Non-radical-dominated catalytic degradation of methylene blue by magnetic CoMoO4/CoFe2O4 composite peroxymonosulfate activators.

In this study, magnetic CoMoO4/CoFe2O4 (CMO/CFO) nanospheres with a core-shell structure were synthesized via two-step hydrothermal methods. The obtained particles were employed as catalysts to activate peroxymonosulfate (PMS) and degrade methylene blue (MB). The physico-chemical characterizations of the synthesized CMO/CFO showed that the CMO shell contributed to the enhancement of redox conversion and the increase in the concentration of oxygen vacancies (OVs). By examining reactive oxygen species (ROS) in the CMO/CFO/PMS system, the MB degradation was dominated by a non-radical pathway, and 1O2 was identified as the most abundant ROS. Besides, the CMO/CFO exhibited faster reaction kinetics than the pristine CFO. Moreover, the magnetic properties guaranteed the recycling and reuse of CMO/CFO, and the removal rate of MB was maintained at ∼94% after continuous use five times. Both the tolerance to SO42-and the wide pH range where the material is applicable make it a promising catalyst for dyeing wastewater treatment.

Efficient Degradation of Ciprofloxacin in Water over Copper-Loaded Biochar Using an Enhanced Non-Radical Pathway.

The development of an efficient catalyst with excellent performance using agricultural biomass waste as raw materials is highly desirable for practical water pollution control. Herein, nano-sized, metal-decorated biochar was successfully synthesized with in situ chemical deposition at room temperature. The optimized BC-Cu (1:4) composite exhibited excellent peroxymonosulfate (PMS) activation performance due to the enhanced non-radical pathway. The as-prepared BC-Cu (1:4) composite displays a superior 99.99% removal rate for ciprofloxacin degradation (initial concentration 20 mg·L-1) within 40 min. In addition, BC-Cu (1:4) has superior acid-base adaptability (3.98~11.95) and anti-anion interference ability. The trapping experiments and identification of reactive oxidative radicals confirmed the crucial role of enhanced singlet oxygen for ciprofloxacin degradation via a BC-Cu (1:4)/PMS system. This work provides a new idea for developing highly active, low-cost, non-radical catalysts for efficient antibiotic removal.

Reusing Sulfur-Poisoned Palladium Waste as a Highly Active, Nonradical Fenton-like Catalyst for Selective Degradation of Phenolic Pollutants.

Recycling of deactivated palladium (Pd)-based catalysts can not only lower the economic cost of their industrial use but also save the cost for waste disposal. Considering that the sulfur-poisoned Pd (PdxSy) with a strong Pd-S bond is difficult to regenerate, here, we propose a direct reuse of such waste materials as an efficient catalyst for decontamination via Fenton-like processes. Among the PdxSy materials with different poisoning degrees, Pd4S stood out as the most active catalyst for peroxymonosulfate activation, exhibiting pollutant-degradation performance rivaling the Pd and Co2+ benchmarks. Moreover, the incorporated S atom was found to tune the surface electrostatic potentials and charge densities of the Pd active site, triggering a shift in catalytic pathway from surface-bound radicals to predominantly direct electron transfer pathway that favors a highly selective oxidation of phenols. The catalyst stability was also improved due to the formation of strong Pd-S bond that reduces corrosion. Our work paves a new way for upcycling of Pd-based industrial wastes and for guiding the development of advanced oxidation technologies toward higher sustainability.

Phenol degradation in waters with high iodide level by layered double hydroxide-peroxodisulfate: Pathways and products.

