One-Dimensional MoS2 Nanoscrolls as Miniaturized Memories.

Dimensionality of materials is closely related to their physical properties. For two-dimensional (2D) semiconductors such as monolayer molybdenum disulfide (MoS2), converting them from 2D nanosheets to one-dimensional (1D) nanoscrolls could contribute to remarkable electronic and optoelectronic properties, yet the rolling-up process still lacks sufficient controllability, which limits the development of their device applications. Herein we report a modified solvent evaporation-induced rolling process that halts at intermediate states and achieve MoS2 nanoscrolls with high yield and decent axial uniformity. The accordingly fabricated nanoscroll memories exhibit an on/off ratio of ∼104 and a retention time exceeding 103 s and can realize multilevel storage with pulsed gate voltages. Such open-end, high-curvature, and hollow 1D nanostructures provide new possibilities to manipulate the hysteresis windows and, consequently, the charge storage characteristics of nanoscale field-effect transistors, thereby holding great promise for the development of miniaturized memories.

Flexible Mesopores in Nanoscrolls: Extraordinarily Large Alteration of Pore Sizes and Their Reversibility.

Flexible porous materials have gained considerable interest for their potential applications in selective absorption and controlled release/storage of specific molecules or compounds. Here, nanoscrolls are proposed as a type of inorganic solids with reversibly flexible mesopores. Nanoscrolls exhibit a rolled-up structure composed of nanosheets with a 1D rod-like morphology, possessing two distinct nanospaces. The first space comprises 1D tubular mesopores located at the center of the rod, while the second space exists in the interlayer regions on the wall of the mesopore, resulting from the layer stacking caused by the scrolling of nanosheets. By replacing the interlayer cations on the nanoscroll walls with other cations, a drastic alteration in the size of the 1D mesopores is observed. For instance, exchanging bulky dodecylammonium cations with small NH4 + cations leads to a substantial change in pore size, with differences ranging from 10 to 20 nm-a notably larger variation compared to previous reports on flexible porous materials. Importantly, the alteration of pore size induced by the exchange reaction is found to be reversible. This reversible alteration in pore size holds promise for applications in host-guest chemistry involving large moieties such as nanoparticles and enzymes.

Rolling up 2D WSe2 Nanosheets to 1D Anisotropic Nanoscrolls for Polarization-Sensitive Photodetectors.

The intrinsic low-symmetry crystal structures or external geometries of low-dimensional materials are crucial for polarization-sensitive photodetection. However, these inherently anisotropic materials are limited in variety, and their anisotropy is confined to specific crystal directions. Transforming 2D semiconductors, such as WSe2, from isotropic 2D nanosheets into anisotropic 1D nanoscrolls expands their application in polarization photodetection. Despite this considerable potential, research on polarization photodetection based on nanoscrolls remains scarce. Here, the uniform crystalline orientation of WSe2 nanoscrolls is achieved conveniently and efficiently by applying ethanol droplets to vapor deposition-grown bilayer WSe2 nanosheets. Angle-resolved polarized Raman spectroscopy of WSe2 nanoscrolls demonstrates vibrational anisotropy. Photodetectors based on these nanoscrolls show competitive overall performance with a broadband detection range from 405 to 808 nm, a competitive on/off ratio of ≈900, a high detectivity of 3.4 × 108 Jones, and a fast response speed of ≈30 ms. Additionally, WSe2 nanoscroll-based photodetectors exhibit strong polarization-sensitive detection with a maximum dichroic ratio of 1.5. More interestingly, due to high photosensitivity, the WSe2 nanoscroll detectors can easily record sequential puppy images. This work reveals the potential of WSe2 nanoscrolls as excellent polarization-sensitive photodetectors and provides new insights into the development of high-performance optoelectronic devices.

Rhodamine 6G/Transition Metal Dichalcogenide Hybrid Nanoscrolls for Enhanced Optoelectronic Performance.

