The edges of 2D materials have emerged as promising electrochemical catalyst systems, yet their performance still lags behind that of noble metals. Here, we demonstrate the potential of oriented electric fields (OEFs) to enhance the electrochemical activity of 2D materials edges. By atomically engineering the edge of a fluorographene/graphene/MoS2 heterojunction nanoribbon, strong and localized OEFs were realized as confirmed by simulations and spatially resolved spectroscopy. The observed fringing OEF results in an enhancement of the heterogeneous charge transfer rate between the edge and the electrolyte by 2 orders of magnitude according to impedance spectroscopy. Ab initio calculations indicate a field-induced decrease in the reactant adsorption energy as the origin of this improvement. We apply the OEF-enhanced edge reactivity to hydrogen evolution reactions (HER) and observe a significantly enhanced electrochemical performance, as evidenced by a 30% decrease in Tafel slope and a 3-fold enhanced turnover frequency. Our findings demonstrate the potential of OEFs for tailoring the catalytic properties of 2D material edges toward future complex reactions.

• Keywords
• 2D edges, 2D materials, HER, electrochemistry, oriented electric fields,
• Publication type
• Journal Article MeSH

2D oxide nanomaterials constitute a broad range of materials, with a wide array of current and potential applications, particularly in the fields of energy storage and catalysis for sustainable energy production. Despite the many similarities in structure, composition, and synthetic methods and uses, the current literature on layered oxides is diverse and disconnected. A number of reviews can be found in the literature, but they are mostly focused on one of the particular subclasses of 2D oxides. This review attempts to bridge the knowledge gap between individual layered oxide types by summarizing recent developments in all important 2D oxide systems including supported ultrathin oxide films, layered clays and double hydroxides, layered perovskites, and novel 2D-zeolite-based materials. Particular attention is paid to the underlying similarities and differences between the various materials, and the subsequent challenges faced by each research community. The potential of layered oxides toward future applications is critically evaluated, especially in the areas of electrocatalysis and photocatalysis, biomass conversion, and fine chemical synthesis. Attention is also paid to corresponding novel 3D materials that can be obtained via sophisticated engineering of 2D oxides.

• Keywords
• 2D catalysts, 2D zeolites, energy transitions, environmentally friendly catalysis, layered oxides,
• MeSH
• Catalysis MeSH
• Nanostructures chemistry   MeSH
• Oxides chemistry   MeSH
• Publication type
• Journal Article MeSH
• Review MeSH
• Names of Substances
• Oxides MeSH

Noble gases, notably xenon, play a pivotal role in diverse high-tech applications. However, manufacturing xenon is an inherently challenging task, due to its unique properties and trace abundance in the Earth's atmosphere. Consequently, there is a pressing need for the development of efficient methods for the separation of noble gases. Using mild fluorographene chemistry, nitrogen-doped graphene (GNs) materials are synthesized with abundant aromatic regions and extensive nitrogen doping within the vacancies and holes of the aromatic lattice. Due to the organized interlayer "nanochannels", nitrogen functional groups, and defects within the two-dimensional (2D) structures, GNs exhibits effective selectivity for Xe over Kr at low pressure. This enhanced selectivity is attributed to the stronger binding affinity of Xe to GN compared to Kr. The adsorption is governed by London dispersion forces, as revealed by theoretical calculations using symmetry-adapted perturbation theory (SAPT). Investigation of other GNs differing in nitrogen content, surface area, and pore sizes underscores the significance of nitrogen functional groups, defects, and interlayer nanochannels over the surface area in achieving superior selectivity. This work offers a new perspective on the design and fabrication of functionalized graphene derivatives, exhibiting superior noble gas storage and separation activity exploitable in gas production technologies.

