Peroxymonosulfate-assisted photocatalysis system enhanced magnetic Fe3O4@P-C3N4 treatment of tetracycline wastewater: Multi-pathways mediated electrons migration to generate reactive species.

Photocatalytic wastewater purification is essential for environmental remediation, but rapid carrier recombination and limited oxidative capacity hinder progress. This study proposes an innovative strategy by integrating homogeneous and heterogeneous electron acceptors into a g-C3N4-based photocatalytic system, significantly enhancing the multipath utilization of photogenerated electrons. A novel Fe3O4@P-C3N4 was developed to activate an advanced peroxymonosulfate-assisted photocatalysis (PAP) system, achieving complete degradation and significant mineralization of tetracycline (TC) in real water environments, outperforming others reported in the last five years. Phytic acid, as a key precursor, modifies the hollow tubular morphology and introduces phosphorus (P) heteroatoms as electronic trapping centers, enhancing the visible light response and carrier separation, thereby promoting the Fe2+/Fe3+ cycle and the formation of reactive species. Density functional theory (DFT) calculations pinpointed TC's vulnerable sites and synergically identified reactive species, revealing almost non-toxic degradation processes. Moreover, the recyclable magnetic Fe3O4@P-C3N4/PAP system demonstrates practical application potential and leaching stability in cyclic and continuous testing. This study offers unique insights into the strategic design of photocatalysts and catalytic environments, potentially advancing practical wastewater remediation.

Activation of peroxymonosulfate by novel magnetically recyclable CoFe2O4/MXene quantum dots composites for rapid degradation of tetracycline: Synergistic performance and mechanisms.

Tetracycline (TC), a commonly used antibiotic in wastewater, poses environmental and health risks, thus demanding advanced catalysts for its effective removal. In this work, for the first time, we integrated cobalt ferrite (CoFe2O4) and MXene quantum dots (MQDs) to form magnetic heterojunctions for rapid degradation of TC in the presence of peroxymonosulfate (PMS). Anchoring MQDs on the CoFe2O4 nanoparticles remarkably promoted the overall degradation rate of TC to 98.2% within 20 min via both radical and non-radical pathways. The first-order kinetic constant was 0.170 min-1, 3.5 and 15.5 times higher than that of CoFe2O4 and MQDs alone, respectively. Quenching experiments revealed that the addition of p-benzoquinone (p-BQ) and furfuryl alcohol (FFA) reduced the degradation of TC within 20 min to 56.2% and 28.4%, respectively, indicating that the primary reactive oxygen species for TC degradation in the CoFe2O4/MQDs + PMS system are •O2- and 1O2. CoFe2O4/MQDs also exhibited superparamagnetic property, which enabled their effective recovery by external magnetic field. Their reusability was verified by retaining 81.4% of catalytic efficacy in the consecutive 8th cycle. The CoFe2O4/MQDs + PMS system also exhibited excellent practicability in natural water samples as the degradation rates in both tap water and lake water environments exceeded 90%. Three potential pathways for TC degradation were proposed based on the liquid chromatography-mass spectrometry (LC-MS) characterizations and TC progressively transformed into 13 intermediates. This work may contribute to the ongoing efforts to develop advanced catalysts and strategies for mitigating the environmental impact of antibiotic pollution, offering a pathway toward sustainable and efficient water treatment technologies.

Hydroxyl radical mediated extracellular degradation of tetracycline under aerobic and anaerobic conditions stimulated by bio-FeS nanoparticles.

The extracellular degradation of antibiotics facilitated by bio-nanoparticles is significant in the field of waste valorization. Among different bio-nanoparticles, bio-FeS nanoparticles stand out for their convenient and cost-effective synthesis. Nevertheless, there is a lack of understanding regarding the extracellular degradation of pollutants driven by bio-FeS nanoparticles. Hence, this study aimed to investigate the role of bio-FeS nanoparticles in the extracellular degradation of tetracycline under aerobic and anaerobic conditions. The findings demonstrated that bio-FeS nanoparticles generated hydroxyl radical (·OH), which significantly contributes to the degradation of tetracycline in both aerobic and anaerobic environments. The production of ·OH in anaerobic conditions was primarily attributed to the limited formation of FeS2 during the biosynthesis of nanoparticles, which was very different from aerobic conditions. The bio-FeS nanoparticles facilitated extracellular electron transport by promoting electron shuttles and Fe(II)/Fe(III) cycling, resulting in the continuous production of ·OH. The degradation pathways showed differences under aerobic and anaerobic conditions, with intermediates exhibiting higher toxicity and greater cellular damage under aerobic conditions. However, in anaerobic conditions, bio-FeS nanoparticles enabled the successful integration of intracellular and extracellular degradation of tetracycline. This research proposed a new avenue for biocatalysis and environmental remediation.

