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There is a high interest in living organism-compatible materials associated with electrically active interfaces. Bacteria/electrode interfaces implement smart, functional systems with responses, based on which it is possible to elaborate self-regulating energy generation systems. Carbon materials have a number of advantages, such as biocompatibility, low electrical resistance, and the possibility of increasing the electrode surface on an industrial scale. The most promising approach for the industrial production of electrodes is 3D printing. We propose a 3D-printed carbon electrode – a novel lightweight material for electrodes in bioelectrochemical systems for efficient bioelectricity utilization. The pyrolytic process for manufacturing carbon electrodes is promising for upscaling and industrial applications. However, there is a problem of volume loss when 3D-printed polymers are pyrolyzed in an inert environment. We propose a new strategy for the thermal treatment of 3D-printed polymers that allow for reduced volume loss under pyrolytic carbonization. In addition, to achieve a higher electrode surface area, the graphene aerogel could be impregnated into the 3D-printed scaffolds. Chemical modification of graphene surface can enhance biocompatibility. Specifically, the oxidation of graphene leads to forming a hydrophilic and biocompatible material. We tune graphene hydrophilic properties and electrical conductivity via control over the thermal reduction of the oxidized form of graphene–graphene oxide 1 . Such sponge morphology affords 3D-printed carbon scaffolds an excellent lightweight host scaffold for microorganisms, in which the graphene nanowalls are homogeneously occupied by S. oneidensis MR-1. We demonstrate a novel sustainable method to produce graphene-based lightweight 3D printed electrode materials for green energy production from biomass. The proposed technology creates the opportunity for novel, innovative, disruptive graphene applications that can lead to the establishment of new energy-related industries and facilitate many startups in the ecosystem. Acknowledgments This work was supported by the Ministry of Education (Singapore) through the Research Centre of Excellence program (grant EDUN C-33-18-279-V12, I-FIM). References Xuanye Leng, Ricardo J. Vazquez, Samantha R. McCuskey, Glenn Quek, Yude Su, Konstantin G. Nikolaev, Mariana C.F. Costa, Siyu Chen, Musen Chen, Kou Yang, Jinpei Zhao, Mo Lin, Zhaolong Chen, Guillermo C. Bazan, Kostya S. Novoselov, Daria V. Andreeva, Carbon, 205, 2023, 33-39.

Nanoholes, etched under an electron beam at room temperature in single-layer graphene sheets as a result of their interaction with metal impurities, are shown to heal spontaneously by filling up with either nonhexagon, graphene-like, or perfect hexagon 2D structures. Scanning transmission electron microscopy was employed to capture the healing process and study atom-by-atom the regrown structure. A combination of these nanoscale etching and reknitting processes could lead to new graphene tailoring approaches.

Materials science is being rapidly transformed by machine learning tools. This paper introduces a machine learning approach for predicting energy and other derived properties in metal-organic frameworks (MOFs). Using neural networks, our approach generates embedding characteristics for both local atomic structures and the overall MOF system by extracting hidden representations of pairwise interactions among atoms inside MOFs. These networks are trained using total energies derived from density functional theory computations, and they are shared for all paired terms. The model performs better than others in terms of total energy prediction, with a mean absolute error of about 0.09 eV/atom. Furthermore, we demonstrate the transferability of the learned features to accurately predict band gaps. t-Distributed stochastic neighbor embedding is utilized to gain insights into the meaningful patterns within the MOF space, while a K-means clustering model is carried out to detect distinct groups of MOFs.

A promising way to address modern environmental and energy supply challenges is via rapid implementation of decarbonization and hydrogen production technologies. Development of gas separation membranes with high selectivity and permeability is essential for these processes but is still a grand bottleneck. Our research focuses on achieving precise control of gas diffusion pathways through on-demand regulation of material interactions in nanometer-thick composite membranes. We combine 2D covalent organic frameworks (COFs) and graphene oxide (GO) to create COF-GO composite membranes with desirable nanosheet stacking, controllable thicknesses and pathways for gases. By pH-assisted self-assembly, we fine-tune material interactions and achieve simultaneous enhancement of permeability and selectivity by increasing membrane thickness and regulating the interactions between COF and GO nanosheets by pH. This work paves the way for tailored, performing gas separation with superior long-term stability. It guides the unique 2D transport mechanism to be utilized under practical conditions. Our research offers a novel strategy for the design of composite membranes from two-dimensional (2D) materials for gas separation technologies. It contributes to sustainable decarbonization and hydrogen production solutions, bringing us closer to a greener, more environmentally friendly future.

We present the science and technology roadmap for graphene, related two-dimensional crystals, and hybrid systems, targeting an evolution in technology, that might lead to impacts and benefits reaching into most areas of society. This roadmap was developed within the framework of the European Graphene Flagship and outlines the main targets and research areas as best understood at the start of this ambitious project. We provide an overview of the key aspects of graphene and related materials (GRMs), ranging from fundamental research challenges to a variety of applications in a large number of sectors, highlighting the steps necessary to take GRMs from a state of raw potential to a point where they might revolutionize multiple industries. We also define an extensive list of acronyms in an effort to standardize the nomenclature in this emerging field.

