Degradation Of Tetracycline Antibiotics Research Articles

Simple synthesis of 2D/3D mpg-C3N4/ZnO nanocages with built-in driven Z-scheme heterostructures: Photocatalytic degradation of tetracycline antibiotics and lifting the limitation of the complex water environment

Tetracycline antibiotics have attracted attention due to their difficulty in being degraded by the natural environment. In this work, 2D/3D mesoporous graphitic carbon nitride (mpg-C3N4)/ zinc oxide (ZnO) hollow nanocage (MCNZH) complexes with Z-scheme heterostructure were prepared for the photocatalytic degradation of tetracycline antibiotics. The catalysts were characterized by SEM, TEM, BET, XRD, FT-IR, EIS, etc. The degradation of tetracycline hydrochloride (40 mg L–1) by MCNZH (1.2 g L–1) can reach 92.08 %. Further, the energy band structure of the catalysts were calculated and the possible degradation mechanism was proposed. The results showed that ·OH– and ·O2– were the main active species, and the internal electric field suppressed the compounding of photogenerated carriers. The catalysts exhibited broad-spectrum degradation of tetracycline antibiotics. Practical sample spiking experiments on soil and river water confirmed its practicability, which provide great significance for the application of the photocatalytic technology in the practical environmental purification.

Bifunctional Pt-loaded steel slag matrix composites for the detection and degradation of tetracycline antibiotics

In this paper, a method for the simultaneous detection and degradation of tetracycline antibiotics (TCs) in water was investigated. Calcium silicate hydrate (CSH), FeO and calcium aluminate hydrate (CAH) were isolated from steel slag as carriers for Pt monomers. The produced Pt-modified modified steel slag (ALANH-Pt) possessed both peroxidase activity and photocatalytic properties. As a result, a sensitive and selective colorimetric sensor was exploited on the basis of ALANH-Pt for tetracycline (TC), oxytetracycline (OTC), and doxycycline (DOX), which exhibited a detection limit (LOD) of 1.696 μM, 0.999 μM and 3.607 μM, respectively. In addition, the degradation rate for TCs could be achieved 82 % within 60 min. The possible mechanisms of detection and degradation are discussed based on ESR spectroscopy, revealing the generation of hydroxyl radicals (OH), superoxide radicals (O2−) and holes (h+). The degradation pathway of TC was inferred by HPLC-MS. The selectivity of the colorimetric sensing platform and the application of the bifunctional ALANH-Pt to real water samples were investigated. This work provides a new idea that allows for the simultaneous detection and degradation of TCs, and offers a new approach to the utilization of steel slag.

Fe-doped TiO2/PVDF-HFP electrospun membranes for tetracycline photocatalytic degradation under visible light

Heterogeneous photocatalysis operated under visible light is considered an efficient and ecofriendly method to remove pharmaceuticals from water streams. However, the recovery of the nano-sized catalyst particles limits this technology to small-scale applications. In this study, we prepared Fe-doped P25 TiO2 photocatalysts and immobilized them over PVDF-HFP electrospun membranes for the photocatalytic degradation of Tetracycline antibiotic under visible light. To ensure uniform distribution of the nanoparticles on the fibers, the electrospinning voltage and the weight percentage of TiO2 were varied, and two preparation methods were applied to disperse the catalyst in the polymeric solution. In order to maximize the visible light exposure of the membranes, 3D printed membrane holders with square and circular shapes were designed to immerse the membrane in Tetracycline solution. The results showed that immobilizing P25 catalysts on the fibers of the membranes limited their visible light absorption when the light source was assembled on the top of the aqueous reaction medium. This occurred due to the membrane's opacity limited light penetration, resulting in uneven irradiation throughout its depth. Based on this, a new photocatalytic reactor design was proposed with immersed light illumination source to reduce the distance between the membrane and the light source for improved activation of the P25 particles. In this design, a 3D-printed vertical membrane holder was also included to accommodate a larger membrane surface area and therefore minimize the required spatial area for large industrial applications.

