Wide pH Adaptability Research Articles

Cerium-regulated Mg3FeO4@biochar activated persulfate to enhance degradation of aqueous tetracycline: The dominant role of cerium

The role of cerium (Ce) in Ce-regulated Mg3FeO4@biochar (CMF@BC) and the mechanism by which CMF@BC activates persulfate (PS) remain unclear. In this work, a novel CMF@BC was synthesized through the simple impregnation–pyrolysis process and utilized as a PS activator for the removal of aqueous tetracycline (TC). Under the optimal degradation conditions, the removal efficiency and mineralization rate of TC reached 92.7 % and 84.2 % within 60 min, respectively, the corresponding rate constant was 0.0487 min−1. The CMF@BC catalyst exhibited extremely high stability and excellent reusability after five cycles. The characterization results identified Fe2+ and oxygen vacancies as major catalytic sites. The Ce dopant inhibited the aggregation of metal ions of Mg3FeO4 during the high-temperature pyrolysis process and the Ce3+/Ce4+ redox cycle promoted Fe2+ regeneration, thus improving the catalyst performance. The degradation process was dominated by non-free radical (1O2) pathways. The possible TC-removal pathway was inferred from liquid chromatography–mass spectrometry results and density functional theory calculations. The toxicity of the degradation products was also evaluated. The CMF@BC catalyst displayed excellent catalytic performance and recyclability, wide pH adaptability, and a low ion-leaching rate, confirming its broad application prospects as a PS activator in antibiotic wastewater treatment.

Preparation and application of wood-supported piezocatalyst with high efficiency and stability via partial hydrolysis of wood cellulose and hemicellulose with Lewis acid

The conveniently recoverable piezocatalyst with self-floating and stable performance has drawn wide attention. Herein, MoS2 was anchored on 1-cm-square eucalyptus wood blocks via a facile hydrothermal/solvothermal process to fabricate two floating piezocatalysts, i.e., MoS2/unpretreated wood (MUW) and MoS2/pretreated wood (MPW). FeCl3 solution was used as a Lewis acid to pretreat the wood through partial hydrolyzing cellulose and hemicellulose for an purpose to creat rich micropores for MoS2 loading in the wood and to form MoFe heterojunction. The piezocatalytic properties and performance of the prepared wood were systematically studied. The scanning electron microscopy confirms MoS2 was anchored on wood surface. The macroscopic photos show that MoS2 penetrated through the MPW interior whereas it was only loaded on the wood surface layer. The X-ray photoelectron spectroscopy reveals the shift of Mo 3d and S 2p, verifying the heterojunction formation of MPW. The Fourier transform infrared spectra prove the partial hydrolysis of wood matrix. In comparison to MUW, MPW had excellent piezocatalytic property, wide pH adaptability, convenient recyclability and high stability. Sildenafil and Cr6+ ions could be completely removed in 20 and 15 min, respectively, by MPW. Contrastly, the removal efficiency of sildenafil and Cr6+ by MUW was 78.6 % and 68.3 % in 20 and 15 min, respectively. After five cycles of use, the removal ratio of sildenafil was 62.4 % by MUW and 90.5 % by MPW in 20 min. The mineralization efficiency of sildenafil reached 99.2 % in 30 min by MPW, and various types of N/S-containing intermediates were effectively degraded. The electron spin resonance characterization and active species scavenging experiments displayed that e− and •O2− were major active species responsible for Cr6+ piezoreduction by MUW and MPW, while •O2− and •OH were the dominant species accounting for sildenafil degradation by MUW and MPW, respectively. And •OH was not generated in the MUW piezocatalysis process. MPW had higher piezoelectric current and lower resistance at the electron transfer interface than MUW. Conclusively, this study paves a new pathway for preparing new floating piezocatalysts with easy recyclability and high stability from biomass for wastewater treatment.

