Synergistic Effects of Co and Fe on the Oxygen Evolution Reaction Activity of LaCox Fe1-x O3.

In a combined experimental and theoretical study we assess the role of Co incorporation on the OER activity of LaCox Fe1-x O3 . Phase pure perovskites were synthesized up to x = 0 . 300 in 0.025/0.050 steps. HAADF STEM and EDX analysis points towards FeO2 -terminated (001)-facets in LaFeO3 , in accordance with the stability diagram obtained from density functional theory calculations with a Hubbard U term (DFT+U). Linear sweep voltammetry conducted in a rotating disk electrode setup shows a reduction of the OER overpotential and a nonmonotonic trend with x, with double layer capacitance measurements indicating an intrinsic nature of activity. This is supported by DFT+U results that show reduced overpotentials for both Fe and Co reaction sites with the latter reaching values of 0.32-0.40 V, ∼0.3 V lower than for Fe. This correlates with a stronger reduction of the binding energy difference of the *O and *OH intermediates towards an optimum value of 1.6 eV for x = 0 . 250 , the OH deprotonation being the potential limiting step in most cases. Significant variations of the magnetic moments of both surface and subsurface Co and Fe during OER demonstrate that the beneficial effect is a result of a concerted action involving many surrounding ions, which extends the concept of the active site.

The Effect of Water on the 2-Propanol Oxidation Activity of Co-Substituted LaFe1- Cox O3 Perovskites.

Perovskites are interesting oxidation catalysts due to their chemical flexibility enabling the tuning of several properties. In this work, we synthesized LaFe1-x Cox O3 catalysts by co-precipitation and thermal decomposition, characterized them thoroughly and studied their 2-propanol oxidation activity under dry and wet conditions to bridge the knowledge gap between gas and liquid phase reactions. Transient tests showed a highly active, unstable low-temperature (LT) reaction channel in conversion profiles and a stable, less-active high-temperature (HT) channel. Cobalt incorporation had a positive effect on the activity. The effect of water was negative on the LT channel, whereas the HT channel activity was boosted for x>0.15. The boost may originate from a slower deactivation rate of the Co3+ sites under wet conditions and a higher amount of hydroxide species on the surface comparing wet to dry feeds. Water addition resulted in a slower deactivation for Co-rich catalysts and higher activity in the HT channel state.

Monitoring Catalytic 2-Propanol Oxidation over Co3O4 Nanowires via In Situ Photoluminescence Spectroscopy.

Spectroscopic methods enabling real-time monitoring of dynamic surface processes are a prerequisite for identifying how a catalyst triggers a chemical reaction. We present an in situ photoluminescence spectroscopy approach for probing the thermocatalytic 2-propanol oxidation over mesostructured Co3O4 nanowires. Under oxidative conditions, a distinct blue emission at ∼420 nm is detected that increases with temperature up to 280 °C, with an intermediate maximum at 150 °C. Catalytic data gained under comparable conditions show that this course of photoluminescence intensity precisely follows the conversion of 2-propanol and the production of acetone. The blue emission is assigned to the radiative recombination of unbound acetone molecules, the n ↔ π* transition of which is selectively excited by a wavelength of 270 nm. These findings open a pathway for studying thermocatalytic processes via in situ photoluminescence spectroscopy, thereby gaining information about the performance of the catalyst and the formation of intermediate products.