Rationalizing Graphene-ZnO Composites for Gas Sensing via Functionalization with Amines.

The rational design of composites based on graphene/metal oxides is one of the pillars for advancing their application in various practical fields, particularly gas sensing. In this study, a uniform distribution of ZnO nanoparticles (NPs) through the graphene layer was achieved, taking advantage of amine functionalization. The beneficial effect of amine groups on the arrangement of ZnO NPs and the efficiency of their immobilization was revealed by core-level spectroscopy, pointing out strong ionic bonding between the aminated graphene (AmG) and ZnO. The stability of the resulting Am-ZnO nanocomposite was confirmed by demonstrating that its morphology remains unchanged even after prolonged heating up to 350 °C, as observed by electron microscopy. On-chip multisensor arrays composed of both AmG and Am-ZnO were fabricated and thoroughly tested, showing almost tenfold enhancement of the chemiresistive response upon decorating the AmG layer with ZnO nanoparticles, due to the formation of p-n heterojunctions. Operating at room temperature, the fabricated multisensor chips exhibited high robustness and a detection limit of 3.6 ppm and 5.1 ppm for ammonia and ethanol, respectively. Precise identification of the studied analytes was achieved by employing the pattern recognition technique based on linear discriminant analysis to process the acquired multisensor response.

Adaptive Peptide Molecule as the Promising Highly-Efficient Gas-Sensor Material: In Silico Study.

Gas sensors are currently employed in various applications in fields such as medicine, ecology, and food processing, and serve as monitoring tools for the protection of human health, safety, and quality of life. Herein, we discuss a promising direction in the research and development of gas sensors based on peptides-biomolecules with high selectivity and sensitivity to various gases. Thanks to the technique developed in this work, which uses a framework based on the density-functional tight-binding theory (DFTB), the most probable adsorption centers were identified and used to describe the interaction of some analyte molecules with peptides. The DFTB method revealed that the physical adsorption of acetone, ammonium, benzene, ethanol, hexane, methanol, toluene, and trinitrotoluene had a binding energy in the range from -0.28 eV to -1.46 eV. It was found that peptides may adapt to the approaching analyte by changing their volume up to a maximum value of approx. 13%, in order to confine electron clouds around the adsorbed molecule. Based on the results obtained, the prospects for using the proposed peptide configurations in gas sensor devices are good.

Graphene Amination towards Its Grafting by Antibodies for Biosensing Applications.

The facile synthesis of biografted 2D derivatives complemented by a nuanced understanding of their properties are keystones for advancements in biosensing technologies. Herein, we thoroughly examine the feasibility of aminated graphene as a platform for the covalent conjugation of monoclonal antibodies towards human IgG immunoglobulins. Applying core-level spectroscopy methods, namely X-ray photoelectron and absorption spectroscopies, we delve into the chemistry and its effect on the electronic structure of the aminated graphene prior to and after the immobilization of monoclonal antibodies. Furthermore, the alterations in the morphology of the graphene layers upon the applied derivatization protocols are assessed by electron microscopy techniques. Chemiresistive biosensors composed of the aerosol-deposited layers of the aminated graphene with the conjugated antibodies are fabricated and tested, demonstrating a selective response towards IgM immunoglobulins with a limit of detection as low as 10 pg/mL. Taken together, these findings advance and outline graphene derivatives' application in biosensing as well as hint at the features of the alterations of graphene morphology and physics upon its functionalization and further covalent grafting by biomolecules.

Composites Based on Poly(ε-caprolactone) and Graphene Oxide Modified with Oligo/Poly(Glutamic Acid) as Biomaterials with Osteoconductive Properties.

