Ultrafiltration Membranes Functionalized with Copper Oxide and Zwitterions for Fouling Resistance.

Polymeric membrane fouling is a long-standing challenge for water filtration. Metal/metal oxide nanoparticle functionalization of the membrane surface can impart anti-fouling properties through the reactivity of the metal species and the generation of radical species. Copper oxide nanoparticles (CuO NPs) are effective at reducing organic fouling when used in conjunction with hydrogen peroxide, but leaching of copper ions from the membrane has been observed, which can hinder the longevity of the CuO NP activity at the membrane surface. Zwitterions can reduce organic fouling and stabilize NP attachment, suggesting a potential opportunity to combine the two functionalizations. Here, we coated polyethersulfone (PES) ultrafiltration membranes with polydopamine (PDA) and attached the zwitterionic compound, thiolated 2-methacryloyloxyethyl phosphorylcholine (MPC-SH), and CuO NPs. Functionalized membranes resulted in a higher flux recovery ratio (0.694) than the unfunctionalized PES control (0.599). Copper retention was high (>96%) for functionalized membranes. The results indicate that CuO NPs and MPC-SH can reduce organic fouling with only limited copper leaching.

Electrochemical nutrient removal from natural wastewater sources and its impact on water quality.

In this study, a suite of natural wastewater sources is tested to understand the effects of wastewater composition and source on electrochemically driven nitrogen and phosphorus nutrient removal. Kinetics, electrode behavior, and removal efficiency were evaluated during electrochemical precipitation, whereby a sacrificial magnesium (Mg) anode was used to drive precipitation of ammonium and phosphate. The electrochemical reactor demonstrated fast kinetics in the natural wastewater matrices, removing up to 54% of the phosphate present in natural wastewater within 1 min, with an energy input of only 0.04 kWh.m-3. After 1 min, phosphate removal followed a zero-order rate law in the 1 min - 30 min range. The zero-order rate constant (k) appears to depend upon differences in wastewater composition, where a faster rate constant is associated with higher Cl- and NH4+ concentrations, lower Ca2+ concentrations, and higher organic carbon content. The sacrificial Mg anode showed the lowest corrosion resistance in the natural industrial wastewater source, with an increased corrosion rate (vcorr) of 15.8 mm.y-1 compared to 1.9-3.5 mm.y-1 in municipal wastewater sources, while the Tafel slopes (ß) showed a direct correlation with the natural wastewater composition and origin. An overall improvement of water quality was observed where important water quality parameters such as total organic carbon (TOC), total suspended solids (TSS), and turbidity showed a significant decrease. An economic analysis revealed costs based upon experimental Mg consumption are estimated to range from 0.19 $.m-3 to 0.30 $.m-3, but costs based upon theoretical Mg consumption range from 0.09 $.m-3 to 0.18 $.m-3. Overall, this study highlights that water chemistry parameters control nutrient recovery, while electrochemical treatment does not directly produce potable water, and that economic analysis should be based upon experimentally-determined Mg consumption data. Synopsis Statement: Magnesium-driven electrochemical precipitation of natural wastewater sources enables fast kinetics for phosphate removal at low energy input.

Electroless Production of Fertilizer (Struvite) and Hydrogen from Synthetic Agricultural Wastewaters.

The drive toward sustainable phosphorus (P) recovery from agricultural and municipal wastewater streams has intensified. However, combining P recovery with energy conservation is perhaps one of the greatest challenges of this century. In this study, we report for the first time the simultaneous electroless production of struvite and dihydrogen from aqueous ammonium dihydrogen phosphate (NH4H2PO4) solutions in contact with either a pure magnesium (Mg) or a Mg alloy as the anode and 316 stainless steel (SS) as the cathode placed in a bench-scale electrochemical reactor. During the electroless process (i.e., in the absence of external electrical power), the open circuit potential (OCP), the formation of struvite on the anode, and the generation of dihydrogen at the cathode were monitored. We found that struvite is formed, and that struvite crystal structure/morphology and precipitate film thickness are affected by the concentration of the HnPO4n-3/NH4+ in solution and the composition of the anode. The pure Mg anode produced a porous 0.6-4.1 µm thick film, while the AZ31 Mg alloy produced a more compact 1.7-9.9 µm thick struvite film. Kinetic analyses revealed that Mg dissolution to Mg2+ followed mostly a zero-order kinetic rate law for both Mg anode materials, and the rate constants (k) depended upon the struvite layer morphology. Fourier-transform infrared spectrometry, X-ray diffraction, and scanning electron microscopy indicated that the synthesized struvite was of high quality. The dihydrogen and Mg2+ in solution were detected by a gas chromatography-thermal conductivity detector and ion chromatography, respectively. Furthermore, we fully demonstrate that the reactor was able to remove ∼73% of the HnPO4n-3 present in a natural poultry wastewater as mainly struvite. This study highlights the feasibility of simultaneously producing struvite and dihydrogen from wastewater effluents with no energy input in a green and sustainable approach.

