Unravelling the origin of reaction-driven aggregation and fragmentation of atomically dispersed Pt catalyst on ceria support.

Metal-support interaction plays a crucial role in governing the stability and activity of atomically dispersed platinum catalysts on ceria support. The migration and aggregation of platinum atoms during the catalytic reaction leads to the redistribution of active sites. In this study, by utilizing a multimodal characterization scheme, we observed the aggregation of platinum atoms at high temperatures under reverse water gas shift reaction conditions and the subsequent fragmentation of platinum clusters, forming "single atoms" upon cooling. Theoretical simulations of both effects uncovered the roles of carbon monoxide binding on perimeter Pt sites in the clusters and hydrogen coverage in the aggregation and fragmentation mechanisms. This study highlights the complex effects of adsorbate and supports interactions with metal sites in Pt/ceria catalysts that govern their structural transformations under in situ conditions.

Iterative Bragg peak removal on X-ray absorption spectra with automatic intensity correction.

This study introduces a novel iterative Bragg peak removal with automatic intensity correction (IBR-AIC) methodology for X-ray absorption spectroscopy (XAS), specifically addressing the challenge of Bragg peak interference in the analysis of crystalline materials. The approach integrates experimental adjustments and sophisticated post-processing, including an iterative algorithm for robust calculation of the scaling factor of the absorption coefficients and efficient elimination of the Bragg peaks, a common obstacle in accurately interpreting XAS data, particularly in crystalline samples. The method was thoroughly evaluated on dilute catalysts and thin films, with fluorescence mode and large-angle rotation. The results underscore the technique's effectiveness, adaptability and substantial potential in improving the precision of XAS data analysis. While demonstrating significant promise, the method does have limitations related to signal-to-noise ratio sensitivity and the necessity for meticulous angle selection during experimentation. Overall, IBR-AIC represents a significant advancement in XAS, offering a pragmatic solution to Bragg peak contamination challenges, thereby expanding the applications of XAS in understanding complex materials under diverse experimental conditions.

Biomimetic Control over Bimetallic Nanoparticle Structure and Activity via Peptide Capping Ligand Sequence.

The controlled design of bimetallic nanoparticles (BNPs) is a key goal in tailoring their catalytic properties. Recently, biomimetic pathways demonstrated potent control over the distribution of different metals within BNPs, but a direct understanding of the peptide effect on the compositional distribution at the interparticle and intraparticle levels remains lacking. We synthesized two sets of PtAu systems with two peptides and correlated their structure, composition, and distributions with the catalytic activity. Structural and compositional analyses were performed by a combined machine learning-assisted refinement of X-ray absorption spectra and Z-contrast measurements by scanning transmission electron microscopy. The difference in the catalytic activities between nanoparticles synthesized with different peptides was attributed to the details of interparticle distribution of Pt and Au across these markedly heterogeneous systems, comprising Pt-rich, Au-rich, and Au core/Pt shell nanoparticles. The total amount of Pt in the shells of the BNPs was proposed to be the key catalytic activity descriptor. This approach can be extended to other systems of metals and peptides to facilitate the targeted design of catalysts with the desired activity.

Migration and aggregation of Pt atoms on metal oxide-supported ceria nanodomes control reverse water gas shift reaction activity.

Single-atom catalysts (SACs) are particularly sensitive to external conditions, complicating the identification of catalytically active species and active sites under in situ or operando conditions. We developed a methodology for tracing the structural evolution of SACs to nanoparticles, identifying the active species and their link to the catalytic activity for the reverse water gas shift (RWGS) reaction. The new method is illustrated by studying structure-activity relationships in two materials containing Pt SACs on ceria nanodomes, supported on either ceria or titania. These materials exhibited distinctly different activities for CO production. Multimodal operando characterization attributed the enhanced activity of the titania-supported catalysts at temperatures below 320 ˚C to the formation of unique Pt sites at the ceria-titania interface capable of forming Pt nanoparticles, the active species for the RWGS reaction. Migration of Pt nanoparticles to titania support was found to be responsible for the deactivation of titania-supported catalysts at elevated temperatures. Tracking the migration of Pt atoms provides a new opportunity to investigate the activation and deactivation of Pt SACs for the RWGS reaction.

Synthesis of a diruthenium µ-η4-α-diimine complex via dehydrogenative coupling of cyclic amines and its role in dehydrogenative oxidation of pyrrolidine.

