Trailblazing Kr/Xe Separation: The Birth of the First Kr-Selective Material.

Efficient separation of Kr from Kr/Xe mixtures is pivotal in nuclear waste management and dark matter research. Thus far, scientists have encountered a formidable challenge: the absence of a material with the ability to selectively adsorb Kr over Xe at room temperature. This study presents a groundbreaking transformation of the renowned metal-organic framework (MOF) CuBTC, previously acknowledged for its Xe adsorption affinity, into an unparalleled Kr-selective adsorbent. This achievement stems from an innovative densification approach involving systematic compression of the MOF, where the crystal size, interparticle interaction, defects, and evacuation conditions are synergistically modulated. The resultant densified CuBTC phase exhibits exceptional mechanical resilience, radiation tolerance, and notably an unprecedented selectivity for Kr over Xe at room temperature. Simulation and experimental kinetic diffusion studies confirm reduced gas diffusion in the densified MOF, attributed to its small pore window and minimal interparticle voids. The lighter Kr element demonstrates facile surface passage and higher diffusivity within the material, while the heavier Xe encounters increased difficulty entering the material and lower diffusivity. This Kr-selective MOF not only represents a significant breakthrough in Kr separation but also demonstrates remarkable processability and scalability to kilogram levels. The findings presented herein underscore the transformative potential of engineered MOFs in addressing complex challenges, heralding a new era of Kr separation technologies.

Functionalized maghemite nanoparticles for enhanced adsorption of uranium from simulated wastewater and magnetic harvesting.

Maghemite (γ-Fe2O3) nanoparticles (MNPs) were functionalized with 3-aminopropyltriethoxysilane (APTES) to give APTES@Fe2O3 (AMNP) which was then reacted with diethylenetriamine-pentaacetic acid (DTPA) to give a nanohybrid DTPA-APTES@Fe2O3 (DAMNP). Nano-isothermal titration calorimetry shows that DTPA complexation with uranyl ions in water is exothermic and has a stoichiometry of two DTPA to three uranyl ions. Density functional theory calculations indicate the possibility of several complexes between DTPA and UO22+ with different stoichiometries. Interactions between uranyl ions and DAMNP functional groups are revealed by X-photoelectron and Fourier transform infrared spectroscopies. Spherical aberration-corrected Scanning Transmission Electron Microscopy visualizes uranium on the particle surface. Adsorbent performance metrics were evaluated by batch adsorption studies under different conditions of pH, initial uranium concentration and contact time, and the results expressed in terms of equilibrium adsorption capacities (qe) and partition coefficients (PC). By either criterion, performance increases from MNP to AMNP to DAMNP, with the maximum uptake at pH 5.5 in all cases: MNP, qe = 63 mg g-1, PC = 127 mg g-1 mM-1; AMNP, qe = 165 mg g-1, PC = 584 mg g-1 mM-1; DAMNP, qe = 249 mg g-1, PC = 2318 mg g-1 mM-1 (at 25 °C; initial U concentration 0.63 mM; 5 mg adsorbent in 10 mL of solution; contact time, 3 h). The pH maximum is related to the predominance of mono- and di-cationic uranium species. Uptake by DAMNPs follows a pseudo-first-order or pseudo-second-order kinetic model and fits a variety of adsorption models. The maximum adsorption capacity for DAMNPs is higher than for other functionalized magnetic nanohybrids. This adsorbent can be regenerated and recycled for at least 10 cycles with less than 10% loss in activity, and shows high selectivity. These findings suggest that DAMNP could be a promising adsorbent for the recovery of uranium from nuclear wastewaters.

Recurrent heel ulcers with calcaneal osteomyelitis in myelomeningocele: Treatment by partial calcanectomy and posterior transfer of tibialis anterior tendon.

OVERVIEW: Calcaneus deformity of the foot is common in patients with myelodysplasia, mainly due to muscle imbalance. This deformity, especially in ambulatory patients, can result in gait problems and development of pressure sores, which can be complicated by calcaneal osteomyelitis. MATERIAL AND METHODS: This retrospective cross-sectional study included 12 patients (18 feet), with calcaneus deformity due to myelomeningocele, and presented with penetrating heel ulcers complicated by calcaneal osteomyelitis. The mean age of the included cases was 11 years. The ulcers were unilateral in six patients and bilateral in six. Sensation was absent on the plantar aspect of the foot in all cases. The treatment was done in two stages; The first stage was eradication of infection and obtaining good soft tissue coverage, and the second stage was obtaining motor balance to achieve a more plantigrade and braceable foot. RESULTS: The average follow-up period was 19.2 months. In the final follow-up, twelve feet were graded as good, five as fair and one as poor according to Legaspi grading system. CONCLUSION: The combination of partial calcanectomy and subsequent transfer of tibialis anterior tendon, to improve the foot position and gait, can efficiently prevent ulcer recurrence in myelomeningocele patients with calcaneal deformity. LEVEL OF CLINICAL EVIDENCE: 4: Retrospective case series study.

Uranium In Situ Electrolytic Deposition with a Reusable Functional Graphene-Foam Electrode.

