Mechanical insight into direct singlet oxygen generation pathway: Pivotal role of FeN4 sites and selective organic contaminants removal

Zhang, Liang; Sun, Yifei; Ge, Rile; Zhou, Wenhui; Ao, Zhimin; Wang, Junhu

doi:10.1016/j.apcatb.2023.123130

Cited by 30 publications

(8 citation statements)

References 60 publications

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“…The domination of 1 O 2 in SMX degradation was further ascertained by the reaction in the solution containing 50% D 2 O. Because 1 O 2 exhibited a kinetic solvent isotopic effect, the quenching rate constants of 1 O 2 by H 2 O ( k H 2 O ) and D 2 O ( k D 2 O ) were 2.5 × 10 5 and 1.6 × 10 4 M –1 s –1 , respectively. , In other words, the 1 O 2 -induced reactions were approximately 15.6 times slower in pure D 2 O than in pure H 2 O. As such, the degradation rate constant of SMX by 1 O 2 in solution containing D 2 O ( k obs, H 2 O, D 2 O ) can be calculated according to eq …”

Section: Resultsmentioning

confidence: 99%

Sulfur Vacancies in Pyrite Trigger the Path to Nonradical Singlet Oxygen and Spontaneous Sulfamethoxazole Degradation: Unveiling the Hidden Potential in Sediments

Zhu,

Wang,

Sun

et al. 2024

Environ. Sci. Technol.

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Pharmaceutical residues in sediments are concerning as ubiquitous emerging contaminants. Pyrite is the most abundant sulfide minerals in the estuarine and coastal sediments, making it a major sink for pharmaceutical pollutants such as sulfamethoxazole (SMX). However, research on the adsorption and redox behaviors of SMX on the pyrite surface is limited. Here, we investigated the impact of the nonphotochemical process of pyrite on the fate of coexisting SMX. Remarkably, sulfur vacancies (SVs) on pyrite promoted the generation of nonradical species (hydrogen peroxide, H 2 O 2 and singlet oxygen, 1 O 2 ), thereby exhibiting prominent SMX degradation performance under darkness. Nonradical 1 O 2 contributed approximately 73.1% of the total SMX degradation. The SVs with high surrounding electron density showed an advanced affinity for adsorbing O 2 and then initiated redox reactions in the sediment electron-storing geobattery pyrite, resulting in the extensive generation of H 2 O 2 through a two-electron oxygen reduction pathway. Surface Fe(III) (hydro)oxides on pyrite facilitated the decomposition of H 2 O 2 to 1 O 2 generation. Distinct nonradical products were observed in all investigated estuarine and coastal samples with the concentrations of H 2 O 2 ranging from 1.96 to 2.94 μM, while the concentrations of 1 O 2 ranged from 4.63 × 10 −15 to 8.93 × 10 −15 M. This dark-redox pathway outperformed traditional photochemical routes for pollutant degradation, broadening the possibilities for nonradical species use in estuarine and coastal sediments. Our study highlighted the SV-triggered process as a ubiquitous yet previously overlooked source of nonradical species, which offered fresh insights into geochemical processes and the dynamics of pollutants in regions of frequent redox oscillations and sulfur-rich sediments.

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Section: Resultsmentioning

confidence: 99%

Sulfur Vacancies in Pyrite Trigger the Path to Nonradical Singlet Oxygen and Spontaneous Sulfamethoxazole Degradation: Unveiling the Hidden Potential in Sediments

Zhu,

Wang,

Sun

et al. 2024

Environ. Sci. Technol.

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“…This study provides a novel and in-depth understanding of Co-based single-atom catalysts with dual reactive sites in PMS-AOPs for organic purification. Inspired by this work, Fe-NC configurations combined with FeN 4 sites and iron clusters were also prepared using a similar pyrolysis method, which also showed excellent refractory organic compound oxidation efficiency, even under high salinity, high humic acid content, and in a wide pH range (Figure D). Notably, the 1 O 2 directly generated by Fe-pyridinic N moieties was confirmed as the predominant reactive species (Figure E).…”

Section: Physicochemical Mechanism Of Pbas/pbds In the Fenton-like Pr...mentioning

confidence: 99%

Section: Physicochemical Mechanism Of Pbas/pbds In the Fenton-like Pr...mentioning

confidence: 99%

“…Prussian blue analogues (PBAs), as metal–organic frameworks (MOFs) constructed via octahedral [M 1 (CN) 6 ] 3– groups bridged by M 2 ions, have been widely used in energy, catalysis, , biomedicine, and environmental applications , owing to their ordered pore structure, large surface area, tunability, and environmental friendliness. − Generally, two metal sites exist in the octahedral sites linked by cyanide chains. Recently, various strategies have been developed to fabricate PBAs, such as coprecipitation, aerogel deposition, and thermal decomposition.…”

Section: Introductionmentioning

confidence: 99%

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Prussian Blue Analogues and Their Derivatives: From Elaborate Microstructure Design to Boosted Fenton-Like Application

Zhang,

Xia

et al. 2024

Acc. Mater. Res.

