Rotation Electron Diffraction Research Articles

STEM SerialED: achieving high-resolution data for ab initio structure determination of beam-sensitive nanocrystalline materials.

Serial electron diffraction (SerialED), which applies a snapshot data acquisition strategy for each crystal, was introduced to tackle the problem of radiation damage in the structure determination of beam-sensitive materials by three-dimensional electron diffraction (3DED). The snapshot data acquisition in SerialED can be realized using both transmission and scanning transmission electron microscopes (TEM/STEM). However, the current SerialED workflow based on STEM setups requires special external devices and software, which limits broader adoption. Here, we present a simplified experimental implementation of STEM-based SerialED on Thermo Fisher Scientific STEMs using common proprietary software interfaced through Python scripts to automate data collection. Specifically, we utilize TEM Imaging and Analysis (TIA) scripting and TEM scripting to access the STEM functionalities of the microscope, and DigitalMicrograph scripting to control the camera for snapshot data acquisition. Data analysis adapts the existing workflow using the software CrystFEL, which was developed for serial X-ray crystallography. Our workflow for STEM SerialED can be used on any Gatan or Thermo Fisher Scientific camera. We apply this workflow to collect high-resolution STEM SerialED data from two aluminosilicate zeolites, zeolite Y and ZSM-25. We demonstrate, for the first time, ab initio structure determination through direct methods using STEM SerialED data. Zeolite Y is relatively stable under the electron beam, and STEM SerialED data extend to 0.60 Å. We show that the structural model obtained using STEM SerialED data merged from 358 crystals is nearly identical to that using continuous rotation electron diffraction data from one crystal. This demonstrates that accurate structures can be obtained from STEM SerialED. Zeolite ZSM-25 is very beam-sensitive and has a complex structure. We show that STEM SerialED greatly improves the data resolution of ZSM-25, compared with serial rotation electron diffraction (SerialRED), from 1.50 to 0.90 Å. This allows, for the first time, the use of standard phasing methods, such as direct methods, for the ab initio structure determination of ZSM-25.

Radiation-Induced De Novo Defects in Metal-Organic Frameworks Boost CO2 Sorption.

Defects in metal-organic frameworks (MOFs) can significantly change their local microstructures, thus notably leading to an alteration-induced performance in sorption or catalysis. However, achieving de novo defect engineering in MOFs under ambient conditions without the scarification of their crystallinity remains a challenge. Herein, we successfully synthesize defective ZIF-7 through 60Co gamma ray radiation under ambient conditions. The obtained ZIF-7 is defect-rich but also has excellent crystallinity, enhanced BET surface area, and hierarchical pore structure. Moreover, the amount and structure of these defects within ZIF-7 were determined from the two-dimensional (2D) 13C-1H frequency-switched Lee-Goldburg heteronuclear correlation (FSLG-HETCOR) spectra, continuous rotation electron diffraction (cRED), and high-resolution transmission electron microscopy (HRTEM). Interestingly, the defects in ZIF-7 all strongly bind to CO2, leading to a remarkable enhancement of the CO2 sorption capability compared with that synthesized by the solvothermal method.

Wavy Two-Dimensional Conjugated Metal-Organic Framework with Metallic Charge Transport.

Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) have emerged as a new class of crystalline layered conducting materials that hold significant promise for applications in electronics and spintronics. However, current 2D c-MOFs are mainly made from organic planar ligands, whereas layered 2D c-MOFs constructed by curved or twisted ligands featuring novel orbital structures and electronic states remain less developed. Herein, we report a Cu-catecholate wavy 2D c-MOF (Cu3(HFcHBC)2) based on a fluorinated core-twisted contorted hexahydroxy-hexa-cata-hexabenzocoronene (HFcHBC) ligand. We show that the resulting film is composed of rod-like single crystals with lengths up to ∼4 μm. The crystal structure is resolved by high-resolution transmission electron microscopy (HRTEM) and continuous rotation electron diffraction (cRED), indicating a wavy honeycomb lattice with AA-eclipsed stacking. Cu3(HFcHBC)2 is predicted to be metallic based on theoretical calculation, while the crystalline film sample with numerous grain boundaries apparently exhibits semiconducting behavior at the macroscopic scale, characterized by obvious thermally activated conductivity. Temperature-dependent electrical conductivity measurements on the isolated single-crystal devices indeed demonstrate the metallic nature of Cu3(HFcHBC)2, with a very weak thermally activated transport behavior and a room-temperature conductivity of 5.2 S cm-1. Furthermore, the 2D c-MOFs can be utilized as potential electrode materials for energy storage, which display decent capacity (163.3 F g-1) and excellent cyclability in an aqueous 5 M LiCl electrolyte. Our work demonstrates that wavy 2D c-MOF using contorted ligands are capable of intrinsic metallic transport, marking the emergence of new conductive MOFs for electronic and energy applications.

