The electro-reduction of CO2 paired with wastewater electro-oxidation processes is a promising method for producing value-added products and decreasing energy consumption. In an H-type cell, the electrocatalytic mineralization of AMD 10B in an aqueous medium over novel β-PbO2 anode paired with the CO2 electrocatalytic reduction converts to methanol and formic acid at Pt/PANI@ZnO cathode. The proposed anode electrode showed a very high surface-to-volume ratio, high-performance electrocatalytic degradation, and a long service lifetime. Experimental results indicate in the anode compartment, a good COD removal efficiency (93%) and the lowest specific energy consumption, 4.6 kWh m−3 were obtained. Simultaneously, results obtained from the catholyte analysis showed Faradaic efficiency of 57% and 41% with a total cathodic energy efficiency of 34% at 15 mA cm−2 for methanol and formic acid, respectively. The lowest cell voltage was obtained (3.92 V) by using NaCl in the anolyte.
