Achieving ultrafast and highly selective capture of radiotoxic tellurite ions on iron-based metal-organic frameworks through coordination bond-dominated conversion.

Chemically durable and effective adsorbents for radiotoxic TeOx2- (TeIV and TeVI) anions remain in great demand for contamination remediation. Herein, a low-cost iron-based metal-organic framework (MIL-101(Fe)) was used as an adsorbent to capture TeOx2- anions from contaminated solution with ultrafast kinetics and record-high adsorption capacity of 645 mg g-1 for TeO32- and 337 mg g-1 for TeO42-, outperforming previously reported adsorbents. Extended X-ray absorption fine structure (EXAFS) and density functional theory (DFT) calculations confirmed that the capture of TeOx2- by MIL-101(Fe) was mediated by the unique C-O-Te and Fe-O-Te coordination bonds at corresponding optimal adsorption sites, which enabled the selective adsorption of TeOx2- from solution and further irreversible immobilization under the geological environment. Meanwhile, MIL-101(Fe) works steadily over a wide pH range of 4-10 and at high concentrations of competing ions, and it is stable under ß-irradiation even at high dose of 200 kGy. Moreover, the MIL-101(Fe) membrane was fabricated to efficiently remove TeO32- ions from seawater for practical use, overcoming the secondary contamination and recovery problems in powder adsorption. Finally, the good sustainability of MIL-101(Fe) was evaluated from three perspectives of technology, environment, and society. Our strategy provides an alternative to traditional removal methods that should be attractive for Te contamination remediation.

Elucidating the exceptional halide ion etching of bimetallic Ag-Cu oxides for efficient adsorption and porous nanostructure formation.

Elucidating the interactions between halide ions and bimetallic oxides can help understand their influences on the physicochemical properties of bimetallic oxides and ultimately lead to better performance, but this has not yet been explored. We report here the first study of the interaction of halide ions with two phase-pure bimetallic Ag-Cu oxides, Ag2Cu2O3 and Ag2Cu2O4, which have different chemical valences of Ag and Cu atoms. We found that halide ions have an aggressive etching effect on both bimetallic oxides, leading to a dramatic evolution of crystal structures and morphology. Halide ions act like "nano-carving knives", selectively etching out silver atoms to form silver halides and leaving a porous CuO skeleton. We revealed that Ag2Cu2O4 underwent a redox reaction with iodide ions (I-) to produce additional I3- in the solution, which was not observed in Ag2Cu2O3. Interestingly, according to the revealed interactions, both bimetallic oxides are confirmed as superior adsorbents to remove I- from wastewater in terms of a record-high uptake capacity, fast adsorption kinetics, and excellent selectivity for I-. Furthermore, such a halide etching can be turned into a powerful synthetic strategy. The out-etched silver halides were dissolved to give robust porous CuO nanostructures, which are proved to be excellent glucose-sensing electrodes with high sensitivity, excellent anti-interference, and stability, showing great application potential. This work contributes to improving the understanding of the mechanisms of halide ion-metal oxide interactions and ultimately to innovative applications.

Activation characterization of a novel quinary alloy Ti-Zr-V-Hf-Nb non-evaporable getters by x-ray photoelectron spectroscopy.

The first results on the activation process and mechanisms of novel quinary alloy Ti-Zr-V-Hf-Nb non-evaporable getter (NEG) film coatings with copper substrates were presented. About 1.075 µm of Ti-Zr-V-Hf-Nb NEG film coating was deposited on the copper substrates by using the DC sputtering method. The NEG activation at 100, 150, and 180 °C, respectively, for 2 h was in situ characterized by x-ray photoelectron spectroscopy (XPS). The as-deposited NEG film mainly comprised the high valence state metallic oxides and the sub-oxides, as well as a small number of metals. The in situ XPS studies indicated that the concentrations of the high-oxidized states of Ti, Zr, V, Hf, and Nb gradually decreased and that of the lower valence metallic oxides and metallic states increased in steps, when the activation temperature increased from 100 to 180 °C. This outcome manifested that these novel quinary alloy Ti-Zr-V-Hf-Nb NEG film coatings could be activated and used for producing ultra-high vacuum.

