Manganese Species Research Articles

Overlooked Complexation and Competition Effects of Phenolic Contaminants in a Mn(II)/Nitrilotriacetic Acid/Peroxymonosulfate System: Inhibited Generation of Primary and Secondary High-Valent Manganese Species.

Organic contaminants with lower Hammett constants are typically more prone to being attacked by reactive oxygen species (ROS) in advanced oxidation processes (AOPs). However, the interactions of an organic contaminant with catalytic centers and participating ROS are complex and lack an in-depth understanding. In this work, we observed an abnormal phenomenon in AOPs that the degradation of electron-rich phenolics, such as 4-methoxyphenol, acetaminophen, and 4-presol, was unexpectedly slower than electron-deficient phenolics in a Mn(II)/nitrilotriacetic acid/peroxymonosulfate (Mn(II)/NTA/PMS) system. The established quantitative structure-activity relationship revealed a volcano-type dependence of the degradation rates on the Hammett constants of pollutants. Leveraging substantial analytical techniques and modeling analysis, we concluded that the electron-rich phenolics would inhibit the generation of both primary (Mn(III)NTA) and secondary (Mn(V)NTA) high-valent manganese species through complexation and competition effects. Specifically, the electron-rich phenolics would form a hydrogen bond with Mn(II)/NTA/PMS through outer-sphere interactions, thereby reducing the electrophilic reactivity of PMS to accept the electron transfer from Mn(II)NTA, and slowing down the generation of reactive Mn(III)NTA. Furthermore, the generated Mn(III)NTA is more inclined to react with electron-rich phenolics than PMS due to their higher reaction rate constants (8314 ± 440, 6372 ± 146, and 6919 ± 31 M-1 s-1 for 4-methoxyphenol, acetaminophen, and 4-presol, respectively, as compared with 671 M-1 s-1 for PMS). Consequently, the two-stage inhibition impeded the generation of Mn(V)NTA. In contrast, the complexation and competition effects are insignificant for electron-deficient phenolics, leading to declined reaction rates when the Hammett constants of pollutants increase. For practical applications, such complexation and competition effects would cause the degradation of electron-rich phenolics to be more susceptible to water matrixes, whereas the degradation of electron-deficient phenolics remains largely unaffected. Overall, this study elucidated the intricate interaction mechanisms between contaminants and reactive metal species at both the electronic and kinetic levels, further illuminating their implications for practical treatment.

Mechanism of β-MnO2 particle for the peroxymonosulfate activation under electric field: the promoting effect of carbamazepine on Mn(III) and reactive oxygen species production

In this study, β-MnO2 was introduced into electro-peroxymonosulfate process as particle electrodes (E/PMS/β-MnO2) to reveal the pathway of reactive manganese species (RMnS) and its promoting effect on reactive oxygen species (ROS) production. A significant synergistic was observed in the E/PMS/β-MnO2 process, the reaction constant was 3 times higher than that in the E/PMS process. The mechanism experiments revealed the generation pathway of Mn(III)aq during the E/PMS/β-MnO2 process. The pyrophosphate complex experiments and electrochemical analysis demonstrated that Mn(III)aq was dominantly generated through the electron transfer between carbamazepine (CBZ) and Mn(IV) under electric field conditions, rather than the reduction process in the cathode area. Furthermore, quenching experiments and competition kinetics method demonstrated the production of Mn(III)aq has the potential to enhance the formation of reactive oxygen species (ROS), especially •OH and SO4•−. In addition, Mn(V)aq and Mn(VI)aq was proved unable to be produced during the E/PMS/β-MnO2 process. Different from other similar electrochemical studies, 1O2 was mainly generated by the reaction betweenO2•− and •OH in this research. It was observed that the inclusion of Cl— facilitated the removal of CBZ, whereas the addition of humic acid (HA) had negligible impact on CBZ removal during the E/PMS/β-MnO2 process. At last, the results of various water matrices effects and toxicology analysis showed that the E/PMS/β-MnO2 process has satisfactory performance in practical application. This study could provide new insights for electro-persulfate treatment processes.

