Operando Laboratory-Based Multi-Edge X-Ray Absorption Near-Edge Spectroscopy of Solid Catalysts

Laboratory-based X-ray absorption spectroscopy (XAS) and especially X-ray absorption near-edge structure (XANES) offers new opportunities in catalyst characterization and presents not only an alternative, but also a complementary approach to precious beamtime at synchrotron facilities. We successfully designed a laboratory-based setup for performing operando , quasi-simultaneous XANES analysis at multiple K edges, more specifically, operando XANES of mono-, bi-, and trimetallic CO 2 hydrogenation catalysts containing Ni, Fe, and Cu. Detailed operando XANES studies of the multi-element solid catalysts revealed metal-dependent differences in the reducibility and re-oxidation behavior and their influence on the catalytic performance in CO 2 hydrogenation. The applicability of operando laboratory-based XANES at multiple K edges paves the way for advanced multi-element catalyst characterization complementing detailed studies at synchrotron facilities.Peer reviewe

In Situ X-ray Raman Scattering Spectroscopy of the Formation of Cobalt Carbides in a Co/TiO2 Fischer–Tropsch Synthesis Catalyst

We present in situ experiments to study the possible formation of cobalt carbides during Fischer–Tropsch synthesis (FTS) in a Co/TiO2 catalyst at relevant conditions of pressure and temperature. The experiments were performed by a combination of X-ray Raman scattering (XRS) spectroscopy and X-ray diffraction (XRD). Two different experiments were performed: (1) a Fischer–Tropsch Synthesis (FTS) reaction of an ∼14 wt % Co/TiO2 catalyst at 523 K and 5 bar under H2 lean conditions (i.e., a H2:CO ratio of 0.5) and (2) carburization of pure cobalt (as reference experiment). In both experiments, the Co L3-edge XRS spectra reveal a change in the oxidation state of the cobalt nanoparticles, which we assign to the formation of cobalt carbide (Co2C). The C K edge XRS spectra were used to quantify the formation of different carbon species in both experiments.Peer reviewe

Detecting Cage Crossing and Filling Clusters of Magnesium and Carbon Atoms in Zeolite SSZ-13 with Atom Probe Tomography

The conversion of methanol to valuable hydrocarbon molecules is of great commercial interest, as the process serves as a sustainable alternative for the production of, for instance, the base chemicals for plastics. The reaction is catalyzed by zeolite materials. By the introduction of magnesium as a cationic metal, the properties of the zeolite, and thereby the catalytic performance, are changed. With atom probe tomography (APT), nanoscale relations within zeolite materials can be revealed: i.e., crucial information for a fundamental mechanistic understanding. We show that magnesium forms clusters within the cages of zeolite SSZ-13, while the framework elements are homogeneously distributed. These clusters of just a few nanometers were analyzed and visualized in 3-D. Magnesium atoms seem to initially be directed to the aluminum sites, after which they aggregate and fill one or two cages in the zeolite SSZ-13 structure. The presence of magnesium in zeolite SSZ-13 increases the lifetime as well as the propylene selectivity. By using operando UV-vis spectroscopy and X-ray diffraction techniques, we are able to show that these findings are related to the suppression of aromatic intermediate products, while maintaining the formation of polyaromatic compounds. Further nanoscale analysis of the spent catalysts showed indications of magnesium redistribution after catalysis. Unlike zeolite H-SSZ-13, for which only a homogeneous distribution of carbon was found, carbon can be either homogeneously or heterogeneously distributed within zeolite Mg-SSZ-13 crystals as the magnesium decreases the coking rate. Carbon clusters were isolated, visualized, and analyzed and were assumed to be polyaromatic compounds. Small one-cage-filling polyaromatic compounds were identified; furthermore, large-cage-crossing aromatic molecules were found by isolating large coke clusters, demonstrating the unique coking mechanism in zeolite SSZ-13. Short-length-scale evidence for the formation of polyaromatic compounds at acid sites is discovered, as clear nanoscale relations between aluminum and carbon atoms exist

Operando Laboratory-based Multi-edge X-ray Absorption Near-Edge Spectroscopy of Solid Catalysts

