Assembling and Regulating of Transition Metal-Based Heterophase Vanadates as Efficient Oxygen Evolution Catalysts.

Developing efficient, durable, and low-cost earth-abundant elements-based oxygen evolution reaction (OER) catalysts by rapid and scalable strategies is of great importance for future sustainable electrochemical hydrogen production. The earth-abundant high-valency metals, especially vanadium, can modulate the electronic structure of 3d metal oxides and oxyhydroxides and offer the active sites near-optimal adsorption energies for OER intermediates. Here, the authors propose a facile assembling and regulating strategy to controllably synthesize a serial of transition metal (CoFe, NiFe, and NiCo)-based vanadates for efficient OER catalysis. By tuning the reaction concentrations, NiFe-based vanadates with different crystallinities can be facilely regulated, where the catalyst with moderate heterophase (mixed crystalline and amorphous structures) shows the best OER catalytic activity in terms of low overpotential (267 mV at the current density of 10 mA cm-2 ), low Tafel slope (38 mV per decade), and excellent long-term durability in alkaline electrolyte, exceeding its noble metal-based counterparts (RuO2 ) and most current existing OER catalysts. This work not only reports a facile and controllable method to synthesize a series of vanadates-based catalysts with heterophase nanostructures for high-performance OER catalysis, but also may expand the scope of designing cost-effective transition metal-based electrocatalysts for water splitting.

Precipitation Stripping of V(V) as a Novel Approach for the Preparation of Two-Dimensional Transition Metal Vanadates.

Cobalt, nickel, manganese and zinc vanadates were synthesized by a hydrometallurgical two-phase method. The extraction of vanadium (V) ions from alkaline solution using Aliquat® 336 was followed by the production of metal vanadates through precipitation stripping. Precipitation stripping was carried out using solutions of the corresponding metal ions (Ni (II), Co (II), Mn (II) and Zn (II), 0.05 mol/L in 4 mol/L NaCl), and the addition time of the strip solution was varied (0, 1 and 2 h). The time-dependent experiments showed a notable influence on the composition, structure, morphology and crystallinity of the two-dimensional vanadate products. Inspired by these findings, we selected two metallic vanadate products and studied their properties as alternative cathode materials for nonaqueous sodium and lithium metal batteries.

The alluaudite-type crystal structures of Na2(Fe/Co)2Co(VO4)3 and Ag2(Fe/Co)2Co(VO4)3.

Single crystals of the title compounds, disodium di(cobalt/iron) cobalt tris-(orthovanadate), Na2(Fe/Co)2Co(VO4)3, and disilver di(cobalt/iron) cobalt tris-(orthovanadate), Ag2(Fe/Co)2Co(VO4)3, were grown from a melt consisting of stoichiometric mixtures of three metallic cation precursors and vanadium pentoxide. The difficulty to distinguish between cobalt and iron by using X-ray diffraction alone forced us to explore several models, assuming an oxidation state of +II for Co and +III for Fe and a partial cationic disorder in the Wyckoff site 8f containing a mixture of Co and Fe with a statistical distribution for the Na compound and an occupancy ratio of 0.4875:0.5125 (Co:Fe) for the Ag compound. The alluaudite-type structure is made up from [10-1] chains of [(Co,Fe)2O10] double octa-hedra linked by highly distorted [CoO6] octa-hedra via a common edge. The chains are linked through VO4 tetra-hedra, forming polyhedral sheets perpendicular to [010]. The stacking of the sheets defines two types of channels parallel to [001] where the Na(+) cations (both with full occupancy) or Ag(+) cations (one with occupancy 0.97) are located.