ABSTRACT
Perovskite oxide is a promising alternative to noble metal electrocatalysts for the oxygen evolution reaction (OER). However, as one of the most active oxide catalysts, cubic SrCoO3 presents poor OER performance relative to the theoretically predicted activity. Appropriate introduction of a guest component in the lattice and surface could largely promote the OER activity. Herein, we present a thermal-induced phase-segregation strategy to synthesize a heterostructured SrCo0.8Fe0.5-xO3-δ/FexOy (SC8F5) catalyst for OER. This novel perovskite/Fe3O4 heterostructure allows us to enhance the electrical conductivity ability, increase the Co oxidation state, and activate the surface oxygen to active oxygen species (O22-/O-) for efficient OER. In contrast to the poor stability of SrCo0.8Fe0.2O3-δ, we found that the SC8F5 heterostructure with segregated Fe3O4 on the surface can mitigate surface reconstruction and stabilize the catalyst structure, thereby increasing catalytic stability.
ABSTRACT
The electro-oxidation of methanol to formate is an interesting example of the potential use of renewable energies to add value to a biosourced chemical commodity. Additionally, methanol electro-oxidation can replace the sluggish oxygen evolution reaction when coupled to hydrogen evolution or to the electroreduction of other biomass-derived intermediates. But the cost-effective realization of these reaction schemes requires the development of efficient and low-cost electrocatalysts. Here, a noble metal-free catalyst, Ni1- x Fex Se2 nanorods, with a high potential for an efficient and selective methanol conversion to formate is demonstrated. At its optimum composition, Ni0.75 Fe0.25 Se2 , this diselenide is able to produce 0.47 mmol cm-2 h-1 of formate at 50 mA cm-2 with a Faradaic conversion efficiency of 99%. Additionally, this noble-metal-free catalyst is able to continuously work for over 50 000 s with a minimal loss of efficiency, delivering initial current densities above 50 mA cm-2 and 2.2 A mg-1 in a 1.0 m KOH electrolyte with 1.0 m methanol at 1.5 V versus reversible hydrogen electrode. This work demonstrates the highly efficient and selective methanol-to-formate conversion on Ni-based noble-metal-free catalysts, and more importantly it shows a very promising example to exploit the electrocatalytic conversion of biomass-derived chemicals.
ABSTRACT
In this work, mesoporous Ni-Co composite oxides were synthesized by a facile liquid-precipitation method without the addition of surfactant, and their ability to catalyse a low temperature CO oxidation reaction was investigated. To explore the effect of the synergetic interaction between Ni and Co on the physicochemical properties and catalytic performance of these catalysts, the as-prepared samples were characterized using XRF, XRD, LRS, N2-physisorption (BET), SEM, TEM, XPS, H2-TPR, O2-TPD and in situ DRIFTS characterization techniques. The results are as follows: (1) the doping of cobalt can reduces the size of NiO, thus massive amorphous NiO have formed and highly dispersed on the catalyst surface, resulting in the formation of abundant surface Ni2+ ions; (2) Ni2+ ions partially substitute Co3+ ions to form a Ni-Co spinel solid solution, generating an abundance of surface oxygen vacancies, which are vital for CO oxidation; (3) the Ni0.8Co0.2 catalyst exhibits the highest catalytic activity and a satisfactory stability for CO oxidation, whereas a larger cobalt content results in a decrease in activity, suggesting that the amorphous NiO phase is the dominant active phase instead of Co3O4 for CO oxidation; (4) the introduction of Co can alter the morphology of catalyst from plate-like to flower-like and then to dense granules. This morphological variation is related to the textural properties and catalytic performance of the catalysts. Lastly, a possible mechanism for CO oxidation reaction is tentatively proposed.
