2D Nanocrystals Research Articles

Chiral Inorganic Nanomaterials Characterized by Advanced TEM: A Qualitative and Quantitative Study.

Chiral inorganic nanomaterials (CINMs) have garnered significant interest due to their exceptional optical, electronic, and catalytic properties, offering promising advancements in energy conversion, data storage, catalysis, and biomedicine. While traditional optical spectrophotometers reveal the chiroptical performance of CINMs on an ensemble level, the direct structural visualization for the qualitative and quantitative discernment of their chiral features has become increasingly distinct with the advancements of transmission electron microscopy (TEM) techniques. The need for reasonable and high-standard discrimination requirements of CINMs has driven the progress of chirality-based TEM technologies. Therefore, this review in the good season takes the initiative to summarize the current advancements in TEM technologies for CINMs characterization, emphasizing a qualitative analysis of chiral atomic-level features, 0D, 1D, and 2D nanocrystals, and assembled nanomaterials. Then, the quantitative methods for determining chirality is also highlighted, such as 3D electron tomography, and further address the evolution of chiral structures monitored by the Ex-situ and In-situ TEM technologies. By providing a roadmap for the current challenges and proposing future advancements in TEM technologies for the qualitative, quantitative, and real-time analysis of CINMs, it can drive innovations in the field of chiral nanomaterials as well as the development of TEM technologies.

Chirality and Curvature on Protein Adsorption and Osteogenesis

AbstractHere we designed enantiomeric lipid‐mimetic glutamic acid derivatives (L/D‐UG) and investigated their self‐assembled chiral nanostructures’ interaction with the protein adsorption as well as the osteogenesis. It was found that L or D‐UG molecules can self‐assemble into vesicle bilayers and two‐dimensional (2D) nanocrystals via a kinetic and thermodynamic control, respectively. These chiral vesicles and 2D crystals showed differentiated adsorption of proteins, determined by their curvature and chirality. Specifically, fibronectin constituted by L‐amino acids adsorbed preferentially on L‐UG 2D crystal in a semi‐random pattern and L‐2D nanocrystal show as the most effective structures to promote bone regeneration. The controlled vesicle and 2D crystal assemblies with different chirality and curvature helps to clarify their determine roles in protein adsorption and osteogenesis.

Synthesis Route to Single-Walled Zeolite Nanotubes Enabled by Tetrabutylammonium Hydroxide.

Single-walled zeolite nanotubes (ZNT) were recently synthesized in a narrow compositional window. ZNT structural features-thin zeolitic walls and large mesopores-can allow for easy access of small molecules to zeolite micropores, but they also impart processing limitations for these materials, such as challenges with conventional aqueous ion-exchange conditions. Conventional solid- and liquid-phase ion exchange of calcined NaOH-derived ZNT (NaH-ZNT) results in structural degradation to either 2D sheet-like phases, 3D nanocrystals, or amorphous phases, motivating different direct synthesis routes and unconventional ion-exchange procedures of uncalcined ZNT precursors. Here, a modified synthesis route for ZNT synthesis is introduced that facilitates facile ion exchange as well as incorporation of additional non-Al heteroatoms in the zeolite framework. Tetrabutylammonium hydroxide (TBAOH) is used as a hydroxide source and co-OSDA, enabling synthesis of new compositions of ZNT, otherwise unachievable by post-modification of previously reported NaH-ZNT. By varying the gel composition, synthesis temperature, crystallization time, hydroxide source, silicon source, and aluminum source, productive conditions for the new TBAOH synthesis are developed, leading to increased strong acid site density in the ZNT. The collected results demonstrate the sensitivity of the ZNT synthesis to many key parameters and show that the ZNT forms only when Si/(Al + T) ∼ 30 in these synthesis gels and with specific Si and Al sources, and always in the presence of trace Na+. Catalytic testing, via the tandem CO2 hydrogenation to methanol and methanol to aromatics reaction, shows that ZNTs provide adequate catalytic activity (acidity), relative to their conventional 3D counterparts in converting methanol to aromatic compounds.

Versatile stochastic model for predictive KMC simulation of fcc metal nanostructure evolution with realistic kinetics.

