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Top-down liquid-phase exfoliation (LPE) and bottom-up hot-injection synthesis are scalable methods to produce Generally thought off as two entirely different fields, we show that similar stabilization mechanisms apply to colloids of molybdenum disulfide (MoS2) produced by both methods. By screening the colloidal stability of MoS2 produced in a hot-injection synthesis in a wide range of solvents, we observe that colloidal stability can be understood based on solution thermodynamics, wherein matching the solubility parameter of solvent and nanomaterial maximizes colloidal stability. Identical to MoS2 produced through LPE, optimal solvents to disperse MoS2 produced from the bottom-up have similar solubility parameters of approximate to 22 MPa1/2 and include aromatic solvents with polar functionalities, such as o-dichlorobenzene, and polar aprotic solvents, such as N,N-dimethylformamide. We further complemented our findings by nuclear magnetic resonance (NMR) spectrscopy, highlighting that organic surfactants, such as oleylamine and oleic acid, have a minimal affinity toward the nanocrystal surface and engage in a highly dynamic adsorption/desorption equilibrium. We thus conclude that hot injection yields MoS2 colloids with comparable surfaces as those produced by LPE. These similarities might offer the prospect of using established procedures developed for LPE nanomaterials to postprocess colloidally synthesized dispersions of 2D colloids as processable inks.

Transition-metal dichalcogenide (TMD) nano-sheets have become an intensively investigated topic in the field of 2D nanomaterials, especially due to the direct semiconductor nature, and the broken inversion symmetry in the odd-layer number, of some of their family members. These properties make TMDs attractive for different technological applications such as photovoltaics, optoelectronics, valleytronics, and hydrogen evolu-tion reactions. Among them, MoX2 (X = S and Se) are turned to direct gap when their thickness is thinned down to monolayer, and thus, efforts toward obtaining large-scale monolayer TMDs are crucial for technological applications. Colloidal synthesis of TMDs has been developed in recent years, as it provides a cost-efficient and scalable way to produce few-layer TMDs having homogeneous size and thickness, yet obtaining a monolayer has proven challenging. Here, we present a method for the colloidal synthesis of mono-and few-layer MoX2 (X = S and Se) using elemental chalcogenide and metal chloride as precursors. Using a synthesis with slow injection of the MoCl5 precursor under a nitrogen atmosphere, and optimizing the synthesis parameters with a design of experiments approach, we obtained a MoX2 sample with the semiconducting (1H) phase and optical band gaps of 1.96 eV for H-1-MoS2 and 1.67 eV for 1H-MoSe2, respectively, consistent with a large monolayer yield in the ensemble. Both display photoluminescence at cryogenic and room temperature, paving the way for optical spectroscopy studies and photonic applications of colloidal TMD nanosheets.

Large‐scale production of two‐dimensional (2D) materials still is a crucial point toward its practical applications. Violet phosphorus (VP) with a wide bandgap accelerates and broadens the potential applications of elemental phosphorus in optoelectronics. Here, we demonstrate the scalable production of solution‐processable violet phosphorus flakes stably dispersed in several solvents. The exfoliated VP flakes exhibit thickness‐dependent visible photoluminescence characteristics, which covers the shortcoming of black phosphorus. Meanwhile, the VP‐based field‐effect transistor reveals relatively competitive electrical properties to other liquid‐phase exfoliated 2D materials. Our study paves the way for a wide range of applications of optical devices, energy storage, catalysis, and sodium batteries based on large‐scale VP flakes.

Made available in DSpace on 2021-06-25T10:19:28Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-01-01 A simple, efficient, environmentally friendly, and inexpensive synthesis route was developed to obtain a magnetic nano-hybrid (GH) based on graphene and cobalt ferrite. Water with a high content of natural organic matter (NOM) was used as solvent and a source of carbon. The presence of NOM in the composition of GH was confirmed by FTIR and Raman spectroscopy, which evidenced the formation of graphene, as also corroborated by XRD analyses. The diffractograms and TEM images showed the formation of a hybrid nanomaterial composed of graphene and cobalt ferrite, with crystallite and particle sizes of 0.83 and 4.0 nm, respectively. The heterogeneous electro-Fenton process (EF-GH) achieved 100% degradation of bisphenol A (BPA) in 50 min, with 80% mineralization in 7 h, at pH 7, using a current density of 33.3 mA cm−2. The high catalytic performance was achieved at neutral pH, enabling substantial reduction of the costs of treatment processes. This work contributes to understanding the role of NOM in the synthesis of a magnetic nano-hybrid based on graphene and cobalt ferrite, for use in heterogeneous catalysis. This nano-hybrid has excellent potential for application in the degradation of persistent organic pollutants found in aquatic environments. Graphical abstract: [Figure not available: see fulltext.] Chemistry Department Federal University of Sergipe (UFS) Chemical Engineering Department Federal University of Sergipe (UFS) Institute of Chemistry UNESP National Institute of Alternative Technologies for Detection Toxicological Evaluation and Removal of Micropollutants and Radioactive Materials (INCT-DATREM), P.O. Box 355 Institute of Chemistry UNESP National Institute of Alternative Technologies for Detection Toxicological Evaluation and Removal of Micropollutants and Radioactive Materials (INCT-DATREM), P.O. Box 355

