Non-radical Species Research Articles

Mechanistic insights into the roles of copper in enhanced peroxymonosulfate activation for tetracycline degradation by copper ferrite composite catalyst

Tetracycline (TC) pollution has attracted great attention due to its wide use, non-biodegradability and potential carcinogenicity. Bimetallic catalysts/peroxymonosulfate (PMS) systems have been considered as powerful technologies for TC degradation. Although the excellent catalytic activity of copper ferrite (CuFe2O4) composite oxides for PMS has been already elucidated, the roles of increased Cu in the degradation especially from non-radical pathways are not clarified clearly. In this study, we prepared a series of CuO/CuFe2O4/Fe2O3 (CCF) catalysts to confirm the key role of molar ratios of Cu: Fe (ranging from 1:2 to 2:1) in the enhanced degradation. The optimized CCF-3 catalyst with the Cu: Fe molar ratio of 2:1 showed the best degradation efficiency up to 95.6 % and the fastest apparent degradation rate of 0.135 min−1 towards TC. In addition, the CCF-3/PMS system showed excellent adaptability and good stability in TC degradation. Importantly, a novel molecular-scale mechanism was proposed. Both radical (SO4∙-, ∙OH, O2∙ –) and non-radical (1O2, direct electron transfer) pathways were associated with the CCF-3/PMS catalytic system, where 1O2 played the dominant roles. The increased Cu significantly boosted the non-radical pathways via promoting the formation of oxygen vacancies (Ov) and its further conversion to 1O2, and facilitating electron transfer between bimetallic Cu/Fe interface. This work provides a deep insight into the formation and reaction mechanisms of non-radical species for CCF/PMS systems, and a novel foundation for the design of CuFe2O4 composite catalysts

Construction of a multiple reactive species-mediated Co9S8/NBC-PMS Fenton-like system for tetracycline degradation with broadened adaptability to water background

A Fenton-like system based on peroxymonosulfate (PMS) oxidant has high potential for antibiotic degradation, However, various complex water background factors, including pH, coexisting ions, and dissolved organic matter, can adversely affect degradation efficiency. This work constructed a PMS oxidative Fenton-like system activated by cobalt polysulfide/N-doped biochar composite (Co9S8/NBC) for the degradation of tetracycline (TC) and achieving approximately 99 % removal of TC. Furthermore, the removal efficiency was maintained above 90 % across a broad pH range (3−11), in the presence of various coexisting anions (Cl−, NO3− and CO32−), even at high concentrations of humic acid. The characterization of Co9S8/NBC through various techniques confirmed that Co9S8 nanoparticles were uniformly loaded within the porous NBC structure. Electron paramagnetic resonance and reactive oxygen species (ROSs) quenching experiment revealed that the effectiveness of TC degradation in the Co9S8/NBC/NBC-PMS system arises from the cooperation of radical and non-radical species rather than the single mechanism. Moreover, the analysis of the contribution ratios of ROSs to TC degradation indicates that the contribution of non-free radicals exceeds that of free radicals, and it is capable of adapting to changes in pH. The characterization of the post-reaction catalyst suggested that Co9S8 and NBC synergistically participated in the activation of PMS. Moreover, the practical examination proved that the disabled Co9S8/NBC catalyst can recover the catalytic activity via a reheat treatment, the leaching concentration of Co ions was lower than the emission limit of China. The river water and lake water as the matrix water have little negative impact on the degradation of TC. The Co9S8/NBC-PMS system is expected to provide a practical pathway for the treatment of antibiotic wastewater.

Selective oxidation of electron-rich pollutants in peroxymonosulfate-activated electro-Fenton system: the role of microenvironment-regulated cathode

