No abstract

Herein, two mixed-valence Mn16-containing polyanions, (Mn16) [MnIII10MnII6O6(OH)6(PO4)4(A-a-SiW9O34)4]28- (Mn16-Cs) and [MnIII4MnII12(OH)12(PO4)4(A-a-SiW9O34)4]28- (Mn16-Rb), were successfully fabricated on an indium tin oxide (ITO)-coated glass electrode and a glass carbon electrode (GCE) by a layer-by-layer assembly method. Moreover, four composite films, i.e. [PDDA/Mn16-Cs]n, [PDDA/Mn16-Rb]n, [Mn16-Cs/Rubpy]n, and [Mn16-Rb/Rubpy]n (PDDA: poly(diallyldimethylammonium chloride); Rubpy: tris(2,2'-bipyridyl)ruthenium(ii) chloride; n = 1-10), were constructed for comparison and characterized by UV-visible spectroscopy, cyclic voltammetry (CV), and X-ray photoelectron spectroscopy (XPS). Their electrocatalytic activities towards water oxidation were studied under the same experimental conditions. The results of the controlled experiments indicate that (1) all the four films exhibit expected electrocatalytic activities towards water oxidation; (2) the electrocatalytic activity of Mn16-Cs is better than that of Mn16-Rb in solution and composite films; and (3) the electrocatalytic activities of the composite film [Mn16/Rubpy]n are better than those of the composite film [PDDA/Mn16]n.

With the increase in gas population, the demand for clean and renewable energy is increasing. Hydrogen energy has a high combustion conversion energy while water is its combustion product. In recent years, a way to convert water into hydrogen and oxygen has been found by human beings inspired by plant photosynthesis. However, water decomposition consumes a significant amount of energy and is expensive. People expect to obtain a water decomposition catalyst with low cost and high efficiency. This work selected a six-manganese containing polyoxometalate with a similar structure characteristic to photosynthesizing PSII to fabricate with graphite C3N4 nanosheets for the construction of composite film (Mn6SiW/g-C3N4NSs) electrode via layer by layer self-assembly technology, which was used for the photo-electrochemical decomposition of water under visible light conditions. The binary composite film electrode displayed good catalytic efficiency. The photoelectric density of the composite electrode is 46 μA/cm2 (at 1.23 V vs. Ag/AgCl) and 239 μA/cm2 (at 1.5 V vs. Ag/AgCl). Compared with the g-C3N4NSs electrode alone, the photoelectric density of the composite electrode increased by 1 time. The reason is attributed to the fact that Mn6SiW has a similar structure characteristic to photosynthesizing PSII and high electron transferability. The construction of the composite film containing low-cost Mn6SiW to modify g-C3N4NSs can effectively improve the photocatalytic decomposition of water, thus this study provides valuable reference information for the development of low-cost and high-performance photo-electrocatalytic materials.

A composite film containing g-C3N4NS and SiMoW was constructed by LBL assembly to realize fluorescence switch regulation.