Neutral Conditions Research Articles

Low-Coordinated Conductive ZnCu Metal-Organic Frameworks for Highly Selective H2O2 Electrosynthesis.

Direct electrosynthesis of hydrogen peroxide (H2O2) with high production rate and high selectivity through the two-electron oxygen reduction reaction (2e-ORR) offers a sustainable alternative to the energy-intensive anthraquinone technology but remains a challenge. Herein, a low-coordinated, 2Dconductive Zn/Cu metal-organic framework supported on hollow nanocube structures (ZnCu-MOF (H)) is rationally designed and synthesized. The as-prepared ZnCu-MOF (H) catalyst exhibits substantially boosted electrocatalytic kinetics, enhanced H2O2 selectivity, and ultra-high Faradaic efficiency for 2e-ORR process in both alkaline and neutral conditions. Electrochemical measurements, operando/quasi in situ spectroscopy, and theoretical calculation demonstrate that the introduction of Cu atoms with low-coordinated structures induces the transformation of active sites, resulting in the beneficial electron transfer and the optimized energy barrier, thereby improving the electrocatalytic activity and selectivity.

Comparison of Learning Golf Putting Skill in Different Choices: A Test of the OPTIMAL Theory

Background: The OPTIMAL theory of motor learning posits that autonomy support (AS), enhanced expectancies (EE), and an external focus of attention (EF) facilitate improved motor learning and performance. However, the applicability of this theory by simultaneously presenting all three factors in task-related and Irrelevant choices in learning golf skills has not been investigated. Objectives: The purpose of this study was to investigate the sequential implementation of AS, EE, and EF factors in golf putting tasks. Methods: During a pre-test under neutral conditions and acquisition phase (six blocks), thirty-six participants attempted to putt golf balls into a hole cup placed in the center of four circles with different diameters on the green. The participants were divided into two groups for optimized practices: The optimal group with task-relevant choices and the optimal group with task-irrelevant choices, both groups performed the optimized factors (EE, AS, and EF) successively and identically to each other. After 24 hours, learning was measured by a retention test. Results: The optimized group with relevant choices performed better than the optimized group with irrelevant choices in the autonomy variable. In the retention test, the aiming accuracy score of both groups increased compared to the pre-test, but no significant difference was observed in the learning rate between the two optimized groups. Conclusions: The present findings demonstrate that the key factors of OPTIMAL theory can be further benefited by task-related choices during practice for beginners' learning.

Antiepileptic drug-loaded and multifunctional iron oxide@silica@gelatin nanoparticles for acid-triggered drug delivery

The current study developed an innovative design for the production of smart multifunctional core-double shell superparamagnetic nanoparticles (NPs) with a focus on the development of a pH-responsive drug delivery system tailored for the controlled release of Phenytoin, accompanied by real-time monitoring capabilities. In this regard, the ultra-small superparamagnetic iron oxide@silica NPs (IO@Si MNPs) were synthesized and then coated with a layer of gelatin containing Phenytoin as an antiepileptic drug. The precise saturation magnetization value for the resultant NPs was established at 26 emu g-1. The polymeric shell showed a pH-sensitive behavior with the capacity to regulate the release of encapsulated drug under neutral pH conditions, simultaneously, releasing more amount of the drug in a simulated tumorous-epileptic acidic condition. The NPs showed an average size of 41.04 nm, which is in the desired size range facilitating entry through the blood–brain barrier. The values of drug loading and encapsulation efficiency were determined to be 2.01 and 10.05%, respectively. Moreover, kinetic studies revealed a Fickian diffusion process of Phenytoin release, and diffusional exponent values based on the Korsmeyer-Peppas equation were achieved at pH 7.4 and pH 6.3. The synthesized NPs did not show any cytotoxicity. Consequently, this new design offers a faster release of PHT at the site of a tumor in response to a change in pH, which is essential to prevent epileptic attacks.

