| 1. |
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| 2. |
- Backes, Claudia, et al.
(författare)
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Production and processing of graphene and related materials
- 2020
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Ingår i: 2D Materials. - : IOP Publishing. - 2053-1583. ; 7:2
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Tidskriftsartikel (refereegranskat)abstract
- 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 I 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 II 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 employing a theoretical data-mining approach. The exfoliation of LMs usually results in a heterogeneous dispersion of flakes with different lateral size and thickness. This is a critical bottleneck for applications, and hinders the full exploitation of GRMs produced by solution processing. The establishment of procedures to control the morphological properties of exfoliated GRMs, which also need to be industrially scalable, is one of the key needs. Section III deals with the processing of flakes. (Ultra)centrifugation techniques have thus far been the most investigated to sort GRMs following ultrasonication, shear mixing, ball milling, microfluidization, and wet-jet milling. It allows sorting by size and thickness. Inks formulated from GRM dispersions can be printed using a number of processes, from inkjet to screen printing. Each technique has specific rheological requirements, as well as geometrical constraints. The solvent choice is critical, not only for the GRM stability, but also in terms of optimizing printing on different substrates, such as glass, Si, plastic, paper, etc, all with different surface energies. Chemical modifications of such substrates is also a key step. Sections IV-VII are devoted to the growth of GRMs on various substrates and their processing after growth to place them on the surface of choice for specific applications. The substrate for graphene growth is a key determinant of the nature and quality of the resultant film. The lattice mismatch between graphene and substrate influences the resulting crystallinity. Growth on insulators, such as SiO2, typically results in films with small crystallites, whereas growth on the close-packed surfaces of metals yields highly crystalline films. Section IV outlines the growth of graphene on SiC substrates. This satisfies the requirements for electronic applications, with well-defined graphene-substrate interface, low trapped impurities and no need for transfer. It also allows graphene structures and devices to be measured directly on the growth substrate. The flatness of the substrate results in graphene with minimal strain and ripples on large areas, allowing spectroscopies and surface science to be performed. We also discuss the surface engineering by intercalation of the resulting graphene, its integration with Si-wafers and the production of nanostructures with the desired shape, with no need for patterning. Section V deals with chemical vapour deposition (CVD) onto various transition metals and on insulators. Growth on Ni results in graphitized polycrystalline films. While the thickness of these films can be optimized by controlling the deposition parameters, such as the type of hydrocarbon precursor and temperature, it is difficult to attain single layer graphene (SLG) across large areas, owing to the simultaneous nucleation/growth and solution/precipitation mechanisms. The differing characteristics of polycrystalline Ni films facilitate the growth of graphitic layers at different rates, resulting in regions with differing numbers of graphitic layers. High-quality films can be grown on Cu. Cu is available in a variety of shapes and forms, such as foils, bulks, foams, thin films on other materials and powders, making it attractive for industrial production of large area graphene films. The push to use CVD graphene in applications has also triggered a research line for the direct growth on insulators. The quality of the resulting films is lower than possible to date on metals, but enough, in terms of transmittance and resistivity, for many applications as described in section V. Transfer technologies are the focus of section VI. CVD synthesis of graphene on metals and bottom up molecular approaches require SLG to be transferred to the final target substrates. To have technological impact, the advances in production of high-quality large-area CVD graphene must be commensurate with those on transfer and placement on the final substrates. This is a prerequisite for most applications, such as touch panels, anticorrosion coatings, transparent electrodes and gas sensors etc. New strategies have improved the transferred graphene quality, making CVD graphene a feasible option for CMOS foundries. Methods based on complete etching of the metal substrate in suitable etchants, typically iron chloride, ammonium persulfate, or hydrogen chloride although reliable, are time- and resource-consuming, with damage to graphene and production of metal and etchant residues. Electrochemical delamination in a low-concentration aqueous solution is an alternative. In this case metallic substrates can be reused. Dry transfer is less detrimental for the SLG quality, enabling a deterministic transfer. There is a large range of layered materials (LMs) beyond graphite. Only few of them have been already exfoliated and fully characterized. Section VII deals with the growth of some of these materials. Amongst them, h-BN, transition metal tri- and di-chalcogenides are of paramount importance. The growth of h-BN is at present considered essential for the development of graphene in (opto) electronic applications, as h-BN is ideal as capping layer or substrate. The interesting optical and electronic properties of TMDs also require the development of scalable methods for their production. Large scale growth using chemical/physical vapour deposition or thermal assisted conversion has been thus far limited to a small set, such as h-BN or some TMDs. Heterostructures could also be directly grown. Section VIII discusses advances in GRM functionalization. A broad range of organic molecules can be anchored to the sp(2) basal plane by reductive functionalization. Negatively charged graphene can be prepared in liquid phase (e.g. via intercalation chemistry or electrochemically) and can react with electrophiles. This can be achieved both in dispersion or on substrate. The functional groups of GO can be further derivatized. Graphene can also be noncovalently functionalized, in particular with polycyclic aromatic hydrocarbons that assemble on the sp(2) carbon network by pi-pi stacking. In the liquid phase, this can enhance the colloidal stability of SLG/FLG. Approaches to achieve noncovalent on-substrate functionalization are also discussed, which can chemically dope graphene. Research efforts to derivatize CNMs are also summarized, as well as novel routes to selectively address defect sites. In dispersion, edges are the most dominant defects and can be covalently modified. This enhances colloidal stability without modifying the graphene basal plane. Basal plane point defects can also be modified, passivated and healed in ultra-high vacuum. The decoration of graphene with metal nanoparticles (NPs) has also received considerable attention, as it allows to exploit synergistic effects between NPs and graphene. Decoration can be either achieved chemically or in the gas phase. All LMs,
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| 3. |
- Durso, M., et al.
