Atomic Scale Responses of High Entropy Oxides to Redox Environments.

The potential of high entropy oxides (HEOs) as high-performance energy storage materials and catalysts has been mainly understood through their bulk structures. However, the importance of their surfaces, which may play an even more critical role, remains largely unknown. In this study, we employed advanced scanning transmission electron microscopy to investigate the atomic-scale structural and chemical responses of CeYLaHfTiZrO HEOs to high-temperature redox environments.

Significant Roles of Surface Hydrides in Enhancing the Performance of Cu/BaTiO H Catalyst for CO Hydrogenation to Methanol.

Tuning the anionic site of catalyst supports can impact reaction pathways by creating active sites on the support or influencing metal-support interactions when using supported metal nanoparticles. This study focuses on CO hydrogenation over supported Cu nanoparticles, revealing a 3-fold increase in methanol yield when replacing oxygen anions with hydrides in the perovskite support (Cu/BaTiO H yields ~146 mg/h/gCu vs. Cu/BaTiO yields ~50 mg/h/gCu).

Neutron Scattering Studies of Heterogeneous Catalysis.

Understanding the structural dynamics/evolution of catalysts and the related surface chemistry is essential for establishing structure-catalysis relationships, where spectroscopic and scattering tools play a crucial role. Among many such tools, neutron scattering, though less-known, has a unique power for investigating catalytic phenomena. Since neutrons interact with the nuclei of matter, the neutron-nucleon interaction provides unique information on light elements (mainly hydrogen), neighboring elements, and isotopes, which are complementary to X-ray and photon-based techniques.

Ultrasonication-Induced Strong Metal-Support Interaction Construction in Water Towards Enhanced Catalysis.

The development of facile methodologies to afford robust supported metal nanocatalysts under mild conditions is highly desirable yet challenging, particularly via strong metal-support interactions (SMSI) construction. State-of-the-art approaches capable of generating SMSI encapsulation mainly focus on high temperature annealing in reductive/oxidative atmosphere. Herein, ultra-stable metal nanocatalysts based on SMSI construction were produced by leveraging the instantaneous high-energy input from ultrasonication under ambient conditions in H O, which could rapidly afford abundant active intermediates, Ti ions, and oxygen vacancies within the scaffolds to induce the SMSI overlayer formation.

Adsorbate-Induced Strong Metal-Support Interactions: Implications for Catalyst Design.

Since the discovery of strong metal-support interactions (SMSIs) over supported metal catalysts in the 1970s, researchers have studied ways to harness this type of catalyst reconstruction to achieve enhanced stability of metal particles against sintering and to create catalytic sites with novel electronic and bonding properties. The motivation to elucidate performance-structure relationships in catalytic transformations has led researchers to take a closer look into catalytic surfaces under reaction conditions rather than a postreaction analysis. These investigations of operating catalysts have made it clear that SMSIs are more common than initially thought.

Measuring and directing charge transfer in heterogenous catalysts.

Precise control of charge transfer between catalyst nanoparticles and supports presents a unique opportunity to enhance the stability, activity, and selectivity of heterogeneous catalysts. While charge transfer is tunable using the atomic structure and chemistry of the catalyst-support interface, direct experimental evidence is missing for three-dimensional catalyst nanoparticles, primarily due to the lack of a high-resolution method that can probe and correlate both the charge distribution and atomic structure of catalyst/support interfaces in these structures. We demonstrate a robust scanning transmission electron microscopy (STEM) method that simultaneously visualizes the atomic-scale structure and sub-nanometer-scale charge distribution in heterogeneous catalysts using a model Au-catalyst/SrTiO-support system.

Ultrasound-mediated synthesis of nanoporous fluorite-structured high-entropy oxides toward noble metal stabilization.

High-entropy oxides (HEOs) are an emerging class of advanced ceramic materials capable of stabilizing ultrasmall nanoparticle catalysts. However, their fabrication still relies on high-temperature thermal treatment methodologies affording nonporous architectures. Herein, we report a facile synthesis of single-phase, fluorite-structured HEO nanocrystals via an ultrasound-mediated co-precipitation strategy under ambient conditions.

Manipulating Copper Dispersion on Ceria for Enhanced Catalysis: A Nanocrystal-Based Atom-Trapping Strategy.

Due to tunable redox properties and cost-effectiveness, copper-ceria (Cu-CeO ) materials have been investigated for a wide scope of catalytic reactions. However, accurately identifying and rationally tuning the local structures in Cu-CeO have remained challenging, especially for nanomaterials with inherent structural complexities involving surfaces, interfaces, and defects. Here, a nanocrystal-based atom-trapping strategy to access atomically precise Cu-CeO nanostructures for enhanced catalysis is reported.

Machine Learning Method Reveals Hidden Strong Metal-Support Interaction in Microscopy Datasets.

Forming an ultra-thin, permeable encapsulation oxide-support layer on a metal catalyst surface is considered an effective strategy for achieving a balance between high stability and high activity in heterogenous catalysts. The success of such a design relies not only on the thickness, ideally one to two atomic layers thick, but also on the morphology and chemistry of the encapsulation layer. Reliably identifying the presence and chemical nature of such a trace layer has been challenging.

Photoinduced Strong Metal-Support Interaction for Enhanced Catalysis.

Strong metal-support interaction (SMSI) construction is a pivotal strategy to afford thermally robust nanocatalysts in industrial catalysis, but thermally induced reactions (>300 °C) in specific gaseous atmospheres are generally required in traditional procedures. In this work, a photochemistry-driven methodology was demonstrated for SMSI construction under ambient conditions. Encapsulation of Pd nanoparticles with a TiO overlayer, the presence of Ti species, and suppression of CO adsorption were achieved upon UV irradiation.

Neutron Scattering Investigations of Hydride Species in Heterogeneous Catalysis.

In heterogeneous catalysis, hydrides on the surface or in the bulk play a critical role as either active components or reaction intermediates in many hydrogen-involving reactions, but characterization of the nature and structure of these hydride species remains challenging. Neutron scattering, which is extremely sensitive to light elements, such as hydrogen, has shown great potential in meeting this challenge. In this Minireview, recent advances in neutron studies of hydride species, mainly over the two most typical classes of catalysts-metals and oxides-are surveyed.

Controlling Reaction Selectivity through the Surface Termination of Perovskite Catalysts.

Although perovskites have been widely used in catalysis, tuning of their surface termination to control reaction selectivity has not been well established. In this study, we employed multiple surface-sensitive techniques to characterize the surface termination (one aspect of surface reconstruction) of SrTiO (STO) after thermal pretreatment (Sr enrichment) and chemical etching (Ti enrichment). We show, by using the conversion of 2-propanol as a probe reaction, that the surface termination of STO can be controlled to greatly tune catalytic acid/base properties and consequently the reaction selectivity over a wide range, which is not possible with single-metal oxides, either SrO or TiO .