Individual differences in emotion-induced blindness: Are they reliable and what do they measure?

The emotion-induced-blindness (EIB) paradigm has been extensively used to investigate attentional biases to emotionally salient stimuli. However, the low reliability of EIB scores (the difference in performance between the neutral and emotionally salient condition) limits the effectiveness of the paradigm for investigating individual differences. Here, across two studies, we investigated whether we could improve the reliability of EIB scores. In Experiment 1, we introduced a mid-intensity emotionally salient stimuli condition, with the goal of obtaining a wider range of EIB magnitudes to promote reliability. In Experiment 2, we sought to reduce the attentional oddball effect, so we created a modified EIB paradigm by removing the filler images. Neither of these approaches improved the reliability of the EIB scores. Reliability for the high- and mid-intensity EIB difference scores were low, while reliability of the scores for absolute performance (neutral, high-, and mid-intensity) were high and the scores werealso highly correlated, even though overall performance in the emotionally salient conditions were significantly worse than in the neutral conditions. Given these results, we can conclude that while emotionally salient stimuli impair performance in the EIB task compared with the neutral condition, the strong correlation between the emotionally salient and neutral conditions means that while EIB can be used to investigate individual differences in attentional control, it is not selective to individual differences in attentional biases to emotionally salient stimuli.

Red‐Shifting ESIPT Fluorescence by Site‐Specific Functionalization in 2‐(2’‐hydroxyphenyl)benzazole Derivatives

We describe the synthesis, full photophysical study, and ab initio calculations of 2‐(2’‐hydroxyphenyl)benzazole (HBX) fluorophores substituted, at the meta position of the phenol group, by pyridine derivatives. HBX are commonly used as model dyes to study the stimuli‐induced modulation of the Excited State Intramolecular Proton Transfer (ESIPT) process. The meta‐substituted fluorophores reported herein, display a photophysical profile different from the previously reported ortho‐ and para‐substituted HBO pyridine isomers. Indeed, while all dyes undergo spontaneous deprotonation in neutral conditions, leading to highly emissive anionic species; upon protonation, ortho‐ and para‐pyridine substitution leads to resonance‐stabilized keto isomers, formed after ESIPT. Protonated meta derivatives, unable to stabilize their excited structure by such electronic delocalization process, display sizable intramolecular charge transfer (ICT) processes, translating into significantly redshifted emission. In addition, all dyes present a strong emission intensity, not only in neutral and acidic solutions, but also in the solid‐state. The nature of the emissive transitions was confirmed in each case by theoretical calculations combining Time‐Dependent Density Functional Theory (TD‐DFT) and second‐order Coupled Cluster (CC2) methods.

Engineering a Carotenoid Cleavage Oxygenase for Coenzyme-Free Synthesis of Vanillin from Ferulic Acid.

One-pot biosynthesis of vanillin from ferulic acid without providing energy and cofactors adds significant value to lignin waste streams. However, naturally evolved carotenoid cleavage oxygenase (CCO) with extreme catalytic conditions greatly limited the above pathway for vanillin bioproduction. Herein, CCO from Thermothelomyces thermophilus (TtCCO) was rationally engineered for achieving high catalytic activity under neutral pH conditions and was further utilized for constructing a one-pot synthesis system of vanillin with Bacillus pumilus ferulic acid decarboxylase. TtCCO with the K192N-V310G-A311T-R404N-D407F-N556A mutation (TtCCOM3) was gradually obtained using substrate access channel engineering, catalytic pocket engineering, and pocket charge engineering. Molecular dynamics simulations revealed that reducing the site-blocking effect in the substrate access channel, enhancing affinity for substrates in the catalytic pocket, and eliminating the pocket's alkaline charge contributed to the high catalytic activity of TtCCOM3 under neutral pH conditions. Finally, the one-pot synthesis of vanillin in our study could achieve a maximum rate of up to 6.89 ± 0.3 mM h-1. Therefore, our study paves the way for a one-pot biosynthetic process of transforming renewable lignin-related aromatics into valuable chemicals.