Chemical Structure of Fe-Ni Nanoparticles for Efficient Oxygen Evolution Reaction Electrocatalysis.

Bimetallic iron-nickel-based nanocatalysts are perhaps the most active for the oxygen evolution reaction (OER) in alkaline electrolytes. Recent developments in literature have suggested that the ratio of iron and nickel in Fe-Ni thin films plays an essential role in the performance and stability of the catalysts. In this work, the metallic ratio of iron to nickel was tested in alloy bimetallic nanoparticles. Similar to thin films, nanoparticles with iron-nickel atomic compositions where the atomic iron percentage is ≤50% outperformed nanoparticles with iron-nickel ratios of >50%. Nanoparticles of Fe20Ni80, Fe50Ni50, and Fe80Ni20 compositions were evaluated and demonstrated to have overpotentials of 313, 327,, and 364 mV, respectively, at a current density of 10 mA/cm2. While the Fe20Ni80 composition might be considered to have the best OER performance at low current densities, Fe50Ni50 was found to have the best current density performance at higher current densities, making this composition particularly relevant for electrolysis conditions. However, when stability was evaluated through chronoamperometry and chronopotentiometry, the Fe80Ni20 composition resulted in the lowest degradation rates of 2.9 µA/h and 17.2 µV/h, respectively. These results suggest that nanoparticles with higher iron and lower nickel content, such as the Fe80Ni20 composition, should be still taken into consideration while optimizing these bimetallic OER catalysts for overall electrocatalytic performance. Characterization by electron microscopy, diffraction, and X-ray spectroscopy provides detailed chemical and structural information on as-synthesized nanoparticle materials.

Scalable Chitosan-Graphene Oxide Membranes: The Effect of GO Size on Properties and Cross-Flow Filtration Performance.

Chitosan (CS)-graphene oxide (GO) composite films were fabricated, characterized, and evaluated as pressure-driven water filtration membranes. GO particles were incorporated into a chitosan polymer solution to form a suspension that was cast as a membrane via evaporative phase inversion allowing for scale-up for cross-flow testing conditions. Morphology and composition results for nano and granular GO in the CS matrix indicate that the particle size of GO impacts the internal membrane morphology as well as the structural order and the chemical composition. Performance of the membranes was evaluated with cationic and anionic organic probe molecules and revealed charge-dependent mechanisms of dye removal. The CSGO membranes had rejections of at least 95% for cationic methylene blue with mass balances obtained from measurements of the feed, concentrate, and permeate. This result suggests the dominant mechanism of removal is physical rejection for both GO particle sizes. For anionic methyl orange, the results indicate sorption as the dominant mechanism of removal, and performance is dependent on both GO particle size and time, with micrometer-scale GO removing 68-99% and nanometer-scale GO showing modest removal of 29-64%. The pure water flux for CSGO composite membranes ranged from 2-4.5 L/m2 h at a transmembrane pressure of 344 kPa (3.44 bar), with pure water permeance ranging from 5.8 × 10-3 to 0.01 L/m2 h kPa (0.58-1.3 L/m2 h bar). Based on the 41 µm membrane thickness obtained from microscopy, the hydraulic permeability ranged from 0.24-0.54 L µm/m2 h kPa (24.4-54.1 L µm/m2 h bar).