In this study, the degradation efficiency and electricity generation of the azo dyes affected by the functional groups and molecular structure in a solar photocatalytic fuel cell (PFC) system were investigated and discussed in detail. Four different azo dyes such as, Acid Orange 7 (AO7), Acid Red 18 (AR18), Reactive Black 5 (RB5), Reactive Red 120 (RR120) with different molecular structure were evaluated. The degradation efficiency of AO7, AR18, RB5 and RR120 achieved 5.6 ± 0.3%, 11.1 ± 0.6%, 41.9 ± 0.9% and 52.1 ± 1.3%, respectively, after 6 h irradiated under solar light. In addition, the maximum power density, Pmax for AO7, AR18, RB5 and RR120 was 0.0269 ± 0.01, 0.111 ± 0.03, 1.665 ± 0.67 and 4.806 ± 1.79 mW cm−2, respectively. Meanwhile, the concentration of COD for AO7, AR18, RB5 and RR120 reduced to 16 ± 0.1, 10 ± 0.3, 7 ± 0.6 and 3 ± 0.9 mg L−1, respectively. The concentration ratio of benzene / naphthalene, benzene / azo bond and naphthalene / azo bond, respectively, was analyzed to investigate the impact of the functional groups over photodegradation of the azo dyes in PFC. Electron releasing groups (-OH and –NH2) and electron withdrawing groups (-SO3Na) which attached to the naphthalene or benzene ring also played a pivotal role in the degradation mechanism.