Microbial Degradation of Tetracycline Antibiotics: Mechanisms and Environmental Implications.

The escalating global consumption of tetracyclines (TCs) as broad-spectrum antibiotics necessitates innovative approaches to mitigate their pervasive environmental persistence and associated risks. While initiatives such as China's antimicrobial reduction efforts highlight the urgency of responsible TC usage, the need for efficient degradation methods remains paramount. Microbial degradation emerges as a promising solution, offering novel insights into degradation pathways and mechanisms. Despite challenges, including the optimization of microbial activity conditions and the risk of antibiotic resistance development, microbial degradation showcases significant innovation in its cost-effectiveness, environmental friendliness, and simplicity of implementation compared to traditional degradation methods. While the published reviews have summarized some aspects of biodegradation of TCs, a systematic and comprehensive summary of all the TC biodegradation pathways, reactions, intermediates, and final products including ring-opening products involved with enzymes and mechanisms of each bacterium and fungus reported is necessary. This review aims to fill the current gap in the literature by offering a thorough and systematic overview of the structure, bioactivity mechanism, detection methods, microbial degradation pathways, and molecular mechanisms of all tetracycline antibiotics in various microorganisms. It comprehensively collects and analyzes data on the microbial degradation pathways, including bacteria and fungi, intermediate and final products, ring-opening products, product toxicity, and the degradation mechanisms for all tetracyclines. Additionally, it points out future directions for the discovery of degradation-related genes/enzymes and microbial resources that can effectively degrade tetracyclines. This review is expected to contribute to advancing knowledge in this field and promoting the development of sustainable remediation strategies for contaminated environments.

Sonocatalytic performance of Bi2WO6 nanoparticles for degradation of tetracycline antibiotics

Sonocatalytic performance of Bi2WO6 nanoparticles for degradation of tetracycline antibiotics

Facile synthesis of MIL-88A/PVA sponge for rapid tetracycline antibiotics degradation via sulfate radical-advanced oxidation processes

MIL-88A is a metal–organic framework (MOF) material known for its excellent performance in advanced oxidation processes (AOPs). However, due to its powdery nature, MIL-88A may undergo loss during catalytic degradation in flowing solutions, making continuous degradation removal challenging. Herein, we report the synthesis of MIL-88A/PVA sponge composite material by the in-situ integration of MIL-88A with PVA sponge. The composite sponge exhibits excellent removal efficiency of tetracycline antibiotics under the conditions of sulfate radical-advanced oxidation processes (SR-AOPs), achieving a degradation rate exceeding 99.0% within 2 min. Additionally, through fixed-bed column experiments, 1 kg of MIL-88A/PVA can treat 2160 L of wastewater within 24 h, indicating promising industrial applicability. It’s worth noting that this material can be customized into any desired block shape as needed. This work offers a highly promising solution for the application of MOF-based bulk-type catalysts in the treatment of antibiotic pollution using SR-AOPs.

Floating MIL-88A(Fe)@expanded perlites catalyst for continuous photo-Fenton degradation toward tetracyclines under artificial light and real solar light

In this work, MIL-88A(Fe) was immobilized onto the expanded perlites to fabricate the floating MIL-88A(Fe)@expanded perlites (M@EP) catalyst via high throughput batch synthesis method under room temperature. The as-prepared M@EP could efficiently activate H2O2 to achieve 100% tetracycline antibiotics (TCs) removal under both artificial low power UV light (UVL) and real sunlight (SL) irradiation. The toxicological evaluation, growth experiment of mung beans and antimicrobial estimation revealed the decreasing aquatic toxicity of the TCs intermediates compared to those of the pristine TCs. A self-designed continuous bed reactor was employed to investigate the long-term operation of the M@EP. The findings demonstrated that the antibiotics mixture can be continuously degraded up to 7 days under UVL and 5 daytimes under SL irradiation, respectively. More importantly, ca. 76.9% and 81.6% of total organic carbon (TOC) removal efficiencies were accomplished in continuous bed reactor under UVL and SL irradiation, respectively. This work advances the immobilized MOFs on floating supports for their practical application in large-scale wastewater purification through advanced oxidation processes. Environmental implicationThis work presented the high throughput production and photo-Fenton degradation application of floating MIL-88A(Fe)@expanded perlites (M@EP). Three tetracycline antibiotics (TCs) were selected as model pollutants to test the degradation ability of M@EP in batch experiment and continuous operation under artificial light and solar light. The complete TCs degradation could be accomplished in self-designed device up to 7 d under UV light and 5 d under real solar light. This work tapped a new door to push MOFs-based functional materials in the real water purification.