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Metrics & MoreArticle Recommendations CONSPECTUS: Heterogeneous Fenton-like reaction is a promising process for refractory wastewater treatment. Among the various heterogeneous Fenton-like catalysts, Prussian blue (PB) and Prussian blue analogues (PBAs) show great potential for hydrogen peroxide and persulfate activation owing to their low toxicity, simple preparation, and high activity. To further improve the catalytic activity of PBAs and their derivatives (PBDs), many efforts have been made to overcome the instability of the crystal structure and develop feasible methodologies to prepare PBAs/PBDs with diverse morphologies and compositions. In this Account, our recent achievements on novel synthetic strategies to obtain PBAs/PBDs with controlled morphologies, geometric sites, and electronic structures were systematically summarized. The physicochemical properties of the PBAs/PBDs and their contribution to the catalytic reaction in the advanced oxidation processes (AOPs) were also discussed. First, we focus on developing a novel synthesis technology (such as "copolymer-comorphology" conception) of PBAs with controllable morphology. By regulating the chelating agents, surfactants, metal ions, and preparation conditions and constructing a heterojunction, the stability of PBAs/PBDs was significantly improved to overcome their instability during redox reaction. Notably, to inherit the characteristics of PBAs, a topological transformation strategy was applied to fabricate metal oxides with morphologies similar to those of PBAs through thermal calcination under an aerobic atmosphere. Subsequently, this strategy has been extensively applied to prepare single-atom catalysts, metal nitrides, and zerovalent metals via thermal treatment under inert/reducing atmospheres. These novel strategies provide guidance for devising controllable PBAs/PBDs materials with superior activity and stability during cycling tests not only in Fenton-like reactions but also in other catalytic systems. In addition to the physicochemical property optimization, the relationship between the deliberately designed electronic structure and the catalytic activity of PBAs/PBDs was first explored in depth using 57 Fe Mossbauer spectroscopy. Moreover, benefiting from these efficient techniques and conscientious explorations, our research not only elucidated the important descriptors for the intrinsic oxidation pathways but also revealed the significant effect of external energy (ultraviolet and visible light) on the catalytic pathways in PBAs/PBDs-dominant Fenton-like systems. These findings provide a novel inspiration for further application of additional energy. Finally, the recent challenges and development prospects of PBAs/PBDs in AOPs are comprehensively discussed. Overall, this Account provides comprehensive insights into PBAs/PBDs fabrication strategies, physicochemical properties, local electronic structures, and the intrinsic correlation between these characteristics and catalytic mechanisms using advanced analysis techniques and paves the way...

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“…Two typical types of oxidation processes as radical and nonradical processes were reported in the Fenton-like reaction. − Hydroxyl radicals ( • OH) are usually the primary reactive oxygen species (ROS) with H 2 O 2 as the oxidant . In recent years, singlet oxygen ( 1 O 2 ) as a nonradical ROS has attracted more attention because of properties such as the excellent catalytic activity in high-salinity wastewater treatment, long lifetime, moderate oxidation potential, and selectively oxidizing capacity for electron-rich organic contaminants .…”

Section: Introductionmentioning

confidence: 99%

Singlet Oxygen Formation Mechanism for the H₂O₂-Based Fenton-like Reaction Catalyzed by the Carbon Nitride Homojunction

Jiang,

Meng,

Nan

2024

Inorg. Chem.

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The singlet oxygen ( 1 O 2 ) oxidation process activated by metal-free catalysts has recently attracted considerable attention for organic pollutant degradation; however, the 1 O 2 formation remains controversial. Simultaneously, the catalytic activity of the metal-free catalyst limits the practical application. In this study, carbon nitride (HCCN) containing an intramolecular homojunction, a kind of metal-free catalyst, exhibits excellent activity compared to g-C 3 N 4 (CN) and crystalline carbon nitride (HCN) for tetracycline hydrochloride degradation through the H 2 O 2 -based Fenton-like reaction. The rate constant for HCCN increased about 16.1 and 8.9 times than that of CN and HCN, respectively. The activity of HCCN was enhanced, and the dominant reactive oxygen species (ROS) changed from hydroxyl radicals ( • OH) to 1 O 2 with an increase in pH from 4.5 to 11.5. A novel formation pathway of 1 O 2 was revealed. This result is different from the normal reference, in which • OH is always the primary ROS in the H 2 O 2 -based Fenton-like reaction. This study may provide a possible strategy for the investigation on the nonradical oxidation process in the Fenton-like reaction.

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Mechanical insight into direct singlet oxygen generation pathway: Pivotal role of FeN4 sites and selective organic contaminants removal

Cited by 30 publications

References 60 publications

Sulfur Vacancies in Pyrite Trigger the Path to Nonradical Singlet Oxygen and Spontaneous Sulfamethoxazole Degradation: Unveiling the Hidden Potential in Sediments

Sulfur Vacancies in Pyrite Trigger the Path to Nonradical Singlet Oxygen and Spontaneous Sulfamethoxazole Degradation: Unveiling the Hidden Potential in Sediments

Prussian Blue Analogues and Their Derivatives: From Elaborate Microstructure Design to Boosted Fenton-Like Application

Singlet Oxygen Formation Mechanism for the H₂O₂-Based Fenton-like Reaction Catalyzed by the Carbon Nitride Homojunction

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Mechanical insight into direct singlet oxygen generation pathway: Pivotal role of FeN4 sites and selective organic contaminants removal

Cited by 30 publications

References 60 publications

Sulfur Vacancies in Pyrite Trigger the Path to Nonradical Singlet Oxygen and Spontaneous Sulfamethoxazole Degradation: Unveiling the Hidden Potential in Sediments

Sulfur Vacancies in Pyrite Trigger the Path to Nonradical Singlet Oxygen and Spontaneous Sulfamethoxazole Degradation: Unveiling the Hidden Potential in Sediments

Prussian Blue Analogues and Their Derivatives: From Elaborate Microstructure Design to Boosted Fenton-Like Application

Singlet Oxygen Formation Mechanism for the H2O2-Based Fenton-like Reaction Catalyzed by the Carbon Nitride Homojunction

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Singlet Oxygen Formation Mechanism for the H₂O₂-Based Fenton-like Reaction Catalyzed by the Carbon Nitride Homojunction