Imogolite Nanotubes Research Articles

Exploring Colloidal Phase Transitions of Imogolite Nanotubes by Evaporation Induced Self‐Assembly in Levitation

AbstractEvaporation‐induced self‐assembly (EISA) is a versatile method for generating organized superstructures from colloidal particles, offering diverse design possibilities through the manipulation of colloid size, shape, substrate nature, and environmental conditions. While some work highlighted the potential of EISA to investigate phase transitions of inorganic liquid crystals, the influence of sample environment to determine their phase diagrams is often overlooked. In this work, the self‐assembly of lyotropic liquid crystals is compared by EISA on substrates, and by acoustic levitation (absence of substrate). The focus is on imogolite nanotubes, a model colloidal system of 1D charged objects, due to their tunable morphology and rich liquid‐crystalline phase behavior. It demonstrates the feasibility to obtain phase transitions in levitating droplets and on soft hydrophobic substrates, whereas self‐assembly is limited on rigid hydrophilic supports. Moreover, the aspect ratio of the nanotubes proves to be a pivotal factor, influencing both transitions and the resulting materials shape and surface. Besides material shaping, acoustic levitation emerges as a promising method for studying phase transitions by EISA, toward the rapid establishment of phase diagrams from diluted to highly concentrated states using a limited volume of sample.

Pressure-induced structural modifications of imogolite nanotubes and of their methylated analogues

Structural modifications of single-walled aluminosilicate clay nanotubes have been studied under hydrostatic pressure by in situ synchrotron X-ray scattering. Imogolite nanotubes (INT) of nominal composition (OH)3Al2O3SiOH, and methyl-modified imogolite nanotubes (m-INT), (OH)3Al2O3SiCH3, have hydrophilic and hydrophobic internal cavities, respectively. Nanotube chiralities also differ, with zigzag (INT) and armchair (m-INT) chirality. In this work, pressure-induced changes in nanotube morphology and atomic structure are studied as a function of chirality, affinity of the inner cavity, and the pressure-transmitting medium used. Radial deformation and collapse of nanotubes are evidenced below 3 GPa, followed by the formation of a lamellar phase at higher pressures. In the case of INT, the collapse pressure value depends on the pressure transmitting medium chosen. Axial compressibility is measured, and a pseudo Young's modulus Y is determined to be equal to ∼265 GPa for INT and below 80 GPa for m-INT, underpinning the role of nanotube chirality in mechanical properties.

Nonclassical Growth Mechanism of Double-Walled Metal-Oxide Nanotubes Implying Transient Single-Walled Structures.

The formation of imogolite nanotubes is reported to be a kinetic process involving intermediate roof-tile nanostructures. Here, the structural evolution occurring during the synthesis of aluminogermanate double-walled imogolite nanotubes is in situ monitored, thanks to an instrumented autoclave allowing the control of the temperature, the continuous measurement of pH and pressure, and the regular sampling of gas and solution. Chemical analyses confirm the completion of the precursor's conversion with the release of CO2, ethanol, and dioxane as main side products. The combination of microscopic observations, infrared, and absorption spectroscopies with small and wide-angle X-ray scattering experiments unravel a unique growth mechanism implying transient single-walled nanotubes instead of the self-assembly of stacked proto-imogolite tiles. The growth formation of these transient nanotubes is followed at the molecular level by Quick-X-ray absoprtion specotrscopy experiments. Multivariate data analysis evidences that the near neighboring atomic environment of Ge evolves from monotonous to a more complex one as the reaction progresses. The following transformation into a double-walled nanotube takes place at a nearly constant mean radius, as demonstrated by the simulation of X-ray scattering diagrams. Overall, transient nanotubes appear to serve for the anchoring of a new wall, corresponding to a mechanism radically different from that proposed in the literature.

Dried hybrid imogolite nanotubes as solids with a changeable surface area: an insight into textural properties based on the correlation between nitrogen gas adsorption, immersion calorimetry into water, and small angle X-ray scattering.

