Open Access

Show Abstract ▼

Abstract: MFM-520(Zn) confines dimers of NO2 with a high adsorption of 4.52 mmol g−1 at 1 bar at 298 K. The synthesis and the incommensurate structure of Cu-doped MFM-520(Zn) are reported. The introduction of paramagnetic Cu2+ sites allows investigation of the electronic and geometric structure of metal site by in situ electron paramagnetic resonance (EPR) spectroscopy upon adsorption of NO2. By combining continuous wave and electron-nuclear double resonance spectroscopy, an unusual reverse Berry distorted coordination geometry of the Cu2+ centers is observed. Interestingly, Cu-doped MFM-520(Zn0.95Cu0.05) shows enhanced adsorption of NO2 of 5.02 mmol g−1 at 1 bar at 298 K. Whereas MFM-520(Zn) confines adsorbed NO2 as N2O4, the presence of monomeric NO2 at low temperature suggests that doping with Cu2+ centers into the framework plays an important role in tuning the dimerization of NO2 molecules in the pore via the formation of specific host-guest interactions.

Open Access

Show Abstract ▼

Abstract: Efficient nitrogen oxides (NOx) removal from the urban atmosphere is still a target for the researchers. Herein, a Zn2Al-CO3 based layered double hydroxide (LDH) was doped with increasing amounts of Eu3+ (0.01–0.04) and the photocatalytic oxidation of NOx gases was investigated. The LDHs were synthesized by a facile coprecipitation method at room temperature and ambient pressure. The successful Eu3+ substitution in the LDH layers induces a shift in the M−O bonds that modifies the electronic band structure of the doped photocatalysts. Compared to the undoped LDH, the NOx removal efficiency was enhanced by ∼ 17–25 % under UV–Vis light irradiation. Remarkably, a NOx removal efficiency of ∼ 47 % was attained by the optimally doped LDH under Visible irradiation (420 nm), surpassing raw LDH (∼ 9 %). Moreover, the Eu3+ doped LDHs retained its photocatalytic efficiency during long periods of irradiation during consecutive tests with high selectivity (>90 %). Photoluminescence studies indicated that Eu3+ was located in a non-centrosymmetric position, thereby producing structural disorder within the lattice. Eu doping promoted charge separation and a higher production of ⋅OH radicals as verified by time-resolved photoluminescence and electron paramagnetic resonance, respectively. We believe this work reports unprecedent results obtained by Eu-doping of Zn2Al-based LDHs under visible light for NOx photooxidation and serves as a new strategy to prepare functional LDHs for other photocatalytic applications.

Show Abstract ▼

Abstract: Aerosols contribute to ambient air pollution and, via processes such as cloud droplet formation, affect air quality and climate. Organic compounds often play a major role in aerosol composition, varying with time, location, season, and environment. Cooking food releases fatty acids into the air, and cooking emissions contribute around 10% to UK emissions of PM2.5 (aerosols up to two and a half microns wide). These aerosol particles can be deposited onto surfaces such as windows. A thin, layered film of material builds up over time, creating a persistent crust that is only slowly broken down by other chemicals in the atmosphere. In work recently selected as the best 2022 paper in Environmental Science: Atmospheres, a team led by researchers at the University of Birmingham created ultra-thin films, just a few tens of nanometres in thickness, approximating real-world pollution samples. Using X-ray and neutron techniques to study the nanoscale composition of the films and the changes in their surface structures as they aged, the researchers found that the self-organised layered structure can trap toxic pollutants and form a barrier that can prevent their breakdown. They also showed that the film's surface becomes rougher and attracts more water from humidity, an effect with implications for the formation and lifetime of aerosols in the atmosphere.

Open Access

Show Abstract ▼

Abstract: The past 60+ years of global nuclear activity has resulted a signifcant legacy of radioactive contaminated lands which have high economic costs associated with their remediation. Developing clean-up technologies that are environmentally friendly, economically viable and effective in the long-term is key, with in-situ remediation techniques as an important option. However, questions remain regarding the most favorable methods of remediation, and the long-term stability of any immobilised radionuclide(s). Here, we used sediment microcosms to assess the long-term (300 day) stability of immobilised U and Sr formed during anoxic microbial and chemical treatments, and assessed their stability during re-oxidation scenarios (with oxygen or nitrate additions, 100 days). We used six contrasting treatment approaches which resulted in 89 - >99%, and 65 – 95% removal efficiencies for U and Sr, respectively. These included two Zero Valent Iron (ZVI) based products (NANOFER 25S and Carbo-Iron); a slow-release electron donor (Metals Remediation Compound, MRC) to stimulate U(VI) bioreduction alongside a readily bioavailable electron donor control (lactate/acetate mix); electron donor (lactate/acetate) with elevated sulfate to stimulate metal and sulfate reduction; glycerol phosphate to promote both bioreduction of U(VI) and biomineralization of inorganic U/Sr phopshates; and finally a natural attenuation (no remediation agent added) control. X-ray Absorption Spectroscopy (XAS) revealed that whilst aqueous U was removed from solution via multiple mechanisms including sorption, reduction and incorporation, aqueous Sr was mostly removed via outer sphere complexation mechanisms. Re-oxidation with air led to increased U remobilisation (≤89%) compared to nitrate oxidation (≤73%), but neither oxygen or nitrate re-oxidation led to significant Sr remobilisation (≤38%), suggesting Sr speciation may be stable over extended timescales post remediation. Treatments amended with ZVI or glycerol phosphate not only removed the most U and Sr from solution (>99%) but they also retained the most U and Sr following re-oxidation (retaining ≥75% of the originally added U and Sr). XAS analyses suggests that enhanced immbilisation, as seen in the treatments amended with ZVI or glycerol phosphate, may be due to the U/Sr incorporation into mineral phases (i.e., iron oxyhydorxide and phospate pahses) This suggests that optimal (bio)remediation strategies should target both reduction and biomineralisation mechanisms to facilitate radionuclide-mineral incorporation, promoting longer-term stability.

Open Access

Show Abstract ▼

Abstract: Pb/Zn smelter slag is a hazardous industrial waste from the Imperial Smelting Process (ISP). The speciation of zinc, lead, copper and arsenic in the slag controls their recovery or fate in the environment but has been little investigated. X-ray Absorption Spectroscopy (XAS) was applied to this complex poorly crystalline material for the first time to gain new insights about speciation of elements at low concentration. Zn, Cu, As K-edge and Pb L3-edge XAS was carried out for a Pb/Zn slag from a closed ISP facility in England, supported by Fe, S and P K-edge XAS. Results are presented in the context of a full review of the literature. X-ray fluorescence showed that concentrations of Zn, Pb, Cu and As were 8.4, 1.6, 0.48 and 0.45 wt.%, respectively. Wüstite (FeO) was the only crystalline phase identified by X-ray diffraction, but XAS provided a more complete understanding of the matrix. Zn was found to be mainly present in glass, ZnS, and possibly solid solutions with Fe oxides; Pb was mainly present in glass and apatite minerals (e.g., Pb5(PO4)3OH); Cu was mainly speciated as Cu2S, with some metallic Cu and a weathering product, Cu(OH)2; As speciation was likely dominated by arsenic (III) and (V) oxides and sulfides.