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A unidirectional flow solar photocatalytic fuel cell (PFC) was successfully developed for the first time to offer alternative for electricity generation and simultaneous wastewater treatment. This study was focused on the synthesis of α-, δ- and β-MnO2 by wet chemical hydrothermal method for application as the cathodic catalyst in PFC. The crystallographic evolution was performed by varying the ratios of KMnO4 to MnSO4. The mechanism of the PFC with the MnO2/C as cathode was also discussed. Results showed that the catalytic activity of