Activation of H2O2 using a single-atom Cu catalyst for efficient tetracycline degradation

The abuse of antibiotics has caused serious harm to the ecological environment and human health. Fenton-like advanced oxidation technology is a green and effective treatment means, but how to improve the Fenton reaction efficiency and wide pH adaptability is still a big challenge. Herein, we designed and developed a single-atom catalyst Cu1-CN with graphite-phase carbon nitride as the carrier by loading a low amount of metal Cu. The N atom anchors the copper atom in the form of a coordination bond, and the single atom Cu site has excellent performance in activating H2O2. Not only a short period of time (10 min) oxidation degradation of tetracycline (degradation rate 80 %), and in a broad range of pH (3.2 ∼ 9.5) still maintaining high removal performance (efficiency more than 70 %). Combined with X-ray absorption fine structure characterization and density functional theory (DFT) calculations, it is considered that isolated Cu atom and N atom cooperate to construct highly reactive Cu-N4 active centre, which completes the task of H2O2 activation. This study provides a new theoretical basis and technical support for the degradation of antibiotic pollutants by single-atom Fenton-like reaction.

Unveiling the versatile performance of transition metal sulfides in peroxymonosulfate activation

Advanced oxidation processes (AOPs) are promising treatment options for environmental remediation to reduce chemical oxygen demand (COD) and emerging contaminants. Transition metal sulfides (TMSs) are a class of common catalysts in AOPs, but actually, they also widely exist in the environment in the form of sulfide minerals and seriously contaminated water bodies as black-odorous substances. Therefore, it is crucial to find out their roles during water decontamination using AOPs. This study investigated different mechanisms and performance of four common TMSs (FeS, CuS, CoS and MnS) in peroxymonosulfate (PMS)-based AOPs for the removal of a representative micropollutant tetracycline (TC). The results showed that CoS/PMS was the most efficient with 100 % TC removal within 1 min, followed by FeS/PMS (100 %, 10 min) with the apparent rate constant (kobs) of 0.45 min−1. TC removal by CuS (kobs = 0.10 min−1) and MnS (kobs = 0.02 min−1) took 30 min with 96 % and 82 % removal, respectively. Interestingly, the dominant reactive species were different in these systems, i.e., high-valent iron (Fe(IV)) in FeS/PMS, mainly radicals (•OH, SO4•−, O2•−) and singlet oxygen (1O2) in CuS/PMS, and Co(IV) and 1O2 in CoS/PMS. In comparison, TC was removed in MnS/PMS mainly through cooperative adsorption, reduction and oxidation by MnS. Low valent sulfur species, such as S2− and S22−, may participate in the valence cycles of metals or TC reduction. The above four systems had a wide pH (3.6–11.1) adaptability and a strong anti-interference ability to co-existing Cl−, SO42− and NO3−, but could be hindered by CO32−, PO43− and humic acid. This study provides novel insights into the TMS-based catalysts in AOPs, which will pave the way for advancing AOP technology.

Ferrate (VI) oxidation of sulfamethoxazole enhanced by magnetized sludge-based biochar: Active sites regulation and degradation mechanism analysis

Developing non radical systems for antibiotic degradation is crucial for addressing the inefficiency of conventional radical systems. In this study, novel magnetic-modified sludge biochar (MASBC) was synthesized to significantly enhance the oxidative degradation of sulfamethoxazole (SMX) by ferrate (Fe (VI)). In the Fe (VI)/MASBC system, 90.46% of SMX at a concentration of 10 μM and 49.34% of the total organic carbon (TOC) could be removed under optimal conditions of 100 μM of Fe (VI) and 0.40 g/L of MASBC within 10 min. Furthermore, the Fe (VI)/MASBC system was demonstrated with broad-spectrum removal capability towards sulfonamides in single or mixture. Quenching experiments, EPR analyses, and electrochemical experiments revealed that direct electron transfer (DET) and •O2− were mainly responsible for the removal of SMX, with functional groups (e.g., -OH, C=O) and Fe-O (redox of Fe (III)/Fe (II)) acting as the active sites, while the probe experiments showed that Fe (IV)/Fe (V) made a minor contribution to the degradation of SMX. Benefiting from the DET, the Fe (VI)/MASBC system exhibited a wide pH adaptation range (e.g., from 5.0 to 10.0) and strong anti-interference ability. The N atoms and their neighboring atoms in SMX were the prior degradation sites, with the cleavage of bond and ring opening. The degradation products showed low or non-toxicity according to ECOSAR program assessment. The removal of SMX remained within a reasonable range of 71.33%–90.46% over five consecutive cycles. Also, the Fe (VI)/MASBC system was demonstrated to be effectively applied for successful SMX removal in various water matrices, including ultrapure water, tap water, lake water, Yangtze River water, and wastewater. Therefore, this study offered new insights into the mechanism of Fe (VI) oxidation and would contribute to the efficient treatment of organic pollutants.