Stochastic lattice-gas models provide the natural framework for analysis of the surface diffusion-mediated evolution of crystalline metal nanostructures on the appropriate time scale (often 101-104s) and length scale. Model behavior can be precisely assessed by kinetic Monte Carlo simulation, typically incorporating a rejection-free algorithm to efficiently handle the broad range of Arrhenius rates for hopping of surface atoms. The model should realistically prescribe these rates, or the associated barriers, for a diversity of local surface environments. However, commonly used generic choices for barriers fail, even qualitatively, to simultaneously describe diffusion for different low-index facets, for terrace vs step edge diffusion, etc. We introduce an alternative Unconventional Interaction-Conventional Interaction formalism to prescribe these barriers, which, even with few parameters, can realistically capture most aspects of behavior. The model is illustrated for single-component fcc metal systems, mainly for the case of Ag. It is quite versatile and can be applied to describe both the post-deposition evolution of 2D nanostructures in homoepitaxial thin films (e.g., reshaping and coalescence of 2D islands) and the post-synthesis evolution of 3D nanocrystals (e.g., reshaping of nanocrystals synthesized with various faceted non-equilibrium shapes back to 3D equilibrium Wulff shapes).

Chirality and Curvature on Protein Adsorption and Osteogenesis.

Here we designed enantiomeric lipid-mimetic glutamic acid derivatives (L/D-UG) and investigated their self-assembled chiral nanostructures' interaction with the protein adsorption as well as the osteogenesis. It was found that L or D-UG molecules can self-assemble into vesicle bilayers and two-dimensional (2D) nanocrystals via a kinetic and thermodynamic control, respectively. These chiral vesicles and 2D crystals showed differentiated adsorption of proteins, determined by their curvature and chirality. Specifically, fibronectin constituted by L-amino acids adsorbed preferentially on L-UG 2D crystal in a semi-random pattern and L-2D nanocrystal show as the most effective structures to promote bone regeneration. The controlled vesicle and 2D crystal assemblies with different chirality and curvature helps to clarify their determine roles in protein adsorption and osteogenesis.

CsPbBr3 Perovskite Crack Platelet Nanocrystals and Their Biexciton Generation.

Lead halide perovskite nanocrystals have been extensively studied in recent years as efficient optical materials for their bright and color-tunable emissions. However, these are mostly confined to their 3D nanocrystals and limited to the anisotropic nanostructures. By exploring the Cs-sublattice-induced metal(II) ion exchange with Pb(II), crack CsPbBr3 perovskite platelet nanocrystals having polar surfaces in all three directions are reported here, which remained different than reported standard square platelets. The crack platelets are also passivated with halides to enhance their brightness. Further, as these crack and passivated crack platelets have defects and polar surfaces, the exciton and biexciton generation in these platelets is investigated using femtosecond photoluminescence and transient absorption measurement at ambient as well as cryogenic temperatures, correlated with time-resolved single-particle photoluminescence spectroscopy, and compared with standard square platelets having nonpolar facets. These investigations revealed that the crack platelets and passivated crack platelets possess enhanced biexciton emission compared to square platelets due to the presence of polar surfaces in all three directions. These results provide insights into not only the design of the anisotropic nanostructures of ionic nanocrystals but also the possibility of tuning the single exciton to biexciton generation efficiency, which has potential applications in optoelectronic systems.

Two-dimensional crystallization of precise side-chain giant molecules with constant building blocks ratio

This paper describes the two-dimensional (2D) crystallization of side-chain giant molecules (SCGMs) having the fixed number ratio of two types of functionalized building blocks with 1:1. SCGMs are regarded to a certain degree as size-amplified versions of universal synthetic polymers that are prepared by precisely connecting molecular nanoparticles (MNPs) to polymer chains. Our previous experimental results have shown that individually changing the number ratio of one of the building blocks would significantly affect the structural parameters of molecular crystals, mainly the longitudinal thickness. Herein, we systematically discussed the 2D crystallization of two categories of POSS-based SCGMs with constant building blocks ratio. Solution self-assembly of such SCGMs resulted in well-defined 2D nanosheets with similar structural configurations, showing great tolerance in the number of building blocks. Subsequently, we proposed a “sandwiched-type” mode to illustrate the bilayer 2D supramolecular framework, in which crystalline blocks pack in head-to-head manner. In addition, sequence isomers provide an ideal platform to further verify that the thickness of 2D nanocrystal is linked with the tethering density determined by the number ratio of building blocks. We believe that this study could be a better complement to our previous work and then make us to be more in-depth understand the crystallization mechanism of SCGMs.