Powdered samples of three imogolite materials with an inner surface covered with Si-CH3 groups (hybrid IMO-CH3) were prepared by ambient drying at 323 K, freeze drying, and spray drying. Reliable estimates of the intra-tube (SA), inter-tube (SB), and inter-bundle (SC) specific surface areas of these samples were inferred from a model-guided correlation between the results of measurements by small angle X-ray scattering (SAXS), nitrogen gas adsorption, and immersion calorimetry into water. Since the SAXS studies indicated no significant deformations of IMO-CH3 nanotubes upon drying, further studies by gaseous N2 adsorption at 77 K indicated the intra-tube and inter-bundle specific surface areas as being only accessible to this adsorbate. The outer curved surfaces of IMO nanotubes, including the inter-tube surface areas, were evaluated based on the calorimetric measurements of the enthalpy of immersion into water, using the enthalpy of immersion per unit surface area for a modelled curved surface of gibbsite as the conversion factor. Given the uncertainty in the determination of surface areas, the IMO-CH3 samples were found to possess the limiting values of specific surface areas ranging between 1150 and 1480 m2 g-1. In contrast to the two other materials, ambient-dried IMO-CH3 was characterized by the highest value of SC parameter due to the much smaller bundles formed by the constituent imogolite nanotubes. The accessibility of these surface areas, together with the hydrophobic and hydrophilic surface domains, was demonstrated to depend on the nature of the surrounding medium and the size of the adsorbing species.

Multivariate regression analysis of factors regulating the formation of synthetic aluminosilicate nanoparticles.

Interest is growing in nanoparticles made of earth abundant materials, like alumino(silicate) minerals. Their applications are expanding to include catalysis, carbon sequestration reactions, and medical applications. It remains unclear, however, what factors control their formation and abundance during laboratory synthesis or on a larger industrial scale. This work investigates the complex system of physicochemical conditions that influence the formation of nanosized alumino(silicate) minerals. Samples were synthesized and analyzed by powder X-ray diffraction, in situ and ex situ small angle X-ray scattering, and transmission electron microscopy. Regression analyses combined with linear combination fitting of powder diffraction patterns was used to model the influence of different synthesis conditions including concentration, hydrolysis ratio and rate, and Al : Si elemental ratio on the particle size of the initial precipitate and on the phase abundances of the final products. These models show that hydrolysis ratio has the strongest control on the overall phase composition, while the starting reagent concentration also plays a vital role. For imogolite nanotubes, we determine that increasing concentration, and relatively high or low hydrolysis limit nanotube production. A strong relationship is also observed between the distribution of nanostructured phases and the size of precursor particles. The confidences were >99% for all linear regression models and explained up to 85% of the data variance in the case of imogolite. Additionally, the models consistently predict resulting data from other experimental studies. These results demonstrate the use of an approach to understand complex chemical systems with competing influences and provide insight into the formation of several nanosized alumino(silicate) phases.

Imogolite Nanotubes and Their Permanently Polarized Bifunctional Surfaces for Photocatalytic Hydrogen Production.

To date, imogolite nanotubes (INTs) have been primarily used for environmental applications such as dye and pollutant degradation. However, imogolite's well-defined porous structure and distinctive electro-optical properties have prompted interest in the system's potential for energy-relevant chemical reactions. The imogolite structure leads to a permanent intrawall polarization arising from the presence of bifunctional surfaces at the inner and outer tube walls. Density functional theory simulations suggest such bifunctionality to encompass also spatially separated band edges. Altogether, these elements make INTs appealing candidates for facilitating chemical conversion reactions. Despite their potential, the exploitation of imogolite's features for photocatalysis is at its infancy, thence relatively unexplored. This perspective overviews the basic physical-chemical and optoelectronical properties of imogolite nanotubes, emphasizing their role as wide bandgap insulator. Imogolite nanotubes have multifaceted properties that could lead to beneficial outcomes in energy-related applications. This work illustrates two case studies demonstrating a step-forward on photocatalytic hydrogen production achieved through atomic doping or metal co-catalyst. INTs exhibit potential in energy conversion and storage, due to their ability to accommodate functions such as enhancing charge separation and influencing the chemical potentials of interacting species. Yet, tapping into potential for energy-relevant application needs further experimental research, computational, and theoretical analysis.

Ti-Modified Imogolite Nanotubes as Promising Photocatalyst 1D Nanostructures for H2 Production.