Activating peroxymonosulfate with MOF-derived NiO-NiCo2O4/titanium membrane for water treatment: A non-radical dominated oxidation mechanism

Traditional peroxymonosulfate (PMS) catalytic membranes dominated by radical pathways often face interference from complex components in water bodies. Herein, we employed a controlled electro-deposition technique to coat a Ni-Co metal–organic framework (MOF) precursor onto titanium hollow fiber membrane (THFM), followed by high-temperature calcination to synthesize a MOF-derived NiO-NiCo2O4/THFM (M−NNCO−THFM) PMS catalytic membrane. Then, the M−NNCO−THFM filtration integrated with PMS activation (MFPA process) for water treatment. Experimental results demonstrated that the M−NNCO−THFM MFPA process successfully achieved complete phenol (PE) removal via a non-radical-dominated degradation pathway, involving singlet oxygen (1O2) and electron transfer, while exhibiting wide pH adaptability and exceptional stability in complex water matrices. Mechanism analysis revealed that the electron transfer process was significantly enhanced by the MOF-derived heterojunction structure, which increased the flat-band potential from 0.39 eV to 0.56 eV, thereby facilitating efficient electron transfer for PE removal. The non-radical 1O2 pathway was primarily due to the cycling of metal valence states (Ni2+/Co3+), leading to the reduction of Co2+ and its reaction with PMS, resulting in the generation of reactive species. Furthermore, electrochemical measurements indicated that the M−NNCO−THFM exhibited lower charge transfer resistance and enhanced charge transfer efficiency compared to non-MOF-derived NNCO-THFM, corresponding to the superior catalytic performance and electrochemically active surface area of M−NNCO−THFM.

In-situ evaluation the fluctuation of hypochlorous acid in acute liver injury mice models with a mitochondria-targeted NIR ratiometric fluorescent probe

Acute liver injury (ALI) is a frequent and devastating liver disease that has been made more prevalent by the excessive use of chemicals, drugs, and alcohol in modern life. Hypochlorous acid (HClO), an important biomarker of oxidative stress originating mainly from the mitochondria, has been shown to be intimately connected to the development and course of ALI. Herein, a novel BODIPY-based NIR ratiometric fluorescent probe Mito-BS was constructed for the specific recognition of mitochondrial HClO. The probe Mito-BS can rapidly respond to HClO within 20 s with a ratiometric fluorescence response (from 680 nm to 645 nm), 24-fold fluorescence intensity ratio enhancement (I645/I680), a wide pH adaptation range (5−9) and the low detection limit (31 nM). The probe Mito-BS has been effectively applied to visualize endogenous and exogenous HClO fluctuations in living zebrafish and cells based on its low cytotoxicity and prominent mitochondria-targeting ability. Furthermore, the fluorescent probe Mito-BS makes it possible to achieve the non-invasive in-situ diagnosis of ALI through in mice, and provides a feasible strategy for early diagnosis and drug therapy of ALI and its complications.

Monodispersed and Organic Amine Modified La(OH)3 Nanocrystals for Superior Advanced Phosphate Removal.