Electro-Fenton technologies driven by peroxymonosulfate (PMS) activation have been extensively explored for abatement of organic pollutants from water. Unfortunately, a great diversity of matrix components in contaminated water scenarios inevitably and significantly compromises the efficiency of the generated radicals toward target pollutants. Thus, selective oxidation of the electro-Fenton technologies is urgently desired for cost effective and sustainable water treatment, but challenged by the traditional electron transfer pathway from cathode to PMS to mainly form SO4•− and HO• radicals. In this study, we successfully realized selective generation of 1O2, a non-radical species specific for electron-rich pollutants, by regulating the second-shell coordination environment of single-atom Fe in carbonaceous cathode. The doped electron-accepting B drives directional electron transfer from PMS to electrode and inhibiting the undesirable radical pathways. Besides, the electrochemical reduction of H+ in-situ generated from the dissociation of H-O in PMS is favourable for the formation of 1O2 as high as 163.4 μmol.L−1min−1. Fast and preferential removal of sulfonamides pollutants in different water matrices demonstrated the excellent matrix tolerance of the newly developed electro-Fenton process. A pilot electrochemical device was designed to further selective remove phenols in real-scenario application. No residual phenol was detected (<0.01 mg/L) with TOC removal around 50% (down to 23.9±0.3 mg L−1) during the continuous 24-h operation. This study is also believed to shed new light on how to achieve desirable electrochemical reactions via microenvironmental regulation in response to sustainable water decontamination and beyond.

Atomically dispersed Fe-N4 sites in activation of peroxymonosulfate for wastewater purification: Mechanism of non-radical pathways and their quantification

Single-atom catalysts are promising alternatives to homogeneous and heterogeneous catalysts in the advanced oxidation processes for contaminant degradation; however, quantifying the exact contribution of nonradical reactive oxygen species has remained challenging. Herein, Fe single atoms anchored on nitrogen-doped carbonaceous substrates (Fe SAs-N-C) were synthesized for peroxymonosulfate (PMS) activation toward pollutant degradation. Fe SAs-N-C achieved high activity within 30 min, which is 17.20 and 5.08 times higher than those of N-C catalysts without or with Fe nanoparticles, respectively. A synergistic mechanism of singlet oxygen (1O2) and electron transfer for dominating pollutant degradation was revealed. The former contributed 78.50 % while the latter contributed 21.50 % in pollutant elimination. Density functional theory calculations uncovered that the O atom in −SO4 moiety of PMS was adsorbed on the Fe atoms, leading to the OH bond elongation and generating 1O2. While the absorbed O atom in OO bond near to −SO4 moiety of PMS tended to enlarge the OO bond and accelerate the electron transfer. The adsorbed PMS was prone to being decomposed into 1O2 due to a lower energy barrier (0.43 eV) of 1O2 rate-determining step than that of electron transfer (0.95 eV). Fe-N4 sites are both electron transfer channels and 1O2 formation sites. This work provides insights into the quantitative contributions of non-radical active species to pollutant degradation.

The catalytic pathways on niobium-cerium loading catalysts for methylene blue elimination in the Fenton-like system: Roles of oxygen vacancies

The oxidation pathways affected by asymmetric and symmetric Ov sites on catalysts in the Fenton-like process should be illustrated in detail. Based on the experimental and theoretical results, it can be revealed that the asymmetric Ov sites favored nonradical species (1O2) formation by triggering H2O2 and DO to produce surface O2·-, and the migration distance between the species and pollutant was shortened due to the excellent adsorption of methylene blue (MB) on the sites. OH species were liable to be generated on the symmetric Ov sites. Calcination and the amount of medium strong acid sites of the support may be important roles in the formation of asymmetric Ovs for the Nb-Ce loading catalyst prepared by impregnation. This work unravels the different catalytc pathways of asymmetric and symmetric Ovs dominated, and also provides a facile strategy to control the oxidation pathway as desirable in the H2O2-Fenton-like system.

Periodate activation with polyaniline-derived carbon for bisphenol A degradation: Insight into the roles of nitrogen dopants and non-radical species formation