(författare)
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Biomimetic graphene for enhanced interaction with the external membrane of astrocytes
- 2018
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Ingår i: Journal of Materials Chemistry B. - : Royal Society of Chemistry (RSC). - 2050-7518 .- 2050-750X. ; 6:33, s. 5335-5342
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Tidskriftsartikel (refereegranskat)abstract
- Graphene and graphene substrates display huge potential as material interfaces for devices and biomedical tools targeting the modulation or recovery of brain functionality. However, to be considered reliable neural interfaces, graphene-derived substrates should properly interact with astrocytes, favoring their growth and avoiding adverse gliotic reactions. Indeed, astrocytes are the most abundant cells in the human brain and they have a crucial physiological role to maintain its homeostasis and modulate synaptic transmission. In this work, we describe a new strategy based on the chemical modification of graphene oxide (GO) with a synthetic phospholipid (PL) to improve interaction of GO with brain astroglial cells. The PL moieties were grafted on GO sheets through polymeric brushes obtained by atom-transfer radical-polymerization (ATRP) between acryloyl-modified PL and GO nanosheets modified with a bromide initiator. The adhesion of primary rat cortical astrocytes on GO-PL substrates increased by about three times with respect to that on glass substrates coated with standard adhesion agents (i.e. poly-d-lysine, PDL) as well as with respect to that on non-functionalized GO. Moreover, we show that astrocytes seeded on GO-PL did not display significant gliotic reactivity, indicating that the material interface did not cause a detrimental inflammatory reaction when interacting with astroglial cells. Our results indicate that the reported biomimetic approach could be applied to neural prosthesis to improve cell colonization and avoid glial scar formation in brain implants. Additionally, improved adhesion could be extremely relevant in devices targeting neural cell sensing/modulation of physiological activity.
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| 4. |
- Lancellotti, Lidia, et al.
(författare)
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Selective ion transport in large-area graphene oxide membrane filters driven by the ionic radius and electrostatic interactions
- 2024
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Ingår i: Nanoscale. - 2040-3372 .- 2040-3364. ; 16:14, s. 7123-7133
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Tidskriftsartikel (refereegranskat)abstract
- Filters made of graphene oxide (GO) are promising for purification of water and selective sieving of specific ions; while some results indicate the ionic radius as the discriminating factor in the sieving efficiency, the exact mechanism of sieving is still under debate. Furthermore, most of the reported GO filters are planar coatings with a simple geometry and an area much smaller than commercial water filters. Here, we show selective transport of different ions across GO coatings deposited on standard hollow fiber filters with an area >10 times larger than typical filters reported. Thanks to the fabrication procedure, we obtained a uniform coating on such complex geometry with no cracks or holes. Monovalent ions like Na+ and K+ can be transported through these filters by applying a low electric voltage, while divalent ions are blocked. By combining transport and adsorption measurements with molecular dynamics simulations and spectroscopic characterization, we unravel the ion sieving mechanism and demonstrate that it is mainly due to the interactions of the ions with the carboxylate groups present on the GO surface at neutral pH.
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| 5. |
- Khaliha, Sara, et al.