Advanced phosphate removal is critical for alleviating the serious and widespread aquatic eutrophication, strongly depending on the development of superior adsorption materials to overcome low chemical affinity and sluggish mass transfer at low phosphate concentrations. Herein, the first synthesis of monodispersed and organic amine modifiedlanthanum hydroxide nanocrystals (OA-La(OH)3) for advanced phosphate removal by modulating inner Helmholtz plane (IHP), is reported. These OA-La(OH)3 nanocrystals with positively charged surfaces and abundant exposed La sites exhibitspecific affinity toward phosphate, delivering a maximum adsorption capacity of 168mg Pg⁻1 and a wide pH adaptability from 3.0 to 11.0, as well as a robust anti-interference performance, far surpassing those of documented phosphate removal materials. The superior phosphate removal performance of OA-La(OH)3 is attributed to its protonated organic amine in IHP, which enhances the electrostatic attraction around the adsorbent-solution interface. Impressively, OA-La(OH)3 can treat ≈5 000 and ≈3 200 bed volumes of simulated and real phosphate-containing wastewater to below extremely strict standard (0.1mgL⁻1) in a fixed-bed adsorption mode, exhibiting great potential for advanced phosphate removal. This study offers a facile modification strategy to improve phosphate removal performance of nanoscale adsorbents, and sheds light on the structure-reactivity relationship of La-based materials.

Robust Activity and Stability of P-Doped Fe-Carbon Composites Derived from MOF for Bromate Reduction.

Iron-based materials are effective for the reductive removal of the disinfection byproduct bromate in water, while the construction of highly stable and active Fe-based materials with wide pH adaptability remains greatly challenging. In this study, highly dispersed iron phosphide-decorated porous carbon (Fe2P(x)@P(z)NC-y) was prepared via the thermal hydrolysis of Fe@ZIF-8, followed by phosphorus doping (P-doping) and pyrolysis. The reduction performances of Fe2P(x)@P(z)NC-y for bromate reduction were evaluated. Characterization results showed that the Fe, P, and N elements were homogeneously distributed in the carbonaceous matrix. P-doping regulated the coordination environment of Fe atoms and enhanced the conductivity, porosity, and wettability of the carbonaceous matrix. As a result, Fe2P(x)@P(1.0)NC-950 exhibited enhanced reactivity and stability with an intrinsic reduction kinetic constant (kint) 1.53-1.85 times higher than Fe(x)@NC-950 without P-doping. Furthermore, Fe2P(0.125)@P(1.0)NC-950 displayed superior reduction efficiency and prominent stability with very low Fe leaching (4.53-22.98 μg L-1) in a wide pH range of 4.0-10.0. The used Fe2P(0.125)@P(1.0)NC-950 could be regenerated by phosphating, and the regenerated Fe2P(0.125)@P(1.0)NC-950 maintained 85% of its primary reduction activity after five reuse cycles. The study clearly demonstrates that Fe2P-decorated porous carbon can be applied as a robust and stable Fe-based material in aqueous bromate reduction.

Degradation of phenol by Cu-Ni bimetallic-doped sludge biochar as a fenton-like catalyst: Mechanistic study and practical application

In this study, the sewage sludge was converted into sludge biochar (SBC) and doped with Cu-Ni bimetal to synthesize a novel composite catalyst (Cu-Ni@SBC) for the activation of H2O2 for phenol degradation. Characterization results showed that the Cu-Ni bimetal was successfully doped into the SBC and led to the formation of a porous structure with abundant cavities, resulting in a larger specific surface area and higher adsorbed oxygen content. Mechanism analysis revealed a valence state conversion cycle between Cu0-Cu(II), Ni(III)-Ni(II) and Cu-Ni which made Cu-Ni@SBC have higher electron transfer performance. Response surface methodology was applied to determine the optimal preparation and reaction conditions, under which the Fenton-like system composed of Cu-Ni@SBC and H2O2 removed 100 % of phenol and mineralized 69.1 % of TOC from simulated wastewater. In addition, the experimental results showed that the Cu-Ni@SBC material had a relatively wide pH adaptation range (4–8), and the removal efficiency of phenol could reach 76.4 % after 5 cycles of experiments, and the catalytic inhibition rates of the two common coexisting anions, HCO3– and Cl-, were 17.1 % and 0 %, respectively. The results of practical application revealed that the phenol removal efficiency reached 90.44 % and the pollutant mineralization rate could reach 58.5 % within 90 min, which proved that the catalyst was suitable for the advanced degradation of organic matter in coal chemical wastewater. Therefore, Cu-Ni@SBC can be considered as a promising Fenton-like catalyst, and the process method is also of some guiding significance for the treatment of coal chemical wastewater.

