Distribution of Pt single atom coordination environments on anatase TiO2 supports controls reactivity.

Single-atom catalysts (SACs) offer efficient metal utilization and distinct reactivity compared to supported metal nanoparticles. Structure-function relationships for SACs often assume that active sites have uniform coordination environments at particular binding sites on support surfaces. Here, we investigate the distribution of coordination environments of Pt SAs dispersed on shape-controlled anatase TiO2 supports specifically exposing (001) and (101) surfaces. Pt SAs on (101) are found on the surface, consistent with existing structural models, whereas those on (001) are beneath the surface after calcination. Pt SAs under (001) surfaces exhibit lower reactivity for CO oxidation than those on (101) surfaces due to their limited accessibility to gas phase species. Pt SAs deposited on commercial-TiO2 are found both at the surface and in the bulk, posing challenges to structure-function relationship development. This study highlights heterogeneity in SA coordination environments on oxide supports, emphasizing a previously overlooked consideration in the design of SACs.

Uniformity Is Key in Defining Structure-Function Relationships for Atomically Dispersed Metal Catalysts: The Case of Pt/CeO2.

Catalysts consisting of atomically dispersed Pt (Ptiso) species on CeO2 supports have received recent interest due to their potential for efficient metal utilization in catalytic convertors. However, discrepancies exist between the behavior (reducibility, interaction strength with adsorbates) of high surface area Ptiso/CeO2 systems and of well-defined surface science and computational model systems, suggesting differences in Pt local coordination in the two classes of materials. Here, we reconcile these differences by demonstrating that high surface area Ptiso/CeO2 synthesized at low Pt loadings (<0.1% weight) exhibit resistance to reduction and sintering up to 500 °C in 0.05 bar H2 and minimal interactions with CO-properties previously seen only for model system studies. Alternatively, Pt loadings >0.1 weight % produce a distribution of sub-nanometer Pt structures, which are difficult to distinguish using common characterization techniques, and exhibit strong interactions with CO and weak resistance to sintering, even in 0.05 bar H2 at 50 °C-properties previously seen for high surface area materials. This work demonstrates that low metal loadings can be used to selectively populate the most thermodynamically stable adsorption sites on high surface area supports with atomically dispersed metals. Further, the site uniformity afforded by this synthetic approach is critical for the development of relationships between atomic scale local coordination and functional properties. Comparisons to recent studies of Ptiso/TiO2 suggest a general compromise between the stability of atomically dispersed metal catalysts and their ability to interact with and activate molecular species.

Rh single atoms on TiO2 dynamically respond to reaction conditions by adapting their site.

Single-atom catalysts are widely investigated heterogeneous catalysts; however, the identification of the local environment of single atoms under experimental conditions, as well as operando characterization of their structural changes during catalytic reactions are still challenging. Here, the preferred local coordination of Rh single atoms is investigated on TiO2 during calcination in O2, reduction in H2, CO adsorption, and reverse water gas shift (RWGS) reaction conditions. Theoretical and experimental studies clearly demonstrate that Rh single atoms adapt their local coordination and reactivity in response to various redox conditions. Single-atom catalysts hence do not have static local coordinations, but can switch from inactive to active structure under reaction conditions, hence explaining some conflicting literature accounts. The combination of approaches also elucidates the structure of the catalytic active site during reverse water gas shift. This insight on the real nature of the active site is key for the design of high-performance catalysts.

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.

Deconvolution of octahedral Pt3Ni nanoparticle growth pathway from in situ characterizations.

Understanding the growth pathway of faceted alloy nanoparticles at the atomic level is crucial to morphology control and property tuning. Yet, it remains a challenge due to complexity of the growth process and technical limits of modern characterization tools. We report a combinational use of multiple cutting-edge in situ techniques to study the growth process of octahedral Pt3Ni nanoparticles, which reveal the particle growth and facet formation mechanisms. Our studies confirm the formation of octahedral Pt3Ni initiates from Pt nuclei generation, which is followed by continuous Pt reduction that simultaneously catalyzes Ni reduction, resulting in mixed alloy formation with moderate elemental segregation. Carbon monoxide molecules serve as a facet formation modulator and induce Ni segregation to the surface, which inhibits the (111) facet growth and causes the particle shape to evolve from a spherical cluster to an octahedron as the (001) facet continues to grow.

