Molecular spectroscopy for ground-state transfer of ultracold RbCs molecules

We perform one- and two-photon high resolution spectroscopy on ultracold samples of RbCs Feshbach molecules with the aim to identify a suitable route for efficient ground-state transfer in the quantum-gas regime to produce quantum gases of dipolar RbCs ground-state molecules. One-photon loss spectroscopy allows us to probe deeply bound rovibrational levels of the mixed excited (A1{\Sigma}+ - b3{\Pi}0) 0+ molecular states. Two-photon dark state spectroscopy connects the initial Feshbach state to the rovibronic ground state. We determine the binding energy of the lowest rovibrational level |v"=0,J"=0> of the X1{\Sigma}+ ground state to be DX 0 = 3811.5755(16) 1/cm, a 300-fold improvement in accuracy with respect to previous data. We are now in the position to perform stimulated two-photon Raman transfer to the rovibronic ground state.Comment: Submitted to PCCP themed issue: Physics and Chemistry of Cold Molecule

In Situ Growth of Exsolved Nanoparticles under Varying rWGS Reaction Conditions—A Catalysis and Near Ambient Pressure-XPS Study

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 (Nd0.6Ca0.4Fe0.9Co0.1O3-δ, Nd0.6Ca0.4Fe0.97Co0.03O3-δ, and Nd0.6Ca0.4Fe0.97Ni0.03O3-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

High Temperature Water Gas Shift Reactivity of Novel Perovskite Catalysts

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: La0.9Ca0.1FeO3-δ, La0.6Ca0.4FeO3-δ, Nd0.9Ca0.1FeO3-δ, Nd0.6Ca0.4FeO3-δ, Nd0.6Ca0.4Fe0.9Ni0.1O3-δ and Nd0.6Ca0.4Fe0.9Co0.1O3-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

Novel Sample-Stage for Combined Near Ambient Pressure X-ray Photoelectron Spectroscopy, Catalytic Characterization and Electrochemical Impedance Spectroscopy

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 Nd0.6Ca0.4Fe0.9Co0.1O3-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 Catalysts in CO2 Utilization: A Principal Study of Novel Cu-Doped Perovskites for Methanol Synthesis

Six different perovskite-type oxides were investigated with respect to their ability for methanol synthesis via H2 and CO2: Fe-, Mn-, and Ti-based perovskites were prepared with and without Cu doping. For assessment, the catalysts were subjected to preliminary tests at atmospheric pressure to evaluate their ability to activate CO2. Additional catalytic tests with the doped versions of each catalyst type were carried out in a pressured reactor at 21 bar. After the measurements, the catalysts were characterized with X-ray diffraction (XRD) and scanning electron microscopy (SEM). All catalysts were able to produce methanol in the pressure tests. CO2 conversions between 14% and 23% were reached at 400 °C, with the highest methanol selectivity at the lower temperature of 250 °C. The combination of XRD and SEM revealed that the Fe-based and Ti-based perovskites were stable under reaction conditions and that catalytically highly active and stable nanoparticles had formed. The minor formation of CaCO3, which is a deactivating phase, was observed for one catalyst. These nanoparticles showed resistance to coking and sintering. However, the yield and selectivity for methanol need to be improved via the further tailoring of the perovskite composition

Near-Ambient-Pressure X‑ray Photoelectron Spectroscopy Study of Methane-Induced Carbon Deposition on Clean and Copper-Modified Polycrystalline Nickel

ABSTRACT: In order to simulate solid-oxide fuel cell (SOFC)-related coking mechanisms of Ni, methane-induced surface carbide and carbon growth was studied under close-to-real conditions by synchrotron-based near-ambient-pressure (NAP) X-ray photoelectron spectroscopy (XPS) in the temperature region between 250 and 600 °C. Two complementary polycrystalline Ni samples were used, namely, Ni foamserving as a model structure for bulk Ni in cermet materials such as Ni/YSZ and Ni foil. The growth mechanism of graphene/graphite species was found to be closely related to that previously described for ethylene-induced graphene growth on Ni(111). After a sufficiently long “incubation ” period of the Ni foam in methane at 0.2 mbar and temperatures around 400 °C, cooling down to ∼250 °C, and keeping the sample at this temperature for 50−60 min, initial formation of a near-surface carbide phase was observed, which exhibited the same spectroscopic fingerprint as the C2H4 induced Ni2C phase on Ni(111). Only in the presence of this carbidic species, subsequent graphene/graphite nucleation and growth was observed. Vice versa, the absence of this species excluded further graphene/graphite formation. At temperatures above 400 °C, decomposition/bul

Towards the production of ultracold ground-state RbCs molecules: Feshbach resonances, weakly bound states, and the coupled-channel model

We have studied interspecies scattering in an ultracold mixture of 87Rb and 133Cs atoms, both in their lowest-energy spin states. The three-body loss signatures of 30 incoming s- and p-wave magnetic Feshbach resonances over the range 0 to 667 G have been cataloged. Magnetic field modulation spectroscopy was used to observe molecular states bound by up to 2.5 MHz×h. We have created RbCs Feshbach molecules using two of the resonances. Magnetic moment spectroscopy along the magnetoassociation pathway from 197 to 182 G gives results consistent with the observed and calculated dependence of the binding energy on magnetic field strength. We have set up a coupled-channel model of the interaction and have used direct least-squares fitting to refine its parameters to fit the experimental results from the Feshbach molecules, in addition to the Feshbach resonance positions and the spectroscopic results for deeply bound levels. The final model gives a good description of all the experimental results and predicts a large resonance near 790 G, which may be useful for tuning the interspecies scattering properties. Quantum numbers and vibrational wave functions from the model can also be used to choose optimal initial states of Feshbach molecules for their transfer to the rovibronic ground state using stimulated Raman adiabatic passage