(författare)
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Upcycling of plastic membrane industrial scraps and reuse as sorbent for emerging contaminants in water
- 2024
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Ingår i: Environmental Science: Water Research and Technology. - 2053-1419 .- 2053-1400. ; 10:5, s. 1097-1107
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Tidskriftsartikel (refereegranskat)abstract
- Scraps obtained as waste of the industrial production of polysulfone and polysulfone-graphene oxide hollow fiber membranes (PSU-HF and PSU-GO-HF, respectively) were converted into granular materials and used as sorbents of several classes of emerging and standard water contaminants, such as drugs, heavy metal ions, and a mixture of per- and poly-fluoroalkyl substances (PFASs). The millimetric sized granules (PSU and PSU-GO, respectively) outperformed granular activated carbon (GAC), the industrial sorbent benchmark, in the adsorption of lead, diclofenac, and PFOA from tap water. Adsorption mechanism insight was achieved by molecular dynamics simulations, demonstrating the key role of graphene oxide (GO) on PSU-GO material performance. With respect to GAC, PSU-GO adsorption capacity was two times higher for diclofenac and PFOA and ten times higher for lead. Material safety was assessed by surface enhanced Raman spectroscopy, excluding GO nanosheets leaching, and combined potability test. Overall, our work proves that scrap conversion and reuse is a valuable strategy to reduce plastic industrial waste disposal and to integrate standard technology for enhanced water purification.
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| 6. |
- Kovtun, Alessandro, et al.
(författare)
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Graphene oxide–polysulfone filters for tap water purification, obtained by fast microwave oven treatment
- 2019
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Ingår i: Nanoscale. - : Royal Society of Chemistry (RSC). - 2040-3372 .- 2040-3364. ; 11:11, s. 22780-22787
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Tidskriftsartikel (refereegranskat)abstract
- The availability of clean, pure water is a major challenge for the future of our society. 2-Dimensional nanosheets of GO seem promising as nanoporous adsorbent or filters for water purification; however, their processing in macroscopic filters is challenging, and their cost vs. standard polymer filters is too high. Here, we describe a novel approach to combine graphene oxide (GO) sheets with commercial polysulfone (PSU) membranes for improved removal of organic contaminants from water. The adsorption physics of contaminants on the PSU-GO composite follows Langmuir and Brunauer–Emmett–Teller (BET) models, with partial swelling and intercalation of molecules in between the GO layers. Such a mechanism, well-known in layered clays, has not been reported previously for graphene or GO. Our approach requires minimal amounts of GO, deposited directly on the surface of the polymer, followed by stabilization using microwaves or heat. The purification efficiency of the PSU-GO composites is significantly improved vs. benchmark commercial PSU, as demonstrated by the removal of two model contaminants, rhodamine B and ofloxacin. The excellent stability of the composite is confirmed by extensive (100 hours) filtration tests in commercial water cartridges.
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| 7. |
- Mantovani, Sebastiano, et al.
(författare)
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Amino acid-driven adsorption of emerging contaminants in water by modified graphene oxide nanosheets
- 2023
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Ingår i: Environmental Science: Water Research and Technology. - : Royal Society of Chemistry (RSC). - 2053-1419 .- 2053-1400. ; 9:4, s. 1030-1040
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Tidskriftsartikel (refereegranskat)abstract
- Graphene oxide nanosheets have shown promising adsorption properties toward emerging organic contaminants in drinking water. Here, we report a family of graphene oxide nanosheets covalently modified with amino acids and the study on their adsorption properties toward a mixture of selected contaminants, including pharmaceuticals, additives, and dyes. Graphene oxides modified with l-glutamic acid and l-methionine (GO-Glu and GO-Met) were synthesized and purified with a scalable and fast synthetic and purification procedure, and their structure was studied by combined X-ray photoelectron spectroscopy and elemental analysis. An amino acid loading of about 5% and a slight reduction (from 27% down to 14-20% oxygen) were found and associated with the adsorption selectivity. They were compared to unmodified GO, reduced GO (rGO), GO-lysine, and to the reference sample GO-NaOH. Each type of modified GO possesses a higher adsorption capacity toward bisphenol A (BPA), benzophenone-4 (BP4), and carbamazepine (CBZ) than standard GO and rGO, and the adsorption occurred within the first hour of contact time. The maximum adsorption capacity (estimated from the adsorption isotherms) was strictly related to the amino acid loading. Accordingly, molecular dynamics simulations highlighted higher interaction energies for the modified GOs than unmodified GO, as a result of higher van der Waals and hydrophobic interactions between the contaminants and the amino acid side chains on the nanosheet surface.
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| 8. |
- Moro, Giulia, et al.