Ultrasmall Cu2O@His with laccase- and catechol oxidase-like activity: Applications in phenolic drug identification and degradation

Nanozymes constitute a category of nanomaterials exhibiting the potential to replace natural enzymes. Although many types of nanozymes have been widely reported in different fields, fabricating nanozymes with ultrasmall dimensions and expanding their applications is still a great challenge. In this study, we present a cost-effective, one-step methodology for producing ultrasmall Cu2O@His. Comparative to natural laccases, Cu2O@His demonstrates remarkable catalytic capabilities in phenolic catalysis, alongside robust stability and economic viability. Therefore, some potential applications of Cu2O@His as an alternative to natural laccase were explored. Cu2O@His has been utilized not only for the detection of epinephrine but also for the degradation of tetracycline antibiotics. In addition, four kinds of TCs were successfully distinguished by principal component analysis. This work provides new ideas and methods for the development of nanozymes with ultrasmall dimensions and for the study of applications of laccase-like activity.

Efficient photocatalytic degradation of tetracycline antibiotic and melachite green dye using La-BDC MOFs

Efficient photocatalytic degradation of tetracycline antibiotic and melachite green dye using La-BDC MOFs

Interface engineering in a nitrogen-rich COF/BiOBr S-scheme heterojunction triggering efficient photocatalytic degradation of tetracycline antibiotics

Tetracycline (TC) antibiotics, extensively utilized in livestock farming and aquaculture, pose significant environmental challenges. Photocatalysis, leveraging renewable sunlight and reusable photocatalysts, offers a promising avenue for mitigating TC pollution. However, identifying robust photocatalysts remains a formidable challenge. This study introduces a novel hollow-flower-ball-like nanoheterojunction composed of a nitrogen-rich covalent organic framework (N-COF) coupled with BiOBr (BOB), a semiconductor with a higher Fermi level. The synthesized N-COF/BOB S-scheme nanoheterojunction features an expanded contact interface, strengthened chemical bonding, and unique band topologies. The N-COF/BOB composites showcased exceptional TC degradation performance, achieving an 81.2% removal of 60 mg/L TC within 2 h, markedly surpassing the individual efficiencies of N-COF and BOB by factors of 3.80 and 5.96, respectively. Furthermore, the total organic carbon (TOC) removal efficiency highlights a superior mineralization capacity in the N-COF/BOB composite compared to the individual components, N-COF and BOB. The toxicity assessment revealed that the degradation intermediates possess diminished environmental toxicity. This enhanced performance is ascribed to the robust S-scheme nanoheterojunction structure, which promotes efficient photoinduced electron transfer from BOB to N-COF. This process also augments the separation of photogenerated charge carriers, resulting in an increased yield of superoxide radicals (∙O2−) and hydroxyl radicals (∙OH). These reactive species significantly contribute to the degradation and mineralization of TC. Consequently, this study introduces a sustainable approach for addressing emerging antibiotic contaminants, employing COF-based photocatalysts.