Enhancing the degradation of microplastics through combined KMnO4 oxidation and UV radiation

The pervasive issue of microplastics in aquatic environments presents a formidable challenge to traditional water treatment methodologies, including those utilizing KMnO4. This study pioneers advanced oxidation processes (AOPs) method aimed at improving the degradation of PE microplastics by employing a dual treatment strategy that combines KMnO4 oxidation with UV irradiation. Detailed analysis of the surface modifications and chemical functional groups of the treated PE microplastics revealed the establishment of Mn-O-Mn linkages on their surfaces. Weight reductions of 3.9%, 4.9%, and 7.5% were observed for the KMnO4/UVA, KMnO4/UVB, and KMnO4/UVC treatments over seven days, respectively. The emergence of carboxyl and hydroxyl groups played a crucial role in accelerating the degradation process. Notably, the combined application of UVC rays and KMnO4 resulted in the most effective degradation of PE microplastics observed in our study. The process significantly enhanced the formation of MnO2 particles from KMnO4 oxidation, with concentrations ranging from 0.036 to 0.070 mM for KMnO4/UVA, 0.066–0.097 mM for KMnO4/UVB, and 0.086–0.180 mM for KMnO4/UVC. Furthermore, the influence of varying pH levels, KMnO4 concentrations, and different water sources on the degradation efficacy was investigated. The pivotal role of free radicals and reactive manganese species in promoting the degradation of PE microplastics was identified. A comparative evaluation with treatments solely utilizing KMnO4 or UV light highlighted the enhanced effectiveness of the combined approach, demonstrating its potential as an efficient solution for reducing microplastic contamination in aquatic systems.

Unusually high oxidation states of manganese in high optical basicity silicate glasses

Unusually high oxidation states of manganese were stabilized within a cesium-barium silicate (CBS) glass system of extremely high optical basicity. The highest basicity was obtained for the metasilicate glass 40Cs2O–10BaO–50SiO2 (mol%) with an optical basicity of Λ = 0.81. The presence of Mn5+ (d2) as well as Mn6+ (d1) is confirmed by UV–Vis, photoluminescence, and Raman spectroscopy. The UV–Vis spectrum is dominated by the Mn3+ (d4) absorption at 526 nm for low-basicity glasses, which is replaced by a peak at 679 nm (Mn5+) and, finally, a band at 603 nm (Mn6+) in the glass with the highest basicity (Λ = 0.81). In this glass, the Mn5+/Mn6+ ratio varies with the melting conditions. Photoluminescence (PL) spectroscopy under 633 nm excitation confirms the presence of Mn5+, showing the narrow, forbidden 1E →3A2 transition located at 1191 nm with vibrational sidebands at 1245 nm and 1290 nm. The measured static fluorescence intensity due to Mn5+ grows exponentially with increasing optical basicity. The near infrared fluorescence decay was bi-exponential, with time constants of 14 and 51 μs. The absence of Mn4+ in CBS glasses was confirmed by PL and electron paramagnetic resonance (EPR) spectroscopy. Despite initial doping as MnO2, metastable Mn4+ disproportionates into lower and higher valent manganese species, followed by reduction or oxidation of manganese to a stable species as ruled by the basicity of the glass and oxygen availability during melting. A structural study of the glasses by Raman spectroscopy revealed a resonance enhancement effect for the symmetric stretching mode of MnO4-tetrahedra at ∼800 cm−1 with overtones observed at higher frequencies.

Peroxymonosulfate promoted dioxygen activation with Mn(II)-nitrilotriacetic acid complexes for sulfadiazine degradation