Simultaneous enhanced antibiotic pollutants removal and sustained permeability of the membrane involving CoFe2O4/MoS2 catalyst initiated with simple H2O2 backwashing.

Membranes for wastewater treatment should ideally exhibit sustainable high permeate production, enhanced pollutant removal, and intrinsic physical rejection. In this study, CoFe2O4/MoS2 serves as a non-homogeneous phase catalyst; it is combined with polyether sulfone membranes via liquid-induced phase separation to simultaneously sustain membrane permeability and enhance antibiotic pollutant degradation. The prepared catalytic membranes have higher pure water flux (329.34 L m-2 h-1) than pristine polyethersulfone membranes (219.03 L m-2 h-1), as well as higher mean pore size, porosity, and hydrophilicity. Under a moderate transmembrane pressure (0.05 MPa), tetracycline (TC) in synthetic and real wastewater was degraded by the optimal catalytic membrane by 72.7 % and 91.2 %, respectively. Owing to the generation of the reactive oxygen species (ROS) during the Fenton-like reaction process, the catalytic membrane could exclude the natural organics during the H2O2 backwash step and selectively promote fouling degradation in the membrane channel. The irreversible fouling ratio of the catalyzed membrane was significantly reduced, and the flux recovery rate increased by up to 91.6 %. A potential catalytic mechanism and TC degradation pathways were proposed. This study offers valuable insights for designing catalytic membranes with enhanced filtration performance.

Low-coordinated Mn-N2 sites in graphene oxide induce peroxydisulfate activation for tetracycline degradation: Process optimization and theoretical calculation.

Atom-dispersed low-coordinated transition metal-Nx catalysts exhibit excellent efficiency in activating peroxydisulfate (PDS) for environmental remediation. However, their catalytic performance is limited due to metal-N coordination number and single-atom loading amount. In this study, low-coordinated nitrogen-doped graphene oxide (GO) confined single-atom Mn catalyst (Mn-SA/NGO) was synthesized by molten salt-assisted pyrolysis and coupled to PDS for degradation of tetracycline (TC) in water. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (AC-HAADF-STEM) and X-ray absorption fine structure spectroscopy (XAFS) analysis showed the successful doping of single-atom Mn (weight percentage 1.6%) onto GO and the formation of low-coordinated Mn-N2 sites. The optimized parameters obtained by Box-Behnken Design achieved 100% TC removal in both prediction and experimental results. The Mn-SA/NGO + PDS system had strong anti-interference ability for TC removal in the presence of anions. Besides, Mn-SA/NGO possessed good reusability and stability. O2•-, •OH, and 1O2 were the main active species for TC degradation, and the TC mineralization reached 85.1%. Density functional theory (DFT) calculations confirmed that the introduction of single atoms Mn could effectively enhance adsorption and activation of PDS. The findings provide a reference for the synthesis of high-performance single-atom catalysts for effective removal of antibiotics.

Fabrication and optimization of bioelectrochemical system using tetracycline-degrading bacterial strains for antibiotic wastewater treatment.

In this study, a microbial fuel cell was constructed using Raoultella sp. XY-1 to efficiently degrade tetracycline (TC) and assess the effectiveness of the electrochemical system. The degradation rate reached 83.2 ± 1.8 % during the 7-day period, in which the system contained 30 mg/L TC, and the degradation pathway and intermediates were identified. Low concentrations of TC enhanced anodic biofilm power production, while high concentrations of TC decreased the electrochemical activity of the biofilm, extracellular polymeric substances, and enzymatic activities associated with electron transfer. Introducing electrogenic bacteria improved power generation efficiency. A three-strain hybrid system was fabricated using Castellaniella sp. A3, Castellaniella sp. A5 and Raoultella sp. XY-1, leading to the enhanced TC degradation rate of 90.4 % and the increased maximum output voltage from 200 to 265 mV. This study presents a strategy utilizing tetracycline-degrading bacteria as bioanodes for TC removal, while incorporating electrogenic bacteria to enhance electricity generation.

