Highly loaded bimetallic iron-cobalt catalysts for hydrogen release from ammonia.

Ammonia is a storage molecule for hydrogen, which can be released by catalytic decomposition. Inexpensive iron catalysts suffer from a low activity due to a too strong iron-nitrogen binding energy compared to more active metals such as ruthenium. Here, we show that this limitation can be overcome by combining iron with cobalt resulting in a Fe-Co bimetallic catalyst. Theoretical calculations confirm a lower metal-nitrogen binding energy for the bimetallic catalyst resulting in higher activity. Operando spectroscopy reveals that the role of cobalt in the bimetallic catalyst is to suppress the bulk-nitridation of iron and to stabilize this active state. Such catalysts are obtained from Mg(Fe,Co)2O4 spinel pre-catalysts with variable Fe:Co ratios by facile co-precipitation, calcination and reduction. The resulting Fe-Co/MgO catalysts, characterized by an extraordinary high metal loading reaching 74 wt.%, combine the advantages of a ruthenium-like electronic structure with a bulk catalyst-like microstructure typical for base metal catalysts.

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.

Role of Nanoscale Inhomogeneities in Co2FeO4 Catalysts during the Oxygen Evolution Reaction.

Spinel-type catalysts are promising anode materials for the alkaline oxygen evolution reaction (OER), exhibiting low overpotentials and providing long-term stability. In this study, we compared two structurally equal Co2FeO4 spinels with nominally identical stoichiometry and substantially different OER activities. In particular, one of the samples, characterized by a metastable precatalyst state, was found to quickly achieve its steady-state optimum operation, while the other, which was initially closer to the ideal crystallographic spinel structure, never reached such a state and required 168 mV higher potential to achieve 1 mA/cm2. In addition, the enhanced OER activity was accompanied by a larger resistance to corrosion. More specifically, using various ex situ, quasi in situ, and operando methods, we could identify a correlation between the catalytic activity and compositional inhomogeneities resulting in an X-ray amorphous Co2+-rich minority phase linking the crystalline spinel domains in the as-prepared state. Operando X-ray absorption spectroscopy revealed that these Co2+-rich domains transform during OER to structurally different Co3+-rich domains. These domains appear to be crucial for enhancing OER kinetics while exhibiting distinctly different redox properties. Our work emphasizes the necessity of the operando methodology to gain fundamental insight into the activity-determining properties of OER catalysts and presents a promising catalyst concept in which a stable, crystalline structure hosts the disordered and active catalyst phase.

The Roles of Composition and Mesostructure of Cobalt-Based Spinel Catalysts in Oxygen Evolution Reactions.

By using the crystalline precursor decomposition approach and direct co-precipitation the composition and mesostructure of cobalt-based spinels can be controlled. A systematic substitution of cobalt with redox-active iron and redox-inactive magnesium and aluminum in a cobalt spinel with anisotropic particle morphology with a preferred 111 surface termination is presented, resulting in a substitution series including Co3 O4 , MgCo2 O4 , Co2 FeO4 , Co2 AlO4 and CoFe2 O4 . The role of redox pairs in the spinels is investigated in chemical water oxidation by using ceric ammonium nitrate (CAN test), electrochemical oxygen evolution reaction (OER) and H2 O2 decomposition. Studying the effect of dominant surface termination, isotropic Co3 O4 and CoFe2 O4 catalysts with more or less spherical particles are compared to their anisotropic analogues. For CAN-test and OER, Co3+ plays the major role for high activity. In H2 O2 decomposition, Co2+ reveals itself to be of major importance. Redox active cations in the structure enhance the catalytic activity in all reactions. A benefit of a predominant 111 surface termination depends on the cobalt oxidation state in the as-prepared catalysts and the investigated reaction.

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.

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.

Factors Governing the Activity of α-MnO2 Catalysts in the Oxygen Evolution Reaction: Conductivity versus Exposed Surface Area of Cryptomelane.

Cryptomelane (α-(K)MnO2 ) powders were synthesized by different methods leading to only slight differences in their bulk crystal structure and chemical composition, while the BET surface area and the crystallite size differed significantly. Their performance in the oxygen evolution reaction (OER) covered a wide range and their sequence of increasing activity differed when electrocatalysis in alkaline electrolyte and chemical water oxidation using Ce4+ were compared. The decisive factors that explain this difference were identified in the catalysts' microstructure. Chemical water oxidation activity is substantially governed by the exposed surface area, while the electrocatalytic activity is determined largely by the electric conductivity, which was found to correlate with the particle morphology in terms of needle length and aspect ratio in this sample series. This correlation is rather explained by an improved conductivity due to longer needles than by structure sensitivity as was supported by reference experiments using H2 O2 decomposition and carbon black as additive. The most active catalyst R-cryptomelane reached a current density of 10 mA cm-2 at a potential 1.73 V without, and at 1.71 V in the presence of carbon black. The improvement was significantly higher for the catalyst with lower initial activity. However, the materials showed a disappointing catalytic stability during alkaline electrochemical OER, whereas the crystal structure was found to be stable at working conditions.

On tuning microgel character and softness of cross-linked polystyrene particles.

Polystyrene (PS) microgel colloids have often been used successfully to model hard sphere behaviour even though the term "gel" invokes inevitably the notion of a more or less soft, deformable object. Here we systematically study the effect of reducing the cross-link density from 1 : 10 (1 cross-link per 10 monomers) to 1 : 100 on particle interactions and "softness". We report on the synthesis and purification of 1 : 10, 1 : 25, 1 : 50, 1 : 75 and 1 : 100 cross-linked PS particles and their characterization in terms of single particle properties, as well as the behaviour of concentrated dispersions. We are able to tune particle softness in the range between soft PNiPAM-microgels and hard PMMA particles while still allowing the mapping of the microgels onto hard sphere behavior with respect to phase diagram and static structure factors. This is mainly due to a rather homogeneous radial distribution of cross-links in contrast to PNiPAM microgels where the cross-link density decreases radially. We find that up to a cross-link density of 1 : 50 particle form factors are perfectly described by a homogeneous sphere model whereas 1 : 75 and 1 : 100 cross-linked spheres are slightly better described as fuzzy spheres. However the fuzziness is rather small compared to typical PNiPAM microgels so that a hard sphere mapping still holds even for these low cross-link densities. Finally, by varying the reaction conditions - changing from batch to semibatch emulsion polymerization and varying the feed rate or by adjusting the monomer to initiator ratio we can tune the fuzziness or significantly alter the inner structure to a more open, star-like architecture.