Microwave-Driven Exfoliation of Bulk 2H-MoS2 after Acetonitrile Prewetting Produces Large-Area Ultrathin Flakes with Exceptionally High Yield.

2D materials display exciting properties in numerous fields, but the development of applications is hindered by the low yields, high processing times, and impaired quality of current exfoliation methods. In this work we have used the excellent MW absorption properties of MoS2 to induce a fast heating that produces the near-instantaneous evaporation of an adsorbed, low boiling point solvent. The sudden evaporation creates an internal pressure that separates the MoS2 layers with high efficiency, and these are kept separated by the action of the dispersion solvent. Our fast method (90 s) gives high yields (47% at 0.2 mg/mL, 35% at 1 mg/mL) of highly exfoliated material (90% under 4 layers), large area (up to several µm2), and excellent quality (no significant MoO3 detected).

Direct Magnetic Evidence, Functionalization, and Low-Temperature Magneto-Electron Transport in Liquid-Phase Exfoliated FePS3.

Magnetism and the existence of magnetic order in a material is determined by its dimensionality. In this regard, the recent emergence of magnetic layered van der Waals (vdW) materials provides a wide playground to explore the exotic magnetism arising in the two-dimensional (2D) limit. The magnetism of 2D flakes, especially antiferromagnetic ones, however, cannot be easily probed by conventional magnetometry techniques, being often replaced by indirect methods like Raman spectroscopy. Here, we make use of an alternative approach to provide direct magnetic evidence of few-layer vdW materials, including antiferromagnets. We take advantage of a surfactant-free, liquid-phase exfoliation (LPE) method to obtain thousands of few-layer FePS3 flakes that can be quenched in a solvent and measured in a conventional SQUID magnetometer. We show a direct magnetic evidence of the antiferromagnetic transition in FePS3 few-layer flakes, concomitant with a clear reduction of the Néel temperature with the flake thickness, in contrast with previous Raman reports. The quality of the LPE FePS3 flakes allows the study of electron transport down to cryogenic temperatures. The significant through-flake conductance is sensitive to the antiferromagnetic order transition. Besides, an additional rich spectra of electron transport excitations, including secondary magnetic transitions and potentially magnon-phonon hybrid states, appear at low temperatures. Finally, we show that the LPE is additionally a good starting point for the mass covalent functionalization of 2D magnetic materials with functional molecules. This technique is extensible to any vdW magnetic family.

Fabrication of devices featuring covalently linked MoS2-graphene heterostructures.

The most widespread method for the synthesis of 2D-2D heterostructures is the direct growth of one material on top of the other. Alternatively, flakes of different materials can be manually stacked on top of each other. Both methods typically involve stacking 2D layers through van der Waals forces-such that these materials are often referred to as van der Waals heterostructures-and are stacked one crystal or one device at a time. Here we describe the covalent grafting of 2H-MoS2 flakes onto graphene monolayers embedded in field-effect transistors. A bifunctional molecule featuring a maleimide and a diazonium functional group was used, known to connect to sulfide- and carbon-based materials, respectively. MoS2 flakes were exfoliated, functionalized by reaction with the maleimide moieties and then anchored to graphene by the diazonium groups. This approach enabled the simultaneous functionalization of several devices. The electronic properties of the resulting heterostructure are shown to be dominated by the MoS2-graphene interface.

Optimized Liquid-Phase Exfoliation of Magnetic van der Waals Heterostructures: Towards the Single Layer and Deterministic Fabrication of Devices.

Van der Waals magnetic materials are promising candidates for spintronics and testbeds for exotic magnetic phenomena in low dimensions. The two-dimensional (2D) limit in these materials is typically reached by mechanically breaking the van der Waals interactions between layers. Alternative approaches to producing large amounts of flakes rely on wet methods such as liquid-phase exfoliation (LPE). Here, we report an optimized route for obtaining monolayers of magnetic cylindrite by LPE. We show that the selection of exfoliation times is the determining factor in producing a statistically significant amount of monolayers while keeping relatively big flake areas (~1 µm2). We show that the cylindrite lattice is preserved in the flakes after LPE. To study the electron transport properties, we have fabricated field-effect transistors based on LPE cylindrite. Flakes are deterministically positioned between nanoscale electrodes by dielectrophoresis. We show that dielectrophoresis can selectively move the larger flakes into the devices. Cylindrite nanoscale flakes present a p-doped semiconducting behaviour, in agreement with the mechanically exfoliated counterparts. Alternating current (AC) admittance spectroscopy sheds light on the role played by potential barriers between different flakes in terms of electron transport properties. The present large-scale exfoliation and device fabrication strategy can be extrapolated to other families of magnetic materials.

Tunable Proton Conductivity and Color in a Nonporous Coordination Polymer via Lattice Accommodation to Small Molecules.

Nonporous coordination polymers (npCPs) able to accommodate molecules through internal lattice reorganization are uncommon materials with applications in sensing and selective gas adsorption. Proton conduction, extensively studied in the analogue metal-organic frameworks under high-humidity conditions, is however largely unexplored in spite of the opportunities provided by the particular sensitivity of npCPs to lattice perturbations. Here, AC admittance spectroscopy is used to unveil the mechanism behind charge transport in the nonporous 1·2CH3 CN. The conductance in the crystals is found to be of protonic origin. A vehicle mechanism is triggered by the dynamics of the weakly coupled acetonitrile molecules in the lattice that can be maintained by a combination of thermal cycles, even at low humidity levels. An analogue 1·pyrrole npCP is formed by in situ exchange of these weakly bound acetonitrile molecules by pyrrole. The color and conduction properties are determined by the molecules weakly bonded in the lattice. This is the first example of acetonitrile-mediated proton transport in an npCP showing distinct optical response to different molecules. These findings open the door to the design of switchable protonic conductors and capacitive sensors working at low humidity levels and with selectivity to different molecules.

Coupling the pretreatment and hydrolysis of lignocellulosic biomass by the expression of beta-xylosidases.

Thermochemical pretreatment and enzymatic hydrolysis are the areas contributing most to the operational costs of second generation ethanol in lignocellulosic biorefineries. The improvement of lignocellulosic enzyme cocktails has been significant in the recent years. Although the needs for the reduction of the energy intensity and chemical consumption in the pretreatment step are well known, the reduction of the severity of the process strongly affects the enzymatic hydrolysis yield. To explore the formulation requirements of the well known cellulolytic cocktail from Myceliophthora thermophila on mild pretreated raw materials, this cocktail was tested on steam exploded corn stover without acid impregnation. The low hemicellulose yield and significant accumulation of xylobiose compared with the standard pretreated material obtained with dilute acid impregnation evidenced a clear limitation in the conversion of xylan to xylose. In order to complement the beta-xylosidase limitation, a selection of enzymes was expressed and tested in this fungus. A controlled expression of xylosidases from Aspergillus nidulans, Aspergillus fumigatus, and Fusarium oxysporum allowed recovering hemicellulose yields reached with standard acid treated material. The results underline the need of parallel development of the pretreatment process with the optimization of the formulation of the enzymatic cocktails.