Construction of Ultrathin BiVO4-Au-Cu2O Nanosheets with Multiple Charge Transfer Paths for Effective Visible-Light-Driven Photocatalytic Degradation of Tetracycline.

In this study, unique BiVO4-Au-Cu2O nanosheets (NSs) are well designed and multiple charge transfer paths are consequently constructed. The X-ray photoelectron spectroscopy measurement during a light off-on-off cycle and redox capability tests of the photo-generated charge carriers confirmed the formation of Z-scheme heterojunction, which can facilitate the charge carrier separation and transfer and maintain the original strong redox potentials of the respective component in the heterojunction. The ultrathin 2D structure of the BiVO4 NSs provided sufficient surface area for the photocatalytic reaction. The local surface plasmon resonance (LSPR) effect of the electron mediator, Au NPs, enhanced the light absorption and promoted the excitation of hot electrons. The multiple charge transfer paths effectively promoted the separation and transfer of the charge carrier. The synergism of the abovementioned properties endowed the BiVO4-Au-Cu2O NSs with satisfactory photocatalytic activity in the degradation of tetracycline (Tc) with a removal rate of ≈80% within 30 min under visible light irradiation. The degradation products during the photocatalysis are confirmed by using ultra-high performance liquid chromatography-mass spectrometry and the plausible degradation pathways of Tc are consequently proposed. This work paves a strategy for developing highly efficient visible-light-driven photocatalysts with multiple charge transfer paths for removing organic contaminants in water.

Resource utilization of medical waste incineration fly ash to activate peroxydisulfate for tetracycline degradation: Synergy between adsorption and PDS activation.

Medical waste incineration fly ash (MWI FA) is classified as a hazardous solid waste. Therefore, the development of recycling technologies to convert MWI FA into useful products is necessary and challenging. In this study, we developed a sustainable approach for preparing a catalyst through the pyrolysis of water-washed MWI FA (WW FA-x, where x corresponds to the pyrolysis temperature). Subsequently, it was applied as a potent peroxydisulfate (PDS) activator to remove tetracycline (TC) from water. The results showed that the WW FA-800 exhibited remarkable adsorption performance as well as highly efficient catalytic activation of PDS, with a 115 mg/g maximum TC adsorption capacity and 93.5% (reaction kinetic rate = 315 µmol/g/h) TC removal within 60 min. A synergistic effect was achieved by adsorption and PDS activation. TC degradation was primarily driven by non-radical (1O2 and electron transfer) processes. WW FA-800 possesses multiple active sites, including defects, π-π*, O-CO groups, Fe0, and Cu(I). Three possible pathways for TC decomposition have been proposed, with the majority of intermediates exhibiting less toxicity than TC. Furthermore, the WW FA/PDS system exhibited an excellent anti-interference ability, and universality in the degradation of various organic contaminants. Notably, energy consumption was minimal, approximately 2.80 kWh/(g·TC), and the leachability of heavy metals in the WW FA-800 was within acceptable limits. This study provides a MWI FA recycling route for the development of highly active catalysts.

Roles of BOCu sites and graphite nitrogen on persulfate non-radical activation for tetracycline degradation.

The activation of peroxymonosulfate (PMS) by carbon-based catalysts is deemed to be a promising method for the degradation of refractory organic contaminants in wastewater. Herein, a Cu-doping strategy in B and N co-doped carbon nanotubes with highly dispersed BOCu sites and graphite nitrogen were successfully synthesized for activating PMS to degradate tetracycline. The best removal rate of tetracycline within 60 min (97.63 %) was obtained by the 1.5 % Cu-BNC and the degradation rate was increased by 17.9 times. The enhanced catalyst activity was attributed to the promoting the cycle of the Cu(I)/Cu(II) redox pair by the formed BOCu sites, and the accelerating the electron transfer process by the adsorption of graphitic N for PMS. The non-free radical pathway including 1O2 and electron transfer played a dominant role in the 1.5 % Cu-BNC/PMS system. The degradation intermediates of TC were identified and three possible degradation pathways were proposed. Further toxicity analysis of the intermediates showed that the 1.5 % Cu-BNC/PMS system had a significant effect on weakening and reducing the biological toxicity and mutagenicity of TC. Moreover, it presented an excellent degradation performance in raw natural water. In general, the proposed regulation of carbon-based catalysts via the coordination-driven effect provides ideas for efficient wastewater treatment.

