The carbon nanotubes-based materials and their applications for organic pollutant removal:A critical review

The carbon nanotubes(CNTs) as the emerging materials for organic pollutant removal have gradually become a burgeoning research field.Herein,a mini-review of CNTs-based materials curre ntly studies for organic pollutant elimination is presented.This review summarizes the preparation methods of CNTsbased materials.CNTs-based materials can be used as adsorbents to remove organic pollutants in wastewater.The adsorption mechanisms mainly include surface diffusio n,pore diffusion and adsorption reaction.Most importantly,an in-depth overview of CNTs-based materials currently available in advanced oxidation processes(AOPs) applications for wastewater treatment is proposed.CNTs-based materials can catalyze different oxidants(e.g.,hydrogen peroxide(H_2 O_2),persulfates(PMS/PDS),ozone(O_3) and ferrate/permanganate(Fe(Ⅵ)/Mn(Ⅶ)) to generate more reactive oxygen species(ROS) for organic pollutant elimination.Moreover,the possible reaction mechanisms of removing organic pollutants by CNTs-based materials are summarized systematically and discussed in detail.Finally,application potential and future research directions of CNTs-based materials in the environmental remediation field are proposed.     

CoFe2O4 with MoS2-xOy Nanosheets as a Co-catalyst for Enhanced Activation of Peroxydisulfate in Advanced Oxidation Processes

The application of advanced oxidation processes (AOPs) based on sulfate radicals for degrading persistent organic pollutants faces challenges due to the inefficient activation of peroxydisulfate (PDS) oxidant. Herein, a composite CoFe₂O₄/MoS_2-xO_y (CFM) catalyst consisting of CoFe₂O₄ nanoparticles uniformly dispersed on the nanosheets of oxygen-incorporated MoS₂ (MoS_2-xO_y) with flower-like morphology are fabricated through a facile two-step hydrothermal method, which results in the enhanced activation of PDS and a highly efficient degradation of phenolic pollutants. The oxygen-doping in MoS_2-xO_y leads to unsaturated sulfur and active sites on the surface of MoS₂ for accelerating the rate limiting step of Fe^III/Fe^II reduction cycle in PDS-CFM reaction. Aiming at the refractory organic pollutants in actual coking wastewater, CFM co-catalyst is introduced into a hydrogel made up of polyvinyl alcohol (PVA) and coal-tar pitch oxides (PO) to construct a multifunctional CFM@PO/PVA hydrogel. Upon hybrid CFM@PO/PVA, the coupling of the enhanced AOP with solar-driven interfacial vapor generation (SIVG) technology contributes to the degradation efficiency, the removal rate of phenol in solution and the total organic carbon in coking wastewater can reach 98 % and 91 %, respectively. The integration of heterogeneous AOPs with SIVG system provides a feasible strategy for the eco-friendly efficient purification of industrial wastewater.     

COD reduction of waste water streams of active pharmaceutical ingredient – Atenolol manufacturing unit by advanced oxidation-Fenton process

Active pharmaceutical intermediates (API) in waste waters have adverse effects on aquatic life and environment. The API have high COD value and low BOD₃ and hence difficult to treat biologically. In this study, advanced oxidation processes (AOPs) utilizing the H₂O₂/Fe⁺², Fenton reactions were investigated in lab-scale experiments for the degradation of Atenolol containing waste water streams. The experimental results showed that the Fenton process using H₂O₂/Fe⁺² was the most effective treatment process. With Fenton processes, COD reduction of wastewater can be achieved successfully. It is suggested that Fenton processes are viable techniques for the degradation of Atenolol from the waste water stream with relatively low toxic by-products in the effluent which can be easily biodegraded in the activated sludge process. Hence, the Fenton process with H₂O₂/Fe⁺² is considered a suitable pretreatment method to degrade the active pharmaceutical molecules and to improve the biodegradability of waste water.     

