Enhanced photocurrent production from thin films of Ru(ii) metallopolymer/Dawson polyoxotungstate adducts under visible irradiation

Abstract

Thin films of polyoxometalates that are sensitized with a Ru(II) metallopolymer generate significant photocurrents in the presence of benzyl alcohol and visible light. Significantly, the photocurrent generated by the tungstate based adduct, α-[P(2)W(18)O(62)](6-), is approximately seven fold larger than that found for the Dawson polyoxomolybdate α-[S(2)Mo(18)O(62)](4-).

Synthesis and characterization of Lindqvist-type polyoxometalate–porphyrin copolymers

“…8) exhibited peaks corresponding to C 1s (284.6 eV), N 1s (400.3 eV and 398.6 eV) of the porphyrin ligand, the organic part of the spacer and the TBA countercation, while the O 1s (537.2 eV), and V 2p 3 (V 2p 1/2 = 523.4 eV and V 2p 3/2 = 516.0 eV) are coming from the vanadium, and oxygen atoms in the POM. F 1s signals (686.8 eV) and P 2p (133.8 eV) corresponding to PF 6 -trapped in the copolymer structure were also observed. The XPS data thus confirmed that the Lindqvist-type polyoxovanadate TBA 2 [V 6 O 13 {(OCH 2 ) 3 CNHCO(4-C 5 H 4 N)} 2 ] and the H 2 T 2 P porphyrin were incorporated into the films, in agreement with the UV-vis absorption spectra.…”

“…The covalent approach offers several advantages; in particular it should enhance the directionality and the interaction between POMs and organic components such as ferrocenyl [19,20], pyrene and perylene [21][22][23], Ru and Ir complexes [22,24], and porphyrins [25][26][27]. We reported the formation of a mixed POMporphyrin copolymer film with an Anderson type POM [MnMo 6 9À and ZnOEP, via an original electropolymerization/deposition process [29]. Both of them exhibited remarkable photocatalytical properties under visible light illumination.…”

“…To expand the practical application range, their association to a lightharvesting antenna is yet necessary, since POMs themselves are mainly photoactive in the UV part of the solar spectrum. In most POM-dye materials reported in the literature, the hybrids were assembled via electrostatic interactions [5][6][7][8][9][10][11][12][13].…”

Extended visible photosensitivity of carboxyethyltin functionalized polyoxometalates with common organic dyes enabling enhanced photoelectric performance

“…[11][12][13][14][15][16][17][18][19][20] Nevertheless, traditional POMs absorb mainly UV light, which limits their utilization of solar energy. 21,22 Thus, further boosting their photoelectrochemical performances in the visible light region still remains a challenge for POM-based photovoltaic systems.…”

Helical Microporous Nanorods Assembled by Polyoxometalate Clusters for the Photocatalytic Oxidation of Toluene

“…Hence, the diameter of the one-dimensional pores should be smaller 6À in the final product is further confirmed by the Fourier transform infrared spectra (FT-IR, Figure 2 d), the Raman spectra (Figure 2 e), and the X-ray photoelectron spectra (XPS, Figure 2 2 d, the bands at 1090 cm À1 and 960 cm À1 , 910 cm À1 and 770 cm À1 are attributed to the stretching vibrations of the PÀO bonds, the stretching vibrations of the terminal WÀO bonds, the asymmetric vibrations of W-O-W bridges between corner-sharing WO 6 octahedra, and the asymmetric vibrations of W-O-W bridges between edge-sharing WO 6 octahedra, respectively. [18] Correspondingly, the peaks at 990 cm À1 and 970 cm À1 in the Raman spectra are attributed to the stretching vibrations of the PÀO bonds and the terminal WÀO bonds, [19] which are characteristic of the [a-P 2 W 18 O 62 ] 6À .…”