Au/CeO(2) catalysts are highly active for low-temperature CO oxidation and water-gas shift reaction, but they deactivate rapidly because of sintering of gold nanoparticles, linked to the collapse or restructuring of the gold-ceria interfacial perimeters. To date, a detailed atomic-level insight into the restructuring of the active gold-ceria interfaces is still lacking. Here, we report that gold particles of 2-4 nm size, strongly anchored onto rod-shaped CeO(2), are not only highly active but also distinctively stable under realistic reaction conditions. Environmental transmission electron microscopy analyses identified that the gold nanoparticles, in response to alternating oxidizing and reducing atmospheres, changed their shapes but did not sinter at temperatures up to 573 K. This finding offers a new strategy to stabilize gold nanoparticles on ceria by engineering the gold-ceria interfacial structure, which could be extended to other oxide-supported metal nanocatalysts.
Nanocatalysts are characterised by the unique nanoscale properties that originate from their highly reduced dimensions. Extensive studies over the past few decades have demonstrated that the size and shape of a catalyst particle on the nanometre scale profoundly affect its reaction performance. In particular, controlling the catalyst particle morphology allows a selective exposure of a larger fraction of the reactive facets on which the active sites can be enriched and tuned. This desirable surface coordination of catalytically active atoms or domains substantially improves catalytic activity, selectivity, and stability. This phenomenon is called morphology-dependent nanocatalysts: catalyst particles with anisotropic morphologies on the nanometre scale greatly affect the reaction performance by selectively exposing the desired facets. In this review, we highlight important progress in morphology-dependent nanocatalysts based on the use of rod-shaped metal oxides with characteristic redox and acid-base features. The correlation between the catalytic properties and the exposed facets verifies the chemical nature of the morphology effect. Moreover, we provide an overview of the interactions between the rod-shaped oxides and the metal nanoparticles in metal-oxide catalyst systems, involving crystal-facet-selective deposition of metal particles onto different crystal facets in the oxide supports. A fundamental understanding of active sites in morphologically tuneable oxides enclosed by the desired reactive facets is expected to direct the development of highly efficient nanocatalysts.
The rapid development of materials science now enables tailoring of metal and metal oxide particles with tunable size and shape at the nanometre level. As a result, nanocatalysis is undergoing an explosive growth, and it has been seen that the size and shape of a catalyst particle tremendously affects the reaction performance. The size effect of metal nanoparticles has been interpreted in terms of the variation in geometric and electronic properties that governs the adsorption and activation of the reactants as well as the desorption of the products. At the same time, it has been verified that the morphology of a catalyst particle, determined by the exposed crystal planes, also considerably affects the catalytic behavior. This is termed as morphology-dependent nanocatalysis: a catalyst particle with an anisotropic shape alters the reaction performance by selectively exposing specific crystal facets. This perspective article initially surveys the recent progress on morphology-dependent nanocatalysis of precious metal particles to emphasise the chemical nature of the morphology effect. Then, the fabrication of transition metal particles with controllable size/morphology is examined, and their shape is correlated with their catalytic properties, with the aim to clarify the structure-reactivity relationship. Finally, the future outlook presents our personal perspectives on the concept of morphology-dependent nanocatalysis of metal particles, which is a rapidly growing topic in heterogeneous catalysis.
Increasing plant density is one of the most efficient ways of increasing wheat (Triticum aestivum L.) grain production. However, overly dense plant populations have an increased risk of lodging. We examined lignin deposition during wheat stem development and the regulatory effects of plant density using the wheat cultivars shannong23 and weimai8. Plants were cultivated at densities of 75, 225 and 375 plants per m2 during two growing seasons. Our results showed that decreasing plant density enhanced culm quality, as revealed by increased culm diameter, wall thickness and dry weight per unit length, and improved the structure of sclerenchyma and vascular bundles by increasing lignification. In addition, more lignins were deposited in the secondary cell walls, resulting in strong lodging resistance. The guaiacyl unit was the major component of lignin and there was a higher content of the syringyl unit than that of the hydroxybenzyl unit. Furthermore, we hypothesised that the syringyl unit may correlate with stem stiffness. We describe here, to the best of our knowledge, the systematic study of the mechanism involved in the regulation of stem breaking strength by plant density, particularly the effect of plant density on lignin biosynthesis and its relationship with lodging resistance in wheat.
We construct the first Authenticated Key Exchange (AKE) protocol whose security does not degrade with an increasing number of users or sessions. We describe a three-message protocol and prove security in an enhanced version of the classical Bellare-Rogaway security model. Our construction is modular, it can be instantiated efficiently from standard assumptions (such as the SXDH or DLIN assumptions in pairingfriendly groups). For instance, we provide an SXDH-based protocol with only 14 group elements and 4 exponents communication complexity (plus some bookkeeping information). Along the way we develop new, stronger security definitions for digital signatures and key encapsulation mechanisms. For instance, we introduce a security model for digital signatures that provides existential unforgeability under chosen-message attacks in a multiuser setting with adaptive corruptions of secret keys. We show how to construct efficient schemes that satisfy the new definitions with tight security proofs under standard assumptions.
Cobalt hydroxycarbonate nanorods are prepared by precipitation of cobalt acetate with sodium carbonate in ethylene glycol. Structural and chemical analyses of the intermediate phases during the precipitation and aging process revealed that amorphous cobalt hydroxide acetate is formed at the initial stage where ethylene glycol acts as a simple solvent and a coordinating agent. With the slow addition of sodium carbonate, carbonate anions are gradually intercalated into the interlayers by replacing the acetate and hydroxyl anions. This anionexchange process induces a dissolution-recrystallization process in which ethylene glycol serves as a ratecontrolling agent, producing rod-like cobalt hydroxide carbonate. During the aging process, ethylene glycol gradually incorporates into the structure to replace the carbonate and acetate anions; the interlayer structure is collapsed, and the nanorod-shape turns into thin crimped sheets. Co 3 O 4 nanorods with a diameter of about 10 nm and a length of 200-300 nm are then obtained by calcination of the nanorod-shaped cobalt hydroxycarbonate precursor. This spontaneous shape transformation from the precursor to the oxide is attributed to the unique thermal stability of the cobalt hydroxycarbonate nanorods with the presence of ethylene glycol and acetate anions in the interlayers. The Co 3 O 4 nanorods show a much superior catalytic activity for CO oxidation to the conventional spherical Co 3 O 4 nanoparticles, clearly demonstrating the morphology-dependent nanocatalysis.
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