Charge Transfer from Quantum-Confined 0D, 1D, and 2D Nanocrystals.

The properties of colloidal quantum-confined semiconductor nanocrystals (NCs), including zero-dimensional (0D) quantum dots, 1D nanorods, 2D nanoplatelets, and their heterostructures, can be tuned through their size, dimensionality, and material composition. In their photovoltaic and photocatalytic applications, a key step is to generate spatially separated and long-lived electrons and holes by interfacial charge transfer. These charge transfer properties have been extensively studied recently, which is the subject of this Review. The Review starts with a summary of the electronic structure and optical properties of 0D-2D nanocrystals, followed by the advances in wave function engineering, a novel way to control the spatial distribution of electrons and holes, through their size, dimension, and composition. It discusses the dependence of NC charge transfer on various parameters and the development of the Auger-assisted charge transfer model. Recent advances in understanding multiple exciton generation, decay, and dissociation are also discussed, with an emphasis on multiple carrier transfer. Finally, the applications of nanocrystal-based systems for photocatalysis are reviewed, focusing on the photodriven charge separation and recombination processes that dictate the function and performance of these materials. The Review ends with a summary and outlook of key remaining challenges and promising future directions in the field.

Mechanical Properties of Small Quasi-Square Graphene Nanoflakes

The rise of straintronics—the possibility of fine-tuning the electronic properties of nanosystems by applying strain to them—has enhanced the interest in characterizing the mechanical properties of these systems when they are subjected to tensile (or compressive), shear and torsion strains. Four parameters are customarily used to describe the mechanical behavior of a macroscopic solid within the elastic regime: Young’s and shear moduli, the torsion constant and Poisson’s ratio. There are some relations among these quantities valid for elastic continuous isotropic systems that are being used for 2D nanocrystals without taking into account the non-continuous anisotropic nature of these systems. We present in this work computational results on the mechanical properties of six small quasi-square (aspect ratio between 0.9 and 1.1) graphene nanocrystals using the PM7 semiempirical method. We use the results obtained to test the validity of two relations derived for macroscopic homogeneous isotropic systems and sometimes applied to 2D systems. We show they are not suitable for these nanostructures and pinpoint the origin of some discrepancies in the elastic properties and effective thicknesses reported in the literature. In an attempt to recover one of these formulas, we introduce an effective torsional thickness for graphene analogous to the effective bending thickness found in the literature. Our results could be useful for fitting interatomic potentials in molecular mechanics or molecular dynamics models for finite carbon nanostructures, especially near their edges and for twisted systems.

Hydrothermally grown pure and Er-doped ZnS nanocrystals based flexible piezoelectric nanogenerator for energy harvesting and sensing applications

Pure zinc sulphide (ZnS) and Er-doped ZnS nanocrystals were grown by hydrothermal method at low temperature. Powder XRD analysis reveals the formation of wurtzite hexagonal phase structure for both pure and Er-doped ZnS samples. Morphology of 2D nanocrystals for both pure and doped ZnS nanocrystals was confirmed by FESEM technique. Presence of Er element in Er-doped ZnS was confirmed by energy-dispersive X-ray spectroscopy. Further, both pure and Er-doped nanocrystals have been used as piezoelectric fillers in polydimethylsiloxane (PDMS) for the fabrication of flexible piezoelectric nanogenerators. The Er-doped ZnS based nanogenerator showed almost 9 times (∼ 36 V) higher open circuit voltage as compared to pure ZnS based nanogenerator (∼ 4 V). Then, Er-doped ZnS nanocrystals based device was used to harvest the mechanical energy under the human walking and running conditions. Also, this device generated significant electrical signal under the human elbow bending. The output performances of Er-doped ZnS based device indicates that it can be a potential candidate for mechanical energy harvesting under various human body motions as well as for wearable piezoelectric sensor applications.