Periodate-based advanced oxidation processes (PI-AOPs) activated by carbon catalysts have shown promising application prospects in the removal of emerging contaminants. Herein, a series of N-doped carbon catalysts (NC) were prepared by in-situ pyrolysis of N-containing polymers (polyaniline) to unveil the potential mechanism of N dopants on PI activation. The optimized sample NC700 showed a satisfying degradation performance, achieving 100 % removal of bisphenol A (BPA) at a concentration of 10 mg/L within 90 min in the presence of 0.1 mM PI. The impacts of various N types on PI activation were systematically investigated by dynamic fitting and density functional theory computations. These analyses highlighted the crucial role of graphitic N configuration on carbon surface, which exhibited the highest adsorption energy and a positive correlation with the normalized degradation efficiency. The chemical quenching experiments and electrochemical experiments confirmed that the BPA oxidation mechanism was primarily mediated electron transfer by [NC-PI]* complex, with singlet oxygen (1O2) /superoxide radicals (O2•–) playing a supplementary role. In situ ATR-SERAS measurement strengthened the understanding of PI activation by carbon catalyst based on electron transfer pathway. Owing to the non-radical oxidation mechanism, the NC/PI system had a broad pH adaptability and great anti-interference ability against typical wastewater components. This study provides mechanistic insights into the carbon-driven PI activation process for wastewater treatment, advancing the practical application of PI-AOPs.

Endogenously doped mixed-oxide CoO/Co2O3 in ZIF-derived carbon deposited on graphite felt for electrochemical oxidation of pharmaceutics

Some of the important goals in the development of the electro-Fenton (EF) process are to increase the performance of the electrodes while reducing their size as an alternative for expensive electrodes, expanding the active pH range, and also generating reactive oxygen species (ROSs) directly without using other homo/heterogeneous catalysts. This work modified graphite felt (GF) using a rapid and in-situ synthesis with Co/Zn doped mixed-metal ZIF. After calcination, various physicochemical analyses, including XRD, SEM, and XPS, confirmed that a carbonic material doped with mixed-oxide CoO/Co2O3 is embedded on the surface of GF fibers. LSV analysis showed that the modification significantly improved the electrode activity for O2 reduction. The modified CoZnCal-GF electrode showed good performance and higher kinetics in the EF process. It removed 87% of rifampin (RIF) in a short period of 30 min without any homo/heterogeneous catalysts. The selected conditions for this process were 1.0 V, 40 mg/L, and 5.6 for applied voltage, initial RIF concentration, and pH, respectively. The non-radical species 1O2 showed the most important role in removing RIF. LC-MS analysis was performed, and while confirming the complete removal of RIF, it was used to investigate the degradation pathway and identify the produced intermediates.

Efficient photocatalytic water decontamination over a wide pH range by C and O co-doped carbon nitride with tunable band structure

The metal-free, non-toxic, and highly tunable structure of carbon nitride confers unique advantages in photocatalytic advanced oxidation processes. Regulating the generation of radical and non-radical species during photocatalysis to maintain high degradation efficiency across different water matrices is of great practical significance for the application of carbon nitride. In this study, a C and O co-doped modified carbon nitride (UCN) with a high specific surface area was developed for efficient photodegradation of p-chlorophenol (p-Cl) without exogenous oxidants. Characterizations demonstrated that UCN in higher specific surface area exposed more active sites. Additionally, with rising doping levels, UCN exhibited enhanced light absorption capability and a narrower bandgap, which favored the separation of photogenerated electron-hole pairs. The primary active species were identified as holes, accompanied by the generation of superoxide radicals (·O2–) and singlet oxygen (1O2) depending on the pH value. Under acidic conditions, 1O2 was predominantly generated, whereas ·O2– dominated under alkaline conditions. As a result, the removal efficiency of p-Cl was enhanced under both strongly acidic and alkaline conditions. The pseudo-first-order rate constants for p-Cl removal at pH 3, 7, and 11 were 0.0558, 0.0354, and 0.0443 min−1, respectively. Moreover, combining DFT calculations and LC-MS data, analysis on the intermediate products of p-Cl degradation revealed unique characteristics at different pH values, further proving the flexible tunability and providing insights into the practical application of modified carbon nitride.

