2D Building Blocks Research Articles

Protonated Organic Diamines as Templates for Layered and Microporous Structures: Synthesis, Crystal Chemistry, and Structural Trends among the Compounds Formed in Aqueous Systems Transition Metal Halide or Nitrate-Diamine-Selenious Acid.

Systematic studies of crystalline compounds formed in aqueous systems containing aliphatic diamines, divalent transition metal halides, and selenious acid resulted in the discovery of a large family of new complex species corresponding to several new structure types. With ethylenediamine (en), layered (enH2)[M(HSeO3)2X2] compounds are the most commonly formed species which constitute a significant contribution to the family of layered hydrogen selenites containing neutral [M(HSeO3)2] (M = Mg, Mn, Co, Ni, Cu, Zn, Cd) 2D building blocks. In contrast to some previous suggestions, piperazine (pip), as well as its homologue N-methylpiperazine, mostly give rise to quite different, sometimes more complex, structures of varied dimensionality while the (pipH2)[M(HSeO3)2X2] compounds are formed only with M = Cu and Cd. In addition, metal-, halide-, or selenium-free by-product species are observed. The SeIV can be present in a multitude of forms, including H2SeO3, HSeO3-, SeO32-, and Se2O52-, reflecting amazing adaptability to the shape of the templating cations.

1D Van der Waals Polymers with Nonlinear Optical Performance Approaching Theoretical Upper Limit

AbstractNonlinear optical (NLO) materials are of great importance for applications in lasers, atomic clocks, free‐space communication, etc. Herein, inspired by the recent prediction of excellent second harmonic generation (SHG) performance in van der Waals (vdW) materials with 1D building blocks, 14 new NLO materials are found from 244 bulk crystals constructed with 1D polymers using high‐throughput first‐principles calculations. Nearly half of the new NLO materials exhibit superior NLO performance with SHG susceptibilities approaching the theoretical upper limit. The 2D form of 11 candidates inherits the NLO property covering UV, visible, and infrared regions. Bader charge analysis reveals that the SHG susceptibility is determined by the charge difference of ions on the chains. Finally, it is proposed that superior NLO materials can be found in materials with proper bandgaps and large charge differences on the chains. This work not only screens out candidates with outstanding NLO performance in vdW materials with 1D building blocks but also provides a guideline for the search and design of NLO vdW 1D polymer patterns with excellent NLO properties.

Topology Hierarchy of Transition Metal Dichalcogenides Built from Quantum Spin Hall Layers.

The evolution of the physical properties of two-dimensional material from monolayer limit to the bulk reveals unique consequences from dimension confinement and provides a distinct tuning knob for applications. Monolayer 1T'-phase transition metal dichalcogenides (1T'-TMDs) with ubiquitous quantum spin Hall (QSH) states are ideal two-dimensional building blocks of various three-dimensional topological phases. However, the stacking geometry was previously limited to the bulk 1T'-WTe2 type. Here, we introduce the novel 2M-TMDs consisting of translationally stacked 1T'-monolayers as promising material platforms with tunable inverted bandgaps and interlayer coupling. By performing advanced polarization-dependent angle-resolved photoemission spectroscopy as well as first-principles calculations on the electronic structure of 2M-TMDs, we revealed a topology hierarchy: 2M-WSe2 , MoS2, and MoSe2 are weak topological insulators (WTIs), whereas 2M-WS2 is a strong topological insulator (STI). Further demonstration of topological phase transitions by tunning interlayer distance indicates that band inversion amplitude and interlayer coupling jointly determine different topological states in 2M-TMDs. We propose that 2M-TMDs are parent compounds of various exotic phases including topological superconductors and promise great application potentials in quantum electronics due to their flexibility in patterning with two-dimensional materials. This article is protected by copyright. All rights reserved.

3D Printing of Ultralow-Concentration 2D Nanomaterial Inks for Multifunctional Architectures.

The direct 3D printing of ultralight architectures with ultralow-concentration 2D nanomaterial inks is necessary yet challenging. Here, we describe an emulsion-based ink for direct printing using 2D nanomaterials, i.e., MXene and graphene oxide (GO). The electrostatic interactions between the ligands in the oil phase and the 2D nanomaterials in the aqueous phase help form sheet-like surfactants at the interface. The interactions between the anchored ligands among different droplets dictate the rheological characteristics of inks, enabling a gel-like behavior ideally suitable for 3D printing at ultralow concentrations of 2D nanomaterials. The 3D printed foams possess lightweight structures with densities of 2.8 mg cm-3 (GO-based) and 4.1 mg cm-3 (MXene-based), and the latter integrates outstanding electrical conductivity, electromagnetic shielding performance, and thermal insulation comparable to air. This work describes a general approach for direct-printing ultralight porous structures that take advantage of the inherent properties of 2D building blocks.

