Photoelectrochemical cell for simultaneous electricity generation and heavy metals recovery from wastewater

The feasibility of simultaneous recovery of heavy metals from wastewater (e.g., acid mining and electroplating) and production of electricity is demonstrated in a novel photoelectrochemical cell (PEC). The photoanode of the cell bears a nanoparticulate titania (TiO2) film capped with the block copolymer [poly(ethylene glycol)-b-poly(propylene glycol)-b-poly(ethylene glycol)] hole scavenger, which consumed photogenerated holes, while the photogenerated electrons transferred to a copper cathode reducing dissolved metal ions and produced electricity. Dissolved silver Ag+, copper Cu2+, hexavalent chromium as dichromate Cr2O72− and lead Pb2+ ions in a mixture (0.2 mM each) were removed at different rates, according to their reduction potentials. Reduced Ag+, Cu2+ and Pb2+ ions produced metal deposits on the cathode electrode which were mechanically recovered, while Cr2O72− reduced to the less toxic Cr3+ in solution. The cell produced a current density Jsc of 0.23 mA/cm2, an open circuit voltage Voc of 0.63 V and a maximum power density of 0.084 mW/cm2. A satisfactory performance of this PEC for the treatment of lead-acid battery wastewater was observed. The cathodic reduction of heavy metals was limited by the rate of electron-hole generation at the photoanode. The PEC performance decreased by 30% after 9 consecutive runs, caused by the photoanode progressive degradation

Mechanism and experimental study on the photocatalytic performance of Ag/AgCl @ chiral TiO2 nanofibers photocatalyst: the impact of wastewater components

© 2014 Elsevier B.V.The effect of the water matrix components of a secondary effluent of a urban wastewater treatment plant on the photocatalytic activity of Ag/AgCl @ chiral TiO2 nanofibers and the undergoing reaction mechanisms were investigated. These effects were evaluated through the water components-induced changes on the net rate of hydroxyl radical (•OH) generation and modeled using a relative rate technique. Dissolved organic matter DOM (k=-2.8×108M-1s-1) scavenged reactive oxygen species, Cl- (k=-5.3×108M-1s-1) accelerated the transformation from Ag to AgCl (which is not photocatalytically active under visible-light irradiation), while Ca2+ at concentrations higher than 50mM (k=-1.3×109M-1s-1) induced aggregation of Ag/AgCl and thus all of them revealed inhibitory effects. In contrast, NO3- (k=6.9×108M-1s-1) and CO32- (k=3.7×108M-1s-1) improved the photocatalytic activity of Ag/AgCl slightly by improving the rate of HO• generation. Other ubiquitous secondary effluent components including SO42- (k=3.9×105M-1s-1), NH3+ (k=3.5×105M-1s-1) and Na+ (k=2.6×104M-1s-1) had negligible effects. 90% of 17-α-ethynylestradiol (EE2) spiked in the secondary effluent was removed within 12min, while the structure and size of Ag/AgCl @ chiral TiO2 nanofibers remained stable. This work may be helpful not only to uncover the photocatalytic mechanism of Ag/AgCl based photocatalyst but also to elucidate the transformation and transportation of Ag and AgCl in natural water

Dredged-Sediment-Promoted Synthesis of Boron-Nitride-Based Floating Photocatalyst with Photodegradation of Neutral Red under Ultraviolet-Light Irradiation

A novel floating photocatalyst (BN-DS-7) has been successfully synthesized by calcining the mixture of boron nitride (BN) and dredged sediment (DS) with a specific mass ratio (3:7) at 1100 °C for a half hour. BN is synthesized for the first time using an oxygen-limited method, which consists of a nanoplate ∼30 nm in size and has a bandgap at 3.94 eV. The as-synthesized BN can degrade NR under ultraviolet (UV) light irradiation. For BN-DS-7, X-ray photoelectron spectroscopy analysis suggests that BN mainly interacts with DS through the strong coordination between these N atoms in BN and these Si and Al atoms in DS. This leads to BN-DS-7 having good compression strength (∼9 MPa). Thermogravimetric analysis for BN shows that a few BN (∼13%) synthesized via an oxygen-limited method will pyrolyze at 1100 °C and the released gas can be sealed in the inside of DS at 1100 °C, resulting in that BN-DS-7 can float on the water surface. Photodegradation results show that BN-DS-7 can degrade 84% of NR (20 mg/L) under UV-light irradiation for 5 h, and the active species are •OH and photoinduced hole. Total organic carbon analysis for NR solution before and after photodegradation show that ∼70% of NR has been mineralized into inorganic carbons. This work is helpful to develop a new type of BN-based floating material and enlarge the application field of DS