Designing 3D-MoS2 Sponge as Excellent Cocatalysts in Advanced Oxidation Processes for Pollutant Control

3D-MoS₂ can adsorb organic molecules and provide multidimensional electron transport pathways, implying a potential application for environment remediation. Here, we study the degradation of aromatic organics in advanced oxidation processes (AOPs) by a 3D-MoS₂ sponge loaded with MoS₂ nanospheres and graphene oxide (GO). Exposed Mo⁴⁺ active sites on 3D-MoS₂ can significantly improve the concentration and stability of Fe²⁺ in AOPs and keep the Fe³⁺/Fe²⁺ in a stable dynamic cycle, thus effectively promoting the activation of H₂O₂/peroxymonosulfate (PMS). The degradation rate of organic pollutants in the 3D-MoS₂ system is about 50 times higher than without cocatalyst. After a 140 L pilot-scale experiment, it still maintains high efficiency and stable AOPs activity. After 16 days of continuous reaction, the 3D-MoS₂ achieves a degradation rate of 120 mg L⁻¹ antibiotic wastewater up to 97.87 %. The operating cost of treating a ton of wastewater is only US$ 0.33, suggesting huge industrial applications.     

Designing 3D‐MoS2 Sponge as Excellent Cocatalysts in Advanced Oxidation Processes for Pollutant Control

3D‐MoS₂ can adsorb organic molecules and provide multidimensional electron transport pathways, implying a potential application for environment remediation. Here, we study the degradation of aromatic organics in advanced oxidation processes (AOPs) by a 3D‐MoS₂ sponge loaded with MoS₂ nanospheres and graphene oxide (GO). Exposed Mo⁴⁺ active sites on 3D‐MoS₂ can significantly improve the concentration and stability of Fe²⁺ in AOPs and keep the Fe³⁺/Fe²⁺ in a stable dynamic cycle, thus effectively promoting the activation of H₂O₂/peroxymonosulfate (PMS). The degradation rate of organic pollutants in the 3D‐MoS₂ system is about 50 times higher than without cocatalyst. After a 140 L pilot‐scale experiment, it still maintains high efficiency and stable AOPs activity. After 16 days of continuous reaction, the 3D‐MoS₂ achieves a degradation rate of 120 mg L^?1 antibiotic wastewater up to 97.87 %. The operating cost of treating a ton of wastewater is only US$ 0.33, suggesting huge industrial applications.     

In-situ construction of Co(OH)2 nanoparticles decorated biochar for highly efficient degradation of tetracycline hydrochloride via peracetic acid activation

Peracetic acid(CH₃C(O)OOH, PAA)-based heterogeneous advanced oxidation process(AOP) has attacked intensive interests due to production of various reactive species. Herein, Co(OH)₂ nanoparticles decorated biochar(Co(OH)2_/BC) was fabricated by a simple and controllable method, which was used to degrade tetracycline hydrochloride(TTCH) in water through PAA activation. The results indicated that 100% TTCH(C0= 10 μmol/L) degradation efficiency was realized within 7 mi...     

H2S Removal from Groundwater by Chemical Free Advanced Oxidation Process Using UV-C/VUV Radiation

Sulfide species may be present in groundwater due to natural processes or due to anthropogenic activity. H₂S contamination poses odor nuisance and may also lead to adverse health effects. Advanced oxidation processes (AOPs) are considered promising treatments for hydrogen-sulfide removal from water, but conventional AOPs usually require continuous chemical dosing, as well as post-treatment, when solid catalysts are applied. Vacuum-UV (VUV) radiation can generate ·OH in situ via water photolysis, initiating chemical-free AOP. The present study investigated the applicability of VUV-based AOP for removal of H₂S both in synthetic solutions and in real groundwater, comparing combined UV-C/VUV and UV-C only radiation in a continuous-flow reactor. In deionized water, H₂S degradation was much faster under the combined radiation, dominated by indirect photolysis, and indicated the formation of sulfite intermediates that convert to sulfate at high radiation doses. Sulfide was efficiently removed from natural groundwater by the two examined lamps, with no clear preference between them. However, in anoxic conditions, common in sulfide-containing groundwater, a small advantage for the combined lamp was observed. These results demonstrate the potential of utilizing VUV-based AOP for treating H₂S contamination in groundwater as a chemical-free treatment, which can be especially attractive to remote small treatment facilities.     

