A simple one-step synthetic route to access a range of metal-doped polyoxovanadate clusters

Abstract

A simple one-step synthetic route to access a range of metal-doped polyoxovanadate clusters.

The use of mixed-metal single source precursors for the synthesis of complex metal oxides

“…The use of mixed-metal (heterometallic) complexes or frameworks, which contain more than one metal, as SSPs provides alternative synthetic routes to access CMOs. 11,39,40 Using an SSP has been reported to display advantages such as simplifying material synthesis; 26,27 access to unusual or otherwise inaccessible products; 12,30,41 or materials with enhanced performance. [42][43][44] By incorporating all of the required metals into one precursor, the stoichiometry is defined at the molecular level.…”

“…30,43,44,46 An SSP may contain a perfect inter-metal stoichiometry for conversion to a pure phase mixed-metal oxide, or alternatively, can contain a mixture of metals which transform into two or more (interpenetrated) oxide phases (previously defined by Veith as a type 3 SSP). 11,47,48 Mixed-metal SSP compounds are often soluble in organic solvents (and sometimes water), allowing convenient routes to fabricate thin films of CMOs, by straightforward techniques (such as drop-casting and spin-coating), 26,27,35,49,50 spray pyrolysis, 51 sol-gel processes 11,15,52 or (aerosol-assisted) CVD. 53 The use of a single precursor under mild reaction conditions also simplifies CMO synthesis for applications that demand excellent material homogeneity across a large scale.…”

“…We define this broad group of materials as complex metal oxides (CMOs) which include mixed-metal oxides (AxByOz), heterometal doped metal oxides (B:AxOy) or composite metal oxides with a mixture of oxide phases (AwOx/ByOz). Today, many types of mixed-metal oxides are accessible from SSPs including perovskites (ABO3), [10][11][12][13][14][15][16] pyrochlores (A2B2O7), 17 spinels (AB2O4), [18][19][20][21][22][23][24][25] metal vanadates [Mx(VO4)y], 26,27 feldspars (MAl2Si2O8) 28 and Aurivilius phases (Bi2O2)(An−1BnO3n+1). 29…”

Molecular Vanadium Oxides for Energy Conversion and Energy Storage: Current Trends and Emerging Opportunities

“…[21,23,27] Thef unctionalization of molybdates and tungstates with redox-active heterometals has been widely used to tune their redox behavior and resulting reactivity for applications such as,w ater oxidation, [11,12] hydrogen evolution, [16] photooxidation chemistry, [28] and battery applications. [29] However,u ntil recently,t he functionalization of POVs with metals was mainly used for structural stabilization, [27,[30][31][32] precursor synthesis, [33,34] or to access new cluster topologies. [21,23,27] Over recent years,h owever, POVc hemistry has moved from exploring structures to functions,w hich has enabled ground-breaking research in many areas of energy conversion and storage.I nt his Review,w ew ill showcase the recent developments in the redox tuning of POVs.W ehighlight the unique advantages of POVs that can be exploited in energy research and identify areas which-from the authors point of view-offer new possibilities for fundamental and application-driven research over the coming years.…”

Molekulare Vanadiumoxide für Energiewandlung und Energiespeicherung: Derzeitige Trends und zukünftige Möglichkeiten

“…B. fürW asseroxidation, [11,12] Wasserstoffentwicklung, [16] Photooxidationschemie [28] oder Batterieanwendungen. [29] Bis vor kurzem wurde Metallfunktionalisierung in POVs jedoch meist zur Strukturstabilisierung, [27,[30][31][32] Vorstufensynthese [33,34] oder als Zugang zu neuen Clustertopologien genutzt. [21,23,27] In den vergangenen Jahren verschob sich der Schwerpunkt der POV-Chemie jedoch von Struktur zu Funktion, was zu fundamental wichtigen Arbeiten in vielen Bereichen der Energiewandlung und -speicherung führte.Indiesem Aufsatz werden wir die neuen Entwicklungen im POM-Redox-Tuning vorstellen.…”