Achieving metal-like catalysis from semiconductor for on-surface synthesis.

Free of posttransfer, on-surface synthesis (OSS) of single-atomic-layer nanostructures directly on semiconductors holds considerable potential for next-generation devices. However, due to the high diffusion barrier and abundant defects on semiconductor surfaces, extended and well-defined OSS on semiconductors has major difficulty. Furthermore, given semiconductors' limited thermal catalytic activity, initiating high-barrier reactions remains a significant challenge. Herein, using TiO2(011) as a prototype, we present an effective strategy for steering the molecule adsorption and reaction processes on semiconductors, delivering lengthy graphene nanoribbons with extendable widths. By introducing interstitial titanium (Tiint) and oxygen vacancies (Ov), we convert TiO2(011) from a passive supporting template into a metal-like catalytic platform. This regulation shifts electron density and surface dipoles, resulting in tunable catalytic activity together with varied molecule adsorption and diffusion. Cyclodehydrogenation, which is inefficient on pristine TiO2(011), is markedly improved on Tiint/Ov-doped TiO2. Even interribbon cyclodehydrogenation is achieved. The final product's dimensions, quality, and coverage are all controllable. Tiint doping outperforms Ov in producing regular and prolonged products, whereas excessive Tiint compromises molecule landing and coupling. This work demonstrates the crucial role of semiconductor substrates in OSS and advances OSS on semiconductors from an empirical trial-and-error methodology to a systematic and controllable paradigm.

Toward Fully Multiferroic van der Waals SpinFETs: Basic Design and Quantum Calculations.

Manipulating spin transport enhances the functionality of electronic devices, allowing them to surpass physical constraints related to speed and power. For this reason, the use of van der Waals multiferroics at the interface of heterostructures offers promising prospects for developing high-performance devices, enabling the electrical control of spin information. Our work focuses primarily on a mechanism for multiferroicity in two-dimensional van der Waals materials that stems from an interplay between antiferromagnetism and the breaking of inversion symmetry in certain bilayers. We provide evidence for spin-electrical couplings that include manipulating van der Waals multiferroic edges via external voltages and the subsequent control of spin transport including for fully multiferroic spin field-effect transistors.

Bottom-up Synthesis and Characterization of Porous 12-Atom-Wide Armchair Graphene Nanoribbons.

Although several porous carbon/graphene nanoribbons (GNRs) have been prepared, a direct comparison of the electronic properties between a nonporous GNR and its periodically perforated counterpart is still missing. Here, we report the synthesis of porous 12-atom-wide armchair-edged GNRs from a bromoarene precursor on a Au(111) surface via hierarchical Ullmann and dehydrogenative coupling. The selective formation of porous 12-GNRs was achieved through thermodynamic and kinetic reaction control combined with tailored precursor design. The structure and electronic properties of the porous 12-GNR were elucidated by scanning tunneling microscopy/spectroscopy and density functional theory calculations, revealing that the pores induce a 2.17 eV band gap increase compared to the nonporous 12-AGNR on the same surface.

Electronic Structure of Isolated Graphene Nanoribbons in Solution Revealed by Two-Dimensional Electronic Spectroscopy.

Structurally well-defined graphene nanoribbons (GNRs) are nanostructures with unique optoelectronic properties. In the liquid phase, strong aggregation typically hampers the assessment of their intrinsic properties. Recently we reported a novel type of GNRs, decorated with aliphatic side chains, yielding dispersions consisting mostly of isolated GNRs. Here we employ two-dimensional electronic spectroscopy to unravel the optical properties of isolated GNRs and disentangle the transitions underlying their broad and rather featureless absorption band. We observe that vibronic coupling, typically neglected in modeling, plays a dominant role in the optical properties of GNRs. Moreover, a strong environmental effect is revealed by a large inhomogeneous broadening of the electronic transitions. Finally, we also show that the photoexcited bright state decays, on the 150 fs time scale, to a dark state which is in thermal equilibrium with the bright state, that remains responsible for the emission on nanosecond time scales.

Template Selection Strategy for Synthesis of One-Dimensional CrSbSe3 Ferromagnetic Semiconductor Nanoribbons.

