Small concentrations, big results: µM addition of photoactive iron oxides with PMS, PDS, or H2O2, leads to enhanced removal of viruses at near-neutral pH.

The photo-Fenton process is effective for pathogen removal, and its low-cost versions can be applied in resource-poor contexts. Herein, a photo-Fenton-like system was proposed using low concentrations of iron oxides (hematite and magnetite) and persulfates (peroxymonosulfate - PMS, and peroxydisulfate - PDS), which exhibited excellent inactivation performance towards MS2 bacteriophages. In the presence of bacteria, MS2 inactivation was inhibited in H2O2 and PDS systems but promoted in PMS-involved systems. The inactivation efficacy of all the proposed systems for mixed bacteria and viruses was greater than that of the sole bacteria, showing potential practical applications. The inactivation performance of humic acid-incorporated iron oxides mediating photo-Fenton-like processes was also studied; except for the PMS-involved system, the inactivation efficacy of the H2O2- and PDS-involved systems was inhibited, but the PDS-involved system was still acceptable (< 2 h). Reactive species exploration experiments indicated that ·OH was the main radical in the H2O2 and PDS systems, whereas 1O2 played a key role in the PMS-involved system. In summary, hematite- and magnetite-mediated persulfate-assisted photo-Fenton-like systems at low concentrations can be used as alternatives to the photo-Fenton process for virus inactivation in sunny areas, providing more possibilities for point-of-use drinking water treatment in developing countries.

Designing sequence-defined peptoids for fibrillar self-assembly and silicification.

In the biological environment, mineral crystals exquisitely controlled by biomacromolecules often show intricate hierarchical structures and superior mechanical properties. Among these biominerals, spicules, hybrid silica/protein superstructures serving as skeletal elements in demosponges, represent an excellent example for motivating the synthesis of silica materials. Herein, by designing sequence-defined peptoids containing side chains with a strong binding to silica, we demonstrated that self-assembly of these peptoids into fiber structures enables the mimicking of both biocatalytic and templating functions of silicatein filaments for the formation of silica fibers at near-neutral pH and ambient temperature. We further showed that the presence of amino groups is significant for the nucleation of silica on self-assembled peptoid nanofibers. Molecular dynamics simulation further confirmed that having silica-binding of amino side chains is critical for self-assembled peptoid fibers in triggering silica formation. We demonstrated that tuning inter-peptoid interactions by varying carboxyl and amino side chains significantly influences the assembly kinetics and final morphologies of peptoid assemblies as scaffolds for directing silica mineralization to form silica spheres, fibers, and sheets. The formation of silica shell on peptoid fibers increased the mechanical property of peptoid hydrogel materials by nearly 1000-fold, highlighting the great potential of using silicification to enhance the mechanical property of hydrogel materials for applications including tissue engineering. Since peptoids are highly robust and programmable, we expect that self-assembly of peptoids containing solid-binding side chains into hierarchical materials opens new opportunities in the design and synthesis of highly tunable scaffolds that direct the formation of composite nanomaterials.

Effective removal of the rotifer Brachionus calyciflorus from a Chlorella vulgaris microalgal culture by homogeneous solar photo-Fenton at neutral pH.

In this study, a citrate-modified photo-Fenton process was successfully applied to decontaminate a Chlorella vulgaris microalgae culture spiked with the rotifer Brachionus calyciflorus (5 individuals mL-1). The applied treatment (1 mg L-1 Fe2+, 20 mg L-1 H2O2, 17.5 mg L-1 citric acid) had only moderate effects on viability and regrowth of the microalgae since, after a short post-treatment delay of a few days, they reached final cell densities similar to that obtained for microalgae cultures that were not spiked. The decontamination was effective as no regrowth of rotifers was observed in the microalgae cultures after treatment. The efficacy of the citrate-modified photo-Fenton treatment was also studied with a higher starting concentration of 20 rotifers mL-1 and was compared with a solar light/H2O2 treatment. Results show that both treatments had similar efficacies on the rotifer elimination, but that the citrate-modified photo-Fenton treatment had a lower negative impact on the regrowth of microalgae than the solar light/H2O2 treatment. However, when microalgae cultures were spiked with 20 rotifers mL-1, rotifers were only partially inactivated and post-treatment regrowth occurred, which highlights the importance to apply the photo-Fenton process at an early stage of a contamination to achieve full rotifer elimination. In any case, a contamination with 5 rotifers mL-1 is already a significant threat as numbers above 1000 rotifers mL-1 were reached after 14 days and caused the microalgae culture to fail. Overall, our treatment suggests that the citrate-modified solar photo-Fenton process is an environmentally friendly solution to support the maintenance of contaminant-free microalgal cultures.