Effective degradation of tetracycline in aqueous solution by an electro-Fenton process using chemically modified carbon/α-FeOOH as catalyst.

This study applied an electro-Fenton process using chemically modified activated carbon derived from rubber seed shells loaded with α-FeOOH (RSCF) as catalyst to remove tetracycline residues from aquatic environment. Catalyst characteristics were evaluated using SEM, EDS, XRD, and XPS, showing successful insertion of iron onto the activated carbon. The effects of the parameters were investigated, and the highest treatment efficiency was achieved at pH of 3, Fe: H2O2 ratio (w/w) of 500:1, catalyst dose of 1 g/L, initial TCH concentration of 100 mg/L, and electric current of 150 mA, with more than 90% of TCH being eliminated within 30 min. Furthermore, even after five cycles of use, the treatment efficiency remains above 90%. The rate constant is calculated to be 0.218 min-1, with high regression coefficients (R 2 = 0.93). The activation energy (Ea) was found to be 32.2 kJ/mol, indicating that the degradation of TCH was a simple reaction with a low activation energy. These findings showed that the RSCF is a highly efficient and cost-effective catalyst for TCH degradation. Moreover, the use of e-Fenton process has the advantage of high efficiency, low cost thanks to the recyclability of the catalyst, and environmental friendliness thanks to less use of H2O2.

Tetracycline degradation by dual-frequency ultrasound combined with peroxymonosulfate.

Tetracycline has received a great deal of interest for the harmful effects of substance abuse on ecosystems and humanity. The effects of different processes on the degradation of tetracycline were compared, with dual-frequency ultrasound (DFUS) in combination with peroxymonosulfate (PMS) being the most effective for the tetracycline degradation. Free radical scavenging experiments showed that O2∙-,SO4∙- and •OH were the main reactive radicals in the degradation of tetracycline. According to the major intermediates of tetracycline degradation identified, three possible degradation pathways were proposed, which are of significance for translational studies of tetracycline degradation. Notably, these intermediates were found to be significantly less toxicity. The number of active bubbles in the degradation vessel was calculated using a semi-empirical formula, and a higher value of 1.44 × 108 L-1s-1 of bubbles was obtained when using dual-frequency ultrasound at 20 kHz (210 W/L) and 80 kHz (85.4 W/L). Therefore, compared to 20 kHz, although the yield of strong oxidizing substances from individual active bubbles decreased slightly, a significant increment of the number of active bubbles still resulted in a higher synergistic effect, and the combination of DFUS and PMS should be effective in promoting the generation of reactive free radicals and mass transfer processes within the degradation vessel, which provides a method for efficient removal of tetracycline from wastewater.

Boosting tetracycline degradation of BaTiO3-based piezo-catalysts via modulating phase boundary and band structure.

Piezoelectric catalysis, which converts mechanical energy into chemical activity, has important applications in environmental remediation. However, the piezo-catalytic activity of various piezoelectric materials is limited by the weak piezoelectricity as well as the mismatched band-gap, leading to inefficient electron-hole pair generation and difficult carrier migration. Here, a simple strategy combining phase boundary and energy band structure modulation was innovatively proposed to enhance the piezo-catalytic activity of BaTiO3 ferroelectric by Ce ions selecting different doping sites. Thanks to the coexistence of tetragonal (P4mm) and orthorhombic (Amm2) phases effectively flattened the Gibbs free-energy and thus enhanced the piezoelectric activity, as well as suitable energy bandwidth facilitating the carrier migration were realized in the B-sites doped Ba(Ti0.95Ce0.05)O3. The degradation rate constant k of tetracycline (TC) was high to 30.56 × 10-3 min-1, which was 2.03 times higher than that of pure BaTiO3 and superior to most representative lead-free perovskite piezoelectric materials. Theoretical calculations validated that the charge density and high O2 and OH- adsorption energy on the Ba(Ti0.95Ce0.05)O3 surface promoted more efficient •O2- and •OH radicals conversion and bettered response to piezo-catalytic reaction. This work is important to design high-performance piezo-catalysts by synergistic regulation of phase boundary and energy band structure in perovskite materials for long-term antibiotic tetracycline removal.