A Fluorescent Three-Dimensional Covalent Organic Framework Formed by the Entanglement of Two-Dimensional Sheets.

Herein, we report the introduction of steric hindrance in molecular building blocks to prevent π···π stacking, thus allowing two-dimensional (2D) covalent organic sheets to form three-dimensional (3D) covalent organic frameworks (COFs) through entanglement. Starting from the rationally designed precursors containing a bulky anthracene unit in the vertical direction, a highly crystalline COF (3D-An-COF) was successfully synthesized. Very interestingly, 3D-An-COF was determined as an entangled 2D square net (sql) structure, and the high-resolution data (1.1 Å) obtained by the continuous rotation electron diffraction technique allowed us to directly locate all non-hydrogen atoms. Structurally, the presence of an anthracene group outside the C2h symmetry plane strongly reduces the π···π interactions and promotes the formation of square entanglements. In addition, 3D-An-COF is fluorescent and can be used as a sensor to detect the trace amount of antibiotics in water. This study provides a new strategy for the structural diversification of 3D COFs and will certainly motivate us to construct more entangled COFs for interesting applications in the future.

Study on the formation mechanism of δ-titanium hydride by rotation electron diffraction

Rotation electron diffraction method was used to study the structures and crystallographic orientations of the face centered tetragonal structured γ-titanium hydride and the face centered cubic structured δ-titanium hydride by collecting the diffraction information of the hydrides and the matrix at the same time. It was found that the FCC001 δ-hydride is the result of phase transformation caused by continuing to charge hydrogen into γ-hydride. Therefore, we got the complete map of the paths in which hexagonal close-packed titanium transforms to stable δ-titanium hydrides with the increase of hydrogen atoms.

Near IR Bandgap Semiconducting 2D Conjugated Metal-Organic Framework with Rhombic Lattice and High Mobility.

Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) are emerging as a unique class of electronic materials. However, 2D c-MOFs with band gaps in the Vis-NIR and high charge carrier mobility are rare. Most of the reported conducting 2D c-MOFs are metallic (i.e. gapless), which largely limits their use in logic devices. Herein, we design a phenanthrotriphenylene-based, D2h -symmetric π-extended ligand (OHPTP), and synthesize the first rhombic 2D c-MOF single crystals (Cu2 (OHPTP)). The continuous rotation electron diffraction (cRED) analysis unveils the orthorhombic crystal structure at the atomic level with a unique slipped AA stacking. The Cu2 (OHPTP) is a p-type semiconductor with an indirect band gap of ≈0.50 eV and exhibits high electrical conductivity of 0.10 S cm-1 and high charge carrier mobility of ≈10.0 cm2 V-1 s-1 . Theoretical calculations underline the predominant role of the out-of-plane charge transport in this semiquinone-based 2D c-MOF.

Eine halbleitende 2D metallorganische Gerüstverbindung mit einer Bandlücke im nahen IR, rhombischem Gitter und hoher Ladungsträgermobilität

AbstractZweidimensionale konjugierte metallorganische Gerüstverbindungen (2D c‐MOFs) gehören zu einer einzigartigen Gruppe elektronischer Materialien. 2D c‐MOFs mit Bandlücken im sichtbaren oder nahen IR‐Bereich und hohen Ladungsträger‐mobilitäten sind jedoch rar. Die meisten literaturbekannten halbleitenden 2D c‐MOFs sind metallisch, was ihre Verwendung in logischen Bauelementen stark einschränkt. Im Folgenden konzipieren wir einen Phenanthrotriphenylen basierten, D2h‐symmetrischen, π‐konjugierten Liganden (OHPTP) und synthetisieren die ersten rhombischen 2D c‐MOF Einkristalle (Cu2(OHPTP)). Kontinuierliche Rotations‐Elektronendiffraktometrie (cRED) belegt die orthorhombische Kristallstruktur mit versschobene AA‐Schichtung auf atomarer Ebene. Cu2(OHPTP) ist ein p‐Typ Halbleiter mit einer indirekten Bandlücke von ≈0.50 eV, einer hohen elektrischen Leitfähigkeit von 0.10 S cm−1 und einer hohen Ladungsträgermobilität von ≈10.0 cm2 V−1 s−1. Theoretische Berechnungen unterstreichen die dominierende Rolle des Ladungstransports zwischen den Schichten in diesem Semichinon verknüpften 2D c‐MOF.

