Evaluation of two processing routes for the synthesis of molybdenum oxide with cobalt addition

Molybdenum oxides are very interesting technologic materials, which present several industrial uses. The addition of a second metal may enhance its catalytic properties as well as change electronic behavior. Several methodologies for adding a second metal can be found in the literature, however, the comparison between them is hardly ever found. Here two processing routes were tested for the synthesis of molybdenum oxide with cobalt addition: solid-state and wet routes. Ammonium molybdate and cobalt nitrate were used as starting materials and cobalt addition was carried out before calcination. Starting materials were characterized by SEM, FTIR, XRF, and XRD. Calcination products were evaluated by SEM, XRF, XRD and UV-vis spectroscopy. Calcined products whose doping was performed via solid-state presented smaller crystal size (~25 nm), larger cobalt retention (deviation, δ ~10%) and slightly smaller band gap in comparison to those doped via the wet route (~40 nm and δ>11%).

Redox-Promoted Tailoring of the High-Temperature Electrical Performance in Ca3Co4O9 Thermoelectric Materials by Metallic Cobalt Addition

This paper reports a novel composite-based processing route for improving the electrical performance of Ca3Co4O9 thermoelectric (TE) ceramics. The approach involves the addition of metallic Co, acting as a pore filler on oxidation, and considers two simple sintering schemes. The (1-x)Ca3Co4O9/xCo composites (x = 0%, 3%, 6% and 9% vol.) have been prepared through a modified Pechini method, followed by one- and two-stage sintering, to produce low-density (one-stage, 1ST) and high-density (two-stage, 2ST) ceramic samples. Their high-temperature TE properties, namely the electrical conductivity (σ), Seebeck coefficient (α) and power factor (PF), were investigated between 475 and 975 K, in air flow, and related to their respective phase composition, morphology and microstructure. For the 1ST case, the porous samples (56%–61% of ρth) reached maximum PF values of around 210 and 140 μWm−1·K−2 for the 3% and 6% vol. Co-added samples, respectively, being around two and 1.3 times higher than those of the pure Ca3Co4O9 matrix. Although 2ST sintering resulted in rather dense samples (80% of ρth), the efficiency of the proposed approach, in this case, was limited by the complex phase composition of the corresponding ceramics, impeding the electronic transport and resulting in an electrical performance below that measured for the Ca3Co4O9 matrix (224 μWm−1·K−2 at 975K).