Imogolite nanotubes (INTs) are predicted as a unique 1D material with spatial separation of conduction and valence band edges but their large band gaps have inhibited their use as photocatalysts. The first step toward using these NTs in photocatalysis and exploiting the polarization-promoted charge separation across their walls is to reduce their band gap. Here, the modification of double-walled aluminogermanate INTs by incorporation of titanium into the NT walls is explored. The precursor ratio x = [Ti]/([Ge]+[Ti]) is modulated between 0 and 1. Structural and optical properties are determined at different scales and the photocatalytic performance is evaluated for H2 production. Although the incorporation of Ti atoms into the structure remains limited, the optimal condition is found around x = 0.4 for which the resulting NTs reveal a remarkable hydrogen production of ≈1500µmol g-1 after 5h for a noble metal-free photocatalyst, a 65-fold increase relative to a commercial TiO2-P25. This is correlated to a lowering of the recombination rate of photogenerated charge carriers for the most active structures. These results confirm the theoretical predictions regarding the potential of modified INTs as photoactive nanoreactors and pave the way for investigating and exploiting their polarization properties for energy applications.

Dimerization Effects and Negative Strain Energy in Silicon Monosulfide Nanotubes.

We report on the construction and characterization of silicon monosulfide nanotubes that were obtained by rolling up two-dimensional materials isoelectronic to phosphorene in the recently discovered layered Pmma and β phases. We relaxed and studied the nanotube structures using computational methods within density functional theory (DFT). We found that the nanotubes with a thick Pmma layer remain stable at room temperature, and their electronic properties depend on their diameters. Small-diameter nanotubes display metallic character, while nanotubes with increasing diameter show semiconducting ground states due to the dimerization in the silicon-silicon distances that opens a gap, leading to interesting optical properties in the near-infrared region. Furthermore, we discovered β SiS monolayer nanotubes having negative strain energies, similar to the well-known imogolite inorganic nanotubes. The combined thermal stability, compelling optical properties, and diverse applications of these silicon monosulfide nanotubes underscore the demand for novel synthesis methods to fully explore their potential in various fields.

The atomic structure of imogolite nanotubes: A 50 years old issue reinvestigated by X-ray scattering experiments and molecular dynamics simulations

Imogolites are clay nanotubes consisting of a curved di-octahedral gibbsite-like layer [OH3AlO3] and of isolated OHSiO3 tetrahedra connected by three mutual oxygen atoms to the octahedra, with N silicon tetrahedra along a circumference. There is a consensus that synthetic imogolites have a larger N value than natural ones, which may depend on the method of synthesis. However, N values reported in the literature over the last fifty years are given as uncertain or are not consistent. In this work, we reinvestigate the structure of synthetic imogolite nanotubes for which a value of N = 12 was reported. We perform X-ray scattering experiments on nanotubes in suspension and on the same sample as a dry powder after removing water. The analysis of diffractograms is based on Molecular Dynamics simulations allowing us to obtain imogolite nanotubes with different N values. We find that the sample is made of a mixture of nanotubes with N = 13 and N = 14. Our study points towards strong deformation of the nanotubes, assembled in bundles, in their dry state, which has to be taken into account in the analysis of measured diffractograms.

Ultrasonic assisted highly porous PPy/JSAC/IMO [PJ-IMO] nanocomposite for hydrogen fuel cell and asymmetric supercapacitor (PJ-IMO||JSAC) applications

Environmental pollution due to irrepressible consumption of fossil fuel and thereby chaotic global temperature enforce the scientific community to search for alternative clean and green energy sources. Hydrogen is considered as a clean, green and alternative energy carrier that has the potential to overcome various environmental issues including the energy crisis. Hence, the present work focuses on the preparation of novel nanocomposite [PPy/JSAC/IMO (PJ-IMO)] comprise of conducting polymer namely polypyrrole (PPy), activated carbon from jack fruit seed (JSAC) and natural clay imogolite (IMO) nanotube where a facile ultrasonic method was adopted for the preparation of PJ-IMO nanocomposite. The structural, morphological and elemental composition of the prepared PJ-IMO nanocomposite reveals that the PPy and IMO were anchored at the surface of JSAC. A drastic increment in the specific surface area of PJ-IMO nanocomposite (1354 m2 g−1) was observed compared to PPy/JSAC (PJ) nanocomposite (892 m2 g−1) and pristine PPy (39 m2 g−1). The prepared PJ-IMO exhibits 7.4 wt% hydrogen storage capacity at 50 °C, desorption of stored hydrogen at 104 °C and very good cyclic stability even after 34 cycles. The calculated binding energy (0.33–0.50 eV) of stored hydrogen falls in the recommended range of US Department of Energy (DOE-2025) targets. The electrochemical hydrogenation studies show that a maximum hydrogen discharge capacity of 3820 mAh/g at 42nd cycle, columbic efficiency of 93.1 %, hydrogen retention rate of 73.8 % and corrosion resistance of 26.3 mA/cm2 respectively. The as-fabricated PJ-IMO||JSAC asymmetric supercapacitor (ASC) has an energy density of 203 Wh kg−1 at 0.5 Ag−1 and power density of 2398 W kg−1 at 2 A g−1. The prepared ASC could able to power blue LEDs for 10 min and motor fan for 7 min. Hence, these excellent characteristics proved that the prepared PJ-IMO nanocomposite may serve as an excellent weakly chemisorbed hydrogen storage material and electrode for electrochemical energy storage applications in the near future.