Laboratory-based X-ray absorption spectroscopy (XAS) and especially X-ray absorption near-edge structure (XANES) offers new opportunities in catalyst characterization and presents not only an alternative, but also a complementary approach to precious beamtime at synchrotron facilities. We successfully designed a laboratory-based setup for performing operando , quasi-simultaneous XANES analysis at multiple K edges, more specifically, operando XANES of mono-, bi-, and trimetallic CO 2 hydrogenation catalysts containing Ni, Fe, and Cu. Detailed operando XANES studies of the multi-element solid catalysts revealed metal-dependent differences in the reducibility and re-oxidation behavior and their influence on the catalytic performance in CO 2 hydrogenation. The applicability of operando laboratory-based XANES at multiple K edges paves the way for advanced multi-element catalyst characterization complementing detailed studies at synchrotron facilities

The EC-Earth3 Earth system model for the Coupled Model Intercomparison Project 6

The Earth system model EC-Earth3 for contributions to CMIP6 is documented here, with its flexible coupling framework, major model configurations, a methodology for ensuring the simulations are comparable across different high-performance computing (HPC) systems, and with the physical performance of base configurations over the historical period. The variety of possible configurations and sub-models reflects the broad interests in the EC-Earth community. EC-Earth3 key performance metrics demonstrate physical behavior and biases well within the frame known from recent CMIP models. With improved physical and dynamic features, new Earth system model (ESM) components, community tools, and largely improved physical performance compared to the CMIP5 version, EC-Earth3 represents a clear step forward for the only European community ESM. We demonstrate here that EC-Earth3 is suited for a range of tasks in CMIP6 and beyond.Peer reviewe

Methane-to-methanol conversion over zeolite Cu-SSZ-13, and its comparison with the selective catalytic reduction of NOx with NH3

The direct conversion of methane into methanol is considered as one of the holy grails in hydrocarbon chemistry and recently it was found that small pore zeolites, such as Cu-SSZ-13, Cu-SSZ-16 and Cu-SSZ-39, are active for this process. Here, we propose a reaction mechanism based on spectroscopic evidence for the methane-to-methanol reaction over Cu-SSZ-13 (Si/Al = 20). Using in situ FT-IR and operando UV-vis-NIR DRS, performed on a series of different Cu-ion-exchanged SSZ-13 zeolites, both a mono-nuclear site or a dimeric copper active site are consistent with the observations of this study. These proposed active site(s) are characterized by a [small nu]OH at [similar]3654 cm-1 and a charge transfer (CT) transition at [similar]29 000 cm-1. We have further evidence to complete the full catalytic cycle to methanol, including the formation of the reaction intermediate Cu(CH3)(H2O), which is characterized by overtone transitions, i.e., a 2[small nu]CH at [similar]4200 cm-1 and a 2[small nu]OH at [similar]5248 cm-1. We found that increasing the pre-oxidation temperature from 450 [degree]C to 550 [degree]C resulted in a 15% increase in methanol production, as well as a concomitant increase of the 29 000 cm-1 CT transition. Furthermore, Cu-exchanged SSZ-13 zeolites, which perform well in the NH3-SCR reaction at 200 [degree]C (the low temperature regime), also show a high activity in the methane-to-methanol reaction and vice versa, leading us to believe that this material has a similar if not the same active site for both the catalytic reduction of NO and the stepwise reaction towards methanol

Methane-to-methanol conversion over zeolite Cu-SSZ-13, and its comparison with the selective catalytic reduction of NOx with NH3