Enhanced visible light photo-Fenton catalysis by Fe-doping oligo-layer natural molybdenite with efficient carrier spatial-driven Fe3+/Fe2+ cycle.

Developing cost-effective and efficient photo-Fenton catalysts is crucial for advancing photo-Fenton technology. MoS2 is a representative transition metal disulfide with attractive photoresponsiveness, making it ideal for preparing composite photo-Fenton catalysts. In this study, natural molybdenite was innovatively utilized as a source of MoS2 (OM) to synthesize a low-cost and efficient Fe@MoS2 (OMF) composite photo-Fenton catalyst by comminution and adsorption, which was then applied to the remediation of antibiotic-contaminated water. The OMF composites exhibited significant catalytic activity, with a kinetic rate constant of 0.022 min-1, which was 3.1 times higher than that of the original OM (0.007 min-1), indicating a 3% increase. This was attributed to the synergistic effect of many photogenerated electrons and reversible Mo4+/Mo6+ redox pairs, which accelerated the regeneration of Fe2+. After three cyclic tests, the concentrations of dissolved Fe2+ and Mo2+ ions remained below 0.38 mg/L and 0.17 mg/L, respectively. This indicates the high reusability of the catalyst in cyclic experiments. Ultimately, the main active species, •OH and •O2 -, were generated during the photo-Fenton process, contributing significantly to TC degradation. This study may serve as a reference for the development and application of natural mineral composite photo-Fenton catalysts in the treatment of organic wastewater.

A novel BiOBr/rGO photocatalysts for degradation of organic and antibiotic pollutants under visible light irradiation: Tetracycline degradation pathways, kinetics, and mechanism insight.

In this study, the BiOBr/rGO nanocomposite photocatalysts are fabricated by a facile solvothermal method. The BiOBr growth on reduced graphene oxide (rGO) sheet could improve BiOBr's photocatalytic activity by increasing its adsorption ability, surface area, and charge carriers' separation efficiency. The prepared nanocomposites were characterized by XRD, Raman, FESEM, EDS, XPS, and UV-visible DRS. The BiOBr/rGO (BRG) nanocomposites showed improved photocatalytic activity for the photodegradation of Rhodamine B (RhB) dye and Tetracycline (TC) under visible light irradiation. Rhodamine B and tetracycline degradation efficiency were about 96% and 73% within 120 min under visible light irradiation. The PL analysis indicates that BiOBr/rGO nanocomposite exhibited maximum separation efficiency of photoinduced charge carriers. The trapping test confirmed that O2- and h+ are significant active photodegradation species. The GC-MS spectra detected the two plausible transformation routes of tetracycline degradation. The current work presented a low-cost and facile approach for fabricating Bi-based composites.

Introducing Br, K, and cyano group into carbon nitride for efficient photocatalytic hydrogen peroxide production then in situ tetracycline mineralization.

In this work, Br, K-doped and cyano group-rich carbon nitride (CN) were prepared via pyrolysis of molten urea and 6-Bromopyridine-3-carbaldehyde, followed by re-calcination with potassium thiocyanate. The hydrogen peroxide (H2O2) evolution and in situ tetracycline (TC) mineralization performances of the prepared samples were studied. The optimal sample could produce 9127 µmol g-1 h-1 H2O2 from 10 vol% ethanol solution and air atmosphere, which was 10.9 times higher than that of pristine CN. With addition of 4 mg L-1 Fe2+ ions, 97.2% of TC (10 mg L-1) and 98.7% of total organic carbon were removed in 30 min under the actions of holes, hydroxyl and superoxide radicals. The high H2O2 yield and TC mineralization ratio were attributed to the increased light absorption, efficient electrons-holes separation, enhanced surface O2 adsorption (0.3878 mmol g-1), and accelerated conversion from Fe3+ to Fe2+ ions. Meanwhile, the system possessed good reusability in H2O2 evolution and TC removal. It is expected that this work can provide new ideas to design CN-based photo-Fenton system to treat wastewater.

