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The influence of geometry on the local and global packing of particles is important to many fundamental and applied research themes, such as the structure and stability of liquids, crystals and glasses. Here we show by experiments and simulations that a binary mixture of hard-sphere-like nanoparticles crystallizing into a MgZn2 Laves phase in bulk spontaneously forms icosahedral clusters in slowly drying droplets. Using advanced electron tomography, we are able to obtain the real-space coordinates of all the spheres in the icosahedral clusters of up to about 10,000 particles. The local structure of 70–80% of the particles became similar to that of the MgCu2 Laves phase. These observations are important for photonic applications. In addition, we observed in simulations that the icosahedral clusters nucleated away from the spherical boundary, which is distinctly different from that of the single species clusters. Our findings open the way for particle-level studies of nucleation and growth of icosahedral clusters, and of binary crystallization.The authors investigate out-of-equilibrium crystallization of a binary mixture of sphere-like nanoparticles in small droplets. They observe the spontaneous formation of an icosahedral structure with stable MgCu2 phases, which are promising for photonic applications.

Self-assembly of inorganic nanoparticles has been used to prepare hundreds of different colloidal crystals, but almost invariably with the restriction that the particles must be densely packed. Here, we show that non–close-packed nanoparticle arrays can be fabricated through the selective removal of one of two components comprising binary nanoparticle superlattices. First, a variety of binary nanoparticle superlattices were prepared at the liquid-air interface, including several arrangements that were previously unknown. Molecular dynamics simulations revealed the particular role of the liquid in templating the formation of superlattices not achievable through self-assembly in bulk solution. Second, upon stabilization, all of these binary superlattices could be transformed into distinct “nanoallotropes”—nanoporous materials having the same chemical composition but differing in their nanoscale architectures.

Development of low-cost and high-performance oxygen evolution reaction catalysts is key to implementing polymer electrolyte membrane water electrolysers for hydrogen production. Iridium-based oxides are the state-of-the-art acidic oxygen evolution reaction catalysts but still suffer from inadequate activity and stability, and iridium’s scarcity motivates the discovery of catalysts with lower iridium loadings. Here we report a mass-selected iridium–tantalum oxide catalyst prepared by a magnetron-based cluster source with considerably reduced noble-metal loadings beyond a commercial IrO 2 catalyst. A sensitive electrochemistry/mass-spectrometry instrument coupled with isotope labelling was employed to investigate the oxygen production rate under dynamic operating conditions to account for the occurrence of side reactions and quantify the number of surface active sites. Iridium–tantalum oxide nanoparticles smaller than 2 nm exhibit a mass activity of 1.2 ± 0.5 kA g Ir –1 and a turnover frequency of 2.3 ± 0.9 s −1 at 320 mV overpotential, which are two and four times higher than those of mass-selected IrO 2 , respectively. Density functional theory calculations reveal that special iridium coordinations and the lowered aqueous decomposition free energy might be responsible for the enhanced performance. Low-cost, high-performance oxygen evolution catalysts would facilitate implementation of water electrolysers for hydrogen production. Here the authors report a low-iridium mass-selected iridium–tantalum oxide catalyst with high intrinsic activity in acid and carefully evaluate oxygen production to account for parasitic reactions.

Assembling binary mixtures of nanoparticles into crystals, gives rise to collective properties depending on the crystal structure and the individual properties of both species. However, quantitative 3D real-space analysis of binary colloidal crystals with a thickness of more than 10 layers of particles has rarely been performed. Here we demonstrate that an excess of one species in the binary nanoparticle mixture suppresses the formation of icosahedral order in the self-assembly in droplets, allowing the study of bulk-like binary crystal structures with a spherical morphology also called supraparticles. As example of the approach, we show single-particle level analysis of over 50 layers of Laves phase binary crystals of hard-sphere-like nanoparticles using electron tomography. We observe a crystalline lattice composed of a random mixture of the Laves phases. The number ratio of the binary species in the crystal lattice matches that of a perfect Laves crystal. Our methodology can be applied to study the structure of a broad range of binary crystals, giving insights into the structure formation mechanisms and structure-property relations of nanomaterials. 3D real-space analysis of thick nanoparticle crystals is non-trivial. Here, the authors demonstrate the structural analysis of a bulk-like Laves phase by imaging an off-stoichiometric binary mixture of hard-sphere-like nanoparticles in spherical confinement by electron tomography, enabling defect analysis on the single-particle level.

The rapid progress in materials science that enables the design of materials down to the nanoscale also demands characterization techniques able to analyze the materials down to the same scale, such as transmission electron microscopy. As Belgium’s foremost electron microscopy group, among the largest in the world, EMAT is continuously contributing to the development of TEM techniques, such as high-resolution imaging, diffraction, electron tomography, and spectroscopies, with an emphasis on quantification and reproducibility, as well as employing TEM methodology at the highest level to solve real-world materials science problems. The lab’s recent contributions are presented here together with specific case studies in order to highlight the usefulness of TEM to the advancement of materials science.

It remains a challenge to identify the active sites of bismuth catalysts in the electrochemical CO 2 reduction reaction. Here we show through in situ characterization that the activation of bismuth oxyhalide electrocatalysts to metallic bismuth is guided by the halides. In situ X-ray diffraction results show that bromide promotes the selective exposure of planar bismuth surfaces, whereas chloride and iodide result in more disordered active sites. Furthermore, we find that bromide-activated bismuth catalysts outperform the chloride and iodide counterparts, achieving high current density (>100 mA cm –2 ) and formic acid selectivity (>90%), suggesting that planar bismuth surfaces are more active for the electrochemical CO 2 reduction reaction. In addition, in situ X-ray absorption spectroscopy measurements reveal that the reconstruction proceeds rapidly in chloride-activated bismuth and gradually when bromide is present, facilitating the formation of ordered planar surfaces. These findings show the pivotal role of halogens on selective facet exposure in activated bismuth-based electrocatalysts during the electrochemical CO 2 reduction reaction. Bismuth is a promising catalyst for formic acid production from CO 2 electroreduction, but its active site and phase under operation remain elusive. Now, a series of bismuth oxyhalide nanoplatelets has been evaluated using in situ techniques during the electrochemical CO 2 reduction reaction, revealing insights about the active bismuth phase.

A high dispersion of the active metal phase of transition metals on oxide supports is important when designing efficient heterogeneous catalysts. Besides nanoparticles, clusters and even single metal atoms can be attractive for a wide range of reactions. However, many industrially relevant catalytic transformations suffer from structure sensitivity, where reducing the size of the metal particles below a certain size substantially lowers catalytic performance. A case in point is the low activity of small cobalt nanoparticles in the hydrogenation of CO and CO 2 . Here we show how engineering of catalytic sites at the metal–oxide interface in cerium oxide–zirconium dioxide (ceria–zirconia)-supported cobalt can overcome this structure sensitivity. Few-atom cobalt clusters dispersed on 3 nm cobalt(II)-oxide particles stabilized by ceria–zirconia yielded a highly active CO 2 methanation catalyst with a specific activity higher than that of larger particles under the same conditions. Metal utilization is important for the overall efficiency of heterogeneous catalysts, but reducing the amount of precious active phases is challenging due to intrinsic properties such as structure sensitivity. Now Hensen and colleagues engineer the interfaces of supported cobalt catalysts to overcome such structure sensitivity limitations in CO 2 hydrogenation.