Linker Vacancy Engineering of a Robust ftw-type Zr-MOF for Hexane Isomers Separation.

Discrimination of physically similar molecules by porous solids represents an important yet challenging task in industrially relevant chemical separations. Precisely controlled pore dimension and/or tailored pore surface functionality are crucial to achieve high-efficiency separation. Metal-organic frameworks (MOFs) are promising candidates for these challenging separations in light of their structural diversity as well as highly adjustable pore dimension/functionality. We report here a microporous, ftw-type Zr-based MOF structure, HIAM-410 (HIAM=Hoffmann Institute of Advanced Materials), built on hexanuclear Zr6 cluster and pyrene-1,3,6,8-tetracarboxylate (ptc4- ). Its crystallographic structure has been determined using continuous rotation electron diffraction (cRED) technique combined with Rietveld refinement against powder X-ray diffraction data, aided by low-dose high-resolution transmission electron microscopy (HRTEM) imaging. The compound features exceptional framework stability that is comparable to the prototype MOF UiO-66. Interestingly, the linker vacancies in the pristine MOF structure could be partially restored by post-synthetic linker insertion. Its separation capability of hexane isomers is enhanced substantially upon the linker vacancy engineering. The restored structure exhibits efficient splitting of monobranched and dibranched hexane isomers at both room temperature and industrially relevant temperature.

Linker Vacancy Engineering of a Robust ftw‐type Zr‐MOF for Hexane Isomers Separation

AbstractDiscrimination of physically similar molecules by porous solids represents an important yet challenging task in industrially relevant chemical separations. Precisely controlled pore dimension and/or tailored pore surface functionality are crucial to achieve high‐efficiency separation. Metal‐organic frameworks (MOFs) are promising candidates for these challenging separations in light of their structural diversity as well as highly adjustable pore dimension/functionality. We report here a microporous, ftw‐type Zr‐based MOF structure, HIAM‐410 (HIAM=Hoffmann Institute of Advanced Materials), built on hexanuclear Zr6 cluster and pyrene‐1,3,6,8‐tetracarboxylate (ptc4−). Its crystallographic structure has been determined using continuous rotation electron diffraction (cRED) technique combined with Rietveld refinement against powder X‐ray diffraction data, aided by low‐dose high‐resolution transmission electron microscopy (HRTEM) imaging. The compound features exceptional framework stability that is comparable to the prototype MOF UiO‐66. Interestingly, the linker vacancies in the pristine MOF structure could be partially restored by post‐synthetic linker insertion. Its separation capability of hexane isomers is enhanced substantially upon the linker vacancy engineering. The restored structure exhibits efficient splitting of monobranched and dibranched hexane isomers at both room temperature and industrially relevant temperature.

Covalent organic framework atropisomers with multiple gas-triggered structural flexibilities.

Covalent organic frameworks (COFs) are emerging crystalline porous polymers, showing great potential for applications but lacking gas-triggered flexibility. Atropisomerism was experimentally discovered in 1922 but has rarely been found in crystals with infinite framework structures. Here we report atropisomerism in COF single crystals. The obtained COF atropisomers, namely COF-320 and COF-320-A, have identical chemical and interpenetrated structures but differ in the spatial arrangement of repeating units. In contrast to the rigid COF-320 structure, its atropisomer (COF-320-A) exhibits unconventional gas sorption behaviours with one or more sorption steps in isotherms at different temperatures. Single-crystal structures determined from continuous rotation electron diffraction and in situ powder X-ray diffraction demonstrate that these adsorption steps originate from internal pore expansion with or without changing the crystal space group. COF-320-A recognizes different gases by expanding its internal pores continuously (crystal-to-amorphous transition) or discontinuously (crystal-to-crystal transition) or having mixed transition styles, distinguishing COF-320-A from existing soft/flexible porous crystals. These findings extend atropisomerism from molecules to crystals and propel COFs into the covalently linked soft porous crystal regime, further advancing applications of soft porous crystals in gas sorption, separation and storage.

