We present an overview of the main techniques for production and processing of graphene and related materials (GRMs), as well as the key characterization procedures. We adopt a ‘hands-on’ approach, providing practical details and procedures as derived from literature as well as from the authors’ experience, in order to enable the reader to reproduce the results. Section is devoted to ‘bottom up’ approaches, whereby individual constituents are pieced together into more complex structures. We consider graphene nanoribbons (GNRs) produced either by solution processing or by on-surface synthesis in ultra high vacuum (UHV), as well carbon nanomembranes (CNM). Production of a variety of GNRs with tailored band gaps and edge shapes is now possible. CNMs can be tuned in terms of porosity, crystallinity and electronic behaviour. Section covers ‘top down’ techniques. These rely on breaking down of a layered precursor, in the graphene case usually natural crystals like graphite or artificially synthesized materials, such as highly oriented pyrolythic graphite, monolayers or few layers (FL) flakes. The main focus of this section is on various exfoliation techniques in a liquid media, either intercalation or liquid phase exfoliation (LPE). The choice of precursor, exfoliation method, medium as well as the control of parameters such as time or temperature are crucial. A definite choice of parameters and conditions yields a particular material with specific properties that makes it more suitable for a targeted application. We cover protocols for the graphitic precursors to graphene oxide (GO). This is an important material for a range of applications in biomedicine, energy storage, nanocomposites, etc. Hummers’ and modified Hummers’ methods are used to make GO that subsequently can be reduced to obtain reduced graphene oxide (RGO) with a variety of strategies. GO flakes are also employed to prepare three-dimensional (3d) low density structures, such as sponges, foams, hydro- or aerogels. The assembly of flakes into 3d structures can provide improved mechanical properties. Aerogels with a highly open structure, with interconnected hierarchical pores, can enhance the accessibility to the whole surface area, as relevant for a number of applications, such as energy storage. The main recipes to yield graphite intercalation compounds (GICs) are also discussed. GICs are suitable precursors for covalent functionalization of graphene, but can also be used for the synthesis of uncharged graphene in solution. Degradation of the molecules intercalated in GICs can be triggered by high temperature treatment or microwave irradiation, creating a gas pressure surge in graphite and exfoliation. Electrochemical exfoliation by applying a voltage in an electrolyte to a graphite electrode can be tuned by varying precursors, electrolytes and potential. Graphite electrodes can be either negatively or positively intercalated to obtain GICs that are subsequently exfoliated. We also discuss the materials that can be amenable to exfoliation, by ...

The different exfoliation routes of graphite to produce graphene by sonication in solvent, chemical oxidation and electrochemical oxidation are compared. The exfoliation process and roughening of a flat graphite substrate is directly visualized at the nanoscale by scanning probe and electron microscopy. The etching damage in graphite and the properties of the exfoliated sheets are compared by Raman spectroscopy and X‐ray diffraction analysis. The results show the trade‐off between exfoliation speed and preservation of graphene quality. A key step to achieve efficient exfoliation is to couple gas production and mechanical exfoliation on a macroscale with non‐covalent exfoliation and preservation of graphene properties on a molecular scale.

We describe a fast and versatile method to functionalize high-quality graphene with organic molecules by exploiting the synergistic effect of supramolecular and covalent chemistry. With this goal, we designed and synthesized molecules comprising a long aliphatic chain and an aryl diazonium salt. Thanks to the long chain, these molecules physisorb from solution onto CVD graphene or bulk graphite, self-assembling in an ordered monolayer. The sample is successively transferred into an aqueous electrolyte, to block any reorganization or desorption of the monolayer. An electrochemical impulse is used to transform the diazonium group into a radical capable of grafting covalently to the substrate and transforming the physisorption into a covalent chemisorption. During covalent grafting in water, the molecules retain the ordered packing formed upon self-assembly. Our two-step approach is characterized by the independent control over the processes of immobilization of molecules on the substrate and their covalent tethering, enabling fast (t < 10 s) covalent functionalization of graphene. This strategy is highly versatile and works with many carbon-based materials including graphene deposited on silicon, plastic, and quartz as well as highly oriented pyrolytic graphite.

A facile and efficient method based on electrochemistry for the production of graphene‐based materials for electronics is demonstrated. Uncharged acetonitrile molecules are intercalated in graphite by electrochemical treatment, owing to the synergic action of perchlorate ions dissolved in acetonitrile. Then, acetonitrile molecules are decomposed with microwave irradiation, which causes gas production and rapid graphite exfoliation, with an increase in the graphite volume of up to 600 %. Upon further processing and purification, highly dispersible nanosheets are obtained that can be processed into thin layers by roll‐to‐roll transfer or into thicker electrodes with excellent capacitance stability upon extensive charging/discharging cycles. The good exfoliation yield (>50 % of monolayers), minimal oxidation damage and good electrochemical stability of the nanosheets obtained were confirmed by scanning force and electron microscopy, as well as Raman spectroscopy and galvanostatic analyses.

A main advantage of graphene oxide (GO) over other materials is the high tunability of its surface functional groups and of its electric conductivity. However, the complex chemical composition of GO renders difficult to unravel the correlation between structural and electric properties. Here, we use a combination of electron spectroscopy and electrochemistry to correlate the surface chemistry of GO to its electrical conductivity and electrocatalytic properties with respect to two molecules of high biological interest: β-nicotinamide adenine dinucleotide (NADH) and vitamin C. We demonstrate that the electrocatalytic properties of the material are due to hydroxyl, carbonyl and carboxyl groups residues that, even if already present on pristine GO, become electroactive only upon GO reduction. The results of this study demonstrate the advantages in the use of GO in amperometric biosensing and in enzymatic biofuel cells: it allows the oxidation of the target molecules at low potential values, with a sensitivity >15 times higher with respect to standard, carbon-based electrode materials. Finally, we demonstrate that the right amount of chemical groups to achieve such high performance can be obtained also by direct electrochemical exfoliation of bulk graphite, without passing through GO production, thus rendering this approach suitable for cheap, large-scale applications.

Sodium, in contrast to other metals, cannot intercalate in graphite, hindering the use of this cheap, abundant element in rechargeable batteries. Here, we report a nanometric graphite-like anode for Na+ storage, formed by stacked graphene sheets functionalized only on one side, termed Janus graphene. The asymmetric functionalization allows reversible intercalation of Na+, as monitored by operando Raman spectroelectrochemistry and visualized by imaging ellipsometry. Our Janus graphene has uniform pore size, controllable functionalization density, and few edges; it can store Na+ differently from graphite and stacked graphene. Density functional theory calculations demonstrate that Na+ preferably rests close to -NH2 group forming synergic ionic bonds to graphene, making the interaction process energetically favorable. The estimated sodium storage up to C6.9Na is comparable to graphite for standard lithium ion batteries. Given such encouraging Na+ reversible intercalation behavior, our approach provides a way to design carbon-based materials for sodium ion batteries.

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