CrSbSe3─the only experimentally validated one-dimensional (1D) ferromagnetic semiconductor─has recently attracted significant attention. However, all reported synthesis methods for CrSbSe3 nanocrystals are based on top-down methods. Here we report a template selection strategy for the bottom-up synthesis of CrSbSe3 nanoribbons. This strategy relies on comparing the formation energies of potential binary templates to the ternary target product. It enables us to select Sb2Se3 with the highest formation energy, along with its 1D crystal structure, as the template instead of Cr2Se3 with the lowest formation energy, thereby facilitating the transformation from Sb2Se3 to CrSbSe3 by replacing half of the Sb atoms in Sb2Se3 with Cr atoms. The as-prepared CrSbSe3 nanoribbons exhibit a length of approximately 5 µm, a width ranging from 80 to 120 nm, and a thickness of about 5 nm. The single CrSbSe3 nanoribbon presents typical semiconductor behavior and ferromagnetism, confirming the intrinsic ferromagnetism in the 1D CrSbSe3 semiconductor.

Tip Growth of Quasi-Metallic Bilayer Graphene Nanoribbons with Armchair Chirality.

Graphene nanoribbons (GNRs), quasi one-dimensional (1D) narrow strips of graphene, have shown promise for high-performance nanoelectronics due to their exceptionally high carrier mobility and structurally tunable bandgaps. However, producing chirality-uniform GNRs on insulating substrates remains a big challenge. Here, we report the successful growth of bilayer GNRs with predominantly armchair chirality and ultranarrow widths (<5 nm) on insulating hexagonal boron nitride (h-BN) substrates using chemical vapor deposition (CVD). The growth of GNRs is catalyzed by transition metal nanoparticles, including Fe, Co, and Ni, through a unique tip-growth mechanism. Notably, GNRs catalyzed by Ni exhibit a high purity (97.3%) of armchair chirality. Electron transport measurements indicate that the ultrathin bilayer armchair GNRs exhibit quasi-metallic behavior. This quasi-metallicity is further supported by density functional theory (DFT) calculations, which reveal a significantly reduced bandgap in bilayer armchair GNRs. The chirality-specific GNRs reported here offer promising advancements for the application of graphene in nanoelectronics.

Atomically Engineered Encapsulation of SnS2 Nanoribbons by Single-Walled Carbon Nanotubes for High-Efficiency Lithium Storage.

Rechargeable lithium-ion batteries are integral to contemporary energy storage, yet current anode material systems struggle to meet the increasing demand for extended range capabilities. This work introduces a novel composite anode material composed of one-dimensional 2H-phase tin disulfide (SnS2) nanoribbons enclosed within cavities of single-walled carbon nanotubes (SnS2@SWCNTs), achieved through precise atomic engineering. Employing aberration-corrected transmission electron microscopy, we precisely elucidated the crystal structure of SnS2 within the confines of the SWCNTs. This deliberate design effectively addresses the inherent limitations of SnS2 as a lithium-ion anode material, including its low electrical conductivity, considerable volume expansion effects, and unstable solid electrolyte interface membrane. Testing confirmed that SnS2 transforms into the Li5Sn2 alloy phase after full lithiation and back to SnS2 after delithiation, showing excellent reversibility. The composite also benefits from edge effects, improving lithium storage through stronger binding and lower migration barriers, which were supported by calculations. This pioneering work advances high-performance anode materials for applications.

Tunable Magnetic Coupling in Graphene Nanoribbon Quantum Dots.

Carbon-based quantum dots (QDs) enable flexible manipulation of electronic behavior at the nanoscale, but controlling their magnetic properties requires atomically precise structural control. While magnetism is observed in organic molecules and graphene nanoribbons (GNRs), GNR precursors enabling bottom-up fabrication of QDs with various spin ground states have not yet been reported. Here the development of a new GNR precursor that results in magnetic QD structures embedded in semiconducting GNRs is reported. Inserting one such molecule into the GNR backbone and graphitizing it results in a QD region hosting one unpaired electron. QDs composed of two precursor molecules exhibit nonmagnetic, antiferromagnetic, or antiferromagnetic ground states, depending on the structural details that determine the coupling behavior of the spins originating from each molecule. The synthesis of these QDs and the emergence of localized states are demonstrated through high-resolution atomic force microscopy (HR-AFM), scanning tunneling microscopy (STM) imaging, and spectroscopy, and the relationship between QD atomic structure and magnetic properties is uncovered. GNR QDs provide a useful platform for controlling the spin-degree of freedom in carbon-based nanostructures.

