The structural diversity of zeolites depends strongly on the use of organic structure-directing agents (OSDAs) that guide their formation. Low-dimensional zeolitic materials, such as layered or chain-like phases, can serve as key intermediates in topotactic condensation pathways, yet the mechanisms governing their formation and transformation remain poorly understood. Here, we report three low-dimensional zeolitic materials, EMM-75P, EM-L01, and EM-L02, synthesized using benzimidazolium cations as OSDAs. Their structures were determined by three-dimensional electron diffraction (3D ED), including the atomic structure of the OSDAs, revealing their confinement within the framework to shed light on their structure-directing role. The bulky benzimidazolium OSDAs prevent the formation of materials with three-dimensional framework structures and instead direct the formation of low-dimensional zeotypes. Upon calcination, the two-dimensional layered aluminosilicate zeotype EMM-75P undergoes topotactic condensation to form a three-dimensional zeolite, EMM-75, with a previously unreported zeolite framework topology. Aluminosilicate EM-L01 is a 2D analogue of STF/SFF zeolite frameworks and partially condensed to an STF-topology upon calcination, whereas EM-L02, a 1D silicate composed of double 6-ring chains, packed analogous to the CHA zeolite framework, collapses during the thermal treatment. The detailed structural characterization of these three materials provides insights into the mechanism of topotactic condensation and demonstrates how such pathways can lead to new zeolite materials.

Organic semiconductors continue to make substantial performance gains from photovoltaics to electronics. However, understanding how differences in solid-state structure give rise to large differences in energy transport properties remains unresolved. We report that microcrystals of two perylene diimide (PDI) derivatives differing only in their terminal groups [cyclohexyl (CH) and 4-heptyl (ST)] have exciton diffusion coefficients differing by more than two orders of magnitude. Applying state-of-the-art techniques for microcrystal structure determination, we report the crystal structures of CH-PDI and two polymorphs of ST-PDI. Scanning electron diffraction reveals a range of crystallographic defects in ST-PDI microcrystals, attributed to polymorph intergrowths, while electron energy loss spectroscopy links these defects to nanoscale electronic structure changes. Computational modeling demonstrates that rotational disorder explains the difference in exciton diffusion coefficients. Our observations establish the importance of defect-induced orientational disorder as a source of extrinsic energetic disorder, highlighting the need for defect management in organic semiconductor technologies.

Carmine is a red pigment made from dried cochineal, a scale insect that has been a source of brilliant scarlet reds in clothing and art for more than two millennia, with records dating back to 700 BC. Since the 16th century, it has been intensely traded all over the world and was one of the most important trade goods for the Spanish empire at its economic peak. Despite still being used on an industrial scale, with hundreds of metric tonnes produced annually, the exact molecular and crystal structures of the dyestuff remains undetermined. Notably, both modern-day commercial carmine and pigments prepared following historical recipes show strikingly similar diffraction patterns, indicating a common crystalline structure. Here we show that the crystal structure of carmine can, at last, be determined using three-dimensional electron diffraction measurements, revealing a tetranuclear complex that assembles into a nanoporous supramolecular structure with pore diameters of approximately 1.8 nm, held together by intermolecular hydrogen bonding. Our results establish a definite structure of carmine, unveiling a surprisingly complicated arrangement in a long-used commodity with economic and cultural impact, while also highlighting the serendipitous creation of a man-made supramolecular material that dates back hundreds if not thousands of years.

