The design of active and durable catalysts for the H₂O/O₂ interconversion is one of the major challenges of electrocatalysis for renewable energy. The oxygen evolution reaction (OER) is catalyzed by SrRuO₃ with low potentials (ca. 1.35 V_RHE), but the catalyst’s durability is insufficient. Here we show that Na doping enhances both activity and durability in acid media. DFT reveals that whereas SrRuO₃ binds reaction intermediates too strongly, Na doping of ~0.125 leads to nearly optimal OER activity. Na doping increases the oxidation state of Ru, thereby displacing positively O p-band and Ru d-band centers, weakening Ru-adsorbate bonds. The enhanced durability of Na-doped perovskites is concomitant with the stabilization of Ru centers with slightly higher oxidation states, higher dissolution potentials, lower surface energy and less distorted RuO₆ octahedra. These results illustrate how high OER activity and durability can be simultaneously engineered by chemical doping of perovskites.

Nanocrystalline samples of lithium manganese oxide with cubic spinel structure have been prepared by combustion of reaction mixtures containing Li(I) and Mn(II) nitrates that operate as oxidisers, and sucrose that acts as fuel. The samples were characterised by X-ray diffraction, transmission electron microscopy, thermal analysis, and impedance and electrochemical measurements. The effect of the fuel content on the purity and morphology of the products was analysed. The samples as prepared showed small amounts of Mn₂O₃ and Mn₃O₄ as impurities, depending on the amount of sucrose used in the synthesis. Annealing at 700 °C led to single-phase cubic spinels. In these phases, the smallest average particle size (ca. 30 nm) corresponded to the sample obtained with a hyperstoichiometric amount of fuel. This sample showed the Li_1.05Mn_1.95O₄ composition as deduced from the thermal and electrochemical data. No variation in conductivity associated with the cubic⇔orthorhombic phase transition was observed. The electrochemical behaviour as positive electrode showed good cyclability at high current densities (reversible capacity of 73 mAh g⁻¹ at 2.46 mA cm⁻²).

Nanosize crystalline cathode materials of LiNi_yMn_{2 − y}O₄ (0 < y ≤ 0.5) composition and spinel-type structure have been obtained by a single-step sucrose-aided self-combustion method. The as-prepared samples contained some amorphous organic impurities that were removed after a short period of heating at 500 °C. The pure single-phase spinels have been characterized by X-ray diffraction, transmission electron microscopy, chemical analysis, and nitrogen sorption isotherms. The samples consist of particles (ca. 24 nm size) that are aggregated in clusters (ca. 1 µm size) in which mesopores (10–80 nm size) appear among the particles. Additional heating at 800° and 1000 °C produces a slight increase in the cubic lattice parameter and a pronounced increase in particle size (>100 nm). Electrical conductivity decreases as the Ni content increases in accordance with an electron hopping mechanism between Mn³⁺ and Mn⁴⁺ ions. The 500 °C- and 800 °C-heated LiNi_0.5Mn_1.5O₄ samples show good electrochemical behaviour at 4.7 V as cathode materials. The capacity (132.7 mA h g⁻¹) found is close to the nominal capacity (146.7 mA h g⁻¹) and remains constant for current densities in the range C/24–2C (where C = 2.6 mA cm⁻²). At higher current densities (2C–10C) the capacity decreases progressively. The cyclability at the C current density is ca. 99.7% for both samples.