Photo- and Electrochromism of Polyoxometalates and Related Materials

The photo-induced synthesis of metal nanoparticles (NPs) was reviewed with a closer look at those based on photochemistry. Recent developments in metal NPs research, photochemistry, and photoprocessing techniques have allowed researchers to devise various photo-induced synthetic strategies to obtain metal NPs under a variety of conditions. We begin by outlining the classical method. The photochemical synthesis of metal NPs including direct photoreduction and photosensitization has been developed to achieve decent yields. We focused on stabilization and functionalization method of NPs in photochemical synthesis, which has enabled us to fabricate a variety of metal nanostructures and composite materials. In addition, we mention an alternative approach, that is, laser ablation at the solid–liquid interface. Some of the most innovative studies dealing with the three-dimensional fabrication of metal NPs are highlighted, together with new directions such as potential applications for a light-driven actuator, bioimaging, and three-dimensional processing. This review is concluded with the future perspectives for the photo-induced synthesis of metal NPs.

Light as a construction tool of metal nanoparticles : Synthesis and mechanism

In this review article, we consider the use of molecular oxygen in reactions mediated by polyoxometalates. Polyoxometalates are anionic metal oxide clusters of a variety of structures that are soluble in liquid phases and therefore amenable to homogeneous catalytic transformations. Often, they are active for electron transfer oxidations of a myriad of substrates and upon reduction can be reoxidized by molecular oxygen. For example, the phosphovanadomolybdate, H5PV2Mo10O40, can oxidize Pd(0) thereby enabling aerobic reactions catalyzed by Pd and H5PV2Mo10O40. In a similar vein, polyoxometalates can stabilize metal nanoparticles, leading to additional transformations. Furthermore, electron transfer oxidation of other substrates such as halides and sulfur-containing compounds is possible. More uniquely, H5PV2Mo10O40 and its analogues can mediate electron transfer-oxygen transfer reactions where oxygen atoms are transferred from the polyoxometalate to the substrate. This unique property has enabled correspond...

Dioxygen in Polyoxometalate Mediated Reactions

Polyoxometalate cluster anions (POMs) control formation and morphology, and serve as protecting ligands, for structurally and compositionally diverse nanostructures. While numerous examples of POM-protected metal(0) nanoparticle syntheses and reactions can now be found in the literature, the use of POMs to prepare nano-scale analogs of binary inorganic materials, such as metal-oxides, sulfides and halides, is a relatively recent development. The first part of this critical review summarizes the use of POMs as protecting ligands for metal(0) nanoparticles, as well as their use as templates for the preparation of new inorganic materials. Here, key findings that reveal general trends are given additional emphasis. In the second part of the review, new information concerning the structure of POM-protected metal(0) nanoparticles is systematically developed. This information, obtained by the combined use of cryogenic transmission microscopy (cryo-TEM) and UV-vis spectroscopy, provides a new perspective on the formation and structure of POM-decorated nanoparticles, and on the rational design of catalytic and other functional POM-based nano-assemblies.

Polyoxometalate-decorated nanoparticles

The phase evolution, under thermal treatment, of the 12-molybdo(tungsto)phosphoric acids and their related 1-vanado-substituted compounds has been studied by in situ X-ray diffraction methods. The anhydrous acid temperature range is clearly observed for the 12-molybdo(tungsto)phosphoric acid parents via formation of a tetragonal phase. However, the vanadium monosubstituted acids seem to transform into the 12-metallo parents. In the case of the 1-vanado-11-tungstophosphoric acid a curious evolution, via a very stable cubic lattice, suggests thermal stabilization of the 12-tungstophosphate anion through the formation of an anhydrous VO2+ salt.

Lyman Chalkley

Papers

The Extent of the Photochemical Reduction of Phosphotungstic Acid