From crystal phase mixture to pure metal-organic frameworks – Tuning pore and structure properties

In this study, a sonochemical route for the preparation of a new Hf-MIL-140A metal–organic framework from a mixture of UiO-66/MIL-140A is presented. The sonochemical synthesis route not only allows the phase-pure MIL-140A structure to be obtained but also induces structural defects in the MIL-140A structure. The synergic effect between the sonochemical irradiation and the presence of a highly acidic environment results in the generation of slit-like defects in the crystal structure, which increases specific surface area and pore volume. The BET-specific surface area in the case of sonochemically derived Zr-MIL-140A reaches 653.3 m2/g, which is 1.5 times higher than that obtained during conventional synthesis. The developed Hf-MIL-140A structure is isostructural to Zr-MIL-140A, which was confirmed by synchrotron X-ray powder diffraction (SR-XRD) and by continuous rotation electron diffraction (cRED) analysis. The obtained MOF materials have high thermal and chemical stability, which makes them promising candidates for applications such as gas adsorption, radioactive waste removal, catalysis, and drug delivery.

Serial rotation electron diffraction for rapid phase analysis to accelerate materials development.

Serial rotation electron diffraction for rapid phase analysis to accelerate materials development.

High-throughput phase elucidation of polycrystalline materials using serial rotation electron diffraction

Rapid phase elucidation of polycrystalline materials is essential for developing new materials of chemical, pharmaceutical and industrial interest. Yet, the size and quantity of many crystalline phases are too small for routine X-ray diffraction analysis. This has become a workflow bottleneck in materials development, especially in high-throughput synthesis screening. Here we demonstrate the application of serial rotation electron diffraction (SerialRED) for high-throughput phase identification of complex polycrystalline zeolite products. The products were prepared from a combination of multiple framework T atoms ([Si,Ge,Al] or [Si,Ge,B]) and a simple organic structure-directing agent. We show that using SerialRED, five zeolite phases can be identified from a highly complex mixture. This includes phases with ultra-low contents undetectable using X-ray diffraction and phases with identical crystal morphology and similar unit cell parameters. By automatically and rapidly examining hundreds of crystals, SerialRED enables high-throughput phase analysis and allows the exploration of complex synthesis systems. It provides new opportunities for rapid development of polycrystalline materials.

Rationally Fabricating Three-Dimensional Covalent Organic Frameworks for Propyne/Propylene Separation

Efficient propyne/propylene separation to obtain polymer-grade propylene is a crucial and challenging process in industrial production, but it has not yet been realized in the covalent organic framework (COF) field. Addressing this challenge, we synthesize two three-dimensional COF adsorbents via a [8 + 4] construction approach based on an octatopic aldehyde monomer. Upon using the continuous rotation electron diffraction technique and structural simulation, both COFs are successfully determined as rare flu topology. Various characterization techniques prove that both COFs exhibit high crystallinity, high porosity, and good stability. Attributed to their interconnected micropores and nonpolar pore environment, these COFs can efficiently remove trace amounts of propyne from the propyne/propylene (1/99, and 0.1/99.9, v/v) mixture to obtain high-purity propylene (>99.99%), validated by dynamic breakthrough experiments. This work paves a new avenue for propyne/propylene separation using COFs as highly efficient adsorbents.

Single-Crystalline Hydrogen-Bonded Crosslinked Organic Frameworks and Their Dynamic Guest Sorption

