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@ARTICLE{Koposova:811872,
      author       = {Koposova, Ekaterina and Liu, Xiao and Pendin, Andrey and
                      Thiele, Björn and Shumilova, Galina and Ermolenko, Yury and
                      Offenhäusser, Andreas and Mourzina, Youlia},
      title        = {{I}nfluence of {M}eso-{S}ubstitution of the {P}orphyrin
                      {R}ing on {E}nhanced {H}ydrogen {E}volution in a
                      {P}hotochemical {S}ystem},
      journal      = {The journal of physical chemistry / C},
      volume       = {120},
      number       = {26},
      issn         = {1932-7455},
      address      = {Washington, DC},
      publisher    = {Soc.},
      reportid     = {FZJ-2016-04214},
      pages        = {13873 - 13890},
      year         = {2016},
      abstract     = {This study establishes the relationships between the
                      structure of a series of meso-substituted tin(IV) porphyrins
                      and their efficiency as photosensitizers for hydrogen
                      generation in the Sn(IV)P/Pt–TiO2 nanocomposite system.
                      The electrochemical properties of a series of SnPs, the
                      catalytic performance of Pt nanomodifications, and the
                      morphology of the Pt/TiO2 nanocomposites were characterized
                      by electrochemical and electron microscopy methods. The
                      dependence of photocatalytic performance on the structure
                      for a series of Sn(IV) meso-substituted phenyl porphyrins
                      was studied, and possible mechanisms are discussed employing
                      the results of the electrochemical studies. It was found
                      that the time course and type of the photochemically reduced
                      species of Sn(IV)Ps, which are essential intermediates, are
                      important factors and depend on the electronegativity of the
                      metal center, the character of meso-substituents of the
                      porphyrin ring, and pH and are correlated with the redox
                      potential sequence of the respective Sn(IV)Ps: SnTMPyP >
                      SnTPyP > SnTPPS > SnTPPC. Optimization of the experimental
                      parameters was performed with regard to the SnPs with
                      different functional groups, pH values, concentrations of
                      Pt/TiO2, light intensity, and Pt nanoparticles with
                      different surface stabilizers. Finally, the maximum hydrogen
                      yield under visible light was obtained from the system of
                      Sn(IV) meso-tetra(4-pyridyl)porphyrin dichloride (SnTPyP)
                      sensitized TiO2/Pt prepared by the citrate method/EDTA at pH
                      9.0. This demonstrates that the photochemically reduced
                      species of SnTPyP are relatively long lived, so they have
                      enough time to complete electron transfer to TiO2 and/or Pt.
                      The adsorption of SnTPyP on the TiO2/Pt surface is therefore
                      not essential for hydrogen generation. Moreover, this study
                      demonstrates for the first time the synergic effect of the
                      excitation of TiO2 and mostly Q-bands of Sn(IV)P (wavelength
                      range 390–650 nm), which enhances the efficiency of
                      photocatalytic hydrogen generation in the system. The Soret
                      band of Sn(IV)TPyP was found to produce a minor (about
                      $23\%)$ contribution to the photocatalytic activity of the
                      porphyrin sensitizer in this system. Possible processes
                      involved are discussed, and mechanisms are proposed
                      explaining different aspects of a series of photocatalytic
                      systems with SnPs and Pt catalysts for hydrogen production
                      under visible light. These structure–function
                      relationships are essential to effectively harness solar
                      energy for hydrogen production as well as for a wide range
                      of energy and environmentally related problems.},
      cin          = {PGI-8 / IBG-2},
      ddc          = {540},
      cid          = {I:(DE-Juel1)PGI-8-20110106 / I:(DE-Juel1)IBG-2-20101118},
      pnm          = {134 - Electrolysis and Hydrogen (POF3-134) / 582 - Plant
                      Science (POF3-582)},
      pid          = {G:(DE-HGF)POF3-134 / G:(DE-HGF)POF3-582},
      typ          = {PUB:(DE-HGF)16},
      UT           = {WOS:000379457000003},
      doi          = {10.1021/acs.jpcc.6b01467},
      url          = {https://juser.fz-juelich.de/record/811872},
}