Revealing the role of oxygen-containing functional groups on graphene oxide for the highly efficient adsorption of thorium ions.

Oxygen-containing functional groups on the surface of carbon materials can promote the adsorption capacity of radioactive thorium ions (Th(IV)), but their effect on the adsorption of Th(IV) has not been systematically revealed. Herein, to elucidate the nature of oxygen-containing group-mediated Th(IV) adsorption, a series of graphene oxide nanoflakes (GONFs) with different contents of oxygen-containing groups on the surface were prepared. The experimental results showed that the high adsorption of Th(IV) not only resulted from the oxygen content, but also was related to the type of oxygen-containing functional groups on GONFs. Subsequent density functional theory (DFT) calculations revealed that the high adsorption capacity for Th(IV) originated from the oxygen-containing groups and their adjacent activated sp2 carbon atoms. More importantly, the coordination of Th(IV) with oxygen functional groups induced the aggregation of GONFs, leading to the sedimentation of GONFs, which facilitated the separation of adsorbents and enabled the GONFs to be a more practical adsorbent for Th(IV). This work deepens our understanding of the role of oxygen-containing groups on Th(IV) adsorption and provides a new strategy for the design and synthesis of high-performance surface oxygen-containing carbon-based adsorbents with practical application potential.

Ultra-selective ion sieve for thorium recovery from rare earth elements using oxygen-rich microporous carbon adsorption.

The ultra-selective extraction of thorium ions (Th(IV)) from lanthanides is of significance to both solve the radioactive pollution issue in rare earth (RE) production and sustainably provide thorium fuel for the liquid fluoride thorium reactors (LFTR). However, it remains a great challenge. Here, we reported an oxygen-rich microporous carbon for ultra-selective extraction of Th(IV) from rare earth elements (REEs) in a wide pH range. This selectivity was derived from the synergy of the oxygen-rich nature, microporous structure of the carbons, the chemical valence, and the ionic size of Th(IV) species. This oxygen-rich microporous carbon presented an ultra-high distribution coefficient (Kd) of 1.15 × 108 mL g-1 for Th(IV) at pH 4.9 in the presence of 15 REEs and revealed outstanding performance for Th(IV) extraction from three simulated RE solutions with high ionic strength of lanthanides. Meanwhile, an exceptional adsorption capacity of 624.98 mg g-1 was obtained in the single Th(IV) solution. Both values were superior to those of reported adsorbents. More importantly, the new adsorbent developed here could be prepared from cigarette butts. These features ensured the oxygen-rich carbon as a promising and cost-effective adsorbent for high-purity thorium extraction from REEs.

Structural and Secondary Electron Yield Properties of Titanium-Palladium Films with Laser-Treated Copper Substrate for Application in Neutron Generators.

Secondary electron emission (SEE) of the oxygen-free high-conductivity copper (OFHC) target surface in neutron generators limits the stability and improvement of the neutron yield. A novel-type target of titanium-palladium films coated on laser-treated OFHC target substrate was proposed and explored in this work to obtain low secondary electron yield (SEY) without introducing any components. The combination of Ti-Pd films and laser-treated OFHC substrate can effectively suppress secondary electron emission and enhance the adsorption ability to hydrogen isotopes with the existence of Pd film. The surface morphologies, surface chemical states, and SEYs of Ti-Pd films with laser-treated OFHC substrate were studied systematically for the first time. The XPS results showed that the laser-treated OFHC substrate surface was basically covered by Pd film. However, the Pd film surface was partially oxidized, with percentages of 21.31 and 10.02% for PdO and PdO2, respectively. The SEYs of Ti-Pd films with laser-treated OFHC substrate were all below 1 within the investigated primary energy range of 100-3000 eV, which would be sufficient for application in neutron generators. Specifically, the maximum SEY (δmax) of laser-treated OFHC substrate coated by Ti-Pd films was 0.87 with corresponding incident electron energy of 400 eV.