Microstructural Effects in the Development of Near-Neutral pH Stress Corrosion Cracks in Pipelines.

The corrosion and stress corrosion cracking (SCC) behaviors of 20#, X60, and X80 pipeline steels in a near-neutral pH environment were investigated by means of electrochemical measurement, immersion test, and interrupted slow strain rate tensile (SSRT) test. The propensity for SCC, as indicated by the stress threshold value for crack initiation, was found to be dependent on the type of steel microstructure. Cracks were initiated in the high-strength steel X80 at a stress less than its yield strength, whereas in the other lower-grade steels, the initiation of cracks occurred after the yielding point. The threshold stress of SCC initiation in the near-neutral pH environment for 20#, X60, and X80 steels were 130.64% σys, 106.79% σys, and 86.92% σys, respectively. The SCC of 20# and X60 were characterized by the formation of transgranular and intergranular cracks, while X80 steel was only by transgranular cracking. The occurrence of corrosion had a great effect on crack initiation and the growth at the later stage. The latter involved hydrogen effects. A correlation between SCC sensitivity and the yield strength of the steel has been identified.

Gas Crossover Regulation by Porosity-Controlled Glass Sheet Achieves Pure Hydrogen Production by Buffered Water Electrolysis at Neutral pH.

Near-neutral pH water electrolysis driven by renewable electricity can reduce the costs of clean hydrogen generation, but its low efficiency and gas crossover in industrially relevant conditions remain a challenge. Here, it was shown that electrolyte engineering could suppress the crossover of dissolved gases such as O2 by regulating their diffusion flux. In addition, a hydrophilized mechanically stable glass sheet was found to block the permeation of gas bubbles, further enhancing the purity of evolved gas from water electrolysis. This sheet had a lower resistance than conventional diaphragms such as Zirfon due to its high porosity and small thickness. A saturated K-phosphate solution at pH 7.2 was used as an electrolyte together with the hydrophilized glass sheet as a gas-separator. This led to a near-neutral pH water electrolysis with 100 mA cm-2 at a total cell voltage of 1.56 V with 99.9 % purity of produced H2 .

Strategies to Develop Earth-Abundant Heterogeneous Oxygen Evolution Reaction Catalysts for pH-Neutral or pH-Near-Neutral Electrolytes.

The anodic oxygen evolution reaction (OER) is the bottleneck of water splitting to produce hydrogen due to its sluggish kinetics. In order to lower the energy cost, highly active and cost-efficient OER catalysts need to be used to overcome the OER reaction barrier, especially in neutral pH. Compared to alkaline or acidic electrolytes, pH-neutral or pH-near-neutral electrolytes are considered to be cheaper and safer, and water from rivers and the sea could be used directly under such conditions. However, OER under neutral pH is challenging compared to the OER catalysts for alkaline conditions. Therefore, OER catalysts for neutral or near-neutral pH have not been pursued significantly and, hence, there are limited advances in this area. Here, the progress made in the research and development of earth-abundant heterogeneous catalysts for OER in three pH-neutral or pH-near-neutral systems, namely, the phosphate system, the carbonate system, and the borate system, are systematically reviewed and summarized for the first time. Strategies to develop high-performance OER catalysts for neutral pH are reviewed and summarized. In addition, future challenges and opportunities in this field are discussed, which may shed some light on the future developments of earth-abundant heterogeneous catalysts for OER in neutral or near-neutral pH.

Accelerating FeIII-Aqua Complex Reduction in an Efficient Solid-Liquid-Interfacial Fenton Reaction over the Mn-CNH Co-catalyst at Near-Neutral pH.