ConspectusPorous organic framework materials constructed by periodically aligned molecular entities offer chemically tailored microenvironments to absorb molecules and ions for various applications. Fundamentally understanding the microenvironments of these porous organic materials─from pore size, shape, and dynamics to potential substrate binding sites─is critical for the rational design of porous organic materials. The solid-state structures of these porous organic materials, such as covalent organic frameworks (COFs), can provide unambiguous atomic-level structural details. However, it remains challenging to synthesize these materials as single crystals that can be fully characterized by single-crystal X-ray diffraction (SCXRD) or rotational electron diffraction (RED) analysis. In addition, the balance of single crystallinity, permanent porosity, and good chemical stability requires delicate control of the assembly of the molecular building blocks and covalent crosslinking during synthesis. In this Account, we discuss the development of hydrogen-bonded crosslinked organic frameworks (HCOFs) possessing balanced single crystallinity and high chemical stability. HCOFs are obtained through covalently crosslinking molecular crystals that are preorganized via hydrogen bonding. Due to the dual hydrogen-bonded network and covalent crosslinking, HCOFs can deform upon guest adsorption by breaking the hydrogen bonds and subsequently restore their original form through the desorption of guests by re-establishing the hydrogen-bonded networks. Thus, HCOFs can dynamically adjust their pore sizes according to the framework–substrate interactions. In the discussion, we link HCOFs with COFs and single-crystalline 2D polymers by comparing their synthetic approaches to accessing high crystallinity. The method to synthesize HCOFs allows for the employment of various flexible building blocks and linking motifs that are largely avoided in the current design regimes of COFs and 2D polymers. We also draw the connections between HCOFs and hydrogen-bonded organic frameworks (HOFs) by highlighting their shared design principles for constructing hydrogen-bonding networks with large voids. Compared to their hydrogen-bonded precursor crystals, reinforcing the hydrogen-bonded networks with covalent linkages endows HCOFs with enhanced chemical and structural stability. In addition, we emphasize that the structure elucidation of HCOFs often requires combined SCXRD analysis and experimental evidence, with the methods and challenges thoroughly discussed. The details are presented in the following sequence: (1) synthesizing single-crystalline COFs by matching the polycondensation rate to the nucleation rate and their subsequent analyses by SCXRD/RED; (2) obtaining single-crystalline polymers and networks through topochemical reactions; (3) constructing HOFs with designed voids using highly directional hydrogen bonding building blocks; and (4) developing HCOFs via monomer crystal engineering followed by single-crystal to single-crystal (SCSC) synthesis and studying their unique dynamic guest sorption behaviors. We hope this Account will inspire researchers to expand the synthetic methods for advancing HCOFs with detailed solid-state structures, as well as designing porous organic framework materials with dynamic sorption capabilities to enhance their performance for applications in molecular storage, separation, catalysis, etc.

Single-Crystalline Imine-Linked Two-Dimensional Covalent Organic Frameworks Separate Benzene and Cyclohexane Efficiently.

Two-dimensional (2D) covalent organic frameworks (COFs) are composed of structurally precise, permanently porous, layered macromolecular sheets, which are traditionally synthesized as polycrystalline solids with crystalline domain lengths smaller than 100 nm. Here, we polymerize imine-linked 2D COFs as suspensions of faceted single crystals in as little as 5 min at moderate temperature and ambient pressure. Single crystals of two imine-linked 2D COFs were prepared, consisting of a rhombic 2D COF (TAPPy-PDA) and a hexagonal 2D COF (TAPB-DMPDA). The sizes of TAPPy-PDA and TAPB-DMPDA crystals were tuned from 720 nm to 4 μm and 450 nm to 20 μm in width, respectively. High-resolution transmission electron microscopy revealed that the COF crystals consist of layered, 2D polymers comprising single-crystalline domains. Continuous rotation electron diffraction resolved the unit cell and crystal structure of both COFs, which are single-crystalline in the a-b plane but disordered in the stacking c dimension. Single crystals of both COFs were incorporated into gas chromatography separation columns and exhibited unusual selective retention of cyclohexane over benzene, with single-crystalline TAPPy-PDA significantly outperforming single-crystalline TAPB-DMPDA. Polycrystalline TAPPy-PDA exhibited no separation, while polycrystalline TAPB-DMPDA exhibited poor separation and the opposite order of elution, retaining benzene more than cyclohexane, indicating the importance of improved material quality for COFs to exhibit properties that derive from their precise, crystalline structures. This work represents the first example of synthesizing imine-linked 2D COF single crystals at ambient pressure and short reaction times and demonstrates the promise of high-quality COFs for molecular separations.

Benzoquinone-intercalated vanadium oxide in the electrolyte with Al3+ for zinc-ion storage: dual-pillar effect and reversible disorder–order conversion

