Application of MnO  x -CeO  x /BC in electrocatalyzation-ozonation coupled treatment of landfill leachate

doi:10.19965/j.cnki.iwt.2025-0033

Abstract

Abstract:

The biochar catalyst loaded with MnO _x -CeO _x (MnO _x -CeO _x /BC) was prepared by crosslinking-carbonization method. The structure of the catalyst was characterized, and the mechanism and degradation effects of COD, UV₂₅₄ and TOC in the biochemical effluent of landfill leachate under the electrocatalytic-ozone coupling system were investigated. The synthesized MnO _x -CeO _x /BC catalyst exhibited abundant oxygen vacancy formation during the Ce⁴⁺ to Ce³⁺ transition. The Mn-Ce bimetallic synergy further facilitated efficient electron transfer, thereby significantly improved catalytic performance. Moreover, in contrast to the pristine BC support, the catalyst displayed a well-defined rod-like morphology with an enhanced specific surface area and a highly porous structure, which collectively provided ample active sites for efficient pollutant degradation. When the ozone concentration was 8.1 mg/L, the dosage of MnO _x -CeO _x /BC was 60 g/L, the current density was 20 mA/cm², and the initial pH was 7, MnO _x -CeO _x /BC exhibited the best catalytic degradation performance, with the removal rates of COD, UV₂₅₄, and TOC in the biochemical effluent of landfill leachate reaching 86.5%, 92.9%, and 80% within 60 min, respectively. After six consecutive experiments, the removal rates of COD and UV₂₅₄ by MnO _x -CeO _x /BC remained above 70% and 80%, respectively. Additionally, the free radical quenching experiments demonstrated that ·OH was the main active substance during the degradation process of landfill leachate.

Key words: catalytic ozonation, electrocatalysis, MnO _x -CeO _x, biocarbon, biological effluent from landfill leachate

摘要：

通过交联-碳化法制备了负载MnO _x -CeO _x 的生物炭催化剂（MnO _x -CeO _x /BC），对催化剂结构进行表征，并探究了在电催化-臭氧化耦合的体系下，该催化剂对垃圾渗滤液生化出水中COD、UV₂₅₄及TOC的降解效果以及作用机理。合成的MnO _x -CeO _x /BC催化剂在Ce⁴⁺转化为Ce³⁺过程中产生丰富的氧空位，同时Mn-Ce双金属协同效应促进了电子转移，显著提升催化活性。此外，与BC载体相比，该催化剂呈现独特的棒状形貌，具有更高的比表面积和丰富的孔隙结构，为污染物降解提供了充足的活性位点。在臭氧质量浓度为8.1 mg/L，MnO _x -CeO _x /BC投加量为60 g/L，电流密度为20 mA/cm²和初始pH为7时，MnO _x -CeO _x /BC具有最佳的催化降解性能，60 min内对垃圾渗滤液生化出水中的COD、UV₂₅₄、TOC去除率分别达到了86.5%、92.9%、80%。在经过6次连续实验后，MnO _x -CeO _x /BC对COD、UV₂₅₄的去除率分别保持在70%、80%以上。此外，自由基猝灭实验表明·OH是该工艺处理垃圾渗滤液过程中主要的活性物质。

关键词: 催化臭氧氧化, 电催化, MnO _x -CeO _x, 生物炭, 垃圾渗滤液生化出水

CLC Number:

X703.1

Shanshan YU, Fanrong ZHOU, Jun JIA, Fan PAN, Yunqing ZHU. Application of MnO _x -CeO _x /BC in electrocatalyzation-ozonation coupled treatment of landfill leachate[J]. Industrial Water Treatment, 2025, 45(12): 184-197.

余姗姗, 周凡嵘, 贾军, 潘凡, 朱云庆. MnO _x -CeO _x /BC在电催化-臭氧化耦合处理垃圾渗滤液中的应用[J]. 工业水处理, 2025, 45(12): 184-197.

