An in-depth understanding of the fundamental structure of catalysts during operation is indispensable for tailoring future efficient and selective catalysts. We report the evolution of the structure and oxidation state of ZrO(2)-supported Pd nanocatalysts (∼5 nm) during the in situ reduction of NO with H(2) using X-ray absorption fine-structure spectroscopy and X-ray photoelectron spectroscopy. Prior to the onset of the reaction (≤120 °C), a NO-induced redispersion of our initial metallic Pd nanoparticles over the ZrO(2) support was observed, and Pd(δ+) species were detected. This process parallels the high production of N(2)O observed at the onset of the reaction (>120 °C), while at higher temperatures (≥150 °C) the selectivity shifts mainly toward N(2) (∼80%). Concomitant with the onset of N(2) production, the Pd atoms aggregate again into large (6.5 nm) metallic Pd nanoparticles, which were found to constitute the active phase for the H(2)-reduction of NO. Throughout the entire reaction cycle, the formation and stabilization of PdO(x) was not detected. Our results highlight the importance of in situ reactivity studies to unravel the microscopic processes governing catalytic reactivity.
The rapid cadence of MOSFET scaling is stimulating the development of new technologies and accelerating the introduction of new semiconducting materials as silicon alternative. In this context, 2D materials with a unique layered structure have attracted tremendous interest in recent years, mainly motivated by their ultra-thin body nature and unique optoelectronic and mechanical properties. The development of scalable synthesis techniques is obviously a fundamental step towards the development of a manufacturable technology. Metal-organic chemical vapor deposition has recently been used for the synthesis of large area TMDs, however, an important milestone still needs to be achieved: the ability to precisely control the number of layers and surface uniformity at the nano-to micro-length scale to obtain an atomically flat, self-passivated surface. In this work, we explore various fundamental aspects involved in the chemical vapor deposition process and we provide important insights on the layer-dependence of epitaxial MoS film's structural properties. Based on these observations, we propose an original method to achieve a layer-controlled epitaxy of wafer-scale TMDs.
Unraveling the complex interaction between catalysts and reactants under operando conditions is a key step toward gaining fundamental insight in catalysis. We report the evolution of the structure and chemical composition of size-selected micellar Pt nanoparticles (∼1 nm) supported on nanocrystalline γ-Al(2)O(3) during the catalytic oxidation of 2-propanol using X-ray absorption fine-structure spectroscopy. Platinum oxides were found to be the active species for the partial oxidation of 2-propanol (<140 °C), while the complete oxidation (>140 °C) is initially catalyzed by oxygen-covered metallic Pt nanoparticles, which were found to regrow a thin surface oxide layer above 200 °C. The intermediate reaction regime, where the partial and complete oxidation pathways coexist, is characterized by the decomposition of the Pt oxide species due to the production of reducing intermediates and the blocking of O(2) adsorption sites on the nanoparticle surface. The high catalytic activity and low onset reaction temperature displayed by our small Pt particles for the oxidation of 2-propanol is attributed to the large amount of edge and corner sites available, which facilitate the formation of reactive surface oxides. Our findings highlight the decisive role of the nanoparticle structure and chemical state in oxidation catalytic reactions.
The experimental study of the bonding geometry of a (100)Ge surface exposed to H2S in the gas phase at 330°C shows that 1 ML S coverage with (2×1) surface reconstruction can be achieved. The amount of S on the Ge surface and the observed surface periodicity can be explained by the formation of disulfide bridges between Ge–Ge dimers on the surface. First-principles molecular dynamics simulations confirm the preserved (2×1) reconstruction after dissociative adsorption of H2S molecules on a (100)Ge (2×1) surface, and predict the formation of (S–H)–(S–H) inter-Ge dimer bridges, i.e., disulfide bridges interacting via hydrogen bonding. The computed energy band gap of this atomic configuration is shown to be free of surface states, a very important finding for the potential application of Ge in future high performance integrated circuits.
We have gained insight into the internal degree of atomic disorder in isolated sizeselected Fe nanoparticles (NPs) (~2 -6 nm in size) supported on SiO 2 /Si(111) and Al 2 O 3 (0001) from precise measurements of the low-energy (low-E) part of the phonon density of states [PDOS, g(E)] via 57 Fe nuclear resonant inelastic X-ray scattering (NRIXS), combined with transmission electron microscopy (TEM) measurements. An intriguing size-dependent trend was observed, namely, an increase of the low-E excess density of phonon states (as compared to the PDOS of bulk bcc Fe) with increasing NP size. This is unexpected, since usually the enhancement of the density of low-E phonon modes is attributed to low-coordinated atoms at the NP surface, whose relative content increases with decreasing NP size due to the increase in the surface-to-volume ratio. OurNPs are covered by a Ti coating layer, which essentially restores the local neighbourhood of surface Fe surface atoms towards bulk-like coordination, reducing the surface effect.Our data can be qualitatively explained by the existence of low-coordinated Fe atoms 2 located at grain boundaries or other defects with structural disorder in the interior of the large NPs (~3 -6 nm), while our small NPs (~2 nm) are single-grain and, therefore, characterized by a higher degree of structural order. This conclusion is corroborated by the observation of Debye behaviour at low energy [g(E) ~ E n with n ~ 2] for the small NPs, but non-Debye behaviour (with n ~ 1.4) for the large NPs. The PDOS was used to determine thermodynamic properties of the Fe NPs. Finally, our results demonstrate that, in combination with TEM, NRIXS is a suitable technique to investigate atomic disorder/defects in NPs. We anticipate that our findings are universal for similar NPs with bcc structure.Keywords: Fe, nanoparticle, nuclear resonant inelastic x-ray scattering, atomic force microscopy, transmission electron microscopy, x-ray photoelectron spectroscopy, phonon density of states.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.