The low light absorption efficiency has seriously hindered the application of two-dimensional transition metal dichalcogenide (TMDC) nanosheets in the field of optoelectronic devices. Various approaches have been used to improve the performance of TMDC nanosheets. Preparation of one-dimensional TMDC nanoscrolls in combination with photoactive materials has been a promising method to improve their properties recently. In this work, we report a facile method to enhance the optoelectronic performance of TMDC nanoscrolls by wrapping the photoactive organic dye rhodamine (R6G) into them. After R6G molecules were deposited on monolayer TMDC nanosheets by the solution method, the R6G/MoS2 nanoscrolls with lengths up to hundreds of microns were prepared in a short time by dropping a mixture of ammonia and ethanol solution on the R6G/MoS2 nanosheets. The as-obtained R6G/MoS2 nanoscrolls were well characterized by optical microscopy, atomic force microscopy, Raman spectroscopy, and transmission electron microscopy to prove the encapsulation of R6G. There are multiple type II heterojunction interfaces in the R6G/MoS2 nanoscrolls, which can promote the generation of photo-induced carriers and the following electron-hole separation. The separated electrons were transported rapidly along the axial direction of the R6G/MoS2 nanoscrolls, which greatly improves the efficiency of light absorption and photoresponse. Under the irradiation of an incident 405 nm laser, the photoresponsivity, carrier mobility, external quantum efficiency, and detectivity of R6G/MoS2 nanoscrolls were enhanced to 66.07 A/W, 132.93 cm2V-1s-1, 20,261%, and 1.25 × 1012 cm·Hz1/2W-1, which are four orders of magnitude higher than those of monolayer MoS2 nanosheets. Our work indicates that the R6G/TMDC hybrid nanoscrolls could be promising materials for high-performance optoelectronic devices.

Recent Advances in Rolling 2D TMDs Nanosheets into 1D TMDs Nanotubes/Nanoscrolls.

Transition metal dichalcogenides (TMDs) van der Waals (vdW) 1D heterostructures are recently synthesized from 2D nanosheets, which open up new opportunities for potential applications in electronic and optoelectronic devices. The most recent and promising strategies in regards to forming 1D TMDs nanotubes (NTs) or nanoscrolls (NSs) in this review article as well as their heterostructures that are produced from 2D TMDs are summarized. In order to improve the functionality of ultrathin 1D TMDs that are coaxially combined with boron nitride nanotubes and single-walled carbon nanotubes. 1D heterostructured devices perform better than 2D TMD nanosheets when the two devices are compared. The photovoltaic effect in WS2 or MoS2 NTs without a junction may exceed the Shockley-Queisser limit for the above-band-gap photovoltage generation. Photoelectrochemical hydrogen evolution is accelerated when monolayer WS2 or MoS2 NSs are incorporated into a heterojunction. In addition, the photovoltaic performance of the WSe2 /MoS2  NSs junction is superior to that of the performance of MoS2 NSs. The summary of the current research about 1D TMDs can be used in a variety of ways, which assists in the development of new types of nanoscale optoelectronic devices. Finally, it also summarizes the current challenges and prospects.

QD/2D Hybrid Nanoscrolls: A New Class of Materials for High-Performance Polarized Photodetection and Ultralow Threshold Laser Action.

Nanoscrolls are a class of nanostructures where atomic layers of 2D materials are stacked consecutively in a coaxial manner to form a 1D spiral topography. Self-assembly of chemical vapor deposition grown 2D WS2 monolayer into quasi-1D van der Waals scroll structure instigates a plethora of unique physiochemical properties significantly different from its 2D counterparts. The physical properties of such nanoscrolls can be greatly manipulated upon hybridizing them with high-quantum-yield colloidal quantum dots, forming 0D/2D structures. The efficient dissociation of excitons at the heterojunctions of QD/2D hybridized nanoscrolls exhibits a 3000-fold increased photosensitivity compared to the pristine 2D-material-based nanoscroll. The synergistic effects of confined geometry and efficient QD scatterers produce a nanocavity with multiple feedback loops, resulting in coherent lasing action with an unprecedentedly low lasing threshold. Predominant localization of the excitons along the circumference of this helical scroll results in a 12-fold brighter emission for the parallel-polarized transition compared to the perpendicular one, as confirmed by finite-difference time-domain simulation. The versatility of hybridized nanoscrolls and their unique properties opens up a powerful route for not-yet-realized devices toward practical applications.

High-Performance Photodiode Based on Atomically Thin WSe2 /MoS2 Nanoscroll Integration.

