Abstract
The development of hybrid polymers incorporating polyoxometalates (POMs) is a promising approach to elaborate new functional materials. To expand the practical applications, their association to a visible-light photosensitizer is needed.In this context, we have developed a method of electropolymerization of POMs based on nucleophilic attack onto the electrogenerated porphyrin dications. 1-2 The formation of hybrid POM-porphyrin copolymeric films (Fig. 1, film I) can be obtained by the electro-oxidation of porphyrin in the presence of the POM bearing two pyridyl groups (Py-POM-Py) 3 . This process is feasible for various type of POMs such as Dawson, Lindqvist or Keggin type POMs 4-6 . Stable 1D isoporphyrin 7 – POM or 3D isoporphyrin – PIM copolymers (PIM = PolyIodoMetalate; Fig. 2) have been also develop recently showing interesting efficiency even upon the NIR illumination.A second methodology is also proposed to form hybrid POM-porphyrin films (Fig. 1, films II or III): first the formation of cationic polyporphyrin electropolymer. Then, by metathesis reaction, the (partial) exchange onto the surface of the initial counter ions by the POMn- or by the nanoparticles stabilized with POMn- (POMn-@M, M = Ag, Au, Pt, etc.). 8 The photovoltaic performances of these hybrid materials have been investigated by photocurrent transient measurements under visible-light illumination 9-11 given by now good efficiency. In order to increase the efficiency, mesoporous ITO electrodes (nanofiber formed by electrospun or porous ITO electrode obtained using a colloidal co-assembly approach) have been used and will be discussed (Fig. 2). L. Ruhlmann, A. Schulz, A. Giraudeau, J.-H. Fuhrhop, J. Am. Chem. Soc., 1999, 121, 6664. Z. Huo, J.-P. Gisselbrecht, R. Farha, M. Goldmann, E. Saint-Aman, C. Bucher, L. Ruhlmann, Electrochimica Acta, 2014, 122, 108. D. Schaming, C. Allain, R. Farha, M. Goldmann, S. Lobstein, A. Giraudeau, B. Hasenknopf, L. Ruhlmann, Langmuir, 2010, 26, 5101. I. Azcarate, I. Ahmed, R. Farha, M. Goldmann, X. Wang, H. Xu, B. Hasenknopf, E. Lacôte, L. Ruhlmann, Dalton Trans. 2013, 42, 12688. Z. Huo, I. Azcarate, R. Farha, M. Goldmann, H. Xu, B. Hasenknopf, E. Lacôte, L. Ruhlmann, J. solid State Electrochemistry, 2015, 19, 2611. Z. Huo,D. Zang,S. Yang,R. Farha,M. Goldmann,B. Hasenknopf, H. Xu, L. Ruhlmann, Electrochimica Acta, 2015, 179, 326. M. Boudiaf, Y. Liang, R. Lamare, J. Weiss, H. Ibrahim, M. Goldmann, E. Bentouhami, V. Badets, S. Choua, N. Le Breton, A. Bonnefont, L. Ruhlmann, Electrochimica Acta, 2019, 309, 432-449. Z. Huo,A. Bonnefont, C. Bucher, L Ruhlmann, Electrochimica Acta, 2018, 274, 177. I. Ahmed, R. Farha, M. Goldmann, L. Ruhlmann, Chem. Comm. 2013, 49, 496. I. Ahmed, R. Farha, Z. Huo, C. Allain, X. Wang, H. Xu, M. Goldmann, B. Hasenknopf, L. Ruhlmann, Electrochimica Acta, 2013, 110, 726. I. Azcarate, Z. Huo, R. Farha, M. Goldmann,H. Xu, B. Hasenknopf, E. Lacôte, L. Ruhlmann, Chem. Eur. J. 2015, 21, 8271. Figure 1
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