The direct conversion of methane into methanol is considered as one of the holy grails in hydrocarbon chemistry and recently it was found that small pore zeolites, such as Cu-SSZ-13, Cu-SSZ-16 and Cu-SSZ-39, are active for this process. Here, we propose a reaction mechanism based on spectroscopic evidence for the methane-to-methanol reaction over Cu-SSZ-13 (Si/Al = 20). Using in situ FT-IR and operando UV-vis-NIR DRS, performed on a series of different Cu-ion-exchanged SSZ-13 zeolites, both a mono-nuclear site or a dimeric copper active site are consistent with the observations of this study. These proposed active site(s) are characterized by a [small nu]OH at [similar]3654 cm-1 and a charge transfer (CT) transition at [similar]29 000 cm-1. We have further evidence to complete the full catalytic cycle to methanol, including the formation of the reaction intermediate Cu(CH3)(H2O), which is characterized by overtone transitions, i.e., a 2[small nu]CH at [similar]4200 cm-1 and a 2[small nu]OH at [similar]5248 cm-1. We found that increasing the pre-oxidation temperature from 450 [degree]C to 550 [degree]C resulted in a 15% increase in methanol production, as well as a concomitant increase of the 29 000 cm-1 CT transition. Furthermore, Cu-exchanged SSZ-13 zeolites, which perform well in the NH3-SCR reaction at 200 [degree]C (the low temperature regime), also show a high activity in the methane-to-methanol reaction and vice versa, leading us to believe that this material has a similar if not the same active site for both the catalytic reduction of NO and the stepwise reaction towards methanol

Nanoscale tomography reveals the deactivation of automotive copper-exchanged zeolite catalysts

Copper-exchanged zeolite chabazite (Cu-SSZ-13) was recently commercialized for the selective catalytic reduction of NOX with ammonia in vehicle emissions as it exhibits superior reaction performance and stability compared to all other catalysts, notably Cu-ZSM-5. Herein, the 3D distributions of Cu as well as framework elements (Al, O, Si) in both fresh and aged Cu-SSZ-13 and Cu-ZSM-5 are determined with nanometer resolution using atom probe tomography (APT), and correlated with catalytic activity and other characterizations. Both fresh catalysts contain a heterogeneous Cu distribution, which is only identified due to the single atom sensitivity of APT. After the industry standard 135,000 mile simulation, Cu-SSZ- 13 shows Cu and Al clustering, whereas Cu-ZSM-5 is characterized by severe Cu and Al aggregation into a copper aluminate phase (CuAl2O4 spinel). The application of APT as a sensitive and local characterization method provides identification of nanometer scale het- erogeneities that lead to catalytic activity and material deactivation

Nanoscale tomography reveals the deactivation of automotive copper-exchanged zeolite catalysts

Copper-exchanged zeolite chabazite (Cu-SSZ-13) was recently commercialized for the selective catalytic reduction of NOX with ammonia in vehicle emissions as it exhibits superior reaction performance and stability compared to all other catalysts, notably Cu-ZSM-5. Herein, the 3D distributions of Cu as well as framework elements (Al, O, Si) in both fresh and aged Cu-SSZ-13 and Cu-ZSM-5 are determined with nanometer resolution using atom probe tomography (APT), and correlated with catalytic activity and other characterizations. Both fresh catalysts contain a heterogeneous Cu distribution, which is only identified due to the single atom sensitivity of APT. After the industry standard 135,000 mile simulation, Cu-SSZ- 13 shows Cu and Al clustering, whereas Cu-ZSM-5 is characterized by severe Cu and Al aggregation into a copper aluminate phase (CuAl2O4 spinel). The application of APT as a sensitive and local characterization method provides identification of nanometer scale het- erogeneities that lead to catalytic activity and material deactivation

Oxygen Vacancies in Reduced Rh/ and Pt/Ceria for Highly Selective and Reactive Reduction of NO into N2 in excess of O2

Currently commercial NOx removal (DeNOx) abatement systems for lean-burn engines exceed regulation limits on the road for NOx emissions. Commercial DeNOx catalysts exhibit poor performance in the selective conversion of NO to N2, especially at high temperature and high gas hourly space velocities (GHSV). In this study, oxygen vacancies of reduced ceria and Pt/ or Rh/ceria are found to be the efficient and selective catalytic sites for NO reduction to N2. Even at low concentrations, NO can compete with an excess of O2 at 600 °C and a high GHSV of 170 000 L L−1 h−1, conditions in which SCR and NSR DeNOx system are not able to function well. N2O is not detected over the whole range of conditions, whereas NO2 is only formed upon oxidation of the catalyst, after both NO and O2 start to appear. For consideration of the fuel economy, the working temperature should be between 250 and 600 °C. Above 600 °C, most of the injected fuel was combusted with O2. Below 250 °C, ceria support will not be reduced by fuel and the oxidation rate of the deposited carbon through oxygen from ceria lattice will be too low