Self-assembled structures of 2D materials with novel physical and chemical properties, such as the good electrical and optoelectrical performance in nanoscrolls, have attracted a lot of attention. However, high photoresponse speed as well as high responsivity cannot be achieved simultaneously in the nanoscrolls. Here, a photodiode consisting of single MoS2 nanoscrolls and a p-type WSe2 is demonstrated and shows excellent photovoltaic characteristics with a large open-circuit voltage of 0.18 V and high current intensity. Benefiting from the heterostructure, the dark current is suppressed resulting in an increased ratio of photocurrent to dark current (two orders of magnitude higher than the single MoS2 nanoscroll device). Furthermore, it yields high responsivity of 0.3 A W-1 (corresponding high external quantum efficiency of ≈75%) and fast response time of 5 ms, simultaneously. The response speed is increased by three orders of magnitude over the single MoS2 nanoscroll device. In addition, broadband photoresponse up to near-infrared could be achieved. This atomically thin WSe2 /MoS2 nanoscroll integration not only overcomes the disadvantage of MoS2 nanoscrolls, but also demonstrates a single nanoscroll-based heterostructure with high performance, promising its potential in the future optoelectronic applications.

Theoretical Prediction of a Giant Anisotropic Magnetoresistance in Carbon Nanoscrolls.

Snake orbits are trajectories of charge carriers curving back and forth that form at an interface where either the magnetic field direction or the charge carrier type are inverted. In ballistic samples, their presence is manifested in the appearance of magnetoconductance oscillations at small magnetic fields. Here we show that signatures of snake orbits can also be found in the opposite diffusive transport regime. We illustrate this by studying the classical magnetotransport properties of carbon tubular structures subject to relatively weak transversal magnetic fields where snake trajectories appear in close proximity to the zero radial field projections. In carbon nanoscrolls, the formation of snake orbits leads to a strongly directional dependent positive magnetoresistance with an anisotropy up to 80%.

Rolling Up a Monolayer MoS2 Sheet.

MoS2 nanoscrolls are formed by argon plasma treatment on monolayer MoS2 sheet. The nanoscale scroll formation is attributed to the partial removal of top sulfur layer in MoS2 during the argon plasma treatment process. This convenient, solvent-free, and high-yielding nanoscroll formation technique is also feasible for other 2D transition metal dichalcogenides.

Chitosan-grafted folic acid decorated one-dimensional GONS: A biocompatible drug cargo for targeted co-delivery of anticancer agents.

In conventional chemotherapy, the cancer cells can become highly resilient due to a phenomenon known as multi-drug resistance (MDR). The co-delivery of chemotherapeutic agents assisted with novel nanocarrier-based targeted DDS may counter the MDR issues and subsequently improve their therapeutic efficacy. In line with this, the present work deals with the development of 1D graphene oxide nanoscrolls (GONS)-based nano delivery system for co-delivery of chemosensitizer along with the chemotherapeutic agent. Herein, the 1D GONS nanocarrier was initially functionalized with chitosan (CS) biopolymer and folic acid (FA) further to enhance their biocompatibility and target-specific co-delivery. The resultant GONS-CS-FA (GCF) nanocarriers were co-loaded with doxorubicin (DOX) and caffeic acid (CA) at different weight proportions with respect to nanocarrier and drug composition. The optimum loading efficiency of 51.14 ± 1.47 % (DOX) and 49.70 ± 1.19 % (CA) was observed for GCF: drug ratio of 2.5 with drug composition of 1:1. In vitro release at pH 5 yielded ~83 % DOX and 75 % CA, compared to ~71 % DOX and 61 % CA at pH 7.4 over 7 days, suggesting a higher and targeted drug release in the cancer microenvironment. Cytotoxicity tests revealed selective apoptosis in cancer cells (A549) while maintaining cytocompatibility with normal cells (HEK293).

Unveiling the Mechanism of Spontaneous Nanoscroll Formation from Janus Transition Metal Dichalcogenide Nanoribbons.