The hydrothermal synthesis of the new aluminum metal-organic framework (Al-MOF) CAU-63 [Al₇(OH)₁₂O₃(2,4-HPydc)₃] and two new Al coordination polymers (CPs) Al-Pydc-CP1 [Al₂(OH)₅(2,4-HPydc)] and Al-Pydc-CP2 [Al(OH)(H₂O)(2,4-Pydc)] linked by anions of lutidinic acid (pyridine-2,4-dicarboxylic acid, 2,4-H₂Pydc) is reported. High-throughput investigations of the Al³⁺/2,4-H₂Pydc/NaOH/H₂O system were carried out to determine the fields of formation. An increase of the molar ratio of metal to linker was found to be the key parameter for the formation of higher condensed inorganic building units (IBU), changing from dimeric to one- and two-dimensional structures. The crystal structures were determined by 3D electron diffraction with subsequent Rietveld refinement against powder X-ray diffraction data. The pyridine nitrogen atoms of the linker molecules coordinate to aluminum ions in all three compounds, resulting in crystal structures deviating from the typically observed MIL-53 and CAU-10 type frameworks. The coordination polymers Al-Pydc-CP1 and Al-Pydc-CP2 contain edge-sharing Al–O/N polyhedra leading to dimeric and helical IBUs, while in CAU-63, tetrameric [Al₄O₁₄N₂] units are bridged by Al³⁺ ions, leading to a honeycomb Al–O–N network with organic moieties interconnecting the layers. This linkage results in channel-like ultramicropores, which are accessible to H₂O and NH₃ molecules but too small to adsorb N₂ and even CO₂.

Natural biocomposites such as wood and plant cell walls exhibit prominent mechanical properties largely attributed to the nanoscale organization of fibrous components, such as cellulose, which often adopt chiral arrangements. However, resolving the three-dimensional (3D) arrangement of these structures at the nanoscale remains a significant challenge, particularly in beam-sensitive materials. This study introduces a method for 3D reconstruction of orientation based on scanning electron diffraction (SED), enabling the quantitative mapping of chiral supramolecular organization with sub-100 nm spatial resolution. By acquiring low-dose SED data at multiple tilt angles and applying a symmetry-based reconstruction algorithm, we resolved the 3D orientation of cellulose fibrils in native oat husk and birch wood. Our results reveal a multilayered cell wall architecture with alternating helical handedness, providing precise measurements of 3D fibril orientation. This method reveals complex hierarchical structures at the nanoscale, enabling rapid data acquisition and analysis using widely available instrumentation. The ability to resolve such chiral organization provides insights into material properties as well as opportunities for designing bioinspired materials with tunable mechanical and functional properties that extend far beyond natural biocomposite materials.

Pesticides have become a common environmental pollutant in bodies of water in recent decades, negatively affecting the aquatic ecosystems along with their living organisms. In this regard, thiabendazole (TBZ) has emerged as one of the most detected pesticides in wastewater due to its widespread application in agriculture. Despite its toxicological effects and persistence, no technology is currently available for its efficient removal. Recent adsorption strategies using eco-friendly porous materials have emerged as an effective, low-cost, and easy-to-operate alternative for water pollutant removal. Among them, metal–organic frameworks (MOFs) were selected here as attractive adsorbents due to their outstanding water stability and a priori, compatible pore sizes with the TBZ molecule. Upon screening of 8 MOFs with different natures and structures, the most promising material was the microporous bismuth(III)-ellagate SU-101, with remarkable removal efficiencies (89% in just 5 min). The material was successfully shaped into micrometric pellets and packed into a column for its suitable implementation in a continuous flow device, simulating a real decontamination environment by using pollutant-doped tap water. This SU-101 column was able to efficiently eliminate TBZ during 4.6 consecutive days, with the absence of significant MOF degradation (< 1.5%), and was successfully regenerated (88%) preserving functionality over 2 cycles. These resulting outcomes pave the way for further SU-101 implementation in real decontamination processes.

Transparent wood composites provide new functionalities through active additives distributed at the nanoscale. Scalable nanotechnology includes processing where nanoparticles and molecules are brought into the dense wood cell wall. A novel cell wall swelling step through green chemistry is therefore investigated. Sub-zero centigrade NaOH treatment provides extensive cell wall swelling. Cell wall accessibility is vastly increased so that chemicals can readily impregnate the nanostructured cell wall. Transparent wood with a thickness of up to 15 mm can therefore be fabricated. The optical transmittance and the attenuation coefficient are improved since the polymer is distributed inside the cell wall as a matrix for the nanoscale cellulose fibrils. The proposed technology paves the way for scalable wood nanoengineering.