Energy transfer enhanced photoluminescence of 2D/3D CsPbBr3 hybrid assemblies.

Energy transfer has been proven to be an effective method to optimize optoelectronic conversion efficiency by improving light absorption and mitigating nonradiative losses. We prepared 2D/3D CsPbBr3 hybrid assemblies at different reaction temperatures using the hot injection method and found that the photoluminescence quantum yields (PLQYs) of these hybrids were greatly enhanced from 53.4% to 72.57% compared with 3D nanocrystals (NCs). Femtosecond transient absorption measurements were used to study the PLQY enhancement mechanisms, and it was found that the hot carrier lifetime improved from 0.36 to 1.88ps for 2D/3D CsPbBr3 hybrid assemblies owing to the energy transfer from 2D nanoplates to 3D NCs. The energy transfer benefits the excited carrier accumulation and prolonged hot carrier lifetime in 3D NCs in hybrid assemblies, as well as PLQY enhancement in materials.

Rewritable Photoluminescence and Structural Color Display for Dual-Responsive Optical Encryption.

Optical encryption using coloration and photoluminescent (PL) materials can provide highly secure data protection with direct and intuitive identification of encrypted information. Encryption capable of independently controlling wavelength-tunable coloration as well as variable light intensity PL is not adequately demonstrated yet. Herein, a rewritable PL and structural color (SC) display suitable for dual-responsive optical encryption developed with a stimuli-responsive SC of a block copolymer (BCP) photonic crystal (PC) with alternating in-plane lamellae, of which a variety of 3D and 2D perovskite nanocrystals is preferentially self-assembled with characteristic PL, is presented. The SC of a BCP PC is controlled in the visible range with different perovskite precursor doping times. The perovskite nanocrystals developed in the BCP PC are highly luminescent, with a PL quantum yield of ≈33.7%, yielding environmentally stable SC and PL dual-mode displays. The independently programmed SC and PL information is erasable and rewritable. Dual-responsive optical encryption is demonstrated, in which true Morse code information is deciphered only when the information encoded by SCs is properly combined with PL information. Numerous combinations of SC and PL realize high security level of data anticounterfeiting. This dual-mode encryption display offers novel optical encryption with high information security and anti-counterfeiting.

Revealing Two Distinct Formation Pathways of 2D Wurtzite‐CdSe Nanocrystals Using In Situ X‐Ray Scattering

AbstractUnderstanding the mechanism underlying the formation of quantum‐sized semiconductor nanocrystals is crucial for controlling their synthesis for a wide array of applications. However, most studies of 2D CdSe nanocrystals have relied predominantly on ex situ analyses, obscuring key intermediate stages and raising fundamental questions regarding their lateral shapes. Herein, the formation pathways of two distinct quantum‐sized 2D wurtzite‐CdSe nanocrystals — nanoribbons and nanosheets — by employing a comprehensive approach, combining in situ small‐angle X‐ray scattering techniques with various ex situ characterization methods is studied. Although both nanostructures share the same thickness of ≈1.4 nm, they display contrasting lateral dimensions. The findings reveal the pivotal role of Se precursor reactivity in determining two distinct synthesis pathways. Specifically, highly reactive precursors promote the formation of the nanocluster‐lamellar assemblies, leading to the synthesis of 2D nanoribbons with elongated shapes. In contrast, mild precursors produce nanosheets from a tiny seed of 2D nuclei, and the lateral growth is regulated by chloride ions, rather than relying on nanocluster‐lamellar assemblies or Cd(halide)2–alkylamine templates, resulting in 2D nanocrystals with relatively shorter lengths. These findings significantly advance the understanding of the growth mechanism governing quantum‐sized 2D semiconductor nanocrystals and offer valuable guidelines for their rational synthesis.

