Chen Li,Lei Wang,Xudong Wang,Mengxiao Kong,Quan Zhang,Guangyuan Li
Thermally induced graft copolymerization of sodium styrene sulfonate (SSS) with ozone-preactivated poly(vinylidene fluoride) (PVDF) produced a PVDF-g-PSSS copolymer . Sulfonic acid proton exchange membranes (PVDF-g-PSSA) were then prepared using the solvent evaporation method. They were investigated with a Fourier transform infrared spectrometer and an X-ray diffractometer. The results indicate that the proton conductivity of the prepared membranes reached 0.046 S/cm when the degree of grafting was 50.52%. Results from a quartz crystal microbalance with dissipation monitoring indicated that the PVDF-g-PSSA membrane showed superior antifouling performance to that of a Nafion membrane. The performance of the prepared membrane in dual-chamber microbial fuel cells was also evaluated and compared with that of Nafion 117. Although the microbial fuel cell with the prepared membrane generated lower maximum power density (106.7 mW/m 2 ) than that with Nafion 117 (132.0 mW/m 2 ), it was more cost-effective because of its lower price and more simplified preparation process. In addition, its chemical oxygen demand (COD) removal (85%) was much higher than that of Nafion 117 (74%).
Sulfonated titanium dioxide (S-TiO 2 ) was prepared by the grafting of sulfonic groups onto TiO 2 , and doped into the PVDF-g-PSSA as a highly efficient inorganic additive, thus achieving simultaneous improvement of the proton conductivity and anti-fouling property of the synthesized S-TiO 2 /PPSSA proton exchange membrane (PEM). The S-TiO 2 /PPSSA membrane was implemented in microbial fuel cell (MFC) for the first time, and its physicochemical properties and performance in MFC were studied. A new technique of combining Quartz crystal microbalance with dissipation with membrane spin-coated sensors made by a spin coating method was utilized to provide an insight into the anti-fouling property of the prepared membranes. The implementation of Fourier transform infrared spectrometry and X-ray photoelectron spectroscopy demonstrated TiO 2 was successfully introduced into the sulphonic groups. The S-TiO 2 /PPSSA-5.0 membrane has a significant increase in the water uptake (40.9%) and proton conductivity (0.067 S/cm) compared with the PVDF-g-PSSA membrane. QCM-D results indicated that it has better anti-fouling property than pristine membrane and Nafion 117. Moreover, the MFC with the S-TiO 2 /PPSSA-5.0 membrane exhibited a maximum power density of 130.54 mW/m 2 , very close to that of Nafion 117 (132.02 mW/m 2 ), but had the highest COD removal of 91% and least bio-fouling adsorption. These results demonstrate that the blending of sulfonated organic polymers and sulfonated inorganic additives can improve the electrochemical and anti-fouling properties of the composite membranes, which is a new concept for the preparation of PEM suitable for MFC. The S-TiO 2 /PPSSA-5.0 composite PEM is an appropriate candidate separator for the large-scale application of MFCs.
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