Doping strategy-tuned non-radical pathway on manganese oxide for catalytic degradation of parabens

Wang, Xiaopei; Bi, Xiuru; Yao, Nan; Elmacı, Gökhan; Ertürk, Ali; Lv, Qianru; Zhao, Ping; Meng, Xu

doi:10.1016/j.cej.2022.136180

Cited by 68 publications

(7 citation statements)

References 53 publications

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“…After spectral decomposition, two chemical states of Mn, i.e., Mn 3+ and Mn 4+ , could be distinguished, and the ratios of them were 54.1 and 45.9%, which is in accordance with other reported δ-MnO 2 because of K + ions inside of tunnel to support the layered structure. − The coexistence of Mn 3+ and Mn 4+ species is favorable for PMS activation as it involves a charge transfer process. Moreover, the relatively high ratio of Mn 3+ is advantageous as an electron donor for PMS activation. , As to the O 1s spectrum (Figure c), three curves were fitted as lattice oxygen (Mn–O–Mn), adsorbed hydroxy (Mn–O–H), and O V s with the ratios of ∼57.0, 25.8, and 17.2%, respectively. Because of the preferred exposure of (001) facet of δ-MnO 2 , a high ratio of edge Mn atoms gave a lot of sites for the formation of Mn–O–H.…”

Section: Resultsmentioning

confidence: 99%

“…Moreover, the relatively high ratio of Mn 3+ is advantageous as an electron donor for PMS activation. 36,37 As to the O 1s spectrum (Figure 2c), three curves were fitted as lattice oxygen (Mn−O−Mn), adsorbed hydroxy (Mn−O−H), and O V s with the ratios of ∼57.0, 25.8, and 17.2%, respectively. Because of the preferred exposure of (001) facet of δ-MnO 2 , a high ratio of edge Mn atoms gave a lot of sites for the formation of Mn−O−H.…”

Section: Characterization Of 3d-mnsn-cfmentioning

confidence: 99%

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MnO₂ Nanosheet Nets on Carbon Fiber as Fixed Catalysts for a Highly Efficient, Nonradical Fenton-like Process in Wastewater Refractory Pollutant Treatment

Zhang

et al. 2023

ACS Appl. Nano Mater.

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The development of highly efficient fixed catalysts is a significant concern in practical wastewater treatment using the peroxymonosulfate (PMS)-based Fenton-like process. In this study, we successfully synthesized a three-dimensional (3D) δ-MnO 2 nanosheet (MNSN) net grown on a carbon-fiber (CF) sheet (3D-MNSN-CF) through a simple hydrothermal strategy. This novel catalyst demonstrated exceptional efficiency and stability in activating PMS for degrading refractory organics. The 3D-MNSN-CF catalyst was composed of wrinkled, ultrathin δ-MnO 2 nanosheets (∼4.3 nm) grown on CF, forming a uniform 3D net structure with a covering thickness of approximately 7.6 μm (mass ratio ∼ 2.17%). This unique morphology provided a fixed Mn-based catalyst with a highly exposed (001) facet, intrinsic Mn 3+ /Mn 4+ redox pair, and a high ratio of oxygen vacancies (O V s). These features enabled the 3D-MNSN-CF/PMS system to exhibit a remarkable removal ratio of approximately 100% for tetracycline hydrochloride (TC) degradation. The system also showed a high rate constant (k value) of approximately 0.15 min −1 and a specific activity (ε) of 3.46 L min −1 g −1 based on the MnO 2 ratio, surpassing many reported Mn-based catalysts. Moreover, the 3D-MNSN-CF catalyst maintained excellent performance over a wide pH range from 2 to 11. Furthermore, we discovered that electron-rich oxygen-containing groups exhibited an inhibition effect by competing adsorption with PMS, hindering the generation of radicals. Additionally, the results indicated that singlet oxygen ( 1 O 2 ) was the main reactive species responsible for TC removal, while only a small amount of radicals contributed to the process. The catalyst's excellent performance was also demonstrated in treating various refractory organics and real wastewater, and it exhibited splendid stability for recycling use.

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Section: Resultsmentioning

confidence: 99%

Section: Characterization Of 3d-mnsn-cfmentioning

confidence: 99%

MnO₂ Nanosheet Nets on Carbon Fiber as Fixed Catalysts for a Highly Efficient, Nonradical Fenton-like Process in Wastewater Refractory Pollutant Treatment

Zhang

et al. 2023

ACS Appl. Nano Mater.

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“…In SR-AOPs, a free radical, such as SO 4 – • , could be formed through perdisulfate (PDS) or peroxymonosulfate (PMS) activation with heat, light, semiconductors, and heterogeneous catalyst. − Among these methods, heterogeneous catalyst activation has been largely applied because of its high performance, low energy demand, recycling efficiency, and low cost. Recently, OMS-2 consisting of two edge-sharing MnO 6 octahedra has received extensive attention.…”

Section: Introductionmentioning

confidence: 99%

Peroxymonosulfate Activation by Cu–OMS-2 Nanofibers for Efficient Degradation of N-Containing Heterocycles in Aquatic Solution

