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While the role of crystal facets is well known in traditional heterogeneous catalysis, this effect has not yet been thoroughly studied in plasmon-assisted catalysis, where attention has primarily focused on plasmon-derived mechanisms. Here, we investigate plasmon-assisted electrocatalytic CO2 reduction using different shapes of plasmonic Au nanoparticles - nanocube (NC), rhombic dodecahedron (RD), and octahedron (OC) - exposing {100}, {110}, and {111} facets, respectively. Upon plasmon excitation, Au OCs doubled CO Faradaic efficiency (FECO) and tripled CO partial current density (jCO) compared to a dark condition, with NCs also improving under illumination. In contrast, Au RDs maintained consistent performance irrespective of light exposure, suggesting minimal influence of light on the reaction. Temperature experiments ruled out heat as the main factor to explain such differences. Atomistic simulations and electromagnetic modeling revealed higher hot carrier abundance and electric field enhancement on Au OCs and NCs than RDs. These effects now dominate the reaction landscape over the crystal facets, thus shifting the reaction sites when comparing dark and plasmon-activated processes. Plasmon-assisted H2 evolution reaction experiments also support these findings. The dominance of low-coordinated sites over facets in plasmonic catalysis suggests key insights for designing efficient photocatalysts for energy conversion and carbon neutralization. Crystal facets are known to be important in traditional heterogeneous catalysis, yet this effect has not been studied in plasmon-assisted catalysis. Here, the authors investigate the impact facets have on CO2 reduction using plasmonic Au NPs. [ABSTRACT FROM AUTHOR]

Colloidal lead halide perovskite nanocrystals have potential for lighting applications due to their optical properties. Precise control of the nanocrystal dimensions and composition is a prerequisite for establishing practical applications. However, the rapid nature of their synthesis precludes a detailed understanding of the synthetic pathways, thereby limiting the optimisation. Here, we deduce the formation mechanisms of anisotropic lead halide perovskite nanocrystals, 1D nanorods and 2D nanoplatelets, by combining in situ X-ray scattering and photoluminescence spectroscopy. In both cases, emissive prolate nanoclusters form when the two precursor solutions are mixed. The ensuing antisolvent addition induces the divergent anisotropy: The intermediate nanoclusters are driven into a dense hexagonal mesophase, fusing to form nanorods. Contrastingly, nanoplatelets grow freely dispersed from dissolving nanoclusters, stacking subsequently in lamellar superstructures. Shape and size control of the nanocrystals are determined primarily by the antisolvent's dipole moment and Hansen hydrogen bonding parameter. Exploiting the interplay of antisolvent and organic ligands could enable more complex nanocrystal geometries in the future. Lead halide perovskite nanocrystals show bright and colour-pure emission in the visible range, which can be tuned by nanocrystal size and composition. Here authors present the formation mechanisms of anisotropic lead halide perovskite nanocrystals, 1D nanorods and 2D nanoplatelets, by combining in situ X-ray scattering and photoluminescence spectroscopy. [ABSTRACT FROM AUTHOR]

Silicification of DNA origami structures increases their stability and provides chemical protection. Yet, it is unclear whether the whole DNA framework is embedded or if silica just forms an outer shell and how silicification affects the origami's internal structure. Employing in situ small-angle X-ray scattering (SAXS), we show that addition of silica precursors induces substantial condensation of the DNA origami at early reaction times by almost 10 %. Subsequently, the overall size of the silicified DNA origami increases again due to increasing silica deposition. We further identify the SAXS Porod invariant as a reliable, model-free parameter for the evaluation of the amount of silica formation at a given time. Contrast matching of the DNA double helix Lorentzian peak reveals silica growth also inside the origami. The less polar silica forming within the origami structure, replacing more than 40 % of the internal hydration water, causes a hydrophobic effect: condensation. DNA origami objects with flat surfaces show a strong tendency towards aggregation during silicification, presumably driven by the same entropic forces causing condensation. Maximally condensed origami displayed thermal stability up to 60 °C. Our studies provide insights into the silicification reaction allowing for the formulation of optimized reaction protocols. DNA origami can be coated in a layer of silica to improve chemical and thermal stability however; it is unclear if this is a surface or interpenetrating layer. Here, the authors use in situ small-angle X-ray scattering to study silica deposition and observe internal silica formation resulting in DNA origami condensation and structure shrinkage. [ABSTRACT FROM AUTHOR]

Organic semiconductors (OSC) are widely used for consumer electronic products owing to their attractive properties such as flexibility and low production cost. Atomically thin transition metal dichalcogenides (TMDs) are another class of emerging materials with superior electronic and optical properties. Integrating them into van der Waals (vdW) heterostructures provides an opportunity to harness the advantages of both material systems. However, building such heterojunctions by conventional physical vapor deposition (PVD) of OSCs is challenging, since the growth is disrupted due to limited diffusion of the molecules on the TMD surface. Here we report wafer-scale (3-inch) fabrication of transferable OSC nanosheets with thickness down to 15 nm, which enable the realization of heterojunction devices. By controlled dissolution of a poly(acrylic acid) film, on which the OSC films were grown by PVD, they can be released and transferred onto arbitrary substrates. OSC crystal quality and optical anisotropy are preserved during the transfer process. By transferring OSC nanosheets (p-type) onto prefabricated electrodes and TMD monolayers (n-type), we fabricate and characterize various electronic devices including unipolar, ambipolar and antiambipolar field-effect transistors. Such vdW p-n heterojunction devices open up a wide range of possible applications ranging from ultrafast photodetectors to conformal electronics. [ABSTRACT FROM AUTHOR]

The key to fabricating complex, hierarchical materials is the control of chemical reactions at various length scales. To this end, the classical model of nucleation and growth fails to provide sufficient information. Here, we illustrate how modern X-ray spectroscopic and scattering in situ studies bridge the molecular- and macro- length scales for assemblies of polyhedrally shaped CoO nanocrystals. Utilizing high energy-resolution fluorescence-detected X-ray absorption spectroscopy, we directly access the molecular level of the nanomaterial synthesis. We reveal that initially Co(acac)3 rapidly reduces to square-planar Co(acac)2 and coordinates to two solvent molecules. Combining atomic pair distribution functions and small-angle X-ray scattering we observe that, unlike a classical nucleation and growth mechanism, nuclei as small as 2 nm assemble into superstructures of 20 nm. The individual nanoparticles and assemblies continue growing at a similar pace. The final spherical assemblies are smaller than 100 nm, while the nanoparticles reach a size of 6 nm and adopt various polyhedral, edgy shapes. Our work thus provides a comprehensive perspective on the emergence of nano-assemblies in solution. The understanding of nucleation and growth of nanostructures plays a key role in complex materials design. Here, the authors illustrate how X-ray in situ studies link transformation at the molecular- and macro- length scales during the emergence of cobalt oxide assemblies. [ABSTRACT FROM AUTHOR]

The article discusses how advances in the control of the shape, bonding direction and valency of DNA-coated nanoparticles allow the synthesis of nanoparticle crystallites of increasing complexity. Topics include DNA-assisted crystallization of nanoparticle superlattices, lattices synthetized from DNA-linked nanoparticles resembling close-packed structure, use of X-ray diffraction in analyzing crystal growth, and formation of uniform single crystals from nanoparticles.