Bifunctional activation of peroxymonosulfate over CuS/g-C3N4 composite for efficient degradation of tetracycline antibiotics

Graphitic carbon nitride (g-C3N4) modified by CuS was fabricated for efficient bifunctional activation of peroxymonosulfate (PMS) and degradation of tetracycline (TC) in water. On the one hand, PMS could be activated by metal ions, and reducing sulfur species as electron donors, promoting the Cu(Ⅰ)/Cu(Ⅱ) cycle. On the other hand, under visible light excitation, CuS and g-C3N4 recombination significantly improved the separation efficiency of electron hole pairs, and electrons effectively migrated to PMS, generating more ROSs. The removal efficiency of TC reached 97.46 % in the optimal configuration. In addition, the 35 % CuS/g-C3N4/PMS/Light system exhibited excellent degradation ability of TC in different water matrix. The combination of free radicals (O2•−, •OH and SO4•−) and non-free radical (1O2) pathways enhanced the degradation of TC, in accordance with scavenging experiments and electron paramagnetic resonance (EPR) analysis. Density functional theory (DFT) calculations supported the higher adsorption energy of PMS on CuS/g-C3N4 composite in comparison to pure materials. Overall, this work demonstrates the practical relevance of CuS/g-C3N4/PMS/Light system for the efficient degradation of TC in the application of environmental remediation, offering an innovative approach for diminishing refractory organics and wastewater treatment expenses.

Fabrication of a Z-scheme Bi2MoO6/NiFe layered double hydroxide heterojunction for the visible light-driven degradation of tetracycline antibiotics

Heterojunction catalysts offer promising potential for efficient and sustainable remediation of polluted environments. In this study, Z-scheme Bi2MoO6/NiFe layered double hydroxide (BMO/NiFe) heterojunction catalysts were synthesized using solvothermal process. The surface morphology, crystalline structure, and photochemical characteristics of the synthesized photocatalyst were analyzed by several spectroscopic and electron microscopy methods. BMO, NiFe and BMO/NiFe were efficiently utilized for tetracycline (TC) antibiotics degradation under visible light irradiation. The experimental findings suggest that the BMO/NiFe15 heterojunction catalyst greatly enhances the TC degradation rate to 95 % under 300 W visible light irradiation for 120 min. The rate constant of 0.0219 min−1 indicates a rapid degradation process following pseudo first-order kinetics. Furthermore, the effect of active free radicals, the recyclability of the catalyst and the photocatalytic degradation mechanism of TC were proposed. This novel method opens up possibilities for creating advanced photocatalysts, which can effectively degrade TC in water bodies, addressing the urgent need for its removal from aquatic environments. The present work serves as a primary pathway to design and develop efficient Bi2MoO6-based direct Z-scheme photocatalysts with promising applications in simultaneous wastewater degradation with hydrogen evolution.

Construction of a continuous packed bed laccase reactor for the elimination of tetracyclines in seawater

Tetracycline antibiotics (TCs) are extensively present in the marine environment and have adverse effects on human health and aquatic ecosystems. Laccases are a type of green biocatalyst for TCs degradation. In this study, a continuous packed bed reactor based on the immobilized modified laccase was constructed to degrade TCs at environmentally relevant levels in seawater. Results showed that the chemical modification and immobilization of laccase had a synergistic effect on its activity and stability in seawater: after incubation in seawater for 12 h, the residual activity of free laccase was only 22.3%, while that of the immobilized modified laccase (A/PhA-Lac) was 79.3%. A laccase reactor was constructed based on A/PhA-Lac, and the response surface regression model was established to optimize the laccase reactor operating conditions. The laccase reactor under optimal conditions could continuously degrade TCs (5 μg/L each) in seawater within 10 h and reach the highest removal rate at 4 to 5 h (removal rates of tetracycline, oxytetracycline, and chlorotetracycline were 94.7%, 86.6% and 98.0%, respectively). The luminescent bacteria microtoxicity and seawater microbial community analysis revealed that the laccase reactor significantly mitigated the toxicity of TCs in seawater. This study provided an environmentally friendly and effective method for the elimination of antibiotics in seawater.

