Photocatalytic Hydrogen Evolution Based on Efficient Energy and Electron Transfers in Donor-Bridge-Acceptor Multibranched-Porphyrin-Functionalized Platinum Nanocomposites

Two donorbridgeacceptor conjugates (5,10,15,20-tetrakis[4-(N,N-diphenylaminobenzoate)phenyl] porphyrin (TPPZ) and 5,10,15,20-tetrakis[4-(N,N-diphenylaminostyryl)phenyl] porphyrin (TPPX)) were covalently linked to triphenylamine (TPA) at the meso-position of porphyrin ring. The triphenylamine entities were expected to act as energy donors and the porphyrins to act as an energy acceptor. In this paper, we report on the synthesis of these multibranched-porphyrin-functionalized Pt nanocomposites. The conjugates used here not only served as a stabilizer to prevent agglomeration of Pt nanoparticles, but also as a light-harvesting photosensitizer. The occurrence of photoinduced electron-transfer processes was confirmed by time-resolved fluorescence and photoelectrochemical spectral measurements. The different efficiencies for energy and electron transfer in the two multibranched porphyrins and the functionalized Pt nanocomposites were attributed to diverse covalent linkages. Moreover, in the reduction of water to produce H2, the photocatalytic activity of the Pt nanocomposite functionalized by TPPX, in which the triphenylamine and porphyrin moieties are bonded through an ethylene bridge, was much higher than that of the platinum nanocomposite functionalized by TPPZ, in which the two moieties are bonded through an ester. This investigation demonstrates the fundamental advantages of constructing donorbridgeacceptor conjugates as highly efficient photosensitizers based on efficient energy and electron transfer.