Only gold can pull this off: mechanical exfoliations of transition metal dichalcogenides beyond scotch tape

Following in graphene’s wake, the scotch tape method became the key enabler for the preparation of 2D materials, providing easy access to high-quality materials mainly limited by low yield. At this time, transition metal dichalcogenides (TMDC) received tremendous attention as a promising class of two-dimensional (2D) semiconductors. The motivation to reach the 2D limit of TMDCs and many other layered materials has long been set, and with the rise of gold-mediated exfoliations towards the millimeter scale, the stacking of these 2D single-layer building blocks into artificial 3D lattices is more relevant than ever. On this note, this review presents the recent developments in gold-mediated exfoliations beyond scotch tape, accompanied by a methods walkthrough for such a process. These matured gold exfoliations unlock a whole palette of 2D building blocks, ready for the assembly of macroscopic van der Waals heterostructures, or twistronics. Ultimately, mechanical exfoliation as a key enabler for high-quality single layers, evolved from scotch tape to gold, and became an even more potent tool in the process.

Non‐artificial Layered Heterostructure as Inch‐size Single Crystal for Shortwave Polarized‐Light Array Detector

AbstractLayered heterostructures of different 2D building blocks have invigorated the booming of 2D materials toward high‐performance optoelectronic devices. However, contrary to the typical artificial multi‐component form, the engineering of non‐artificial layered heterostructure into single‐phase crystals and resultant properties are largely overlooked. Here, for the first time, an inch‐sized single crystal of a non‐artificial layered heterostructure is exploited, (PbBr2)2(AMTP)2PbBr4 (1, AMTP is 4‐ammoniomethyltetrahydropyran), serving as polarization‐sensitive candidate. Notably, it adopts an interleaved architecture of 2D perovskite slabs with the distinct non‐perovskite lattice, thus forming a self‐assembled perovskite‐intergrowth layered heterostructure. This motif leads to new electronic transitions distributed across two sublattices and affords an inherent in‐plane anisotropy ratio of ≈1.6, beyond some known inorganic materials (e.g., GeSe: 1.44; GeAs: 1.49). Combining this in‐plane anisotropy and wide bandgap (≈2.9 eV), lateral crystal array of 1 enables shortwave polarized‐light detection with ultrahigh responsivity and detectivity under weak illumination compared to some inorganic polarized detectors. As the first demonstration of inch‐sized single crystals of non‐artificial layered heterostructure, this study affords a new platform to explore candidates toward high‐performance optoelectronic devices.

Two-Dimensional Hybrid Nanosheet-Based Supercapacitors: From Building Block Architecture, Fiber Assembly, and Fabric Construction to Wearable Applications.

Fiber-based supercapacitors (F-SCs) have inspired widespread interest in the fields of wearable technology, energy, and carbon neutralization due to their highly deformable flexibility, fast charging/discharging capability, long-term stability, and energy conservation ability. In this review, we summarize the latest developments for fabricating fibrous electrodes of F-SCs where advanced micro two-dimensional (2D) building blocks (e.g., MXene and graphene) are chemically assembled and constructed into ordered mesofibers and multifunctional macrofabrics. Diverse fundamental principles of 2D hybrid nanosheets with respect to surface controls, pseudocapacitive modifications, and microstructural manipulations, promoting rapid electron transfer and charge conduction, are introduced. Additionally, various spinning methods for assembling and fabricating sophisticated fibers with advanced nano/microstructures, including hierarchical skeletons, anisotropic backbones, surface/entire porous frameworks, and vertical-aligned networks, for boosting ionic kinetic transport/storage are presented. Likewise, the structure-activity relationships between the porous structure and electrochemical performance are clarified. Moreover, multifunctional fabrics in terms of high flexibilities/strengths, superior electrical conductivities, and stabilized operations, which realize large energy density, deformable capability, and robust stability under harsh conditions, are emphasized. In particular, the potential power-supply applications, including flexible electronic devices, self-powered functions, and energy-sensor systems, are highlighted. Finally, a short conclusion and outlook, along with the current challenges and future opportunities of next-generation F-SCs, are proposed.

Structural DNA Nanotechnology: Immobile Holliday Junctions to Artifi.

