Engineering of Ruthenium-Iron Oxide Colloidal Heterostructures Leads to Improved Yields in CO2 Hydrogenation to Hydrocarbons.
Angewandte Chemie (International ed. in English)
Catalytic CO2 reduction to fuels and chemicals is one of the major pursuits in reducing greenhouse gas emissions. One such popular approach utilizes the reverse water-gas shift reaction, followed by Fischer-Tropsch synthesis, and iron is a well-known candidate for this process. Some attempts have been made to modify and improve its reactivity, but resuted in limited success. In this work, using ruthenium-iron oxide colloidal heterodimers we demonstrate that close contact between the two phases promotes the reduction of iron oxide via a proximal hydrogen spillover effect, leading to the formation of ruthenium-iron core-shell structures active for the reaction at significantly lower temperatures than in bare iron catalysts. Furthermore, by engineering the iron oxide shell thickness, we achieve a fourfold increase in hydrocarbon yield compared to the heterodimers. In general, our work shows how rational design of colloidal heterostructures can result in materials with significantly improved catalytic performance in CO2 conversion processes.
View details for DOI 10.1002/anie.201910579
View details for PubMedID 31545533
- Catalyst deactivation via decomposition into single atoms and the role of metal loading NATURE CATALYSIS 2019; 2 (9): 748–55
Structural evolution of atomically dispersed Pt catalysts dictates reactivity.
The use of oxide-supported isolated Pt-group metal atoms as catalytic active sites is of interest due to their unique reactivity and efficient metal utilization. However, relationships between the structure of these active sites, their dynamic response to environments and catalytic functionality have proved difficult to experimentally establish. Here, sinter-resistant catalysts where Pt was deposited uniformly as isolated atoms in well-defined locations on anatase TiO2 nanoparticle supports were used to develop such relationships. Through a combination of in situ atomic-resolution microscopy- and spectroscopy-based characterization supported by first-principles calculations it was demonstrated that isolated Pt species can adopt a range of local coordination environments and oxidation states, which evolve in response to varied environmental conditions. The variation in local coordination showed a strong influence on the chemical reactivity and could be exploited to control the catalytic performance.
View details for DOI 10.1038/s41563-019-0349-9
View details for PubMedID 31011216
Density-dependent deactivation mechanism in supported catalysts by high-temperature decomposition of particles into single atoms
AMER CHEMICAL SOC. 2019
View details for Web of Science ID 000478860502379
- Role of Co2C in ZnO-promoted Co Catalysts for Alcohol Synthesis from Syngas CHEMCATCHEM 2019; 11 (2): 799–809
In situ observation of phase changes of a silica-supported cobalt catalyst for the Fischer-Tropsch process by the development of a synchrotron-compatible insitu/operando powder X-ray diffraction cell.
Journal of synchrotron radiation
2018; 25 (Pt 6): 1673–82
In situ characterization of catalysts gives direct insight into the working state of the material. Here, the design and performance characteristics of a universal insitu synchrotron-compatible X-ray diffraction cell capable of operation at high temperature and high pressure, 1373 K, and 35 bar, respectively, are reported. Its performance is demonstrated by characterizing a cobalt-based catalyst used in a prototypical high-pressure catalytic reaction, the Fischer-Tropsch synthesis, using X-ray diffraction. Cobalt nanoparticles supported on silica were studied insitu during Fischer-Tropsch catalysis using syngas, H2 and CO, at 723 K and 20 bar. Post reaction, the Co nanoparticles were carburized at elevated pressure, demonstrating an increased rate of carburization compared with atmospheric studies.
View details for PubMedID 30407177
Synthesis of Colloidal Pd/Au Dilute Alloy Nanocrystals and Their Potential for Selective Catalytic Oxidations.
Journal of the American Chemical Society
Selective oxidations are crucial for the creation of valuable chemical building blocks but often require expensive and unstable stoichiometric oxidants such as hydroperoxides and peracids. To date, many catalysts that contain a single type of active site have not been able to attain the desired level of selectivity for partially oxidized products over total combustion. However, catalysts containing multiple types of active sites have proven to be successful for selective reactions. One category of such catalysts is bimetallic alloys, in which catalytic activity and selectivity can be tuned by modifying the surface composition. Traditional catalyst synthesis methods using impregnation struggle to create catalysts with sufficient control over surface chemistry to accurately tune the ensemble size of the desired active sites. Here we describe the synthesis of colloidal nanocrystals of dilute alloys of palladium and gold. We show that when supported on titania (TiO2), tuning the composition of the Pd/Au nanocrystal surface provides a synergistic effect in the selective oxidation of 2-propanol to acetone in the presence of H2 and O2. In particular, we show that certain Pd/Au surface ratios exhibit activity and selectivity far superior to Pd or Au individually. Through precise structural characterization we demonstrate that isolated atoms of Pd exist in the most active catalysts. The synergy between isolated Pd atoms and Au allows for the formation of reactive oxidizing species, likely hydroperoxide groups, responsible for selective oxidation while limiting oxygen dissociation and, thus, complete combustion. This work opens the way to more efficient utilization of scarce noble metals and new options for catalyzed selective oxidations.