Efficient Near‐Infrared Light‐Emitting Diodes Based on CdHgSe Nanoplatelets

AbstractCadmium mercury selenide (CdHgSe) nanocrystals exhibit a unique combination of low‐energy optical absorption and emission, which can be tuned from the visible to the infrared range through both quantum confinement and adjustment of their composition. Owing to this advantage, such nanocrystals have been studied as a promising narrow‐band infrared light emitter. However, the electroluminescence of CdHgSe‐based nanocrystals has remained largely unexplored, despite their potential for emitting light in the telecom wavelength range. Further benefits to their optical properties are expected from their shape control, in particular the formation of 2D nanocrystals, as well as from a proper design of their heterostructures. In this work, a colloidal synthesis of CdHgSe/ZnCdS core/shell nanoplatelets (NPLs) starting from CdSe template NPLs employing a cation exchange strategy is developed. The heterostructures synthesized exhibit photoluminescence that can be tuned from ≈1300 to 1500 nm. These near‐infrared‐active NPLs are employed in light‐emitting diodes, demonstrating low turn‐on voltage and high external quantum efficiency.

Retrospect and Prospect: Nanoarchitectonics of Platinum‐Group‐Metal‐Based Materials

AbstractNanoarchitectonics, a concept encompassing nanoscale microstructures and atomic arrangements in materials, enables the precise modification of materials for desired applications by controlling their physical and chemical properties, as well as surface charge or energy. Particularly in metal materials, where surface reactions play a critical role, nanoarchitecture becomes the most influential factor affecting activity, selectivity, and stability. Focusing on platinum‐group metals (PGMs) due to their inherently high efficiency in energy and environmental applications, this article provides a comprehensive review of synthetic methods for the morphological control of metal nanomaterials. The morphological control is classified into atomic arrangements in 0D, 1D, and 2D nanocrystals, as well as nanoporous structures, and the mechanisms of major reactions are covered in detail. Each chapter is supplemented with a table featuring several examples, facilitating the reader's understanding of the structural controls of PGMs. Finally, the article outlines future challenges in achieving novel metal nanoarchitecture. The hope is that this review provides valuable insights into the synthesis of PGM‐based nanomaterials and serves as a guide for designing and synthesizing innovative metal nanostructures for diverse applications.

Hydrophobic Chain-Induced Conversion of Three-Dimensional Perovskite Nanocrystals to Gold Nanocluster-Grafted Two-Dimensional Platelets for Photoinduced Electron Transfer Substrate Formulation.

Considering the augmentation of new generation energy harvesting devices and applications of electron-hole separation therein, conversion of 3D cubic CsPbBr3 perovskite nanocrystals into 2D-platelets through ligand-ligand hydrophobic interactions has been conceived here. Cationic surfactants with various chain length coated the gold nanoclusters (AuNCs) that interact with oleic acid (OA) and oleylamine (OAm) coated 3D CsPbBr3 nanocrystals to disintegrate the crystallinity of the perovskites and reformation of AuNC-grafted 2D-platelets of unusually large size. The planar perovskite-derivatives act as an exciton donor to the embedded AuNCs through photoinduced electron transfer (PET). This process is controlled by the optimum surfactant chain length. Transient absorption spectroscopy shows that the fastest radical growth time (4 ps) was with the 14-carbon containing tail of the surfactant, followed by the 16-carbon (45 ps) and the 12-carbon (290 ps) ones. PET is administered by the energy gaps of the participating candidates that control the transition dynamics. Our findings can be a potential tool to develop metal nanocluster-based hybrid 2D perovskite-derived platelets for optoelectronic applications.

Real-Time In Situ Observation of CsPbBr3 Perovskite Nanoplatelets Transforming into Nanosheets.

The manipulation of nano-objects through heating is an effective strategy for inducing structural modifications and therefore changing the optoelectronic properties of semiconducting materials. Despite its potential, the underlying mechanism of the structural transformations remains elusive, largely due to the challenges associated with their in situ observations. To address these issues, we synthesize temperature-sensitive CsPbBr3 perovskite nanoplatelets and investigate their structural evolution at the nanoscale using in situ heating transmission electron microscopy. We observe the morphological changes that start from the self-assembly of the nanoplatelets into ribbons on a substrate. We identify several paths of merging nanoplates within ribbons that ultimately lead to the formation of nanosheets dispersed randomly on the substrate. These observations are supported by molecular dynamics simulations. We correlate the various paths for merging to the random orientation of the initial ribbons along with the ligand mobility (especially from the edges of the nanoplatelets). This leads to the preferential growth of individual nanosheets and the merging of neighboring ones. These processes enable the creation of structures with tunable emission, ranging from blue to green, all from a single material. Our real-time observations of the transformation of perovskite 2D nanocrystals reveal a route to achieve large-area nanosheets by controlling the initial orientation of the self-assembled objects with potential for large-scale applications.

