Tailoring Pore Size and Catalytic Activity in Cobalt Iron Layered Double Hydroxides and Spinels by Microemulsion-Assisted pH-Controlled Co-Precipitation.

Cobalt iron containing layered double hydroxides (LDHs) and spinels are promising catalysts for the electrochemical oxygen evolution reaction (OER). Towards development of better performing catalysts, the precise tuning of mesostructural features such as pore size is desirable, but often hard to achieve. Herein, a computer-controlled microemulsion-assisted co-precipitation (MACP) method at constant pH is established and compared to conventional co-precipitation. With MACP, the particle growth is limited and through variation of the constant pH during synthesis the pore size of the as-prepared catalysts is controlled, generating materials for the systematic investigation of confinement effects during OER. At a threshold pore size, overpotential increased significantly. Electrochemical impedance spectroscopy (EIS) indicated a change in OER mechanism, involving the oxygen release step. It is assumed that in smaller pores the critical radius for gas bubble formation is not met and therefore a smaller charge-transfer resistance is observed for medium frequencies.

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.

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.

Topotactic Synthesis of Porous Cobalt Ferrite Platelets from a Layered Double Hydroxide Precursor and Their Application in Oxidation Catalysis.

Monocrystalline, yet porous mosaic platelets of cobalt ferrite, CoFe2 O4 , can be synthesized from a layered double hydroxide (LDH) precursor by thermal decomposition. Using an equimolar mixture of Fe2+ , Co2+ , and Fe3+ during co-precipitation, a mixture of LDH, (FeII CoII )2/3 FeIII1/3 (OH)2 (CO3 )1/6 ⋅m H2 O, and the target spinel CoFe2 O4 can be obtained in the precursor. During calcination, the remaining FeII fraction of the LDH is oxidized to FeIII leading to an overall Co2+ :Fe3+ ratio of 1:2 as required for spinel crystallization. This pre-adjustment of the spinel composition in the LDH precursor suggests a topotactic crystallization of cobalt ferrite and yields phase pure spinel in unusual anisotropic platelet morphology. The preferred topotactic relationship in most particles is [111]Spinel ∥[001]LDH . Due to the anion decomposition, holes are formed throughout the quasi monocrystalline platelets. This synthesis approach can be used for different ferrites and the unique microstructure leads to unusual chemical properties as shown by the application of the ex-LDH cobalt ferrite as catalyst in the selective oxidation of 2-propanol. Compared to commercial cobalt ferrite, which mainly catalyzes the oxidative dehydrogenation to acetone, the main reaction over the novel ex-LDH cobalt is dehydration to propene. Moreover, the oxygen evolution reaction (OER) activity of the ex-LDH catalyst was markedly higher compared to the commercial material.