О СУБСТРАТНОЙ СПЕЦИФИЧНОСТИ И НЕКОТОРЫХ СВОЙСТВАХ ВНЕКЛЕТОЧНОЙ ОКСИДАЗЫ ИЗ БАЗИДИОМИЦЕТА NEONOTHOPANUS NAMBI

An extracellular enzyme with oxidase activity was isolated from the mycelium of the higher fungus Neonothopanus nambi by mild treatment of the biomass with β-glucosidase. A substrate specificity and some properties of the isolated extracellular oxidase were studied in the present work. Experiments revealed that the extracellular oxidase exhibited activity with most phenolic compounds chosen as model substrates. It is important to note that the enzyme exhibited a catalytic function in the reactions without the addition of exogenous hydrogen peroxide and other mediators. The highest catalytic activity of the enzyme was observed with veratryl alcohol and dihydric phenols, hydroquinone and guaiacol. The enzyme showed lower activity with aromatic azo compounds (ABTS, DAB, o-dianisidine). In reactions with dihydric phenol resorcinol and monophenol, the enzyme efficiency was extremely low. The kinetic parameters of the enzymatic reactions with actively oxidized substrates were determined. The addition of a divalent metal ion chelator (EDTA) did not affect the activity of the enzyme, while the addition of the SH reagent (DTT) increased the catalytic efficiency of the studied oxidase. The totality of the data obtained indicates that the extracellular oxidase of the N. nambi fungus catalyzes the oxidation of a wide range of aromatic compounds under slightly acidic and neutral conditions without the addition of additional mediators (in particular, hydrogen peroxide). This creates the prerequisites for studying the applicability of the enzyme in biomedical analytics.

Element mobility during basalt-water-CO2 interaction: observations in natural systems vs. laboratory experiments and implication for carbon storage

Today, carbon dioxide removal from the atmosphere is the most ambitious challenge to mitigate climate changes. Basalt rocks are abundant on the Earth’s surface (≈ 10%) and very abundant in the ocean floors and subaerial environments. Glassy matrix and minerals constituting these rocks contain metals (Ca2+, Mg2+, Fe2+) that can react with carbonic acid to form metal carbonates (CaCO3, MgO3 and FeCO3). Here, we present a data compilation of the chemical composition of waters circulating in basalt aquifers worldwide and the results of simple basalt-water-CO2 experiments. Induced or naturally occurring weathering of basalts rocks release elements in waters and elemental concentration is closely dependent on water CO2 concentration (and hence on water pH). We also performed two series of experiments where basaltic rock powder interacts with CO2-charged waters for one month at room temperature. Laboratory experiments evidenced that in the first stages of water-rock interaction, the high content of CO2 dissolved in water accelerates the basalt weathering process, releasing in the water not only elements that can form carbonate minerals but also other elements, which depending on their concentration can be essential or toxic for life. Relative mobility of elements such as Fe and Al, together with rare earth elements, increases at low pH conditions, while it decreases notably at neutral pH conditions. The comparison between experimental findings and natural evidence allowed to better understand the geochemical processes in basaltic aquifers hosted in active and inactive volcanic systems and to discuss these findings in light of the potential environmental impact of CO2 storage in mafic and ultramafic rocks.