The Effects of Oxygen Functional Groups on Graphene Oxide on the Efficient Adsorption of Radioactive Iodine.

Oxygen-containing functional groups tend to induce a strong interaction between solid adsorbents and iodine molecules, yet have not been systematically investigated. Herein, on the basis of a series of nitric acid-treated graphene oxide (GO) with different contents of oxygen functional groups for iodine adsorption, it was found that the iodine uptake capacity is proportionate to the oxygen content and the diversities of oxygen-containing groups. The density functional theory (DFT) calculation results also suggest that oxygen-containing groups result in strong interactions between iodine molecules and the adsorbents through a covalent bond-forming process, among which -OH groups possess a higher adsorption energy averagely. Such theoretical and experimental work deepens our understanding of the effects of oxygen functional groups on iodine adsorption and provides novel ideas for future design and synthesis of high-performance solid adsorbents for radioactive iodine.

The Removal of Platinum Group Metals, Cs, Se, and Te from Nuclear Waste Glass Using Liquid Sb Extraction and Phase Separation Methods.

Recovery of platinum group metals (PGMs: Pd, Ru, Rh), Cs, Se, and Te from molten borosilicate glass containing simulated high level radwaste through the combination of liquid metal extraction and phase separation method under reductive heat-treatment was studied. In this process, the PGMs were extracted in recovered liquid metal phase, where Sb and Bi metals were used as the collecting metals. Meanwhile, Cs, Se, and Te were enriched in the phase separated potassium-rich materials on glass surface, which were extracted by water. The type of liquid metals had profound influence on the extraction behaviors of PGMs and other fission products from the glass melt. As a result, except the near extraction efficiency of Pd, Sb showed higher affinity for Ru and Rh than Bi metal. The higher phase separation efficiency of potassium-rich materials led to the higher extraction efficiencies of Cs, Se, and Te in liquid Sb extraction than Bi. Among the examined conditions, using liquid Sb extraction, the Pd, Ru, and Rh extraction efficiencies were 78.6%, 62.1% and 100% in liquid Sb metal phase, and 93.76% of Cs, 60.4% of Se, and 23.65% of Te in leachate were obtained.

The Activation of Ti-Zr-V-Hf Non-Evaporable Getter Films with Open-Cell Copper Metal Foam Substrates.

Secondary electron emission (SEE) inhibition and vacuum instability are two important issues in accelerators that may induce multiple effects in accelerators, such as power loss and beam lifetime reduction. In order to mitigate SEE and maintain high vacuum simultaneously, open-cell copper metal foam (OCMF) substrates with Ti-Zr-V-Hf non-evaporable getter (NEG) coatings are first proposed, and the properties of surface morphology, surface chemistry and secondary electron yield (SEY) were analyzed for the first time. According to the experimental results tested at 25 °C, the maximum SEY (δmax) of OCMF before and after Ti-Zr-V-Hf NEG film deposition were 1.25 and 1.22, respectively. The XPS spectra indicated chemical state changes of the metal elements (Ti, Zr, V and Hf) of the Ti-Zr-V-Hf NEG films after heating, suggesting that the NEG films can be activated after heating and used as getter pumps.

The Effect of Ultrasonic Cleaning on the Secondary Electron Yield, Surface Topography, and Surface Chemistry of Laser Treated Aluminum Alloy.

Laser ablation technique is a novel method for obtaining a surface with a low secondary electron yield (SEY) that can mitigate electron cloud in high-energy accelerators. Before the installation of laser processed aluminum alloy, surface cleaning is of the essence to reduce the contaminations of ultra-high vacuum systems for providing appropriate pressure for beam operation consequently. Laser processed aluminum alloy is one of the crucial candidates for the vacuum system construction of future accelerators. Moreover, ultrasonic cleaning is an essential procedure for most materials applied in vacuum systems. Therefore, in order to verify the stability of the laser created structures by ultrasonic cleaning and evaluate the impact of the cleaning on the SEYs, the surface topographies, and the surface chemistries of laser treated aluminum alloy, SEY measurements and related tests were performed. After ultrasonic cleaning, the SEYs of laser treated aluminum alloy increased from 0.99, 1.05, and 1.16 to 1.43, 1.74, and 1.38, respectively. Compared to the surface roughness of uncleaned laser treated aluminum samples, the cleaned laser treated ones decreased from 10.7, 7.5, and 14.5 to 9.4, 6.9, and 12.9, respectively. The results indicate that ultrasonic cleaning can induce the SEY increase of laser processed aluminum alloy. The correlative mechanism between the surface morphology, the surface chemistry, and SEY increase were analyzed for the first time.

