ENVIRONMENTAL SCIENCE & TECHNOLOGY
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2023
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IF 11.4
Yang Zong,Long Chen,Yunqiao Zeng,Jun Xu,Hua Zhang,Xiaomeng Zhang,Wen Liu,Deli Wu
Electron paramagnetic resonance (EPR) spectroscopy using sterically hindered amine is extensively applied to detect singlet oxygen (1O2) possibly generated in advanced oxidation processes. However, EPR-detectable 1O2 signals were observed in not only the 1O2-dominated hydrogen peroxide (H2O2)/hypochlorite (NaClO) reaction but surprisingly also the 1O2-absent Fe(II)/H2O2, UV/H2O2, and ferrate [Fe(VI)] process with even stronger intensities. By taking advantage of the characteristic reaction between 1O2 and 9,10-diphenyl-anthracene and near-infrared phosphorescent emission of 1O2, 1O2 was excluded in the Fe(II)/H2O2, UV/H2O2, and Fe(VI) process. The false detection of 1O2 was ascribed to the direct oxidation of hindered amine to piperidyl radical by reactive species [e.g., •OH and Fe(VI)/Fe(V)/Fe(IV)] via hydrogen transfer, followed by molecular oxygen addition (forming a piperidylperoxyl radical) and back reaction with piperidyl radical to generate a nitroxide radical, as evidenced by the successful identification of a piperidyl radical intermediate at 100 K and theoretical calculations. Moreover, compared to the highly oxidative species (e.g., •OH and high-valence Fe), the much lower reactivity of 1O2 and the profound nonradiative relaxation of 1O2 in H2O resulted it too selective and inefficient in organic contaminant destruction. This study demonstrated that EPR-based 1O2 detection could be remarkably misled by common oxidative species and thereby jeopardize the understandings on 1O2.
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高影响因子
Environmental Science-Nano
·
2023
·Vol. 10
·期 5
·1428-1440
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IF 7.3
Xixi Chen,Yanjun Li,Wanyi Fu,Shuanghong Tian,Yulong Yang,Kai Yang,Xuanbo Xu,Xihui Zhang
The importance of nonradical Fenton-like catalysis in environmental fields has motivated research for effective singlet oxygen (1O2) production, but realizing the accurate design and regulation of active sites for manipulating oriented 1O2 generation is still highly challenging. In this study, α-, β-, and γ-MnO2 catalysts with different oxygen vacancy (OV) abundance were fabricated to activate H2O2 to generate 1O2 for the degradation of oxytetracycline (OTC). The OV-rich α-MnO2 had a high OTC removal efficiency (>93.5%) at the pH range from 4.0 to 11.0. Moreover, α-MnO2 exhibited great applicability for a real water matrix, and the total removal of various kinds of emerging contaminants from hospital wastewater reached up to 97.4%. The excellent performances of α-MnO2 were attributed to the rich contents of OVs that induced the oriented generation of 1O2. Theoretical density functional theory (DFT) calculations validated that the OV-rich α-MnO2 had the highest H2O2 adsorption ability (−1.39 eV) and the lowest energy barrier (0.41 eV) for the dissociation of *OH to form the *O intermediate, which promoted the oriented formation of 1O2. This work provides a strategy of manipulating the oriented generation of 1O2 towards water decontamination via regulating the abundance of oxygen vacancies in α-MnO2 nanocatalysts.