Site Engineering of Covalent Organic Frameworks for Regulating Peroxymonosulfate Activation to Generate Singlet Oxygen with 100 % Selectivity

Singlet oxygen (¹O₂) is an excellent reactive oxygen species (ROSs) for the selective conversion of organic matter, especially in advanced oxidation processes (AOPs). However, due to the huge dilemma in synthesizing single-site type catalysts, the control and regulation of ¹O₂ generation in AOPs is still challenging and the underlying mechanism remains largely obscure. Here, taking advantage of the well-defined and flexibly tunable sites of covalent organic frameworks (COFs), we report the first achievement in precisely regulating ROSs generation in peroxymonosulfate (PMS)-based AOPs by site engineering of COFs. Remarkably, COFs with bipyridine units (BPY-COFs) facilitate PMS activation via a nonradical pathway with 100 % ¹O₂, whereas biphenyl-based COFs (BPD-COFs) with almost identical structures activate PMS to produce radicals (⋅OH and SO₄^.−). The BPY-COFs/PMS system delivers boosted performance for selective degradation of target pollutants from water, which is ca. 9.4 times that of its BPD-COFs counterpart, surpassing most reported PMS-based AOPs systems. Mechanism analysis indicated that highly electronegative pyridine-N atoms on BPY-COFs provide extra sites to adsorb the terminal H atoms of PMS, resulting in simultaneous adsorption of O and H atoms of PMS on one pyridine ring, which facilitates the cleavage of its S−O bond to generate ¹O₂.     

CoN1O2 Single-Atom Catalyst for Efficient Peroxymonosulfate Activation and Selective Cobalt(IV)=O Generation

High-valent metal-oxo (HVMO) species are powerful non-radical reactive species that enhance advanced oxidation processes (AOPs) due to their long half-lives and high selectivity towards recalcitrant water pollutants with electron-donating groups. However, high-valent cobalt-oxo (Co^IV=O) generation is challenging in peroxymonosulfate (PMS)-based AOPs because the high 3d-orbital occupancy of cobalt would disfavor its binding with a terminal oxygen ligand. Herein, we propose a strategy to construct isolated Co sites with unique N₁O₂ coordination on the Mn₃O₄ surface. The asymmetric N₁O₂ configuration is able to accept electrons from the Co 3d-orbital, resulting in significant electronic delocalization at Co sites for promoted PMS adsorption, dissociation and subsequent generation of Co^IV=O species. CoN₁O₂/Mn₃O₄ exhibits high intrinsic activity in PMS activation and sulfamethoxazole (SMX) degradation, highly outperforming its counterpart with a CoO₃ configuration, carbon-based single-atom catalysts with CoN₄ configuration, and commercial cobalt oxides. Co^IV=O species effectively oxidize the target contaminants via oxygen atom transfer to produce low-toxicity intermediates. These findings could advance the mechanistic understanding of PMS activation at the molecular level and guide the rational design of efficient environmental catalysts.     

The Photo-Fenton Oxidation — A cheap and efficient wastewater treatment method

Advanced Oxidation Processes (AOPs) for wastewater treatment are gaining more importance since biological treatment plants are often not sufficient for highly contaminated or toxic wastewaters. In order to find out the most efficient and cheap AOP, investigations were concentrated on methods that can use sunlight. The systems TiO₂/UV, Fe²⁺/H₂O₂/UV (Photo-Fenton reaction), Fe²⁺/O₂/UV and Fe²⁺/O₃/UV were compared. Since the Photo-Fenton system was the most effective, pilot plant experiments with industrial wastewaters and sunlight experiments were carried out. Finally a rough cost estimate shows that Photo-Fenton treatment with sunlight is far cheaper than other available AOPs, namely ozonization.     

