The photocatalytic water reduction reaction on CdS nanorods was studied as function of Pt cluster size. Maximum H2 production is found for Pt46. This effect is attributed to the size dependent electronic properties (e.g., LUMO) of the clusters with respect to the band edges of the semiconductor. This observation may be applicable for the study and interpretation of other systems and reactions, e.g. H2O oxidation or CO2 reduction.
The sensitivity, or insensitivity, of catalysed reactions to catalyst structure is a commonly employed fundamental concept. Here we report on the nature of nano-catalysed ethylene hydrogenation, investigated through experiments on size-selected Ptn (n=8–15) clusters soft-landed on magnesia and first-principles simulations, yielding benchmark information about the validity of structure sensitivity/insensitivity at the bottom of the catalyst size range. Both ethylene-hydrogenation-to-ethane and the parallel hydrogenation–dehydrogenation ethylidyne-producing route are considered, uncovering that at the <1 nm size-scale the reaction exhibits characteristics consistent with structure sensitivity, in contrast to structure insensitivity found for larger particles. The onset of catalysed hydrogenation occurs for Ptn (n≥10) clusters at T>150 K, with maximum room temperature reactivity observed for Pt13. Structure insensitivity, inherent for specific cluster sizes, is induced in the more active Pt13 by a temperature increase up to 400 K leading to ethylidyne formation. Control of sub-nanometre particle size may be used for tuning catalysed hydrogenation activity and selectivity.
Employing rationally designed model systems with precise atom-by-atom particle size control, we demonstrate by means of combining noninvasive in situ indirect nanoplasmonic sensing and ex situ scanning transmission electron microscopy that monomodal size-selected platinum cluster catalysts on different supports exhibit remarkable intrinsic sintering resistance even under reaction conditions. The observed stability is related to suppression of Ostwald ripening by elimination of its main driving force via size-selection. This study thus constitutes a general blueprint for the rational design of sintering resistant catalyst systems and for efficient experimental strategies to determine sintering mechanisms. Moreover, this is the first systematic experimental investigation of sintering processes in nanoparticle systems with an initially perfectly monomodal size distribution under ambient conditions.
We introduce size-selected subnanometer cluster catalysts deposited on thin films of colloidal semiconductor nanocrystals as a novel platform to obtain atomic scale insight into photocatalytic generation of solar fuels. Using Pt-cluster-decorated CdS nanorod films for photocatalytic hydrogen generation as an example, we determine the minimum amount of catalyst necessary to obtain maximum quantum efficiency of hydrogen generation. Further, we provide evidence for tuning photocatalytic activities by precisely controlling the cluster catalyst size.
The nature of the nano-catalyzed hydrogenation of ethylene, yielding benchmark information pertaining to the concept of structure sensitivity/insensitivity and its applicability at the bottom of the catalyst particle size-range, is explored with experiments on size-selected Ptn (n=7-40) clusters softlanded on MgO, in conjunction with first-principles simulations. As in the case of larger particles both the direct ethylene hydrogenation channel and the parallel hydrogenation-dehydrogenation ethylidyne-producing route must be considered, with the fundamental uncovering that at the <1 nm size-scale the reaction exhibits characteristics consistent with structure sensitivity, in contrast to the structure insensitivity found for larger particles. In this size-regime, the chemical properties can be modulated and tuned by a single atom, reflected by the onset of low temperature hydrogenation at T >150 K catalyzed by Pt n (n≥10) clusters, with maximum room temperature reactivity observed for Pt 13 using a pulsed molecular beam technique. Structure insensitive behavior, inherent for specific cluster sizes at ambient temperatures, can be induced in the more active sizes, e.g. Pt 13 , by a temperature increase, up to 400 K, which opens dehydrogenation channels leading to ethylidyne formation. This reaction channel was, however found to be attenuated on Pt 20 , as catalyst activity remained elevated after the 400 K step. Pt 30 displayed behavior which can be understood from extrapolating bulk properties to this size range; in particular the calculated d-band center. In the non-scalable subnanometer size regime, however, precise control of particle size may be used for atom-by-atom tuning and manipulation of catalyzed hydrogenation activity and selectivity.
Metal oxide thin films grown on metal single crystals are commonly used to model heterogeneous catalyst supports. The structure and properties of thin silicon dioxide films grown on metal single crystals have only recently been thoroughly characterized and their spectral properties well established. We report the successful growth of a threedimensional, vitreous silicon dioxide thin film on the Pt(111) surface and reproduce the closed bilayer structure previously reported. The confirmation of the three dimensional nature of the film is unequivocally shown by the infrared absorption band at 1252 cm −1 .Temperature programmed desorption was used to show that this three-dimensional thin film covers the Pt(111) surface to such an extent that its application as a catalyst support for clusters/nanoparticles is possible. The growth of a three-dimensional film was seen to be directly correlated with the amount of oxygen present on the surface after the silicon evaporation process. This excess of oxygen is tentatively attributed to atomic oxygen being generated in the evaporator. The identification of atomic oxygen as a necessary building block for the formation of a three-dimensional thin film opens up new possibilities for thin film growth on metal supports, whereby simply changing the type of oxygen enables thin films with different atomic structures to be synthesized. This is a novel approach to tune the synthesis parameters of thin films to grow a specific structure and expands the options for modeling common amorphous silica supports under ultra high vacuum conditions.
Nanoparticles (NPs) are revolutionizing many areas of science and technology, often delivering unprecedented improvements to properties of the conventional materials. However, despite important advances in NPs synthesis and applications, numerous challenges still remain. Development of alternative synthetic method capable of producing very uniform, extremely clean and very stable NPs is urgently needed. If successful, such method can potentially transform several areas of nanoscience, including environmental and energy related catalysis. Here we present the first experimental demonstration of catalytically active NPs synthesis achieved by the helium nanodroplet isolation method. This alternative method of NPs fabrication and deposition produces narrowly distributed, clean, and remarkably stable NPs. The fabrication is achieved inside ultralow temperature, superfluid helium nanodroplets, which can be subsequently deposited onto any substrate. This technique is universal enough to be applied to nearly any element, while achieving high deposition rates for single element as well as composite core-shell NPs.
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