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CHEMICAL ENGINEERING JOURNAL
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2018
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IF 6.735
Jinhong Fan,Hehe Qin,Simin Jiang
Peroxymonosulfate (PMS) is an alternative to hydrogen peroxide in advanced oxidation processes. Herein, we present a simple one-pot synthetic approach for the Mn-doped graphite phase carbon nitride (g-C 3 N 4 ) materials and make it as a catalyst to activate PMS for acetaminophen (ACT) degradation. Fabricated Mn-g-C 3 N 4 composites (MnCN) were characterized by SEM, EDS, XRD, XPS, and FTIR. Results showed that Mn was uniformly dispersed in the structure of g-C 3 N 4 mostly in the form of Mn-N coordination. The effects of pH, contents of doped Mn, catalyst dosage, and reusability of catalyst and corresponding kinetic study were conducted to determine the catalytic performance of MnCN. High reaction efficiency was obtained in a wide pH range of 3.2–9. 100% removal of ACT in 15 min under optimized conditions with initial pH 6.5, 0.8 g/L of PMS and 200 mg/L of catalyst of 0.5-MnCN. Additionally, the reaction mechanism of the PMS/MnCN system was investigated using the electron spin resonance technique, quenching studies as well as different organics with electron-donating or electron-withdrawing groups. No PMS decomposition was detected without substrates. No inhibition effect by ethanol or tert -Butyl alcohol and complete inhibition effect by benzoquinone and partly by furfuryl alcohol, as well as ESR spectrum of TEMP- 1 O 2 were observed, suggesting that the activation of PMS proceeded in a new way, which is different from traditional sulfate radical-based advanced oxidation processes. A possible mechanism was proposed for ACT removal. PMS was first bounded to Mn-N sites to generate the superoxide anion. Then singlet oxygen produced by superoxide anion would react with ACT by replacing the electron-donating group of acylamino.
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ENVIRONMENTAL SCIENCE & TECHNOLOGY
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2019
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IF 7.149
Qiuying Yi,Jiahui Ji,Bin Shen,Chencheng Dong,Jun Liu,Jinlong Zhang,Mingyang Xing
As an important reactive oxygen species (ROS) with selective oxidation, singlet oxygen (1O2) has wide application prospects in biology and the environment. However, the mechanism of 1O2 formation, especially the conversion of superoxide radicals (·O2–) to 1O2, has been a great controversy. This process is often disturbed by hydroxyl radicals (·OH). Here, we develop a molybdenum cocatalytic Fenton system, which can realize the transformation from ·O2– to 1O2 on the premise of minimizing ·OH. The Mo0 exposed on the surface of molybdenum powder can significantly improve the Fe3+/Fe2+ cycling efficiency and weaken the production of ·OH, leading to the generation of ·O2–. Meanwhile, the exposed Mo6+ can realize the transformation of ·O2– to 1O2. The molybdenum cocatalytic effect makes the conventional Fenton reaction have high oxidation activity for the remediation of organic pollutants and prompts the inactivation of Staphylococcus aureus, as well as the adsorption and reduction of heavy metal ions (Cu2+, Ni2+, and Cr6+). Compared with iron powder, molybdenum powder is more likely to promote the conversion from Fe3+ to Fe2+ during the Fenton reaction, resulting in a higher Fe2+/Fe3+ ratio and better activity regarding the remediation of organics. Our findings clarify the transformation mechanism from ·O2– to 1O2 during the Fenton-like reaction and provide a promising REDOX Fenton-like system for water treatment.
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BIOMACROMOLECULES
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2017
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IF 5.246
Liu-Yuan Xia,Xiaodong Zhang,Meng Cao,Zhan Chen,Fu-Gen Wu
Benefiting from their inherent localized and controlled release properties, hydrogels are ideal delivery systems for therapeutic drugs or nanoparticles. In particular, applications of hydrogels for the delivery and release of photoresponsive drugs or nanoparticles are receiving increasing attention. However, the effect of the hydrogel matrix on the fluorescence emission and singlet oxygen generation efficiency of the embedded photosensitizers (PSs) has not been clarified. Herein, meso-tetrakis(1-methylpyridinium-4-yl)porphyrin (TMPyP) as a water-soluble PS was encapsulated into an injectable hydrogel formed by glycol chitosan and dibenzaldehyde-terminated telechelic poly(ethylene glycol). Compared to free TMPyP solution, the TMPyP encapsulated in the hydrogel exhibits three distinct advantages: (1) more singlet oxygen was generated under the same laser irradiation condition; (2) much longer tumor retention was observed due to the low fluidity of the hydrogel; and (3) the fluorescence intensity of TMPyP was significantly enhanced in the hydrogel due to its decreased self-quenching effect. These excellent characteristics lead to remarkable anticancer efficacy and superior fluorescence emission property of the TMPyP–hydrogel system, promoting the development of imaging-guided photodynamic therapy.
