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• The genesis of Pd nanocatalysts on Al 2 O 3 can be adequately followed by in situ ETEM. • Fast tomography in ETEM unravels the 3D evolution of NPs during calcination. • Oxidation and reduction of Pd NPs is followed down to the atomic scale in ETEM. • In situ tracking of Pd NPs in ETEM evidences that they grow by Ostwald Ripening. The quality of metallic nanoparticles (NPs) used in heterogeneous catalysis relies through many aspects on their small size, on the homogeneity of their spatial distribution on their supports and on their ability to resist to sintering or coalescence. It is thus very important to quantify these parameters and understand the mechanisms controlling the growth of NPs during the genesis process of the catalyst. Whereas conventional Transmission Electron Microscopy (TEM) is currently used for these purposes, it most frequently remains a 'static' method where results are obtained in high vacuum and post mortem, i.e. after the typical drying, calcination and reduction steps without the possibility to follow directly the evolution of both NPs and supports during those treatments. Environmental TEM (ETEM) unlocks this blocking and allows elementary mechanisms, such as Ostwald Ripening and coalescence to be unravelled through direct in situ observations. We report here an ETEM study of the preparation of Pd-based narrow NPs, less than 5 nm in size, deposited on a δ-alumina support. We focused on 3 main objectives: (i) quantifying the sizes of NPs at each preparation step performed in situ under environmental (i.e. respectively oxygen or air and hydrogen atmospheres at working temperatures) and comparing them to post mortem measurements; (ii) identify the oxidation state of the NPs through an in situ High Resolution imaging study of their crystallographic structure; (iii) explore the possibilities of environmental tri-dimensional (3D) studies by tilt series based Electron Tomography. This last item represents a challenging breakthrough in the characterization of nanocatalysts; it will be demonstrated that the use of modern instruments (microscope and accessories) allows tomographic acquisitions to be performed very fast, within a few minutes and even seconds, which opens the way to the 3D tracking of microstructures almost in real time during their evolution under gas and at high temperature. [ABSTRACT FROM AUTHOR]

The spreading of a liquid droplet on flat surfaces is a well-understood phenomenon, but little is known about how liquids spread on a rough surface. When the surface roughness is of the nanoscopic length scale, the capillary forces dominate and the liquid droplet spreads by wetting the nanoscale textures that act as capillaries. Here, using a combination of advanced nanofabrication and liquid-phase transmission electron microscopy, we image the wetting of a surface patterned with a dense array of nanopillars of varying heights. Our real-time, high-speed observations reveal that water wets the surface in two stages: 1) an ultrathin precursor water film forms on the surface, and then 2) the capillary action by nanopillars pulls the water, increasing the overall thickness of water film. These direct nanoscale observations capture the previously elusive precursor film, which is a critical intermediate step in wetting of rough surfaces. [ABSTRACT FROM AUTHOR]

[Display omitted] • Cobalt-bismuth nanoparticles in carbon nanotubes supported catalysts. • Noticeable increase in catalyst stability on the promotion. • Migration of metallic bismuth occurring leading to its redispersion. • Enhancement of cobalt reduction on the promotion. • Preferential bismuth localization at the steps and edges of cobalt nanoparticles. Metal nanoparticles on the surface of porous supports have found numerous applications in different areas of science. Fischer-Tropsch synthesis, which proceeds on the surface of cobalt metal nanoparticles, is an efficient way to convert renewables and fossil feedstocks into alternative fuels. The stability of cobalt catalysts is an essential and even crucial parameter and can be significantly improved by promotion. In this paper, a combination of operando Quick-XAS, NAP-XPS, high resolution electron microscopy imaging, DFT modeling alongside with Fischer-Tropsch catalytic experiments has provided deep insights into the evolution of bismuth promoter and structure of cobalt-bismuth nanoparticles in the catalysts supported by carbon nanotubes. We uncovered noticeable migration of metallic bismuth occurring during the reduction step, which leads to bismuth redispersion over the surface of cobalt nanoparticles. Cobalt reduction is facilitated in the presence of bismuth. The working Fischer-Tropsch catalyst contains cobalt-bismuth bimetallic nanoparticles, with bismuth located in the nanoparticle shell. The promotion with bismuth has resulted in a noticeable increase in catalyst stability. Characterization and DFT modeling suggest preferential localization of bismuth mobile promoter at the steps and edges of cobalt nanoparticles, which hinders cobalt sintering and carbon deposition and improves the catalyst stability. [ABSTRACT FROM AUTHOR]

[Display omitted] • Elucidation of the promotion with antimony and tin on iron catalysts. • 7–10 times increase in the intrinsic activity of iron surface sites. • In-situ identification of the structure of working catalysts. • Strong interaction of the promoters and iron active phase. • Iron antimony bimetallic nanoparticles in activated catalysts. Fischer-Tropsch synthesis provides an important opportunity for utilization of biomass and plastic waste. Iron catalysts are the catalysts of choice for light olefin synthesis using Fischer-Tropsch reaction. In this paper, we investigate strong promoting effects of antimony and tin on the catalytic performance of silica supported iron Fischer-Tropsch catalysts using a combination of advanced and in-situ techniques. The catalyst doping with these elements added via impregnation results in a major increase in the reaction rate and much better catalyst stability. No enhancement of iron dispersion was observed after the promotion, while somewhat higher extent of iron carbidization was observed in the antimony promoted catalysts. Iron-bismuth bimetallic nanoparticles are detected by several techniques. In the working catalysts, the promoters are located in close proximity to the iron nanoparticles. The promotion leads to the 7–10 times increase in the intrinsic activity of iron surface sites due to their interaction with the promoters. [ABSTRACT FROM AUTHOR]