Manganese oxide integrated catalytic ceramic membrane for degradation of organic pollutants using sulfate radicals

Hong Wu, Xinyuan Xu, Lei Shi, Yu Yin, Lai-chang Zhang, Zhentao Wu, Xiaoguang Duan, Shaobin Wang, Hongqi Sun

Research output: Contribution to journalArticle

Abstract

Membrane separation and advanced oxidation processes (AOPs) have been respectively demonstrated to be effective for a variety of water and/or wastewater treatments. Innovative integration of membrane with catalytic oxidation is thus expected to be more competing for more versatile applications. In this study, ceramic membranes (CMs) integrated with manganese oxide (MnO2) were designed and fabricated via a simple one-step ball-milling method with a high temperature sintering. Functional membranes with different loadings of MnO2 (1.67%, 3.33% and 6.67% of the total membrane mass) were then fabricated. The micro-structures and compositions of the catalytic membranes were investigated by a number of advanced characterisations. It was found that the MnO2 nanocatalysts (10–20 nm) were distributed uniformly around the Al2O3 particles (500 nm) of the membrane basal material, and can provide a large amount of active sites for the peroxymonosulfate (PMS) activation which can be facilitated within the pores of the catalytic membrane. The catalytic degradation of 4-hydroxylbenzoic acid (HBA), which is induced by the sulfate radicals via PMS activation, was investigated in a cross-flow membrane unit. The degradation efficiency slightly increased with a higher MnO2 loading. Moreover, even with the lowest loading of MnO2 (1.67%), the effectiveness of HBA degradation was still prominent, shown by that a 98.9% HBA degradation was achieved at the permeated side within 30 min when the initial HBA concentration was 80 ppm. The stability and leaching tests revealed a good stability of the catalytic membrane even after the 6th run. Electron paramagnetic resonance (EPR) and quenching tests were used to investigate the mechanism of PMS activation and HBA degradation. Both sulfate radicals (SO4˙−) and hydroxyl radicals (˙OH) were generated in the catalytic membrane process. Moreover, the contribution from non-radical process was also observed. This study provides a novel strategy for preparing a ceramic membrane with the function of catalytic degradation of organic pollutants, as well as outlining into future integration of separation and AOPs.
Original languageEnglish
Article number115110
JournalWater Research
Volume167
Early online date24 Sep 2019
DOIs
Publication statusPublished - 15 Dec 2019

Fingerprint

Ceramic membranes
Manganese oxide
Organic pollutants
manganese oxide
organic pollutant
ceramics
sulfate
membrane
Membranes
Degradation
degradation
Acids
acid
Chemical activation
oxidation
Sulfates
Oxidation
Catalytic oxidation
Ball milling
Wastewater treatment

Bibliographical note

© 2019, Elsevier. Licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/

Keywords

  • Manganese oxides
  • Catalytic membrane
  • Sulfate radicals
  • 4-Hydroxylbenzoic acid (HBA); AOPs

Cite this

Wu, Hong ; Xu, Xinyuan ; Shi, Lei ; Yin, Yu ; Zhang, Lai-chang ; Wu, Zhentao ; Duan, Xiaoguang ; Wang, Shaobin ; Sun, Hongqi. / Manganese oxide integrated catalytic ceramic membrane for degradation of organic pollutants using sulfate radicals. In: Water Research. 2019 ; Vol. 167.
@article{0438be756eda46e5a712640115c690a2,
title = "Manganese oxide integrated catalytic ceramic membrane for degradation of organic pollutants using sulfate radicals",
abstract = "Membrane separation and advanced oxidation processes (AOPs) have been respectively demonstrated to be effective for a variety of water and/or wastewater treatments. Innovative integration of membrane with catalytic oxidation is thus expected to be more competing for more versatile applications. In this study, ceramic membranes (CMs) integrated with manganese oxide (MnO2) were designed and fabricated via a simple one-step ball-milling method with a high temperature sintering. Functional membranes with different loadings of MnO2 (1.67{\%}, 3.33{\%} and 6.67{\%} of the total membrane mass) were then fabricated. The micro-structures and compositions of the catalytic membranes were investigated by a number of advanced characterisations. It was found that the MnO2 nanocatalysts (10–20 nm) were distributed uniformly around the Al2O3 particles (500 nm) of the membrane basal material, and can provide a large amount of active sites for the peroxymonosulfate (PMS) activation which can be facilitated within the pores of the catalytic membrane. The catalytic degradation of 4-hydroxylbenzoic acid (HBA), which is induced by the sulfate radicals via PMS activation, was investigated in a cross-flow membrane unit. The degradation efficiency slightly increased with a higher MnO2 loading. Moreover, even with the lowest loading of MnO2 (1.67{\%}), the effectiveness of HBA degradation was still prominent, shown by that a 98.9{\%} HBA degradation was achieved at the permeated side within 30 min when the initial HBA concentration was 80 ppm. The stability and leaching tests revealed a good stability of the catalytic membrane even after the 6th run. Electron paramagnetic resonance (EPR) and quenching tests were used to investigate the mechanism of PMS activation and HBA degradation. Both sulfate radicals (SO4˙−) and hydroxyl radicals (˙OH) were generated in the catalytic membrane process. Moreover, the contribution from non-radical process was also observed. This study provides a novel strategy for preparing a ceramic membrane with the function of catalytic degradation of organic pollutants, as well as outlining into future integration of separation and AOPs.",
keywords = "Manganese oxides, Catalytic membrane, Sulfate radicals, 4-Hydroxylbenzoic acid (HBA); AOPs",
author = "Hong Wu and Xinyuan Xu and Lei Shi and Yu Yin and Lai-chang Zhang and Zhentao Wu and Xiaoguang Duan and Shaobin Wang and Hongqi Sun",
note = "{\circledC} 2019, Elsevier. Licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/",
year = "2019",
month = "12",
day = "15",
doi = "10.1016/j.watres.2019.115110",
language = "English",
volume = "167",
journal = "Water Research",
issn = "0043-1354",
publisher = "Elsevier",

}

Manganese oxide integrated catalytic ceramic membrane for degradation of organic pollutants using sulfate radicals. / Wu, Hong; Xu, Xinyuan; Shi, Lei; Yin, Yu; Zhang, Lai-chang; Wu, Zhentao; Duan, Xiaoguang; Wang, Shaobin; Sun, Hongqi.