• Keywords
• 2D materials, defect engineering, noble gas separation, selectivity, symmetry‐adapted perturbation theory (SAPT), xenon,
• Publication type
• Journal Article MeSH

As the field of low-dimensional materials (1D or 2D) grows and more complex and intriguing structures are continuing to be found, there is an emerging need for techniques to characterize the nanoscale mechanical properties of all kinds of 1D/2D materials, in particular in their most practical state: sitting on an underlying substrate. While traditional nanoindentation techniques cannot accurately determine the transverse Young's modulus at the necessary scale without large indentations depths and effects to and from the substrate, herein an atomic-force-microscopy-based modulated nanomechanical measurement technique with Angstrom-level resolution (MoNI/ÅI) is presented. This technique enables non-destructive measurements of the out-of-plane elasticity of ultra-thin materials with resolution sufficient to eliminate any contributions from the substrate. This method is used to elucidate the multi-layer stiffness dependence of graphene deposited via chemical vapor deposition and discover a peak transverse modulus in two-layer graphene. While MoNI/ÅI has been used toward great findings in the recent past, here all aspects of the implementation of the technique as well as the unique challenges in performing measurements at such small resolutions are encompassed.

• Keywords
• 2D materials, atomic force microscopy, indentation, nanomechanics,
• Publication type
• Journal Article MeSH

The human body involves a large number of systems subjected to contact stresses and thus experiencing wear and degradation. The limited efficacy of existing solutions constantly puts a significant financial burden on the healthcare system, more importantly, patients are suffering due to the complications following a partial or total system failure. More effective strategies are highly dependent on the availability of advanced functional materials demonstrating excellent tribological response and good biocompatibility. In this article, we review the recent progress in implementing two-dimensional (2D) materials into bio-applications involving tribological contacts. We further summarize the current challenges for future progress in the field.

• Keywords
• Biotribology, Friction, Medical devices, Two-dimensional materials, Wear,
• MeSH
• Humans MeSH
• Friction * MeSH
• Check Tag
• Humans MeSH
• Publication type
• Journal Article MeSH
• Review MeSH

In recent years, two-dimensional (2D) materials have attracted a lot of research interest as they exhibit several fascinating properties. However, outside of 2D materials derived from van der Waals layered bulk materials only a few other such materials are realized, and it remains difficult to confirm their 2D freestanding structure. Despite that, many metals are predicted to exist as 2D systems. In this review, the authors summarize the recent progress made in the synthesis and characterization of these 2D metals, so called metallenes, and their oxide forms, metallene oxides as free standing 2D structures formed in situ through the use of transmission electron microscopy (TEM) and scanning TEM (STEM) to synthesize these materials. Two primary approaches for forming freestanding monoatomic metallic membranes are identified. In the first, graphene pores as a means to suspend the metallene or metallene oxide and in the second, electron-beam sputtering for the selective etching of metal alloys or thick complex initial materials is employed to obtain freestanding single-atom-thick 2D metal. The data show a growing number of 2D metals/metallenes and 2D metal/ metallene oxides having been confirmed and point to a bright future for further discoveries of these 2D materials.

• Keywords
• 2D metals/metallenes, freestanding single-atom-thick membrane, in situ TEM, single-element 2D materials,
• Publication type
• Journal Article MeSH
• Review MeSH

Two-dimensional materials are responsible for changing research in materials science. After graphene and its counterparts, graphane, fluorographene, and others were introduced, waves of renewed interest in 2D binary compounds occurred, such as in metal oxides, transition-metal dichalcogenides (most often represented by MoS2 ), metal oxy/hydroxide borides, and MXenes, to name the most prominent. Recently, interest has turned to two-dimensional monoelemental structures, such as monolayer black phosphorus and, very recently, to monolayer arsenic, antimony, and bismuth. Here, a short overview is provided of the area of exponentially increasing research in arsenene, antimonene, and bismuthene, which belong to the fifth main group of elements, the so-called pnictogens. A short review of historical work is provided, the properties of bulk allotropes of As, Sb, and Bi discussed, and then theoretical and experimental research on mono- and few-layered arsenene, antimonene, and bismuthene addressed, discussing their structures and properties.