Ce/Fe bimetallic MOF derivatives in situ modified bulk carbon aerogel composite cathode for efficient heterogeneous electro-fenton degradation of chloramphenicol

In this study, we utilized a Ce-modified iron-based metal-organic framework derivative to in situ modify bulk CA (Ce/Fe@C-CA) as a bifunctional composite cathode to degrade chloramphenicol (CAP) in the heterogeneous electro-Fenton (EF) process. The composite cathode exhibited satisfactory CAP degradation efficiency, wide pH adaptability (2–9) and low metal leaching. Under the appropriate conditions (pH = 5, current density = 6 mA/cm2), 94.89% of CAP degradation efficiency was obtained within 60 min. The introduction of Ce increased the oxygen vacancy content, enhanced the cathodic electrochemical activity, promoted the production of a variety of reactive oxygen species and participates in the degradation of CAP, of which ·OH and 1O2 were dominant. Meanwhile, the electron transfer and synergistic catalysis between Ce and Fe promoted the regeneration of the metal active site, which was beneficial to improve the reuse stability of the Ce/Fe@C-CA cathode. The degradation pathway of CAP was obtained by DFT calculations and UPLC-MS/MS detection. This study not only proposed a novel bifunctional electro-Fenton cathode, but also provided a effective strategy for the treatment of actual pharmaceutical wastewater.

Efficiency and Cost of the “Fenton+Recapter” Combined Process for Treating the Electroplating Nickel Wastewater

The aim of this work was to investigate the “Fenton+Recapter” combined process for treating electroplating nickel wastewater. Firstly, five commonly used dithiocarbamate heavy recapters (DTC types) were compared and selected through trial tests. Then, the optimization of the sole Fenton process was carried out, including the dosing molar ratio of Fe2+/H2O2, the dosage of H2O2 and the reaction time. At last, the optimization and cost analysis of the combination process was carried out to meet the nickel wastewater treatment standards and to determine the optimal fit point. The experimental results showed that DTC-2 was a more suitable heavy recapter, with advantages of wide pH adaptation range (3.0-11.0), strong anti-interference, fast Ni removal rate, and low cost (1.20 ¥/t). The optimal molar ratio of Fe2+/H2O2 in the sole Fenton process was determined to be 0.8, which resulted in the optimum breaking effect and a 98.5% removal rate of Ni. The optimization of the combined process parameters showed that when the dosage of heavy recapter DTC-2 (1%) was 0.08 mg/L, 0.19 mg/L, 0.5 mg/L, 1.25 mg/L, 7.5 mg/L, and 25 mL/L respectively, the residual concentration of Ni in Fenton effluent was 0.2 mg/L, 0.3 mg/L, 0.5 mg/L, 0.7 mg/L, 1.0 mg/L, and 1.5 mg/L, which all could meet the discharge standards (concentration of Ni ≤0.1 mg/L). The best fit for the “Fenton+Recapter” combined process was to first treat nickel wastewater with Fenton until the Ni concentration was about 1.0 mg/L, and then use heavy recapter DTC-2 to capture and treat the wastewater until it meets the standard discharge. Under this condition, the treatment cost of the combined process was the lowest (7.79 ¥/t).