The sluggish regeneration rate of FeII and low operating pH still restrict the wider application of classical Fenton process (FeII/H2O2) for practical water treatment. To overcome these challenges, we exploit the Mn-CNH co-catalyst to construct a solid-liquid interfacial Fenton reaction and accelerate the FeIII/FeII redox cycle at the interface for sustainably generating •OH from H2O2 activation. The Mn-CNH co-catalyst exhibits an excellent regeneration rate of FeII (∼65%) and a high tetracycline removal rate (Kobs) of 0.0541 min-1, which is 19.0 times higher than that of the FeII/H2O2 system (0.0027 min-1) at a near-neutral pH (pH ≈ 5.8), and it also attains 100% degradation of sulfamethoxazole, rhodamine B, and methyl orange. The cyclic mechanism of FeIII/FeII is further elucidated in an atomic scale by combining characterizations and density functional theory calculations, including FeaqIII specific adsorption and the electron-transfer process. Mn active sites can accumulate electrons from the matrix and adsorb FeaqIII to form Mn-Fe bonds at the solid-liquid interface, which accelerate electron transfer from Mn-CNH to FeaqIII and promote the regeneration of FeII at a wide pH range with a lower energy barrier. The regeneration rate of FeII in the Mn-CNH/FeII/H2O2 system outperforms the benchmark Fenton system and other typical metal nanomaterials, which has great potential to be widely applied in actual environment remediation.

Delivering the Full Potential of Oxygen Evolving Electrocatalyst by Conditioning Electrolytes at Near-Neutral pH.

This study reports on the impact of identity and compositions of buffer ions on oxygen evolution reaction (OER) performance at a wide range of pH levels using a model IrOx electrocatalyst. Rigorous microkinetic analysis employing kinetic isotope effects, Tafel analysis, and temperature dependence measurement was conducted to establish rate expression isolated from the diffusion contribution of buffer ions and solution resistance. It was found that the OER kinetics was facile with OH- oxidation compared to H2 O, the results of which were highlighted by mitigating over 200 mV overpotential in the presence of buffer to reach 10 mA cm-2 . This improvement was ascribed to the involvement of the kinetics of the local OH- supply by the buffering action. Further digesting the kinetic data at various buffer pKa and the solution bulk pH disclosed a trade-off between the exchange current density and the Tafel slope, indicating that the optimal electrolyte condition can be chosen at a different range of current density. This study provides a quantitative guideline for electrolyte engineering to maximize the intrinsic OER performance that electrocatalyst possesses especially at near-neutral pH.

Mechanistic insights into a novel nitrilotriacetic acid-Fe0 and CaO2 process for efficient anaerobic digestion sludge dewatering at near-neutral pH.

Traditional Fenton or Fenton-like oxidation has been widely studied for waste activated sludge dewaterability. However, the narrow pH range (2.0-4.0) and the instabilities of Fe2+ and H2O2 have hindered its commercial application. Owing to the high alkalinity of anaerobic digestion (AD) sludge, traditional Fenton or Fenton-like oxidation is economically unfeasible for its dewatering. In this study, we successfully demonstrated a novel and feasible method that used nitrilotriacetic acid (NTA)-Fe0 combined with CaO2 (NTA-Fe0/CaO2) at near-neutral pH (∼6.0) (a slight pH adjustment) in which capillary suction time ratio (CST0/CST) and centrifuged weight reduction (CWR) improved by 6 folds and 42.98 ± 0.37%, respectively, under the optimal conditions. The presence of NTA accelerated the Fe0 corrosion, Fe2+ stability and turnover between Fe2+ and Fe3+. As such, Fe0 could effectively catalyze CaO2 to produce hydroxyl radicals (•OH) under near-neutral conditions. Accordingly, various molecular weight hydrophilic compounds in different extracellular polymeric substances fractions were significantly reduced after treatment. The hydrophilic functional groups especially protein molecules were largely reduced. Consequently, the viscosity of sludge and particle size effectively decreased, while the release of bound water, surface charge, flocculation, and flowability of sludge were improved. The cost-benefit analysis further demonstrated the NTA-Fe0/CaO2 treatment has high reusability and stability and is also more economical over the FeCl3/CaO and Fenton's reagent/CaO treatments. In summary, the NTA-Fe0/CaO2 process is a cost-effective and practically feasible technology for improving AD sludge dewaterability.

