In-Situ H2O2 Cleaning for Fouling Control of Manganese-Doped Ceramic Membrane through Confined Catalytic Oxidation Inside Membrane

This work presents an effective approach for manganese-doped Al2O3 ceramic membrane (Mn-doped membrane) fouling control by in-situ confined H2O2 cleaning in wastewater treatment. An Mn-doped membrane with 0.7 atomic percent Mn doping in the membrane layer was used in a membrane bioreactor with the aim to improve the catalytic activity toward oxidation of foulants by H2O2. Backwashing with 1 mM H2O2 solution at a flux of 120 L/m2/h (LMH) for 1 min was determined to be the optimal mode for in-situ H2O2 cleaning, with confined H2O2 decomposition inside the membrane. The Mn-doped membrane with in-situ H2O2 cleaning demonstrated much better fouling mitigation efficiency than a pristine Al2O3 ceramic membrane (pristine membrane). With in-situ H2O2 cleaning, the transmembrane pressure increase (ΔTMP) of the Mn-doped membrane was 22.2 kPa after 24-h filtration, which was 40.5% lower than that of the pristine membrane (37.3 kPa). The enhanced fouling mitigation was attributed to Mn doping, in the Mn-doped membrane layer, that improved the membrane surface properties and confined the catalytic oxidation of foulants by H2O2 inside the membrane. Mn3+/Mn4+ redox couples in the Mn-doped membrane catalyzed H2O2 decomposition continuously to generate reactive oxygen species (ROS) (i.e., HO• and O21), which were likely to be confined in membrane pores and efficiently degraded organic foulants.

Theoretical and Experimental Considerations for a Rapid and High Throughput Measurement of Catalase In Vitro

A rapid and high throughput protocol to measure the catalase activity in vitro has been designed. Catalase is an enzyme with unusual kinetic properties because it does not follow the standard Michaelis–Menten model and is inactivated by H2O2. This makes the analysis of the two rate equations of the second-ordered reactions of the kinetic model rather complex. A two-degree polynomial fitting of the experimental data is proposed after transforming the exponential form of the integrated rate equation of the [H2O2] into a polynomial using the Taylor series. The fitting is validated by establishing an experimental linear relationship between the initial rate of the H2O2 decomposition and the protein concentration, regardless of the suicide inactivation that catalase might undergo beyond t > 0. In addition, experimental considerations are taken into account to avoid statistical bias in the analysis of the catalase activity. ANOVA analyses show that the proposed protocol can be utilized to measure the initial rate of the H2O2 decomposition by catalase in 32 samples in triplicates if kept below 8 mM min−1 in the microplate wells. These kinetic and statistical analyses can pave the way for other antioxidant enzyme activity assays in microplate readers at small scale and low cost.

Scavenger with Protonated Phosphite Ions for Incredible Nanoscale ZrO2-Abrasive Dispersant Stability Enhancement and Related Tungsten-Film Surface Chemical–Mechanical Planarization

For scaling-down advanced nanoscale semiconductor devices, tungsten (W)-film surface chemical mechanical planarization (CMP) has rapidly evolved to increase the W-film surface polishing rate via Fenton-reaction acceleration and enhance nanoscale-abrasive (i.e., ZrO2) dispersant stability in the CMP slurry by adding a scavenger to suppress the Fenton reaction. To enhance the ZrO2 abrasive dispersant stability, a scavenger with protonate-phosphite ions was designed to suppress the time-dependent Fenton reaction. The ZrO2 abrasive dispersant stability (i.e., lower H2O2 decomposition rate and longer H2O2 pot lifetime) linearly and significantly increased with scavenger concentration. However, the corrosion magnitude on the W-film surface during CMP increased significantly with scavenger concentration. By adding a scavenger to the CMP slurry, the radical amount reduction via Fenton-reaction suppression in the CMP slurry and the corrosion enhancement on the W-film surface during CMP performed that the W-film surface polishing rate decreased linearly and notably with increasing scavenger concentration via a chemical-dominant CMP mechanism. Otherwise, the SiO2-film surface polishing rate peaked at a specific scavenger concentration via a chemical and mechanical-dominant CMP mechanism. The addition of a corrosion inhibitor with a protonate-amine functional group to the W-film surface CMP slurry completely suppressed the corrosion generation on the W-film surface during CMP without a decrease in the W- and SiO2-film surface polishing rate.

