Preparation of Mn/TiO2 catalysts using recovered manganese from spent alkaline batteries for low-temperature NH3-SCR.

Black mass (BM) from spent alkaline Zn-MnO2 batteries was used for the first time as a Mn source in the preparation of Mn/TiO2 catalysts for low-temperature NH3-selective catalytic reduction (SCR) of NOx. To recover Mn species and eliminate alkali and Zn species, BM powder underwent DI-water washing, followed by carbothermal reduction. The resulting slags were further dissolved in HNO3, loaded onto TiO2 particles with ball milling, and then subjected to calcination. Nearly 100% of Zn species were removed from the BM via carbothermal reduction at 950 °C for 4 h with 5.0 wt% activated carbon. The resulting catalyst, derived from the treated BM, achieved similar NOx conversion (97%) as the catalyst prepared using a reagent-grade Mn chemical at 160 °C but a higher NOx-to-N2 conversion rate at 78%. The promoted N2 selectivity was attributed to a high Mn4+/Ti ratio and the presence of impurities from BM, such as Fe3+ ions, which enhanced oxidation ability of the catalyst. Conversely, insufficient removal of Zn or carbon additives in the slags led to a decreased Mn concentration, an increased proportion of Mn2+/Mn3+ species, increased surface OH groups, and reduced oxidation ability on the surface, thus reducing NOx conversion and N2 selectivity.

A microgel of CdSe quantum dots for fluorescent bisphenol A detection.

A fluorescent microgel for BPA detection has been successfully prepared by cross-linking linear poly(styrene-co-glycidyl methacrylate) (poly (STY-co-GMA)) with L-cysteine-capped CdSe quantum dots (Lcys-caped CdSe QDs). The microgel contained specific binding sites created by the covalent grafting of the copolymer onto the QDs via the GMA units, allowing for selective trapping of BPA molecules through π-π and hydrogen bond interactions with phenyl, carboxylic, and amine groups. After binding, electron transfer from the QDs to the analyte quenched the fluorescence at a wavelength of 547 nm when excited at 400 nm. The rational compositional and structural design allows the microgel to accurately detect BPA concentrations over a wide dynamic range of 1.0×10-1 to 1.0×105 µg/L with a low detection limit (7.0×10-2 to 8.0×10-2 µg/L) in deionized, drinking, and tap waters within just 2.0 min. On top of that, the sensitivity for BPA detection was 2.0-4.6 times higher than that of the other 3 structural analogues, even molecular imprinting was not involved. The influence of the STY/GMA compositions in the copolymers and environmental conditions, including pH and ionic strength, on the sensing performance was determined. Moreover, the sensing mechanism and the selectivity with respect to the molecular features were elucidated.

Retarded Charge Recombination to Enhance Photocatalytic Performance for Water-Free CO2 Reduction Using Perovskite Nanocrystals as Photocatalysts.

Femtosecond transient absorption spectral (TAS) investigations were performed to understand the carrier relaxation mechanism for perovskite nanocrystals Cs1-xFAxPbBr3 (CF, x = 0.45) and CsPbBr3 (CS), which served as efficient photocatalysts for splitting of CO2 into CO and O2 in the absence of water. Upon light irradiation for 12 h, formation of deep trap states was found for both CS and CF samples with spectral characteristics of the TAS photobleach (PB) band showing a long spectral tail extending to the long wavelength region. The charge recombination rates at the shallow surface states, bulk states, and deep-trapped surface state were found to be significantly retarded for the CF sample than for the CS sample, in agreement with the photocatalytic performances for CO product yields of the CF catalyst being greater by a factor of 3 compared to those of the CS catalyst.

Inactivation of Escherichia coli by dual-functional zerovalent Fe/Al composites in water.