The reaction of [Cp‡Ru(µ-H)4RuCp‡] (1: Cp‡ = 1,2,4-tri-tert-butylcyclopentadienyl) with cyclic amines at 180 °C afforded a µ-η4-α-diimine complex, [(Cp‡Ru)2(µ-η4-C2nH4n-4N2)] (5a-c: n = 4, 5, 6), via dehydrogenative coupling of two cyclic amine molecules. An intermediate µ-η2-1-pyrroline complex, [{Cp‡Ru(µ-H)}2(µ-η2-C4H7N)] (2a), was synthesized by the photoreaction of 1 with pyrrolidine and 5a was shown to be formed via the disproportionation of 2a upon thermolysis yielding 1 and a µ-imidoyl complex, [(Cp‡Ru)2(µ-η2:η2-C4H6N)(µ-H)] (3a). Complex 3a was transformed into 5avia the incorporation of 1-pyrroline, which was formed by the reaction of 2a with H2. DFT calculations on the model complexes supported by C5H5 groups at the B3LYP level suggested that the µ-η4-α-diimine ligand is formed via the insertion of a terminal cyclic aminocarbene ligand into the Ru-C bond of the µ-imidoyl group followed by the elimination of hydrogen. Although 5a was inert under an Ar atmosphere, it catalyzed the dehydrogenative oxidation of pyrrolidine under an atmosphere of hydrogen to yield γ-butyrolactam. An active species possessing a terminal cyclic aminocarbene ligand was generated via the heterolytic activation of hydrogen at the Ru-N bond followed by C-C bond cleavage.

Single-Atom Cobalt Catalysts Coupled with Peroxidase Biocatalysis for C-H Bond Oxidation.

This paper reports a robust strategy to catalyze in situ C-H oxidation by combining cobalt (Co) single-atom catalysts (SACs) and horseradish peroxidase (HRP). Co SACs were synthesized using the complex of Co phthalocyanine with 3-propanol pyridine at the two axial positions as the Co source to tune the coordination environment of Co by the stepwise removal of axial pyridine moieties under thermal annealing. These structural features of Co sites, as confirmed by infrared and X-ray absorption spectroscopy, were strongly correlated to their reactivity. All Co catalysts synthesized below 300 °C were inactive due to the full coordination of Co sites in octahedral geometry. Increasing the calcination temperature led to an improvement in catalytic activity for reducing O2, although molecular Co species with square planar coordination obtained below 600 °C were less selective to reduce O2 to H2O2 through the two-electron pathway. Co SACs obtained at 800 °C showed superior activity in producing H2O2 with a selectivity of 82-85% in a broad potential range. In situ production of H2O2 was further coupled with HRP to drive the selective C-H bond oxidation in 2-naphthol. Our strategy provides new insights into the design of highly effective, stable SACs for selective C-H bond activation when coupled with natural enzymes.

Migration and Precipitation of Platinum in Anion-Exchange Membrane Fuel Cells.

Despite the recent progress in increasing the power generation of Anion-exchange membrane fuel cells (AEMFCs), their durability is still far lower than that of Proton exchange membrane fuel cells (PEMFCs). Using the complementary techniques of X-ray micro-computed tomography (CT), Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray (EDX) spectroscopy, we have identified Pt ion migration as an important factor to explain the decay in performance of AEMFCs. In alkaline media Pt+2 ions are easily formed which then either undergo dissolution into the carbon support or migrate to the membrane. In contrast to PEMFCs, where hydrogen cross over reduces the ions forming a vertical "Pt line" within the membrane, the ions in the AEM are trapped by charged groups within the membrane, leading to disintegration of the membrane and failure. Diffusion of the metal components is still observed when the Pt/C of the cathode is substituted with a FeCo-N-C catalyst, but in this case the Fe and Co ions are not trapped within the membrane, but rather migrate into the anode, thereby increasing the stability of the membrane.

Synthesis and characterisation of tetranuclear ruthenium polyhydrido clusters with pseudo-tetrahedral geometry.

Dicationic tetranuclear ruthenium octahydride [(Cp*Ru)4H8]2+ (5) with tetrahedral geometry was obtained by reaction of dinuclear ruthenium tetrahydride (Cp*Ru)2(µ-H)4 (1) with an excess of Brønsted acids, such as HBF4·OEt2, in toluene. Monocationic tetraruthenium heptahydride [(Cp*Ru)4H7]+ (7) was obtained by dropwise addition of a diluted acid to a rigorously stirred solution of 1 at ambient temperature. Dication 5 was converted into monocationic heptahydrido complex 7 in high yield by treatment with sodium methoxide or sodium hydride. The direct conversion of 5 into neutral hexahydrido complex (Cp*Ru)4H6 (8) was achieved in a highly efficient manner by treating 5 with LiAlH4 in tetrahydrofuran (THF). The conversion of 5 into 8 was reversible, and the addition of a Brønsted acid to 8 gave 5via the formation of 7 as an intermediate. Tetranuclear complex 8 was directly obtained from 1 by heating it in THF at 70 °C. Complex 8' and tetraruthenium tetrahydride (CpEtRu)4H4 (10'), where 8' and 10' possessed η5-C5EtMe4 ligands instead of Cp* ligands, were mutually related by the elimination/addition of dihydrogen. The structures of 5, 7, 8, and 10' were determined by X-ray diffraction, and the Ru4 core structure and the coordination mode of hydrido ligands were discussed based on density functional theory (DFT) calculations for model compounds where the methyl groups of Cp* ligands were replaced with hydrogen atoms.