Enhanced etching terminal wastewater treatment and H2 production by in-situ deposited heavy metals on carbon dots/g-C3N4 photocathode microbial electrolysis cells

Sustainable and cost-effective semiconducting photocathodes of microbial electrolysis cells (MECs) are attractively promising for efficient treatment of actual industrial wastewaters containing complex recalcitrant organics and multiple heavy metals. Herein carbon dots/graphitic carbon nitride (CDs/g-C3N4) photocathodes were employed to achieve efficient treatment of actual etching terminal wastewater (ETW) with simultaneous H2 production in MECs, allowing the effluent meeting national discharge standards (GB39731-2020). The progressively in-situ deposited heavy metals on the CDs/g-C3N4 photocathodes, formed as metal oxides/CDs/g-C3N4 after simple calcinations, further enhanced the ETW treatment (recalcitrant organics mineralization: 42.2 mg/L/h vs. 35.5 mg/L/h; heavy metal removal: Cu(II): 9.9 mg/L/h vs. 7.4 mg/L/h, Ni(II): 4.7 mg/L/h vs. 3.5 mg/L/h, Zn(II): 0.7 mg/L/h vs. 0.5 mg/L/h) and H2 production (0.1138 m3/m3/d vs. 0.0662 m3/m3/d). The importation of heavy metals, formed as metal oxides/CDs/g-C3N4 altered the proportion of reactive oxidative species and thus promoted mineralization of recalcitrant organics, besides offering additional electrochemical removal of heavy metals with simultaneous more H2 production. This study demonstrates a new feasible protocol for achieving efficient ETW treatment, and gives a comprehensive appreciation of the effect of in-situ deposited heavy metals on the CDs/g-C3N4 photocathodes, which has a profound effect on subsequent ETW treatment with simultaneous H2 production.