Electrocatalytic biofilm reactor for effective and energy-efficient azo dye degradation: the synergistic effect of MnO<sub><i>x</i></sub>/Ti flow-through anode and biofilm on the cathode

doi:10.1007/s11783-023-1649-5

Front. Environ. Sci. Eng.

2023, Vol. 17

Issue (4) : 49 https://doi.org/10.1007/s11783-023-1649-5

RESEARCH ARTICLE

Electrocatalytic biofilm reactor for effective and energy-efficient azo dye degradation: the synergistic effect of MnO_x/Ti flow-through anode and biofilm on the cathode

Yinghui Mo^1,²(

), Liping Sun^1,², Lu Zhang^1,², Jianxin Li^1,³, Jixiang Li^4,⁵, Xiuru Chu⁶, Liang Wang^1,²(

)

¹. State Key Laboratory of Separation Membranes and Membrane Processes, National Center for International Joint Research on Membrane Science and Technology, Tiangong University, Tianjin 300387, China
². School of Environmental Science and Engineering, Tiangong University, Tianjin 300387, China
³. School of Materials Science and Engineering, Tiangong University, Tianjin 300387, China
⁴. Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 200120, China
⁵. University of Chinese Academy of Sciences, Beijing 100049, China
⁶. Tianjin Water Engineering Co., Ltd., Tianjin 300222, China

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Abstract

● MnO_x/Ti flow-through anode was coupled with the biofilm-attached cathode in ECBR.

● ECBR was able to enhance the azo dye removal and reduce the energy consumption.

● Mn^IV=O generated on the electrified MnO_x/Ti anode catalyzed the azo dye oxidation.

● Aerobic heterotrophic bacteria on the cathode degraded azo dye intermediate products.

● Biodegradation of intermediate products was stimulated under the electric field.

Dyeing wastewater treatment remains a challenge. Although effective, the in-series process using electrochemical oxidation as the pre- or post-treatment of biodegradation is long. This study proposes a compact dual-chamber electrocatalytic biofilm reactor (ECBR) to complete azo dye decolorization and mineralization in a single unit via anodic oxidation on a MnO_x/Ti flow-through anode followed by cathodic biodegradation on carbon felts. Compared with the electrocatalytic reactor with a stainless-steel cathode (ECR-SS) and the biofilm reactor (BR), the ECBR increased the chemical oxygen demand (COD) removal efficiency by 24 % and 31 % (600 mg/L Acid Orange 7 as the feed, current of 6 mA), respectively. The COD removal efficiency of the ECBR was even higher than the sum of those of ECR-SS and BR. The ECBR also reduced the energy consumption (3.07 kWh/kg COD) by approximately half compared with ECR-SS. The advantages of the ECBR in azo dye removal were attributed to the synergistic effect of the MnO_x/Ti flow-through anode and cathodic biofilms. Catalyzed by Mn^IV=O generated on the MnO_x/Ti anode under a low applied current, azo dyes were oxidized and decolored. The intermediate products with improved biodegradability were further mineralized by the cathodic aerobic heterotrophic bacteria (non-electrochemically active) under the stimulation of the applied current. Taking advantage of the mutual interactions among the electricity, anode, and bacteria, this study provides a novel and compact process for the effective and energy-efficient treatment of azo dye wastewater.

Keywords Azo dye removal Electrocatalytic biofilm reactor Anodic oxidation Electricity-stimulated biodegradation Energy consumption

Corresponding Author(s): Yinghui Mo,Liang Wang

Issue Date: 22 November 2022

Cite this article:

Yinghui Mo,Liping Sun,Lu Zhang, et al. Electrocatalytic biofilm reactor for effective and energy-efficient azo dye degradation: the synergistic effect of MnO_x/Ti flow-through anode and biofilm on the cathode[J]. Front. Environ. Sci. Eng., 2023, 17(4): 49.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-023-1649-5
https://academic.hep.com.cn/fese/EN/Y2023/V17/I4/49

Fig.1 Schematic diagram of the electrocatalytic biofilm reactor (ECBR) operated in the continuous mode after startup.

Fig.2 The cathodic (a) and total COD (b) removal efficiencies during the startup of the electrocatalytic biofilm reactor (ECBR).