MoO3 is a versatile two-dimensional transition metal oxide having applications in areas such as energy storage devices, electronic devices and catalysis. To efficiently utilize the properties of MoO3 arising from its two-dimensional nature exfoliation is necessary. In this work, the exfoliation of MoO3 is carried out in 2-butanone for the first time. The achieved concentration of the dispersion is about 0.57 mg·mL−1 with a yield of 5.7%, which are the highest values reported to date. These high values of concentration and yield can be attributed to a favorable matching of energies involved in exfoliation and stabilization of MoO3 nanosheets in 2-butanone. Interestingly, the MoO3 dispersion in 2-butanone retains its intrinsic nature even after exposure to sunlight for 24 h. The composites of MoO3 nanosheets were used as an electrode material for supercapacitors and showed a high specific capacitance of 201 F·g−1 in a three-electrode configuration at a scan rate of 50 mV·s−1.

2D materials have opened a new field in materials science with outstanding scientific and technological impact. A largely explored route for the preparation of 2D materials is the exfoliation of layered crystals with weak forces between their layers. However, its application to covalent crystals remains elusive. Herein, a further step is taken by introducing the exfoliation of germanium, a narrow-bandgap semiconductor presenting a 3D diamond-like structure with strong covalent bonds. Pure α-germanium is exfoliated following a simple one-step procedure assisted by wet ball-milling, allowing gram-scale fabrication of high-quality layers with large lateral dimensions and nanometer thicknesses. The generated flakes are thoroughly characterized by different techniques, giving evidence that the new 2D material exhibits bandgaps that depend on both the crystallographic direction and the number of layers. Besides potential technological applications, this work is also of interest for the search of 2D materials with new properties, The authors acknowledge the financial support from the Spanish Ministry of Science and Innovation, through the “María de Maeztu” Programme for Units of Excellence in R&D (CEX2018-000805-M and CEX2019-000919-M) and MINECO-FEDER projects PID2019-111742GB-C31, PID2019-111742GB-C32, PCI2018-093081, PID2019-109539GB-C43, MAT2015-666888-C3-3R, MICINN projects FIS2017-82415-R, RTI2018- 097895-B-C43 and PID2019-111742GA-I00, the Comunidad Autónoma de Madrid through S2018/NMT-4321 (NanomagCOST-CM), the Generalitat Valenciana (CIDEGENT/2018/001 grant and iDiFEDER/2018/061 co-financed by FEDER) and the Deutsche Forschungsgemeinschaft (DFG, FLAG-ERA AB694/2-1), the European Union Seventh Framework Programme under Grant agreement No. 604391 Graphene Flagship. The authors thank the European Research Council (ERC Starting Grant 2D-PnictoChem 804110 to G.A.). W.S.P. acknowledges the computer resources and assistance provided by the Centro de Computación Científica of the Universidad Autónoma de Madrid and the computer resources at MareNostrum and technical support provided by Barcelona Supercomputing Center (FI-2019-2-0007)

Phosphorene is a new two-dimensional material that has recently attracted much attention owing to its fascinating electrical, optical, thermal and chemical properties. Here, we report on high-quality exfoliation of black phosphorus nanosheets, with controllable size produced in large quantities by liquid-phase exfoliation using N -methyl-2-pyrrolidone (NMP) as a solvent under ambient conditions. The as-synthesized few layers show a great potential for solar energy conversion based on the optical results shown in this work.

