Maximizing noble metal utilization in solid catalysts by control of nanoparticle location.

Maximizing the utilization of noble metals is crucial for applications such as catalysis. We found that the minimum loading of platinum for optimal performance in the hydroconversion of -alkanes for industrially relevant bifunctional catalysts could be reduced by a factor of 10 or more through the rational arranging of functional sites at the nanoscale. Intentionally depositing traces of platinum nanoparticles on the alumina binder or the outer surface of zeolite crystals, instead of inside the zeolite crystals, enhanced isomer selectivity without compromising activity.

Control and Impact of Metal Loading Heterogeneities at the Nanoscale on the Performance of Pt/Zeolite Y Catalysts for Alkane Hydroconversion.

The preparation of zeolite-based bifunctional catalysts with low noble metal loadings while maintaining optimal performance has been studied. We have deposited 0.03 to 1.

Influence of Nanoscale Intimacy and Zeolite Micropore Size on the Performance of Bifunctional Catalysts for -Heptane Hydroisomerization.

In this study, Pt nanoparticles on zeolite/γ-AlO composites (50/50 wt) were located either the zeolite or the γ-AlO binder, hereby varying the average distance (intimacy) between zeolite acid sites and metal sites from "closest" to "nanoscale". The catalytic performance of these catalysts was compared to physical mixtures of zeolite and Pt/γ-AlO powders, which provide a "microscale" distance between sites. Several beneficial effects on catalytic activity and selectivity for -heptane hydroisomerization were observed when Pt nanoparticles are located on the γ-AlO binder in nanoscale proximity with zeolite acid sites, as opposed to Pt nanoparticles located inside zeolite crystals.

Stability of Colloidal Iron Oxide Nanoparticles on Titania and Silica Support.

Using model catalysts with well-defined particle sizes and morphologies to elucidate questions regarding catalytic activity and stability has gained more interest, particularly utilizing colloidally prepared metal(oxide) particles. Here, colloidally synthesized iron oxide nanoparticles (Fe O -NPs, size ∼7 nm) on either a titania (Fe O /TiO) or a silica (Fe O /SiO) support were studied. These model catalyst systems showed excellent activity in the Fischer-Tropsch to olefin (FTO) reaction at high pressure.

Bad neighbour, good neighbour: how magnetic dipole interactions between soft and hard ferrimagnetic nanoparticles affect macroscopic magnetic properties in ferrofluids.

Fluids responding to magnetic fields (ferrofluids) offer a scene with no equivalent in nature to explore long-range magnetic dipole interactions. Here, we studied the very original class of binary ferrofluids, embedding soft and hard ferrimagnetic nanoparticles. We used a combination of X-ray magnetic spectroscopy measurements supported by multi-scale experimental techniques and Monte-Carlo simulations to unveil the origin of the emergent macroscopic magnetic properties of the binary mixture.

Assessment of the Location of Pt Nanoparticles in Pt/zeolite Y/γ-AlO Composite Catalysts.

The location of Pt nanoparticles was studied in Pt/zeolite Y/γ-AlO composite catalysts prepared by HPtCl ⋅ 6HO (CPA) or Pt(NH)(NO) (PTA) as Pt precursors. The aim of this study is to validate findings from Transmission Electron Microscopy (TEM) by using characterization techniques that sample larger amounts of catalyst per measurement. Quantitative X-ray Photoelectron Spectroscopy (XPS) showed that the catalyst prepared with CPA led to a significantly higher Pt/Al atomic ratio than the catalyst prepared with PTA confirming that the 1-2 nm sized Pt nanoparticles in the former catalyst were located on the open and mesoporous γ-AlO component, whereas they were located in the micropores of zeolite Y in the latter.

Growth of Supported Gold Nanoparticles in Aqueous Phase Studied by in Situ Transmission Electron Microscopy.

Nanoparticle growth has long been a significant challenge in nanotechnology and catalysis, but the lack of knowledge on the fundamental nanoscale aspects of this process has made its understanding and prediction difficult, especially in a liquid phase. In this work, we successfully used liquid-phase transmission electron microscopy (LP-TEM) to image this process in real time at the nanometer scale, using an Au/TiO catalyst in the presence of NaCl as a case study. In situ LP-TEM clearly showed that the growth of Au nanoparticles occurred through a form of Ostwald ripening, whereby particles grew or disappeared, probably via monomer transfer, without clear correlation to particle size in contrast to predictions of classical Ostwald ripening models.

Impact of the Spatial Organization of Bifunctional Metal-Zeolite Catalysts on the Hydroisomerization of Light Alkanes.

Improving product selectivity by controlling the spatial organization of functional sites at the nanoscale is a critical challenge in bifunctional catalysis. We present a series of composite bifunctional catalysts consisting of one-dimensional zeolites (ZSM-22 and mordenite) and a γ-alumina binder, with platinum particles controllably deposited either on the alumina binder or inside the zeolite crystals. The hydroisomerization of n-heptane demonstrates that the catalysts with platinum particles on the binder, which separates platinum and acid sites at the nanoscale, leads to a higher yield of desired isomers than catalysts with platinum particles inside the zeolite crystals.

The Origin of Metal Loading Heterogeneities in Pt/Zeolite Y Bifunctional Catalysts.

Preparing catalysts with highly dispersed metal nanoparticles and narrow particle size distribution has been in the focus of numerous studies. Besides size and size distribution, the location of metal nanoparticles within and local metal loading of the support can have significant impact on catalytic performance. This study revealed that great variations in Pt loading between individual Pt/zeolite Y crystals occurred irrespective of the metal deposition method, namely ion-exchange (IE) or incipient wetness impregnation (IWI).