Degradation mechanism of fipronil and its transformation products, matrix effects and toxicity during the solar/photo-Fenton process using ferric citrate complex.

This study presents the degradation of fipronil in sewage treatment plant (STP) effluent by photo-Fenton at near neutral pH (pH 6.0) using Fe3+/Citrate complex. 83% of fipronil degradation was reached using a molar iron/citrate ratio of 1:3 (192 µmol L-1 of Fe3+/576 µmol L-1 of citrate). Photo-Fenton reduced the toxicity of treated solutions as according to the survival of Drosophila melanogaster exposed to non-treated and treated samples. Control experiments performed in distilled water using 32 µmol L-1 of Fe3+/96 µmol L-1 of citrate achieved 98% of fipronil degradation within 100 kJ m-2 (UV-A radiation, k = 30 × 10-3 kJ-1 m2 and t1/2 = 23 kJ m-2), thus indicating that fipronil degradation is impaired by natural organic matter and inorganic ions present in STP effluent. Degradation was faster under solar radiation, as the same efficiency (98%) was obtained after 75 kJ m-2 (k = 63 × 10-3 kJ-1 m2 and t1/2 = 11 kJ m-2). In addition, pathways of fipronil degradation using Fe3+/Citrate under solar and UV-A radiation were investigated and transformation products proposed. Results revealed that the HO• attack occurred preferentially in the pyrazole ring. Eight transformation products were identified by UHPLC-Q-TOF-MS and four are unprecedented in the literature. Control experiments in distilled water demonstrated that toxicity reduction is related to fipronil degradation and that transformation products are less toxic than fipronil. Furthermore, toxicity of STP fortified with fipronil was reduced after photo-Fenton. These results demonstrate the feasibility of applying this process using Fe3+/Citrate complex for fipronil degradation in a real matrix.

Rosmarinic acid enhanced Fe(III)-mediated Fenton oxidation removal of organic pollutants at near neutral pH.

In this study, we reported that the presence of rosemary acid (RA) could strongly enhance the Fe(III)-mediated Fenton oxidation of 2,4-DCP as the model contaminant at near neutral pH. This enhancement was verified by the strong chelating and reducing ability of RA, which could prevent ion precipitation and accelerate the Fe3+/Fe2+ cycle. Radical quenching experiments and electron paramagnetic resonance confirmed the existence and roles of hydroxyl radicals in the Fe3+/RA/H2O2 system. Lot size optimized experiments were executed to achieve efficient 2,4-DCP degradation (99.93%) under the optimum conditions of 100 µmol/L Fe3+, 100 µmol l/L RA and 8 mmol/L H2O2 within 60 min. In addition, co-existing metal ions, inorganic anions and natural organic matters were proved that they could inhibit removal efficiency and rate at varying degrees. Total organic carbon and chloride ion measurements were employed to probe the mineralization of organic matters (including RA and 2,4-DCP). This study provides a new modified Fenton system to enhance the oxidation removal of refractory organics in water and will enrich the understanding on effective H2O2 activation at neutral pH.

Unconventional electro-Fenton process operating at a wide pH range with Ni foam cathode and tripolyphosphate electrolyte.

We propose an unconventional electro-Fenton (EF) system with a nickel-foam (Ni-F) cathode and tripolyphosphate (3-PP) electrolyte at near-neutral pH (EF/Ni-F-3-PP) to overcome pH restrictions in EF while preventing Ni-F corrosion. Response surface modelling was used to optimize the main operating parameters with a model prediction analysis (R2 = 0.99): pH = 5.8, Fe2+ = 3.0 mM and applied current = 349.6 mA. Among the three variables, the pH exerted the highest influence on the process. Under optimal conditions, 100 % of phenol removal was achieved in 25 min with a pseudo-first-order apparent rate constant (kapp) of 0.2 min-1, 3.2-fold higher than the kapp of EF/Ni-F with SO42- electrolyte at pH 3. A mineralization yield of 81.5 % was attained after 2 h; furthermore, it was found that 3-PP enhanced H2O2 accumulation by preventing bulk H2O2 decomposition. Finally, toxicity evaluation revealed the formation of toxic by-products at the early stages of treatment, which were totally depleted after 2 h, demonstrating the detoxifying capacity of the system. In conclusion, this study shows for the first time the potential of Ni-F as a cathode for EF under near-neutral conditions, rendered possible by the 3PP electrolyte. Under these conditions, the Ni-F corrosion issue could be alleviated.