Cu-exchanged chabazite zeolites are used industrially as catalysts for abatement of NO_x pollution from diesel engines; however, catalyst activity is adversely impacted by exposure to high temperature steam. This occurs due to both dealumination of the zeolite framework and aggregation of Cu²⁺ cations into larger oxide agglomerates that are less active. Under oxidation-limited conditions in the presence of coadsorbed NH₃, hydrothermal aging of Cu-chabazite leads to a surprising increase in the rate of NO_x reduction per redox-active Cu cation at low temperatures (200 °C). A combination of electron microscopy, electron diffraction, NMR spectroscopy, and reaction kinetics analyses reveals that, although a portion of Cu species sinter into large agglomerates during aging, activity is maintained by the remaining Cu²⁺ cations that are stabilized by pairs of framework aluminum sites. These sites exhibit lower activation enthalpies for ammonia exchange dynamics, manifesting enhanced mobility of Cu²⁺ ions that persist as the extent of aging increases. The results yield insights into the complicated physicochemical processes and ramifications associated with deactivation of technologically important Cu-CHA zeolite catalysts, including the dynamics of adsorbed intermediates and the macroscopic reaction properties of the selective catalytic reduction of NO_x over active Cu species.

The use of redox active metal oxides to support noble metals is critical in the design of highly-active CO oxidation catalysts for gas emissions control. Unfortunately, supports promoting the activity, such as CeO₂, tend also to promote acute catalyst deactivation by turning highly-active metallic Pt clusters into less-active PtO_x species, under practical reaction conditions (high-temperature and/or the excess of O₂). This leads to a problematic activity/stability tradeoff where Pt/CeO₂ catalysts, highly-active, and Pt on non-reducible supports, highly stable, are bookends. Herein, we report a method to trap Pt at V-shaped pockets/stepped sites of CeO₂ that break this undesired correlation by showing both high activity and stability in the CO oxidation reaction. XAS, CO-DRIFT, XPS, HAADF-STEM, and DFT are used to infer that the generation of low order metallic Pt clusters connected to two crystallographic planes of the support is key to inhibit (deactivating) re-oxidation paths of the metal, as a result of the high-energy required to form disordered/distorted PtO_x ensembles at these positions. This new material allows, thus, to operate outside the commonly observed, limiting, activity/stability tradeoff.

Zeolites are crystalline microporous materials constructed by corner-sharing tetrahedra (SiO₄ and AlO₄), with many industrial applications as ion exchangers, adsorbents and heterogeneous catalysts. However, the presence of micropores impedes the use of zeolites in areas dealing with bulky substrates. Introducing extrinsic mesopores, that is, intercrystal/intracrystal mesopores, in zeolites is a solution to overcome the diffusion barrier. Still, those extrinsic mesopores are generally disordered and non-uniform; moreover, acidity and crystallinity are always, to some extent, impaired. Thus, synthesizing thermally stable zeolites with intrinsic mesopores that are of uniform size and crystallographically connected with micropores, denoted here as intrinsic mesoporous zeolite, is highly desired but still not achieved. Here we report ZMQ-1 (Zeolitic Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, no. 1), an aluminosilicate zeolite with an intersecting intrinsic meso-microporous channel system delimited by 28 × 10 × 10-rings, in which the 28-ring has a free diameter of 22.76 Å × 11.83 Å, which reaches the mesopore domain. ZMQ-1 has high thermal and hydrothermal stability with tunable framework Si/Al molar ratios. ZMQ-1 is the first aluminosilicate zeolite with an intrinsic meso-microporous channel system. The Brønsted acidity of ZMQ-1 imparts high activity and unique selectivity in the catalytic cracking of heavy oil. The position of the organic structure-directing agent (OSDA) used for ZMQ-1 synthesis was determined from three-dimensional electron diffraction (3D ED) data, which shows the unique structure-directing role of the OSDA in the formation of the intrinsic meso-microporous zeolite. This provides an incentive for preparing other stable mesopore-containing zeolites.