Due to the atomic asymmetry, Janus transition metal dichalcogenide monolayers possess spontaneous curling and can even form one-dimensional nanoscrolls. Unveiling this spontaneous formation mechanism of nanoscrolls is of great importance for precise structural control. In this paper, we successfully simulate the process of Janus MoSSe nanoscroll formation from flat nanoribbons, based on molecular dynamics (MD) simulations with hybrid potentials. The spontaneous scrolling is purely driven by the relaxation of intrinsic strain in Janus MoSSe. The final structure of nanoscroll is strongly affected by the length of nanoribbon with a nonmonotonous relation. To further understand the mechanism, we establish a thermodynamic model to determine the inner radius of MoSSe nanoscrolls, which is shown to be related to spontaneous curvature, bending stiffness, interlayer van der Waals interaction, interlayer distance, and length of initial nanoribbon. The results correspond well with MD simulations of nanoscrolls from flat nanoribbons and the molecular static simulations of directly built nanoscrolls. Moreover, the inner radii of MoSeTe and MoSTe nanoscrolls are predicted based on the model. Our results provide insights into the Janus TMD nanoscroll formation and a pathway for controllable fabrication of nanoscrolls.

Nanoscrolls of Janus Monolayer Transition Metal Dichalcogenides.

Tubular structures of transition metal dichalcogenides (TMDCs) have attracted attention in recent years due to their emergent physical properties, such as the giant bulk photovoltaic effect and chirality-dependent superconductivity. To understand and control these properties, it is highly desirable to develop a sophisticated method to fabricate TMDC tubular structures with smaller diameters and a more uniform crystalline orientation. For this purpose, the rolling up of TMDC monolayers into nanoscrolls is an attractive approach to fabricating such a tubular structure. However, the symmetric atomic arrangement of a monolayer TMDC generally makes its tubular structure energetically unstable due to considerable lattice strain in curved monolayers. Here, we report the fabrication of narrow nanoscrolls by using Janus TMDC monolayers, which have an out-of-plane asymmetric structure. Janus WSSe and MoSSe monolayers were prepared by the plasma-assisted surface atom substitution of WSe2 and MoSe2 monolayers, respectively, and then were rolled by solution treatment. The multilayer tubular structures of Janus nanoscrolls were revealed by scanning transmission electron microscopy observations. Atomic resolution elemental analysis confirmed that the Janus monolayers were rolled up with the Se-side surface on the outside. We found that the present nanoscrolls have the smallest diameter of about 5 nm, which is almost the same as the value predicted by the DFT calculation. The difference in work functions between the S- and Se-side surfaces was measured by Kelvin probe force microscopy, which is in good agreement with the theoretical prediction. Strong interlayer interactions and anisotropic optical responses of the Janus nanoscrolls were also revealed by Raman and photoluminescence spectroscopy.

Formation and stability of nanoscrolls composed of graphene and hexagonal boron nitride nanoribbons: insights from molecular dynamics simulations.

CONTEXT: Nanoscrolls are tube-shaped structures formed when a sheet or ribbon of material is rolled into a cylinder, creating a hollow tube with a diameter on the nanoscale, similar to the papyrus. Carbon nanoscrolls have unique properties that make them useful in various applications, such as energy storage, catalysis, and drug delivery. In this study, we employed classical molecular dynamics simulations to investigate the formation and stability of nanoscrolls composed of graphene and hexagonal boron nitride (hBN) nanoribbons. Using a carbon nanotube (CNT) as a template to trigger their collapsing, we found that graphene/graphene, graphene/hBN, and hBN/hBN could form CNT-wrapped nanoscrolls at ultrafast speeds. We also confirmed that these nanoscrolls are thermally stable and discussed the other products formed from the interaction of these complexes and their temperature dependence. Gr/Gr and hBN/Gr nanoscrolls exhibit similar interlayer distances, while hBN/hBN nanoscrolls have wider interlayer distances than the other two composite nanoscrolls. These features suggest that hBN/hBN composite nanoscrolls could more efficiently capture small molecules because of their greater interlayer spacing. METHODS: We conducted molecular dynamics simulations using the Forcite package in the Biovia Materials Studio software, which employs the Universal and Dreiding force fields. We considered an NVT ensemble with a fixed time step of 1.0 fs for a duration of 500 ps. The velocity Verlet algorithm was adopted to integrate the equations of motion of the entire system. We employed the Nosé-Hoover-Langevin thermostat to control the system temperature. The simulations were carried out without periodic boundary conditions, so there was no pressure coupling.