One-dimensional, multi-fluid model of the plasma-wall transition. II. Negative ions

The plasma-wall transition is investigated by a one-dimensional steady-state multifluid model, which was presented in detail in Part I [T. Gyergyek et al., AIP Adv. 14, 045201 (2024)]. In this work, the plasma-wall transition is analyzed for the case where the plasma consists of singly charged positive ions, electrons, and singly charged negative ions. When the temperature and initial density of the negative ions are varied, a transition between two types of solutions of the model is observed. We call them the low and high solution, with respect to the absolute value of the potential drop. When the density and temperature of the negative ions are above a critical value, the low solution is observed. As the mass of the positive ions increases, these critical values also increase, but only until the ion mass is below about 1000 electron masses. With larger ion masses, the critical density of the negative ions and the temperature no longer change. In the low solution, the potential drop in front of the sheath is determined by the negative ions and is smaller in absolute terms than in the case of the high solution, where the potential drop in front of the sheath is determined by the electrons. If the problem is analyzed on the pre-sheath scale, the transition between the low and high solution is very sharp. However, when the neutrality condition is replaced by the Poisson equation, this transition becomes blurred and the solutions of the model equations exhibit oscillations. The role of the smallness parameter is highlighted. It is shown how the initial electric field is determined. Deviation of the negative ion density profile from the Boltzmann relation is discussed.

Allylthiourea‐mediated self‐healing hydrogels based on poly(vinyl alcohol): Enhanced cell viability/biocompatibility and sustained drug release

AbstractHydrogel‐based materials represent promising candidates for drug delivery. In our research, we synthesized a series of hydrogels—PVATU‐1 (2:1), PVATU‐2 (1:1), and PVATU‐3 (0.5:1)—by adjusting the poly(vinyl alcohol) (PVA) ratio while maintaining a constant ratio of allylthiourea (ATU) monomer and glutaraldehyde cross‐linker, aiming to understand their impacts on gelation. These PVATU hydrogels displayed impressive swelling in neutral conditions and exhibited visible self‐healing capabilities. Notably, PVATU‐1 shows superior mechanical strength among the variants. Surface analysis using AFM and SEM unveiled porous structures within the hydrogels, while thermal stability tests indicated their resilience up to 200°C. DSC analysis revealed minimal variation in glass transition temperatures (Tg), affirming stability. A distinct endothermic peak around 250–350°C across all hydrogels confirmed their semi‐crystalline nature, corroborated by powder XRD. Noteworthy, PVATU‐1 demonstrated optimal loading and releasing efficiency for levofloxacin, with 74.5% loading and 82.8% releasing efficiency within 18 h. Biocompatibility assessments on HeLa cells affirmed the nontoxicity of PVATU hydrogel treatments.

Bioinspired Tetranuclear Manganese Cubane Complex as an Efficient Molecular Electrocatalyst for Two‐electron Water Oxidation Towards Hydrogen Peroxide

Stable homogenous two‐electron water oxidation electrocatalysts are highly demanded to understand the precise mechanism and reaction intermediates of electrochemical H2O2 production.Here we report a tetranuclear manganese complex with a cubane structure which can electrocatalyze water oxidation to hydrogen peroxide under alkaline and neutral conditions. Such a complex demonstrates an optimal Faradaic efficiency (FE) of 87%, which is the highest FE(H2O2) among reported homogeneous and heterogeneous electrocatalysts. In addition, active species were identified and co‐catalysts were excluded through ESI‐MS characterization. Furthermore, we identified water binding sites and isolated one‐electron oxidation intermediate by chemical oxidation of the catalyst in the presence of water substrates. It is evident that efficient proton‐accepting electrolytes avoid rapid proton building‐up at electrode and substantially improve reaction rate and selectivity. Accordingly, we propose a two‐electron catalytic cycle model for water oxidation to hydrogen peroxide with the bioinspired molecular electrocatalyst. The present work is expected to provide an ideal platform to elucidate the two‐electron WOR mechanism at the atomic level.

Bioinspired Tetranuclear Manganese Cubane Complex as an Efficient Molecular Electrocatalyst for Two-electron Water Oxidation Towards Hydrogen Peroxide.