A nanocrystalline oxygen-deficient bismuth oxide as an efficient adsorbent for effective visible-light-driven photocatalytic performance toward organic pollutant degradation.

In this work, a simple binary oxygen-deficient Bi2O4-x oxide was prepared, and its crystal structure, optical property, band structure and electronic structure were systematically investigated. Plane-wave-based density functional theory (DFT) calculations were also carried out to determine that Bi2O4-x is a typical indirect-gap semiconductor with the bandgap of 1.1 eV. Bi2O4-x adsorbed ca. 99% of rhodamine B and methyl orange, ca. 95% of methylene blue and ca. 80% of phenol in the dark within initial 30 min. The interaction of the oxygen-deficient structure-induced hydroxyls with pollutant molecules is responsible for the excellent adsorption capacity. Due to its excellent adsorption capacity, Bi2O4-x showed much higher photocatalytic degradation activity toward these pollutants (except for methylene blue) under visible light irradiation than the well-studied Bi2O4, Bi2O3 and P25, which had poor or negligible adsorption capacity toward the pollutants. Methylene blue was degraded by Bi2O4-x with further Pd loading. The photocatalytic mechanism of the oxygen-deficient Bi2O4-x were explored. The scavenging test results showed that direct h+ oxidation contributes to the high photocatalytic activity of the oxygen-deficient Bi2O4-x. This study highlights the potential of developing Bi2O4-x-based materials as a new class with both excellent adsorption capacity and highly efficient photocatalytic activity toward versatile pollutants.

Recovery of palladium, cesium, and selenium from heavy metal alkali borosilicate glass by combination of heat treatment and leaching processes.

Reductive heat-treatment and leaching process were applied to a simulated lead or bismuth soda-potash-borosilicate glass with palladium, cesium, and selenium to separate these elements. In the reductive heat treatment, palladium is extracted in liquid heavy metal phase generated by the reduction of the heavy metal oxides, whereas cesium and selenium are concentrated in phase separated Na-K-rich materials on the glass surface. From the materials, cesium and selenium can be extracted in water, and the selenium extraction was higher in the treatment of the bismuth containing glass. The chemical forms of palladium in the glass affected the extraction efficiencies of cesium and selenium. Among the examined conditions, in the bismuth glass treatment, the cesium and selenium extraction efficiencies in water were over 80%, and that of palladium in liquid bismuth was over 80%.

Phase separation of cesium from lead borosilicate glass by heat treatment under a reducing atmosphere.

A phase-separation technique for removing sodium from glass using a heat-treatment method under a reducing atmosphere was previously developed for sodium recovery from waste glass. In this study, this technique was applied to cesium-containing lead borosilicate glass to concentrate the cesium in phase-separated sodium-rich materials for efficient cesium extraction. The theoretical phase-separation temperature of the sodium-rich phase was simulated by thermodynamic equilibrium calculations and was predicted to occur below 700°C for lead borosilicate glass. Experimentally, a simulated lead borosilicate glass was melted at 1000°C and subsequently annealed below 700°C under a CO-containing reducing atmosphere. The phase separation of cesium was found to occur with sodium enrichment on the glass surface that was in contact with the gas phase, promoting cesium extraction from the treated glass using water. The cesium extraction efficiency was affected by the surface area of the treated glass that was in contact with water, and under the examined conditions, the cesium extraction efficiency was up to 66%. Phase separation using reductive heat treatment, combined with a water leaching technique, is suggested to be effective for extracting cesium incorporated in borosilicate glass waste.