In the field of peroxymonosulfate (PMS) activation technology, there is a pressing need to reduce PMS consumption and enhance its utilization rate. The present study demonstrates that the introduction of dissolved oxygen (DO) into the Mn(II)-nitrilotriacetic acid (NTA)-activated PMS system significantly enhances the degradation efficiency of sulfadiazine and increases the PMS utilization rate from approximately 15.0 to 41.3 %. Mechanistic analysis reveals that the Mn(II)-NTA/PMS system generates sulfate radicals as well as intermediate valent manganese species in the absence of DO; while in the presence of DO, Mn(II) is oxidized to Mn(III) by dioxygen to form superoxide anions and Mn(III), which can be further oxidized by PMS to higher valence states such as Mn(V) and Mn(VII). Consequently, the production of free radicals decreases while intermediate valent manganese species become more abundant. Additionally, O2•− can also reduce both Mn(VII) and Mn(IV) back to their lower oxidation state (Mn(II)). The cooperative interactions between these active species enhance the efficiency of catalytic cycles of manganese species. Moreover, the influence of multiple factors, the degradation products, and their associated toxicity assessment were investigated. Overall, this research provides valuable insights into the design of highly efficient PMS and DO activation systems.

Hydrogeochemical analysis of processes affecting HCH removal using ZVI-based treatment technology

In the 1960s, ca. 3000–5000 tons of HCH residue were disposed of in an overburden dump at the Hájek kaolin/uranium mine site (Czech Republic). The dump leachate, which has a 136 μg/l average total content of hexachlorocyclohexane (HCH) isomers, discharges into a local creek and contaminates the ecosystem. A full-scale prototype for the treatment of dump leachate comprised three sequential stages: 1) permeable reactive modules filled with macro-zerovalent iron (mZVI), 2) a biosorption module and 3) an aerobic wetland module. After commissioning, HCH removal efficiency reached 95%, but decreased to 70% over the following 230 days, primarily due to the efficiency of the mZVI modules dropping from 76% to 39%. Hydrogeochemical analysis and geochemical modelling revealed that the reduction in efficiency was mainly caused by passivation of mZVI surfaces and clogging of mZVI pore spaces through precipitation of goethite, calcite and rhodochrosite, or siderite and magnetite instead of goethite where boundary conditions for O2 differed. XRD analysis of the solid phase from the mZVI modules confirmed the geochemical modelling results. The major part of the precipitated products (46–66 wt%) comprised a ferric hydroxide amorphous phase, especially in the initial mZVI module inlet, with goethite the second most abundant precipitate (10–40 wt%). Siderite and calcite also mainly precipitated in the initial module inlet. In conclusion, mZVI appears to be a suitable reductant for HCH; however, the longevity of the ZVI-based treatment system was negatively affected by precipitates in the presence of high concentrations of iron, manganese and carbonate species.

Development of a New Permanganate/Chlorite Process for Water Decontamination.

Development of new technologies with strong selectivity for target pollutants and low sensitivity toward a water matrix remains challenging. Herein, we introduced a novel strategy that used chlorite as an activator for Mn(VII) at pH 4.8, turning the inert reactivity of the pollutants toward Mn(VII) into a strong reactivity. This paved a new way for triggering reactions in water decontamination. By utilizing sulfamethoxazole (SMX) as a typical pollutant, we proposed coupled pathways involving electron transfer across hydrogen bonds (TEHB) and oxidation by reactive manganese species. The results indicated that a hydrogen bonding complex, SMX-ClO2-*, formed through chlorite binding the amino group of SMX initially in the TEHB route; such a complex exhibited a stronger reduction capability toward Mn(VII). Chlorite, in the hydrogen bonding complex SMX-ClO2-*, can then complex with Mn(VII). Consequently, a new reactive center (SMX-ClO2--Mn(VII)*) was formed, initiating the transfer of electrons across hydrogen bonds and the preliminary degradation of SMX. This is followed by the involvement of the generated Mn(V)-ClO2-/Mn(III) in the reduction process of Mn(VII). Such a process showed pH-dependent degradation, with a removal ratio ranging from 80% to near-stagnation as pH increased from 4.8 to 7. Combining with pKa analysis showed that the predominant forms of contaminants were crucial for the removal efficiency of pollutants by the Mn(VII)/chlorite process. The impact of the water matrix was demonstrated to have few adverse or even beneficial effects. With satisfactory performance against numerous contaminants, this study introduced a novel Mn(VII) synergistic strategy, and a new reactivity pattern focused on reducing the reduction potential of the contaminant, as opposed to increasing the oxidation potential of oxidants.

