Transfer and Atomic Emission Spectral Analysis.

Molten salt electrolysis is normally conducted with solid anode, such as noble metal or graphite, which has defects such as high cost or emission of carbon oxide. Herein, we report that a microplasma based on atmospheric-pressure glow discharge could act as a kind of gaseous anode for electrolysis in molten salt. When the Ag/Ag+ redox couple was chosen as the research object, the microplasma anode could initiate charge-transfer reactions in the molten salt and Ag could be electrodeposited with current efficiency of above 90%. The microplasma anode has also shown excellent anticorrosive performance in both chloride and carbonate molten salt. Furthermore, the microplasma anode could potentially serve as an excitation source of atomic emission spectrometry (AES), making it possible to determine the concentration of Ag ions in the molten salt in situ and in real-time. With properties such as being carbon-free and having corrosion resistance and extensive utilization for analysis, the microplasma anode has opened a new direction for molten salt electrochemistry.

On-off-on luminescent pyrophosphate probe based on the use of Mn-doped ZnS quantum dots and using Eu(III) as a mediator.

A selective phosphorescent on-off-on probe with long decay lifetime has been designed for the detection of pyrophosphate ions (PPi). The detection scheme is based on the use of europium(III)-modulated Mn(II)-doped ZnS quantum dots capped with N-acetyl-L-cysteine. Both the aggregation of quantum dots and electron transfer induced by Eu(III) ions cause phosphorescence to be quenched ("off" state). Phosphorescence is, however, restored on addition of PPi to the system ("on" state). The effect is attributed to the removal of Eu(III) from the carboxy groups on the surface of the quantum dots owing to the stronger interaction between PPi and Eu(III). A linear relationship exists between phosphorescence intensity (best measured at excitation/emission wavelengths of 316/594 nm) and PPi concentration in the 400 nM to 6000 nM with a detection limit of 145 nM. An additional attractive feature is provided by the long-lived phosphorescence (1920 µs) of the quantum dots. It can be used to eliminate interference by short-lived fluorescence in biological samples by performing time resolved measurements. The probe was applied to the determination of PPi in spiked in urine samples and gave recoveries in the range from 98 to 105% with RSDs of <2.0%. Graphical abstract Schematic of a long-lived phosphorescent on-off-on probe for the sensitive and selective detection of pyrophosphate ions (PPi). It is based on the use of Eu(III)-modulated Mn(II)-doped ZnS quantum dots (QDs). Phosphorescence is quenched of QDs after the addition of Eu3+but restored after the addition of PPi.

Dispersion-aggregation-dispersion colorimetric detection for mercury ions based on an assembly of gold nanoparticles and carbon nanodots.

Mercury is a common heavy metal element in natural systems and is highly toxic to the human body. Herein, a novel colorimetric detection of Hg2+ ions is proposed based on the aggregation of gold nanoparticles (AuNPs) induced by carbon quantum dots (CDs) with the assistance of glutathione (GSH). In this sensing system, the AuNP/CDs composite forms through Au-N bonds. Simultaneously, the color of the solution turns from wine red to blue. The well-dispersed AuNPs can be restored after the addition of GSH, because GSH competes with CDs to bind onto the surface of AuNPs and protect AuNPs from aggregation. In the presence of Hg2+ ions, GSH can chelate with Hg2+ to form a complex, which subsequently enables CDs to facilitate the aggregation of the AuNPs again. Therefore, according to the red-to-blue color change, a colorimetric sensor is established for the sensitive and selective detection of Hg2+ with a detection limit of 7.5 nM. Moreover, this sensor is successfully used to detect Hg2+ spiked in environmental water. This very simple and cost-effective strategy will promote the development of a colorimetric sensor for the determination of other metal ions in biological and environmental fields.

Heteroatom-Doped Carbon Dots (CDs) as a Class of Metal-Free Photocatalysts for PET-RAFT Polymerization under Visible Light and Sunlight.