Graphene has emerged as one of the most versatile materials ever discovered due to its extraordinary electronic, optical, thermal, and mechanical properties. However, device fabrication is a well-known challenge and requires novel fabrication methods to realize the complex integration of graphene-based devices. Here, we demonstrate direct laser writing of reduced graphene oxide using femtosecond-laser irradiation at lambda = 795 nm. We perform a systematic study of the reduction process of graphene oxide to graphene by varying both the laser fluence and the pulse repetition rate. Our observations show that the reduction has both thermal and non-thermal features, and suggest that we can achieve better resolution and conductivity using kHz pulse trains than using MHz pulse trains or a continuous wave laser. Our reduced graphene oxide lines written at 10-kHz exhibit a 5 order-of-magnitude decrease in resistivity compared to a non-irradiated control sample. This study provides new insight into the reduction process of graphene oxide and opens doors to achieving a high degree of flexibility and control in the fabrication of graphene layers. (C) 2018 Elsevier Ltd. All rights reserved.

Functionalization of graphite is crucial for efficient and effective exfoliation to graphene. When negative charges are fixed to the edges of natural graphite, the resulting anionic graphite shows negative charging in a polar solvent. This enhanced negative charging is assumed to contribute the exfoliation of graphite during liquid-phase exfoliation (LPE). In this study, we prepared large anionic graphite flakes (~10 &mu, m) by salt-assisted ball milling, as well as natural graphite flakes of the same size for comparison. During the LPE process, centrifugation speed and solvent type have dominant effects on graphene concentration and quality (e.g., size and thickness), so we investigated these factors for anionic graphite flakes in detail. The anionic graphite showed higher exfoliation efficiency in every type of solvent (isopropanol, methyl ethyl ketone, acetone, and water-based cosolvent) compared with the natural graphite. Monolayer graphene, with an average size of 80&ndash, 200 nm, was obtained with relatively high yield (&gt, 10%) at only 3 min of sonication. The small size of graphene was due to edge fragmentation during the LPE process. The recyclability of the sediment and the characterization of the exfoliated powders for anionic graphene were also investigated.

Two-dimensional (2D) materials are a rapidly growing area of interest for wearable electronics, due to their flexible and unique electrical properties. All-textile-based wearable electronic components are key to enable future wearable electronics. Single component electrical elements have been demonstrated; however heterostructure-based assemblies, combining electrically conductive and dielectric textiles such as all-textile capacitors are currently missing. Here we demonstrate a superhydrophobic conducting fabric with a sheet resistance Rs ∼ 2.16 kΩ □−1, and a pinhole-free dielectric fabric with a relative permittivity er ∼ 2.35 enabled by graphene and hexagonal boron nitride inks, respectively. The different fabrics are then integrated to engineer the first example of an all-textile-based capacitive heterostructure with an effective capacitance C ∼ 26 pF cm−2 and a flexibility of ∼1 cm bending radius. The capacitor sustains 20 cycles of repeated washing and more than 100 cycles of repeated bending. Finally, an AC low-pass filter with a cut-off frequency of ∼15 kHz is integrated by combining the conductive polyester and the capacitor. These results pave the way toward all-textile vertically integrated electronic devices.

Single- and few-layered InSe flakes are produced by the liquid-phase exfoliation of beta-InSe single crystals in 2-propanol, obtaining stable dispersions with a concentration as high as 0.11 g/L. Ultracentrifugation is used to tune the morphology, i.e., the lateral size and thickness of the as-produced InSe flakes. We demonstrate that the obtained InSe flakes have maximum lateral sizes ranging from 30 nm to a few um, and thicknesses ranging from 1 to 20 nm, with a max population centred at ~ 5 nm, corresponding to 4 Se-In-In-Se quaternary layers. We also show that no formation of further InSe-based compounds (such as In2Se3) or oxides occurs during the exfoliation process. The potential of these exfoliated-InSe few-layer flakes as a catalyst for hydrogen evolution reaction (HER) is tested in hybrid single-walled carbon nanotubes/InSe heterostructures. We highlight the dependence of the InSe flakes morphologies, i.e., surface area and thickness, on the HER performances achieving best efficiencies with small flakes offering predominant edge effects. Our theoretical model unveils the origin of the catalytic efficiency of InSe flakes, and correlates the catalytic activity to the Se vacancies at the edge of the flakes., 39 pages