Sustainable activation of peroxymonosulfate by the Mo(IV) in MoS2 for the remediation of aromatic organic pollutants

Although MoS₂ has been proved to be a very ideal cocatalyst in advanced oxidation process (AOPs), the activation process of peroxymonosulfate (PMS) is still inseparable from metal ions which inevitably brings the risk of secondary pollution and it is not conducive to large-scale industrial application. In this study, the commercial MoS₂, as a durable and efficient catalyst, was used for directly activating PMS to degrade aromatic organic pollutant. The commercial MoS₂/PMS catalytic system demonstrated excellent removal efficiency of phenol and the total organic carbon (TOC) residual rate reach to 25%. The degradation rate was significantly reduced if the used MoS₂ was directly carried out the next cycle experiment without any post-treatment. Interestingly, the commercial MoS₂ after post-treated with H₂O₂ can exhibit good stability and recyclability for cyclic degradation of phenol. Furthermore, the mechanism for the activation of PMS had been investigated by density functional theory (DFT) calculation. The renewable Mo⁴⁺ exposed on the surface of MoS₂ was deduced as the primary active site, which realized the direct activation of PMS and avoided secondary pollution. Taking into account the reaction cost and efficient activity, the development of commercial MoS₂ catalytic system is expected to be applied in industrial wastewater.     

Hydroxyl radical induced from hydrogen peroxide by cobalt manganese oxides for ciprofloxacin degradation

Advanced oxidation processes (AOPs) are promising technology to remove organic pollutant in water. However, the main problem in the AOPs is the low generation of hydroxyl radical (^?OH) owing to the low decomposition efficiency of hydrogen peroxide (H₂O₂). Herein, the spinel type cobalt acid manganese (MnCo₂O₄) with flower morphology was fabricated through a co-precipitation method. In situ Fourier transform infrared spectroscopy confirms that the MnCo₂O₄ with the optimal molar ratio of Co and Mn precursors (CM3, Co:Mn = 3) has more Lewis acid sites compared with single metal oxide catalysts (Co₃O₄ and Mn₂O₃), leading to the excellent performances for H₂O₂ decomposition rate constant on CM3, which is about 15.03 and 4.21 times higher than those of Co₃O₄ and Mn₂O₃, respectively. As a result, the obtained CM3 shows a higher ciprofloxacin degradation ratio than that of Co₃O₄ and Mn₂O₃. Furthermore, CM3 shows an excellent stability during several cycles. This work proposes effective catalysts for ciprofloxacin decomposition and provides feasible route for treating practical environmental problems.     

Magnetically separable ZnO/ZnFe2O4 and ZnO/CoFe2O4 photocatalysts supported onto nitrogen doped graphene for photocatalytic degradation of toxic dyes

Advanced oxidation processes (AOPs) counting heterogeneous photocatalysis has confirmed as one of the preeminent method for waste water remediation. In the present work, we have successfully fabricated novel visible-light-driven nitrogen-doped graphene (NG) supported magnetic ZnO/ZnFe₂O₄ (ZnO/ZF/NG) and ZnO/CoFe₂O₄ (ZnO/CF/NG) nanocomposites. ZnO synthesized via direct precipitation method. Hydrothermal method was used for the preparation of nitrogen-doped graphene supported magnetic ZnO/ZF (ZnO/ZnFe₂O₄) and ZnO/CF (ZnO/CoFe₂O₄) nanocomposites. The procured materials were scrutinized by assorted characterizations to acquire information on their chemical composition, crystalline structure and photosensitive properties. The absorption and photocatalytic performance of photocatalysts were studied via UV–Visible spectra. Photodegradation performance of the synthesized nanocomposites was estimated toward mineralization of methyl orange (MO) and malachite green (MG) dyes in aqueous solution. The high surface area of ZnO/ZF/NG and ZnO/CF/NG was suitable for adsorptive removal of MO and MG dyes. The photodegradation performance of heterojunction photocatalysts was superior to bare photocatalyst in 140 min under visible-light irradiation. Spectrophotometer, GC–MS (Gas chromatography–mass spectrometry) elucidation was carried out to expose the possible intermediates formed. Both ZnO/ZF/NG and ZnO/CF/NG were rapidly isolated from the aqueous phase by applying an external magnetic field in 20 sec and 2 min, respectively. The photocatalytic performance and stability of ZnO/ZF/NG and ZnO/CF/NG nanocomposites were confirmed by conducting 10 consecutive regeneration cycles. Owing to recyclability of ZnO/ZF/NG and ZnO/CF/NG, these heterogeneous nanocomposites might be used as cost-effective for treatment of discarded water. The observations endorse that the synthesized ternary heterogeneous nanocomposites facilitates wastewater decontamination using photocatalytic technology.     