Nuclear fission produces 400 GWe which represents 11% of the global electricity output. Uranium is the essential element as both fission fuel and radioactive waste. Therefore, the recovery of uranium is of great importance. Here, an in situ electrolytic deposition method to extract uranium from aqueous solution is reported. A functionalized reduced graphene oxide foam (3D-FrGOF) is used as the working electrode, which acts as both a hydrogen evolution reaction catalyst and a uranium deposition substrate. The specific electrolytic deposition capacity for U(VI) ions with the 3D-FrGOF is 4560 mg g-1 without reaching saturation, and the Coulombic efficiency can reach 54%. Moreover, reduction of the uranium concentration in spiked seawater from 3 ppm to 19.9 ppb is achieved, which is lower than the US Environmental Protection Agency uranium limits for drinking water (30 ppb). Furthermore, the collection electrode can be efficiently regenerated and recycled at least nine times without much efficiency fading, by ejecting into 2000 ppm concentrated uranium solution in a second bath with reverse voltage bias. All these findings open new opportunities in using free-standing 3D-FrGOF electrode as an advanced separation technique for water treatment.

Metal-Organic Framework-Polyacrylonitrile Composite Beads for Xenon Capture.

Mechanically robust forms of HKUST-1 metal-organic frameworks (MOFs) were fabricated by embedding the MOF crystals in a passive polyacrylonitrile (PAN) matrix at different MOF loadings of 10-90 mass %. PAN is highly porous and acts as a scaffold that holds the active MOF adsorbent in place. These MOF-PAN composites were then evaluated for capturing Xe. Data presented herein show that the PAN matrix does not notably interfere with the Xe capture process, where the Xe capacities scale somewhat linearly with the increase in MOF loadings within the composites. Also, γ radiation exposures to the composites revealed that they are highly tolerant to these types of radiation fields.

Triboelectric Nanogenerator versus Piezoelectric Generator at Low Frequency (<4 Hz): A Quantitative Comparison.

Triboelectric nanogenerators (TENGs) and piezoelectric generators (PGs) are generally considered the two most common approaches for harvesting ambient mechanical energy that is ubiquitous in our everyday life. The main difference between the two generators lies in their respective working frequency range. Despite the remarkable progress, there has been no quantitative studies on the operating frequency band of the two generators at frequency values below 4 Hz, typical of human motion. Here, the two generators are systematically compared based on their energy harvesting capabilities below 4 Hz. Unlike PGs, the TENG demonstrates higher power performance and is almost independent of the operating frequency, making it highly efficient for multi-frequency operation. In addition, PGs were shown to be inapplicable for charging capacitors when a rectifier was attached to the system. The results of this work reveal the tremendous potential of flexible TENGs for harvesting energy at low frequency.

Radiation-resistant metal-organic framework enables efficient separation of krypton fission gas from spent nuclear fuel.

Capture and storage of volatile radionuclides that result from processing of used nuclear fuel is a major challenge. Solid adsorbents, in particular ultra-microporous metal-organic frameworks, could be effective in capturing these volatile radionuclides, including 85Kr. However, metal-organic frameworks are found to have higher affinity for xenon than for krypton, and have comparable affinity for Kr and N2. Also, the adsorbent needs to have high radiation stability. To address these challenges, here we evaluate a series of ultra-microporous metal-organic frameworks, SIFSIX-3-M (M = Zn, Cu, Ni, Co, or Fe) for their capability in 85Kr separation and storage using a two-bed breakthrough method. These materials were found to have higher Kr/N2 selectivity than current benchmark materials, which leads to a notable decrease in the nuclear waste volume. The materials were systematically studied for gamma and beta irradiation stability, and SIFSIX-3-Cu is found to be the most radiation resistant.

Facile fabrication of a novel BiPO4 phase junction with enhanced photocatalytic performance towards aniline blue degradation.

A novel BiPO4 photocatalyst has been fabricated via a facile precipitation route using dimethyl sulfoxide (DMSO) as a solvent. The physical and chemical properties of the BiPO4 photocatalyst material were analyzed using XRD, Rietveld refinements XRD, FE-SEM, TEM, HR-TEM, EDS, XPS, FT-IR, Raman spectra, UV-Vis (DRS), and PL. The results confirm that hexagonal phase BiPO4 (HBIP) nanorods were successfully synthesized. FE-SEM images reveal that the addition of surfactant "CTAB" during preparation can control the surface morphology of BiPO4. The Rietveld refinement technique revealed the formation of a monazite monoclinic (nMBIP) and monoclinic (mMBIP) phase junction resulting from the calcination of HBIP at 500 °C. The photocatalytic behavior of the as-synthesized hexagonal and monoclinic BiPO4 nanostructures towards aniline blue (AB) degradation under UV light was systematically investigated. Among all catalysts, the phase junction (nMBIP-mMBIP) structure demonstrated the highest photocatalytic activity. The degradation rate of AB over the (nMBIP-mMBIP) phase junction structure was 3.4 times higher than that by HBIP. These results suggested that the surface-phase junction provides a synergistic effect for the electron-hole transfer process.