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Zeolites are crystalline inorganic solids with microporous structures, having widespread applications in the fields of catalysis, separation, adsorption, microelectronics, and medical diagnosis. A major drawback of zeolites is the mass transfer limitation due to the small size of the micropores (less than 1 nm). Numerous efforts have been dedicated to integrating mesopores with the microporous zeolite structures by using templating and/or destructive approaches. Here we provide a new strategy for hierarchical pore size zeolite synthesis, without using supramolecular or hard templates. The branching epitaxial growth behavior, as a result of aluminum-zoning, contributes to the formation of the hierarchical porous zeolite structures. [ABSTRACT FROM AUTHOR]

Ni can be used as a catalyst for dry reforming of methane (DRM), replacing more expensive and less abundant noble metal catalysts (Pt, Pd, and Rh) with little sacrifice in activity. Ni catalysts deactivate quickly under realistic DRM conditions. Rare earth oxides such as CeO 2 , or as CeO 2 -ZrO 2 -Al 2 O 3 (CZA), are supports that improve both the activity and stability of Ni DRM systems due to their redox activity. However, redox-active supports can also enhance the undesired reverse water gas shift (RWGS) reaction, reducing the hydrogen selectivity. In this work, Ni on CZA was coated with an ultrathin Al 2 O 3 overlayer using atomic layer deposition (ALD) to study the effects of the overlayer on catalyst activity, stability, and H 2 /CO ratio. A low-conversion screening method revealed improved DRM activity and lower coking rate upon the addition of the Al 2 O 3 ALD overcoat, and improvements were subsequently confirmed in a high-conversion reactor at long times onstream. The overcoated samples gave an H 2 /CO ratio of ∼1 at high conversion, much greater than uncoated catalysts, and no evidence of deactivation. Characterization of used (but still active) catalysts using several techniques suggests that active Ni is in formal oxidation state >0, Ni-Ce-Al is most likely present as a mixed oxide at the surface, and a nominal thickness of 0.5 nm for the Al 2 O 3 overcoat is optimal., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Devices driven by above-equilibrium "hot" electrons are appealing for photocatalytic technologies, such as in situ H 2 O 2 synthesis, but currently suffer from low (<1%) overall quantum efficiencies. Gold nanostructures excited by visible light generate hot electrons that can inject into a neighboring semiconductor to drive electrochemical reactions. Here, we designed and studied a metal-insulator-metal (MIM) structure of Au nanoparticles on a ZnO/TiO 2 /Al film stack, deposited through room-temperature, lithography-free methods. Light absorption, electron injection efficiency, and photocatalytic yield in this device are superior in comparison to the same stack without Al. Our device absorbs >60% of light at the Au localized surface plasmon resonance (LSPR) peak near 530 nm-a 5-fold enhancement in Au absorption due to critical coupling to an Al film. Furthermore, we show through ultrafast pump-probe spectroscopy that the Al-coupled samples exhibit a nearly 5-fold improvement in hot-electron injection efficiency as compared to a non-Al device, with the hot-electron lifetimes extending to >2 ps in devices photoexcited with fluence of 0.1 mJ cm -2 . The use of an Al film also enhances the photocatalytic yield of H 2 O 2 more than 3-fold in a visible-light-driven reactor. Altogether, we show that the critical coupling of Al films to Au nanoparticles is a low-cost, lithography-free method for improving visible-light capture, extending hot-carrier lifetimes, and ultimately increasing the rate of in situ H 2 O 2 generation.

We report an aberration-corrected electron microscopy analysis of the adhesion and atomic structures of gold nanoparticle catalysts supported on ceria nanocubes and nanorods. Under oxidative conditions, the as-prepared gold nanoparticles on the ceria nanocubes have extended atom layers at the metal-support interface. In contrast, regular gold nanoparticles and rafts are present on the ceria nanorod supports. Under the reducing conditions of water-gas shift reaction, the extended gold atom layers and rafts vanish. In addition, the gold particles on the nanocubes change in morphology and increase in size while those on the nanorods are almost unchanged. The size, morphology, and atomic interface structures of gold strongly depend on the surface structures of ceria supports ((100) surface versus (111) surface) and the reaction environment (reductive versus oxidative). These findings provide insights into the deactivation mechanisms and the shape-dependent catalysis of oxide supported metal catalysts.

