Adsorption and reaction of CO on (Pd–)Al2O3 and (Pd–)ZrO2: vibrational spectroscopy of carbonate formation

γ-Alumina is widely used as an oxide support in catalysis, and palladium nanoparticles supported by alumina represent one of the most frequently used dispersed metals. The surface sites of the catalysts are often probed via FTIR spectroscopy upon CO adsorption, which may result in the formation of surface carbonate species. We have examined this process in detail utilizing FTIR to monitor carbonate formation on γ-alumina and zirconia upon exposure to isotopically labelled and unlabelled CO and CO2. The same was carried out for well-defined Pd nanoparticles supported on Al2O3 or ZrO2. A water gas shift reaction of CO with surface hydroxyls was detected, which requires surface defect sites and adjacent OH groups. Furthermore, we have studied the effect of Cl synthesis residues, leading to strongly reduced carbonate formation and changes in the OH region (isolated OH groups were partly replaced or were even absent). To corroborate this finding, samples were deliberately poisoned with Cl to an extent comparable to that of synthesis residues, as confirmed by Auger electron spectroscopy. For catalysts prepared from Cl-containing precursors a new CO band at 2164 cm−1 was observed in the carbonyl region, which was ascribed to Pd interacting with Cl. Finally, the FTIR measurements were complemented by quantification of the amount of carbonates formed via chemisorption, which provides a tool to determine the concentration of reactive defect sites on the alumina surface

Surface composition changes of CuNi-ZrO2 during methane decomposition: An operando NAP-XPS and density functional study

AbstractBimetallic CuNi nanoparticles of various nominal compositions (1:3, 1:1, 3:1) supported on ZrO2 were employed for operando spectroscopy and theoretical studies of stable surface compositions under reaction conditions of catalytic methane decomposition up to 500°C. The addition of Cu was intended to increase the coke resistance of the catalyst. After synthesis and (in situ) reduction the CuNi nanoparticles were characterized by HR-TEM/EDX, XRD, FTIR (using CO as probe molecule) and NAP-XPS, all indicating a Cu rich surface, even when the overall nanoparticle composition was rich in Ni. Density functional (DF) theory modelling, applying a recently developed computational protocol based on the construction of topological energy expressions, confirmed that in any studied composition Cu segregation on surface positions is an energetically favourable process, with Cu preferentially occupying corner and edge sites. Ni is present on terraces only when not enough Cu atoms are available to occupy all surface sites.When the catalysts were applied for methane decomposition they were inactive at low temperature but became active above 425°C. Synchrotron-based operando NAP-XPS indicated segregation of Ni on the nanoparticle surface when reactivity set in for CuNi-ZrO2. Under these conditions C 1s core level spectra revealed the presence of various carbonaceous species at the surface. DF calculations indicated that both the increase in temperature and especially the adsorption of CHx groups (x=0-3) induce the segregation of Ni atoms on the surface, with CH3 providing the lowest and C the highest driving force.Combined operando and theoretical studies clearly indicate that, independent of the initial surface composition after synthesis and reduction, the CuNi-ZrO2 catalyst adopts a specific Ni rich surface under reaction conditions. Based on these findings we provide an explanation why Cu rich bimetallic systems show improved coke resistance

Directing Intrinsic Chirality in Gold Nanoclusters: Preferential Formation of Stable Enantiopure Clusters in High Yield and Experimentally Unveiling the “Super” Chirality of Au144_{144}

Chiral gold nanoclusters offer significant potential for exploring chirality at a fundamental level and for exploiting their applications in sensing and catalysis. However, their widespread use is impeded by low yields in synthesis, tedious separation procedures of their enantiomeric forms, and limited thermal stability. In this study, we investigated the direct synthesis of enantiopure chiral nanoclusters using the chiral ligand 2-MeBuSH in the fabrication of Au$_{25}$, Au$_{38}$, and Au$_{144}$ nanoclusters. Notably, this approach leads to the unexpected formation of intrinsically chiral clusters with high yields for chiral Au$_{38}$ and Au$_{144}$ nanoclusters. Experimental evaluation of chiral activity by circular dichroism (CD) spectroscopy corroborates previous theoretical calculations, highlighting the stronger CD signal exhibited by Au$_{144}$ compared to Au$_{38}$ or Au$_{25}$. Furthermore, the formation of a single enantiomeric form is experimentally confirmed by comparing it with intrinsically chiral Au$_{38}$(2-PET)$_{24}$ (2-PET: 2-phenylethanethiol) and is supported theoretically for both Au$_{38}$ and Au$_{144}$. Moreover, the prepared chiral clusters show stability against diastereoisomerization, up to temperatures of 80°C. Thus, our findings not only demonstrate the selective preparation of enantiopure, intrinsically chiral, and highly stable thiolate-protected Au nanoclusters through careful ligand design but also support the predicted “super” chirality in the Au$_{144}$ cluster, encompassing hierarchical chirality in ligands, staple configuration, and core structure