Efficient degradation of fluoroquinolone antibiotics in the landfill leachate by sludge biochar activated peracetic acid: Radical vs non-radical process

Peracetic acid (PAA) has been increasingly used as a disinfectant and oxidant in wastewater treatment. The activation of PAA was crucial for the oxidation of refractory contaminants in the wastewater. Herein, the sludge biochar (SDBC) was fabricated, and then used as the activator for PAA to degrade fluoroquinolone antibiotics (FQs). Results show that FQs underwent rapid degradation by SDBC/PAA system at neutral pH, and the first-order rate constant (kobs) of enrofloxacin (ENR, 0.0886 min−1) was higher than those of ciprofloxacin (CIP, 0.0313 min−1) and ofloxacin (OFL, 0.0327 min−1). FQs degradation conformed the first order kinetics. Scavenging experiments and EPR analysis indicated both radical and non-radical process contributed to FQs degradation, with non-radical process act as the dominant role. The abundant π electrons and carbon-containing functional groups on the surface of SDBC facilitated electron transfer, resulting in PAA activation for 1O2 generation; while the iron species on SDBC could also activate PAA to generate the organic radicals, i.e., CH3COO· and CH3COOO·. The degradation of FQs underwent the defluorination, decomposition and shedding of piperazine rings, and the toxicity of FQs was significantly diminished after treatment by SDBC/PAA. SDBC had excellent activity and reusability in PAA activation, and SDBC/PAA process could resist the interference by the complicated water matrices with wide pH adaptability. Hence, the non-radical dominated degradation of FQs by SDBC/PAA maintained high efficiency in the real landfill leachate. This work provides a promising strategy to eliminate antibiotics and its biological activity in the complicated water matrices.

Fe-N coordination moieties regulate the defect formation in carbon nanomaterial for efficient peroxydisulfate activation: Significant role of surface complex

An iron (Fe)-modified carbon dots (CDs) doped ZIF-8 zeolite imidazole metal-organic frame pyrolyzed composite (5Fe@NC) was prepared and then evaluated as a peroxydisulfate (PDS) activator for the oxidative removal of organic pollutants. The 5Fe@NC/PDS system not only has a good recovery performance, wide pH adaptability, and low activation energy, but also is resistant to environmental interference. The quenching experiments, electron paramagnetic resonance (EPR) detection, and electrochemical analysis all revealed that unlike the widely reported singlet oxygen (1O2) dominated nonradical mechanism, an electron transfer process (ETP) involving a surface bound PDS complex played the main role in pollutants’ degradation by 5Fe@NC/PDS system. The FeNx, defect, graphitic N and hydroxyl group (-OH) acting as active sites, prompted the 5Fe@NC-PDS complex to capture electrons (e−) from acetaminophen (ACT). This study provides a new approach for xFe@NCs rational design, and deepen the understanding of FeNx activation mechanism of PDS in carbon nanomaterials.

ZIF-8-derived magnetic FCZ@C-600 composite for efficient adsorptive removal of unsymmetrical dimethylhydrazine from wastewater

Efficient and convenient removal of hazardous unsymmetrical dimethylhydrazine (UDMH) remains challenging for ecological security and human health. In this work, ZIF-8-derived magnetic porous carbons (FCZ@Cs) were synthesized via layer-by-layer self-assembly and pyrolysis using chitosan as an external carbon source. The optimal pyrolysis temperature of FCZ@Cs is 600 °C and the maximum adsorption capacity of FCZ@C-600 for UDMH is 185.70 mg/g at 298 K. Moreover, FCZ@C-600 has wide pH adaptability and good resistance to acid, natural organic matter, and interfering ions. UDMH adsorption onto FCZ@C-600 and ZIF-8-600 conforms to pseudo-second-order and Langmuir models. Thermodynamic studies demonstrate that the adsorption performance is endothermic and favorable. Mechanisms investigations further identify electrostatic interactions, diffusion, and hydrogen/coordination bonds as the greatest contributors to UDMH adsorption. Notably, magnetic FCZ@C-600 can be readily separated by a magnet and exhibits high stability with an adsorption capacity of 42.05 mg/g after six cycles. Furthermore, the leaching concentration of Fe and Zn can be as low as 0.3 mg/L and 1.0 mg/L (pH ≥ 4), respectively. UDMH wastewater after adsorption also shows good biosafety. This work provides insights into the development of emerging metal-organic framework-derived adsorbents with multifunctionality and good sustainability for efficient wastewater treatment.