Pincer manganese-catalyzed C–H phosphinomethylation of indoles and naphthols with methanol as C1 block

We here report a facile manganese-catalyzed three-component phosphinomethylation of indoles and naphthols using methanol as a sustainable C1 source and an acceptorless dehydrogenation strategy. A set of indoles, naphthols, and phosphines with different substituents could efficiently undergo the acceptorless dehydrogenative cross-coupling and furnish the corresponding C–H phosphinomethylated indoles and naphthols in moderate to good yields. Mechanistic studies indicate that this transformation proceeds with the dehydrogenation of methanol to form a formaldehyde-coordinated manganese species as the key intermediate.

Role of reactive manganese and oxygen species in the KMnO4/Na2SO3 process for purification of algal-rich water and membrane fouling alleviation

Ultrafiltration (UF) is a highly efficient technique for algal-rich water purification, but it is heavily contaminated due to the complex water characteristics. To solve this problem, potassium permanganate (KMnO4) oxidation enhanced with sodium sulfite (Na2SO3) was proposed as a pretreatment means. The results showed that the end-normalized flux was elevated from 0.10 to 0.91, and the reversible fouling resistance was reduced by 99.95%. The membrane fouling mechanism also changed obviously, without the generation of cake filtration. Regarding the properties of algal-rich water, the zeta potential was decreased from −29.50 to −5.87 mV after KMnO4/Na2SO3 pretreatment, suggesting that the electrostatic repulsion was significantly reduced. Meanwhile, the fluorescent components in algal-rich water were significantly eliminated, and the removal of dissolved organic carbon was increased to 67.46%. In the KMnO4/Na2SO3 process, reactive manganese species (i.e., Mn(V), Mn(III) and MnO2) and reactive oxygen species (i.e., SO4•− and •OH) played major roles in purifying algal-rich water. Specifically, SO4•−, •OH, Mn(V) and Mn(III) could effectively oxidize algal pollutants. Simultaneously, the in-situ adsorption and coagulation of MnO2 could accelerate the formation of flocs by decreasing the electrostatic repulsion between cells, and protect the algal cells from being excessive oxidized. Overall, the KMnO4/Na2SO3 process showed significant potential for membrane fouling alleviation in purifying algal-rich water.

Revisiting the synergistic oxidation of peracetic acid and permanganate(Ⅶ) towards micropollutants: The enhanced electron transfer mechanism of reactive manganese species

Synergistic actions of peroxides and high-valent metals have garnered increasing attentions in wastewater treatment. However, how peroxides interact with the reactive metal species to enhance the reactivity remains unclear. Herein, we report the synergistic oxidation of peracetic acid (PAA) and permanganate(Ⅶ) towards micropollutants, and revisit the underlying mechanism. The PAA-Mn(VII) system showed remarkable efficiency with a 28-fold enhancement on sulfamethoxazole (SMX) degradation compared to Mn(Ⅶ) alone. Extensive quenching experiments and electron spin resonance (ESR) analysis revealed the generation of unexpected Mn(V) and Mn(VI) beyond Mn(III) in the PAA-Mn(VII) system. The utilization efficiency of Mn intermediates was quantified using 2,2′-azino-bis(3-ethylbenzothiazoline)-6-sulfonate (ABTS), and the results indicated that PAA could enhance the electron transfer efficiency of reactive manganese (Mn) species, thus accelerating the micropollutant degradation. Density functional theory (DFT) calculations showed that Mn intermediates could coordinate to the O1 of PAA with a low energy gap, enhancing the oxidation capacity and stability of Mn intermediates. A kinetic model based on first principles was established to simulate the time-dependent concentration profiles of the PAA-Mn complexes and quantify the contributions of the PAA-Mn(III) complex (50.8 to 59.3 %) and the PAA-Mn(Ⅴ/Ⅵ) complex (40.7 to 49.2 %). The PAA-Mn(VII) system was resistant to the interference from complex matrix components (e.g., chloride and humic acid), leading to the high efficiency in real wastewater. This work provides new insights into the interaction of PAA with reactive manganese species for accelerated oxidation of micropollutants, facilitating its application in wastewater treatment.