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CHEMICAL ENGINEERING JOURNAL
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2023
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IF 15.1
Yifeng Zeng,Fan Wang,Dongqin He,Jianqiang Sun,Jun Li,Hongwei Luo,Xiangliang Pan
Bone char is a hydroxyapatite-rich product obtained by calcining animal bones. However, the role of inorganic hydroxyapatite is often overlooked in bone char-catalyzed persulfate systems. In this work, iron was doped into swine bone-derived biochar (Fe-BC) by simple impregnation, and the Fe-BC catalysts were used for the first time to activate peroxymonosulfate (PMS). The obtained Fe-BC/PMS system could rapidly degrade the target pollutants (0.0529 s −1 , 90 s) employing singlet oxygen ( 1 O 2 ) as the dominant reactive oxygen species (ROS). The characterization results demonstrated that iron was mainly intercalated into the catalyst by substituting calcium sites in swine bone biochar, and the Fe-BC composition was significantly affected by annealing temperature. A comprehensive study including quenching experiments, electron paramagnetic resonance (EPR), chemical probes, and linear sweep voltammetry (LSV) revealed that 1 O 2 was the dominant ROS. According to the characterization results, 1 O 2 was generated from the conversion of superoxide radical (O 2 •− ) and the self-dissociation of PMS. Iron was the main active site of Fe-BC catalysts, and the carbon defects and oxygen-containing groups also played roles in catalyzing PMS. The Fe-BC/PMS system exhibited outstanding oxidative capability over a wide pH range (3.0–9.0) and was resistant to interference from some high concentrations of anions (Cl − , NO 3 – , and SO 4 2− ). This work provides a new perspective on using animal bone-derived biochar catalysts in advanced oxidation processes.
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ENVIRONMENTAL RESEARCH
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2022
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IF 8.431
Yong Cheng,Han-Qing Zhao,Aqiang Ding,Fei Chen,Jun Liu,Dazhi Fang,Chenglong Li,Yongkui Huang,Peili Lu
The widespread application of quaternary ammonium compounds (QAC) has posed a serious hazard to the environment and human being, and high concentration of Cl − in QAC wastewater may further increase the difficulty of pollutants elimination . In this study, such a QAC wastewater under high salinity conditions was chosen as the target, the prepared Ti/(Ru x Ir y )O 2 anode exhibited favorable catalytic performance for the oxidation and mineralization of QAC under high salinity conditions. Increasing the Ru/Ir ratio of Ti-based electrode coating also slightly promoted the inner catalytic capacity. The combination of electron paramagnetic resonance (EPR) and quenching experiments indicates that 1 O 2 served as a main reactive specie in the Ti/(Ru x Ir y )O 2 electrooxidation system. The increase of pH could decrease the removal efficiency of QAC for the reduced 1 O 2 yield, and the rise of Cl − concentration could favor the QAC oxidation, and Cl − was a better electrolyte to promote the oxidation of organic contaminants when compared to Na 2 SO 4 or Na 2 CO 3 . Additionally, the conversion pathway of the model pollutant was tentatively investigated, the results demonstrated that there were almost no halogenated final products residual by electrocatalytic oxidation with Ti/(Ru x Ir y )O 2 anode. This study not only elucidate the reaction mechanism of Ti/(Ru x Ir y )O 2 anode electrocatalytic oxidation of high salinity QAC wastewater, but also may provide an efficacious and eco-friendly method for the treatment of high salinity QAC wastewater.