MXene-supported MIL-88A(Fe) as persulfate activator for removal of tetracycline.

The poor conductivity, poor stability, and agglomeration of iron-based metal organic framework MIL-88A(Fe) limit its application as persulfate (PS) activator in water purification. Herein, MXene-supported MIL-88A(Fe) composites (M88A/MX) were synthesized to enhance its adsorption and catalytic capability for tetracycline (TC) removal. Scanning electron microscope (SEM), X-ray diffractometer (XRD), Fourier transform infrared spectrometer (FT-IR), and X-ray photoelectron spectroscopy (XPS) were used to characterize prepared materials, confirming the successful attachment of MIL-88A(Fe) to the surface of MXene. M88A/MX-0.2 composites, prepared with 0.2 g MXene addition, exhibit optimal degradation efficiency, reaching 98% under conditions of 0.2 g/L M88A/MX-0.2, 1.0 mM PS, 20 ppm TC, and pH 5. The degradation rate constants of M88A/MX-0.2 were 0.03217 min-1, which was much higher than that of MIL-88A(Fe) (0.00159 min-1) and MXene (0.00626 min-1). The removal effects of reaction parameters, such as dosage of M88A/MX-0.2 and PS; initial solution pH; and the presence of the common co-existing constituents (humic acid and the inorganic anions) were investigated in detail. Additionally, the reuse of M88A/MX-0.2 showed that the composites had good cycling stability by recurrent experiments. The results of electron paramagnetic resonance (EPR) and quenching experiments indicated that ·OH, ·SO4-, and ·O2- were involved in the M88A/MX-0.2/PS system where persulfate oxidation process was activated with prepared M88A/MX-0.2. In addition, the intermediates of photocatalytic degradation were determined by HPLC-MS, and the possible degradation pathways of the target molecules were inferred. This study offered a new avenue for sulfate-based degradation of Fe-based metal organic framework.

From waste to catalyst: Growth mechanisms of ZSM-5 zeolite from coal fly ash & rice husk ash and its performance as catalyst for tetracycline degradation in fenton-like oxidation.

Coal fly ash (CFA), an industrial solid waste, can be utilized to synthesize Zeolite Socony Mobil-5 (ZSM-5) by incorporating an external silica source. In this study, a series of ZSM-5 zeolites were synthesized using rice husk ash (RHA) as the primary silica source and CFA as the primary aluminum source under controlled hydrothermal reaction conditions, and the growth mechanism of ZSM-5 was investigated. The process of ZSM-5 growth was featured by the transformation of hyperpoly silico-aluminate in CFA and RHA into monomers. These monomers formed crystal nuclei connected in a five-membered ring structure under the influence of Tetrapropyl ammonium hydroxide (TPAOH). The surplus monomeric silica-aluminate grew on the nucleus surface due to the addition of the silica source within RHA (RHA-SiO2), ultimately resulting in the development of ZSM-5 zeolite. Characterization results demonstrated that RHA-SiO2 exhibited favorable physical and chemical properties during the ZSM-5 synthesis, with a crystallinity of 99.03%, a specific surface area of 321.19 m2/g, a weight loss of only 3.06% at 800 °C and a total acidity of 0.65 mmol/g. To evaluate the catalytic performance of ZSM-5, Fe/Cu-modified ZSM-5 was developed and used as the catalyst for the degradation of tetracycline (TC) in Fenton-like oxidation. The results indicated that Fe/Cu-ZSM-5 exhibited excellent activity and stability as the catalyst for TC degradation and mineralization. The maximum TC degradation rate reached 99.02% in 10 min and the TOC removal could be up to 69.32% in 2 h. Characterization results indicated that the Fe/Cu ions redox cycle accelerated the generation of active species (1O2 and ˙OH) in Fenton-like systems. The ZSM-5 zeolite synthesized from solid waste demonstrated superb stability and catalytic activity, leading to the effective removal of TC. Since real wastewater generally contains various pollutants, future research efforts should focused on multi-pollutant treatment.