Preparation of Cobalt Nanocrystals Supported on Metal Oxides To Study Particle Growth in Fischer-Tropsch Catalysts.

Colloidal synthesis of nanocrystals (NC) followed by their attachment to a support and activation is a promising route to prepare model catalysts for research on structure-performance relationships. Here, we investigated the suitability of this method to prepare well-defined Co/TiO and Co/SiO catalysts for the Fischer-Tropsch (FT) synthesis with high control over the cobalt particle size. To this end, Co-NC of 3, 6, 9, and 12 nm with narrow size distributions were synthesized and attached uniformly on either TiO or SiO supports with comparable morphology and Co loadings of 2-10 wt %.

Impact of the electron beam on the thermal stability of gold nanorods studied by environmental transmission electron microscopy.

In-situ transmission electron microscopy experiments are of great interest to nanoscience and nanotechnology. However, it is known that the electron beam can have a significant impact on the structure of the sample which makes it important to carefully interpret in-situ data. In this work, we studied the thermal stability of CTAB-stabilized gold nanorods under different gaseous environments in an environmental transmission electron microscope and compared the outcome to ex-situ heating experiments.

Influence of Metal Deposition and Activation Method on the Structure and Performance of Carbon Nanotube Supported Palladium Catalysts.

The effects of the metal deposition and activation methods on metal particle size and distribution were investigated for carbon nanotube supported Pd catalysts. The Pd precursor was loaded by incipient wetness impregnation, ion adsorption, and deposition precipitation and was activated by thermal treatment under a nitrogen atmosphere or in the liquid phase by reduction by formaldehyde or sodium borohydride. Regardless of the metal precursor loading method, activation under a N atmosphere at 500 °C led to homogeneously distributed 4 nm Pd particles.

Manufacture of highly loaded silica-supported cobalt Fischer-Tropsch catalysts from a metal organic framework.

The development of synthetic protocols for the preparation of highly loaded metal nanoparticle-supported catalysts has received a great deal of attention over the last few decades. Independently controlling metal loading, nanoparticle size, distribution, and accessibility has proven challenging because of the clear interdependence between these crucial performance parameters. Here we present a stepwise methodology that, making use of a cobalt-containing metal organic framework as hard template (ZIF-67), allows addressing this long-standing challenge.

Scale-dependent diffusion anisotropy in nanoporous silicon.

Nanoporous silicon produced by electrochemical etching of highly B-doped p-type silicon wafers can be prepared with tubular pores imbedded in a silicon matrix. Such materials have found many technological applications and provide a useful model system for studying phase transitions under confinement. This paper reports a joint experimental and simulation study of diffusion in such materials, covering displacements from molecular dimensions up to tens of micrometers with carefully selected probe molecules.

Anisotropic Shape Changes of Silica Nanoparticles Induced in Liquid with Scanning Transmission Electron Microscopy.

Liquid-phase transmission electron microscopy (TEM) is used for in-situ imaging of nanoscale processes taking place in liquid, such as the evolution of nanoparticles during synthesis or structural changes of nanomaterials in liquid environment. Here, it is shown that the focused electron beam of scanning TEM (STEM) brings about the dissolution of silica nanoparticles in water by a gradual reduction of their sizes, and that silica redeposites at the sides of the nanoparticles in the scanning direction of the electron beam, such that elongated nanoparticles are formed. Nanoparticles with an elongation in a different direction are obtained simply by changing the scan direction.

Nanoscale intimacy in bifunctional catalysts for selective conversion of hydrocarbons.

The ability to control nanoscale features precisely is increasingly being exploited to develop and improve monofunctional catalysts. Striking effects might also be expected in the case of bifunctional catalysts, which are important in the hydrocracking of fossil and renewable hydrocarbon sources to provide high-quality diesel fuel. Such bifunctional hydrocracking catalysts contain metal sites and acid sites, and for more than 50 years the so-called intimacy criterion has dictated the maximum distance between the two types of site, beyond which catalytic activity decreases.

Mesoscale Characterization of Nanoparticles Distribution Using X-ray Scattering.

The properties of many functional materials depend critically on the spatial distribution of an active phase within a support. In the case of solid catalysts, controlling the spatial distribution of metal (oxide) nanoparticles at the mesoscopic scale offers new strategies to tune their performance and enhance their lifetimes. However, such advanced control requires suitable characterization methods, which are currently scarce.

Tailoring and visualizing the pore architecture of hierarchical zeolites.

Recently the concept of hierarchical zeolites invoked more explicit attention to enhanced accessibility of zeolites. By realizing additional meso-/macroporosity with the intrinsic microporosity of zeolites, a hierarchical pore system arises which facilitates mass transport while maintaining the zeolite shape selectivity. A great number of synthesis strategies have been developed for tailoring the pore architecture of hierarchical zeolites.

Heterogeneities of the nanostructure of platinum/zeolite y catalysts revealed by electron tomography.

To develop structure-performance relationships for important catalysts, a detailed characterization of their morphology is essential. Using electron tomography, we determined in three dimensions the structure of Pt/zeolite Y bifunctional catalysts. Optimum experimental conditions enabled for the first time high-resolution 3D imaging of Pt particles as small as 1 nm located inside zeolite micropores.

Towards stable catalysts by controlling collective properties of supported metal nanoparticles.

Supported metal nanoparticles play a pivotal role in areas such as nanoelectronics, energy storage/conversion and as catalysts for the sustainable production of fuels and chemicals. However, the tendency of nanoparticles to grow into larger crystallites is an impediment for stable performance. Exemplarily, loss of active surface area by metal particle growth is a major cause of deactivation for supported catalysts.