View details for PubMedID 30220200
Synergistic effect in colloidal Pd/Au single atom alloy nanocrystals for selective oxidations
AMER CHEMICAL SOC. 2018
View details for Web of Science ID 000447600002071
- Beating Heterogeneity of Single-Site Catalysts: MgO-Supported Iridium Complexes ACS CATALYSIS 2018; 8 (4): 3489–98
Biomimetic oxidation catalyst from polymer-nanocrystal composite material
AMER CHEMICAL SOC. 2018
View details for Web of Science ID 000435537702408
Uniform Pt/Pd bimetallic nanocrystals demonstrate platinum effect on palladium methane combustion activity and stability
AMER CHEMICAL SOC. 2018
View details for Web of Science ID 000435537702178
Direct observation of the kinetics of gas–solid reactions using in situ kinetic and spectroscopic techniques
Reaction Chemistry & Engineering
2018; 3: 668-675
View details for DOI 10.1039/C8RE00020D
Low-Temperature Restructuring of CeO2-Supported Ru Nanoparticles Determines Selectivity in CO2 Catalytic Reduction.
Journal of the American Chemical Society
2018; 140 (42): 13736–45
CO2 reduction to higher value products is a promising way to produce fuels and key chemical building blocks while reducing CO2 emissions. The reaction at atmospheric pressure mainly yields CH4 via methanation and CO via the reverse water-gas shift (RWGS) reaction. Describing catalyst features that control the selectivity of these two pathways is important to determine the formation of specific products. At the same time, identification of morphological changes occurring to catalysts under reaction conditions can be crucial to tune their catalytic performance. In this contribution we investigate the dependency of selectivity for CO2 reduction on the size of Ru nanoparticles (NPs) and on support. We find that even at rather low temperatures (210 °C), oxidative pretreatment induces redispersion of Ru NPs supported on CeO2 and leads to a complete switch in the performance of this material from a well-known selective methanation catalyst to an active and selective RWGS catalyst. By utilizing in situ X-ray absorption spectroscopy, we demonstrate that the low-temperature redispersion process occurs via decomposition of the metal oxide phase with size-dependent kinetics, producing stable single-site RuO x/CeO2 species strongly bound to the CeO2 support that are remarkably selective for CO production. These results show that reaction selectivity can be heavily dependent on catalyst structure and that structural changes of the catalyst can occur even at low temperatures and can go unseen in materials with less defined structures.
View details for PubMedID 30252458
High-Energy-Resolution X-ray Absorption Spectroscopy for Identification of Reactive Surface Species on Supported Single-Site Iridium Catalysts
CHEMISTRY-A EUROPEAN JOURNAL
2017; 23 (59): 14760–68
We report high-energy-resolution X-ray absorption spectroscopy detection of ethylene and CO ligands adsorbed on catalytically active iridium centers isolated on zeolite HY and on MgO supports. The data are supported by density functional theory and FEFF X-ray absorption near-edge modelling, together with infrared (IR) spectra. The results demonstrate that high-energy-resolution X-ray absorption spectra near the iridium LIII (2p3/2 ) edge provide clearly ascribable, distinctive signatures of the ethylene and CO ligands and illustrate effects of supports and other ligands. This X-ray absorption technique is markedly more sensitive than conventional IR spectroscopy for characterizing surface intermediates, and it is applicable to samples having low metal loadings and in reactive atmospheres and is expected to have an increasing role in catalysis research by facilitating the determination of mechanisms of solid-catalyzed reactions through identification of reaction intermediates in working catalysts.
View details for PubMedID 28749554
Understanding and controlling the activity and stability of Pd/Pt oxide catalysts for methane activation
AMER CHEMICAL SOC. 2017
View details for Web of Science ID 000429525601603
- Uniform Pt/Pd Bimetallic Nanocrystals Demonstrate Platinum Effect on Palladium Methane Combustion Activity and Stability ACS CATALYSIS 2017; 7 (7): 4372–80