Seeking Sustainability: Multiobjective Evolutionary Optimization for Urban Wastewater Reuse in China

Sustainable design and implementation of wastewater reuse in China have to achieve an optimum compromise among water resources augmenting, pollutants reduction and economic profit. A systematic framework with a multiobjective optimization model is first developed considering the trade-offs among wastewater reuse supplies and demands, costs and profits, as well as pollutants reduction. Pareto fronts of wastewater reuse optimization for 31 provinces of China are obtained through nondominated sorting genetic algorithm trials. The control strategies for each province are selected on the basis of regional water resources and water environment status. On the national level, the control strategies of wastewater reuse scale, BOD₅ reduction, and economic profit are 15.39 billion cubic meters, 176.31 kilotons, and 9.68 billion RMB Yuan, respectively. The driving forces of water resources augmenting and water pollution control play more important roles than economic profit during wastewater reuse expanding in China. According to the optimal allocations, reclaimed wastewater should be intensively used in municipal, domestic, and recreative sectors in the regions suffering from quantity-related water scarcity, while it should be focused on industrial users in the regions suffering from quality-related water scarcity. The results present a general picture of wastewater reuse for policy makers in China

Combining Heterojunction Engineering with Surface Cocatalyst Modification To Synergistically Enhance the Photocatalytic Hydrogen Evolution Performance of Cadmium Sulfide Nanorods

Photocatalytic decomposition of water to hydrogen is an energy conversion process just like photosynthesis. Herein, for the first time, CoP-modified CdS/g-C₃N₄ composite nanorods were synthesized on the basis of the concept of combining heterojunction engineering with cocatalyst modification. The obtained CoP-CdS/g-C₃N₄ composites exhibit excellent photocatalytic activity and good photostability when applied as a photocatalyst for water reduction. The H₂ production rate reaches up to 23 536 μmol g^–1 h^–1, which was about 14 times higher than that of pure CdS. Furthermore, the stability of the composite was obviously improved. The outstanding performance of the CoP-CdS/g-C₃N₄ composites can be attributed to the following reasons: (1) Intimate contact between CdS and g-C₃N₄ can effectively promote the electron–hole pair spacial separation. (2) The introduction of CoP as cocatalyst on the CdS/g-C₃N₄ nanorods can further extract photogenerated electrons from CdS/g-C₃N₄ and lower the overpotential of H⁺ reduction

Electrolyte Cations Binding with Extracellular Polymeric Substances Enhanced <i>Microcystis</i> Aggregation: Implication for <i>Microcystis</i> Bloom Formation in Eutrophic Freshwater Lakes

The hydrodynamic and structural properties of <i>Microcystis</i> extracellular polymeric substances (EPS) in electrolytes with different valences and ionic strengths were investigated via using dynamic light scattering, the fluorescence excitation emission matrix coupled with parallel factor (EEM–PARAFAC) analysis, two-dimensional correlation spectroscopy (2D-COS), and cryogenic transmission electron microscopy (Cryo-TEM). The hydrodynamic diameters of EPS colloids exhibited no variation for monovalent NaCl but a substantial increase for divalent CaCl₂ and MgCl₂. However, the negative electrophoretic mobilities for all complexes indicated that charge neutralization would not be the main mechanism for EPS aggregation. Application of EEM–PARAFAC and 2D-Fourier transform infrared (FTIR)–COS revealed obvious electrolyte binding potential with both fluorescent phenolic and aromatic compounds and nonfluorescent polysaccharides. The complexation model showed that divalent Ca²⁺ and Mg²⁺ exhibited a strong binding capability with phenolic −OH, aromatic CC, and polysaccharide C–O groups, while the monovalent electrolyte exhibited negligible association with these groups. Such a strong complexation can bridge each individual biomolecule together to form EPS aggregates and <i>Microcystis</i> colonies, as supported by <i>in situ</i> Cryo-TEM and light microscope observation, respectively. Given the increased concentration in natural ecosystems, electrolyte cations, especially divalent cations, would play increased roles in <i>Microcystis</i> bloom formation and thus should be considered

Dye-sensitized photoelectrochemical cell on plasmonic Ag/AgCl @ chiral TiO2 nanofibers for treatment of urban wastewater effluents, with simultaneous production of hydrogen and electricity

