H.V. Bui
Please Note
8 records found
1
From Single Atoms to Nanoparticles
Autocatalysis and Metal Aggregation in Atomic Layer Deposition of Pt on TiO2 Nanopowder
A fundamental understanding of the interplay between ligand-removal kinetics and metal aggregation during the formation of platinum nanoparticles (NPs) in atomic layer deposition of Pt on TiO2 nanopowder using trimethyl(methylcyclo-pentadienyl)platinum(IV) as the precursor and O2 as the coreactant is presented. The growth follows a pathway from single atoms to NPs as a function of the oxygen exposure (PO2 × time). The growth kinetics is modeled by accounting for the autocatalytic combustion of the precursor ligands via a variant of the Finke–Watzky two-step model. Even at relatively high oxygen exposures (<120 mbar s) little to no Pt is deposited after the first cycle and most of the Pt is atomically dispersed. Increasing the oxygen exposure above 120 mbar s results in a rapid increase in the Pt loading, which saturates at exposures >> 120 mbar s. The deposition of more Pt leads to the formation of NPs that can be as large as 6 nm. Crucially, high PO2 (≥5 mbar) hinders metal aggregation, thus leading to narrow particle size distributions. The results show that ALD of Pt NPs is reproducible across small and large surface areas if the precursor ligands are removed at high PO2.
We tailored the size distribution of Pt nanoparticles (NPs) on graphene nanoplatelets at a given metal loading by using low-temperature atomic layer deposition carried out in a fluidized bed reactor operated at atmospheric pressure. The Pt NPs deposited at low temperature (100 °C) after 10 cycles were more active and stable towards the propene oxidation reaction than their high-temperature counterparts. Crucially, the gap in the catalytic performance was retained even after prolonged periods of time (>24 hours) at reaction temperatures as high as 450 °C. After exposure to such harsh conditions the Pt NPs deposited at 100 °C still retained a size distribution that is narrower than the one of the as-synthesized NPs obtained at 250 °C. The difference in performance correlated with the difference in the number of facet sites as estimated after the catalytic test. Our approach provides not only a viable route for the scalable synthesis of stable supported Pt NPs with tailored size distributions but also a tool for studying the structure-function relationship.
Understanding and Controlling the Aggregative Growth of Platinum Nanoparticles in Atomic Layer Deposition
An Avenue to Size Selection
Although the gas-phase production of nanostructured solids has already been carried out in industry for decades, only in recent years has research interest in this topic begun to increase. Nevertheless, despite the remarkable scientific progress made recently, many long-established processes are still used in industry. Scientific advancements can potentially lead to the improvement of existing industrial processes, but also to the development of completely new routes. This paper aims to review state-of-the-art synthesis and processing technologies, as well as the recent developments in academic research. Flame reactors that produce inorganic nanoparticles on industrial- and lab-scales are described, alongside a detailed overview of the different systems used for the production of carbon nanotubes and graphene. We discuss the problems of agglomeration and mixing of nanoparticles, which are strongly related to synthesis and processing. Finally, we focus on two promising processing techniques, namely nanoparticle fluidization and atomic layer deposition.
Superior thermal quenching and degradation of phosphors are required for long lifetime lighting devices, such as light-emitting diodes, which can be realized through composition modification. Here, Al-N bonds in AlON: Eu2+ phosphors are substituted by higher bond order of Si-C. Photoluminescence (PL) results show thermal quenching (at 150 °C) and thermal degradation (after 600 °C treatment in air) are improved by 5% and 8% with a small decrease of PL intensity in 5% SiC doped AlON: Eu2+ phosphor. To explain these observations, first-principles computational study was performed to understand the Si and C configuration in AlON:Eu2+. The calculations reveal that Si and C elements are not randomly distributed in AlON lattice. It was found that Si prefers occupying tetrahedral sites (Td-Si) and the insertion of C in Td-Si is always energetically favorable, which results in the formation of SiC4 and SiNC3 clusters. Thus, the Al-N substitution by Si-C induces a stronger local structure, which accounts for the emission redshift and better thermal stability.
Atomic and molecular layer deposition
Off the beaten track
Atomic layer deposition (ALD) is a gas-phase deposition technique that, by relying on self-terminating surface chemistry, enables the control of the amount of deposited material down to the atomic level. While mostly used in semiconductor technology for the deposition of ceramic oxides and nitrides on wafers, ALD lends itself to the deposition of a wealth of materials on virtually every substrate. In particular, ALD and its organic counterpart molecular layer deposition (MLD), have opened up attractive avenues for the synthesis of novel nanostructured materials. However, as most ALD processes were developed and optimized for semiconductor technology, these might not be optimal for applications in fields such as catalysis, energy storage, and health. For this reason, novel applications for ALD often require new surface chemistries, process conditions, and reactor types. As a result, recent developments in ALD technology have marked a considerable departure from the standard set by well-established ALD processes. The aim of this review is twofold: firstly, to capture the recent departure of ALD from its original development; and secondly, to pinpoint the unexplored paths through which ALD can advance further in terms of synthesis of novel materials. To that end, we provide a review of the recent developments of ALD and MLD of materials that are gaining increasing attention on various substrates, with particular emphasis on high-surface-area substrates. Furthermore, we present a critical review of the effects of the process conditions, namely, temperature, pressure, and time on ALD growth. Finally, we also give a brief overview of the recent advances in ALD reactors and energy-enhanced ALD processes.
Surface modification of cellulosic paper is demonstrated by employing plasma assisted atomic layer deposition. Al2O3 thin films are deposited on paper substrates, prepared with different fiber sizes, to improve their barrier properties. Thus, a hydrophobic paper is created with low gas permeability by combining the control of fiber size (and structure) with atomic layer deposition of Al2O3 films. Papers are prepared using Kraft softwood pulp and thermomechanical pulp. The cellulosic wood fibers are refined to obtain fibers with smaller length and diameter. Films of Al2O3, 10, 25, and 45 nm in thickness, are deposited on the paper surface. The work demonstrates that coating of papers prepared with long fibers efficiently reduces wettability with slight enhancement in gas permeability, whereas on shorter fibers, it results in significantly lower gas permeability. Wettability studies on Al2O3 deposited paper substrates have shown water wicking and absorption over time only in papers prepared with highly refined fibers. It is also shown that there is a certain fiber size at which the gas permeability assumes its minimum value, and further decrease in fiber size will reverse the effect on gas permeability.