Activities of Na0.5Bi0.5TiO3@C core-shell composites in piezo-photocatalytic degradation of tetracycline antibiotic

The Na0.5Bi0.5TiO3 and Na0.5Bi0.5TiO3@C core-shell catalysts were synthesized successfully using the solvothermal method. A few of Ti4+ was reduced to Ti3+ with the help of glucose in the solvothermal process, which results in the formation of oxygen vacancies in the NBT@C catalysts. Meanwhile, the excessive glucose was carbonized, which accumulated on the surface of Na0.5Bi0.5TiO3 and formed Na0.5Bi0.5TiO3@C core-shell composites. The phase, microstructure, optical and piezoelectric properties, as well as the catalytic activities of the synthesized catalysts were characterized. The Na0.5Bi0.5TiO3@C core-shell composites show higher photocatalytic activity that of pure Na0.5Bi0.5TiO3 on account of more visible light absorbance. And the piezo-photocatalytic activities to tetracycline of the synthesized catalysts are highest due to the synergetic effects of photocatalysis and piezocatalysis.

Enhanced photocatalysis activity of Co0.5Mg0.5Fe2O4/rGO nanocomposites for tetracycline antibiotic degradation

This study investigated cobalt-magnesium ferrite (Co0.5Mg0.5Fe2O4) with reduced graphene oxide (rGO) as a dominant photocatalyst for the photo-degradation of tetracycline. Co0.5Mg0.5Fe2O4/rGO nanocomposite degraded 93 % of the tetracycline (TC-HCL) after 120 min of visible radiation, which can be attributed to the improved adsorption capacity and the significantly better transfer and separation of photoexcited (e-h+) pairs.Additionally, the Co0.5Mg0.5Fe2O4/rGO nanocomposite had higher stability and recyclability. Based on observed intermediates, possible processes of tetracycline degradation were proposed, where the •OH and •O2- played a major part. Photodegradation of TC-HCL was also provided using the LC-MS approach. The Co0.5Mg0.5Fe2O4/rGO nanocomposite was found to have a new potential for enhanced photocatalytic performance, making it a suitable photocatalyst for wastewater treatment.

Synthesis of ZnO/NiO/g-C3N4 Nanocomposite Materials for Photocatalytic Degradation of Tetracycline Antibiotic

In this study, an approach was utilized to improve the photocatalytic efficacy of g-C3N4 by creating a composite photocatalyst through co-precipitation. This process involved incorporating NiO and ZnO into the structure, resulting in enhanced photocatalytic activity. The Scanning Electron Microscopy (SEM) showcases interesting aggregation behavior, revealing extensive arrays of ZnO/NiO/g-C3N4 particles. Ultraviolet–Visible Diffuse Reflectance Spectroscopy (UV-Vis DRS) confirms the composite's strong light absorption, especially in the visible spectrum. X-ray diffraction (XRD) analysis provides conclusive evidence of successful material synthesis. The degradation of tetracycline antibiotics under visible light exposure demonstrates an impressive photochemical degradation efficiency of 78.43%. Additionally, the composite exhibits impressive cycles of reuse, retaining its high photocatalytic activity even after four reaction cycles. This performance surpasses that of comparison samples. The synergistic integration of NiO and g-C3N4 within ZnO proves to be crucial in enhancing photocatalytic activity by enhancing electron-hole separation and mitigating recombination processes. This composite photocatalyst shows a wide potential for efficiently eliminating tetracycline antibiotics from water systems. Copyright © 2023 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Novel Z-scheme Nb2O5/C3N5 photocatalyst for boosted degradation of tetracycline antibiotics by visible light-assisted activation of persulfate system

Photocatalytic-assisted activation of persulfate (PDS) is regarded as a promising method for the rapid and efficient degradation of refractory pollutants in the water environment. In this study, a novel Nb2O5/C3N5 (NOCN) p-n heterojunctions composite was created by loading n-type Nb2O5 onto p-type C3N5 via an in-situ facile one-step calcination method. The NOCN/PDS system exhibited excellent performance in degrading tetracycline (TC) antibiotics under visible light and had great cyclic stability. The degradation efficiency of the coupled system reached 95 %, surpassing the pure C3N5 and PDS systems by 3.5 times and 2.4 times, respectively. The degradation rate of target pollutants was improved by the coupled system with the photocatalytic activation of PDS. The photogenerated electrons (e-) in NOCN were able to activate PDS effectively, which facilitated the creation of more reactive species. The Photoluminescence (PL) and other photoelectrochemical data demonstrated that the interfacial charge separation and photoresponsivity were remarkably enhanced in the coupled system. According to Mott-Schooky and electron spin resonance (ESR) characterization, it was confirmed that the reaction mechanism was the Z-scheme charge transfer mechanism based on p-n heterojunctions in the NOCN/PDS system. In addition, LC-MS analyses, TOC monitoring and biotoxicity analyses detected that the target pollutants were degraded to weakly bio-toxic micromolecules. In conclusion, this work provides valuable insights into the application of visible light-activated PDS technology in the degradation of organic pollutants, highlighting its potential for practical implementation.