The underestimated role of manganese in modulating the nutrient structure in a eutrophic seasonally-stratified reservoir

Accumulation and subsequent release of nutrients have great potential to trigger algal blooms in lakes and reservoirs. We conducted high vertical resolution (2 m interval) monitoring at ∼monthly intervals over a year for hydrological parameters, Chl-a, ammonium (NH4+), nitrate (NO3−) and different species of phosphorus (P) and manganese (Mn) in a 40-meter-deep subtropical reservoir (Shanmei Reservoir) in Fujian, southern China. In this seasonally stratified reservoir featured with high nutrient loading, the consistent trend in the ratio of dissolved inorganic nitrogen (DIN) to dissolved inorganic phosphorus (DIP) between the euphotic zone and the hypolimnion, coupled with its mirrored correlation with Chl-a concentration indicates that upward flux from the hypolimnion affects phytoplankton growth in the euphotic zone. The monthly variation of the depth-integrated multiple species of N and P indicates that during the stratification period in the hypoxic hypolimnion, approximately 80% of the DIP is removed, leading to a remarkable decoupling phenomenon between NH4+ and DIP. This process effectively increases the ratio of DIN to DIP in the hypolimnion, thereby significantly reducing the potential of algal blooms caused by the upward flux. A robust positive linear correlation between iron-manganese bound phosphorus (CBD-P) and particulate Mn was observed during stratification period implying that DIP was scavenged by sediment-released Mn throughout the water column. Vertical profiles during stratification showed that upward diffusion of Mn2+ facilitated the formation of Mn oxide zones near the oxycline. The most significant decrease in DIP inventory occurs when Mn oxide zones migrate either upwards from the bottom or downwards from the oxycline, indicating that the migration of Mn oxides on the vertical profile is a key factor in the decoupling of NH4+and DIP.Our findings underscore the importance of Mn cycling as an underappreciated DIP self-immobilization process in the water column of reservoirs characterized by high nutrient loading. Furthermore, we propose that denitrification and Mn cycling establish a consecutive feedback mechanism, preventing excessive nutrient accumulation in low oxygen bottom water. In the context of global changes, we anticipate a heightened prominence of this feedback mechanism.

Generation of •OH and intermediate manganese species for the efficient removal of micropollutants via photocatalysis of permanganate by indium oxide

Activation of permanganate (Mn(VII)) by generating intermediate manganese species (Mnint, i.e., Mn(V) and Mn(III)) has been demonstrated to be an efficient way to enhance the oxidative ability of Mn(VII). In this work, it was found that the addition of indium oxide (In2O3) could significantly enhance the visible light response of Mn(VII) (Vis/In2O3/Mn(VII)) by selecting flumequine (FLU) as a representative compound. The presence of In2O3 enhanced the degradation of FLU by the Vis/Mn(VII) process with the pseudo-first-order rate constant increasing by around 30 folds. Intermediate Mnint (Mn(V) and Mn(III)) and hydroxyl radicals (•OH) were identified as the major oxidants in the Vis/In2O3/Mn(VII) process, and •OH outcompeted that of Mnint under alkaline conditions. The scavenge of photogenerated e- by Mn(VII) played a critical role in the generation of Mnint, while the reaction of photogenerated h+ with H2O contributed to the generation of •OH. The degradation efficiency of FLU showed a negative relationship with the increase of solution pH, likely due to the electrostatic repulsion between the deprotonated FLU and negatively charged In2O3 surfaces. Increasing Mn(VII) or In2O3 dosages enhanced the degradation of FLU by elevating the concentrations of reactive species. The presence of chloride, bicarbonate, and humic acid slightly inhibited FLU degradation by the Vis/In2O3/Mn(VII) process, due to their competitive scavenging of reactive species. Totally 14 oxidation products were identified during FLU oxidation by the Vis/In2O3/Mn(VII) process, and they were likely generated via hydroxylation, defluorination, dealkylation/decarboxylation/deamination, ring-opening, or oxidation pathways. Good stability and reusability of the In2O3 catalyst were obtained. This work proposed a new activation pathway for Mn(VII) and provided a novel approach for the treatment of emerging contaminants in aqueous environments.