Unzipping Carbon Nanotubes to Sub-5-nm Graphene Nanoribbons on Cu(111) by Surface Catalysis.

Graphene nanoribbons (GNRs) are promising in nanoelectronics for their quasi-1D structures with tunable bandgaps. The methods for controllable fabrication of high-quality GNRs are still limited. Here a way to generate sub-5-nm GNRs by annealing single-walled carbon nanotubes (SWCNTs) on Cu(111) is demonstrated. The structural evolution process is characterized by low-temperature scanning tunneling microscopy. Substrate-dependent measurements on Au(111) and Ru(0001) reveal that the intermediate strong SWCNT-surface interaction plays a pivotal role in the formation of GNRs.

Visualizing Ribbon-to-Ribbon Heterogeneity of Chemically Unzipped Wide Graphene Nanoribbons by Silver Nanowire-Based Tip-Enhanced Raman Scattering Microscopy.

Graphene nanoribbons (GNRs), a quasi-one-dimensional form of graphene, have gained tremendous attention due to their potential for next-generation nanoelectronic devices. The chemical unzipping of carbon nanotubes is one of the attractive fabrication methods to obtain single-layered GNRs (sGNRs) with simple and large-scale production.  The authors recently found that unzipping from double-walled carbon nanotubes (DWNTs), rather than single- or multi-walled, results in high-yield production of crystalline sGNRs. However, details of the resultant GNR structure, as well as the reaction mechanism, are not fully understood due to the necessity of nanoscale spectroscopy. In this regard, silver nanowire-based tip-enhanced Raman spectroscopy (TERS) is applied for single GNR analysis and investigated ribbon-to-ribbon heterogeneity in terms of defect density and edge structure generated through the unzipping process.  The authors found that sGNRs originated from the inner walls of DWNTs showed lower defect densities than those from the outer walls. Furthermore, TERS spectra of sGNRs exhibit a large variety in graphitic Raman parameters, indicating a large variation in edge structures. This work at the single GNR level reveals, for the first time, ribbon-to-ribbon heterogeneity that can never be observed by diffraction-limited techniques and provides deeper insights into unzipped GNR structure as well as the DWNT unzipping reaction mechanism.

Bottom-Up Porous Graphene Synthesis and Its Applications.

Incorporation of regular order pores/holes/defects into semimetalic graphene sheets can tune the band gap up to 1 eV or more introducing semiconducting property and therefore exhibiting promising applications for organic electronics such as field-effect transistors (FETs), molecular sieve membranes, gas sensing, catalysis devices, etc. In this mini review, we focused on bottom-up approaches to introduce periodic homogeneous pores into graphene and nanographene and graphene nanoribbons along with their characteristics and potential applications in various fields.

Selective CO2 Photoreduction Enabled by Water-stable Cu-based Metal-organic Framework Nanoribbons.

The goal of photocatalytic CO2 reduction system is to achieve near 100 % selectivity for the desirable product with reasonably high yield and stability. Here, two-dimensional metal-organic frameworks are constructed with abundant and uniform monometallic active sites, aiming to be an emerged platform for efficient and selective CO2 reduction. As an example, water-stable Cu-based metal-organic framework nanoribbons with coordinatively unsaturated single CuII sites are first fabricated, evidenced by X-ray diffraction patterns and X-ray absorption spectroscopy. In situ Fourier-transform infrared spectra and Gibbs free energy calculations unravel the formation of the key intermediate COOH* and CO* is an exothermic and spontaneous process, whereas the competitive hydrogen evolution reaction is endothermic and non-spontaneous, which accounts for the selective CO2 reduction. As a result, in an aqueous solution containing 1 mol L-1 KHCO3 and without any sacrifice reagent, the water-stable Cu-based metal-organic framework nanoribbons exhibited an average CO yield of 82 µmol g-1 h-1 with the selectivity up to 97 % during 72 h cycling test, which is comparable to other reported photocatalysts under similar conditions.

Enhanced magnetism derived from pore-edge spins in thin Fe3GeTe2nanomeshes.