The liquid-phase exfoliation (LPE) method has been gaining increasing interest by academic and industrial researchers due to its simplicity, low cost, and scalability. High-intensity ultrasound energy was exploited to transform graphite to graphene in the solvents of dimethyl sulfoxide (DMSO), N,N-dimethyl formamide (DMF), and perchloric acid (PA) without adding any surfactants or ionic liquids. The crystal structure, number of layers, particle size, and morphology of the synthesized graphene samples were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), ultraviolet visible (UV&ndash, vis) spectroscopy, dynamic light scattering (DLS), and transmission electron microscopy (TEM). XRD and AFM analyses indicated that G-DMSO and G-DMF have few layers while G-PA has multilayers. The layer numbers of G-DMSO, G-DMF, and G-PA were determined as 9, 10, and 21, respectively. By DLS analysis, the particle sizes, polydispersity index (PDI), and zeta potential of graphene samples were estimated in a few micrometers. TEM analyses showed that G-DMSO and G-DMF possess sheet-like fewer layers and also, G-PA has wrinkled and unordered multilayers.

Earth‐abundant transition‐metal‐based catalysts are attractive for alkaline water electrolysis. However, their catalytic properties are often limited by their poor electrical conductivity. Here, we present a strategy for enhancing the electrical conductivity of NiFe layered double hydroxide (LDH) in order to further improve its properties as an electrocatalyst for the oxygen evolution reaction (OER) in alkaline media. We show that NiFe LDH containing metal tetrasulfonate phthalocyanine in the interlayers between the NiFe oxide galleries can be coupled with graphene during liquid‐phase exfoliation by taking advantage of their π‐π stacking capabilities. A substantial enhancement in the electrocatalytic activity of NiFe LDH with respect to the OER was observed. Moreover, the activity and selectivity of the catalyst materials towards the oxygen reduction reaction were investigated, demonstrating that both the metal hydroxide layer and the interlayer species contribute to the electrocatalytic performance of the composite material., Stack the odds! A strategy is presented for boosting the activity of NiFe layered double hydroxide (LDH) towards the oxygen evolution reaction. The strategy consists of enhancing its electrical conductivity by π‐π stacking graphene (G) with phthalocyanine ligands present at the LDH interlayer through liquid‐phase exfoliation. The resulting NiFe LDH/G composites exhibit remarkably higher activities than their separate components.

Among the several methods of producing graphene, the liquid-phase exfoliation of graphite is attractive because of a simple and easy procedure, being expected for mass production. The dispersibility of graphene can be improved by adding a dispersant molecule that interacts with graphene, but the appropriate molecular design has not been proposed. In this study, we focused on aromatic compounds with alkyl chains as dispersing agents. We synthesized a series of alkyl aromatic compounds and evaluated their performance as a dispersant for graphene. The results suggest that the alkyl chain length and solubility in the solvent play a vital role in graphene dispersion.

Although two-dimensional boron (B) has attracted much attention in electronics and optoelectronics due to its unique physical and chemical properties, in-depth investigations and applications have been limited by the current synthesis techniques. Herein, we demonstrate that high-quality few-layer B sheets can be prepared in large quantities by sonication-assisted liquid-phase exfoliation. By simply varying the exfoliating solvent types and centrifugation speeds, the lateral size and thickness of the exfoliated B sheets can be controllably tuned. Additionally, the exfoliated few-layer B sheets exhibit excellent stability and outstanding dispersion in organic solvents without aggregates for more than 50 days under ambient conditions, owing to the presence of a solvent residue shell on the B sheet surface that provides excellent protection against air oxidation. Moreover, we also demonstrate the use of the exfoliated few-layer B sheets for high-performance supercapacitor electrode materials. This as-prepared device exhibits impressive electrochemical performance with a wide potential window of up to 3.0 V, excellent energy density as high as 46.1 Wh/kg at a power density of 478.5 W/kg, and excellent cycling stability with 88.7% retention of the initial specific capacitance after 6000 cycles. This current work not only demonstrates an effective strategy for the synthesis of the few-layer B sheets in a controlled manner but also makes the resulting materials promising for next-generation optoelectronics and energy storage applications. MOE (Min. of Education, S’pore) Accepted version