Tuning interactions of surface‐adsorbed species over Fe−Co/K−Al2O3 catalyst by different K contents: selective CO2 hydrogenation to light olefins

Selective CO2 hydrogenation to light olefins over Fe−Co/K−Al2O3 catalysts was enhanced by tuning bonding strengths of adsorbed species by varying the content of the K promotor. Increasing the K/Fe atomic ratio from 0 to 0.5 increased the olefins/paraffins (O/P) ratio by 25.4 times, but then slightly raised upon ascending K/Fe to 2.5. The positive effect of K addition is attributed to the strong interaction of H adsorbed with the catalyst surface caused by the electron donor from K to Fe species. Although the Fe−Co/K−Al2O3 catalyst with K/Fe=2.5 reached the highest O/P ratio of 7.6, the maximum yield of light olefins of 16.4 % was achieved by the catalyst promoted with K/Fe of 0.5. This is explained by the considerable reduction of amount of H2 adsorbed on the catalyst surface with K/Fe=2.5

The Chemical Evolution of the La0.6Sr0.4CoO3−δ Surface Under SOFC Operating Conditions and Its Implications for Electrochemical Oxygen Exchange Activity

© The Author(s) 2018Owing to its extraordinary high activity for catalysing the oxygen exchange reaction, strontium doped LaCoO3 (LSC) is one of the most promising materials for solid oxide fuel cell (SOFC) cathodes. However, under SOFC operating conditions this material suffers from performance degradation. This loss of electrochemical activity has been extensively studied in the past and an accumulation of strontium at the LSC surface has been shown to be responsible for most of the degradation effects. The present study sheds further light onto LSC surface changes also occurring under SOFC operating conditions. In-situ near ambient pressure X-ray photoelectron spectroscopy measurements were conducted at temperatures between 400 and 790 °C. Simultaneously, electrochemical impedance measurements were performed to characterise the catalytic activity of the LSC electrode surface for O2 reduction. This combination allowed a correlation of the loss in electro-catalytic activity with the appearance of an additional La-containing Sr-oxide species at the LSC surface. This additional Sr-oxide species preferentially covers electrochemically active Co sites at the surface, and thus very effectively decreases the oxygen exchange performance of LSC. Formation of precipitates, in contrast, was found to play a less important role for the electrochemical degradation of LSC.Fonds zur Förderung der wissenschaftlichen Forschung (FWF)212921411

Surface vibrational spectroscopy on noble metal catalysts from ultrahigh vacuum to atmospheric pressure

There is a long-standing question whether results of studies of surface processes under ultrahigh vacuum (UHV) can be truly transferred to the conditions of heterogeneous catalysis. Several in-situ surface-sensitive methods have been developed that can operate in a pressure range from UHV to ambient conditions, that may help to answer this question. By applying in-situ methods to single-crystal surfaces as well as supported nanoparticles, the pressure and materials gaps between surface science and heterogeneous catalysis can be simultaneously bridged. Vibrational spectroscopy techniques, i.e. IR-vis sum frequency generation (SFG) and polarization-modulation infrared reflection absorption spectroscopy (PM-IRAS) are applied to study the adsorption, coadsorption and reaction of small molecules on transition metal surfaces (Pt, Rh, Pd, Au, Ru) from UHV to 1 bar. The goal of these in-situ studies at mbar pressures is, of course, to elucidate the elementary steps of heterogeneous catalytic reactions. Case studies include CO adsorption and dissociation, CO oxidation and hydrogenation, ethylene adsorption and hydrogenation, and methanol decomposition on low-index single-crystal surfaces, defect-rich (stepped or ion-bombarded) single-crystal surfaces, as well as oxide supported metal nanoparticles. The potential of polarization-dependent SFG to determine the molecular orientation of adsorbates and of time-resolved broadband SFG is demonstrated. If available, complementary structural information by high-pressure scanning tunneling microscopy (HP-STM) and compositional analysis by high-pressure photoelectron spectroscopy (HP-XPS) was also included. Implications of the described results on the mechanism, activity and selectivity of catalyzed reactions are discussed