Recently, layered double hydroxide-peroxodisulfate (LDH-PDS) as an advanced oxidation system can effectively remove organics by the pathway of free radical. However, little has been known if there is a potential risk regarding the formation of high toxic iodine byproducts through another pathway when LDH-PDS is used in high iodide waters at coastal areas. Therefore, this study investigated phenol degradation pathways and transformation products to evaluate both removal mechanism and potential risk by LDH-PDS in high iodide waters. The results showed that in LDH-PDS system, with the degradation of PDS, phenol degraded till below detection limit in 1 hr in the presence of iodide, while PDS and phenol were hardly degraded in the absence of iodide, indicating iodide accelerated the transformation of PDS and the degradation of phenol. What is more, it reached the highest phenol removal efficiency under the condition of 100 mg/L LDH, 0.1 mmol/L PDS and 1.0 mmol/L iodide. In LDH-PDS system, iodide was rapidly oxidized by the highly active interlayer PDS, resulting in the formation of reactive iodine including hypoiodic acid, iodine and triiodide instead of free radicals, which contributed rapid degradation of phenol. However, unfortunately toxic iodophenols were detected. Specifically, 2-iodophenol and 4-iodophenol were formed firstly, afterwards 2,4-diiodophenol and 2,6-diiodophenol were produced, and finally iodophenols and diiodophenols gradually decreased and 2,4,6-Triiodophenol were produced. These results indicated that LDH-PDS should avoid to use in high iodide waters to prevent toxic iodine byproduct formation although iodide can accelerate phenol degradation.

Catalytic degradation of acetaminophen by Fe and N Co-doped multi-walled carbon nanotubes.

An Fe and N co-doped carbon nanotube (CNT) (Fe/N-CNT) was successfully prepared using a simple hydrothermal method. CNT, Fe doped CNTs (Fe-CNT), N doped CNTs (N-CNT), and Fe/N-CNT were characterized using scanning electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, and zeta potential analysis. The catalytic activities of the materials were investigated via pharmaceutical (acetaminophen, ACT) degradation using persulfate (PS). The ACT removal rate was in the order: Fe-CNT > N-CNT > Fe-CNT > CNT, for 30 min with 10 mg/L ACT, 0.05 g/L materials, and 0.08 mM PS. The doped N existed as pyridinic-N, pyrrolic-N/N-Fe, graphitic-N, and oxidized-N, while the doped Fe existed as Fe-N, FeO/Fe3O4, and Fe2O3/FeOOH at the edge. The rates of ACT removal and PS decomposition were well correlated with pyrrolic-N/N-Fe. The ACT removal in the Fe/N-CNT + PS system was as high as >98.4% and was not significantly affected by the initial pH of 2.0-8.2 and ten consecutive uses. However, natural organic matter (NOM) inhibited ACT removal by the accumulation on Fe/N-CNT. The results of ACT removal in the presence of radical scavengers, PS decomposition, and cyclic voltammetry showed that the ACT removal was dominantly attributed to a non-radical pathway with the accelerated electron transfer from ACT to PS through the Fe/N-CNT. The results in this study strongly suggest that the Fe/N-CNT + PS system is an excellent process for the degradation of refractory organic pollutants in various water matrices with improved performance and stability attributed by non-radical pathway.

Nanoconfined catalytic membrane assembled by nitrogen-doped carbon encapsulating Fe-based nanoparticles for rapid removal of 2,4-dichlorophenol in wastewater by peroxymonosulfate activation.

Surface-dependent non-radical oxidation of carbon materials-based persulfate systems show a better application prospect in the removal of pollutants in complex wastewater. However, their potential is severely limited by the restricted liquid-to-solid mass transfer efficiency of conventional suspension systems. In this paper, a nitrogen-doped carbon encapsulating iron-based nanoparticles (Fe@NC) was prepared, and loaded onto a polyvinylidene fluoride (PVDF) membrane to construct a novel catalytic membrane Fe@NC/PVDF. The Fe@NC/PVDF/PMS system could achieve 99.74% of 2,4-dicholophenol (2,4-DCP) removal within a retention time of 0.867 s, the kinetic constant is 840 times higher than that of Fe@NC/PMS system, and 2-5 orders of magnitude higher than that of various reported advanced oxidation processes systems. The system exhibits strong anti-interference to various water matrices, long-time operational stability at high flux (306 L·m-2·h-1), universality to pollutants that do not contain strong electron-withdrawing groups and mitigation of membrane fouling. Mechanism studies indicate that the electron transfer pathway dominates the 2,4-DCP removal, and singlet oxygen (1O2) plays an auxiliary role. The higher mass transfer efficiency of the filtration mode releases the full potential of the non-radical pathway. This paper provides theoretical and technical support for the development and efficient utilization of carbon-based materials with excellent persulfate catalytic properties.

