Understanding Structure-Property Relationships of MoO3-Promoted Rh Catalysts for Syngas Conversion to Alcohols.

Rh-based catalysts have shown promise for the direct conversion of syngas to higher oxygenates. Although improvements in higher oxygenate yield have been achieved by combining Rh with metal oxide promoters, details of the structure of the promoted catalyst and the role of the promoter in enhancing catalytic performance are not well understood. In this work, we show that MoO3-promoted Rh nanoparticles form a novel catalyst structure in which Mo substitutes into the Rh surface, leading to both a 66-fold increase in turnover frequency and an enhancement in oxygenate yield. By applying a combination of atomically controlled synthesis, in situ characterization, and theoretical calculations, we gain an understanding of the promoter-Rh interactions that govern catalytic performance for MoO3-promoted Rh. We use atomic layer deposition to modify Rh nanoparticles with monolayer-precise amounts of MoO3, with a high degree of control over the structure of the catalyst. Through in situ X-ray absorption spectroscopy, we find that the atomic structure of the catalytic surface under reaction conditions consists of Mo-OH species substituted into the surface of the Rh nanoparticles. Using density functional theory calculations, we identify two roles of MoO3: first, the presence of Mo-OH in the catalyst surface enhances CO dissociation and also stabilizes a methanol synthesis pathway not present in the unpromoted catalyst; and second, hydrogen spillover from Mo-OH sites to adsorbed species on the Rh surface enhances hydrogenation rates of reaction intermediates.

In situ observation of phase changes of a silica-supported cobalt catalyst for the Fischer-Tropsch process by the development of a synchrotron-compatible in situ/operando powder X-ray diffraction cell.

In situ characterization of catalysts gives direct insight into the working state of the material. Here, the design and performance characteristics of a universal in situ 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 in situ 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.

A Highly Active Molybdenum Phosphide Catalyst for Methanol Synthesis from CO and CO2.

Methanol is a major fuel and chemical feedstock currently produced from syngas, a CO/CO2 /H2 mixture. Herein we identify formate binding strength as a key parameter limiting the activity and stability of known catalysts for methanol synthesis in the presence of CO2 . We present a molybdenum phosphide catalyst for CO and CO2 reduction to methanol, which through a weaker interaction with formate, can improve the activity and stability of methanol synthesis catalysts in a wide range of CO/CO2 /H2 feeds.

Area-Selective Atomic Layer Deposition of Metal Oxides on Noble Metals through Catalytic Oxygen Activation.

Area-selective atomic layer deposition (ALD) is envisioned to play a key role in next-generation semiconductor processing and can also provide new opportunities in the field of catalysis. In this work, we developed an approach for the area-selective deposition of metal oxides on noble metals. Using O2 gas as co-reactant, area-selective ALD has been achieved by relying on the catalytic dissociation of the oxygen molecules on the noble metal surface, while no deposition takes place on inert surfaces that do not dissociate oxygen (i.e., SiO2, Al2O3, Au). The process is demonstrated for selective deposition of iron oxide and nickel oxide on platinum and iridium substrates. Characterization by in situ spectroscopic ellipsometry, transmission electron microscopy, scanning Auger electron spectroscopy, and X-ray photoelectron spectroscopy confirms a very high degree of selectivity, with a constant ALD growth rate on the catalytic metal substrates and no deposition on inert substrates, even after 300 ALD cycles. We demonstrate the area-selective ALD approach on planar and patterned substrates and use it to prepare Pt/Fe2O3 core/shell nanoparticles. Finally, the approach is proposed to be extendable beyond the materials presented here, specifically to other metal oxide ALD processes for which the precursor requires a strong oxidizing agent for growth.

Nanoengineering Heterogeneous Catalysts by Atomic Layer Deposition.

A new generation of catalysts is needed to meet society's energy and resource requirements. Current catalyst synthesis does not fully achieve optimum control of composition, size, and structure. Atomic layer deposition (ALD) is an emerging technique that allows for synthesis of highly controlled catalysts in the form of films, nanoparticles, and single sites. The addition of ALD coatings can also be used to introduce promoters and improve the stability of traditional catalysts. Evolving research shows promise for applying ALD to understand catalytically active sites and create next-generation catalysts using advanced 3D nanostructures.