Smart Pd Catalyst with Improved Thermal Stability Supported on High-Surface-Area LaFeO3 Prepared by Atomic Layer Deposition.

The concept of self-regenerating or "smart" catalysts, developed to mitigate the problem of supported metal particle coarsening in high-temperature applications, involves redispersing large metal particles by incorporating them into a perovskite-structured support under oxidizing conditions and then exsolving them as small metal particles under reducing conditions. Unfortunately, the redispersion process does not appear to work in practice because the surface areas of the perovskite supports are too low and the diffusion lengths for the metal ions within the bulk perovskite too short. Here, we demonstrate reversible activation upon redox cycling for CH4 oxidation and CO oxidation on Pd supported on high-surface-area LaFeO3, prepared as a thin conformal coating on a porous MgAl2O4 support using atomic layer deposition. The LaFeO3 film, less than 1.5 nm thick, was shown to be initially stable to at least 900 °C. The activated catalysts exhibit stable catalytic performance for methane oxidation after high-temperature treatment.

Catalyst Architecture for Stable Single Atom Dispersion Enables Site-Specific Spectroscopic and Reactivity Measurements of CO Adsorbed to Pt Atoms, Oxidized Pt Clusters, and Metallic Pt Clusters on TiO2.

Oxide-supported precious metal nanoparticles are widely used industrial catalysts. Due to expense and rarity, developing synthetic protocols that reduce precious metal nanoparticle size and stabilize dispersed species is essential. Supported atomically dispersed, single precious metal atoms represent the most efficient metal utilization geometry, although debate regarding the catalytic activity of supported single precious atom species has arisen from difficulty in synthesizing homogeneous and stable single atom dispersions, and a lack of site-specific characterization approaches. We propose a catalyst architecture and characterization approach to overcome these limitations, by depositing ∼1 precious metal atom per support particle and characterizing structures by correlating scanning transmission electron microscopy imaging and CO probe molecule infrared spectroscopy. This is demonstrated for Pt supported on anatase TiO2. In these structures, isolated Pt atoms, Ptiso, remain stable through various conditions, and spectroscopic evidence suggests Ptiso species exist in homogeneous local environments. Comparing Ptiso to ∼1 nm preoxidized (Ptox) and prereduced (Ptmetal) Pt clusters on TiO2, we identify unique spectroscopic signatures of CO bound to each site and find CO adsorption energy is ordered: Ptiso ≪ Ptmetal < Ptox. Ptiso species exhibited a 2-fold greater turnover frequency for CO oxidation than 1 nm Ptmetal clusters but share an identical reaction mechanism. We propose the active catalytic sites are cationic interfacial Pt atoms bonded to TiO2 and that Ptiso exhibits optimal reactivity because every atom is exposed for catalysis and forms an interfacial site with TiO2. This approach should be generally useful for studying the behavior of supported precious metal atoms.

In situ atomic-scale observation of oxygen-driven core-shell formation in Pt3Co nanoparticles.

The catalytic performance of core-shell platinum alloy nanoparticles is typically superior to that of pure platinum nanoparticles for the oxygen reduction reaction in fuel cell cathodes. Thorough understanding of core-shell formation is critical for atomic-scale design and control of the platinum shell, which is known to be the structural feature responsible for the enhancement. Here we reveal details of a counter-intuitive core-shell formation process in platinum-cobalt nanoparticles at elevated temperature under oxygen at atmospheric pressure, by using advanced in situ electron microscopy. Initial segregation of a thin platinum, rather than cobalt oxide, surface layer occurs concurrently with ordering of the intermetallic core, followed by the layer-by-layer growth of a platinum shell via Ostwald ripening during the oxygen annealing treatment. Calculations based on density functional theory demonstrate that this process follows an energetically favourable path. These findings are expected to be useful for the future design of structured platinum alloy nanocatalysts.Core-shell platinum alloy nanoparticles are promising catalysts for oxygen reduction, however a deeper understanding of core-shell formation is still required. Here the authors report oxygen-driven formation of core-shell Pt3Co nanoparticles, seen at the atomic scale with in situ electron microscopy at ambient pressure.

Revealing Surface Elemental Composition and Dynamic Processes Involved in Facet-Dependent Oxidation of Pt3Co Nanoparticles via in Situ Transmission Electron Microscopy.