Contribution of 1O2 in the efficient degradation of organic pollutants with Cu0/Cu2O/CuO@N-C activated peroxymonosulfate: A Case study with tetracycline.

Peroxymonosulfate-mediated advanced oxidation processes (PMS-AOPs) degrading organic pollutants (Tetracycline (TC) as an example) in water with singlet oxygen (1O2) as the main reactive oxygen has received more and more attention. However, the generation mechanism of 1O2 is still unclear. Consequently, this study investigates the 1O2 formation mechanism during the activated PMS process using a nitrogen-copper-loaded carbon-based material (Cu0/Cu2O/CuO@N-C), synthesized by thermally decomposing organobase-modified HKUST-1 via a one-pot method. It was discovered that incorporating an organobase (Benzylamine) into the metal organic framework (MOF) precursor directs the MOF's self-assembly process and supplements its nitrogen content. This modification modulates the Nx-Cu-Oy active site formation in the material, selectively producing 1O2. Additionally, 1O2 was identified as the dominant reactive oxygen species in the Cu0/Cu2O/CuO@N-C-PMS system, contributing to TC degradation with a rate of 70.82%. The TC degradation efficiency remained high in the pH range of 3-11 and sustained its efficacy after five consecutive uses. Finally, based on the intermediates of TC degradation, three possible degradation pathways were postulated, and a reduction in the ecotoxicity of the degradation products was predicted. This work presents a novel and general strategy for constructing nitrogen-copper-loaded carbon-based materials for use in PMS-AOPs.

Developing Prussian blue/wood-derived biochar catalyst for persistent organic pollutant degradation: Preparation, characterization, and mechanism.

Biomass-derived biochar shows broad promise for persistent organic pollutants (POPs) degradation and thus establishes a more sustainable homestead. However, effective catalytic performance is still challenging. Herein, an efficient catalyst (Prussian blue decorated wood-derived biochar, PBB) was constructed by introducing Prussian blue (PB) into wood-based biochar to activate peroxymonosulfate (PMS) for removing POPs. After anchoring of PB, the degradation performance of biochar was enhanced (degradation efficiency of methylene blue (MB, 20 mg/L) increased from 52% of biochar to 95% of PBB within 60 min). The PBB presents effective MB degradation performance with a wide pH value (3.0 < pH < 11.0) or co-existing diverse anions (Cl-, NO3-, H2PO4-, and HCO3-). Electron paramagnetic resonance (EPR) analysis as well as electrochemical tests confirmed that the non-radical pathway (1O2) is the key to biochar activation of PMS, but by restricting PB into the biochar, the radical pathway (SO4•- and •OH), the non-radical pathway (1O2), and direct electron transfer can work together to activate PMS. In addition, the degradation efficiency could remain about 80% after five-time cyclic tests. This work elucidates the role of PB nanoparticles in enhancing biochar catalysts, which can inspire the development of a carbon-neutralized, cost-effective, and effective strategy for POPs removal.

Unveiling electron transfer and radical transformation pathways in coupled electrocatalysis and persulfate oxidation reactions for complex pollutant removal.

The degradation of multiple organic pollutants in wastewater via advanced oxidation processes might involve different radicals, of which the types and concentrations vary upon interacting with different pollutants. In this study, electrochemical activation of peroxymonosulfate (E/PMS) using advanced activated carbon cloth (ACC) as electrode was applied for simultaneous degradation of mixed pollutants, e.g., metronidazole (MNZ) and p-chloroaniline (PCA). 92.5 % of MNZ and 91.4 % of PCA can be degraded at the cathode and anode at a low current density and PMS concentration, respectively. The rate constants for the simultaneous removal of MNZ and PCA in the E/PMS/MNZ(PCA) system were 118 times and 6 times higher than those in the sole PMS system, and 2.5 times and 1.6 times higher than those in the E/Na2SO4/MNZ(PCA) system, respectively. Different electrochemical characteristics, EPR spectra and radical quenching tests verified that the degradation of MNZ and PCA in the optimal system proceeded primarily through non-radical-dominated oxidation, involving electron transfer and 1O2 effect. The system also exhibited low energy consumption (0.215 kWh/m-3·order-1), broad operational pH range, excellent removal efficiency for water matrix, and low by-products toxicity, indicating its strong potential for practical applications. The ACC, with its super stable, low cost, and electrochemical activity, make it as a promising materials applicable in the E/PMS system for degradation of multiple pollutants. The study further elucidated the mechanism of pollutant interaction with electrode materials in terms of radical and non-radical transformation, providing fundamental insight into the application of this system for treatment of complex wastewater.