It was synthesized oxygen-deficient (1, 2, 3-BQ)-VO formulated as (1, 2, 3-BQ)0.25V2O5·0.5H2O (BQ = benzoquinone) via a facile one-step hydrothermal technique. Continuous rotation electron diffraction (cRED), Rietveld refinement and spherical aberration-corrected transmission election microscopy unravel the successful pre-intercalation of the BQ organic species into the layered vanadium oxide, in which two neighboring V-O-V monolayers are observed with the (001) facet as the division plane. (1, 2, 3-BQ)-VO possesses a good electrochemical property in 3 M Zn(CF3SO3)2. And in the electrolyte with Al3+, it shows improved rate capability and remarkably enhanced cycling performance. Its average capacity is up to an unprecedented value of 446/400 mAh/g at 0.2/1 A/g with a capacity retention exceeding 100 % over 550 cycles at 1 A/g (411 mAh/g), which is associated with the dynamic reversible conversion between disorder and order on the (001) facets. The inserted Al3+ into the inner channel of (1, 2, 3-BQ)-VO during the discharge process, not only acts as the interlayer pillar to prevent the collapse of the layered structure, but also can improve the crystallinity of the charged (1, 2, 3-BQ)-VO sample due to the more ordered atomic arrays from the interlayer (00l) facets. And the dual pillars of BQ and Al3+ in the sample can boost the exposure of active sites, thus enhance the storage capacity. In addition, density functional theory (DFT) calculations disclose a small Zn2+ diffusion barrier of 0.85 eV in (1, 2, 3-BQ)-VO. Moreover, it is found that the electrolyte with Al3+ is not only beneficial for the modification of the (1, 2, 3-BQ)-VO cathode, but also can inhibit the Zn dendrite formation at the Zn anode.

Stabilization of Extra-Large-Pore Zeolite by Boron Substitution for the Production of Commercially Applicable Catalysts.

Stable extra-large-pore zeolites are desirable for industrial purposes due to their ability to accommodate bulky reactants and diffusion through channels. Although there are several extra-large pore zeolites reported, stable ones are rare. Thus, their stabilization is a feasible strategy for industrial applications. Here, an extra-large-pore zeolite EWT with boron substitution is presented, and the resulting zeolite B-RZM-3 increased the thermal stability from 600 °C in its silica form to 850 °C. The crystal structure, determined by combining continuous rotation electron diffraction (cRED) and powder X-ray diffraction (PXRD), shows that B atoms preferentially substitute the interrupted (HO)T(OT)3 (Q3 ) sites and are partially converted into 3-coordination to relax framework deformation upon heating. After Al-reinsertion post-treatment, Al-B-RZM-3 shows higher ethylbenzene selectivity and ethylene conversion rate per mol acid site than commercial ZSM-5 and Beta zeolite in benzene alkylation reaction. Synthesizing extra-large-pore zeolite in borosilicate form is a potential approach to stabilize interrupted zeolites for commercial applications.

Rationally fabricating 3D porphyrinic covalent organic frameworks with scu topology as highly efficient photocatalysts

<h2>Summary</h2> The exploration of highly crystalline three-dimensional (3D) covalent organic frameworks (COFs) with new topologies remains challenging. In this work, we rationally designed and synthesized two highly crystalline 3D COFs, constructed by an octatopic linker and porphyrin-based tetratopic linkers through an [8 + 4] approach. The COF structures were successfully determined as non-interpenetrated <b>scu</b> topology using the continuous rotation electron diffraction (cRED) technique and structural simulation. The <b>scu</b> network was further verified by both high-resolution transmission electron microscopy (TEM) and pore size distribution based on N₂ sorption isotherms. Due to the exposed catalytic porphyrin sites, good photoelectric activity, and high structure robustness, these COFs can serve as highly efficient heterogeneous photocatalysts for various reactions, including oxidative amine coupling and cycloaddition reactions between tertiary aniline and maleimide, with a broad substrate scope (22 examples). This work enriches the topological varieties of 3D COFs and provides a class of highly efficient photocatalysts.

Aluminosilicate Zeolite EMM-28 Containing Supercavities Determined by Continuous Rotation Electron Diffraction.

A new aluminosilicate zeolite, denoted EMM-28, has been successfully synthesized on a large scale using 1,1-(3,3-(1,3-phenylene)bis(propane-3,1-diyl))bis(1-methylpyrrolidinium) hydroxide as an organic structure directing agent (OSDA), which was scaled up to an ∼20 g scale with a yield of 77%. It crystallizes as thin plates (40–100 nm in thickness), and the corresponding powder X-ray diffraction (PXRD) pattern shows significant peak broadening which makes it insufficient for structure determination. Continuous rotation electron diffraction (cRED) data collected from 13 crystals were successfully used to solve and refine the structure of EMM-28. This illustrates that cRED data are capable of performing structure determination despite limited PXRD data quality. EMM-28 has a unique framework structure containing supercavities, >21 Å in size, connected by one-dimensional 10-ring channels. High-resolution transmission electron microscopy (HRTEM) confirmed the structure model. The structure of EMM-28 is related to several known zeolite structures with large cavities.