Stable homogenous two-electron water oxidation electrocatalysts are highly demanded to understand the precise mechanism and reaction intermediates of electrochemical H2O2 production.Here we report a tetranuclear manganese complex with a cubane structure which can electrocatalyze water oxidation to hydrogen peroxide under alkaline and neutral conditions. Such a complex demonstrates an optimal Faradaic efficiency (FE) of 87%, which is the highest FE(H2O2) among reported homogeneous and heterogeneous electrocatalysts. In addition, active species were identified and co-catalysts were excluded through ESI-MS characterization. Furthermore, we identified water binding sites and isolated one-electron oxidation intermediate by chemical oxidation of the catalyst in the presence of water substrates. It is evident that efficient proton-accepting electrolytes avoid rapid proton building-up at electrode and substantially improve reaction rate and selectivity. Accordingly, we propose a two-electron catalytic cycle model for water oxidation to hydrogen peroxide with the bioinspired molecular electrocatalyst. The present work is expected to provide an ideal platform to elucidate the two-electron WOR mechanism at the atomic level.

An ESIPT-Based Fluorescent Probe for Wash-Free Cell Membrane Imaging.

The cell membrane tracking is important for studying the membrane function and diagnosing membrane-related diseases, so the development of fluorescent molecule specifically lighting up cell membrane is highly desirable. In this work, we designed and readily prepared a fluorescent dye (BOHI) that can target cell membrane. The pH-dependent emission spectra reveal that BOHI shows fluorescence based on the excited-state intramolecular proton transfer (ESIPT) under acidic and neutral conditions, while the blue-shifted emission from the phenolate anion of BOHI was observed when pH ≥ 9. Among various solvents, the weakest fluorescence emission was observed in H2O, which is favorable to wash-free imaging. The fluorescence intensity of BOHI is greatly affected by surfactants. The anionic surfactant can induce intense green fluorescence, while very weak fluorescence was observed in the solution of cationic surfactant. Hela cells images show that BOHI can specifically targets and lights up cell membrane.

Green and sustainable degradation of ofloxacin in Fe3O4/clinoptilolite electro-Fenton system under neutral condition

BackgroundIn order to overcome the drawbacks of the pH value adjustment and Fe2+addition of traditional electro-Fenton in refractory organic wastewater treatment, we set up an electro-Fence system (FCC-EF) with multiple functions of adsorption, catalysis, and green regeneration for efficient and green degradation of ofloxacin (OFLO) wastewater under neutral condition. MethodsThe Fe3O4/clinoptilolite catalyst with adsorption function was prepared by hydrothermal synthesis method, and then characterized by energy dispersive spectrometer (EDS), transmission electron microscopy (TEM) and X-ray Diffractometer (XRD). The Fe3O4/clinoptilolite's chemical composition and oxidation state was investigated by X-ray photoelectron spectros (XPS). The degradation of OFLO and the total organic carbon (TOC) were determined through HPLC and a TOC analyzer, respectively. FindingsThe results indicate that in multi-cycle operation under current density of 6 mA·cm−2 and pH = 7, FCC-EF has a 100 % removal rate for OFLO and 80.4 ± 0.2 % removal rate for TOC at 165 min, while no iron ions are detected. The internal cycling of Fe3+/Fe2+ within Fe3O4 crystals is performed in FCC-EF. The green regeneration of Fe3O4/clinoptilolite and the efficient degradation of OFLO in multi-cycle operation could be simultaneously achieved under neutral condition.

MOF-on-MOF-derived Fe[sbnd]Zr bimetal oxides supported on hierarchically porous carbonized wood to promote photo-Fenton degradation of ciprofloxacin