DNA nanotechnology marvels the scientific world with its capabilities to design, engineer, and demonstrate nanoscale shapes. This review is a condensed version walking the reader through the structural developments in the field over the past 40 years starting from the basic design rules of the double-stranded building block to the most recent advancements in self-assembled hierarchically achieved structures to date. It builds from the fundamental motivation of building 3-dimensional (3D) lattice structures of tunable cavities going all the way up to artificial nanorobots fighting cancer. The review starts by covering the most important developments from the fundamental bottom-up approach of building structures, which is the 'tile' based approach covering 1D, 2D, and 3D building blocks, after which the top-down approach using DNA origami and DNA bricks is also covered. Thereafter, DNA nanostructures assembled using not so commonly used (yet promising) techniques like i-motifs, quadruplexes, and kissing loops are covered. Highlights from the field of dynamic DNA nanostructures have been covered as well, walking the reader through various approaches used within the field to achieve movement. The article finally concludes by giving the authors a view of what the future of the field might look like while suggesting in parallel new directions that fellow/future DNA nanotechnologists could think about.

Nanocomposites Prepared from Carbon Nanotubes and the Transition Metal Dichalcogenides WS2 and MoS2 via Surfactant-Assisted Dispersions as Electrocatalysts for Oxygen Reactions.

Fuel cells are emerging devices as clean and renewable energy sources, provided their efficiency is increased. In this work, we prepared nanocomposites based on multiwalled carbon nanotubes (MWNTs) and transition metal dichalcogenides (TMDs), namely WS2 and MoS2, and evaluated their performance as electrocatalysts for the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR), relevant to fuel cells. The one- and two-dimensional (1D and 2D) building blocks were initially exfoliated and non-covalently functionalized by surfactants of opposite charge in aqueous media (tetradecyltrimethylammonium bromide, TTAB, for the nanotubes and sodium cholate, SC, for the dichalcogenides), and thereafter, the three-dimensional (3D) MoS2@MWNT and WS2@MWNT composites were assembled via surfactant-mediated electrostatic interactions. The nanocomposites were characterized by scanning electron microscopy (SEM) and structural differences were found. WS2@MWNT and MoS2@MWNT show moderate ORR performance with potential onsets of 0.71 and 0.73 V vs. RHE respectively, and diffusion-limiting current densities of −1.87 and −2.74 mA·cm−2, respectively. Both materials present, however, better tolerance to methanol crossover when compared to Pt/C and good stability. Regarding OER performance, MoS2@MWNT exhibits promising results, with η10 and jmax of 0.55 V and 17.96 mA·cm−2, respectively. The fabrication method presented here is cost-effective, robust and versatile, opening the doors for the optimization of electrocatalysts’ performance.

Tunable capacitance in all-inkjet-printed nanosheet heterostructures

Heterostructures constructed from two-dimensional (2D) building blocks have shown promise for field-effect transistors, memory devices, photosensors and other electronic applications. 2D nanosheet crystals are typically constructed into multilayer heterostructures using layer-by-layer methods, which cannot be used to fabricate large-scale and thick heterostructures, due to the time-consuming nature and low efficiency of the process. An alternative approach to deposit different 2D materials in the controllable fashion is by inkjet printing. Here we show the fabrication of supercapacitors based on 2D heterostructures by inkjet printing Ti3C2Tx MXene nanosheets as electrodes, followed by inkjet printing graphene oxide nanosheets as solid-state electrolyte. The free water molecules trapped between graphene oxide sheets facilitate proton movement through the layered solid electrolyte. The as-made heterostructures show high areal capacitance, good cycling stability and high areal energy and power densities comparable with existing printed supercapacitors. Moreover, the specific capacitance can be increased further by addition of liquid electrolytes.

Atomic-Scale Studies of Overlapping Grain Boundaries between Parallel and Quasi-Parallel Grains in Low-Symmetry Monolayer ReS2

Summary Grain boundaries (GBs) are significant microstructures that dominate properties of polycrystalline two-dimensional (2D) materials. Low-symmetry rhenium disulfide monolayers provide an ideal platform to investigate diverse configurations of GBs and their orientation-dependent characteristics. Here, we utilize the preferential deposition of platinum-based nanoparticles on grain edges to rapidly locate nanoscale-wide overlapping GBs during microscopic-scale observation. Atomic-resolution investigations by aberration-corrected annular dark-field scanning transmission electron microscopy reveal diverse overlapping GBs constructed by parallel grains with transversal displacement. They prefer to align along several primary lattice directions with different interlayer atomic registries. Calculations show that the electronic band structures of overlapping GBs are strongly direction dependent, suggesting their potential in tunable electronic and photonic devices. Incommensurate overlapping GBs formed by quasi-parallel grains with ultrasmall twist angles are also observed. These results unveil the rich polymorphism of GBs and new opportunities to tailor properties of anisotropic 2D materials via GB engineering.