Evidence and importance of intermediate nanostructures in the journey from molecular precursors to allophane and imogolite nanocrystals

Nanoparticles often-called proto-imogolites have been identified as an intermediate in the formation process of imogolite nanotubes as early as 1979. Their composition and structure are now well documented in the case of synthetic imogolite. One specific characteristic of proto-imogolite is that they have a curved shape with a local structure close to the one of imogolite. During a growth stage, they evolve toward nanocrystals (allophane, imogolite). Their thorough characterization has so far been difficult. Using synchrotron Small Angle X-ray Scattering coupled with Raman spectroscopy, we observe that proto-imogolites form during the initial stage of the co-precipitation of aluminum and silicon molecular precursors thanks to a reorganization process. The shape of the initial proto-imogolites, before the growth stage, depends on the synthesis conditions and controls the characteristics of the final product. We show using cryo-TEM images that, at the end of the growth stage, non-tubular nanostructures continue to coexist with nanotubes. Protocols to quantify remaining non-tubular nano-objects and purify the samples are discussed.

Is imogolite a suitable adsorbent agent for the herbicides like diuron and atrazine?

Nanotubular minerals are gained researchers’ interest for environmental applications and their use as adsorbents due to their structural characteristics. Imogolite mineral belongs to aluminosilicates and can be characterised as a promising sorbent due to its abundant nature as it has both natural and synthetic origins. In the present study, the potential interactions of imogolite mineral with the herbicides diuron and atrazine have been investigated via theoretical approaches to characterise the mineral as a potential adsorbent for water or soil treatment applications. Force Field calculations showed stronger interactions between imogolite outer surface and herbicides. Diuron molecules had a better adaptation to the nanotubular shape by torsion, unlike atrazine molecules, when herbicides interacted with the inner surface due to their molecule length and rigidity. The release of the herbicides from the imogolite nanotube showed the unstable nature of both herbicides when they were loaded on the inner part of imogolite, which is in agreement with the sorption studies that proved the preference for herbicides on the outer surface and the edges of the minerals. Water molecules played a crucial role in the complexes related to imogolite properties as its inner surface is more hydrophilic. When herbicides were loaded on the outer surface, water molecules were the intermediate medium for the sorption of herbicides creating hydrogen bonds. In contrast, on the inner surface, the herbicide molecules had a competed behaviour to water. From a theoretical point of view, imogolite is a feasible sorbent for herbicides, especially when loaded on the mineral's outer part, creating high stability of complexes.

Synergistic Flame Retardant Effect between Ionic Liquid Functionalized Imogolite Nanotubes and Ammonium Polyphosphate in Epoxy Resin

Ionic liquid functionalized imogolite nanotubes (INTs-PF6-ILs) were introduced into the epoxy resin (EP)/ammonium polyphosphate (APP) system to investigate the flame retardant performance and thermal properties using the limiting oxygen index (LOI) test, the UL-94 test, and the cone calorimeter test (CCT). The results suggested that a synergistic effect exists between INTs-PF6-ILs and APP on the char formation and anti-dripping behavior of EP composites. For the EP/APP, an UL-94 V-1 rating was obtained for the loading of 4 wt% APP. However, the composites containing 3.7 wt% APP and 0.3 wt% INTs-PF6-ILs could pass the UL-94 V-0 rating without dripping behavior. In addition, compared with the EP/APP composite, the fire performance index (FPI) value and fire spread index (FSI) value of EP/APP/INTs-PF6-ILs composites were remarkably reduced by 11.4% and 21.1%, respectively. Moreover, the char formed by EP/APP composites was intumescent, but of poor quality. In contrast, the char for EP/APP/INTs-PF6-ILs was strong and compact. Therefore, it can resist the erosion due to heat and gas formation and protect the inside of the matrix. This was the main reason for the good flame retardant property of EP/APP/INTs-PF6-ILs composites.