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SCIENCE OF THE TOTAL ENVIRONMENT
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2022
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IF 10.753
Hangbo Xu,Cao Fang,Changsheng Shao,Lamei Li,Qing Huang
Cold atmospheric plasma (CAP) possesses the ability of high-efficiency disinfection. It is reported that mixtures of reactive oxygen species (ROS) including · OH, 1 O 2 , O 2 − and H 2 O 2 generated from CAP have better antimicrobial ability than mimicked solution of mixture of single ROS type, but the reason is not clear. In this study, CAP was applied to treat yeasts in water in order to investigate the fungal inactivation efficiency and mechanism. The results showed that plasma treatment for 5 min could result in >2-log reduction of yeast cells, and application of varied ROS scavengers could significantly increase the yeast survival rate, indicating that · OH and 1 O 2 played the pivotal role in yeast inactivation. Moreover, the synergistic effect of 1 O 2 with other plasma-generated ROS was revealed. 1 O 2 could diffuse into cells and induce the depolarization of mitochondrial membrane potential (MMP), and different levels of MMP depolarization determined different cell death modes. Mild damage of mitochondria during short-term plasma treatment could lead to apoptosis. For long-term plasma treatment, the cell membrane could be severely damaged by the plasma-generated · OH, so a large amount of 1 O 2 could induce more depolarization of MMP, leading to increase of intracellular O 2 − and Fe 2+ which subsequently caused cell inactivation. 1 O 2 could also induce protein aggregation and increase of RIP1/RIP3 necrosome, leading to necroptosis. With participation of 1 O 2 , endogenous · OH could also be generated via Fenton and Haber-Weiss reactions during plasma treatment, which potentiated necroptosis. Adding l -His could mitigate membrane damage, inhibit the drop of MMP and the formation of necrosome, and thus prevent the happening of necroptosis. These findings may deepen the understanding of plasma sterilization mechanisms and provide guidance for microbial killing in the environment.
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JOURNAL OF HAZARDOUS MATERIALS
·
2021
·
IF 10.588
Zhaoyu Bai,Songxue Wang,Jiayu Tian,Shanshan Gao,Ruijun Zhang,Xiwen Liu
In this study, a series of aluminum-based layered metal oxide with various divalent metals (M 2+ Al-LMOs) were prepared and employed in activation of peroxymonosulfate (PMS) for bisphenol A (BPA) degradation. The BPA removal rates of M 2+ Al-LMOs were ordered as: CoAl(100%) > MnAl(75.6%) > CuAl(63.2%) > NiAl(9.0%) > MgAl = ZnAl-LMO(0%). CoAl-LMO showed the highest kinetic constant (k = 1.329 µmol −1 g cat −1 s −1 ), which was 3.95 times of MnAl-LMO, 5.36 times of CuAl-LMO, 88.6 times of NiAl-LMO and 443 times of MgAl-LMO and ZnAl-LMO, respectively, and also exhibited the highest TOC removal rate (83.3%). The surface-bound sulfate radical (SO 4 ·− ) and singlet oxygen ( 1 O 2 ) were elucidated as the dominant reactive oxygen species (ROS) for BPA degradation. The M 2+ Al-LMOs/PMS system not only displayed wide applicability in different pH and inorganic anions environments, but also had excellent stability and reusability. This work provides a novel family of M 2+ Al-LMOs to activate PMS for water treatment .
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ACS Applied Materials & Interfaces
·
2021
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IF 9.229
Yan Gu,Tiefeng Xu,Zhexin Zhu,Xiufang Chen,Wenxing Chen,Wangyang Lu
The local coordination structure of metal atoms in single-atom catalysts (SACs) greatly influences their catalytic performance. And for most SACs, single metal atoms were anchored on carbon materials with N or C coordination. However, the rational design of oxygen-containing SACs and analyzing its structure–performance relationship remain challenging. Herein, we used amino-rich compounds to tailor the metatungstate and fix the W atoms and finally obtained the oxygen-containing W-SACs. The structural evolution of tungsten and its coordination atoms were tracked by electrospray ionization high-definition mass spectrometry. Furthermore, aberration-corrected transmission electron microscopy, X-ray absorption fine-structure spectroscopy, and first-principles calculation results revealed that different from the traditional SACs, the WO2N2 moiety (W coordinated with two O atoms and two N atoms) may be the favored structure for W species. This special structure promoted the energy transfer for enhancing singlet oxygen generation. This work presents an efficient way to prepare more high-efficiency SACs by atomic-scale tailoring and structural evolution tracking at the molecular level.