The growth of two-dimensional van der Waals magnetic materials presents attractive opportunities for exploring new physical phenomena and valuable applications. Among these materials, Fe3GeTe2(FGT) exhibits a variety of remarkable properties and has garnered significant attention. Herein, we have for the first time created a nanomesh structure-a honeycomb-like array of hexagonal nanopores-with the zigzag pore-edge atomic structure on thin FGT flakes with and without oxidation of the pore edges. It is revealed that the magnitude of ferromagnetism (FM) significantly increases in both samples compared with bulk flakes without nanomeshes. Critical temperature annealing results in the formation of zigzag pore edges and interpore zigzag-edge nanoribbons. We unveil that the non-oxide (O) termination of the Fe dangling bonds on these zigzag edges enhances FM behavior, while O-termination suppresses this FM by introducing antiferromagnetic behavior through edge O-Fe coupling. FGT nanomeshes hold promise for the creation of strong FM and their effective application in magnetic and spintronic systems.

Numerical characterization of thermal transport in hexagonal tungsten disulfide (WS2) nanoribbons.

In this study, we have investigated the thermal transport characteristics of single-layer tungsten disulfide, WS2nanoribbons (SLTDSNRs) using equilibrium molecular dynamics simulations with the help of Green-Kubo formulation. Using Stillinger-Weber (SW) inter-atomic potential, the calculated room temperature thermal conductivities of 15 nm × 4 nm pristine zigzag and armchair SLTDSNRs are 126 ± 10 W m-1K-1and 110 ± 6 W m-1K-1, respectively. We have explored the dependency of thermal conductivity on temperature, width, and length of the nanoribbon. The study shows that the thermal conductivity of the nanoribbon decreases with the increase in temperature, whereas the thermal conductivity increases with an increase in either the width or length of the ribbon. The thermal conductivity does not increase uniformly as the size of the ribbon changes. We have also observed that the thermal conductivity of SLTDSNRs depends on edge orientations; the zigzag nanoribbon has greater thermal conductivity than the armchair nanoribbon, regardless of temperature or dimension variations. Our study additionally delves into the tunable thermal properties of SLTDSNRs by incorporating defects, namely vacancies such as point vacancy, edge vacancy, and bi-vacancy. The thermal conductivities of nanoribbons with defects have been found to be considerably lower than their pristine counterparts, which aid in enhanced values for the thermoelectric figure of merit (zT). We have varied the vacancy concentration within a range of 0.1% to 0.9% and found that a point vacancy concentration of 0.1% leads to a 64% reduction in the thermal conductivity of SLTDSNRs. To elucidate these phenomena, we have calculated the phonon density of states for WS2under different aspects. The findings of our work provide important understandings of the prospective applications of WS2in nanoelectronic and thermoelectric devices by tailoring the thermal transport properties of WS2nanoribbons.

Toxicity evaluation of novel imidacloprid nanoribbons, using somatic mutation and fitness indexes in Drosophila melanogaster.

Nanoribbons of imidacloprid, a systemic and chloronicotinyl insecticide, were successfully synthesized by laser-induced fragmentation/exfoliation of imidacloprid powders suspended in water, with widths ranging from 160 to 470 nm, lengths in the micron scale, and thickness of a few atoms layers. The aim of the present study was to examine the effects of acute and chronic exposure to imidacloprid (IMC) bulk and compare its effects with synthesized imidacloprid nanoribbons (IMCNR) on larval and adult viability, developmental time, olfactory capacity, longevity, productivity, and genotoxicity in Drosophila melanogaster. Larvae or adults were exposed at 0.01, 0.02, or 0.03 ppm to IMC or IMCNR. Results demonstrated that IMCNR produced a significant reduction in viability and olfactory ability. IMC did not significantly alter viability and olfactory ability. Similarly, marked differences on longevity were detected between treatment with IMC and IMCNR where the lifespan of males treated with IMC was significantly higher than control while IMCNR produced a reduction. As for productivity, developmental time, and genotoxicity, no marked differences were found between both forms of IMC.

Dirac Half-Semimetallicity and Antiferromagnetism in Graphene Nanoribbon/Hexagonal Boron Nitride Heterojunctions.

