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 MnO2/C cathode was mainly predominated by their crystallographic structures which included Mn-O bond strength and tunnel size, following order of α- > δ- > β-MnO2/C. Interestingly, it was discovered that the specific surface areas (SBET) of different crystal phases did not give an impact on the PFC performance. However, the Pmax could be significantly influenced by the micropore surface area (Smicro) in the comparison among α-MnO2. Furthermore, the morphological transformation carried out by altering the hydrothermal duration demonstrated that the nanowire α-M3(24 h)/C with 1:1 ratio of KMnO4 and MnSO4 yielded excellent PFC performance with a Pmax of 2.8680 μW cm-2 and the lowest Rint of 700 Ω.
Photocatalytic fuel cell (PFC) was employed to provide renewable power sources to photoelectro-Fenton (PEF) process to fabricate a double-chambered hybrid system for the treatment of azo dye, Amaranth. The PFC-PEF hybrid system was interconnected by a circuit attached to the electrodes in PFC and PEF. Circuit connection is the principal channel for the electron transfer and mobility between PFC and PEF. Thus, different circuit connections were evaluated in the hybrid system for their influences on the Amaranth dye degradation. The PFC-PEF system under the complete circuit connection condition attained the highest decolourization efficiency of Amaranth (PFC: 98.85%; PEF: 95.69%), which indicated that the complete circuit connection was crucial for in-situ formation of reactive species in dye degradation. Besides, the pivotal role of ultraviolet (UV) light irradiation in the PFC-PEF system for both dye degradation and electricity generation was revealed through various UV light-illuminating conditions applied for PFC and PEF. A remarkable influence of UV light irradiation on the production of hydrogen peroxide and generation and regeneration of Fe2+ in PEF was demonstrated. This study provided a comprehensive mechanistic insight into the dye degradation and electricity generation by the PFC-PEF system.
Cathode in photocatalytic fuel cell (PFC) plays a crucial role in degradation of organic contaminants. In this study, synthesized copper oxide (CuO) was loaded on carbon plate and used as photocathode in PFC for degradation of synthetic azo dye Reactive Black 5 (RB5) and real textile wastewater. Morphology and structural phase of the synthesized CuO were analyzed using scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. Several operating parameters had been investigated such as light irradiation, initial dye concentration, and pH of azo dye solution within 6 h of irradiation time. The lowest initial concentration of RB5 (10 mg L-1) achieved 100% color removal compared to the highest initial concentration (40 mg L-1) which only achieved 77.1% color removal within 6 h of irradiation time. The influence of external resistance was significant in electricity generation but trivial in dye degradation efficiency. The external resistance of 6000 Ω yielded highest maximum power density, with Pmax of 0.2631 μW cm-2, followed by 1000 Ω (0.2196 μW cm-2) and 8000 Ω (0.1587 μW cm-2), respectively. The real textile wastewater with dilution ratio (DR) 1:6 yielded the highest energy conversion efficiency, η (3.62%), followed by DR 1:4 (3.19%) and DR 1:2 (1.96%), respectively.
To enhance dye removal and energy recovery efficiencies in single-pair electrode photocatalytic fuel cell (PFC-AC), dual cathodes PFC (PFC-ACC) and dual photoanodes PFC (PFC-AAC) were established. Results revealed that PFC-AAC yielded the highest decolorization rate (1.44 h-1) due to the promotion of active species such as superoxide radical (•O2-) and hydroxyl radical (•OH) when the number of photoanode was doubled. The results from scavenging test and UV-Vis spectrophotometry disclosed that •OH was the primary active species in dye degradation of PFC. Additionally, PFC-AAC also exhibited the highest power output (17.99 μW) but the experimental power output was much lower than the theoretical power output (28.24 μW) due to the strong competition of electron donors of doubled photoanodes to electron acceptors at the single cathode and its high internal resistance. Besides, it was found that the increments of dye volume and initial dye concentration decreased the decolorization rate but increased the power output due to the higher amount of sacrificial agents presented in PFC. Based on the abovementioned findings and the respective dye intermediate products identified from gas chromatography-mass spectrometry (GC-MS), the possible degradation pathway of RR120 was scrutinized and proposed.