Hierarchically porous cellulose-based carbon aerogels with N-doped skeletons and encapsulated iron-based catalysts for efficient tetracycline catalytic degradation.

Three-dimensional interpenetrating and hierarchically porous carbon material is an efficient catalyst support in water remediation and it is still a daunting challenge to establish the relationship between hierarchically porous structure and catalytic degradation performance. Herein, a highly porous silica (SiO2)/cellulose-based carbon aerogel with iron-based catalyst (FexOy) was fabricated by in-situ synthesis, freeze-drying and pyrolysis, where the addition of SiO2 induced the hierarchically porous morphology and three-dimensional interpenetrating sheet-like network with nitrogen doping. The destruction of cellulose crystalline structure by SiO2 and the iron-catalyzed breakdown of glycosidic bonds synergistically facilitated the formation of electron-rich graphite-like carbon skeleton. The unique microstructure is confirmed to be favorable for the diffusion of reactants and electron transport during catalytic process, thus boosting the catalytic degradation performance of carbon aerogels. As a result, the catalytic degradation efficiency of tetracycline under light irradiation by adding only 5 mg of FexOy/SiO2 cellulose carbon aerogels was as high as 90 % within 60 min, demonstrating the synergistic effect of photocatalysis and Fenton reaction. This ingenious structure design provides new insight into the relationship between hierarchically porous structure of carbon aerogels and their catalytic degradation performance, and opens a new avenue to develop cellulose-based carbon aerogel catalysts with efficient catalytic performance.

Sulfur vacancy-enhanced In2S3-x hollow microtubes for photocatalytic Cr (VI) and tetracycline removal.

Morphological regulation and defect engineering are efficient methods for photocatalytic technology by improving photon absorption and electron dissociation. Herein, In2S3-x hollow microtubes with S-vacancies (MIS) were fabricated via a simple solvothermal reaction using In-based metal-organic frameworks (In-MOFs) as a precursor. Experimental results demonstrate that the hollow structure and optimal S-vacancies can jointly accelerate the photocatalytic reaction, attributed to a larger specific surface area, more active sites, and faster electron transfer efficiency. The champion MIS(2) displayed significantly better photocatalytic activity for Cr(VI) reduction and tetracycline (TC) degradation. The Cr(VI) reduction rate by MIS(2) is 3.67 and 2.82 times higher than those of optimal In2S3 template-free (HIS(2)) and MIS(1) with poor S-vacancies, respectively. The removal efficiency of TC by MIS(2) is 1.37 and 1.15 times higher than those of HIS(2) and MIS(1). Further integration of MIS(2) with aerogel simplifies the recovery process significantly.

Architecture engineering of Fe/Fe2O3@MoS2 enables highly efficient tetracycline remediation via peroxymonosulfate activation: Critical roles of adsorption capacity and redox cycle regulation.

Design and synthesis of high-efficiency multicomponent nanostructure for activating peroxymonosulfate (PMS) to destruct emerging antibiotics remains a daunting challenge. We report herein the simplest one-step hydrothermal construction of hierarchical Fe/Fe2O3@MoS2 architecture composed of MoS2 nanosheets integrated commercial Fe2O3 nanoparticles. The fabricated Fe/Fe2O3@MoS2 architecture can be utilized as an efficient PMS activator to destruct tetracycline hydrochloride (TCH) with a removal efficiency of 90.3 % within 40 min, outperforming Fe2O3 nanoparticles, MoS2 nanosheets analogues and many MoS2-based materials. The Fe/Fe2O3@MoS2/PMS works well under various reaction conditions, and SO4•- and 1O2 are identified as major reactive oxygen species. Thirteen intermediates towards TCH destruction are detected via four pathways, and their acute/chronic toxicity and phytotoxicity are assessed. The origins of Fe/Fe2O3@MoS2/PMS system for efficient degrading TCH are ascribed to the synergy catalysis between Fe2O3 and MoS2, which originate from: (a) the exposed Mo4+ sites on catalyst surface facilitating high-speed electron transfer from MoS2 to Fe3+ and accelerating the Fe2+ regeneration; (b) the generated Fe0 serving as an excellent electron donor to jointly promote Fe3+/Fe2+ redox cycle. This study provides a simple way to establish architecture for synergistically promoting PMS-mediated degradation.