Facile synthesis of defect-rich interfacial Mo/MoO2 for efficient peroxymonosulfate activation and refractory pollutants degradation

Peroxymonosulfate-based advanced oxidation process (PMS-AOP) has shown great potential in sewage purification, and catalyst development capable of efficient PMS activation is a key while challenging element. Herein we reported a facile electro-explosive route to synthesize the oxygen vacancy (Vo)-enriched Mo/MoO2 without using chemical reagents. The detailed studies suggested that the synergy of Mo active site and Vo in the catalyst significantly boosted the activation kinetics of PMS. Evidently, the Mo site of different oxidation states contributed to chemical activation of PMS, while the Vo favored the activation of PMS and the generation of non-radical 1O2 species. As a result, the Mo/MoO2-10 h/PMS system delivered a complete removal of acid orange 7 (AO7) within 4 min, significantly exceeding the activity of Mo/PMS (16%), MoO2-H/PMS (25%) and most of other PMS-based systems. Moreover, the current system showed high potential for removal of different pollutants including antibiotics and organic dyes. Radical quenching experiments and electron paramagneticresonance (EPR) studies revealed that the 1O2 species was significant for AO7 decomposition. This work provided a novel strategy to a batch-scale synthesis of high-performance PMS activator for water remediation in practice.

The promotional role of peroxydisulfate in Arsenic(III) oxidation by Fe(III)/Sulfite: Boosting and regulating the generation of radical and non-radical species

The Fe(III)-activated sulfite (S(IV)) process to yield powerful SO4•−/HO• radicals is increasingly recognized as an appealing advanced oxidation process (AOP). However, its application is constrained by its heavy reliance on dissolved oxygen and the low selectivity of these short-lived radicals. In this work, peroxydisulfate (PDS) was found to indeed amplify the capacity of the Fe(III)/S(IV) system for arsenite (As(III)) oxidation, with increasing the oxidation efficiency and rate constant from 47 % to 95 % and 0.165 min−1 to 0.455 min−1, respectively. The mechanistic study revealed that the predominant reactive species were identified as both radicals (SO4•−/HO•) and non-radical (Fe(IV)O2+ instead of 1O2), with HO• primarily originating from Fe(IV)O2+. Herein, PDS not only acted as an electron acceptor to react with the in-situ formed Fe(II), thus accelerating the Fe(II) ↔ Fe(III) cycle and producing Fe(IV)O2+, but also functioned as a substitute for dissolved oxygen to facilitate SO4•− generation even under anaerobic conditions. Moreover, the generation efficiency and distribution of these oxidizing reactive species were significantly influenced by adjusting experimental parameters (i.e., reagents dosage and solution pH). Overall, this work unveiled an enticing strategy to fine-tune the oxidative prowess and precision of the Fe(III)/S(IV)/PDS system for oxidizing specific contaminants by orchestrating the relative distribution of radicals (SO4•−/HO•) and non-radical (Fe(IV)O2+).

Iron-cobalt loading carbon nitride bimetallic catalyst activates peroxymonosulfate for bisphenol A degradation

In order to reduce metal leaching loss and carbon emissions, an active Peroxymonosulfate (PMS) catalyst (Fe/Co–CN) was prepared using a one-step thermal polycondensation method for the efficient treatment of wastewater containing bisphenol A (BPA). Fe/Co–CN has a low metal leaching (＜1 mg/L) and has good catalytic degradation performance for BPA. The degradation efficiency was 90.7% in 5 min and ∼100% in 10 min, which is much higher than single metal-loaded Fe–CN (77.2%) and Co–CN (73.2%). Nonradical species dominated by 1O2 and high-valent species were the main reactive oxygen species that degraded BPA in the Fe/Co–CN/PMS system. By strictly controlling the energy consumption during the synthesis and application of Fe/Co–CN, lower carbon emissions have been achieved than most catalysts reported. This achievement is of great significance for applying advanced oxidation methods to treat organic micro-pollutants and provides reference for the calculation of PMS catalysts carbon emissions.

Persulfate activation by biochar and iron: Effect of chloride on formation of reactive species and transformation of N,N-diethyl-m-toluamide (DEET)