Development of novel 2D materials with singular and thrilling properties has aroused large interest due to the novel unexpected applications that can be derived from there. In this sense, coordination polymers (CPs) have appeared as matching candidates thanks to their rational chemical design and the added-value properties given by the presence of metal ions. This is the case of switchable spin-crossover systems that have been proposed as excellent candidates for data storage or sensing, among others. Here we report the delamination of crystals of the 2D spin-crossover (SCO) {[Fe(L1)2](ClO4)2}∝ (1) CP by liquid-phase exfoliation (LPE) in water. The application of this top-down technique results in the formation of flakes with controlled thicknesses, down to 1–2 nm thick (mostly mono- and bilayer), that retain the chemical composition and SCO interconversion of the bulk material. Moreover, these flakes can be handled as stable colloidal dispersions for many days. This allows for a controlled transfer to solid substrates and the formation of thermochromic polymeric films as a proof-of-concept of device. These first results will definitely open new venues and opportunities for the investigation and future integration of these original switchable 2D materials in devices., This work was supported by projects MAT2015-70615-R, CTQ2015-65439-R, and FIS2015-64886-C5-3-P from the Spanish Government funds and by European Regional Development Fund (ERDF). Funded by the CERCA Program/Generalitat de Catalunya. ICN2 is supported by the Severo Ochoa program from Spanish Ministry of Economy, Industry and Competitiveness (MINECO, Grant SEV-2013-0295). Funded by the project 2014-SGR-301 (Generalitat de Catalunya). This work was supported by the Fonds National de la Recherche Scientifique-FNRS (PDR T.0102.15) and COST actions CM1305 and CA15128. M. M. D is a chargé de recherches from the F.R.S.-FNRS. S.S.-G. acknowledges the support from MINECO BES-2015-071492 grant. R.R. and P.O. acknowledge support from EU H2020-EINFRA-5-2015 MaX Center of Excellence (Grant 676598).

In article number https://doi.org/10.1002/advs.201801029, Kolleboyina Jayaramulu, Justus Masa, Wolfgang Schuhmann, Roland A. Fischer, and co‐workers report simple and facile synthesis of cobalt‐based 2D zeolite imidazole framework nanosheets [Co‐ZIF‐9(III)] by mechano‐chemical grinding with subsequent liquid‐phase exfoliation. The resultant 2D material exhibits highly efficient oxygen evolution reaction (OER) activity under alkaline conditions, attributed to increased accessibility of redox‐active cobalt oxyhydroxide active sites with a nitrogen coordination environment N4CoOOH, and efficiently mimics Co‐Porphyrin electrocatalysts.

Microbial fuel cells (MFCs) exploit the ability of microorganisms to generate electrical power during metabolism of substrates. However, the low efficiency of extracellular electron transfer from cells to the anode and the use of expensive rare metals as catalysts, such as platinum, limit their application and scalability. In this study we investigate the use of pristine graphene based electrodes at both the anode and the cathode of a MFC for efficient electrical energy production from the metabolically versatile bacterium Rhodopseudomonas palustris CGA009. We achieve a volumetric peak power output (PV) of up to 3.51 ± 0.50 W m-3 using graphene based aerogel anodes with a surface area of 8.2 m2 g-1. We demonstrate that enhanced MFC output arises from the interplay of the improved surface area, enhanced conductivity, and catalytic surface groups of the graphene based electrode. In addition, we show a 500-fold increase in PV to 1.3 ± 0.23 W m-3 when using a graphene coated stainless steel (SS) air cathode, compared to an uncoated SS cathode, demonstrating the feasibility of a platinum-free, graphene catalysed MFCs. Finally, we show a direct application for microwatt-consuming electronics by connecting several of these coin sized devices in series to power a digital clock.

High-quality, few-layer black-phosphorus (BP) flakes are prepared in a common organic solvent with very short processing times using microwave-assisted liquid-phase exfoliation. A comprehensive range of analysis, combined with density-functional theory calculations, confirms that the product prepared using the microwave technique is few-layer BP with small- and large-area flakes. The suspended exfoliated BP sheets show excellent stability, while samples dispersed onto silicon from the suspensions exhibit low oxidation levels after several days in ambient conditions. This straightforward synthesis method is facile, efficient, and extremely fast, and does not involve use of any surfactant or ultrasonication steps and will facilitate future development of phosphorene research. Refereed/Peer-reviewed