Fig.3 COD removal efficiencies of the electrocatalytic biofilm reactor (ECBR) under different treated flow rates (a), currents (b), and AO7 concentrations (c). For (a), when the treated flow rate was 0.5, 0.33, and 0.25 mL/min, the anodic hydraulic retention time was 5, 7.5, and 10 min, and the cathodic hydraulic retention time was 16, 24, and 32 h, respectively; The applied current was 6 mA and the anode influent contained 600 mg/L AO7 and 7 g/L Na₂SO₄. For (b), the anode influent contained 600 mg/L AO7 and 7 g/L Na₂SO₄ and the treated flow rate was 0.25 mL/min. For (c), the treated flow rate was 0.25 mL/min and the applied current was 6 mA.

Fig.4 Comparison in AO7 and COD removal efficiencies in the three systems operated under the same conditions (a) (ECBR: electrocatalytic biofilm reactor; ECR-SS: electrocatalytic reactor-stainless steel mesh cathode; BR: biofilm reactor); The energy consumption of ECBR and ECR-SS (b). The initial AO7 concentration was 600 mg/L and the treated flow rate was 0.25 mL/min in the three systems. The current was 6 mA in ECBR and ECR-SS.

Fig.5 (a) Cyclic voltammetry curves of the MnO_x/Ti flow-through anode in the solutions with and without 600 mg/L AO7 (7 g/L Na₂SO₄ as the background electrolyte) at a scan rate of 10 mV/s (the blue line was totally covered by the red line). (b) AO7 removal efficiencies after the addition of methanol (MeOH) or tert-butanol (TBA) into the anode influent (600 mg/L AO7 and 7 g/L Na₂SO₄).

Fig.6 (a) Cyclic voltammetry curves of biofilm-attached carbon felts obtained in the cathode influent (anode effluent mixed with 3.4 g/L KH₂PO₄, 5.7 g/L K₂HPO₄·3H₂O, and 0.44 g/L NH₄Cl) aerated with N₂ or air and in the nutrient solution (3.4 g/L KH₂PO₄, 5.7 g/L K₂HPO₄·3H₂O, and 0.44 g/L NH₄Cl) aerated with air; (b) Cyclic voltammetry curves of biofilm-attached carbon felts obtained in the 600 mg/L AO7 solution (3.4 g/L KH₂PO₄, 5.7 g/L K₂HPO₄·3H₂O, and 0.44 g/L NH₄Cl as the background electrolytes), the 300 mg/L AO7 solution (3.4 g/L KH₂PO₄, 5.7 g/L K₂HPO₄·3H₂O, and 0.44 g/L NH₄Cl as the background electrolytes), and the cathode influent (24.9 mg/L AO7) aerated with air.

Fig.7 (a) Cyclic voltammetry curves of the pristine carbon felts and biofilm-attached carbon felts in the cathode influent (anode effluent mixed with 3.4 g/L KH₂PO₄, 5.7 g/L K₂HPO₄·3H₂O, and 0.44 g/L NH₄Cl) aerated with air. (b) Electrochemical impedance curves of the pristine carbon felts and biofilm-attached carbon felts in the cathode influent (anode effluent mixed with 3.4 g/L KH₂PO₄, 5.7 g/L K₂HPO₄·3H₂O, and 0.44 g/L NH₄Cl).

Fig.8 (a) BOD₅/COD of the AO7 synthetic wastewater before (anode influent) and after (anode effluent and cathode effluent) treatment in the electrocatalytic biofilm reactor (ECBR). Operation conditions: the AO7 concentration was 600 mg/L; the current was 6 mA; the treated flow rate was 0.25 mL/min. (b) Effect of the current on the cathodic COD removal efficiency. The cathode influent was prepared by adding 3.4 g/L KH₂PO₄, 5.7 g/L K₂HPO₄·3H₂O, and 0.44 g/L NH₄Cl into the anode effluent, which was collected from the outlet of the anode chamber of ECBR treating 600 mg/L AO7 synthetic wastewater under the current of 6 mA and the flow rate of 0.25 mL/min.

Fig.9 Proposed synergetic mechanisms of the MnO_x/Ti flow-through anode and the biofilm in the cathode chamber in the electrocatalytic biofilm reactor for AO7 removal.

Fig.10 Proposed degradation pathways of AO7 in the electrocatalytic biofilm reactor.

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