(författare)
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Amino acid modified graphene oxide for the simultaneous capture and electrochemical detection of glyphosate
- 2024
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Ingår i: Materials Today Chemistry. - 2468-5194. ; 36
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Tidskriftsartikel (refereegranskat)abstract
- Amino acid modified graphene oxide derivatives (GO-AA) are herein proposed as active materials for the capture and consequent electrochemical detection of organic pollutants in aqueous media. Glyphosate (GLY), an herbicide present in many water compartments, was chosen as benchmark species to test the effectiveness of these materials for its electroactive nature, allowing direct evidence of the capture event. L-Lysine, L-Arginine or L-Methionine were grafted on GO surface through epoxide ring opening reaction, promoting the amino acids binding and the concomitant partial reduction of GO. The synthetic process results in a charge resistance drop from 8.1 KΩ for GO to 0.8–2.1 KΩ for the various GO-AA, supporting the applicability of these materials in electrochemical sensing. The resulting GO-Lysine, GO-Arginine and GO-Methionine were exploited for GLY adsorption from water. GO-Lysine was found to have the strongest interaction with GLY, with a removal efficiency of 76 % after 1 h, which is about two-fold higher than those of granular activated carbon, the industrial benchmark adsorbent. GO-AAs outperform the pristine unmodified material also when exploited as active materials for the capturing and following electrochemical detection of GLY. GO-Lysine showed the best sensitivity and allowed the recognition of GLY in water even when present at concentration levels down to 2 μg/L. Molecular dynamics simulations confirmed that the enhanced performance of this material can be ascribed to the hydrogen bond and salt bridge interactions between Lys moieties and GLY, originated from hydrogen bond and salt bridge interactions.
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| 9. |
- Poletti, Fabrizio, et al.
(författare)
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Continuous capillary-flow sensing of glucose and lactate in sweat with an electrochemical sensor based on functionalized graphene oxide
- 2021
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Ingår i: Sensors and Actuators, B: Chemical. - : Elsevier BV. - 0925-4005. ; 344
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Tidskriftsartikel (refereegranskat)abstract
- We describe an electrochemical device for the simultaneous monitoring of glucose and lactate in sweat, based on enzymatic sensors exploiting capillary flow to induce continuous, stable sensing. The enzymes, namely glucose oxidase and lactate oxidase, were anchored to a graphene oxide and chitosan composite (GO-Ch) of original synthesis, to achieve stable deposition of the bioreceptors on the electrochemical platform. We tested both biosensors on a realistic device architecture: they were embedded in a nitrocellulose strip, to exploit capillary force to induce a continuous flux of sweat on the sensor platform, ensuring the constant renewal of sample. We could achieve good sensitivity at potentials close to zero by using Prussian Blue as redox mediator, thus avoiding interference from other chemical species present in the complex matrix. The sensing signal was stable and linear over two hours in a concentration range of glucose and lactate between the limit of quantification (32 and 68 nM, respectively) and the upper limit of linearity (3.8 and 50.0 mM, respectively). The device is simple, robust, stable, and can be easily worn without the direct contact of the active part with the skin, making it suitable for simultaneous monitoring of glucose and lactate in human sweat.
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| 10. |
- Poletti, Fabrizio, et al.
(författare)
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Graphene-Paper-Based Electrodes on Plastic and Textile Supports as New Platforms for Amperometric Biosensing
- 2022
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Ingår i: Advanced Functional Materials. - : Wiley. - 1616-3028 .- 1616-301X. ; 32:7
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Tidskriftsartikel (refereegranskat)abstract
- The possibility of exfoliating graphite into graphene sheets allows the researchers to produce a material, termed “graphene paper” (G-paper), conductive as graphite but more flexible and processable. G-paper is already used for electronic applications, like conductors, antennas, and heaters, outperforming metal conductors thanks to its high flexibility, lightness, chemical stability, and compatibility with polymeric substrates. Here, the effectiveness in the use of G-paper for the realization of electrodes on flexible plastic substrates and textiles, and their applicability as amperometric sensors are demonstrated. The performance of these devices is compared with commercial platforms made of carbon-based inks, finding that they outperform commercial devices in sensing nicotinamide adenine dinucleotide (NADH), a key molecule for enzymatic biosensing; the electrodes can achieve state-of-the-art sensitivity (107.2 μA mm−1 cm−2) and limit of detection (0.6 × 10−6 m) with no need of additional functionalization. Thanks to this property, the stable deposition of a suitable enzyme, namely lactate dehydrogenase, on the electrode surface is used as a proof of concept of the applicability of this new platform for the realization of a biosensor. The possibility of having a single material suitable for antennas, electronics, and now sensing opens new opportunities for smart fabrics in wearable electronic applications.
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