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Peroxymonosulfate activation with an α-MnO2/Mn2O3/Mn3O4 hybrid system: parametric optimization and oxidative degradation of organic dye

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Seema Singh at GIEE, National Taiwan University, Taipei, Taiwan
Seema Singh
  • GIEE, National Taiwan University, Taipei, Taiwan
Ritesh Patidar at Indian Institute of Technology Roorkee
Ritesh Patidar
Vimal Chandra Srivastava at Indian Institute of Technology Roorkee
Vimal Chandra Srivastava
Qicheng Qiao
Qicheng Qiao
Qicheng Qiao
  • This person is not on ResearchGate, or hasn't claimed this research yet.
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Abstract and Figures

The present study proposed the synthesis of low-toxicity and eco-friendly spherically shaped manganese oxides (α-MnO2, Mn2O3, and Mn3O4) by using the chemical precipitation method. The unique variable oxidation states and different structural diversity of manganese-based materials have a strong effect on fast electron transfer reactions. XRD, SEM, and BET analyses were used to confirm the structure morphology, higher surface area, and excellent porosity. The catalytic activity of as-prepared manganese oxides (MnOx) was investigated for the rhodamine B (RhB) organic pollutant with peroxymonosulfate (PMS) activation under the condition of control pH. In acidic conditions (pH = 3), complete RhB degradation and 90% total organic carbon (TOC) reduction were attained in 60 min. The effects of operating parameters such as solution pH, PMS loading, catalyst dosage, and dye concentration on RhB removal reduction were also tested. The different oxidation states of MnOx promote the oxidative–reductive reaction under acidic conditions and enhance the SO4•−/•OH radical formation during the treatment, whereas the higher surface area offers sufficient absorption sites for interaction of the catalyst with pollutants. A scavenger experiment was used to investigate the generation of more reactive species that participate in dye degradation. The effect of inorganic anions on divalent metal ions that genuinely occur in water bodies was also studied. Additionally, separation and mass analysis were used to investigate the RhB dye degradation mechanism at optimum conditions based on the intermediate’s identification. Repeatability tests confirmed that MnOx showed superb catalytic performance on its removal trend.
a XRD pattern of manganese oxides and b BET surface area analysis; c, d SEM images and e EDX image and inset table of elements; f, g mapping and h mixed mapping
a XRD pattern of manganese oxides and b BET surface area analysis; c, d SEM images and e EDX image and inset table of elements; f, g mapping and h mixed mapping
… 
a Comparison of RhB removal with different catalytic systems. b Effect of scavengers on RhB degradation by the MnOx/PMS system ([RhB]o = 10 mg L⁻¹, [MnOx] = 0.06 g L⁻¹, [PMS]o = 0.5 mM, pH = 5, T = 25 °C, [MeOH]/[t-BuOH]/[BQ]/[FFA] = 0.1 M). c Kinetics of the scavengers during RhB degradation
a Comparison of RhB removal with different catalytic systems. b Effect of scavengers on RhB degradation by the MnOx/PMS system ([RhB]o = 10 mg L⁻¹, [MnOx] = 0.06 g L⁻¹, [PMS]o = 0.5 mM, pH = 5, T = 25 °C, [MeOH]/[t-BuOH]/[BQ]/[FFA] = 0.1 M). c Kinetics of the scavengers during RhB degradation
… 
Effect of a solution pH on RhB degradation, b rate constants at different pH values, c TOC reduction and d zeta potential measurement at different pH values with MnOx ([RhB]o = 10 mg L⁻¹, [MnOx] = 0.06 g L⁻¹, [PMS]o = 0.5 mM, pH = 5, T = 25 °C); effect of different types of acids on e RhB decomposition and f TOC removal efficiency at pH 3 with the MnOx/PMS system ([RhB]o = 10 mg L⁻¹, [MnOx] = 0.06 g L⁻¹, [PMS]o = 0.5 mM, pH = 5, T = 25 °C)
Effect of a solution pH on RhB degradation, b rate constants at different pH values, c TOC reduction and d zeta potential measurement at different pH values with MnOx ([RhB]o = 10 mg L⁻¹, [MnOx] = 0.06 g L⁻¹, [PMS]o = 0.5 mM, pH = 5, T = 25 °C); effect of different types of acids on e RhB decomposition and f TOC removal efficiency at pH 3 with the MnOx/PMS system ([RhB]o = 10 mg L⁻¹, [MnOx] = 0.06 g L⁻¹, [PMS]o = 0.5 mM, pH = 5, T = 25 °C)
… 