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APPLIED SURFACE SCIENCE
·
2021
·
IF 6.707
Jiankang Wang,Taiping Xie,Guokang Han,Quanxi Zhu,Yajing Wang,Yuan Peng,Songli Liu,Zhongping Yao
Cost-effective and low-toxicity of MnO 2 is regarded as a promising alternative to Co-based catalyst for peroxymonosulfate (PMS) activation to degrade recalcitrant organic pollutants. However, the sluggish Mn(IV)/Mn(III) redox cycling and limited specific surface area greatly hampered its wide application. To solve this challenge, a mesoporous γ-Fe 2 O 3 @MnO 2 magnetic catalyst with SiO 2 assistance (s-γ-Fe 2 O 3 @MnO 2 ) was synthesized. Physicochemical characterization confirmed part MnO 2 was coated on γ-Fe 2 O 3 surface while the other existed independently. Furthermore, BET surface area of s-γ-Fe 2 O 3 @MnO 2 was more than two times that of the counterpart without SiO 2 assistance (ws-γ-Fe 2 O 3 @MnO 2 ). s-γ-Fe 2 O 3 @MnO 2 exhibited enhanced PMS activation capacity with 97.6% phenol removal efficiency within 80 min, superior to other samples. Various influencing parameters on phenol oxidation were optimized. Reactive oxygen species (ROS) scavenging experiment and electron paramagnetic resonance (EPR) validated co-existence of hydroxyl radicals (·OH) and sulfate radicals (SO 4 · − ) as well as singlet oxygen ( 1 O 2 ) during PMS activation. However, phenol degradation was a non-radical oxidation process dominated by 1 O 2 . A rational reaction mechanism was proposed. Fe(II) promoted Mn(IV)/Mn(III) redox cycling and the enlarged surface area derived from SiO 2 mediated templating synthesis were responsible for the enhanced phenol degradation. This strategy can give a guidance for synthesis of highly efficient catalyst for sewage remediation.
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BIOMACROMOLECULES
·
2021
·
IF 6.988
Jing Li,Junhua Li,Yuji Pu,Sai Li,Wenxia Gao,Bin He
In this study, we reported a nanocomplex (PAF) of PEGylated polygalacturonic acid, 5,10,15,20-tetrakis (4-aminophenyl) porphyrin (TAPP), and Fe3+ for photodynamic therapy (PDT)-enhanced ferroptosis in cancer treatment. PAF exhibited a size of 135 nm and a TAPP and Fe3+ loading content of 6.99 and 0.77%, respectively. The singlet oxygen (1O2) generation capacity of TAPP can be activated and significantly enhanced at acidic pH (4.5–5.0). Besides, the enhanced near-infrared absorption of TAPP at acidic pH enabled a further increase in 1O2 generation capability by a near-infrared laser (760 nm). The polysaccharide-based polymer carrier offers excellent biocompatibility, and PAF displayed a proliferative effect in both normal (L929) and cancer (B16) cells. However, upon light irradiation, PAF exhibited high toxicity to B16 melanoma cells by intracellular reactive oxygen species elevation, glutathione depletion, and lipid peroxidation. PAF displayed a much better anticancer effect than the nanocomplex containing Fe3+ or TAPP alone, indicating the PDT-enhanced ferroptosis in PAF. This study suggested that PDT-enhanced ferroptosis could be a facile and robust strategy of nanotherapeutics with high potency, tumor selectivity, and excellent biocompatibility.
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