A review of the innovations in metal- and carbon-based catalysts explored for heterogeneous peroxymonosulfate (PMS) activation, with focus on radical vs. non-radical degradation pathways of organic contaminants

Chemical Engineering Journal, Год журнала: 2020, Номер 411, С. 127957 - 127957

Опубликована: Дек. 15, 2020

Язык: Английский

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The Intrinsic Nature of Persulfate Activation and N-Doping in Carbocatalysis

Environmental Science & Technology, Год журнала: 2020, Номер 54(10), С. 6438 - 6447

Опубликована: Апрель 17, 2020

Persulfates activation by carbon nanotubes (CNT) has been evidenced as nonradical systems for oxidation of organic pollutants. Peroxymonosulfate (PMS) and peroxydisulfate (PDS) possess discrepant atomic structures redox potentials, while the nature their distinct behaviors in carbocatalytic not investigated. Herein, we illustrated that roles nitrogen species CNT-based persulfate are intrinsically different. In PMS mediated nitrogen-doped CNT (N-CNT), surface chemical modification (N-doping) can profoundly promote adsorption quantity PMS, consequently elevate potential derived N-CNT–PMS* complexes, boost efficiency via an electron-transfer regime. contrast, PDS was enhanced upon incorporating N into due to limited equilibrium PDS, leading a relatively lower oxidative PDS/N-CNT system mediocre degradation rate. However, with equivalent on N-CNT at low quantity, exhibited stronger oxidizing capacity than PMS/N-CNT because intrinsic higher PMS. The rates two were great linearity potentials carbon–persulfate* suggesting shared similar mechanism. Therefore, this study provides new insights heteroatom doping nanocarbons persulfates unveils principles rational design reaction-oriented carbocatalysts persulfate-based advanced processes.

Язык: Английский

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Unraveling the Overlooked Involvement of High-Valent Cobalt-Oxo Species Generated from the Cobalt(II)-Activated Peroxymonosulfate Process

Environmental Science & Technology, Год журнала: 2020, Номер 54(24), С. 16231 - 16239

Опубликована: Ноя. 23, 2020

Sulfate radical (SO4•–) is widely recognized as the predominant species generated from cobalt(II)-activated peroxymonosulfate (PMS) process. However, in this study, it was surprisingly found that methyl phenyl sulfoxide (PMSO) readily oxidized to corresponding sulfone (PMSO2) with a transformation ratio of ∼100% under acidic conditions, which strongly implied generation high-valent cobalt-oxo [Co(IV)] instead SO4•– Co(II)/PMS Scavenging experiments using methanol (MeOH), tert-butyl alcohol, and dimethyl further suggested negligible role hydroxyl (•OH) but favored Co(IV). By employing 18O isotope-labeling technique, formation Co(IV) conclusively verified oxygen atom exchange reaction between H2O revealed. Density functional theory calculation determined thermodynamically favorable than •OH The indicated be highly reactive due existence oxo-wall capable oxidizing organic pollutant rather recalcitrant attack, for example, nitrobenzene. Additionally, degradation intermediates sulfamethoxazole (SMX) process conditions were identified understand interaction representative contaminant. developed kinetic model successfully simulated PMSO loss, PMSO2 production, SMX degradation, and/or PMS decomposition varying supported proposed mechanism. This study might shed new light on

Язык: Английский

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Carbonized polyaniline activated peroxymonosulfate (PMS) for phenol degradation: Role of PMS adsorption and singlet oxygen generation

Applied Catalysis B Environment and Energy, Год журнала: 2021, Номер 286, С. 119921 - 119921

Опубликована: Янв. 22, 2021

Язык: Английский

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Nonradicals induced degradation of organic pollutants by peroxydisulfate (PDS) and peroxymonosulfate (PMS): Recent advances and perspective

The Science of The Total Environment, Год журнала: 2020, Номер 765, С. 142794 - 142794

Опубликована: Окт. 8, 2020

Язык: Английский

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Co3O4 anchored in N, S heteroatom co-doped porous carbons for degradation of organic contaminant: role of pyridinic N-Co binding and high tolerance of chloride

Applied Catalysis B Environment and Energy, Год журнала: 2020, Номер 282, С. 119484 - 119484

Опубликована: Сен. 17, 2020

Язык: Английский

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Engineered carbon supported single iron atom sites and iron clusters from Fe-rich Enteromorpha for Fenton-like reactions via nonradical pathways

Applied Catalysis B Environment and Energy, Год журнала: 2021, Номер 287, С. 119963 - 119963

Опубликована: Фев. 7, 2021

Язык: Английский

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Activation of peroxymonosulfate by biochar-based catalysts and applications in the degradation of organic contaminants: A review

Chemical Engineering Journal, Год журнала: 2021, Номер 416, С. 128829 - 128829

Опубликована: Фев. 24, 2021

Язык: Английский

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Oxygen Vacancy-Induced Nonradical Degradation of Organics: Critical Trigger of Oxygen (O₂) in the Fe–Co LDH/Peroxymonosulfate System

Environmental Science & Technology, Год журнала: 2021, Номер 55(22), С. 15400 - 15411

Опубликована: Ноя. 5, 2021

Ubiquitous oxygen vacancies (Vo) existing in metallic compounds can activate peroxymonosulfate (PMS) for water treatment. However, under environmental conditions, especially oxygenated surroundings, the interactions between Vo and PMS as well organics degradation mechanism are still ambiguous. In this study, we provide a novel insight into activation over Vo-containing Fe–Co layered double hydroxide (LDH). Experimental results show that Vo/PMS is capable of selective via single-electron-transfer nonradical pathway. Moreover, O2 firstly demonstrated most critical trigger system. Mechanistic studies reveal that, with abundant electrons confined vacant electron orbitals Vo, thermodynamically enabled to capture from form O2•– imprinting effect start process. Simultaneously, becomes electron-deficient withdraws sustain electrostatic balance achieve (32% Bisphenol A without PMS). Different conventional activation, collaboration kinetics thermodynamics, endowed ability donate reductant other than an oxidant 1O2. case, 1O2 act indispensable intermediate species accelerate circulation (as high 14.3 mg/L) micro area around promote nano-confinement electron-recycling process 67% improvement degradation. This study provides brand-new perspective natural environments.

Язык: Английский

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Density Functional Theory Calculations for Insight into the Heterocatalyst Reactivity and Mechanism in Persulfate-Based Advanced Oxidation Reactions

ACS Catalysis, Год журнала: 2021, Номер 11(17), С. 11129 - 11159

Опубликована: Авг. 23, 2021

Advanced oxidation processes (AOPs) based on persulfates such as peroxymonosulfate and peroxydisulfate via heterogeneous catalysts have been a research hotspot due to their outstanding performances in removing emerging organic contaminants (OCs). In this Review, we highlight the recent advances theoretical simulations for persulfate-based AOPs (PS-AOPs) using density functional theory (DFT), with emphasis catalyst properties mechanism of persulfate activation over variety (including nanocarbons, metals, metal oxides). Moreover, OCs degradation by diverse reactive oxygen species investigated computations are also summarized. The descriptors computational studies related structure–performance relationships discussed. Finally, challenges future focuses DFT PS-AOPs proposed, including evaluation properties, elucidation mechanism, especially nonradical pathway, rational design on-demand catalysts.

Язык: Английский

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