Vertical Integration of 2D Building Blocks for All‐2D Electronics

Abstract2D materials are promising building blocks for novel electronic devices. It is possible that future electronic devices will be entirely made of 2D materials to fully realize their potential, due to their natural thinness, atomically flat surface/interfaces and diverse properties. In this work, three typical 2D materials, i.e., monolayer molybdenum disulfide (MoS2), hexagonal boron nitride (hBN), and few layer graphene (FLG) serving as semiconducting, dielectric, and contact/gating materials, respectively, are assembled for vertically integrated multilayer devices via the layer‐by‐layer stacking process. An individual layer of all‐2D field effect transistors (FETs) shows comprehensive device performances with parameters of ultralow off‐current ≈100 fA, ultrahigh on/off ratio approaching to 1010, ideal subthreshold swing (SS) ≈100 mV dec−1, and decent room temperature mobility up to 52 cm2 V−1 s−1, benefiting from the effective dual‐gate modulation and high contact quality. Vertically stacked multilayers of all‐2D FETs are successfully achieved with nearly multiplied on‐current density, equivalent device mobility, and persevered on/off ratio and SS of the individual layers. The vertical integration of multilayered devices with different layer functions, e.g., memory, logic and sensor, are further demonstrated. This work provides a technological base for future high‐performance integrated devices based on all‐2D materials.

Frontispiece: Metal Oxide Nanosheets as 2D Building Blocks for the Design of Novel Materials

Two-dimensional metal oxide nanocrystals are often made by a chemical delamination process in water, which involves a layered oxide phase as the starting material. The exfoliated nanosheets have aspect ratios comparable with that of a paper sheet, and they are also very flexible. Oxide nanosheets can be used as building blocks for the construction of improved or entirely new functional materials for a wide range of application areas: nanoelectronics, energy storage, catalysis and tribology, to name just a few. For more details see the Review by J. E. ten Elshof et al. on page 9084 ff.

Metal Oxide Nanosheets as 2D Building Blocks for the Design of Novel Materials

Research into 2‐dimensional materials has soared during the last couple of years. Next to van der Waals type 2D materials such as graphene and h‐BN, less well‐known oxidic 2D equivalents also exist. Most 2D oxide nanosheets are derived from layered metal oxide phases, although few 2D oxide phases can be also made by bottom‐up solution syntheses. Owing to the strong electrostatic interactions within layered metal oxide crystals, a chemical process is usually needed to delaminate them into their 2D constituents. This Review article provides an overview of the synthesis of oxide nanosheets, and methods to assemble them into nanocomposites, mono‐ or multilayer films. In particular, the use of Langmuir–Blodgett methods to form monolayer films over large surface areas, and the emerging use of ink jet printing to form patterned functional films is emphasized. The utilization of nanosheets in various areas of technology, for example, electronics, energy storage and tribology, is illustrated, with special focus on their use as seed layers for epitaxial growth of thin films, and as electrochemically active electrodes for supercapacitors and Li ion batteries.

Advanced Compressible and Elastic 3D Monoliths beyond Hydrogels

Abstract3D monoliths have undergone great progress in the past decades in scientific and engineering fields. Especially, compressible and elastic 3D monoliths (CEMs) hold great promise in a series of applications, such as pressure/strain sensing, energy storage, oil/water separation, and thermal insulation, attributed to their unique mechanical properties and multifunctionality (e.g., conductivity, thermal stability, and high adsorption capacity). Recently, plenty of advanced CEMs have been developed from 1D and 2D building blocks, polymers, and biomass via various methods. Herein, the latest progress in controllable design and preparation of advanced CEMs, which mainly refer to aerogels, sponges, and foams, are reviewed in terms of their structural units and applications. The relationship between structure and mechanical performances of CEMs is discussed. Moreover, their applications in sensing, energy storage and conversion, water treatment, fire‐resistance, and electromagnetic interface shielding are presented. Finally, the challenges and future opportunities of CEMs are also discussed.

Ethanol Assisted Transfer for Clean Assembly of 2D Building Blocks and Suspended Structures

AbstractAs two dimensional materials (2D materials) demonstrate unique and diverse properties, clean transfer methods can serve a cornerstone for creative assembly of these 2D building blocks for both fundamental explorations and versatile applications. One of the major challenges for preserving the pristine properties of 2D materials during transfer and construction is to debond 2D materials from original substrates without inducing structural damage and external contamination. In this work, through both molecular dynamic studies and experimental demonstration, it is found that droplets of ethanol, a common and environmental friendly solvent, can be used to effectively reduce the adhesion energy between 2D materials and substrates, and therefore enable a clean transfer method for 2D mterials. Various assembled structures based on 2D building blocks, such as van der Waals heterostructures, predesigned artificial patterns, 2D materials on suspended devices are all demonstrated. Thermal conductivity measurements of MoS2 nanosheets on a suspended microbridge device also confirm the successful application of suspended 2D transfer. It is expected that this ethanol assisted transfer method can enable clean assembly of 2D building blocks for construction of novel structures and suspended devices.