Jasmine waste derived biochar as green sulfate catalysts dominate non-free radical paths efficiently degraded tetracycline.

Because of the potential environmental harm caused by the extensive application of tetracycline (TC), this study used jasmine waste rich in organic matter as a precursor and one-step carbonization into metal-free carbon-based materials to efficiently activate peroxymonosulfate (PMS) toward degrading TC. The jasmine waste biochar (JWB) with a heating rate of 10 °C min-1 and a heating temperature of 700 °C was selected as the most suitable material based on its catalytic performance. The effects of catalyst dose, PMS dose, initial pH value, coexisting inorganic anions and TC concentration on the JWB/PMS/TC system were thoroughly optimized. The results showed that the degradation efficiency of TC by JWB/PMS system was 90%. Meanwhile, the combination of electron paramagnetic resonance, masking experiments and X-ray photoelectron spectrometry confirmed that JWB degraded TC mainly through the non-radical radical pathway of 1O2 oxidation and mediated the electron transfer to PMS. In addition, some degradation products were analyzed by LC-MS and possible degradation pathways of the system were proposed. Therefore, this paper proposes a novel method for recycling jasmine waste and providing a low-cost catalyst for the oxidation treatment of refractory organic matter.

Iron/nitrogen co-doped biochar derived from salvaged cyanobacterial for efficient peroxymonosulfate activation and ofloxacin degradation: Synergistic effect of Fe/N in non-radical path.

A green, low-cost, high-performance Fe/N co-doped biochar material (Fe-N@C) was synthesized using salvaged cyanobacteria without other extra precursors for peroxymonosulfate (PMS) activation and ofloxacin (OFX) degradation. With the increased pyrolysis temperature, the graphitization degree, the specific surface area and the corresponding groups like OH, COO etc. for Fe-N@C tended to increase, resulting in a greater OFX adsorption. However, the total amount of Fe-NX and graphitic nitrogen groups in the Fe-N@C composites was firstly increased and then decreased, which reached the highest at 800 °C (Fe-N@C-800). All these changes of functional species ascribed to the strong interaction between Fe, N and C led to the highest defect degree of Fe-N@C-800, resulting the highest OFX removal efficiency of 95.0 %. OFX removal experiments indicated the adsorption process promoted the total OFX degradation for different functional groups on Fe-N@C composites separately dominated the process of OFX adsorption and PMS catalysis. Radical quenching and electron paramagnetic resonance (EPR) measurements proved free radical and non-free radical pathways participated in Fe-N@C/PMS system. The non-free radicals based on 1O2 and high-valent iron-oxo species played a more important role in OFX degradation, leading to the minimal effect of co-existing anions and the high universality for other antibiotic pollutants. Fe-NX was utilized as the main catalytic sites and graphitic nitrogen contributed more to the electron transfer for PMS activation, whose synergistic effect efficiently facilitated OFX degradation. Finally, the possible degradation route of OFX in the Fe-N@C-800/PMS system was proposed. All these results will provide the new insights into the intrinsic mechanism of Fe/N species in carbon-based materials for PMS activation.

Efficiently catalytic degradation of tetracycline via persulfate activation with plant-based biochars: Insight into endogenous mineral self-template effect and pyrolysis catalysis.