Nonlinear mechanics of solids is an exciting field that encompasses both beautiful mathematics, such as the emergence of instabilities and the formation of complex patterns, as well as multiple applications. Two-dimensional crystals and van der Waals (vdW) heterostructures allow revisiting this field on the atomic level, allowing much finer control over the parameters and offering atomistic interpretation of experimental observations. In this work, we consider the formation of instabilities consisting of radially-oriented wrinkles around mono- and few-layer "bubbles" in two-dimensional vdW heterostructures. Interestingly, the shape and wavelength of the wrinkles depend not only on the thickness of the two-dimensional crystal forming the bubble, but also on the atomistic structure of the interface between the bubble and the substrate, which can be controlled by their relative orientation. We argue that the periodic nature of these patterns emanates from an energetic balance between the resistance of the top membrane to bending, which favors large wavelength of wrinkles, and the membrane-substrate vdW attraction, which favors small wrinkle amplitude. Employing the classical "Winkler foundation" model of elasticity theory, we show that the number of radial wrinkles conveys a valuable relationship between the bending rigidity of the top membrane and the strength of the vdW interaction. Armed with this relationship, we use our data to demonstrate a nontrivial dependence of the bending rigidity on the number of layers in the top membrane, which shows two different regimes driven by slippage between the layers, and a high sensitivity of the vdW force to the alignment between the substrate and the membrane.

Van der Waals assembly enables the design of electronic states in two-dimensional (2D) materials, often by superimposing a long-wavelength periodic potential on a crystal lattice using moiré superlattices1-9. This twistronics approach has resulted in numerous previously undescribed physics, including strong correlations and superconductivity in twisted bilayer graphene10-12, resonant excitons, charge ordering and Wigner crystallization in transition-metal chalcogenide moiré structures13-18 and Hofstadter's butterfly spectra and Brown-Zak quantum oscillations in graphene superlattices19-22. Moreover, twistronics has been used to modify near-surface states at the interface between van der Waals crystals23,24. Here we show that electronic states in three-dimensional (3D) crystals such as graphite can be tuned by a superlattice potential occurring at the interface with another crystal-namely, crystallographically aligned hexagonal boron nitride. This alignment results in several Lifshitz transitions and Brown-Zak oscillations arising from near-surface states, whereas, in high magnetic fields, fractal states of Hofstadter's butterfly draw deep into the bulk of graphite. Our work shows a way in which 3D spectra can be controlled using the approach of 2D twistronics.

Hexagonal boron nitride is the only substrate that has so far allowed graphene devices exhibiting micron-scale ballistic transport. Can other atomically flat crystals be used as substrates for making quality graphene heterostructures? Here we report on our search for alternative substrates. The devices fabricated by encapsulating graphene with molybdenum or tungsten disulphides and hBN are found to exhibit consistently high carrier mobilities of about 60,000 cm$^{2}$V$^{-1}$s$^{-1}$. In contrast, encapsulation with atomically flat layered oxides such as mica, bismuth strontium calcium copper oxide and vanadium pentoxide results in exceptionally low quality of graphene devices with mobilities of ~ 1,000 cm$^{2}$ V$^{-1}$s$^{-1}$. We attribute the difference mainly to self-cleansing that takes place at interfaces between graphene, hBN and transition metal dichalcogenides. Surface contamination assembles into large pockets allowing the rest of the interface to become atomically clean. The cleansing process does not occur for graphene on atomically flat oxide substrates.

Graphene - a monolayer of carbon atoms densely packed into a hexagonal lattice - has one of the strongest possible atomic bonds and can be viewed as a robust atomic-scale scaffold, to which other chemical species can be attached without destroying it. This notion of graphene as a giant flat molecule that can be altered chemically is supported by the observation of so-called graphene oxide, that is graphene densely covered with hydroxyl and other groups. Unfortunately, graphene oxide is strongly disordered, poorly conductive and difficult to reduce to the original state. Nevertheless, one can imagine atoms or molecules being attached to the atomic scaffold in a strictly periodic manner, which should result in a different electronic structure and, essentially, a different crystalline material. A hypothetical example for this is graphane, a wide-gap semiconductor, in which hydrogen is bonded to each carbon site of graphene. Here we show that by exposing graphene to atomic hydrogen, it is possible to transform this highly-conductive semimetal into an insulator. Transmission electron microscopy reveals that the material retains the hexagonal lattice but its period becomes markedly shorter than that of graphene, providing direct evidence for a new graphene-based derivative. The reaction with hydrogen is found to be reversible so that the original metallic state and lattice spacing are restored by annealing and even the quantum Hall effect recovers. Our work proves the concept of chemical modification of graphene, which promises a whole range of new two-dimensional crystals with designed electronic and other properties.

