Size control of Au nanoparticles from the scalable and solvent-free matrix assembly cluster source

Nanostructured gold is an intriguing system for heterogeneous catalysis at low temperature. Its activity is related to choice of support selection, particle-support interaction, and especially the particle size. Here, we investigate the possibility of controlling the size of Au clusters (nanoparticles) in the novel Matrix Assembly Cluster Source (MACS), a solvent-free nanoparticle source with potential for scale-up to the gram level. The novelty of the MACS is the idea of making clusters by sputtering a pre-condensed matrix of metal atoms embedded in a condensed non-reactive gas, e.g., Ar. This concept, introduced in 2016, has already proved deposition rates several orders of magnitude higher than conventional cluster beam routes. Such scale-up in the cluster production rate is crucial for industrial research on nanocatalysis under realistic reaction condition. Here, we report a systematic study of how Au metal loading in the matrix affects the size distribution of clusters generated. Furthermore, the obtained dependence of cluster size on deposition time provides clear confirmation of cluster formation inside the matrix by ion irradiation, rather than by aggregation of atoms on the TEM support after deposition

Low pressure bottom-up synthesis of metal@oxide and oxide nanoparticles: control of structure and functional properties

Experimental activity on core@shell, metal@oxide, and oxide nanoparticles (NPs) grown with physical synthesis, and more specifically by low pressure gas aggregation sources (LPGAS) is reviewed, through a selection of examples encompassing some potential applications in nanotechnology. After an introduction to the applications of NPs, a brief description of the main characteristics of the growth process of clusters and NPs in LPGAS is given. Thereafter, some relevant case studies are reported: Formation of native oxide shells around the metal cores in core@shell NPs. Experimental efforts to obtain magnetic stabilization in magnetic core@shell NPs by controlling their structure and morphology. Recent advancements in NP source design and new techniques of co-deposition, with relevant results in the realization of NPs with a greater variety of functionalities. Recent results on reducible oxide NPs, with potentialities in nanocatalysis, energy storage, and other applications. Although this list is far from being exhaustive, the aim of the authors is to provide the reader a descriptive glimpse into the physics behind the growth and studies of low pressure gas-phase synthesized NPs, with their ever-growing potentialities for the rational design of new functional materials

Electrocatalytic Behavior of PtCu Clusters Produced by Nanoparticle Beam Deposition

State-of-the-art electrocatalysts for electrolyzer and fuel cell applications currently rely on platinum group metals, which are costly and subject to supply risks. In recent years, a vast collection of research has explored the possibility of reducing the Pt content in such catalysts by alloying with earth-abundant and cheap metals, enabling co-optimization of cost and activity. Here, using nanoparticle beam deposition, we explore the electrocatalytic performance of PtCu alloy clusters in the hydrogen evolution reaction (HER). Elemental compositions of the produced bimetallic clusters were shown by X-ray photoelectron spectroscopy (XPS) to range from 2 at. % to 38 at. % Pt, while high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) combined with energy dispersive X-ray (EDX) spectroscopy indicated that the predominant cluster morphologies could be characterized as either a fully mixed alloy or as a mixed core with a Cu-rich shell. In contrast with previous studies, a monotonic decrease in HER activity with increasing Cu content was observed over the composition range studied, with the current density measured at -0.3 V (vs reversible hydrogen electrode) scaling approximately linearly with Pt at. %. This trend opens up the possibility that PtCu could be used as a reference system for comparing the composition-dependent activity of other bimetallic catalysts

Use of Cold Atmospheric Plasma to Detoxify Hazelnuts from Aflatoxins

Aflatoxins, produced by Aspergillus flavus and A. parasiticus, can contaminate different foodstuffs, such as nuts. Cold atmospheric pressure plasma has the potential to be used for mycotoxin detoxification. In this study, the operating parameters of cold atmospheric pressure plasma were optimized to reduce the presence of aflatoxins on dehulled hazelnuts. First, the effect of different gases was tested (N2, 0.1% O2 and 1% O2, 21% O2), then power (400, 700, 1000, 1150 W) and exposure time (1, 2, 4, and 12 min) were optimized. In preliminary tests on aflatoxin standard solutions, this method allowed to obtain a complete detoxification using a high power for a few minutes. On hazelnuts, in similar conditions (1000 W, 12 min), a reduction in the concentration of total aflatoxins and AFB1 of over 70% was obtained. Aflatoxins B1 and G1 were more sensitive to plasma treatments compared to aflatoxins B2 and G2, respectively. Under plasma treatment, aflatoxin B1 was more sensitive compared to aflatoxin G1. At the highest power, and for the longest time, the maximum temperature increment was 28.9 °C. Cold atmospheric plasma has the potential to be a promising method for aflatoxin detoxification on food, because it is effective and it could help to maintain the organoleptic characteristics