Endogenous mineral of plant such as potassium, calcium and iron may play a crucial role in boosting the physicochemical structure and catalytic activity of high temperature pyrolyzed plant-based biochar while it is often neglected owing to its relative less content. Herein, self-template pyrolyzed plant-based biochars were prepared from two different ash-contained agricultural wastes of peanut hull (PH, 3.2% ash) and cotton straw (CS, 0.8% ash), and aimed at investigating the relationship among the endogenous mineral fractions of plant-based biomass, physicochemical active structure and persulfate (PS) catalytic degradation activity for tetracycline (TC). The results of energy/spectral characterization showed that under the self-template effect and pyrolysis catalysis of endogenous minerals, PH biochar (PBC) possessed much more specific surface area, conjugated graphite domain, C=O and pyrrolic-N surface active functional sites than CS biochar (CBC), enhancing TC removal rate of PBC/PS to 88.37%, twice that of CBC/PS (44.16%). Meanwhile, reactive oxygen quenching and electrochemical experiments showed that electrons transfer and non-free radical pathways based on singlet oxygen contributed 92% of TC removal in PBC/PS system. Remarkably, by comparing the differences in structure and TC removal performance of pre-deashing and non-deashing prepared plant-based biochars, a possible mechanism for endogenous mineral components' self-template effect and pyrolysis catalysis role of plant-based biomass was proposed. This study provides a new insight for revealing the intrinsic mechanism of mineral elements enhancing the active surface structures and catalytic properties of plant-based biochars derived from distinct feedstocks.

Polydopamine-modified MOF-5-derived carbon as persulfate activator for aniline aerofloat degradation.

Residual flotation chemicals in beneficiation wastewater seriously threaten local ecosystems, such as groundwater or soil, and must be treated effectively. Currently, the degradation of organic pollutants using nitrided MOFs-derived carbon to activate persulfate (PDS) has attracted considerable attention. Hence, we developed a new synthetic strategy to load dopamine hydrochloride (PDA) onto MOF-5-derived porous carbon (PC) to form NPC, and the degradation of a typical flotation Aniline aerofloat (AAF) at high salinity by a low dose of the NPC/PDS system was investigated. Several characterization analyses such as TEM, XRD, Raman, FT-IR and XPS demonstrated that the nitrogen-rich indolequinone unit in PDA provided nitrogen to PC during the pyrolysis process. This enabled the core-shell structure of NPC and the synergy among the multiple components to induce the AAF degradation by PDS over a wide pH scale in a short period of time. It was deduced that the degradation of AAF by the NPC-8/PDS system was a non-radical pathway dominated by 1O2, which relied mainly on the conversion of superoxide radicals (O2•-) and surface-bound radicals. Among them, the pyridine N in the sp2 hybrid carbon was considered as a possible active site. This non-radical pathway was resistant to pH changes and background substances in the water, and well overcame the inhibition of the reaction by natural organic substances and inorganic anions in natural water. In this study, A novel approach to the synthesis of homogeneous MOFs nuclear-derived porous carbon was proposed and the application of MOFs-derived porous carbon for AAF remediation of mineral processing wastewater was broadened.

Efficient degradation of levofloxacin using a g-C3N4@glucose-derived carbon catalyst with adjustable N content via peroxymonosulfate activation.

Metal-free carbon-based catalysts hold great promise for the degradation of organic pollutants by peroxymonosulfate (PMS) activation because they avoid the negative effects of metal catalysts such as harmful metal ions leaching. However, these carbon-based catalysts are limited by their high cost and complex synthesis, and the mechanisms for the activation of PMS are unclear. Herein, the N-rich carbon catalysts (GCN-x) derived from glucose and g-C3N4 were facilely synthesized by hydrothermal treatment and carbonization to explore the mechanism of PMS activation. The nitrogen content of catalysts could be adjusted by simply altering the ratio of glucose and g-C3N4. GCN-2.4 with a ratio of glucose and g-C3N4 of 2.4 displayed the highest efficiency for the degradation of pollutants represented by Levofloxacin. The electron paramagnetic resonance and quenching experiments demonstrated that the non-radical pathway was dominant in Levofloxacin degradation and singlet oxygen (1O2) was the main active specie. Further, we found 1O2 was generated from superoxide radical (• O2-) which has rarely been studied. Levofloxacin degradation rate was shown to be positively correlated with both the amount of graphitic N and pyridinic N. Graphitic N and pyridinic N were identified as the catalytic sites. The GCN-2.4/PMS system could also remove multifarious contaminants effectively. Overall, this research advances understanding of the role of N species in PMS activation and has potential practical application in wastewater treatment.