A bimetallic Fe/Al disinfection system was developed to examine the feasibility of inactivation of water borne microorganisms. In this study, the effectiveness and mechanisms of the bimetallic Fe/Al system on the inactivation of model bacteria, Escherichia coli (E. coli), were investigated. Results revealed that the Fe/Al system effectively inactivated E. coli to reach nearly 2 logs (99%) removal within 20 min and 4 logs (99.99%) at 24 h, indicating that the Fe/Al composite was able to sustain a long-term disinfection capacity. The inactivation ability resulted from hydroxyl radicals produced by a Fenton reaction through in-situ self-generated Fe2+ and H2O2 species in the Fe/Al system. In addition to the attack by the radicals, some of E. coli were adsorbed onto the Fe/Al composite (zeta potential of 30-50 mV) as a result of Coulomb interaction. Scanning electron microscope (SEM) images showed that the adsorbed bacteria had damaged pores at the two ends of their rod-like cells. This phenomenon suggested that a micro-electric field between the Fe/Al galvanic couple induced electroporation of the adsorbed E. coli and thus further advanced additional inactivation ability for the bacteria disinfection.

Mechanism of Photocatalytic CO2 Reduction by Bismuth-Based Perovskite Nanocrystals at the Gas-Solid Interface.

We report here a series of nontoxic and stable bismuth-based perovskite nanocrystals (PeNCs) with applications for photocatalytic reduction of carbon dioxide to methane and carbon monoxide. Three bismuth-based PeNCs of general chemical formulas A3Bi2I9, in which cation A+ = Rb+ or Cs+ or CH3NH3+ (MA+), were synthesized with a novel ultrasonication top-down method. PeNC of Cs3Bi2I9 had the best photocatalytic activity for the reduction of CO2 at the gas-solid interface with formation yields 14.9 µmol g-1 of methane and 77.6 µmol g-1 of CO, representing a much more effective catalyst than TiO2 (P25) under the same experimental conditions. The products of the photocatalytic reactions were analyzed using a gas chromatograph coupled with a mass spectrometer. According to electron paramagnetic resonance and diffuse-reflectance infrared spectra, we propose a reaction mechanism for photoreduction of CO2 via Bi-based PeNC photocatalysts to form CO, CH4, and other possible side products.

Physicochemical characteristics of microbial content in a modified anaerobic inclining-baffled reactor (MAI-BR) treating recycled paper mill effluent (RPME).

Microbial content formed in bioreactors plays a significant role in the anaerobic process. Therefore, the physicochemical characteristics of microbial content in a modified anaerobic inclining-baffled reactor (MAI-BR) treating recycled paper mill effluent (RPME) were investigated using Fourier transform infrared (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric (TG), and derivative thermogravimetric (DTG) analyses, scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), Brunauer-Emmett-Teller (BET), and surface area analyzer. FTIR spectra revealed that the microbial content had stronger characteristic peaks corresponding to alcohols, water, lipids carbohydrates, proteins, and mineral compounds. Calcite, muscovite, and lepidolite were the prevalent mineral phases found by XRD analysis. The elemental of these minerals like C, Ca, N, O, and Si was confirmed by XPS results. The microbial content samples from each compartment showed similar thermal behavior. SEM images showed that straight rod-shaped and Methanosaeta-like microorganisms were predominant, whereas C, O, and Ca were noticed by EDS on the surface of granules. The BET surface areas and pores of granules are found to decline throughout the reactor's compartment, where Compartment 1 had the largest values. Thus, the findings of this study establish further understanding of the physicochemical properties of microbial content formed in MAI-BR during the RPME treatment.

Determination of optimal phenanthrene, sulfate and biomass concentrations for anaerobic biodegradation of phenanthrene by sulfate-reducing bacteria and elucidation of metabolic pathway.

Anaerobic biodegradation of phenanthrene (PHE) was investigated using an enrichment culture consists predominantly of sulfate-reducing bacteria (87+/-6%). Aqueous biodegradation experiments were designed using the rotatable central composite design with five levels. The designed concentrations were 2-50 mg L(-1) for PHE, 480-3360 mg L(-1) for sulfate, and 5-50 mg L(-1) for initial biomass. Experimental results indicated that the biomass concentration was the most significant variable, followed by the sulfate and PHE concentrations. The desirability functions methodology (DFM) was applied to find out the maximum specific PHE removal rate (R(s)). The maximum R(s) of 9.0 mg g(-1)VSS d(-1) within the designed ranges was obtained when the initial PHE, sulfate and biomass concentrations were 18.5, 841 and 50 mg L(-1), respectively. The R(s) observed in the present study was higher than the values reported in the previous studies. Subsequently, a confirmation study was performed under the optimal conditions, and the results matched well with the R(s) estimated using DFM. Samples collected during PHE biodegradation experiments inferred the formation of two novel metabolic intermediates, 2-methyl-5-hydroxybenzaldehyde and 1-propenyl-benzene, and subsequently degraded to p-cresol, phenol and hydrocarbons.