The feasibility of simultaneous production of hydrogen and electricity with simultaneous contaminants removal from “actual” urban wastewater within a dye-sensitized photoelectrochemical cell (DSPC) is demonstrated for the first time. The photoanode in the DSPC was a novel nanostructured plasmonic Ag/AgCl @ chiral TiO2 nanofibers (Ag and AgCl nanoparticles supported on chiral TiO2 nanofibers). The electrolyte in the DSPC was actual wastewater to which an estrogen (17-β-ethynylestradiol, EE2) and a heavy metal (Cu2+8 ) were added. The contaminants in the wastewater rather than I-/I3 - (usual electrolyte in conventional DSPCs) acted as electrons bridges for the stabilization of charges in this DSPC. Almost total removal of total organic carbon (TOC), Cu2+, EE2, and 70% removal of total nitrogen (TN) were achieved under visible-light irradiation. A relatively high solar energy conversion efficiency (PCE 3.09%) was recorded and approximately 98% of the electricity was converted to H2 after the consumption of dissolved oxygen (DO), Cu2+ and TN. This performance was attributed to the “symbiotic” relationship between the TiO2 chiral nanofibers and the plasmonic effect of Ag nanoparticles at the photoanode although Ag acting as a recombination site may hinder the generation of electricity. The dye N719 in this study exhibited a temporary sensitization effect, and a more efficient sensitizer is expected to be studied in the future. This study opens up new opportunities for producing renewable energy from wastewater treatment processes including organic and inorganic matter as viable resources

Modeling the Effects of Hydrodynamic Regimes on Microbial Communities within Fluvial Biofilms: Combining Deterministic and Stochastic Processes

To fully understand the effects of hydrodynamics on a microbial community, the roles of niche-based and neutral processes must be considered in a mathematical model. To this end, a two-dimensional model combining mechanisms of immigration, dispersal, and niche differentiation was first established to describe the effects of hydrodynamics on bacterial communities within fluvial biofilms. Deterministic factors of the model were identified via the calculation of Spearman’s rank correlation coefficients between parameters of hydrodynamics and the bacterial community. It was found that turbulent kinetic energy and turbulent intensity were considered as a set of reasonable predictors of community composition, whereas flow velocity and turbulent intensity can be combined together to predict biofilm bacterial biomass. According to the modeling result, the bacterial community could get its favorable assembly condition with a flow velocity ranging from 0.041 to 0.061 m/s. However, the driving force for biofilm community assembly changed with the local hydrodynamics. Individuals reproduction within the biofilm was the main driving force with flow velocity less than 0.05 m/s, while cell migration played a much more important role with velocity larger than 0.05 m/s. The developed model could be considered as a useful tool for improving the technologies of water environment protection and remediation

Cetyltrimethylammonium Bromide-Coated Fe₃O₄ Magnetic Nanoparticles for Analysis of 15 Trace Polycyclic Aromatic Hydrocarbons in Aquatic Environments by Ultraperformance, Liquid Chromatography With Fluorescence Detection

Accurate determination of polycyclic aromatic hydrocarbons (PAHs) in surface waters is necessary for protection of the environment from adverse effects that can occur at concentrations which require preconcentration to be detected. In this study, an effective solid phase extraction (SPE) method based on cetyltrimethylammonium bromide (CTAB)-coated Fe₃O₄ magnetic nanoparticles (MNPs) was developed for extraction of trace quantities of PAHs from natural waters. An enrichment factor of 800 was achieved within 5 min by use of 100 mg of Fe₃O₄ MNPs and 50 mg of CTAB. Compared with conventional liquid–liquid extraction (LLE), C18 SPE cartridge and some newly developed methods, the SPE to determine bioaccessible fraction was more convenient, efficient, time-saving, and cost-effective. To evaluate the performance of this novel sorbent, five natural samples including rainwater, river waters, wastewater, and tap water spiked with 15 PAHs were analyzed by use of ultraperformance, liquid chromatography (UPLC) with fluorescence detection (FLD). Limits of determination (LOD) of PAHs (log <i>K</i>_ow ≥ 4.46) ranged from 0.4 to 10.3 ng/L, with mean recoveries of 87.95 ± 16.16, 85.92 ± 10.19, 82.89 ± 5.25, 78.90 ± 9.90, and 59.23 ± 3.10% for rainwater, upstream and downstream river water, wastewater, and tap water, respectively. However, the effect of dissolved organic matter (DOM) on recovery of PAHs varied among matrixes. Because of electrostatic adsorption and hydrophobicity, DOM promoted adsorption of Fe₃O₄ MNPs to PAHs from samples of water from the field. This result was different than the effect of DOM under laboratory conditions. Because of competitive adsorption with the site of action on the surface of Fe₃O₄ MNPs for CTAB, recoveries of PAHs were inversely proportional to concentrations of Ca²⁺ and Mg²⁺. This novel sorbent based on nanomaterials was effective at removing PAHs at environmentally relevant concentrations from waters containing relevant concentrations of both naturally occurring organic matter and hardness metals