MOF-on-MOF derivatives have served as promising heterogeneous Photo-Fenton (hetero-PF) catalysts, but its self-aggregation instability and limited photocatalytic activity inhibit the effective ciprofloxacin (CIP) removal. In this study, a novel hetero-PF catalyst, dual MOF-derived FeZr bimetal oxide embedded in a wood-converted porous carbon skeleton (ZrO2@Fe3O4/WPC), was successfully synthesized via a straightforward in-situ growth strategy combined with co-pyrolysis. The as-prepared hybrid photocatalysts, featuring a large surface area, effective porous structures, efficient light absorption and a narrow band gap demonstrated superior photo-Fenton activity, accomplishing approximately 99.1 % degradation of CIP within 120 min under neutral conditions. Furthermore, the ZrO2@Fe3O4/WPC hetero-PF system showed satisfactory performance in treating real water matrices. It can be inferred that the abundant heterojunctions, resulting from the synergistic effect of FeZr mixed oxide and the porous carbonized wood substrate, contributed to the rapid separation and migration of photogenerated electron-hole pairs. Meanwhile, the FeZr site in the graphitized carbon framework activates H2O2 to accelerate the generation of the OH and O2− radicals, leading to a heightened degradation efficiency of CIP. Besides, the photodegradation pathway of CIP is obtained by liquid chromatography-mass spectrometry (LC-MS). This study indicates that combining porous carbonized wood and heterometallic MOF derived materials provides a promising method for realizing high-efficiency photo-Fenton degradation of antibiotic water pollutions.

Redox‐Active Organic Molecules Supported by Polyhedral Oligomeric Silsesquioxane

AbstractOrganic redox molecules have attracted considerable attention because of their abundant availability and excellent design flexibility. For practical applications, these molecules must be anchored onto scaffolds such as polymers to prevent crystallization and elution into the electrolyte. In this study, we explore the use of polyhedral oligomeric silsesquioxane (POSS) derivatives as scaffolds for anthraquinone (AQ) and hydroquinone. We investigated the cage structure of POSS and the number of redox units incorporated. Notably, a corner‐opened POSS (CO‐POSS) variant with three AQ units exhibited reversible redox behavior under neutral, acidic, and basic conditions. Furthermore, we examined the air‐battery performance of AQ‐modified CO‐POSS as an anode‐active material.

Translational Research of the Acute Effects of Negative Emotions on Vascular Endothelial Health: Findings From a Randomized Controlled Study.

Provoked anger is associated with an increased risk of cardiovascular disease events. The underlying mechanism linking provoked anger as well as other core negative emotions including anxiety and sadness to cardiovascular disease remain unknown. The study objective was to examine the acute effects of provoked anger, and secondarily, anxiety and sadness on endothelial cell health. Apparently healthy adult participants (n=280) were randomized to an 8-minute anger recall task, a depressed mood recall task, an anxiety recall task, or an emotionally neutral condition. Pre-/post-assessments of endothelial health including endothelium-dependent vasodilation (reactive hyperemia index), circulating endothelial cell-derived microparticles (CD62E+, CD31+/CD42-, and CD31+/Annexin V+) and circulating bone marrow-derived endothelial progenitor cells (CD34+/CD133+/kinase insert domain receptor+ endothelial progenitor cells and CD34+/kinase insert domain receptor+ endothelial progenitor cells) were measured. There was a group×time interaction for the anger versus neutral condition on the change in reactive hyperemia index score from baseline to 40 minutes (P=0.007) with a mean±SD change in reactive hyperemia index score of 0.20±0.67 and 0.50±0.60 in the anger and neutral conditions, respectively. For the change in reactive hyperemia index score, the anxiety versus neutral condition group by time interaction approached but did not reach statistical significance (P=0.054), and the sadness versus neutral condition group by time interaction was not statistically significant (P=0.160). There were no consistent statistically significant group×time interactions for the anger, anxiety, and sadness versus neutral condition on endothelial cell-derived microparticles and endothelial progenitor cells from baseline to 40 minutes. In this randomized controlled experimental study, a brief provocation of anger adversely affected endothelial cell health by impairing endothelium-dependent vasodilation.

Improving NiFe Electrocatalysts through Fluorination-Driven Rearrangements for Neutral Water Electrolysis.