The dielectric constant of interfacial water has been predicted to be smaller than that of bulk water (= 80) because the rotational freedom of water dipoles is expected to decrease near surfaces, yet experimental evidence is lacking. We report local capacitance measurements for water confined between two atomically-flat walls separated by various distances down to 1 nm. Our experiments reveal the presence of an interfacial layer with vanishingly small polarization such that its out-of-plane dielectric constant is only approximately 2. The electrically dead layer is found to be two to three molecules thick. These results provide much needed feedback for theories describing water-mediated surface interactions and behavior of interfacial water, and show a way to investigate the dielectric properties of other fluids and solids under extreme confinement.

Precise graphene patterning is of critical importance for tailor-made and sophisticated two-dimensional nanoelectronic and optical devices. However, graphene-based heterostructures have been grown by delicate multistep chemical vapor deposition methods, limiting preparation of versatile heterostructures. Here, we report one-pot synthesis of graphene/amorphous carbon (a-C) heterostructures from a solid source of polystyrene via selective photo-cross-linking process. Graphene is successfully grown from neat polystyrene regions, while patterned cross-linked polystyrene regions turn into a-C because of a large difference in their thermal stability. Since the electrical resistance of a-C is at least 2 orders of magnitude higher than that for graphene, the charge transport in graphene/a-C heterostructure occurs through the graphene region. Measurement of the quantum Hall effect in graphene/a-C lateral heterostructures clearly confirms the reliable quality of graphene and well-defined graphene/a-C interface. The direct synthesis of patterned graphene from polymer pattern could be further exploited to prepare versatile heterostructures.

The introduction of foreign atoms, such as nitrogen, into the hexagonal network of an sp(2)-hybridized carbon atom monolayer has been demonstrated and constitutes an effective tool for tailoring the intrinsic properties of graphene. Here, we report that boron atoms can be efficiently substituted for carbon in graphene. Single-layer graphene substitutionally doped with boron was prepared by the mechanical exfoliation of boron-doped graphite. X-ray photoelectron spectroscopy demonstrated that the amount of substitutional boron in graphite was ~0.22 atom %. Raman spectroscopy demonstrated that the boron atoms were spaced 4.76 nm apart in single-layer graphene. The 7-fold higher intensity of the D-band when compared to the G-band was explained by the elastically scattered photoexcited electrons by boron atoms before emitting a phonon. The frequency of the G-band in single-layer substitutionally boron-doped graphene was unchanged, which could be explained by the p-type boron doping (stiffening) counteracting the tensile strain effect of the larger carbon-boron bond length (softening). Boron-doped graphene appears to be a useful tool for engineering the physical and chemical properties of graphene.

Molecular self-assembly plays a very important role in various aspects of technology as well as in biological systems. Governed by the covalent, hydrogen or van der Waals interactions - self-assembly of alike molecules results in a large variety of complex patterns even in two dimensions (2D). Prediction of pattern formation for 2D molecular networks is extremely important, though very challenging, and so far, relied on computationally involved approaches such as density functional theory, classical molecular dynamics, Monte Carlo, or machine learning. Such methods, however, do not guarantee that all possible patterns will be considered and often rely on intuition. Here we introduce a much simpler, though rigorous, hierarchical geometric model founded on the mean-field theory of 2D polygonal tessellations to predict extended network patterns based on molecular-level information. Based on graph theory, this approach yields pattern classification and pattern prediction within well-defined ranges. When applied to existing experimental data, our model provides an entirely new view of self-assembled molecular patterns, leading to interesting predictions on admissible patterns and potential additional phases. While developed for hydrogen-bonded systems, an extension to covalently bonded graphene-derived materials or 3D structures such as fullerenes is possible, significantly opening the range of potential future applications.

Two-dimensional transition metal dichalcogenide (TMD) semiconductors provide a unique possibility to access the electronic valley degree of freedom using polarized light, opening the way to valley information transfer between distant systems. Excitons with a well-defined valley index (or valley pseudospin) as well as superpositions of the exciton valley states can be created with light having circular and linear polarization, respectively. However, the generated excitons have short lifetimes (ps) and are also subject to the electron-hole exchange interaction leading to fast relaxation of the valley pseudospin and coherence. Here we show that control of these processes can be gained by embedding a monolayer of WSe$_2$ in an optical microcavity, where part-light-part-matter exciton-polaritons are formed in the strong light-matter coupling regime. We demonstrate the optical initialization of the valley coherent polariton populations, exhibiting luminescence with a linear polarization degree up to 3 times higher than that of the excitons. We further control the evolution of the polariton valley coherence using a Faraday magnetic field to rotate the valley pseudospin by an angle defined by the exciton-cavity-mode detuning, which exceeds the rotation angle in the bare exciton. This work provides unique insight into the decoherence mechanisms in TMDs and demonstrates the potential for engineering the valley pseudospin dynamics in monolayer semiconductors embedded in photonic structures.