Rapid Synthesis of Kaolinite Nanoscrolls through Microwave Processing.

Kaolinite nanoscrolls (NScs) are halloysite-like nanotubular structures of great interest due to their ability to superimpose halloysite's properties and applicability. Especially attractive is the ability of these NScs to serve as reaction vessels for the uptake and conversion of different chemical species. The synthesis of kaolinite NScs, however, is demanding due to the various processing steps that lead to extended reaction times. Generally, three intercalation stages are involved in the synthesis, where the second step of methylation dominates others in terms of duration. The present research shows that introducing microwave processing throughout the various steps can simplify the procedure overall and reduce the synthesis period to less than a day (14 h). The kaolinite nanoscrolls were obtained using two final intercalating agents, aminopropyl trimethoxy silane (APTMS) and cetyltrimethylammonium chloride (CTAC). Both produce abundant NScs, as corroborated by microscopy measurements as well as the surface area of the final products; APTMS intercalated NScs were 63.34 m2/g, and CTAC intercalated NScs were 73.14 m2/g. The nanoscrolls averaged about 1 µm in length with outer diameters of APTMS and CTAC intercalated samples of 37.3 ± 8.8 nm and 24.9 ± 6.1 nm, respectively. The availability of methods for the rapid production of kaolinite nanoscrolls will lead to greater utility of these materials in technologically significant applications.

Activation of peroxymonosulfate by MgCoAl layered double hydroxide: Potential enhancement effects of catalyst morphology and coexisting anions.

The morphology and specific surface area of layered double hydroxide (LDH) are of great significance for optimizing the application of LDH in sewage treatment. Herein, we present a study of the relation between the catalytic property and the morphology of LDH via activating peroxymonosulfate (PMS) for degradation of organic pollutants. The results demonstrated that LDH nanoscrolls possessed a superior performance for methylene blue (MB) degradation, which achieved almost 100% removal in 40 min and the calculated apparent rate constant was about 2.1, 4.5 and 11.5 times higher than that of LDH nanosheets, Co2+ and Co3O4, respectively. According to the results of X-ray photoelectrons spectroscopy (XPS) and electron paramagnetic resonance (EPR), 1O2 was confirmed to play a dominant role in the MB degradation, where the redox cycle of Co3+/Co2+ provided the impetus for the reaction. Moreover, the pH and ion tolerance abilities of LDH nanoscrolls in PMS activating process were determined as well. Remarkably, CO32- and H2PO4- could even promote the generation of •OH and 1O2 to facilitate the progress of reaction. Overall, these findings in the study may provide more opportunities in the preparation of high-efficiency catalysts and give insight into the accelerated degradation of refractory contaminants with surrounding anions.

Fabrication of ultrasound-mediated tunable graphene oxide nanoscrolls.

In this work, a cost-effective and facile method was adopted for the fabrication of graphene oxide nanoscrolls (GONS) by low frequency (20 kHz) ultrasonication with tunable dimensions. The graphene oxide (GO) was synthesized by modified Hummer's method using synthetic graphite as a base material. Later, GO suspension (0.05 g L-1) were made using methanol as solvent and subjected to different ultrasonication conditions. It was found that GO sheets curls themselves into nanoscrolls by overcoming the energy barrier for scrolling with the help of bubble cavitation energy provided by ultrasonication. Also, the effect of ultrasonication power (100-150 W) for irradiation time (0.5-3 h) over the GONS dimensions were investigated. The spiral wounded GONS structures were shown using electron microscopy. Raman Spectroscopy, Thin-film X-Ray Diffraction, Energy Dispersive X-Ray, FT Infrared Spectroscopic analysis were also done to endorse GONS formation. Factors affecting GONS formation such as sonication power and solvent selection were studied as scrolling of GO sheets are strongly dependent on sonication parameters and solvent characteristics. It was found that GONS length varies inversely with irradiation time for identical power density. Also, a solvent with relatively large Hansen solubility parameter, lower dipole movement and less negative value of zeta potential support GONS formation of longer length. Raman analysis overlays the rapid oxygen-defect site cleavage mechanism. The obtained GONS unlocks further developments in various engineering applications like adsorption, drug delivery and filtration membrane.