Factors influencing RhB degradation with the MnOx/PMS system: a, b PMS dose, c, d catalyst dosage, and e, f initial RhB concentration at experimental conditions ([PMS]o = 0.5 mM (except a), catalyst dose = 0.06 g L⁻¹ (except c), [RhB]o = 10 mg L⁻¹ (except e), pH = 3 at temperature = 25 °C)
Factors influencing RhB degradation with the MnOx/PMS system: a, b PMS dose, c, d catalyst dosage, and e, f initial RhB concentration at experimental conditions ([PMS]o = 0.5 mM (except a), catalyst dose = 0.06 g L⁻¹ (except c), [RhB]o = 10 mg L⁻¹ (except e), pH = 3 at temperature = 25 °C)
… 
Effects of inorganic anions a HCO3⁻, b SO4²⁻, c Cl⁻, and d H2PO4⁻ on RhB dye degradation with the MnOx/PMS system at [RhB]o = 10 mg L⁻¹, [MnOx] = 0.06 g L⁻¹, [PMS]o = 0.5 mM, different salts (a [NaHCO3], b [Na2SO4], c [NaCl], d [NaH2PO4] = 0–10 mM), and pH = 3, e Ca²⁺ and f Mg²⁺
+3
Effects of inorganic anions a HCO3⁻, b SO4²⁻, c Cl⁻, and d H2PO4⁻ on RhB dye degradation with the MnOx/PMS system at [RhB]o = 10 mg L⁻¹, [MnOx] = 0.06 g L⁻¹, [PMS]o = 0.5 mM, different salts (a [NaHCO3], b [Na2SO4], c [NaCl], d [NaH2PO4] = 0–10 mM), and pH = 3, e Ca²⁺ and f Mg²⁺
… 
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Vol:.(1234567890)
Environmental Science and Pollution Research (2023) 30:76660–76674
https://doi.org/10.1007/s11356-023-27422-2
1 3
RESEARCH ARTICLE
Peroxymonosulfate activation withanα‑MnO2/Mn2O3/Mn3O4 hybrid
system: parametric optimization andoxidative degradation oforganic
dye
SeemaSingh1,2· RiteshPatidar3· VimalChandraSrivastava4· QichengQiao5· PraveenKumar6· AjaySingh1·
Shang‑LienLo2,7
Received: 2 August 2022 / Accepted: 28 April 2023 / Published online: 27 May 2023
© The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2023
Abstract
The present study proposed the synthesis of low-toxicity and eco-friendly spherically shaped manganese oxides (α-MnO2,
Mn2O3, and Mn3O4) by using the chemical precipitation method. The unique variable oxidation states and different struc-
tural diversity of manganese-based materials have a strong effect on fast electron transfer reactions. XRD, SEM, and BET
analyses were used to confirm the structure morphology, higher surface area, and excellent porosity. The catalytic activity of
as-prepared manganese oxides (MnOx) was investigated for the rhodamine B (RhB) organic pollutant with peroxymonosul-
fate (PMS) activation under the condition of control pH. In acidic conditions (pH = 3), complete RhB degradation and 90%
total organic carbon (TOC) reduction were attained in 60 min. The effects of operating parameters such as solution pH, PMS
loading, catalyst dosage, and dye concentration on RhB removal reduction were also tested. The different oxidation states of
MnOx promote the oxidative–reductive reaction under acidic conditions and enhance the SO4•−/•OH radical formation during
the treatment, whereas the higher surface area offers sufficient absorption sites for interaction of the catalyst with pollutants.
A scavenger experiment was used to investigate the generation of more reactive species that participate in dye degradation.
The effect of inorganic anions on divalent metal ions that genuinely occur in water bodies was also studied. Additionally,
separation and mass analysis were used to investigate the RhB dye degradation mechanism at optimum conditions based
on the intermediate’s identification. Repeatability tests confirmed that MnOx showed superb catalytic performance on its
removal trend.
Keywords Acidic pH· Manganese oxides· Rhodamine B degradation· Repeatability
Responsible Editor: Ricardo A. Torres-Palma
* Shang-Lien Lo
sllo@ntu.edu.tw
1 School ofApplied & Life Sciences, Uttaranchal University,
Dehradun, Uttarakhand248007, India
2 Graduate Institute ofEnvironmental Engineering,
National Taiwan University, 71 Chou-Shan Rd., Taipei,
Taiwan,RepublicofChina
3 Department ofPetroleum Engineering, Rajasthan Technical
University, Kota, Rajasthan324010, India
4 Department ofChemical Engineering, Indian Institute
ofTechnology, Roorkee, Uttarakhand247667, India
5 School ofEnvironment andBiological Engineering,
Nantong College ofScience andTechnology, NantongCity,
Jiangsu226007, People’sRepublicofChina
6 Faculty ofChemistry andChemical Technology, University
ofLjubljana, 1000Ljubljana, Slovenia
7 Water Innovation, Low Carbon andEnvironmental
Sustainability Research Center, National Taiwan University,
Taipei10617, Taiwan
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
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