Fenton-like processes using persulfate for oxidative water treatment and contaminant removal can be enhanced by the addition of redox-active biochar, which accelerates the reduction of Fe(III) to Fe(II) and increases the yield of reactive species that react with organic contaminants. However, available data on the formation of non-radical or radical species in the biochar/Fe(III)/persulfate system are inconsistent, which limits the evaluation of treatment efficiency and applicability in different water matrices. Based on competition kinetics calculations, we employed different scavengers and probe compounds to systematically evaluate the effect of chloride in presence of organic matter on the formation of major reactive species in the biochar/Fe(III)/persulfate system for the transformation of the model compound N,N‑diethyl-m-toluamide (DEET) at pH 2.5. We show that the transformation of methyl phenyl sulfoxide (PMSO) to methyl phenyl sulfone (PMSO2) cannot serve as a reliable indicator for Fe(IV), as previously suggested, because sulfate radicals also induce PMSO2 formation. Although the formation of Fe(IV) cannot be completely excluded, sulfate radicals were identified as the major reactive species in the biochar/Fe(III)/persulfate system in pure water. In the presence of dissolved organic matter, low chloride concentrations (0.1 mM) shifted the major reactive species likely to hydroxyl radicals. Higher chloride concentrations (1 mM), as present in a mining-impacted acidic surface water, resulted in the formation of another reactive species, possibly Cl2•−, and efficient DEET degradation. To tailor the application of this oxidation process, the water matrix must be considered as a decisive factor for reactive species formation and contaminant removal.

UVA light assisted activation of sulfite by metal–organic framework-derived FeOx@C catalyst for organic degradation: Formation and role of non-radical species

Advanced oxidation processes (AOPs) based on sulfite (S(IV)) activation are gaining recognition as a promising Fenton-like strategy, primarily due to their ability to generate potent radicals (e.g., SO4− and HO). However, the existence and role of a non-radical-driven oxidation pathway in the S(IV)-mediated degradation of contaminants remain under debate. Herein, a magnetic iron-carbon composite (FeOx@C) was fabricated using the MOF-templated method and utilized as a stable photocatalyst to activate S(IV) under UVA light, achieving >93.6 % degradation of 20 μM ofloxacin (OFL) with a high degradation rate constant of 0.073 min−1 within 45 min. The catalyst’s porous carbon structure facilitated the transport of substrates to active sites and shortened the diffusion distance between reactive species and contaminants. Adsorbed S(IV) donated one electron to photo-generated holes and exposed Fe(III) sites with the formation of SO5−, which then followed two distinct pathways to produce radicals (SO4−) and non-radicals (Fe(IV) and 1O2) responsible for OFL degradation. By leveraging the synergy of both radicals and non-radicals, this innovative oxidative system showcased robust anti-interference capacities and exceptional performance in degrading contaminants from complex water matrices. This study provides new insights into the significant role of non-radical species in S(IV)-mediated decontamination processes.

Resolving the overlooked photochemical nitrophenol transformation mechanism induced by nonradical species under visible light

Nitrophenols present on the surface of particulates are ubiquitous in the atmosphere. However, its atmospheric photochemical transformation pathway remains unknown, for which the crucial effect of visible light is largely overlooked, resulting in an incomplete understanding of the effects of nitrophenols in the atmospheric environment. This study delves into the photolysis mechanism of 4-nitrophenol (4NP), one of the most abundant atmospheric nitrophenol compounds, on the surface of photoactive particulates under visible light irradiation. Unexpectedly, the nonradical species (singlet oxygen, 1O2) was identified as a dominant factor in driving the visible photolysis of 4NP. The pathways of HONO and p-benzoquinone (C6H4O2) generation were clarified by acquiring direct evidence of C-N and O-H bond breakage in the nitro (-NO2) and hydroxyl (-OH) groups of 4NP. The further decomposition of HONO results in the generation of NO and hydroxyl radicals, which could directly contribute to atmospheric oxidizing capacity and complicate the PM2.5 composition. Significantly, the behavior of 1O2-induced visible photolysis of 4NP was universal on the surface of common particulates in the atmosphere, such as A1 dust and Fe2O3. This work advances the understanding of the photochemical transformation mechanism of particulate-phase atmospheric nitrophenols, which is indispensable in elucidating the role of nitrophenols in atmospheric chemistry.