Chen,

Yang,

Cui

et al. 2023

Langmuir

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In this research, the degradation of different types of N-containing heterocycle (NHC) contaminants by Cu−OMS-2 via peroxymonosulfate (PMS) activation in an aqueous environment was investigated. First, the effects of different reaction parameters were optimized using benzotriazole (BTR) as the model contaminant, and the optimal reaction conditions were 8 mM PMS, 0.35 g/L Cu− OMS-2, and 30 °C. Nine different types of NHC contaminants were effectively degraded under these reaction conditions, and the degradation efficiencies and the mineralization rates of those NHCs were more than 68 and 46%, respectively. Moreover, the Cu−OMS-2/PMS process presented excellent performance at a wide pH ranging from 3.0 to 11.0 and in the presence of some representative anions (NO 3 − and SO 4 2−) and dissolved organic matter (fumaric acid). The inhibition sequence of anions on BTR removal during the Cu−OMS-2/PMS process was H 2 PO 4. It was also found that 74.5 and 71.3% BTR degradation rates were achieved in actual water bodies, such as tap water and Yellow River water, respectively. Besides, the Cu−OMS-2 heterogeneous catalyst had excellent stability and reusability, and the degradation rate of BTR was still at 77.0% after 5 cycles. Finally, electron paramagnetic resonance analysis and scavenging tests showed that 1 O 2 and SO 4 − • were the primary reactive oxygen species. Accordingly, Cu−OMS-2 nanomaterial was an efficient and sustainable heterogeneous catalyst to activate PMS for the decontamination of BTR in water remediation.

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“…[21][22][23] It has been applied in catalysis, adsorption, ion-exchange, battery and semiconductivity since OMS-2 has mild acid and basic properties, porosity, mixed valence of Mn species and rich surface oxygen vacancies. [24][25][26][27][28][29][30][31] In terms of wastewater treatment, dyes and As(III) in wastewater were usually removed via adsorption over MnO 2 with alpha phase. [32] Shi's group investigated adsorption performance of transition metal-doped OMS-2 on diclofenac in aqueous phase and Ce-doped OMS-2 could be an efficient adsorbent.…”

Section: Introductionmentioning

confidence: 99%

“…Cryptomelane‐type manganese oxide octahedral molecular sieve (OMS‐2), a type of MnO 2 with alpha crystal phase, is composed of MnO 6 unites in 2x2 tunnel structure [21–23] . It has been applied in catalysis, adsorption, ion‐exchange, battery and semiconductivity since OMS‐2 has mild acid and basic properties, porosity, mixed valence of Mn species and rich surface oxygen vacancies [24–31] . In terms of wastewater treatment, dyes and As(III) in wastewater were usually removed via adsorption over MnO 2 with alpha phase [32] .…”

Section: Introductionmentioning

confidence: 99%

Adsorption of Rutin from Aqueous Solution over an OMS‐2‐Modified ZrO₂ Nanocomposite

Wang

Chai

et al. 2022

ChemistrySelect

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Adsorption and purification of biological molecules with pharmacological functions over advanced adsorption materials are always a concern. In this work, manganese oxide octahedral molecular sieve (OMS‐2)‐modified ZrO2 nanocomposites (ZrO2‐OMS‐2) were fabricated and their adsorption performance towards rutin from aqueous solution was investigated. As‐obtained nanocomposites were fully characterized by N2 adsorption/desorption isothermal, ICP‐AES, XRD, SEM and TEM, which indicates that OMS‐2‐modification significantly promoted the textural properties of the nanocomposites. 10 mol% Mn amount for ZrO2‐OMS‐2 showed the optimal adsorption capacity for rutin due to the enhanced specific surface aera (104 m2/g) and better ZrO2 dispersion. The adsorption rate of 85 % was realized over 10 mg of the optimal adsorbent and the desorption rate could reach nearly 100 % in 0.2 % TFA/methanol solution. Moreover, the adsorbent could be reused for at least 3 times. The adsorption behavior was fitted the pseudo‐second‐order model and Freundlich model. Kinetic and thermodynamic studies suggested that an endothermic chemosorption from Lewis acid‐base paring on the surface of ZrO2‐OMS‐2 was responsible for the good adsorption. This work shows the positive effect of manganese oxide‐modification for ZrO2 during adsorption process and the potential of ZrO2‐based nanocomposites being adsorbents.

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Doping strategy-tuned non-radical pathway on manganese oxide for catalytic degradation of parabens

Cited by 68 publications

References 53 publications

MnO₂ Nanosheet Nets on Carbon Fiber as Fixed Catalysts for a Highly Efficient, Nonradical Fenton-like Process in Wastewater Refractory Pollutant Treatment

MnO₂ Nanosheet Nets on Carbon Fiber as Fixed Catalysts for a Highly Efficient, Nonradical Fenton-like Process in Wastewater Refractory Pollutant Treatment

Peroxymonosulfate Activation by Cu–OMS-2 Nanofibers for Efficient Degradation of N-Containing Heterocycles in Aquatic Solution

Adsorption of Rutin from Aqueous Solution over an OMS‐2‐Modified ZrO₂ Nanocomposite

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Doping strategy-tuned non-radical pathway on manganese oxide for catalytic degradation of parabens

Cited by 68 publications

References 53 publications

MnO2 Nanosheet Nets on Carbon Fiber as Fixed Catalysts for a Highly Efficient, Nonradical Fenton-like Process in Wastewater Refractory Pollutant Treatment

MnO2 Nanosheet Nets on Carbon Fiber as Fixed Catalysts for a Highly Efficient, Nonradical Fenton-like Process in Wastewater Refractory Pollutant Treatment

Peroxymonosulfate Activation by Cu–OMS-2 Nanofibers for Efficient Degradation of N-Containing Heterocycles in Aquatic Solution

Adsorption of Rutin from Aqueous Solution over an OMS‐2‐Modified ZrO2 Nanocomposite

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MnO₂ Nanosheet Nets on Carbon Fiber as Fixed Catalysts for a Highly Efficient, Nonradical Fenton-like Process in Wastewater Refractory Pollutant Treatment

MnO₂ Nanosheet Nets on Carbon Fiber as Fixed Catalysts for a Highly Efficient, Nonradical Fenton-like Process in Wastewater Refractory Pollutant Treatment

Adsorption of Rutin from Aqueous Solution over an OMS‐2‐Modified ZrO₂ Nanocomposite