Reversible Electrodeposition of Potassium-bridged Molecular Vanadium Oxides: A New Approach Towards Multi-Electron Storage.

Molecular metal oxides, so-called polyoxometalates (POMs), have shown outstanding performance as catalysts and lately attracted interest as materials in energy conversion and storage systems due to their capability of storing and exchanging multiple electrons. Here, we report the first example of redox-driven reversible electrodeposition of molecular vanadium oxide clusters, leading to the formation of thin films. The detailed investigation of the deposition mechanism reveals that the reversibility is dependent on the reduction potential. Correlating electrochemical quartz microbalance studies with X-ray photoelectron spectroscopy (XPS) data gave insight into the redox chemistry and oxidation states of vanadium in the deposited films in dependence on the potential window. A multi-electron reduction of the polyoxovanadate cluster, which facilitates the potassium (K+ ) cation-assisted reversible formation of potassium vanadium oxide thin films was confirmed. At anodic potentials, re-oxidation of the polyoxovanadate and complete stripping of the thin film is observed for films deposited at potentials more positive than -500 mV vs. Ag/Ag+ , while electrodeposition at more negative cathodic potential reduces the electrochemical reversibility of the process and increases the stripping overpotential. As proof of principle, we demonstrate the electrochemical performance of the deposited films for potential use in potassium-ion batteries.

A General Access Route to High-Nuclearity, Metal-Functionalized Molecular Vanadium Oxides.

Molecular metal oxides are key materials in diverse fields like energy storage and conversion, molecular magnetism and as model systems for solid-state metal oxides. To improve their performance and increase the variety of accessible motifs, new synthetic approaches are necessary. Herein, we report a universal, new precursor to access different metal-functionalized polyoxovanadate (POV) clusters. The precursor is synthesized by a novel solid-state thermal treatment procedure. Solution-phase test reactions at room temperature and pressure show that reaction of the precursor with various metal nitrate salts gives access to a range of metal-functionalized POVs. The first nitrate-templated molecular calcium vanadate cluster is reported. We show that this precursor could open new access routes to POV components for molecular magnetism, energy technologies or catalysis.

Effect of Heterometal-Functionalization and Template Exchange on the Redox Chemistry of Molecular Vanadium Oxides.

Polyoxometalates (POMs) have emerged as material of interest in many applications such as energy storage and conversion due to their redox activity and molecularly defined structure. However, especially for polyoxovanadates a lack of understanding between structural modifications and physicochemical properties remains. The present study leverages a lacunary dodecavanadate to systematically investigate the electronic effect of heterometal functionalization. While structural distortion affects the stability of the cluster, the redox potentials correlate with the overall cluster charge. Furthermore, we report the first bromide-templated analogue of this cluster family. While the halide anion is crucial for the formation of the cluster, no major effect on the electrochemical properties is observed. By improving the understanding of structure-property relationship in this work, we hope to enable a more predictable tuning of redox-properties of polyoxovandates.

Bottom-up Design of Bimetallic Cobalt-Molybdenum Carbides/Oxides for Overall Water Splitting.

Earth-abundant transition-metal-based catalysts for electrochemical water splitting are critical for sustainable energy schemes. In this work, we use a rational design method for the synthesis of ultrasmall and highly dispersed bimetallic CoMo carbide/oxide particles deposited on graphene oxide. Thermal conversion of the molecular precursors [H3 PMo12 O40 ], Co(OAc)2 ⋅4 H2 O and melamine in the presence of graphene oxide gives the mixed carbide/oxide (Co6 Mo6 C2 /Co2 Mo3 O8 ) nanoparticle composite deposited on highly dispersed, N,P-doped carbon. The resulting composite shows outstanding electrocatalytic water-splitting activity for both the oxygen evolution and hydrogen evolution reaction, and superior performance to reference samples including commercial 20 % Pt/C & IrO2 . Electrochemical and other materials analyses indicate that Co6 Mo6 C2 is the main active phase in the composite, and the N,P-doping of the carbon matrix increases the catalytic activity. The facile design could in principle be extended to multiple bimetallic catalyst classes by tuning of the molecular metal oxide precursor.

Electrocatalytic Oxygen Evolution by Hierarchically Structured Cobalt-Iron Composites.

The development of scalable routes to highly active and efficient oxygen evolution reaction (OER) electrocatalysts based on earth-abundant materials is crucial for post-fossil fuel energy schemes. Here, we demonstrate how commercial copper foam electrodes can be functionalized for water oxidation using a facile electrodeposition process. The resulting composite electrode features hierarchically structured cobalt-iron-based catalyst particles, which offer channel-like structures for the transport of electrolyte and release of oxygen gas bubbles. We report high electrocatalytic OER performance as demonstrated by high current densities at low overpotentials (293 mV at j = 50 mA cm-2) and long-term stability under technologically relevant alkaline conditions (>24 h in 1.0 M aqueous KOH).

Redox-inactive ions control the redox-activity of molecular vanadium oxides.

Polyoxometalates are key materials for energy conversion and storage due to their unique chemical tunability and electrochemical reactivity. Herein, we report that functionalization of molecular vanadium oxides, polyoxovanadates, with redox-inert Ca2+ cations leads to a significant increase in their electron storage capabilities. The electrochemical performance of the Ca2+-functionalized dodecavanadate [Ca2V12O32Cl(DMF)3]2- (={Ca 2 V 12 }) was thus compared with that of the precursor compound (H2NMe2)2[V12O32Cl]3- (={V 12 }). {Ca 2 V 12 } can store up to five electrons per cluster, while {V 12 } only shows one reversible redox transition. In initial studies, we demonstrated that {Ca 2 V 12 } can be used as an active material in lithium-ion cathodes. Our results show how redox-inert cations can be used as structural and electrostatic stabilizers, leading to major changes in the redox-chemistry of polyoxovanadates.