A clever trilayer assembly strategy for 2D materials

Recently in Matter, Hu et al. developed a trilayer structure composed of 2D materials, intermediate layer, and substrate, which enabled decoupling of the mono-mode instabilities and designable deterministic mode toward self-assembly of atomically thin 2D materials. The strategy is universal for different 2D materials and induces anisotropic piezoresistive and mechanical-optoelectrical coupling effects, being utilized for fabrication of highly sensitive and ultra-fast responsive mechanical sensors. Recently in Matter, Hu et al. developed a trilayer structure composed of 2D materials, intermediate layer, and substrate, which enabled decoupling of the mono-mode instabilities and designable deterministic mode toward self-assembly of atomically thin 2D materials. The strategy is universal for different 2D materials and induces anisotropic piezoresistive and mechanical-optoelectrical coupling effects, being utilized for fabrication of highly sensitive and ultra-fast responsive mechanical sensors. Deterministically self-assembled 2D materials and electronicsHu et al.MatterApril 10, 2023In BriefMode-decoupled instability-driven deterministic self-assemblies, including deterministic mode, scale, direction, and dynamic self-assembly, of atomically thin 2D nanocrystals are achieved by overcoming the key problem of mechanical instability mode manipulation from randomness to determinism. The deterministic self-assemblies endow unique properties distinct from those of their parent 2D materials, such as anisotropic piezoresistive effects. Benefited from the properties induced by deterministic self-assemblies, we report a concept of deterministically self-assembled micro/nano-electronics of 2D materials, such as 3D anisotropic tactile sensors. Full-Text PDF

Colloidal 2D Lead Chalcogenide Nanocrystals: Synthetic Strategies, Optical Properties, and Applications.

Lead chalcogenide nanocrystals (NCs) are an emerging class of photoactive materials that have become a versatile tool for fabricating new generation photonics devices operating in the near-IR spectral range. NCs are presented in a wide variety of forms and sizes, each of which has its own unique features. Here, we discuss colloidal lead chalcogenide NCs in which one dimension is much smaller than the others, i.e., two-dimensional (2D) NCs. The purpose of this review is to present a complete picture of today's progress on such materials. The topic is quite complicated, as a variety of synthetic approaches result in NCs with different thicknesses and lateral sizes, which dramatically change the NCs photophysical properties. The recent advances highlighted in this review demonstrate lead chalcogenide 2D NCs as promising materials for breakthrough developments. We summarized and organized the known data, including theoretical works, to highlight the most important 2D NC features and give the basis for their interpretation.

Sculpting In-plane Fractal Porous Patterns in Two-Dimensional MOF Nanocrystals for Photoelectrocatalytic CO2 Reduction.

Herein, by choosing few-nm-thin two-dimensional (2D) nanocrystals of MOF-5 containing in-planner square lattices as a modular platform, a crystal lattice-guided wet-chemical etching has been rationally accomplished. As a result, two attractive pore patterns carrying Euclidean curvatures; precisely, plus(+)-shaped and fractal-patterned pores via ⟨100⟩ and ⟨110⟩ directional etching, respectively, are regulated in contrast to habitually formed spherical-shaped random etches on MOF surface. In agreement with the theoretical calculations, a diffusion-limited etching process has been optimized to devise high-yield of size-tunable fractal-pores on the MOF surface that tenders for a compatibly high payload of catalytic ReI -complexes using the existing large edge area once modified into a free amine-group-exposed inner pore surface. Finally, on benefiting from the long-range fractal opening in 2D MOF support structure, while loaded on an electrode surface, a facilitated cross-interface charge-transportation and well-exposure of immobilized ReI -catalysts are anticipated, thus realizing enhanced activity and stability of the supported catalyst in photoelectrochemical CO2 -to-CO reduction.