Hydrothermal Fabrication of Carbon-Supported Oxide-Derived Copper Heterostructures : A Robust Catalyst System for Enhanced Electro-Reduction of CO2 to C2H4

Anthropogenic CO can be converted to alternative fuels and value-added products by electrocatalytic routes. Copper-based catalysts are found to be the star materials for obtaining longer-chain carbon compounds beyond 2e products. Herein, we report a facile hydrothermal fabrication of a highly robust electrocatalyst: in-situ grown heterostructures of plate-like CuO−CuO on carbon black. Simultaneous synthesis of copper-carbon catalysts with varied amounts of copper was conducted to determine the optimum blend. It is observed that the optimum ratio and structure have aided in achieving the state of art faradaic efficiency for ethylene >45 % at −1.6 V vs. RHE at industrially relevant high current densities over 160 to 200 mA ⋅ cm. It is understood that the in-situ modification of CuO to CuO during the electrolysis is the driving force for the highly selective conversion of CO to ethylene through the *CO intermediates at the onset potentials followed by C−C coupling. The excellent distribution of Cu-based platelets on the carbon structure enables rapid electron transfer and enhanced catalytic efficiency. It is inferred that choosing the right composition of the catalyst by tuning the catalyst layer over the gas diffusion electrode can substantially affect the product selectivity and promote reaching the potential industrial scale

Influence of defect distribution on the reducibility of CeO2-x nanoparticles

Ceria nanoparticles (NPs) are fundamental in heterogeneous catalysis because of their ability to store or release oxygen depending on the ambient conditions. Their oxygen storage capacity is strictly related to the exposed planes, crystallinity, density and distribution of defects. In this work a study of ceria NPs produced with a ligand-free, physical synthesis method is presented. The NP films were grown by a magnetron sputtering based gas aggregation source and studied by high resolution- and scanning-transmission electron microscopy and x-ray photoelectron spectroscopy. In particular, the influence of the oxidation procedure on the NP reducibility has been investigated. The different reducibility has been correlated to the exposed planes, crystallinity and density and distribution of structural defects. The results obtained in this work represent a basis to obtain cerium oxide NP with desired oxygen transport properties

Influence of size, shape and core\u2013shell interface on surface plasmon resonance in Ag and Ag@MgO nanoparticle films deposited on Si/SiOx

Ag and Ag@MgO core-shell nanoparticles (NPs) with a diameter of d = 3-10 nm were obtained by physical synthesis methods and deposited on Si with its native ultrathin oxide layer SiOx (Si/SiOx). Scanning electron microscopy and transmission electron microscopy (TEM) images of bare Ag NPs revealed the presence of small NP aggregates caused by diffusion on the surface and agglomeration. Atomic resolution TEM gave evidence of the presence of crystalline multidomains in the NPs, which were due to aggregation and multitwinning occurring during NP growth in the nanocluster source. Co-deposition of Ag NPs and Mg atoms in an oxygen atmosphere gave rise to formation of a MgO shell matrix surrounding the Ag NPs. The behaviour of the surface plasmon resonance (SPR) excitation in surface differential reflectivity (SDR) spectra with p-polarised light was investigated for bare Ag and Ag@MgO NPs. It was shown that the presence of MgO around the Ag NPs caused a red shift of the plasmon excitation, and served preserve its existence after prolonged (five months) exposure to air, realizing the possibility of technological applications in plasmonic devices. The Ag NP and Ag@MgO NP film features in the SDR spectra could be reproduced by classical electrodynamics simulations by treating the NP-containing layer as an effective Maxwell Garnett medium. The simulations gave results in agreement with the experiments when accounting for the experimentally observed aggregation