Arsenic sorption and oxidation by natural manganese-oxide-enriched soils: Reaction kinetics respond to varying environmental conditions

Manganese-oxides are some of the strongest oxidants and sorbents in the environment, which impact many geochemical processes. However, nearly all our understanding of manganese-oxides’ reaction kinetics is based on laboratory-synthesized minerals. This study quantifies the oxidative kinetics and adsorptive capacity of five soils rich in pedogenic manganese- and iron-oxides through arsenite oxidation batch reactions over a range of pHs and temperatures to mimic diverse environmental conditions. The two A horizons were less reactive and enriched in manganese(IV), compared to the B horizons, particularly the subsoil containing the manganese-rich wad material. The reaction kinetics fit a pseudo-first-order reaction with distinct fast and slow phases. The baseline reactions were pH 7.2 at 23 °C. Adjusting pH to 4.5 or 9.0 increased the reaction rates. Decreasing the temperature to 4.0 °C reduced the reaction kinetics, while raising the temperature to 40 °C increased the arsenite oxidation rate. pH and temperature changes alter the reaction kinetics due to shifts related to the point of zero charge, the total system energy, and surface passivation from adsorbing arsenic and manganese species. Synchrotron X-ray fluorescence mapping indicates arsenic only penetrates the surficial layers of most manganese-oxide-containing nodules found in the soil. After the arsenite oxidation reaction in the pedogenically weathered subsoil, X-ray absorption spectroscopy demonstrates significant differences in the average manganese oxidation number between the nodules’ outer layers compared to the soil matrix and nodule centers. The kinetic and sorption parameters give critical insight into determining the mobility and species of arsenic and other redox-sensitive contaminants in manganese-containing environmental systems over appropriate timescales.

The crucial role of ligand deprotonation in manganese catalyzed hydrogenation reactions

Hydrogenation catalysts based on the abundant early transition metal manganese recently received growing attention. A common motif found in most of the reported systems is a deprotonatable hydrogen atom in the ligand, usually considered necessary within an outer-sphere mechanism. Here we investigated the mechanism of the catalytic hydrogenation of ketones, focusing on the crucial function of the deprotonatable H atom in the ligand. Therefore, we synthesized phosphine-free Mn(I) complexes of the type [(L)MnBr(CO)3)] utilizing pyridyl-imidazole ligands, having a deprotonatable H atom within the imidazole ring. They were found to be active catalysts for the hydrogenation of ketones with molecular hydrogen. Kinetic and spectroscopic studies together with DFT calculations point towards an inner-sphere mechanism with the hydride transfer to the substrate being the rate determining step. Most importantly, we demonstrate that the NH-motif remains deprotonated throughout the catalytic cycle maintaining an anionic manganese species. Thereby, the anionic ligand is a more potent electron donor which enhances the rate determining hydride transfer.

Permanganate (PM) pretreatment improves medium-chain fatty acids production from sewage sludge: The role of PM oxidation and in-situ formed manganese dioxide

Medium-chain fatty acids (MCFAs) production from sewage sludge is mainly restricted by the complex substrate structure, competitive metabolism and low electron transfer rate. This study proposes a novel permanganate (PM)-based strategy to promote sludge degradation and MCFAs production. Results show that PM pretreatment significantly increases MCFAs production, i.e., attaining 12,036 mg COD/L, and decreases the carbon fluxes of electron acceptor (EA)/electron donor (ED) to byproducts. Further analysis reveals that PM oxidation enhances the release and biochemical conversion of organic components via disrupting extracellular polymers (EPS) structure and reducing viable cells ratio, providing directly available EA for chain elongation (CE). The microbial activity positively correlated with MCFAs generation are apparently heightened, while the competitive metabolism of CE (i.e., methanogensis) can be completely inhibited. Accordingly, the functional bacteria related to critical bio-steps and dissimilatory manganese reduction are largely enriched. Further mechanism exploration indicates that the main contributors for sludge solubilization are 1O2 (61.6 %) and reactive manganese species (RMnS), i.e., Mn(V)/Mn(VI) (22.3 %) and Mn(III) (∼16.1 %). As the main reducing product of PM reaction, manganese dioxide (MnO2) can enable the formation of microbial aggregates, and serve as electron shuttles to facilitate the carbon fluxes to MCFAs during CE process. Overall, this strategy can achieve simultaneous hydrogen recovery, weaken competitive metabolisms and provide electron transfer accelerator for CE reactions.