Efficient removal of tetracycline by H2O2 activated with iron-doped biochar: Performance,mechanism, and degradation pathways

In this study,novel iron-doped biochar（Fe-BC） was produced using a simple method,and it was used as an H₂ O₂ activator for tetracycline（TC） degradation.Generally,iron loading can improve the separation performance and reactivity of biochar（BC）.In the Fe-BC/H₂ O₂ system,92% of the TC was removed within 30 min with the apparent rate constant(k_obs) of 0.155 min^-1,which was 23.85 times that in the case of the BC/H₂ O_2<...     

Virus and bacterial removal ability of TiO2 nanowire-based self-supported hybrid membranes

Development and application of hybrid membranes containing multi-component materials are increasing day by day in the fields of environmental protection and water treatment. In this research, the efficiency of titania nanowire (TiO₂ NW)-based self-supported hybrid membranes was investigated in the removal of Escherichia coli (E. coli) bacteria and MS2 bacteriophages from contaminated water mimicking the microorganism suspension. Furthermore, toxicology tests on the as-prepared membranes were also performed. TiO₂ NWs were coated with iron(III) oxide (Fe₂O₃) and copper(II) oxide (CuO) nanoparticles, respectively, and cellulose was used as reinforcement material. It was found that, the functionalisation strongly affected the MS2 removal ability of as-prepared membranes, which can be due to the electrostatic interactions between the surface of hybrid membrane and the bacteriophages. The most efficient removal (greater than or equal to 99.99%) was obtained with the TiO₂ NW-CuO-cellulose membrane at pH 7.0. The fabricated hybrid membranes were characterized by micro computed tomography (μCT), Raman spectroscopy, Fourier transform infrared spectroscopy (FT-IR), dynamic light scattering (DLS), contact angle measurement and inductively coupled optical emission spectrometry (ICP-OES) techniques. This study shows a simple route of the usage of novel and effective inorganic nanowire-based hybrid membranes for bacteria and virus removal, providing new pathways in the field of water filtration technologies.     

Degradation and toxicity changes in aqueous solutions of chloroacetic acids by Fenton-like treatment using zero-valent iron

Three priority pollutants, i.e. mono-, di-, and trichloroacetic acids, were degraded by the conventional Fenton AOP system (Fe²⁺ and H₂O₂). The results obtained suggest that the degradation decreased in the order: monochloroacetic, dichloroacetic, and trichloroacetic acid. The best of advanced oxidation processes (AOPs) for the degradation of trichloroacetic acid was reductive dechlorination with the use of zero-valent iron (Fe°). The results of Escherichia coli toxicity tests revealed that the reagents’ toxicity after the Fenton treatment process was decreased.     

Removal of water-soluble lignin model pollutants with graphene oxide loaded ironic sulfide as an efficient adsorbent and heterogeneous Fenton catalyst

Advanced oxidation processes (AOPs) have gained extensive attentions in organic decontamination in past decades. Iron-contained compound is an interesting material due to its adsorptive and catalytic performance, which has been applied widely in AOPs. Thus, graphene oxide (GO)-Fe₃S₄ composite was synthesized by a solvothermal process and assessed as an effective adsorptive and catalytic dual functional material in this work. The composite displayed prominent adsorptive and heterogeneous Fenton-like catalytic performance, which was affected by preparation condition and the reactive parameters in catalytic system. Under optimized reactive conditions, the GO-Fe₃S₄ composite yielded rapid degradation of vanillic acid, which the corresponding apparent rate constant was 1.81 × 10^?1 min^?1. Catalytic mechanism analysis revealed that the main oxygen species was hydroxyl radicals bounded on the surface of the composite. And the generation of ?O₂^– was contributed to the conversion of H₂O₂ to ?OH. The analysis of degradation intermediates of vanillic acid and p-hydroxybenzoic showed that these compounds could be mineralized to small molecules. The prominent enhanced heterogeneous Fenton-like catalytic performance of GO-Fe₃S₄ was due to a larger specific surface area, plenty of reductive active sites in the composite and a high mass transfer efficiency of oxidizing radicals in the reactive system.     