Neutral electrolysis to produce hydrogen is prime challenging owing to the sluggish kinetics of water dissociation for the electrochemical reduction of water to molecular hydrogen. An ion-enriched electrode/electrolyte interface for electrocatalytic reactions can efficiently obtain a stable electrolysis system. Herein, we found that interfacial accumulated fluoride ions and the anchored Pt single atoms/nanoparticles in catalysts can improve hydrogen evolution reaction (HER) activity of NiFe-based hydroxide catalysts, prolonging the operating stability at high current density in neutral conditions. NiFe hydroxide electrode obtains an outstanding performance of 1000mA cm-2 at low overpotential of 218mV with 1000 h operation at 100mA cm-2. Electrochemical experiments and theoretical calculations have demonstrated that the interfacial fluoride contributes to promote the adsorption of Pt to proton for sustaining a large current density at low potential, while the Pt single atoms/nanoparticles provide H adsorption sites. The synergy effect of F and Pt species promotes the formation of Pt─H and F─H bonds, which accelerate the adsorption and dissociation process of H2O and promote the HER reaction with a long-term durability in neutral conditions.

Efficient activation of peracetic acid by cobalt modified nitrogen-doped carbon nanotubes for drugs degradation: Performance and mechanism insight

Peracetic acid (PAA) has garnered significant attention as a novel disinfectant owing to its remarkable oxidative capacity and minimal potential to generate byproducts. In this study, we prepared a novel catalyst, denoted as cobalt modified nitrogen-doped carbon nanotubes (Co@N-CNTs), and evaluated it for PAA activation. Modification with cobalt nanoparticles (∼4.8 nm) changed the morphology and structure of the carbon nanotubes, and greatly improved their ability to activate PAA. Co@N-CNTs/PAA catalytic system shows outstanding catalytic degradation ability of antiviral drugs. Under neutral conditions, with a dosage of 0.05 g/L Co@N-CNT-9.8 and 0.25 mM PAA, the removal efficiency of acyclovir (ACV) reached 98.3% within a mere 10 min. The primary reactive species responsible for effective pollutant degradation were identified as acetylperoxyl radicals (CH3C(O)OO•) and acetyloxyl radicals (CH3C(O)O•). In addition, density functional theory (DFT) proved that Co nanoparticles, as the main catalytic sites, were more likely to adsorb PAA and transfer more electrons than N-doped graphene. This study explored the feasibility of PAA degradation of antiviral drugs in sewage, and provided new insights for the application of heterogeneous catalytic PAA in environmental remediation.

Reactive species identification in KCl activated biochar/persulfate system under different pH condition: Theoretical calculation and column experiments

The challenges of remediating polluted water in mine areas are exacerbated by low emission dispersion and long-lasting pollution, particularly the significant fluctuations in pH value. Notably, the treatment of flotation reagent polluted water with variable pH scenarios remains a challenge. In this study, metal-free biochar-based materials (KBBC)/persulfate system was used for flotation reagent contaminated wastewater treatment with a wide pH range. Regarding the intrinsic nature of the biochar-based materials, ball milling enhanced the degree of graphitization, while introducing a hard template of KCl increased the proportion of carbonyl functional groups on their surface, thereby facilitating persulfate activation. Experimental findings revealed that the KBBC/PS system displayed efficient degradation of aniline aerofloat (AAF) as a representative flotation reagent across a wide pH range (pH = 3.6–10.4 with buffer). Investigations on the mechanism indicated that, under acidic and neutral conditions, superoxide radicals and direct electron transfer processes constituted primary pathways for pollutant degradation. Meanwhile, various active species contributed under alkaline conditions with increased involvement of free radicals (•OH and SO4•−) and singlet oxygen. Furthermore, continuous flow experiments were set up to prove the potential applicability of the KBBC/PS process. This study not only deepens the understanding of persulfate activation by metal-free carbon-based materials across a wide pH range but also expands their potential applications in mine-polluted water purification.