Cubically cage-shaped mesoporous ordered silica for simultaneous visual detection and removal of uranium ions from contaminated seawater

A dual-function organic-inorganic mesoporous structure is reported for naked-eye detection and removal of uranyl ions from an aqueous environment. The mesoporous sensor/adsorbent is fabricated via direct template synthesis of highly ordered silica monolith (HOM) starting from a quaternary microemulsion liquid crystalline phase. The produced HOM is subjected to further modifications through growing an organic probe, omega chrome black blue G (OCBBG), in the cavities and on the outer surface of the silica structure. The spectral response for [HOM-OCBBG → U(VI)] complex shows a maximum reflectance at λmax = 548 nm within 1 min response time (tR); the LOD is close to 9.1 μg/L while the LOQ approaches 30.4 μg/L, and this corresponds to the range of concentration where the signal is linear against U(VI) concentration (i.e., 5-1000 μg/L) at pH 3.4 with standard deviation (SD) of 0.079 (RSD% = 11.7 at n = 10). Experiments and DFT calculations indicate the existence of strong binding energy between the organic probe and uranyl ions forming a complex with blue color that can be detected by naked eyes even at low uranium concentrations. With regard to the radioactive remediation, the new mesoporous sensor/captor is able to reach a maximum capacity of 95 mg/g within a few minutes of the sorption process. The synthesized material can be regenerated using simple leaching and re-used several times without a significant decrease in capacity. Graphical abstract: [Figure not available: see fulltext.

Roles of silver nanoclusters in surface-enhanced Raman spectroscopy

The cause for the huge enhancement factors of surface-enhanced Raman spectroscopy (SERS) by the addition of small silver nanoclusters is theoretically investigated by focusing on the difference between resonance Raman activity and surface plasmon effects. First, the resonance and off-resonance Raman spectra are calculated using the incident light wavenumbers of the low-lying charge transfer excitations for the surface (S) and vertex (V) complexes of the pyridine molecule attaching to three small silver nanoclusters: Ag-5, Ag-10, and Ag-20. As a result, it is found that the incident radiation dramatically increases the resonance Raman activities with the enhancement factors up to 10(12). This indicates that the resonance Raman effects are dominant in the enhancement factors of SERS, at least when to use small silver clusters. It is also found that the resonance Raman spectra significantly depend on the adsorption sites given in S or V complexes, and on the inclusion or exclusion of the long-range correction for density functional theory, irrespective of the size of the silver clusters. The electromagnetic field enhancement effects called surface plasmon effects are also examined for the Ag-20 cluster to confirm this conclusion. Consequently, the enhancement in the electric field is roughly evaluated as less than one for the static polarizability of this small cluster. It is, therefore, concluded that the resonance Raman activity effect is dominant in the huge SERS enhancement factors for, at least, small silver nanoclusters

Atomically Thin Hexagonal Boron Nitride Nanofilm for Cu Protection: The Importance of Film Perfection.

Outstanding protection of Cu by high-quality boron nitride nanofilm (BNNF) 1-2 atomic layers thick in salt water is observed, while defective BNNF accelerates the reaction of Cu toward water. The chemical stability, insulating nature, and impermeability of ions through the BN hexagons render BNNF a great choice for atomic-scale protection