Arsenic release from arsenopyrite oxidative dissolution in the presence of citrate under UV irradiation.

Arsenopyrite oxidative dissolution is one of the most important sources of arsenic (As) pollution in the soils and waters around sulfide mining areas. Sunlight and low-molecular-weight organic acids in the environment affect the redox behavior of sulfide minerals. In this work, the As release from arsenopyrite was studied in the presence of citrate under UV irradiation, and the effects of dissolved oxygen and citrate concentrations and pH on As release rate were also investigated. The results indicated that As release from the oxidative dissolution of arsenopyrite is affected by the complexation between citrate and dissolved iron ions. Under dark conditions in air atmosphere, dissolved oxygen, Fe(III)-citrate and the active intermediate product O2- facilitated the release of As at pH 7.0, and the As release rate increased first and then decreased with increasing pH from 5.0 to 9.0. Under UV irradiation in air atmosphere at pH 7.0, the reactive oxygen species (ROS) including O2- and OH generated by Fe(III)-citrate through the photo-Fenton reaction accelerated the As release and oxidation. However, Fe(III)-citrate photolysis led to the rapid flocculation and precipitation of dissolved iron ions, inhibiting the further oxidation of arsenopyrite. With increasing pH from 5.0 to 9.0, the As release rate gradually decreased under UV irradiation. Increases in the concentrations of citrate and dissolved oxygen promoted the formation of Fe(III)-citrate and ROS in the reaction system under both UV irradiation and dark conditions. The present work expands our understanding of the geochemical behavior of As in near-neutral pH environment.

Pretreatment of landfill leachate in near-neutral pH condition by persulfate activated Fe-C micro-electrolysis system.

In this study, a novel persulfate combined with iron-carbon microelectrolysis (PS-ICME) system was explored to pretreat the landfill leachate. In the static batch experiments, response surface methodology (RSM) was used to determine the relationship between three independent variables (pH, the ratio of iron to carbon (Fe-C ratio), persulfate dosage) and response values (Chemical oxygen demand (COD) removal efficiency). Experimental results showed that the COD removal efficiency reached to 62.91% under the optimal conditions: initial pH 7, Fe-C ratio 3, and persulfate dosage 85 mM. The dissolved organic matter (DOM) in landfill leachate was characterized by three-dimensional excitation-emission matrix spectroscopy (3D-EEMs). Combined with electron spin resonance (ESR) spectrum investigation, the enhanced mechanism for landfill leachate pretreated by PS-ICE in near-neutral pH was elucidated. In the column continuous flow experiment, it had been confirmed that dissolved oxygen plays an important role in the PS-ICME system. Based on the above conclusions, PS-ICME system has a satisfactory performance on pretreatment of landfill leachate.

Removal of ß-lactam antibiotics from pharmaceutical wastewaters using photo-Fenton process at near-neutral pH.

In this work, the photo-Fenton process at near-neutral pH was applied for the removal of the ß-lactam antibiotic oxacillin (OXA) in water using artificial and sunlight. Initially, the main variables of the process (Fe(II), H2O2, and light power) were optimized by a statistical factorial design (23 with center points). The experimental design indicated that 90 µmol L-1 of Fe(II), 10 mmol L-1 of H2O2, and 30 W of power light were the favorable conditions for degradation of OXA at 203 µmol L-1. In the photo-Fenton system, the H2O2 alone, UV-light/H2O2, and Fe(II)/H2O2 subsystems presented a significant participation on antibiotic removal. Moreover, based on the primary organic transformation products, a mechanism of OXA degradation was proposed. Under the favorable operational conditions, both the pollutant and the antimicrobial activity were eliminated after 50 min of process application. Although at 480 min of treatment, only 5% of mineralization was achieved, the level of biodegradability of the solutions increased from 0.08 to 0.98. Interestingly, the presence of pharmaceutical additives (glucose, isopropanol, and oxalic acid) had a moderate interference on the efficiency of the pollutant removal. Additionally, the treatment at pilot scale of the ß-lactam antibiotic in a pharmaceutical complex matrix using solar radiation allowed the complete removal of the pollutant and its associated antimicrobial activity in a very short time period (5 min). These results evidenced the applicability of the photo-Fenton process to treat wastewaters from pharmaceutical industry loaded with ß-lactam antibiotics at near neutral pH values efficiently.