Activation of peroxymonosulfate with cobalt embedded in layered δ-MnO2 for degradation of dimethyl phthalate: Mechanisms, degradation pathway, and DFT calculation.

The sulfate radical-based advanced oxidation processes (SR-AOPs) offer huge potential for the removal of organic pollutants. In this study, Co(II)-intercalated δ-MnO2 (Co-δ-MnO2) catalyst was successfully prepared by a simple cation exchange reaction. The obtained Co-δ-MnO2 exhibited high catalytic performance for the removal of dimethyl phthalate (DMP) under the activation of peroxymonosulfate (PMS), with the degradation efficiency reaching 100% within 6 h. Experiments and theoretical calculations revealed that interlayer Co(II) provided unique active sites in Co-δ-MnO2. In addition, radical and non-radical pathways were confirmed to play a role in Co-δ-MnO2/PMS system. •OH, SO4• ̶, and 1O2 were identified to be the dominating reactive species in Co-δ-MnO2/PMS system. This study provided new insights into the design of catalysts and laid a foundation for developing modifiable layered heterogeneous catalysts.

Peroxymonosulfate and peroxydisulfate activation by fish scales biochar for antibiotics removal: Synergism of N, P-codoped biochar.

Social development is accompanied by technological progress, which commonly leads to the expansion of pollution As an essential resource of modern medical treatment, antibiotics have become a hot topic in the aspect of environmental pollution. In this study, we first used fish scales to synthesize N, P-codoped biochar catalyst (FS-BC) as peroxymonosulfate (PMS) and peroxydisulfate (PDS) activator to degrade tetracycline hydrochloride (TC). At the same time, peanut shell biochar (PS-BC) and coffee ground biochar (CG-BC) were prepared as reference materials. Among them, FS-BC exhibited the best catalytic performance due to the excellent defect structure (ID/IG = 1.225) and the synergism of N, P heteroatoms. PS-BC, FS-BC and CG-BC achieved degradation efficiencies of 86.26%, 99.71% and 84.41% for TC during PMS activation and 56.79%, 93.99% and 49.12% during PDS, respectively. In both FS-BC/PMS and FS-BC/PDS systems, non-free radical pathways involved singlet oxygen (1O2), surface-bound radicals mechanism and direct electron transfer mechanism. Structural defects, graphitic N and pyridinic N, P-C groups and positively charged sp2 hybridized C adjacent to graphitic N were all critical active sites. FS-BC has the potential for practical applications and development because of its robust adaptation to pH and anions and stable re-usability. This study not only provides a reference for biochar selection, but also suggests a superior strategy for TC degradation in the environment.

Significant roles of surface functional groups and Fe/Co redox reactions on peroxymonosulfate activation by hydrochar-supported cobalt ferrite for simultaneous degradation of monochlorobenzene and p-chloroaniline.

CoFe2O4/hydrochar composites (FeCo@HC) were synthesized via a facile one-step hydrothermal method and utilized to activate peroxymonosulfate (PMS) for simultaneous degradation of monochlorobenzene (MCB) and p-chloroaniline (PCA). Additionally, the effects of humic acid, Cl-, HCO3-, H2PO4-, HPO42- and water matrices were investigated and degradation pathways of MCB and PCA were proposed. The removal efficiencies of MCB and PCA were higher in FeCo@HC140-10/PMS system obtained under hydrothermal temperature of 140 °C than FeCo@HC180-10/PMS and FeCo@HC220-10/PMS systems obtained under higher temperatures. Radical species (i.e., SO4•-, •OH) and nonradical pathways (i.e., 1O2, Fe (IV)/Co (IV) and electron transfer through surface FeCo@HC140-10/PMS* complex) co-occurred in the FeCo@HC140-10/PMS system, while radical and nonradical pathways were dominant in degrading MCB and PCA respectively. The surface functional groups (i.e., C-OH and CO) and Fe/Co redox cycles played crucial roles in the PMS activation. MCB degradation was significantly inhibited in the mixed MCB/PCA solution over that in the single MCB solution, whereas PCA degradation was slightly promoted in the mixed MCB/PCA solution. These findings are significant for the provision of a low-cost and environmentally-benign synthesis of bimetal-hydrochar composites and more detailed understanding of the related mechanisms on PMS activation for simultaneous removal of the mixed contaminants in groundwater.