• Keywords
• 2D materials, electronics, layered materials, optics, structure, synthesis,
• Publication type
• Journal Article MeSH
• Review MeSH

The design and fabrication of active nanomaterials exhibiting multifunctional properties is a must in the so-called global "Fourth Industrial Revolution". In this sense, molecular engineering is a powerful tool to implant original capabilities on a macroscopic scale. Herein, different bioinspired 2D-MXenes have been developed via a versatile and straightforward synthetic approach. As a proof of concept, Ti3C2Tx MXene has been exploited as a highly sensitive transducing platform for the covalent assembly of active biomolecular architectures (i.e., amino acids). All pivotal properties originated from the anchored targets were proved to be successfully transferred to the resulting bioinspired 2D-MXenes. Appealing applications have been devised for these 2D-MXene prototypes showing (i) chiroptical activity, (ii) fluorescence capabilities, (iii) supramolecular π-π interactions, and (iv) stimuli-responsive molecular switchability. Overall, this work demonstrates the fabrication of programmable 2D-MXenes, taking advantage of the inherent characteristics of the implanted (bio)molecular components. Thus, the current bottleneck in the field of 2D-MXenes can be overcome after the significant findings reported here.

• Keywords
• 2D materials, chiral MXene, electronic devices, fluorescence, molecular switches, supramolecular recognition, surface engineering,
• MeSH
• Nanostructures * MeSH
• Titanium * MeSH
• Publication type
• Journal Article MeSH
• Research Support, Non-U.S. Gov't MeSH
• Names of Substances
• Titanium * MeSH

Kaolinite is a single 2D layer of kaolin or metakaolin (MK), common clays that can be characterized as layered 3D materials. We show that because of its chemical composition, kaolinite can be converted into an amorphous 3D material by chemical means. This dimensional transformation is possible due to the large surface to volume ratio and chemical reactivity of kaolinite. We investigate the formation and influence of quasi- or nanocrystalline phases in MK-based alkali-activated materials (AAM) that are related to the Si/Al ratio. We analyze the formation of an AAM from a MK precursor, which is a 3D bonded network that preserves the layered structure at the nanometer scale. We also exfoliate the remaining layered phase to examine the effects of the alkali-activation in the final sheet structures embedded within the amorphous network. The final material can be used as a cement with no carbon dioxide produced by the transformation reaction.

• Keywords
• 2D materials, Alkali-activation, Clays, Geopolymer, Metakaolin,
• Publication type
• Journal Article MeSH

Two dimensional materials beyond graphene are in forefront research. Two dimensional analogues of graphene of group 14, germanene, are of high importance for their electronic and optical properties. The commonly used deintercalation fabrication approach has reached a major bottleneck in the field due to the lack of versatility derived from the limited library of precursors available for 2D-Ge functionalization with terminal groups. Thus, a chemical procedure that would allow for the on-demand synthesis of functional 2D-Ge derivatives with tuned physicochemical features for task-specific applications is of utmost importance to advance in the field. To fill this gap, click chemistry is herein presented as a straightforward "one-pot" synthetic strategy to simply reach functional 2D-Ge derivatives by covalently assembling ad hoc thiol-rich active molecular components (R'-SH) upon commercially available allyl 2D-Ge (2D-Ge-CH2CHCH2) by taking advantage of a photoinduced thiol-ene click reaction. Consequently, the combination of molecular engineering and Ge-based 2D materials through click chemistry supposes a step forward towards the achievement of a new family of smart 2D-Ge-CH2CH2CH2S-R' derivatives with different (supra)molecular responsiveness, which goes beyond the state-of-the-art in the field. This approach of functionalization of 2D monoelemental post-graphene material germanene is highly innovative and shall provide universal way of functionalization of germananes.

• Publication type
• Journal Article MeSH