A key challenge of photoregulated living radical polymerization is developing efficient and robust photocatalysts. Now carbon dots (CDs) have been exploited for the first time as metal-free photocatalysts for visible-light-regulated reversible addition-fragmentation chain-transfer (RAFT) polymerization. Screening of diverse heteroatom-doped CDs suggested that the P- and S-doped CDs were effective photocatalysts for RAFT polymerization under mild visible light following a photoinduced electron transfer (PET) involved oxidative quenching mechanism. PET-RAFT polymerization of various monomers with temporal control, narrow dispersity (D≈1.04), and chain-end fidelity was achieved. Besides, it was demonstrated that the CD-catalyzed PET-RAFT polymerization was effectively performed under natural solar irradiation.

Time-resolved determination of Fe(II) ions using cysteine-bridged Mn-doped ZnS quantum dots as a phosphorimetric probe.

A time-resolved phosphorescence (TRP) is applied to the highly sensitive determination of Fe(II) ions. The method is based on the use of a phosphorescent probe consisting of cysteine-bridged Mn-doped ZnS quantum dots (Mn/ZnS QDs). The presence of cysteine enhances the phosphorescence of the QDs and also increases the efficiency of quenching caused by Fe(II) ions. This results in strongly improved selectivity for Fe(II). The linear response is obtained in the concentration range of 50-1000 nM with a 19 nM detection limit. Phosphorescence is recorded at excitation/emission peaks of 301/602 nm. The interference of short-lived fluorescent and scattering background from the biological fluids is eliminated by using the TRP mode with a delay time of 200 µs. The determination of Fe(II) in human serum samples spiked at a 150 nM level gave a 92.4% recovery when using the TRP mode, but only 52.4% when using steady-state phosphorescence. This demonstrates that this probe along with TRP detection enables highly sensitive and accurate determination of Fe(II) in serum. Graphical abstract Schematic of a novel phosphorescent method for the detection of Fe2+ ions based on cysteine-bridged Mn-doped ZnS quantum dots. The sensitivity of this assay greatly increases due to the addition of cysteine. Interferences by short-lived auto-fluorescence and the scattering light from the biological fluids is eliminated by using time-resolved phosphorescence mode.

Polydopamine Induced in-Situ Formation of Metallic Nanoparticles in Confined Microchannels of Porous Membrane as Flexible Catalytic Reactor.

Oxidant-regulated polymerization of dopamine was exploited, for the first time, for effective surface engineering of the well-defined cylindrical pores of nuclear track-etched membranes (NTEMs) to develop novel catalytic membrane reactor. First, in the presence of a strong oxidant, controlled synthesis of polydopamine (PDA) with tunable particle size was achieved, allowing a homogeneous deposition to the confined pore channels of NTEMs. The PDA interfaces rich in catechol and amine groups provided enhanced hydrophilicity to promote mass transport across the membrane and abundant nucleation sites for formation and stabilization of metallic nanoparticles (NPs). In-situ reductive growth of multiple metallic NPs, including Pd, Ag, and Au, was then achieved inside the cylindrical pores of NTEMs. Using the functionalized membrane as a catalytic reactor, efficient reduction of 4-nitrophenol (4-NP) was demonstrated in a flow-through mode. Moreover, after dissolution removal of the NTEMs, self-sustained one-dimensional (1D) PDA/M (M = Pd, Ag, or Au) hybrid nanotubes (NTs), with determined aspect ratio and a length reaching up to 10 µm, were obtained for catalysis of 4-NP in a batch reaction mode. This study established a facile and versatile method, by rational tuning of the polymerization behavior of dopamine, for effective modification of confined microscale/nanoscale cavities with different surface characteristics. The integration of PDA chemistry with NTEMs would provide more opportunities for development of novel catalytic membrane reactors as well as for the tailored synthesis of functional 1D nanotubes for broadened applications.