In: Water Research, Vol. 167, 115110, 15.12.2019.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Manganese oxide integrated catalytic ceramic membrane for degradation of organic pollutants using sulfate radicals

AU - Wu, Hong

AU - Xu, Xinyuan

AU - Shi, Lei

AU - Yin, Yu

AU - Zhang, Lai-chang

AU - Wu, Zhentao

AU - Duan, Xiaoguang

AU - Wang, Shaobin

AU - Sun, Hongqi

N1 - © 2019, Elsevier. Licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/

PY - 2019/12/15

Y1 - 2019/12/15

N2 - Membrane separation and advanced oxidation processes (AOPs) have been respectively demonstrated to be effective for a variety of water and/or wastewater treatments. Innovative integration of membrane with catalytic oxidation is thus expected to be more competing for more versatile applications. In this study, ceramic membranes (CMs) integrated with manganese oxide (MnO2) were designed and fabricated via a simple one-step ball-milling method with a high temperature sintering. Functional membranes with different loadings of MnO2 (1.67%, 3.33% and 6.67% of the total membrane mass) were then fabricated. The micro-structures and compositions of the catalytic membranes were investigated by a number of advanced characterisations. It was found that the MnO2 nanocatalysts (10–20 nm) were distributed uniformly around the Al2O3 particles (500 nm) of the membrane basal material, and can provide a large amount of active sites for the peroxymonosulfate (PMS) activation which can be facilitated within the pores of the catalytic membrane. The catalytic degradation of 4-hydroxylbenzoic acid (HBA), which is induced by the sulfate radicals via PMS activation, was investigated in a cross-flow membrane unit. The degradation efficiency slightly increased with a higher MnO2 loading. Moreover, even with the lowest loading of MnO2 (1.67%), the effectiveness of HBA degradation was still prominent, shown by that a 98.9% HBA degradation was achieved at the permeated side within 30 min when the initial HBA concentration was 80 ppm. The stability and leaching tests revealed a good stability of the catalytic membrane even after the 6th run. Electron paramagnetic resonance (EPR) and quenching tests were used to investigate the mechanism of PMS activation and HBA degradation. Both sulfate radicals (SO4˙−) and hydroxyl radicals (˙OH) were generated in the catalytic membrane process. Moreover, the contribution from non-radical process was also observed. This study provides a novel strategy for preparing a ceramic membrane with the function of catalytic degradation of organic pollutants, as well as outlining into future integration of separation and AOPs.

AB - Membrane separation and advanced oxidation processes (AOPs) have been respectively demonstrated to be effective for a variety of water and/or wastewater treatments. Innovative integration of membrane with catalytic oxidation is thus expected to be more competing for more versatile applications. In this study, ceramic membranes (CMs) integrated with manganese oxide (MnO2) were designed and fabricated via a simple one-step ball-milling method with a high temperature sintering. Functional membranes with different loadings of MnO2 (1.67%, 3.33% and 6.67% of the total membrane mass) were then fabricated. The micro-structures and compositions of the catalytic membranes were investigated by a number of advanced characterisations. It was found that the MnO2 nanocatalysts (10–20 nm) were distributed uniformly around the Al2O3 particles (500 nm) of the membrane basal material, and can provide a large amount of active sites for the peroxymonosulfate (PMS) activation which can be facilitated within the pores of the catalytic membrane. The catalytic degradation of 4-hydroxylbenzoic acid (HBA), which is induced by the sulfate radicals via PMS activation, was investigated in a cross-flow membrane unit. The degradation efficiency slightly increased with a higher MnO2 loading. Moreover, even with the lowest loading of MnO2 (1.67%), the effectiveness of HBA degradation was still prominent, shown by that a 98.9% HBA degradation was achieved at the permeated side within 30 min when the initial HBA concentration was 80 ppm. The stability and leaching tests revealed a good stability of the catalytic membrane even after the 6th run. Electron paramagnetic resonance (EPR) and quenching tests were used to investigate the mechanism of PMS activation and HBA degradation. Both sulfate radicals (SO4˙−) and hydroxyl radicals (˙OH) were generated in the catalytic membrane process. Moreover, the contribution from non-radical process was also observed. This study provides a novel strategy for preparing a ceramic membrane with the function of catalytic degradation of organic pollutants, as well as outlining into future integration of separation and AOPs.

KW - Manganese oxides

KW - Catalytic membrane

KW - Sulfate radicals

KW - 4-Hydroxylbenzoic acid (HBA); AOPs

UR - https://linkinghub.elsevier.com/retrieve/pii/S004313541930884X

U2 - 10.1016/j.watres.2019.115110

DO - 10.1016/j.watres.2019.115110

M3 - Article

VL - 167

JO - Water Research

JF - Water Research

SN - 0043-1354

M1 - 115110

ER -