Since catalytic performance of platinum-metal (Pt-M) nanoparticles is primarily determined by the chemical and structural configurations of the outermost atomic layers, detailed knowledge of the distribution of Pt and M surface atoms is crucial for the design of Pt-M electrocatalysts with optimum activity. Further, an understanding of how the surface composition and structure of electrocatalysts may be controlled by external means is useful for their efficient production. Here, we report our study of surface composition and the dynamics involved in facet-dependent oxidation of equilibrium-shaped Pt3Co nanoparticles in an initially disordered state via in situ transmission electron microscopy and density functional calculations. In brief, using our advanced in situ gas cell technique, evolution of the surface of the Pt3Co nanoparticles was monitored at the atomic scale during their exposure to an oxygen atmosphere at elevated temperature, and it was found that Co segregation and oxidation take place on {111} surfaces but not on {100} surfaces.

Quantitative and Atomic-Scale View of CO-Induced Pt Nanoparticle Surface Reconstruction at Saturation Coverage via DFT Calculations Coupled with in Situ TEM and IR.

Atomic-scale insights into how supported metal nanoparticles catalyze chemical reactions are critical for the optimization of chemical conversion processes. It is well-known that different geometric configurations of surface atoms on supported metal nanoparticles have different catalytic reactivity and that the adsorption of reactive species can cause reconstruction of metal surfaces. Thus, characterizing metallic surface structures under reaction conditions at atomic scale is critical for understanding reactivity. Elucidation of such insights on high surface area oxide supported metal nanoparticles has been limited by less than atomic resolution typically achieved by environmental transmission electron microscopy (TEM) when operated under realistic conditions and a lack of correlated experimental measurements providing quantitative information about the distribution of exposed surface atoms under relevant reaction conditions. We overcome these limitations by correlating density functional theory predictions of adsorbate-induced surface reconstruction visually with atom-resolved imaging by in situ TEM and quantitatively with sample-averaged measurements of surface atom configurations by in situ infrared spectroscopy all at identical saturation adsorbate coverage. This is demonstrated for platinum (Pt) nanoparticle surface reconstruction induced by CO adsorption at saturation coverage and elevated (>400 K) temperature, which is relevant for the CO oxidation reaction under cold-start conditions in the catalytic convertor. Through our correlated approach, it is observed that the truncated octahedron shape adopted by bare Pt nanoparticles undergoes a reversible, facet selective reconstruction due to saturation CO coverage, where {100} facets roughen into vicinal stepped high Miller index facets, while {111} facets remain intact.

Adsorbate-mediated strong metal-support interactions in oxide-supported Rh catalysts.

The optimization of supported metal catalysts predominantly focuses on engineering the metal site, for which physical insights based on extensive theoretical and experimental contributions have enabled the rational design of active sites. Although it is well known that supports can influence the catalytic properties of metals, insights into how metal-support interactions can be exploited to optimize metal active-site properties are lacking. Here we utilize in situ spectroscopy and microscopy to identify and characterize a support effect in oxide-supported heterogeneous Rh catalysts. This effect is characterized by strongly bound adsorbates (HCOx) on reducible oxide supports (TiO2 and Nb2O5) that induce oxygen-vacancy formation in the support and cause HCOx-functionalized encapsulation of Rh nanoparticles by the support. The encapsulation layer is permeable to reactants, stable under the reaction conditions and strongly influences the catalytic properties of Rh, which enables rational and dynamic tuning of CO2-reduction selectivity.

Dynamical Observation and Detailed Description of Catalysts under Strong Metal-Support Interaction.

Understanding the structures of catalysts under realistic conditions with atomic precision is crucial to design better materials for challenging transformations. Under reducing conditions, certain reducible supports migrate onto supported metallic particles and create strong metal-support states that drastically change the reactivity of the systems. The details of this process are still unclear and preclude its thorough exploitation. Here, we report an atomic description of a palladium/titania (Pd/TiO2) system by combining state-of-the-art in situ transmission electron microscopy and density functional theory (DFT) calculations with structurally defined materials, in which we visualize the formation of the overlayers at the atomic scale under atmospheric pressure and high temperature. We show that an amorphous reduced titania layer is formed at low temperatures, and that crystallization of the layer into either mono- or bilayer structures is dictated by the reaction environment and predicted by theory. Furthermore, it occurs in combination with a dramatic reshaping of the metallic surface facets.