Half-metals have been envisioned as active components in spintronic devices by virtue of their completely spin-polarized electrical currents. Actual materials hosting half-metallic phases, however, remain scarce. Here, we predict that recently fabricated heterojunctions of zigzag nanoribbons embedded in two-dimensional hexagonal boron nitride are half-semimetallic, featuring fully spin-polarized Dirac points at the Fermi level. The half-semimetallicity originates from the transfer of charges from hexagonal boron nitride to the embedded graphene nanoribbon. These charges give rise to opposite energy shifts of the states residing at the two edges, while preserving their intrinsic antiferromagnetic exchange coupling. Upon doping, an antiferromagnetic-to-ferrimagnetic phase transition occurs in these heterojunctions, with the sign of the excess charge controlling the spatial localization of the net magnetic moments. Our findings demonstrate that such heterojunctions realize tunable one-dimensional conducting channels of spin-polarized Dirac fermions seamlessly integrated into a two-dimensional insulator, thus holding promise for the development of carbon-based spintronics.

Determining the Number of Graphene Nanoribbons in Dual-Gate Field-Effect Transistors.

Bottom-up synthesized graphene nanoribbons (GNRs) are increasingly attracting interest due to their atomically controlled structure and customizable physical properties. In recent years, a range of GNR-based field-effect transistors (FETs) has been fabricated, with several demonstrating quantum-dot (QD) behavior at cryogenic temperatures. However, understanding the relationship between the cryogenic charge-transport characteristics and the number of the GNRs in the device is challenging, as the length and location of the GNRs in the junction are not precisely controlled. Here, we present a methodology based on a dual-gate FET that allows us to identify different scenarios, such as single GNRs, double or multiple GNRs in parallel, and a single GNR interacting with charge traps. Our dual-gate FET architecture therefore offers a quantitative approach for comprehending charge transport in atomically precise GNRs.

Tunable Tail Swing of Nanomillipedes.

The physical properties of graphene nanoribbons (GNRs) are closely related to their morphology; meanwhile GNRs can easily slide on surfaces (e.g., superlubricity), which may largely affect the configuration and hence the properties. However, the morphological evolution of GNRs during sliding remain elusive. We explore the intriguing tail swing behavior of GNRs under various sliding configurations on Au substrate. Two distinct modes of tail swing emerge, characterized by regular and irregular swings, depending on the GNR width and initial position relative to the substrate. The mechanism can be explained by the moiré effect, presenting both symmetric and asymmetric patterns, resembling a mesmerizing nanomillipede. We reveal a compelling correlation between the tail swing mode and the edge wrinkle patterns of GNRs induced by the moiré effect. These findings provide fundamental understanding of how edge effects influence the tribomorphological responses of GNRs, offering valuable insights for precise manipulation and operation of GNRs.

Advanced nanoribbons in water purification: A comprehensive review.

The increasing scarcity of clean water, coupled with the environmental repercussions of municipal and industrial wastewater, underscores the imperative for advancing novel technologies aimed at clean water production and effectively removing impurities and toxic contaminants. Research focusing on ribbon-based technologies has garnered substantial attention in recent years due to their promising applications in various fields. This article presents a comprehensive review of the diverse applications of ribbon in water and wastewater treatment. It delves into the various types of ribbon employed for water purification, elucidating their effectiveness in removing contaminants such as heavy metals, dyes, pesticides, medical waste, oil pollutants, and radioactive waste. We will also discuss methods such as adsorption, membrane separation, and advanced oxidation processes, which help to understand how ribbons remove pollutants from water. This review summarizes the recent progress in the field of water purification and discusses the current state-of-the-art research on the use of ribbons in wastewater treatment. The end of this article gives information about the regeneration and reusability of ribbons and about challenges and prospects.

Exploring Spin Distribution and Electronic Properties in FeN4-Graphene Catalysts with Edge Terminations.

Understanding the spin distribution in FeN4-doped graphene nanoribbons with zigzag and armchair terminations is crucial for tuning the electronic properties of graphene-supported non-platinum catalysts. Since the spin-polarized carbon and iron electronic states may act together to change the electronic properties of the doped graphene, we provide in this work a systematic evaluation using a periodic density-functional theory-based method of the variation of spin-moment distribution and electronic properties with the position and orientation of the FeN4 defects, and the edge terminations of the graphene nanoribbons. Antiferromagnetic and ferromagnetic spin ordering of the zigzag edges were considered. We reveal that the electronic structures in both zigzag and armchair geometries are very sensitive to the location of FeN4 defects, changing from semi-conducting (in-plane defect location) to half-metallic (at-edge defect location). The introduction of FeN4 defects at edge positions cancels the known dependence of the magnetic and electronic proper-ties of undoped graphene nanoribbons on their edge geometries. The implications of the reported results for catalysis are also discussed in view of the presented electronic and magnetic properties.