Kinetics and mechanisms of non-radically and radically induced degradation of bisphenol A in a peroxymonosulfate-chloride system

Bisphenol A, a hazardous endocrine disruptor, poses significant environmental and human health threats, demanding efficient removal approaches. Traditional biological methods struggle to treat BPA wastewater with high chloride (Cl−) levels due to the toxicity of high Cl− to microorganisms. While persulfate-based advanced oxidation processes (PS-AOPs) have shown promise in removing BPA from high Cl− wastewater, their widespread application is always limited by the high energy and chemical usage costs. Here we show that peroxymonosulfate (PMS) degrades BPA in situ under high Cl− concentrations. BPA was completely removed in 30 min with 0.3 mM PMS and 60 mM Cl−. Non-radical reactive species, notably free chlorine species, including dissolved Cl2(l), HClO, and ClO− dominate the removal of BPA at temperatures ranging from 15 to 60 °C. Besides, free radicals, including •OH and Cl2•−, contribute minimally to BPA removal at 60 °C. Based on the elementary kinetic models, the production rate constant of Cl2(l) (32.5 M−1 s−1) is much higher than HClO (6.5 × 10−4 M−1 s−1), and its degradation rate with BPA (2 × 107 M−1 s−1) is also much faster than HClO (18 M−1 s−1). Furthermore, the degradation of BPA by Cl2(l) and HClO were enlarged by 10- and 18-fold at 60 °C compared to room temperature, suggesting waste heat utilization can enhance treatment performance. Overall, this research provides valuable insights into the effectiveness of direct PMS introduction for removing organic micropollutants from high Cl− wastewater. It further underscores the critical kinetics and mechanisms within the PMS/Cl⁻ system, presenting a cost-effective and environmentally sustainable alternative for wastewater treatment.

Developing carbon nitride with tailored defect structure for exceptional nonradical activation of peroxymonosulfate

The nonradical activation of peroxymonosulfate (PMS) over nonmetallic catalyst remains a significant scientific challenge. Herein, we proposed a facile stepwise calcination approach to prepare fragmented carbon nitride (CN) with three coordinate nitrogen (N3C) vacancies (VCN). The defective structure comprising vacant and disintegrated nanosheet synergistically conferred VCN abundant unpaired electrons, providing an exceptional catalytic behavior to evolve nonradical pathway in PMS activation. This featured system allowed generating nonradical reactive species with 100 % selectivity, namely, a major singlet oxygenation and a spot of VCN/PMS complex-triggered oxidation, which enabled a high effectiveness in the degradation of Acid Orange 7 (almost 100 % removal efficiency within 20 min). Impressively, the VCN was also featured with excellent environment serviceability, long-term operational performance, and desirable non-photocatalytic efficiency in the PMS-mediated nonradical oxidation. Overall, this study offers a facile strategy for tailoring CN architecture to achieve PMS nonradical activation and contributes to an efficient strategy for wastewater remediation.

Comet-like Co-MOF with TiO2 nanoparticles decorated used to efficiently activate peroxymonosulfate for larotrectinib degradation through radical and non-radical pathways

Removal of emerging contaminants has drawn great concern due to their potential high risk to eco-environment system and human health. In this study, an emerging and broad-spectrum anticancer pharmaceutical, larotrectinib (LOXO), was focused on to achieve its degradation in water. A heterogenous peroxymonosulfate (PMS) activation system was constructed by using a comet-like Co-based metal–organic framework (Co-MOF) with TiO2 nanoparticles decorated. The optimized material (TiO2/Co-MOF1) showed high PMS activation efficiency, and thus 90.1 % of LOXO could be quickly degraded within 10 min. Scavenger quenching tests and electron paramagnetic resonance (EPR) analysis indicated that both radicals (OH and SO4-) and non-radical species (1O2) contributed to LOXO degradation. The two main components of Co-MOF and TiO2 nanoparticles in the composite showed a synergetic effect on PMS activation: Co-MOF offered coordination cobalt for PMS activation, while TiO2 provided abundant –OH groups for interface complexation to promote the electron transfer. In addition, 1O2 originates from directional conversion of O2– after PMS activation at the material’s surface. Moreover, density functional theory (DFT) calculation suggests that the atoms in LOXO with high Fukui index (f-) representing electrophilic attack are the reactive sites. Toxicity analysis based on quantitative structure–activity relationship (QSAR) verifies the reduced toxicity of degraded intermediates/products. This work proposed an available technology to efficiently activate PMS for anticancer drugs degradation through both radical and non-radical pathways in wastewater.