Potassium permanganate oxidation enhanced by infrared light and its application to natural water

Photocoupled permanganate (PM) is an effective way to enhance the oxidation efficiency of PM, however, the activation of PM by infrared has received little attention. This study aimed to investigate the ability of infrared light to activate PM. When coupled with infrared, the degradation rate of 4-chlorophenol (4-CP) is increased to 3.54 times of PM oxidation alone. The accelerated reaction was due to the formation of vibrationally excited PM by absorbing 3.1 kJ mol-1 infrared energy, which also leads to the primary reactive intermediates Mn(V/IV) in the reaction system. The infrared coupled PM system also showed 1.14–2.34 times promotion effect on other organic pollutants. Furthermore, solar composed of 45% infrared, coupled PM system showed excellent degradation performance, where the degradation of 4-CP in 10 L of tap water and river water was 68 and 23 times faster than in ultrapure water, respectively. The faster-increased degradation rate in natural waters is mainly due to the abundant inorganic ions, which can stabilize the manganese species, and then has a positive effect on 4-CP degradation. In summary, this work develops a energy-efficient photoactivated PM technology that utilizes infrared and provides new insights into the design of novel sunlight-powered oxidation processes for water treatment.

Lean-water electrolyte to stabilize zinc anode and suppress manganese dissolution of cathode for ampere-hour zinc batteries

Rechargeable Zinc battery technologies are regarded as viable candidates for large-scale energy storage due to constitutional safety and inexpensive position. Nevertheless, the strong polarity of H2O molecules initiates the deterioration of both zinc metal anode and cathode. At anode side, radical H2O molecules cause side reactions of zinc corrosion, hydrogen evolution reaction (HER) and dendrite growth. At cathode side, the dissolution of transition metal brings about severe capacity fading of cathodes. Herein, we replace the 90% H2O sheath of Zn2+ solvation with 1,3-propanediol (PDO) molecules to form a lean-water electrolyte, in which the abundant PDO molecules can significantly suppress 99.9% HER and prohibit the Zn dendrite growth, while H2O molecules with a molecular lubrication mechanism enables fast ion transportation. Consequently, at anode side, Zn plating/stripping reversibly processes over 4000 cycles with high average Coulombic efficiency of 99.24% in ZnǀǀCu cell. At cathode side, the decreased water activity and scarce solute-water dissolving surfaces suppress 98.6% dissolution of manganese species. The ZnǀǀMnHCF full cell demonstrates high capacity of 140.7 mAh·g−1 at 0.1 A·g−1 and ultra-long lifespan of 3000 cycles with 85.4% initial capacity retained. More importantly, a 1.4 Ah ZnǀǀMnHCF pouch cell shows excellent lifespan over 150 cycles with charge/discharge run time > 68 days. We expect that this work will promote the practicability of aqueous Zn-ion batteries for grid-scale energy storage.

Facile synthesis of nitrogen vacancy-enriched polymeric carbon nitride via the trace manganese-induced precursor recrystallization process for photocatalytic degradation