Thermal transport in layer-by-layer assembled polycrystalline graphene films

New technologies are emerging which allow us to manipulate and assemble 2-dimensional (2D) building blocks, such as graphene, into synthetic van der Waals (vdW) solids. Assembly of such vdW solids has enabled novel electronic devices and could lead to control over anisotropic thermal properties through tuning of inter-layer coupling and phonon scattering. Here we report the systematic control of heat flow in graphene-based vdW solids assembled in a layer-by-layer (LBL) fashion. In-plane thermal measurements (between 100 K and 400 K) reveal substrate and grain boundary scattering limit thermal transport in vdW solids composed of one to four transferred layers of graphene grown by chemical vapor deposition (CVD). Such films have room temperature in-plane thermal conductivity of ~400 Wm−1 K−1. Cross-plane thermal conductance approaches 15 MWm−2 K−1 for graphene-based vdW solids composed of seven layers of graphene films grown by CVD, likely limited by rotational mismatch between layers and trapped particulates remnant from graphene transfer processes. Our results provide fundamental insight into the in-plane and cross-plane heat carrying properties of substrate-supported synthetic vdW solids, with important implications for emerging devices made from artificially stacked 2D materials.

Influence of Pore Size on the van der Waals Interaction in Two-Dimensional Molecules and Materials.

Despite the importance of porous two-dimensional (2D) molecules and materials in advanced technological applications, the question of how the void space in these systems affects the van der Waals (vdW) scaling landscape has been largely unanswered. Analytical and numerical models presented herein demonstrate that the mere presence of a pore leads to markedly different vdW scaling across nonasymptotic distances, with certain relative pore sizes yielding effective power laws ranging from simple monotonic decay to the formation of minima, extended plateaus, and even maxima. These models are in remarkable agreement with first-principles approaches for the 2D building blocks of covalent organic frameworks (COFs), and reveal that COF macrocycle dimers and periodic bilayers exhibit unique vdW scaling behavior that is quite distinct from their nonporous analogs. These findings extend across a range of distances relevant to the nanoscale, and represent a hitherto unexplored avenue towards governing the self-assembly of complex nanostructures from porous 2D molecules and materials.

Atomically Thin Two-Dimensional Nanosheets with Tunable Spin-Crossover Properties.

Combining the fascinating advantages of ultrathin two-dimensional (2D) nanosheets with the nanostructuration of spin-crossover (SCO) materials represents an attractive target of controlled fabrication of SCO nano-objects at the device level. Here, we demonstrate that through facile-operating ultrasonic force-assisted liquid exfoliation technology the three-dimensional (3D) van der Waals SCO bulk precursor {[Fe(1,3-bpp)2(NCS)2]2 (1, 1,3-bpp = 1,3-di(4-pyridyl)-propane)} can be exfoliated into single-layered 2D nanosheets (NS-1). As a consequence, the magnetism has been tuned from complete paramagnetic (bulk precursors) to SCO transition at around 250 K (2D nanosheets). In addition, the metal-to-ligand charge transition (MLCT), the intraligand π-π* transition and the color display also have been altered both in colloidal suspension and in the solid state. These dramatic changes of physical-chemical properties at different forms and states can be attributed to the efficient cooperativity derived from the interlayer van der Waals interactions within the curly or vertically stacked 2D building blocks.

Redox-Responsive and Thermoresponsive Supramolecular Nanosheet Gels with High Young's Moduli.

Supramolecular gels made from 2D building blocks are emerging as one of the novel multifunctional soft materials for various applications. This study reports on a class of supramolecular nanosheet gels formed through a reversible self-assembly process involving both intramolecular folding and intermolecular self-assembly of poly[oligo(ethylene glycol)-co-(phenyl-capped bithiophenes)]. Such hierarchical self-assembled structure allows the gels to switch between sol and gel states under either redox or thermostimulus. Moreover, the gels illustrate high Young's moduli, compared to their controls that are made from the same oligo(ethylene glycol) and phenyl-capped bithiophenes blocks but have highly covalent-crosslinked structures. The example might open a window for emerging supramolecular 2D materials to develop mechanically robust and stimuli-responsive soft materials without compromising their intrinsic functions.