We describe a general approach for the synthesis of micro-/nanostructured metal chalcogenides from elemental precursors. The excellent solubility of sulfur, selenium, and tellurium in phosphonium ionic liquids promotes fast reactions between chalcogens and various metal powders upon microwave heating, giving crystalline products. This approach is green, universal, and scalable.

An ideal thermoelectric material would be a semiconductor with high electrical conductivity and relatively low thermal conductivity: an "electron crystal, phonon glass". Introducing nanoscale heterostructures into the bulk TE matrix is one way of achieving this intuitively anomalous electron/phonon transport behavior. The heterostructured interfaces are expected to play a significant role in phonon scattering to reduce thermal conductivity and in the energy-dependent scattering of electrical carriers to improve the Seebeck coefficient. A nanoparticle building block assembly approach is plausible to fabricate three-dimensional heterostructured materials on a bulk commercial scale. However, a key problem in applying this strategy is the possible negative impact on TE performance of organic residue from the nanoparticle capping ligands. Herein, we report a wet chemical, surfactant-free, low-temperature, and easily up-scalable strategy for the synthesis of nanoscale heterophase Bi(2)Te(3)-Te via a galvanic replacement reaction. The micro-nano heterostructured material is fabricated bottom-up, by mixing the heterophase with commercial Bi(2)Te(3). This unique structure shows an enhanced zT value of ∼0.4 at room temperature. This heterostructure has one of the highest figures of merit among bismuth telluride systems yet achieved by a wet chemical bottom-up assembly. In addition, it shows a 40% enhancement of the figure of merit over our lab-made material without nanoscale heterostructures. This enhancement is mainly due to the decrease in the thermal conductivity while maintaining the power factor. Overall, this cost-efficient and room-temperature synthesis methodology provides the potential for further improvement and large-scale thermoelectric applications.

We developed a route to synthesize rutile TiO(2) nanocrystals (NCs) with the assistance of 1-butyl-3-methylimidazolium chloride (bmim(+)Cl(-)). The phase transformation from anatase to rutile phase was investigated, and a simple model to describe the phase transformation process was proposed considering that the nucleation and growth of rutile phase were determined by the aggregation manner of anatase NCs and Ostwald ripening process, respectively. It was demonstrated that the surfactant-like nature of the IL used was crucial for controlling the crystallization process via controlling the aggregation manner of the NCs. The phase, shape, and size of TiO(2) NCs could be tuned by the controlling the operating conditions, such as temperature, solution acidity, and reactant concentration of the bmim(+)Cl(-)/TiCl(4)/H(2)O reaction system. Phase-pure rutile multipods and 1D nanorods with different sizes were controllably obtained.

We report an ionic liquid (IL) assisted hydrothermal method to synthesize anatase TiO(2) nanocrystals (NCs), in which TiCl(4) was used as precursor, 1-butyl-3-methylimidazolium chloride (bmim(+)Cl(-)) as IL, and F(-) or SO(4)(2-) ions as phase transformation inhibitor. The surfactant-like nature of IL was found to play a key role in controlling the crystallization process via controlling the aggregation manner of the NCs. The fine-tuning abilities of the operating parameters of the bmim(+)Cl(-)/TiCl(4)/H(2)O system facilitated the controlling over the shape and size of TiO(2) NCs. Phase-pure anatase monodisperse NCs with various shape and size were controllably obtained. Moreover, the aggregation manners of anatase NCs were also studied, and it was demonstrated that the high concentration of HF or H(2)SO(4) could result in aggregation of anatase NCs to form pseudo single crystals.

Herein we present a novel and facile approach to controllably load ultrafine noble metal nanoparticles on titania through in situ redox reaction between the reductive titanium(III) oxide support and metal salt precursors in aqueous solution. A series of noble metal/TiO(2) nanocomposites with uniform metal dispersion, tunable metal particle size, and narrow metal particle size distribution were obtained.