A nitrogen vacancy-enriched polymeric carbon nitride (MNCN-1) is successfully prepared by one-step thermal polymerization of 3-amino-1,2,4-triazole crystals obtained by the recrystallization process induced via trace manganese species in this study. With a small amount, natural pH and anionic coexist conditions, MNCN-1 shows excellent performance in photocatalytic degradation of RhB, and it also shows good removal of antibiotic contaminants. Several analytical techniques results illustrate that the induction of trace manganese species facilitates the formation of nitrogen vacancies, and the nitrogen vacancies play a significant role in optimizing band structure and inhibiting the recombination of photo-generated carriers. MNCN-1 owns the maximum abundance of nitrogen vacancies. The increased N-vacancies cause a negative shift of the conduction potential, thus enhancing the thermodynamic driving forces and the kinetic of active radical generation. The much stronger reduction capability, increased involvement of trapped electrons in the ORR reaction and more abundant reaction centers for O2 molecules make the N-vacancy-enriched MNCN-1 achieve enhanced radicals’ generation through a two-step single-electron reduction reaction (O2 → •O2-→ H2O2). This study expands the strategy of constructing nitrogen-rich vacancies in polymeric carbon nitride, and elucidates the mechanism of its defective structure in enhancing the photocatalytic activity of PCN.

Commercially Accessible High-Performance Aluminum-Air Battery Cathodes through Electrodeposition of Mn and Ni Species on Fuel Cell Cathodes.

This study presents a cost-effective method for producing high-performance cathodes for aluminum-air batteries. Commercial fuel cell cathodes are modified through electrodeposition of nickel and manganese species. The optimal conditions for electrodeposition are determined using a combination of structural (Raman, SEM, TEM) and electrochemical (LSV, EI, discharge curves) characterization techniques. The structural analysis confirms successful incorporation of nickel and manganese species onto the cathode surface. Electrochemical tests demonstrate enhanced electrochemical activity compared to unmodified cathodes. By combining the favorable properties of electrodeposited manganese species with nickel species, a high-performance cathode is obtained. The developed cathode exhibits capacities of 50 mA h cm-2 in aluminum-air batteries across a wide range of current densities. The electrodeposition method proves effective in improving electrochemical performance. A key advantage of this method is its simplicity and cost-effectiveness. The use of commercially available materials and well-established electrodeposition techniques allows for easy scalability and commercialization. This makes it a viable option for large-scale production of high-performance cathodes for the next-generation energy storage devices.

Kinetics and TD-DFT calculations of base-catalyzed oxidation of acriflavine hydrochloride: Removal of dyes colors from wastewater

The oxidation kinetics of acriflavine hydrochloride (AFH) to nitro-acriflavine (N-AFH) by KMnO4 as oxidizing agent in sodium hydroxide medium at a constant ionic strength of 0.5 moldm−3 was studied using spectrophotometric methods. It was found that the reaction went through two distinct steps that could be monitored. In the first stage, coordination species including transient blue pentavalent manganese and/or green hexavalent manganese species may be made quite quickly followed by the decomposition of intermediates in the second slow stage to produce soluble Mn (IV) and the nitroacriflavine as resulting products of oxidation. It has been investigated how several variables such as pH, ionic strength, permanganate ion concentration, and AFH substrate concentration affect oxidation rates. The experimental results demonstrated a first-order dependence in [MnO4−] and fractional first-order kinetics in each of [AFH] and alkali concentration under pseudo-first-order reaction conditions of [MnO4−] >>10 [AFH]. Sodium hydroxide concentrations accelerated the oxidation reaction, and as the alkali concentration rose, so the type of catalyzed is base-catalyzed. Evidence for the creation of a 1:1 intermediate complex was discovered using spectrophotometry and kinetics. In accordance with the kinetic findings, an efficient oxidation process that is compatible with the kinetic data obtained in terms of the activation parameters evaluated was analyzed, proposed, and debated. There are several techniques used to study the nanostructure thin films (AFH)TF and (N- AFH)TF, with using FT-IR, kinetic, isotherms of liquid-phase adsorption, and optical characteristics. A low deposition rate and a chamber pressure of 5 × 105 mbar are used in the PVD method to create (AFH)TF and (N-AFH)TF thin coatings with a 95 nanometer thickness. The isolated molecules (AFH)Iso and (N-AFH)Iso were additionally optimized using time-dependent density functional theory (TD-DFT) using TD-DFTD/Mol3 and Cambridge Serial Total Energy Bundle (TD-FDT/CASTEP). The optimized geometries, vibrational wavenumbers, intensity of vibrational bands, and various atomic charges of 9VC have all been investigated using DFT-B3LYP system using a 6-31G (d,p) basis set.