Cost-effective and scalable preparation of two-dimensional (2D) molybdenum disulfide (MoS2) has been the bottleneck that limits their applications. This paper reports a novel coupled ultrasonication-milling (CUM) process to exfoliate natural molybdenite powders to achieve few-layer MoS2 (FL-MoS2) nanosheets in the solvent of N-methyl-2-pyrrolidone (NMP) with polyvinylpyrrolidone (PVP) molecules. The synergistic effect of ultrasonication and sand milling highly enhanced the exfoliation efficiency, and the precursor of natural molybdenite powders minimizes the synthetic cost of FL-MoS2 nanosheets. The exfoliation of natural molybdenite powders was conducted in a home-made CUM system, mainly consisting of an ultrasonic cell disruptor and a ceramic sand mill. The samples were characterized by X-ray diffraction, UV-vis spectra, Raman spectra, FT-IR, SEM, TEM, AFM, and N2 adsorption-desorption. The factors that influence the exfoliation in the CUM process, including the initial concentration of natural molybdenite powders (C in, 15–55 g L−1), ultrasonic power (P u, 200–350 W), rotation speed of sand mill (ω s, 1500–2250 r.p.m), exfoliation time (t ex, 0.5–6 h), and the molar ratio of PVP unit to MoS2 (R pm, 0–1), were systematically investigated. Under the optimal CUM conditions (i.e., C in = 45 g L−1, P u = 280 W, ω s = 2250 r.p.m and R pm = 0.5), the yield at t ex = 6 h reaches 21.6 %, and the corresponding exfoliation rate is as high as 1.42 g L−1 h−1. The exfoliation efficiency of the CUM mode is much higher than that of either the ultrasonication (U) mode or the milling (M) mode. The synergistic mechanism and influencing rules of the CUM process in exfoliating natural molybdenite powders were elaborated. The as-obtained FL-MoS2 nanosheets have a high specific surface area of 924 m2 g−1 and show highly enhanced electrocatalytic performance in hydrogen evolution reaction and good electrochemical sensing property in detecting ascorbic acid. The CUM process developed has paved a low-cost, green, and highly efficient way towards FL-MoS2 nanosheets from natural molybdenite powders.

2D layered materials, including metal‐di‐chalcogenides and transition metal layered double hydroxides, among others, are intensively studied because of new properties that emerge from their 2D confinement, which are attractive for advanced applications. Herein, 2D cobalt ion (Co2+) and benzimidazole (bIm) based zeolite‐imidazole framework nanosheets, ZIF‐9(III), are reported as exceptionally efficient electrocatalysts for the oxygen evolution reaction (OER). Specifically, liquid‐phase ultrasonication is applied to exfoliate a [Co4(bIm)16] zeolite‐imidazole framework (ZIF), named as ZIF‐9(III) phase, into nanoscale sheets. ZIF‐9(III) is selectively prepared through simple mechanical grinding of cobalt nitrate and benzimidazole in the presence of a small amount of ethanol. The resultant exfoliated nanosheets exhibit significantly higher OER activity in alkaline conditions than the corresponding bulk phases ZIF‐9 and ZIF‐9(III). The electrochemical and physicochemical characterization data support the assignment of the OER activity of the exfoliated nanosheet derived material to nitrogen coordinated cobalt oxyhydroxide N4CoOOH sites, following a mechanism known for Co‐porphyrin and related systems. Thus, exfoliated 2D nanosheets hold promise as potential alternatives to commercial noble metal electrocatalysts for the OER.

International audience; We report the exfoliation of graphite and simultaneous N doping of graphene by two methods: supercritical ammonia treatment and liquid-phase exfoliation with NH4OH. While the supercritical ammonia allowed N doping at a level of 6.4 atom % in 2 h, the liquid-phase exfoliation with NH4OH allowed N doping at a level of 2.7 atom % in 6 h. The N doped graphene obtained via the supercritical ammonia route had few layers (

International audience; The liquid-phase exfoliation of phosphorene, the two-dimensional derivative of black phosphorus, in the solvents dimethyl sulfoxide (DMSO), dimethylformamide (DMF), isopropyl alcohol, N-methyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone is investigated using three molecular-scale “computer experiments”. We modeled solvent–phosphorene interactions using an atomistic force field, based on ab initio calculations and lattice dynamics, that accurately reproduces experimental mechanical properties. We probed solvent molecule ordering at phosphorene/solvent interfaces and discovered that planar molecules such as N-methyl-2-pyrrolidone preferentially orient parallel to the interface. We subsequently measured the energy required to peel a single phosphorene monolayer from a stack of black phosphorus and analyzed the role of “wedges” of solvent molecules intercalating between phosphorene sheets in initiating exfoliation. The exfoliation efficacy of a solvent is enhanced when either molecular planarity “sharpens” this molecular wedge or strong phosphorene–solvent adhesion stabilizes the newly exposed phosphorene surfaces. Finally, we examined the colloidal stability of exfoliated flakes by simulating their aggregation and showed that dispersion is favored when the cohesive energy between the molecules in the solvent monolayer confined between the phosphorene sheets is high (as with DMSO) and is hindered when the adhesion between these molecules and phosphorene is strong; the molecular planarity in solvents like DMF enhances the cohesive energy. Our results are consistent with, and provide a molecular context for, experimental exfoliation studies of phosphorene and other layered solids, and our molecular insights into the significant role of solvent molecular geometry and ordering should complement prevalent solubility-parameter-based approaches in establishing design rules for effective nanomaterial exfoliation media.