Structural and Thermal Stability of Graphyne and Graphdiyne Nanoscroll Structures.

Graphynes and graphdiynes are generic names for families of two-dimensional carbon allotropes, where acetylenic groups connect benzenoid-like hexagonal rings, with the coexistence of sp and sp2 hybridized carbon atoms. The main differences between graphynes and graphdiynes are the number of acetylenic groups (one and two for graphynes and graphdiynes, respectively). Similarly to graphene nanoscrolls, graphyne and graphdiynes nanoscrolls are nanosized membranes rolled into papyrus-like structures. In this work we studied through molecular dynamics simulations, using reactive potentials, the structural and thermal (up to 1000 K) stability of α,ß,γ-graphyne and α,ß,γ-graphdiyne scrolls. Our results demonstrate that stable nanoscrolls can be created for all the structures studied here, although they are less stable than corresponding graphene scrolls. This can be elucidated as a result of the higher graphyne/graphdiyne structural porosity in relation to graphene, and as a consequence, the π-π stacking interactions decrease.

Mimicking a Dog's Nose: Scrolling Graphene Nanosheets.

Inspired by the densely covered capillary structure inside a dog's nose, we report an artificial nanostructure, i. e., poly(sodium p-styrenesulfonate)-functionalized reduced graphene oxide nanoscrolls (PGNS), with high structural perfection and efficient gas sensing applications. A facile supramolecular assembly is introduced to functionalize graphene with the functional polymer, combined with the lyophilization technique to massively transform the planar graphene-based nanosheets to nanoscrolls. Detailed characterizations reveal that the bioinspired nanoscrolls exhibit a wide-open tubular morphology with uniform dimensions that is structurally distinct from the previously reported ones. The detailed morphologies of the graphene-based nanosheets in each scrolling stage during lyophilization are monitored by cryo-SEM. This unravels an asymmetric polymer-induced graphene scrolling mechanism including the corresponding scrolling process, which is directly presented by molecular dynamics simulations. The fabricated PGNS sensors exhibit superior gas sensing performance with reliable repeatability, excellent linear sensibility, and, especially, an ultrahigh response ( Ra/ Rg = 5.39, 10 ppm) toward NO2. The supramolecular assembly combined with the lyophilization technique to fabricate PGNS provides a strategy to design biomimetic materials for gas sensors and chemical trace detectors.

Carbon Nanoscrolls for Aluminum Battery.

This design provides a scalable route for in situ synthesizing of special carbon nanoscrolls as the cathode for an aluminum battery. The frizzy architectures are generated by a few graphene layers convoluting into the hollow carbon scroll, possessing rapid electronic transportation channels, superior anion storage capability, and outstanding ability of accommodating a large volume expansion during the cycling process. The electrochemical performance of the carbon nanoscroll cathode is fully tapped, displaying an excellent reversible discharge capacity of 104 mAh g-1 at 1000 mA g-1. After 55 000 cycles, this cathode retains a superior reversible specific capacity of 101.24 mAh g-1 at an ultrafast rate of 50 000 mA g-1, around 100% of the initial capacity, which demonstrates a superior electrochemical performance. In addition, anionic storage capability and structural stability are discussed in detail. The battery capacity under a wide temperature range from -80 to 120 °C is examined. At a low temperature of -25 °C, the battery delivers a discharge capacity of 62.83 mAh g-1 after 10 000 cycles, obtaining a capacity retention near 100%. In addition, it achieves a capacity of 99.5 mAh g-1 after 4000 cycles at a high temperature of 80 °C, with a capacity retention close to 100%. The carbon nanoscrolls possess an outstanding ultrafast charging/variable discharging rate performance surpassing all the batteries previously reported, which are highly promising for being applied in energy storage fields.

Quantitative theory of diffraction by cylindrical scroll nanotubes.

A quantitative theory of Fraunhofer diffraction by right- and left-handed multiwalled cylindrical scroll nanotubes is developed on the basis of the kinematical approach. The proposed theory is mainly dedicated to structural studies of individual nanotubes by the selected-area electron diffraction technique. Strong and diffuse reflections of the scroll nanotube were studied and explicit formulas that govern relations between the direct and reciprocal lattice of the scroll nanotube are achieved.