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URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2025-0033

https://www.iwt.cn/EN/Y2025/V45/I12/184

Figures/Tables 19

Fig.1 Electrocatalytic-ozonation integrated reactor system

Table 1 Water quality index of ultrafiltration water of landfill leachate

项目

COD/

（mg⋅L^-1）

UV₂₅₄

TOC/

（mg⋅L^-1）

Fig.2 SEM（a-b）of BC and MnO _x -CeO _x /BC and EDS（c） of MnO _x -CeO _x /BC

Fig.3 XRD spectra of BC，MnO _x /BC，CeO _x /BC，MnO _x -CeO _x /BC（a）and MnO _x -CeO _x /BC at 500-900 ℃（b）

Fig.4 FTIR spectra of BC，MnO _x /BC，CeO _x /BC，MnO _x -CeO _x /BC（a）and MnO _x -CeO _x /BC at 500-900 ℃（b）

Fig.5 XPS full spectrum of MnO _x -CeO _x /BC（a） and XPS fine spectrum of C 1s（b），Mn 2p（c），Ce 3d（d）

Fig.6 N₂ adsorption-desorption isotherm（a） and pore size distribution curve（b） for different materials

Table 2 Specific surface area，average pore size，and total pore volume of the materials

样品	比表面积/（m²·g^-1）	平均孔径/nm	总孔容/（cm³·g^-1）
BC	22.05	7.20	0.052 7
MnO _x /BC	6.73	21.01	0.050 9
CeO _x /BC	7.86	17.37	0.050 0
MnO _x -CeO _x /BC	22.57	11.10	0.082 2

Fig.7 Effects of different materials on COD（a），UV₂₅₄（b）and TOC（c）removal rates，the pseudo-first-order reaction kinetics analysis of COD（d）and UV₂₅₄（e）

Fig.8 Effect of carbonization temperature on COD（a）and UV₂₅₄（b）and TOC（c）removal rates，the pseudo-first-order reaction kinetics analysis of COD（d）and UV₂₅₄（e）

Fig.9 Effect of ozone concentration on COD（a），UV₂₅₄（b） and TOC（c） removal，the pseudo-first-order reaction kinetics analysis of COD（d） and UV₂₅₄（e）

Fig.10 Effect of MnO _x -CeO _x /BC dosage on COD（a），UV₂₅₄（b）and TOC（c）removal，the pseudo-first-order reaction kinetics analysis of COD（d）and UV₂₅₄（e）

Fig.11 Effect of current density on COD（a），UV₂₅₄（b）and TOC（c）removal rates，the pseudo-first-order reaction kinetics analysis of COD（d）and UV₂₅₄（e）

Fig.12 Effect of initial pH on COD（a），UV₂₅₄（b） and TOC（c） removal，the pseudo-first-order reaction kinetics analysis of COD（d）and UV₂₅₄（e）

Fig.13 Effect of treatment process on COD（a），UV₂₅₄（b）and TOC（c）removal，and the pseudo-first-order reaction kinetics analysis of COD（d） and UV₂₅₄（e）

Fig.14 MnO _x -CeO _x /BC recycle for 6 times COD and UV₂₅₄ removal rate（a）and metal leaching concentration（b）

Table 3 Leaching concentrations of Mn and Ce metal ions in cycling experiments

循环次数	1	2	3	4	5	6
Mn/（mg·L^-1）	0.098 7	0.095 0	0.092 0	0.089 4	0.086 1	0.085 0
Ce/（mg·L^-1）	0.052 0	0.051 6	0.048 2	0.047 2	0.045 2	0.041 6

Fig.15 Effect of TBA on the removal rates of COD（a），UV₂₅₄（b） and TOC（c），the pseudo-first-order reaction kinetics analysis of COD（d） and UV₂₅₄（e）

Fig.16 3D-EEM of landfill leachate

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