Zero-valent aluminum for reductive removal of aqueous pollutants over a wide pH range: Performance and mechanism especially at near-neutral pH.

Zero-valent aluminum (ZVAl) draws much attention due to its strong reducibility. However, under neutral pH conditions, the reduction ability of ZVAl for pollutant removal has still been suspected because of the formed compact surface film of Al-(hydr)oxide. In this study, unmodified ZVAl was employed to reductively remove aqueous pollutants over a wide pH range, and its performance and mechanism, especially at near-neutral pH, were systematically studied for the first time. Results demonstrated that ZVAl had a wide range of pH applicability from 2 to 12, even in neutral environment. Typical nitro compound nitrobenzene (NB), typical azo dye acid orange 7 (AO7), and typical inorganic heavy metal ion Cr(VI) can be effectively removed at initial pH 7. Based on the changes of pH, ORP, DO, Al ions and TOC of the reaction solution, and the determination of reduction products of NB by UV-Vis and GC-MS, we found that NB removal by ZVAl can be primarily attributed to the reduction role. NB was reduced to nitrosobenzene firstly, and to aniline finally. Meanwhile, the adsorption phenomenon existed in this system. Next, the surface reaction mechanism was deeply revealed through the characterization of ZVAl particles before and after reaction by SEM-EDS, TEM, HRTEM, XRD, and XPS. It was found that ZVAl powders with core/shell structure participated in the redox reaction, and that ZVAl core was corroded, generating Al-(hydr)oxide. ZVAl surface oxide film was not directly removed, instead of a rougher one. Finally, the proposed reductive mechanism of aqueous pollutants by ZVAl was speculated from the angle of electronic competition. In water environment, O2, H2O and pollutants, with a clear competitive relationship, can capture electrons released from ZVAl. When pollutant's opportunities for getting electrons are enhanced, efficiently reductive reactions for pollutant removal can take place, even at near-neutral pH. In a word, ZVAl is a promising material to remove aqueous pollutants over a wide pH range, even in neutral environment, which exhibits its great potential as an effective and environment-friendly agent for pollutant removal from water.

Amorphous Nickel-Cobalt-Borate Nanosheet Arrays for Efficient and Durable Water Oxidation Electrocatalysis under Near-Neutral Conditions.

Electrolytic hydrogen generation needs earth-abundant oxygen evolution reaction electrocatalysts that perform efficiently at mild pH. Here, the development of amorphous nickel-cobalt-borate nanosheet arrays on macroporous nickel foam (NiCo-Bi/NF) as a 3D catalyst electrode for high-performance water oxidation in near-neutral media is reported. To drive a current density of 10 mA cm-2 , the resulting NiCo-Bi/NF demands an overpotential of only 430 mV in 0.1 m potassium borate (K-Bi, pH 9.2). Moreover, it also shows long-term electrochemical durability with maintenance of catalytic activity for 20 h, achieving a high turnover frequency of 0.21 s-1 at an overpotential of 550 mV.

Three-Dimensional Nickel-Borate Nanosheets Array for Efficient Oxygen Evolution at Near-Neutral pH.

Nickel-borate nanosheets array on titanium mesh (Ni-Bi NA/TM) was derived from NiSe2 nanosheets array on titanium mesh (NiSe2 NA/TM) by electrochemical transformation. As a three-dimensional electrode, Ni-Bi NA/TM exhibited high catalytic activity toward the oxygen evolution reaction and required a low overpotential of 430 mV at 10 mA cm-2 in 0.1 m potassium borate (pH 9.2), with outstanding long-term stability and high turnover frequency.