Wet spinning imogolite nanotube fibres: an in situ process study.

Imogolite nanotubes (INTs) form transparent aqueous liquid-crystalline solutions, with strong birefringence and X-ray scattering power. They provide an ideal model system for studying the assembly of one-dimensional nanomaterials into fibres, as well as offering interesting properties in their own right. Here, in situ polarised optical microscopy is used to study the wet spinning of pure INTs into fibres, illustrating the influence of process variables during extrusion, coagulation, washing and drying on both structure and mechanical properties. Tapered spinnerets were shown to be significantly more effective than thin cylindrical channels for forming homogeneous fibres; a result related to simple capillary rheology by fitting a shear thinning flow model. The washing step has a strong influence of structure and properties, combining the removal of residual counter-ions and structural relaxation to produce a less aligned, denser and more networked structure; the timescales and scaling behavior of the processes are compared quantitatively. Both strength and stiffness are higher for INT fibres with a higher packing fraction and lower degree of alignment, indicating the importance of forming a rigid jammed network to transfer stress through these porous, rigid rod assemblies. The electrostatically-stabilised, rigid rod INT solutions were successfully cross-linked using multivalent anions, providing robust gels, potentially useful in other contexts.

Hydrophobic dye solubilization via hybrid imogolite nanotubes probed using second harmonic scattering.

This article explores the organization and interactions of Disperse Orange 3 (DO3) hydrophobic dye molecules within hybrid organic-inorganic imogolite nanotubes. In pure water, the DO3 dye molecules self assemble into large insoluble 2D nanosheets whose structure is also explored by molecular dynamics simulations. The dye molecules are however efficiently solubilized in the presence of hybrid imogolite nanotubes. The filling of the internal hydrophobic cavity of the nanotubes is quantified. The organization of the molecules inside the nanotube is probed using the polarization resolved second harmonic scattering (SHS) technique coupled with simulation. At the highest loading, the dyes fill the nanotube with their principal axis parallel to the nanotube walls showing a strong SHS signal due to this encapsulation.

Shear recovery and temperature stability of Ca2+ and Ag+ glycolipid fibrillar metallogels with unusual β-sheet-like domains.

Low-molecular weight gelators (LMWGs) are small molecules (Mw < ∼1 kDa), which form self-assembled fibrillar network (SAFiN) hydrogels in water. A great majority of SAFiN gels are described by an entangled network of self-assembled fibers, in analogy to a polymer in a good solvent. Here, fibrillation of a biobased glycolipid bolaamphiphile is triggered by Ca2+ or Ag+ ions which are added to its diluted micellar phase. The resulting SAFiN, which forms a hydrogel above 0.5 wt%, has a "nano-fishnet" structure, characterized by a fibrous network of both entangled fibers and β-sheet-like rafts, generally observed for silk fibroin, actin hydrogels or mineral imogolite nanotubes, but generally not known for SAFiN. This work focuses on the strength of the SAFIN gels, their fast recovery after applying a mechanical stimulus (strain) and their unusual resistance to temperature, studied by coupling rheology to small angle X-ray scattering (rheo-SAXS) using synchrotron radiation. The Ca2+-based hydrogel maintains its properties up to 55 °C, while the Ag+-based gel shows a constant elastic modulus up to 70 °C, without the appearance of any gel-to-sol transition temperature. Furthermore, the glycolipid is obtained by fermentation from natural resources (glucose and rapeseed oil), thus showing that naturally engineered compounds can have unprecedented properties, when compared to the wide range of chemically derived amphiphiles.

In2S3 Growth Templated by Aluminogermanate Double‐Walled Imogolite Nanotubes Toward Efficient Visible Light Photocatalysts

Different strategies combining semiconductors and nanomaterials have been explored to enhance the performance of visible light photocatalysts. This work reports the hydrothermal growth of In2S3 on the aluminogermanate double‐walled imogolite nanotubes and the photocatalytic properties of the resulting composites. The reaction conditions are optimized to ensure the linear growth of In2S3, while preserving the tubular structure of imogolite nanotubes. The imogolite–In2S3 composites show enhanced photocatalytic degradation of methyl orange compared to the control In2S3, exhibiting a fourfold increase in the photocatalytic dye degradation rate constant. Interestingly, these composites present a negative photocurrent response, indicating the generation of mobile holes, whereas both In2S3 and imogolite by themselves exhibit typical positive photocurrent behavior. The improvement in the photocatalytic dye degradation and the negative photocurrent response is attributed to the interface formation between In2S3 and imogolite in these composites and the p‐type character of the latter. Templating the colloidal synthesis of semiconducting nanoparticles in confined spaces could bring a step change in the design of catalytic and photocatalytic materials.