Microbial-assisted synthesis of Schwertmannite@g-C3N4 composite for bisphenol AF degradation through visible light-driven peroxymonosulfate activation

Iron-based materials are considered as excellent environmental catalysts due to the characteristics of abundant reserves, low biological toxicities, and rich chemical states for redox reactions. The sea urchin-like microscopic morphology of biosynthesized schwertmannite (Sch) with abundant surface active sites is beneficial to the environmental catalytic process. In this study, flake-type graphitic carbon nitride (g-C3N4) was introduced into the mineralization process of Acidithiobacillus ferrooxidans (A. ferrooxidans) as the additive to regulate the biomineralization process and directly control the morphology and structure of iron-based minerals. Schwertmannite@g-C3N4 composites (Sch-CN) with a desired structure of sea urchin-like well-dispersed biosynthesized Sch loaded on flaky g-C3N4 were successfully prepared by A. ferrooxidans-induced biomineralization process. A Light/Peroxymonosulfate/Sch-CN catalytic system was constructed to degrade the model organic pollutant bisphenol AF (BPAF). The system combined two advanced oxidation systems of photocatalysis and peroxymonosulfate (PMS) activation, showing excellent catalytic degradation ability and wide pH adaptability. In addition, the system was also applicable to the catalytic degradation of other bisphenol pollutants. The mechanism was deduced by the results of quenching experiments and electron paramagnetic resonance (EPR) measurements. Several degradation intermediate products were identified and the probable degradation pathways of BPAF were proposed. The toxicity activities of BPAF solution towards Raphidocelis subcapitata were largely reduced after treatment by the photochemical process. Overall, the Light/PMS/Sch-CN system has great potential in treating bisphenol wastewater.

Photocatalysis-Fenton mechanism of rGO-enhanced Fe-doped carbon nitride with boosted degradation performance towards rhodamine B

A photo-Fenton catalyst Fe‑carbon nitride (g-C3N4)/reduced graphene oxide (rGO) (labeled as FNGO) was prepared via two-step calcination thermal polymerization. rGO as a carrier of Fe-g-C3N4 accelerated the charge transfer and improved the reduction of Fe (III) as compared those of the binary Fe-g-C3N4 catalyst. The FNGO catalyst maintained a high surface area of 264.7 m2/g and its charge transfer rate was 2.77 times higher than Fe-g-C3N4. The decreasing transient photocurrent and increasing electrode resistance of FNGO, Fe-g-C3N4 and g-C3N4 confirm the positive synergistic effect of FeN coordination and rGO in charge transfer. Under the synergistic of visible light irradiation and H2O2, the excellent degradation performance of FNGO towards rhodamine B was achieved (95.3 % removal) at Fe-doping content of 10 wt%, rGO loading content of 0.5 % and H2O2 addition of 1.5 mM. Hydroxyl radicals played a dominant role in the photocatalysis-Fenton system, which was related to the coordination of FeN, the carrier off-domain of rGO, and the Fe (III)/Fe (II) cycle promoted by photogenerated electron and superoxide radicals. The FNGO had a high stability, a wide pH adaptation (3– 11) and a low Fe-leaching. This novel ternary light-driven photo-Fenton catalyst of FNGO enabled efficient decontamination during advanced treatment of wastewater.

Electron-transfer based selective oxidation of organic pollutants via N-doped biochar activated peroxydisulfate: Important role of oxidation potential

