Tunable CHA/AEI Zeolite Intergrowths with A Priori Biselective Organic Structure-Directing Agents: Controlling Enrichment and Implications for Selective Catalytic Reduction of NOx.

A novel ab initio methodology based on high-throughput simulations has permitted designing unique biselective organic structure-directing agents (OSDAs) that allow the efficient synthesis of CHA/AEI zeolite intergrowth materials with controlled phase compositions. Distinctive local crystallographic ordering of the CHA/AEI intergrowths was revealed at the nanoscale level using integrated differential phase contrast scanning transmission electron microscopy (iDPC STEM). These novel CHA/AEI materials have been tested for the selective catalytic reduction (SCR) of NOx, presenting an outstanding catalytic performance and hydrothermal stability, even surpassing the performance of the well-established commercial CHA-type catalyst. This methodology opens the possibility for synthetizing new zeolite intergrowths with more complex structures and unique catalytic properties.

The Nanoscale Ordering of Cellulose in a Hierarchically Structured Hybrid Material Revealed Using Scanning Electron Diffraction.

Cellulose, being a renewable and abundant biopolymer, has garnered significant attention for its unique properties and potential applications in hybrid materials. Understanding the hierarchical arrangement of cellulose nanofibers is crucial for developing cellulose-based materials with enhanced mechanical properties. In this study, the use of Scanning Electron Diffraction (SED) is presented to map the nanoscale orientation of cellulose fibers in a bio-composite material with a preserved wood cell structure. The SED data provides detailed insights into the ordering of cellulose with an extraordinary resolution of ≈15 nm. It enables a quantitative analysis of the fiber orientation over regions as large as entire cells. A highly organized arrangement of cellulose fibers within the secondary cell wall is observed, with a gradient of orientations toward the outer part of the wall. The in-plane fiber rotation is quantified, revealing a uniform orientation close to the middle lamella. Transversely sectioned material exhibits similar trends, suggesting a layered cell wall structure. Based on the SED data, a 3D model depicting the complex helical alignment of fibers throughout the cell wall is constructed. This study demonstrates the unique opportunities SED provides for characterizing the nanoscale hierarchical arrangement of cellulose nanofibers, empowering further research on a range of hybrid materials.

Photonic crystals with rainbow colors by centrifugation-assisted assembly of colloidal lignin nanoparticles.

Photonic crystals are optical materials that are often fabricated by assembly of particles into periodically arranged structures. However, assembly of lignin nanoparticles has been limited due to lacking methods and incomplete understanding of the interparticle forces and packing mechanisms. Here we show a centrifugation-assisted fabrication of photonic crystals with rainbow structural colors emitted from the structure covering the entire visible spectrum. Our results show that centrifugation is crucial for the formation of lignin photonic crystals, because assembly of lignin nanoparticles without centrifugation assistance leads to the formation of stripe patterns rather than photonic crystals. We further prove that the functions of centrifugation are to classify lignin nanoparticles according to their particle size and produce monodispersed particle layers that display gradient colors from red to violet. The different layers of lignin nanoparticles were assembled in a way that created semi-closed packing structures, which gave rise to coherent scattering. The diameter of the lignin nanoparticles in each color layer is smaller than that predicted by a modified Bragg's equation. In situ optical microscope images provided additional evidence on the importance of dynamic rearrangement of lignin nanoparticles during their assembly into semi-closed packing structures. The preparation of lignin nanoparticles combined with the methodology for their classification and assembly pave the way for sustainable photonic crystals.

Coloration and Fire Retardancy of Transparent Wood Composites by Metal Ions.

Transparent wood composites (TWs) offer the possibility of unique coloration effects. A colored transparent wood composite (C-TW) with enhanced fire retardancy was impregnated by metal ion solutions, followed by methyl methacrylate (MMA) impregnation and polymerization. Bleached birch wood with a preserved hierarchical structure acted as a host for metal ions. Cobalt, nickel, copper, and iron metal salts were used. The location and distribution of metal ions in C-TW as well as the mechanical performance, optical properties, and fire retardancy were investigated. The C-TW coloration is tunable by controlling the metal ion species and concentration. The metal ions reduced heat release rates and limited the production of smoke during forced combustion tests. The potential for scaled-up production was verified by fabricating samples with a dimension of 180 × 100 × 1 (l × b × h) mm3.

Structure of the active pharmaceutical ingredient bismuth subsalicylate.

Structure determination of pharmaceutical compounds is invaluable for drug development but remains challenging for those that form as small crystals with defects. Bismuth subsalicylate, among the most commercially significant bismuth compounds, is an active ingredient in over-the-counter medications such as Pepto-Bismol, used to treat dyspepsia and H. pylori infections. Despite its century-long history, the structure of bismuth subsalicylate is still under debate. Here we show that advanced electron microscopy techniques, namely three-dimensional electron diffraction and scanning transmission electron microscopy, can give insight into the structure of active pharmaceutical ingredients that are difficult to characterize using conventional methods due to their small size or intricate structural features. Hierarchical clustering analysis of three-dimensional electron diffraction data from ordered crystals of bismuth subsalicylate revealed a layered structure. A detailed investigation using high-resolution scanning transmission electron microscopy showed variations in the stacking of layers, the presence of which has likely hindered structure solution by other means. Together, these modern electron crystallography techniques provide a toolbox for structure determination of active pharmaceutical ingredients and drug discovery, demonstrated by this study of bismuth subsalicylate.

Facile Processing of Transparent Wood Nanocomposites with Structural Color from Plasmonic Nanoparticles.

Wood is an eco-friendly and abundant substrate and a candidate for functionalization by large-scale nanotechnologies. Infiltration of nanoparticles into wood, however, is hampered by the hierarchically structured and interconnected fibers in wood. In this work, delignified wood is impregnated with gold and silver salts, which are reduced in situ to plasmonic nanoparticles via microwave-assisted synthesis. Transparent biocomposites are produced from nanoparticle-containing wood in the form of load-bearing materials with structural color. The coloration stems from nanoparticle surface plasmons, which require low size dispersity and particle separation. Delignified wood functions as a green reducing agent and a reinforcing scaffold to which the nanoparticles attach, predesigning their distribution on the surface of fibrous "tubes". The nanoscale structure is investigated using scanning transmission electron microscopy (STEM), energy-dispersive spectroscopy (EDS), and Raman microscopy to determine particle size, particle distribution, and structure-property relationships. Optical properties, including response to polarized light, are of particular interest.