Reactive halogen radicals in saline water promote photochemically-assisted formation of manganese oxide nanosheets

Gao, Zhenwei; Skurie, Charlie; Jun, Young‐Shin

doi:10.1039/d2en00410k

Cited by 6 publications

(19 citation statements)

References 48 publications

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“…Our earlier work found that compared with O 2 •– and ROO • , • OH contributed much less to Mn oxidation in our systems. ,, H 2 O 2 was regarded as a reductant for Mn oxide solids, so we did not expect that it played a direct role in Mn oxidation. Nico et al (2002) reported Mn oxidation by O 2 •– and 1 O 2 from photolysis of humic substances; however, 1 O 2 oxidized Mn 2+ to Mn(III) but not to Mn(IV) oxide solids, and only 4% of the formed Mn(III) came from 1 O 2 , while the other 96% came from O 2 •– .…”

Section: Resultsmentioning

confidence: 60%

“…During the photolysis of nitrite, ROS, including O 2 •– and • OH, can also be generated . In the previous studies, , we observed the facilitated oxidation of Mn 2+ by O 2 •– during nitrate photolysis, and explained that nitrite was an intermediate for forming O 2 •– . As illustrated in Figure S5a, the possible generation of nitrite during photolysis of PS-NH 2 could provide a potential mechanism that explains why more Mn 2+ oxidation by O 2 •– was observed from 100 nm PS-NH 2 than from PS-COOH and PS-bare.…”

Section: Resultsmentioning

confidence: 99%

“…•− and ROO • , • OH contributed much less to Mn oxidation in our systems. 37,38,57 H 2 O 2 was regarded as a reductant for Mn oxide solids, 58 so we did not expect that it played a direct role in Mn oxidation. Nico et al (2002) reported Mn oxidation by O 2…”

Section: •−mentioning

confidence: 99%

“…•− and • OH, can also be generated. 63 In the previous studies, 37,57 we observed the facilitated oxidation of Mn 2+ by O 2…”

Section: •−mentioning

confidence: 99%

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Oxidative Roles of Polystyrene-Based Nanoplastics in Inducing Manganese Oxide Formation under Light Illumination

et al. 2022

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Every year, large quantities of plastics are produced and used for diverse applications, growing concerns about the waste management of plastics and their release into the environment. Plastic debris can break down into millions of pieces that adversely affect natural organisms. In particular, the photolysis of micro/nanoplastics can generate reactive oxygen species (ROS). However, their oxidative roles in initiating redox chemical reactions with heavy and transition metals have received little attention. In this study, we investigated whether the photolysis of polystyrene (PS) nanoplastics can induce the oxidation of Mn2+(aq) to Mn oxide solids. We found that PS nanoplastics not only produced peroxyl radicals (ROO•) and superoxide radicals (O2 •–) by photolysis, which both play a role in unexpected Mn oxidation, but also served as a substrate for facilitating the heterogeneous nucleation and growth of Mn oxide solids and controlling the formation rate and crystalline phases of Mn oxide solids. These findings help us to elucidate the oxidative roles of nanoplastics in the oxidation of redox-active metal ions. The production of ROS from nanoplastics in the presence of light can endanger marine life and human health, and affect the mobility of the nanoplastics in the environment via redox reactions, which in turn may negatively impact their environmental remediation.

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Section: Resultsmentioning

confidence: 60%

Section: Resultsmentioning

confidence: 99%

Section: •−mentioning

confidence: 99%

“…•− and • OH, can also be generated. 63 In the previous studies, 37,57 we observed the facilitated oxidation of Mn 2+ by O 2…”

Section: •−mentioning

confidence: 99%

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Oxidative Roles of Polystyrene-Based Nanoplastics in Inducing Manganese Oxide Formation under Light Illumination

et al. 2022

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“…The Mn 4+ oxide formation rate was comparable to or even higher than biologically mediated Mn 4+ oxide formation. In the presence of halide ions, such as bromide and chloride, the oxidation of Mn 2+ (aq) into Mn 4+ was facilitated by newly formed reactive halogen species and promoted δ-MnO 2 formation. , These findings bring to our attention the importance of the photochemically-assisted abiotic pathway (e.g., via the generation of reactive radical species) for redox-active metal oxidation and formation of oxide nanoparticle formation in natural and engineered systems.…”

Section: Theme 3: Dissolution Nucleation and Growthmentioning

confidence: 99%

Oxide– and Silicate–Water Interfaces and Their Roles in Technology and the Environment

et al. 2023

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Interfacial reactions drive all elemental cycling on Earth and play pivotal roles in human activities such as agriculture, water purification, energy production and storage, environmental contaminant remediation, and nuclear waste repository management. The onset of the 21st century marked the beginning of a more detailed understanding of mineral aqueous interfaces enabled by advances in techniques that use tunable high-flux focused ultrafast laser and X-ray sources to provide near-atomic measurement resolution, as well as by nanofabrication approaches that enable transmission electron microscopy in a liquid cell. This leap into atomic-and nanometer-scale measurements has uncovered scale-dependent phenomena whose reaction thermodynamics, kinetics, and pathways deviate from previous observations made on larger systems. A second key advance is new experimental evidence for what scientists hypothesized but could not test previously, namely, interfacial chemical reactions are frequently driven by "anomalies" or "non-idealities" such as defects, nanoconfinement, and other nontypical chemical structures. Third, progress in computational chemistry has yielded new insights that allow a move beyond simple schematics, leading to a molecular model of these complex interfaces. In combination with surfacesensitive measurements, we have gained knowledge of the interfacial structure and dynamics, including the underlying solid surface and the immediately adjacent water and aqueous ions, enabling a better definition of what constitutes the oxide− and silicate−water interfaces. This critical review discusses how science progresses from understanding ideal solid−water interfaces to more realistic systems, focusing on accomplishments in the last 20 years and identifying challenges and future opportunities for the community to address. We anticipate that the next 20 years will focus on understanding and predicting dynamic transient and reactive structures over greater spatial and temporal ranges as well as systems of greater structural and chemical complexity. Closer collaborations of theoretical and experimental experts across disciplines will continue to be critical to achieving this great aspiration.

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Photodegradation of halogenated organic pollutants in wastewater: A review

Huang,

Fang,

et al. 2025

Journal of Industrial and Engineering Chemistry

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Reactive halogen radicals in saline water promote photochemically-assisted formation of manganese oxide nanosheets

Abstract: Halide ions are naturally abundant in oceans and estuaries. Large amounts of highly saline efflux are also generated and discharged to surface water from desalination processes and from unconventional oil...

Cited by 6 publications

References 48 publications

Oxidative Roles of Polystyrene-Based Nanoplastics in Inducing Manganese Oxide Formation under Light Illumination

Oxidative Roles of Polystyrene-Based Nanoplastics in Inducing Manganese Oxide Formation under Light Illumination

Oxide– and Silicate–Water Interfaces and Their Roles in Technology and the Environment

Photodegradation of halogenated organic pollutants in wastewater: A review

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