We fabricate a free-standing few-layer molybdenum disulfide (MoS2)-polymer composite by liquid phase exfoliation of chemically pristine MoS2 crystals and use this to demonstrate a wideband tunable, ultrafast mode-locked fiber laser. Stable, picosecond pulses, tunable from 1,535 nm to 1,565 nm, are generated, corresponding to photon energies below the MoS2 material bandgap. These results contribute to the growing body of work studying the nonlinear optical properties of transition metal dichalcogenides that present new opportunities for ultrafast photonic applications.

International audience; 2D metal chalcogenide (MC) nanosheets (NS) have displayed high capacities as lithium‐ion battery (LiB) anodes. Nevertheless, their complicated synthesis routes coupled with low electronic conductivity greatly limit them as promising LiB electrode material. Here, this work reports a facile single‐walled carbon nanotube (SWCNT) percolating strategy for efficiently maximizing the electrochemical performances of gallium chalcogenide (GaX, X = S or Se). Multiscaled flexible GaX NS/SWCNT heterostructures with abundant voids for Li+ diffusion are fabricated by embedding the liquid‐exfoliated GaX NS matrix within a SWCNT‐percolated network; the latter improves the electron transport and ion diffusion kinetics as well as maintains the mechanical flexibility. Consequently, high capacities (i.e., 838 mAh g−1 per gallium (II) sulfide (GaS) NS/SWCNT mass and 1107 mAh g−1 per GaS mass; the latter is close to the theoretical value) and good rate capabilities are achieved, which can be majorly attributed to the alloying processes of disordered Ga formed after the first irreversible GaX conversion reaction, as monitored by in situ X‐ray diffraction. The presented approach, colloidal solution processing of SWCNT and liquid‐exfoliated MC NS to produce flexible paper‐based electrode, could be generalized for wearable energy storage devices with promising performances.

Two types of graphene-based hybrid materials, graphene-TPP (TPP=tetraphenylporphyrin) and graphene-PdTPP (PdTPP=palladium tetraphenylporphyrin), were prepared directly from pristine graphene through one-pot cycloaddition reactions. The hybrid materials were characterized by thermogravimetric analysis (TGA), by TEM, by UV/Vis, FTIR, Raman, and luminescence spectroscopy, and by fluorescence/phosphorescence lifetime measurements. The presence of the covalent linkages between graphene and porphyrin was confirmed by FTIR and Raman spectroscopy and further supported by control experiments. The presence of TPP (or PdTPP) in the hybrid material was demonstrated by UV/Vis spectroscopy, with TGA results indicating that the graphene-TPP and graphene-PdTPP hybrid materials contained approximately 18% TPP and 20% PdTPP. The quenching of fluorescence (or phosphorescence) and reduced lifetimes suggest excited state energy/electron transfer between graphene and the covalently attached TPP (or PdTPP) molecules.

International Edition: DOI: 10.1002/anie.201605298 German Edition: DOI: 10.1002/ange.201605298, "This is the peer reviewed version of the following article: Angewandte Chemie - International Edition 55.46 (2016): 14345-14349 which has been published in final form at https://doi.org/10.1002/anie.201605298. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions", We report on a fast and simple method to produce highly stable isopropanol/water (4:1) suspensions of few-layer antimonene by liquid-phase exfoliation of antimony crystals in a process that is assisted by sonication but does not require the addition of any surfactant. This straightforward method generates dispersions of few-layer antimonene suitable for on-surface isolation. Analysis by atomic force microscopy, scanning transmission electron microscopy, and electron energy loss spectroscopy confirmed the formation of high-quality few-layer antimonene nanosheets with large lateral dimensions. These nanolayers are extremely stable under ambient conditions. Their Raman signals are strongly thickness-dependent, which was rationalized by means of density functional theory calculations