Dynamic structural evolution of supported palladium-ceria core-shell catalysts revealed by in situ electron microscopy.

The exceptional activity for methane combustion of modular palladium-ceria core-shell subunits on silicon-functionalized alumina that was recently reported has created renewed interest in the potential of core-shell structures as catalysts. Here we report on our use of advanced ex situ and in situ electron microscopy with atomic resolution to show that the modular palladium-ceria core-shell subunits undergo structural evolution over a wide temperature range. In situ observations performed in an atmospheric gas cell within this temperature range provide real-time evidence that the palladium and ceria nanoparticle constituents of the palladium-ceria core-shell participate in a dynamical process that leads to the formation of an unanticipated structure comprised of an intimate mixture of palladium, cerium, silicon and oxygen, with very high dispersion. This finding may open new perspectives about the origin of the activity of this catalyst.

Creating high quality Ca:TiO2-B (CaTi5O11) and TiO2-B epitaxial thin films by pulsed laser deposition.

We demonstrate, in great detail, a completely waterless synthesis route to produce highly crystalline epitaxial thin films of TiO2-B and its more stable variant CaTi5O11, using pulsed laser deposition (PLD).

Water-free titania-bronze thin films with superfast lithium-ion transport.

Using pulsed laser deposition, TiO2 (-) B and its recently discovered variant Ca:TiO2 (-) B (CaTi5O11) are synthesized as highly crystalline thin films for the first time by a completely water-free process. Significant enhancement in the Li-ion battery performance is achieved by manipulating the crystal orientation of the films, used as anodes, with a demonstration of extraordinary structural stability under extreme conditions.

In situ TEM observation of the structural transformation of rutile TiO2 nanowire during electrochemical lithiation.

We present the first direct experimental proof that phase changes occur during the real-time lithiation of rutile TiO2 nanostructures, functioning as the anode of a solid Li-ion battery inside a transmission electron microscope.

Optically significant particle sizes in seawater.

Small particles (<10 µm) are often considered to play the dominant role in controlling scattering and absorption due to their relatively large numbers, which are typically found in the ocean. Here we present an approach for quantifying the size range of particles that contribute significantly to bulk inherent optical properties. We present a numerical assessment of the variability in optically significant particle sizes for simplistic populations that conform to the assumptions of homogeneous, spherical particles, and power-law size distributions. We use numerical predictions from Mie theory to suggest minimum and maximum particle sizes required for accurate predictions and observations of ocean optics for different particle size distributions (PSDs). When considering observed ranges of PSDs, our predictions suggest the need for measurements of optical properties and particles to capture information from particle sizes between diameters of 0.05-2000 µm in order to properly constrain relationships between particles and their associated optical properties. Natural particle populations in the ocean may present more complex PSDs that could be analyzed using the method presented here to establish optically significant size classes.

Surface-termination-dependent Pd bonding and aggregation of nanoparticles on LaFeO(3)(001).

The bonding and morphology of Pd clusters deposited on the LaO- and FeO2-terminated LaFeO3 (001) surface were studied using periodic density functional methods together with scanning transmission electron microscopy. We show that Pd tends to aggregate to three-dimensional (3D) clusters on both terminations since the Pd-Pd cohesive energy is larger than the Pd-LaFeO3 adhesive energy. However, from the kinetic point of view, Pd migration on the LaO termination is facile, while stronger interactions between Pd and the FeO2 termination significantly hinder the migration of Pd. Furthermore, molecular dynamics simulations demonstrate that Pd would agglomerate into 3D metallic and PdOx particles on the LaO and FeO2 terminations, respectively, and hint at the possibility of partial penetration of the PdOx particles into the surface, as observed experimentally.

Self-regeneration of Pd-LaFeO3 catalysts: new insight from atomic-resolution electron microscopy.

Aberration-corrected transmission electron microscopy was used to study atomic-scale processes in Pd-LaFeO(3) catalysts. Clear evidence for diffusion of Pd into LaFeO(3) and out of LaFe(0.95)Pd(0.05)O(3-δ) under high-temperature oxidizing and reducing conditions, respectively, was found, but the extent to which these processes occurred was quite limited. These observations cast doubt that such phenomena play a significant role in a postulated mechanism of self-regeneration of this system as an automotive exhaust-gas catalyst.