Hydrothermal synthesis of Z-scheme photocatalyst Zn2SnO4-g-C3N4 for efficient tetracycline antibiotic removal

Photocatalysis is a promising green technique to eliminate pollutants for environmental remediation so that the design of proficient photocatalyst stands on the cutting edge of material science. In this work, the visible light-responsive Zn2SnO4-g-C3N4 (ZSC) photocatalyst is synthesized using a simple one-step hydrothermal method without any surfactant. The physical and chemical characteristics of the synthesized composites are investigated. The ZSC composites demonstrate significant improvement in visible-light driven photocatalytic performance towards the degradation of tetracycline antibiotics. The formation of a Z-scheme heterojunction plays a crucial role in enhancing the photocatalytic performance of the composites. This work provides the design and preparation of direct Z-scheme photocatalysts using a simple hydrothermal method for environmental remediation.

Enhanced visible-light photocatalytic activity of ZrO2/gCN composite by introducing nitrogen vacancies with H2 plasma treatment

The abuse of tetracycline antibiotics (TCs) has caused serious environmental pollution problems in recent years due to excessive use of biomedicine, healthcare, animal husbandry and other fields. How to effectively remove TCs contaminants from water has been one of research emphasis on environment protection. In this work, we have successfully prepared a composite photocatalyst (P16-ZrO2/gCN) by physical mixing method and H2 plasma treatment at room temperature. The ZrO2 nanoparticles and H2 plasma treatment have synergetic effects on photocatalytic performance of gCN for degradation of TCs, and the highest degradation rate is achieved with 16 mins plasma treatment. According to BET, XPS and EPR results, more mesopores and nitrogen vacancies (NVs) are introduced by H2 plasma treatment. Furthermore, In-situ TRPL spectra illustrate that ZrO2 nanoparticles and H2 plasma treatment facilitate charge transfer process of catalysts. Overall, this work firstly reports utilizing ZrO2 nanoparticles/H2 plasma treatment together to boost photocatalytic performance of gCN and provides a low-cost approach for preparation of other photocatalysts.

Photocatalytic degradation of tetracycline antibiotics by RGO-CdTe composite with enhanced apparent quantum efficiency

RGO-CdTe composite was synthesized using a straightforward, easy-to-realize, one-pot solvothermal technique. The synthesized composite was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Brunauer-Emmett-Teller method (BET), Raman spectra, UV-Vis absorption, and photoluminescence measurement. The RGO-CdTe composite exhibited 83.6% photocatalytic degradation efficiency for the aqueous tetracycline (TC) antibiotic solution and the apparent quantum yield (AQY) for the same was as high as 22.29% which is 2.63 times higher than that of CdTe. The scavenger investigation demonstrated that although hole acts as the leading active species, despite that, superoxide and hydroxyl radicals have also played crucial roles. The initial pH-dependent photocatalytic performance was measured. The zeta potential of the composite at different pH values was evaluated to establish the photocatalytic performance of the RGO-CdTe towards TC degradation at different pH. The recycling experiment depicts that only a 10% degradation performance declines after 5 times recycle use of the RGO-CdTe photocatalyst. An efficient photocurrent generation in RGO-CdTe thin film device has also been observed. Our study establishes as-synthesized composite of RGO-CdTe as a highly potential, and stable photocatalyst for the degradation of antibiotics from the polluted aqueous environment with a very good photoinduced charge generation efficiency in its solid phase.