For persulfate-based advanced oxidation process, the non-radical pathway is an important route due to the selective oxidation of pollutants and its strong tolerance to complex water bodies. However, the selective oxidation mechanism of organic pollutants needs further elaboration. Herein, we demonstrate a facile hydrothermal pretreatment and high-temperature carbonization route to synthesize the nitrogen-doped porous biochar (NHBC-1). Owing to the well-developed hierarchical porous structure, the created internal active defects, and tailored nitrogen dopants, the NHBC-1 catalyst exhibited excellent catalytic activity for peroxydisulfate (PDS) activation. The results show that pyridinic N facilitated the adsorption of PDS on NHBC-1 to form the highly active NHBC-PDS* complex. Meanwhile, graphitic N and the defective structures promoted the electron-transfer process, thus allowing the efficient catalytic performance of the NHBC/PDS system for phenol oxidation via an electron-transfer dominated pathway. In addition, the system exhibited versatile applicability for the remediation of various organic pollutants in different actual water matrices with wide pH adaptability and satisfactory mineralization efficiency. More importantly, the selective oxidation mechanism of organic contaminants was revealed. Specifically, only the pollutant with oxidation potential lower than that of the NHBC-PDS* complex (0.91 V) can be effectively eliminated. This study not only provides a facile route for the rational designing of a cost-affordable biochar catalyst for PDS activation, but also offers valuable insights into the understanding of selective oxidation of organic contaminants via an electron-transfer dominated pathway.

Efficient persulfate activation by photo-excited organic dyes: Mechanism and application for actual dyeing wastewater self-purification

Sulfate Radical-Advanced Oxidation Processes are considered an efficient way for purifying dyeing wastewater, which commonly resists conventional treatment processes owing to the complex components, low biodegradability and high toxicity. However, this emerging technique is associated with issues of secondary pollution and great energy consumption during peroxymonosulfate (PMS) or persulfate (PS) activation processes. Herein, a dye pollutant/PS/visible light self-catalytic system was constructed, based on the photosensitive property of organic dyes for PS activation without catalyst and energy input. In this system, the degradation ratio of 100 mL 10 mg L−1 basic fuchsin, rhodamine B and eosin Y significantly increased by 60%, 76% and 50%, compared with the process without light irradiation. Such improvements were attributable to an efficient photo-induced electron transfer from photo-excited dyes to PS, which has the precondition that the lowest unoccupied molecular orbital (LUMO) energy level of the dye is higher than that of PS, thereby generating oxidizing species like ·SO4−, ·OH and 1O2 for pollutants degradation. Due to the high performance of pollutants simultaneous removal, wide pH adaptability and anti-interference, the complex self-catalytic system consisted of nine dyes and bis-phenol A exhibited the possibility for practical application. Expectedly, the actual dyeing wastewater self-purification system featured a decolorization efficiency of 54% accompanied by the removal of co-existing aromatic proteins and tryptophan-like substances; moreover, the acute bio-toxicity of the raw wastewater greatly decreased by 61.6%. Owing to its high efficiency, eco-friendliness and low consumption, the constructed “using waste to treat waste” system provides a promising way for wastewater treatment.

Nonradical pathway dominated activation of peroxymonosulfate by ZnFe2O4/C composites to eliminate tetracycline hydrochloride: Insight into the cycle of Zn/Fe and electron transfer

Magnetic ZnFe2O4 nanoparticles show promising as heterogeneous catalysts in peroxymonosulfate (PMS) activation because of their ease of separation and good reusability. However, the low catalytic activity and easy agglomeration in clusters or clumps limit the application of ZnFe2O4 nanoparticles. Herein, ZnFe2O4 nanoparticles embedding into carbon substrate are prepared. Owing to the anchoring effect of carbon substrate and the improved electron transfer for ZnFe2O4 nanoparticles, the as-prepared magnetic ZnFe2O4/C composites exhibit efficiently catalytic activity in PMS activation, in which 92.0% of tetracycline hydrochloride (TC) can be eliminated. Moreover, the composites show a wide pH adaptation range (3.04–10.99) and good stability. The catalytic oxidation of TC is mainly based on the nonradical pathways, including contributions of 1O2 and electron transport. The high performance of ZnFe2O4/C in PMS activation is mainly attributed to the accelerated redox cycles of Fe3+/Fe2+ and Zn2+/Zn+ and the improved electron transfer. Three possible TC degradation pathways were proposed, and the biotoxicity assessment results further confirm the high efficiency of the ZnFe2O4/C/PMS system. This work provides a simple strategy for the preparation of magnetic ZnFe2O4/C heterogeneous catalyst and a new insight into PMS activation, which promotes the application of spinel nanomaterials in environmental remediation.