RESUMO
In the field of polyoxometalate (POM) chemistry, different heteroelements are integrated into the cage-like structures, to obtain different structural types of so-called heteropolyanions (HPAs). While it is generally accepted, that some elements favor certain types of structure, a systematic study is still missing. In this article, we present a systematic investigation of the influence of the group 15 elements nitrogen, phosphorous, arsenic, and antimony on the formation of different POM structure types. Our study is comprised of DFT calculations and corresponding experimental structural analysis. In this context, the DFT study establishes the thermodynamics of formation of different coordination geometries with various heteroelements on two POM structure types, the Keggin and the Anderson-Evans structures. Our POM synthesis experiments were performed at two different pH values (1 and 5) and resulted in a variety of heteropolytungstates, which were identified and characterized by elemental analysis as well as single crystal X-ray diffraction and vibrational spectroscopy. With these methods, we were able to establish a clear trend, showing that heavier elements lead to formation of different structure types than lighter elements. These results signify a large step towards a better understanding of POM formation specifically with respect to the choice of heteroelement.
RESUMO
Polyoxometalates (POMs) are a fascinating group of anionic metal-oxide clusters with a broad variety of structural properties and several catalytic applications, especially in the conversion of bio-derived platform chemicals. H8 [PV5 Mo7 O40 ] (HPA-5) is a unique POM catalyst that ideally links numerous fascinating research fields for the following reasons: a) HPA-5 can be synthesized by rational design approaches; b) HPA-5 can be well characterized using multiple analytical tools explaining its catalytic properties; and c) HPA-5 is suitable for multiple important catalytic transformations of bio-based feedstock. This Review combines the fields of synthesis, spectroscopic, electrochemical, and crystallographic characterization of HPA-5 with those of sustainable catalysis and green chemistry. Selected catalytic applications include esterification, dehydration, and delignification of biomass as well as selective oxidation and fractionation of bio-based feedstock. The unique HPA-5 is a fascinating POM that has a broad application scope for biomass valorization.
RESUMO
Adjusting the RedOx activity of polyoxometalate catalysts is a key challenge for the catalysis of selective oxidation reactions. For this purpose, the possibility of influencing the RedOx potential by the introduction of an additional RedOx-active element was investigated. Thereby, Keggin-type polyoxometalates (POMs) with up to three different elements in the metal framework were created. An advanced and reproducible synthetic procedure to incorporate MnII and additionally VV into Keggin-type heteropolyacids alongside comprehensive characterization of the new molecules is presented. The success of our syntheses was confirmed by vibrational spectroscopy (IR and Raman) and elemental analysis. Furthermore, the new compounds were analyzed by NMR spectroscopy to investigate the characteristics of the POMs in solution. The structures of successfully crystalized compounds were determined by single-crystal X-ray diffraction. Moreover, all synthesized compounds were characterized using UV/Vis spectroscopy and electrochemical analysis to get further insights into the electronic transfer processes and redox potentials.