The complementary effect between biochar and ferrihydrite in sustainable Fenton-like oxidation of pollutant

Biochar (BC) and ferrihydrite (Fh) were used together in activation of H₂O₂ for removal of sulfamethazine (SMZ), a refractory antibiotic pollutant. The results show a complementary effect between biochar and ferrihydrite on activation of H₂O₂, namely biochar accelerated Fe(Ⅲ)/Fe(Ⅱ) cycle through electron donation/transfer, while ferrihydrite enhanced the yield of ^•OH through a sustainable release of dissolved Fe. Thus several times more ^•OH was produced in the co-activated system (BC + Fh/H₂O₂) than either in the ferrihydrite-catalyzed Fenton-like system (Fh/H₂O₂) or in the biochar-activated system (BC/H₂O₂). Consequently, a more efficient oxidation of SMZ was observed in BC + Fh/H₂O₂, in which the reaction rate constant (k_obs) is 30.7 times in Fh/H₂O₂ and 6.08 times in BC/H₂O₂, respectively. This research provides a simple and sustainable strategy for enhancing the efficiency of Fenton-like oxidation of pollutants.     

Current trends in the use of zero-valent iron (Fe0) for degradation of pharmaceuticals present in different water matrices

Zero-valent iron (Fe⁰) has recently been proposed as a potential candidate for the degradation of pharmaceuticals, because Fe⁰ can release dissolved iron species, activate molecular oxygen, and react with oxidant species. Additionally, due to its small particle size and large surface area, this catalyst can provide better degradation results, compared to traditional processes. This work focuses on the elimination of pharmaceuticals present in different water matrices, considering the potential harm that these substances can cause in the environment. The mechanisms of pharmaceutical removal using Fe⁰ particles include reduction, adsorption, precipitation, and oxidation processes. Most studies have focused on oxidation processes in the presence of Fe⁰ and radicals derived from oxidants such as hydrogen peroxide (H₂O₂), ozone (O₃), peroxysulfate (SO₅²⁻), peroxodisulfate (S₂O₈²⁻), and oxygen (O₂). Most of the results have shown that high percentages of pharmaceuticals can be removed, degraded, and mineralized. The mechanisms of oxidation and the parameters that influence the degradation of pharmaceuticals, as well as the possible degradation pathways, are discussed here. This review provides information on trends of different processes that use Fe⁰, considering aspects such as particle size, type of matrix, the pharmaceuticals studied, and the results obtained that can improve understanding of new advances in the field of advanced oxidation processes (AOPs) for the degradation and elimination of pharmaceuticals.     

Oxidation of 2-cyanoprop-2-enethioamides with hydrogen peroxide

Oxidation of (E)-3-aryl-2-cyanoprop-2-enethioamides with 32% H₂O₂ under mild conditions gave (E)-3-aryl-2-cyano-1-iminioprop-2-ene-1-sulfenates in 70–88% yields. Under the conditions of the Radziszewski reaction (H₂O₂, 10% aqueous KOH) or upon prolonged treatment with H₂O₂, (E)-3-aryl-2-cyanoprop-2-enethioamides underwent transformations leading to complex mixtures of oxidation products. In some cases, 3-aryloxirane-2,2-dicarboxamides were isolated from those mixtures in low yields (<20%). Treatment of 3-arylamino-2-cyanoprop-2-enethioamides with the system H₂O₂/KOH in ethanol afforded (arylaminomethylidene)malononitriles.