Characterization of Zr-doped TiO2 nanocrystals prepared by a nonhydrolytic sol-gel method at high temperatures.

Highly crystalline and surface-modified Zr-doped TiO(2) nanorods were successfully prepared using a nonhydrolytic sol-gel method that involves the condensation of metal halides with alkoxides in anhydrous trioctylphosphine oxide (TOPO) at either 320 or 400 degrees C. In addition, the interaction of the cross-condensation between the Ti and Zr species was studied by characterizing the morphologies, crystalline structures, chemical compositions, surface properties, and band gaps of the nanocrystals obtained at different reaction temperatures and Zr-to-Ti stoichiometric ratios. Increases in the concentration of Zr(4+) and in the reaction temperature led to large nanorods and regular shapes, respectively. In addition, only the anatase form was observed in the Zr-doped TiO(2) nanorods. The Zr-to-Ti ratios obtained ranged from 0.01 to 2.05, all of which were far below the stoichiometric ratios used during the preparation of the samples (0.25-4). Moreover, the Zr(4+) units accumulated mainly at the surface of the TiO(2) nanocrystals. The band gaps of the Zr-doped TiO(2) nanorods ranged from 2.8 to 3.8 eV, which are smaller than those of pure TiO(2) (3.7 eV) or ZrO(2) (5.2 eV). The Zr-doped anatase TiO(2) nanorods prepared at 400 degrees C at an initial stoichiometric Zr-to-Ti ratio of 2:3 exhibited the highest photoactivities for the decomposition of rhodamine B because of the presence of trace amounts of Zr(4+) (Zr/Ti = 0.03) in the TiO(2) and the regular shapes of these particles. DSC analysis indicated that the temperatures for forming nanocrystalline TiO(2) and ZrO(2) were 207 and 340 degrees C, respectively. Moreover, the reactivities of condensation between the Ti species were reduced when Zr species were involved in the NHSG reactions. The results obtained in this study clearly demonstrate that the faster kinetics for the generation of TiO(2) controls the material properties as well as the photoactivities of the nonhydrolytic sol-gel-derived nanocrystals.

Concentration and fate of persistent organochlorine pesticides in estuarine sediments using headspace solid-phase microextraction.

The concentration and fate of persistent organochlorine pesticides (OCPs) in estuarine surface sediments in Erh-jen and Lan-yang rivers, Taiwan were investigated using headspace solid-phase microextraction (HSSPME) method to evaluate the possible pollution potential and guideline for OCP concentrations in Taiwan. The HSSPME method exhibits a good analytical performance with low detection limits for OCP determination in sediment. In addition, results obtained using the developed HSSPME method were in good agreement with those obtained using Soxhlet extraction in a certified sample. The developed analytical method was further applied to the determination of concentrations of OCP residues in surface sediments from the estuaries of the selected rivers in Taiwan. A total of 20 surface sediments from each river was collected from 10 sampling stations. The total OCP concentrations in sediments from Erh-jen River ranged from 0.17 to 5.04 ng/g-dw with the mean values of 0.25-1.24 ng/g-dw for HCHs, 0.10-0.89 ng/g-dw for cyclodienes and 0.16-0.64 ng/g-dw for DDTs. The concentrations of OCPs in sediments from Lan-yang River were in the range 0.37-0.9 ng/g-dw with an average of lower than 0.5 ng/g-dw. HCHs and DDTs were abundant in the estuarine sediments from the selected rivers. Results obtained in this study show that the origin of OCPs in the surface sediments from Erh-jen River is a combination of erosion of the weathered soils and long-range atmospheric transport, while the OCP concentrations found in Lan-yang River could be regarded as the background levels of OCPs in Taiwan.