Magnetic MgFe2O4/biochar derived from pomelo peel as a persulfate activator for levofloxacin degradation: Effects and mechanistic consideration.

Biochar (BC) has been demonstrated the potential to activate persulfate (PS), but the limited catalytic efficiencies hindered their further application. Herein, an innovative magnetic MgFe2O4/BC (MMB) derived from pomelo peel was prepared for persulfate-based advanced oxidation process (PS-AOPs). Benefitting from the extraordinary properties, levofloxacin (LFX) was efficiently removed in the MMB/PS system. MMB700 exhibited the best catalytic activity, 87.87% of LFX was removed in the MMB700/PS system. In addition, it could maintain 67.90% of LFX degradation efficiency after 3 times of reuse. Quenching experiments, electron spin resonance (ESR) detection, and electrochemical test results indicated that both non-radical pathway and direct electron-transfer pathway advanced LFX degradation. LFX was oxidized by O2·- and 1O2, O2·- acted as the dominant active species. PS activation was induced by the active sites of MMB700. This work not only developed a promising magnetic biochar PS catalyst for antibiotics elimination, but also facilitated insights PS activation mechanisms.

Lignocellulosic biomass derived N-doped and CoO-loaded carbocatalyst used as highly efficient peroxymonosulfate activator for ciprofloxacin degradation.

Burning lignocellulosic biomass wastes in an outdoor atmosphere has placed heavy burden on ecological environment and increased risk on human health. Converting solid agricultural wastes into functional materials is a research hotspot. In this study, N-doped and CoO-loaded carbocatalyst (CoO-N/BC) was successfully synthesized from the cotton stalk biomass via a simple synthesis process of impregnation and carbonization. Compared with cotton stalk biomass derived pristine biochar, the CoO-N/BC possessed a higher specific surface area (466.631 m2 g-1vs 286.684 m2 g-1) as well as a better catalytic performance in the activation of peroxymonosulfate (PMS) for CIP degradation. The superior catalytic efficiency was ascribed to the directional flow of electrons on the well-organized carbon network of CoO-N/BC, which accelerated electron migration and improved electron conduction ability. Based on the results of radical quenching experiment and electron paramagnetic resonance (EPR), both radical and non-radical process conjointly led to the stepwise decomposition of CIP, and singlet oxygen (1O2) mediated non-radical pathway was discovered to play a dominant role. Besides, the carbon-bridge mediated non-radical pathway was proved to accelerate this degradation process through the experiments of prolong the time of adding CIP at different time intervals. Nitrogen doped sites and CoO active sites as well as defects formed in sp2-hybridized carbon network were supposed to be the active sites for PMS. Furthermore, EIS and LSV were employed to confirm the electron transfer mediated non-radical process of reaction system. This work provides a modified strategy for the disposition of lignocellulosic biomass wastes and illuminates the underlying mechanism of heterogeneous catalysis by CoO-N/BC.

Co/N co-doped carbonized wood sponge with 3D porous framework for efficient peroxymonosulfate activation: Performance and internal mechanism.

Renewable wood sponge with lamellar structure, compressibility and three-dimensional porous frameworks exhibits excellent functionalization application potential in various fields. Herein, cobalt and nitrogen (Co/N) co-doped carbonized wood sponge (CoNCWS800) was prepared successfully for peroxymonosulfate (PMS) activation to degrade sulfamethoxazole (SMX). The CoNCWS800 material exhibited admirable catalytic activity in PMS activation to oxidize SMX molecules (99.7% within 60 min). Electron paramagnetic resonance (EPR) analysis, quenching tests and electrochemical experiments confirmed the existence of both radical (SO4·-,·OH and O2·-) and non-radical (1O2 and direct charge transfer) pathways during the SMX degradation process. Co species were verified as major contributors for the generation of multiple radicals via activating PMS. Surface defective structure and ketonic CO groups performed the positive linear correlation with reaction kinetic constants, revealing the critical role of the two active sites in PMS activation via non-radical process. This study provides a unique insight in PMS activation mechanism via both radical and non-radical pathways of wood sponge-based functional materials.