Atomically dispersed copper-zinc dual sites anchored on nitrogen-doped porous carbon toward peroxymonosulfate activation for degradation of various organic contaminants

Single-atom catalysts (SACs) have been widely studied in Fenton-like reactions, wherein their catalytic performance could be further enhanced by adjusting electronic structure and regulating coordination environment, although relevant research is rarely reported. This text elucidates fabrication of dual atom catalyst systems aimed at augmenting their catalytic efficiency. Herein, atomically dispersed copper-zinc (Cu-Zn) dual sites anchored on nitrogen (N)-doped porous carbon (NC), referred to as CuZn-NC, were synthesized using cage-encapsulated pyrolysis and host–guest strategies. The CuZn-NC catalyst exhibited high activity in activation of peroxymonosulfate (PMS) for degradation of organic pollutants. Based on synergistic effects of adjacent Cu and Zn atom pairs, CuZn-NC (PMS) system achieved 94.44 % bisphenol A (BPA) degradation in 24 min. The radical pathway predominated, and coexistence of non-radical species was demonstrated for BPA degradation in CuZn-NC/PMS system. More importantly, CuZn-NC/PMS system showed generality for degradation of various refractory contaminants. Our experiments indicate that CuZn-N sites on CuZn-NC act as active sites for bonding PMS molecules with optimal binding energy, while pyrrolic N sites are considered as adsorption sites for organic molecules. Overall, this research designs diatomic site catalysts (DACs), with promising implications for wastewater treatment.

Peroxymonosulfate-activated photocatalytic degradation of norfloxacin via a dual Z-scheme g-C3N5/BiVO4/CoFe − LDH heterojunction: Operation and mechanistic insights

The design of novel dual Z-scheme heterojunction plays a significant path in eradicating organic contaminants via enriched charge carrier separation. Herein, a wet chemical method was used to synthesize ternary g-C3N5/BiVO4/CoFe–LDH (CBCF) nanocomposites, and their corresponding abilities were characterized as follows: crystal phases, optical properties, surface morphologies, and compositions. The g-C3N5/BiVO4/CoFe–LDH-30% (CBCF-3) sample optimized the removal efficiency of norfloxacin (NOR) by up to 95.3% through peroxymonosulfate (PMS) activation in a visible light medium. The combined effects from the Vis/PMS/CBCF-3 catalytic system led to 7-times higher degradation efficiency than visible light only system. This improved performance was attributed to the generation of reactive radical species because of higher PMS utilization and an effective Z-charge transfer process from well-oriented band structures. Moreover, scavenging tests and electron spin resonance analysis revealed the production of active radical and non-radical species, namely •OH, SO4•−, •O2−, and 1O2. Based on the appropriate experimental analysis, the expected NOR degradation mechanism and possible pathways were proposed. Then, the toxicity evaluation results revealed that the intermediate products may not have an adverse effect on the aquatic ecosystems. This research study provides a positive outcome for wastewater remediation using enriched dual Z-scheme mechanism.

The Surface Confinement of FeO Assists in the Generation of Singlet Oxygen and High-Valent Metal-Oxo Species for Enhanced Fenton-Like Catalysis.

Transition metal compounds (TMCs) have long been potential candidate catalysts in persulfate-based advanced oxidation process (PS-AOPs) due to their Fenton-like catalyze ability for radical generation. However, the mechanism involved in TMCs-catalyzed nonradical PS-AOPs remains obscure. Herein, the growth of FeO on the Fe3O4/carbon precursor is regulated by restricted pyrolysis of MIL-88A template to activate peroxymonosulfate (PMS) for tetracycline (TC) removal. The higher FeO incorporation conferred a 2.6 times higher degradation performance than that catalyzed by Fe3O4 and also a higher interference resistance to anions or natural organic matter. Unexpectedly, the quenching experiment, probe method, and electron paramagnetic resonance quantitatively revealed that the FeO reassigned high nonradical species (1O2 and FeIV═O) generation to replace original radical system created by Fe3O4. Density functional theory calculation interpreted that PMS molecular on strongly-adsorbed (200) and (220) facets of FeO enjoyed unique polarized electronic reception for surface confinement effect, thus the retained peroxide bond energetically supported the production of 1O2 and FeIV═O. This work promotes the mechanism understanding of TMCs-induced surface-catalyzed persulfate activation and enables them better perform catalytic properties in wastewater treatment.