Synergistic Flame Retardant Effect between Ionic Liquid-Functionalized Imogolite Nanotubes and Ammonium Polyphosphate in Unsaturated Polyester Resin.

Imogolite nanotubes (INTs) were synthesized from tetraethoxysilane, aluminum nitrate nonahydrate, and ammonia solution by the method of Arancibia-Miranda, and their dispersion was modified by 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF6) to obtain ionic liquid (IL)-functionalized INTs (INTs-PF6-ILs). Then, the flame retardant INTs-PF6-ILs was complexed with ammonium polyphosphate (APP) and applied to unsaturated polyester resin (UPR). The limiting oxygen index value and the UL-94 level of the UPR/APP/INTs-PF6-ILs composites reached 28 and V-0, respectively. The residual carbon of the composites in thermogravimetric analysis increased by 19.47%, compared with that of pure UPR. The cone calorimeter test result showed that the peak of heat release rate and total heat rate values of the UPR/APP/INTs-PF6-ILs composites were lowered by 41 and 34% than those of the pure UPR, respectively. The effect of heat combustion and the maximum mass loss rate of UPR/APP/INTs-PF6-ILs composites were also greatly decreased. There were no holes or folds observed on the surface of the UPR/APP/INTs-PF6-ILs composites' residual carbon in scanning electron microscopy images. The intact residual carbon could have effectively insulated the heat and oxygen to improve the flame retardant performance.

Water Organization around Inorganic Nanotubes in Suspension Probed by Polarization-Resolved Second Harmonic Scattering

Imogolite nanotube (INT) is a fascinating one-dimensional (1D) material that can be synthesized in the liquid phase. Its behavior in solution is crucial for many applications and depends on the organization of water at the liquid-wall interface. We study here this water organization by using the nonlinear optical technique of polarization-resolved second harmonic scattering (SHS). A microscopic model is proposed to interpret the origin of the coherent SHS signal recovered in this 1D colloidal system. This work demonstrates that the SHS technique is able to probe the shell of water molecules oriented around the nanotubes. Water organization results from the electric field induced by the nanotube walls, and it is strongly dependent on the ionic strength of the suspension.

Massively parallel linear-scaling Hartree-Fock exchange and hybrid exchange-correlation functionals with plane wave basis set accuracy.

We extend our linear-scaling approach for the calculation of Hartree-Fock exchange energy using localized in situ optimized orbitals [Dziedzic et al., J. Chem. Phys. 139, 214103 (2013)] to leverage massive parallelism. Our approach has been implemented in the onetep (Order-N Electronic Total Energy Package) density functional theory framework, which employs a basis of non-orthogonal generalized Wannier functions (NGWFs) to achieve linear scaling with system size while retaining controllable near-complete-basis-set accuracy. For the calculation of Hartree-Fock exchange, we use a resolution-of-identity approach, where an auxiliary basis set of truncated spherical waves is used to fit products of NGWFs. The fact that the electrostatic potential of spherical waves (SWs) is known analytically, combined with the use of a distance-based cutoff for exchange interactions, leads to a calculation cost that scales linearly with the system size. Our new implementation, which we describe in detail, combines distributed memory parallelism (using the message passing interface) with shared memory parallelism (OpenMP threads) to efficiently utilize numbers of central processing unit cores comparable to, or exceeding, the number of atoms in the system. We show how the use of multiple time-memory trade-offs substantially increases performance, enabling our approach to achieve superlinear strong parallel scaling in many cases and excellent, although sublinear, parallel scaling otherwise. We demonstrate that in scenarios with low available memory, which preclude or limit the use of time-memory trade-offs, the performance degradation of our algorithm is graceful. We show that, crucially, linear scaling with system size is maintained in all cases. We demonstrate the practicability of our approach by performing a set of fully converged production calculations with a hybrid functional on large imogolite nanotubes up to over 1400 atoms. We finish with a brief study of how the employed approximations (exchange cutoff and the quality of the SW basis) affect the calculation walltime and the accuracy of the obtained results.