In heterogeneous catalysis, surfaces decorated with uniformly dispersed, catalytically-active (nano)particles are a key requirement for excellent performance. Beside standard catalyst preparation routines—with limitations in controlling catalyst surface structure (i.e., particle size distribution or dispersion)—we present here a novel time efficient route to precisely tailor catalyst surface morphology and composition of perovskites. Perovskite-type oxides of nominal composition ABO₃ with transition metal cations on the B-site can exsolve the B-site transition metal upon controlled reduction. In this exsolution process, the transition metal emerges from the oxide lattice and migrates to the surface where it forms catalytically active nanoparticles. Doping the B-site with reducible and catalytically highly active elements, offers the opportunity of tailoring properties of exsolution catalysts. Here, we present the synthesis of two novel perovskite catalysts Nd_0.6Ca_0.4FeO_3-δ and Nd_0.6Ca_0.4Fe_0.9Co_0.1O_3-δ with characterisation by (in situ) XRD, SEM/TEM and XPS, supported by theory (DFT+U). Fe nanoparticle formation was observed for Nd_0.6Ca_0.4FeO_3-δ. In comparison, B site cobalt doping leads, already at lower reduction temperatures, to formation of finely dispersed Co nanoparticles on the surface. These novel perovskite-type catalysts are highly promising for applications in chemical energy conversion. First measurements revealed that exsolved Co nanoparticles significantly improve the catalytic activity for CO₂ activation via reverse water gas shift reaction.

For an in-depth characterization of catalytic materials and their properties, spectroscopic in-situ (operando) investigations are indispensable. With the rapid development of advanced commercial spectroscopic equipment, it is possible to combine complementary methods in a single system. This allows for simultaneously gaining insights into surface and bulk properties of functional oxides, such as defect chemistry, catalytic characteristics, electronic structure, etc., enabling a direct correlation of structure and reactivity of catalyst materials, thus facilitating effective catalyst development. Here, we present a novel sample-stage, which was specifically developed to pave the way to a lab–based combination of near ambient pressure X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy with simultaneous catalytic operando measurements. This setup is designed to probe different (model) systems under conditions close to real heterogeneous catalysis, with a focus on solid oxide electrochemical cells. In a proof of concept experiment using an electrochemical model cell with the doped perovskite Nd_0.6Ca_0.4Fe_0.9Co_0.1O_3-δ as working electrode, the precise control of the surface chemistry that is possible with this setup is demonstrated. The exsolution behavior of the material was studied, showing that at a lower temperature (500 °C) with lower reducing potential of the gas phase, only cobalt was exsolved, forming metallic particles on the surface of the perovskite-type oxide. Only when the temperature was increased to 600 °C and a cathodic potential was applied (−250 mV) Fe also started to be released from the perovskite lattice.

Perovskite-type oxide materials (nominal composition ABO₃) are a very versatile class of materials, and their properties are tuneable by varying and doping A- and B-site cations. When the B-site contains easily reducible cations (e.g. Fe, Co or Ni), these can exsolve under reducing conditions and form metallic nanoparticles on the surface. This process is very interesting as a novel route for the preparation of catalysts, since oxide surfaces decorated with finely dispersed catalytically active (often metallic) nanoparticles are a key requirement for excellent catalyst performance. Five doped perovskites, namely, La_0.9Ca_0.1FeO_3–δ, La_0.6Ca_0.4FeO_3–δ, Nd_0.9Ca_0.1FeO_3–δ, Nd_0.6Ca_0.4FeO_3–δ and Nd_0.6Ca_0.4Fe_0.9Co_0.1O_3–δ, have been synthesized and characterized by experimental and theoretical methods with respect to their crystal structures, electronic properties, morphology and exsolution behaviour. All are capable of exsolving Fe and/or Co. Special emphasis has been placed on the influence of the A-site elemental composition on structure and exsolution capability. Using Nd instead of La increased structural distortions and, at the same time, hindered exsolution. Increasing the amount of Ca doping also increased distortions and additionally changed the Fe oxidation states, resulting in exsolution being shifted to higher temperatures as well. Using the easily reducible element Co as the B-site dopant significantly facilitated the exsolution process and led to much smaller and homogeneously distributed exsolved particles. Therefore, the Co-doped perovskite is a promising material for applications in catalysis, even more so as Co is catalytically a highly active element. The results show that fine-tuning of the perovskite composition will allow tailored exsolution of nanoparticles, which can be used for highly sophisticated catalyst design.

High temperature water-gas shift (HT-WGS) is an industrially highly relevant reaction. Moreover, climate change and the resulting necessary search for sustainable energy sources are making WGS and reverse-WGS catalytic key reactions for synthetic fuel production. Hence, extensive research has been done to develop improved or novel catalysts. An extremely promising material class for novel highly active HT-WGS catalysts with superior thermal stability are perovskite-type oxides. With their large compositional flexibility, they enable new options for rational catalyst design. Particularly, both cation sites (A and B in ABO₃) can be doped with promoters or catalytically active elements. Additionally, B-site dopants are able to migrate to the surface under reducing conditions (a process called exsolution), forming catalytically active nanoparticles and creating an interface that can strongly boost catalytic performance. In this study, we varied A-site composition and B-site doping (Ni, Co), thus comparing six novel perovskites and testing them for their HT-WGS activity: La_0.9Ca_0.1FeO_3-δ, La_0.6Ca_0.4FeO_3-δ, Nd_0.9Ca_0.1FeO_3-δ, Nd_0.6Ca_0.4FeO_3-δ, Nd_0.6Ca_0.4Fe_0.9Ni_0.1O_3-δ and Nd_0.6Ca_0.4Fe_0.9Co_0.1O_3-δ. Cobalt and Nickel doping resulted in the highest activity observed in our study, highlighting that doped perovskites are promising novel HT-WGS catalysts. The effect of the compositional variations is discussed considering the kinetics of the two partial reactions of WGS-CO oxidation and water splitting.

Perovskite-type oxides are highly flexible materials that show properties that are beneficial for application in reverse water-gas shift processes (rWGS). Due to their stable nature, the ability to incorporate catalytically active dopants in their lattice structure, and the corresponding feature of nanoparticle exsolution, they are promising candidates for a materials design approach. On an industrial level, the rWGS has proven to be an excellent choice for the efficient utilisation of CO₂ as an abundant and renewable carbon source, reflected by the current research on novel and improved catalyst materials. In the current study, a correlation between rWGS reaction environments (CO₂ to H₂ ratios and temperature), surface morphology, and catalytic activity of three perovskite catalysts (Nd_0.6Ca_0.4Fe_0.9Co_0.1O_3-δ, Nd_0.6Ca_0.4Fe_0.97Co_0.03O_3-δ, and Nd_0.6Ca_0.4Fe_0.97Ni_0.03O_3-δ) is investigated, combining catalytic measurements with SEM and NAP-XPS. The materials were found to react dynamically to the conditions showing both activation due to in situ nanoparticle exsolution and deactivation via CaCO₃ formation. This phenomenon could be influenced by choice of material and conditions: less reductive conditions (larger CO₂ to H₂ or lower temperature) lead to smaller exsolved particles and reduced carbonate formation. However, the B-site doping was also important; only with 10% Co-doping, a predominant activation could be achieved.