Enhanced effects of reducing agent on oxalate chelated Fe(II) catalyzed percarbonate system for benzene degradation

The addition of hydroxylamine hydrochloride (HAH), ascorbic acid (ASC), sodium ascorbate (SAS) to the OA-Fe(II)/SPC system could promote the generation of HO• by accelerating Fe(II)/Fe(III) recycles and H2O2 decomposition. The enhancement of HAH on HO• generation surpasses ASC and SAS in the OA-Fe(II)/SPC system. The generation of O2•− was also enhanced by HAH, ASC and SAS, and more significant promotion of O2•− generation was observed with ASC and SAS addition. More effective benzene removal was achieved in an OA-Fe(II)/SPC system with suitable HAH, ASC and SAS addition, compared to the parent system. Excessive HAH, ASC or SAS had a negative effect on benzene removal. Results of scavenger tests showed that HO• is indeed the dominant free radical for benzene removal in every system, but the addition of HAH, ASC and SAS increased the contribution of O2•− to benzene degradation. HAH, ASC and SAS enhanced OA-Fe(II)/SPC systems could be well utilized to acidic and neutral conditions, while HCO3−, high concentration of HA and alkaline conditions were not favorable to benzene removal. Moreover, the addition of HAH, ASC and SAS are conducive to benzene removal in actual groundwater, and HAH was the optimal reducing agent for the enhancement of the OA-Fe(II)/SPC system.

Au Modified F-TiO2 for Efficient Photocatalytic Synthesis of Hydrogen Peroxide

In this work, Au-modified F-TiO2 is developed as a simple and efficient photocatalyst for H2O2 production under ultraviolet light. The Au/F-TiO2 photocatalyst avoids the necessity of adding fluoride into the reaction medium for enhancing H2O2 synthesis, as in a pure TiO2 reaction system. The F− modification inhibits the H2O2 decomposition through the formation of the ≡Ti–F complex. Au is an active cocatalyst for photocatalytic H2O2 production. We compared the activity of TiO2 with F− modification and without F− modification in the presence of Au, and found that the H2O2 production rate over Au/F-TiO2 reaches four times that of Au/TiO2. In situ electron spin resonance studies have shown that H2O2 is produced by stepwise single-electron oxygen reduction on the Au/F-TiO2 photocatalyst.

Hydroxyl Radical Generation by the H2O2/CuII/Phenanthroline System under Both Neutral and Alkaline Conditions: An EPR/Spin-Trapping Investigation

The copper–phenanthroline complex CuI(Phen)2 was the first artificial nuclease studied in biology. The mechanism responsible for this activity involves CuII(Phen)2 and H2O2. Even if H2O2/Cu systems have been extensively studied in biology and oxidative chemistry, most of these studies were carried out at physiological pH only, and little information is available on the generation of radicals by the H2O2/CuII-Phen system. In the context of paper pulp bleaching to improve the bleaching ability of H2O2, this system has been investigated, mostly at alkaline pH, and more recently at near-neutral pH in the case of dyed cellulosic fibers. Hence, this paper aims at studying the production of radicals with the H2O2/CuII-Phen system at near-neutral and alkaline pHs. Using the EPR/spin-trapping method, HO• formation was monitored to understand the mechanisms involved. DMPO was used as a spin-trap to form DMPO–OH in the presence of HO•, and two HO• scavengers were compared to identify the origin of the observed DMPO–OH adduct, as nucleophilic addition of water onto DMPO leads to the same adduct. H2O2 decomposition was enhanced by the addition of CuII–Phen (and only slightly by addition of CuSO4), reaching a level similar to the Fenton reagent at near-neutral pH. This evidences the role of Phen, which improves the effect of CuII by tuning the electronic structure and structural properties of the corresponding CuII complexes.

The kinetics and mechanism of H2O2 decomposition at the U3O8 surface in bicarbonate solution

A transition from catalytic to oxidative H2O2 decomposition on U3O8 was observed with NaHCO3 with significant implications for uranium dissolution.

Theoretical insight into hydroxyl production via H2O2 decomposition over the Fe3O4(311) surface

Fenton's reagent provides a method to produce active hydroxyl radicals (˙OH) for chemical oxidation by mixing iron oxide and hydrogen peroxide, which divides into homogeneous and heterogeneous Fenton's reagent.