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Novel crystallized rutile TiO 2 with microstructures ranging from dendrite-like and leaf-like to flowerlike are fabricated through the autoclaving of amorphous tetrabutyl titanate (TBT) which assembles in the cores of electrospun PVDF nanowires. The microstructures and properties of these materials are determined through a combination of XRD, XPS, SEM and EDS/TEM studies. The nucleation of rutile nanocrystallites is accomplished through the formation of F atom-substituted soluble TiO 6 complexes with Ti-F bonding. The growth of TiO 2 is catalyzed by H 2 O in the hydrothermal solution. The fabricated TiO 2 -PVDF membranes undergo efficient photomethanation conversion (about 36-fold higher than commercial P25) even for the first six hours under UV illumination, as well as having high stability. The F atoms from the PVDF and the effect of the TiO 2 microstructures play a significant role in the corresponding photomethanation ability which can be elucidated from the photoluminescence (PL) studies.

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