The development of new biodegradable biomaterials with osteoconductive properties for bone tissue regeneration is one of the urgent tasks of modern medicine. In this study, we proposed the pathway for graphene oxide (GO) modification with oligo/poly(glutamic acid) (oligo/poly(Glu)) possessing osteoconductive properties. The modification was confirmed by a number of methods such as Fourier-transform infrared spectroscopy, quantitative amino acid HPLC analysis, thermogravimetric analysis, scanning electron microscopy, and dynamic and electrophoretic light scattering. Modified GO was used as a filler for poly(ε-caprolactone) (PCL) in the fabrication of composite films. The mechanical properties of the biocomposites were compared with those obtained for the PCL/GO composites. An 18-27% increase in elastic modulus was found for all composites containing modified GO. No significant cytotoxicity of the GO and its derivatives in human osteosarcoma cells (MG-63) was revealed. Moreover, the developed composites stimulated the proliferation of human mesenchymal stem cells (hMSCs) adhered to the surface of the films in comparison with unfilled PCL material. The osteoconductive properties of the PCL-based composites filled with GO modified with oligo/poly(Glu) were confirmed via alkaline phosphatase assay as well as calcein and alizarin red S staining after osteogenic differentiation of hMSC in vitro.

Toward On-Chip Multisensor Arrays for Selective Methanol and Ethanol Detection at Room Temperature: Capitalizing the Graphene Carbonylation.

The artificial olfaction units (or e-noses) capable of room-temperature operation are highly demanded to meet the requests of society in numerous vital applications and developing Internet-of-Things. Derivatized 2D crystals are considered as sensing elements of choice in this regard, unlocking the potential of the advanced e-nose technologies limited by the current semiconductor technologies. Herein, we consider fabrication and gas-sensing properties of On-chip multisensor arrays based on a hole-matrixed carbonylated (C-ny) graphene film with a gradually changed thickness and concentration of ketone groups of up to 12.5 at.%. The enhanced chemiresistive response of C-ny graphene toward methanol and ethanol, of hundred ppm concentration when mixing with air to match permissible exposure OSHA limits, at room-temperature operation is signified. Following thorough characterization via core-level techniques and density functional theory, the predominant role of the C-ny graphene-perforated structure and abundance of ketone groups in advancing the chemiresistive effect is established. Advancing practice applications, selective discrimination of the studied alcohols is approached by linear discriminant analysis employing a multisensor array's vector signal, and the fabricated chip's long-term performance is shown.

Thermal Stabilization of Nafion with Nanocarbon Materials.

The stability of Nafion-carbon composites is important for the efficient functioning of fuel cells. The thermal decomposition of Nafion, nanostructured carbon materials, such as multi-walled carbon nanotubes, graphene-like materials, and their composites, have been studied using constant heating rate thermogravimetry in air. Materials were characterized by quantitative and qualitative analysis methods, such as thermogravimetry, X-ray photoelectron spectroscopy, scanning, and transmission electron microscopy with field emission. In Nafion-carbon composites, an increase in the thermal stability of the Nafion polymer is observed due to the formation of surface compounds at the Nafion-carbon interface. In this case, the degree of stabilization is affected by both the component composition of the composite and the structure of the nanocarbon material. The greatest effect was obtained in the case of using thermally expanded graphite (few-layer graphene). Nafion is distributed to a greater extent over the surface of the carbon material due to its high structural accessibility. The most thermally stable composite is Nafion-graphene in a mass ratio of components 1:4 with one stage Nafion degradation at 422 °C, whereas the degradation of pristine Nafion occurs in three stages at 341, 413, and 430 °C. The dependences of thermal stability and features of thermal degradation on the composition and structure of composites are discussed.

Template-Directed Polymerization Strategy for Producing rGO/UHMWPE Composite Aerogels with Tunable Properties.

In this paper, we suggest a previously unknown template-directed polymerization strategy for producing graphene/polymer aerogels with elevated mechanical properties, preservation of the nanoscale pore structure, an extraordinary crystallite structure, as well as tunable electrical and hydrophobic properties. The suggested approach is studied using the reduced graphene oxide (rGO)/ultrahigh molecular weight polyethylene (UHMWPE) system as an example. We also develop a novel method of ethylene polymerization with formation of UHMWPE directly on the surface of rGO sheets prestructured as the aerogel template. At a UHMWPE content smaller than 20 wt %, composite materials demonstrate completely reversible deformation and good conductivity. An ultrahigh polymer content (more than 80 wt %) results in materials with pronounced plasticity, improved hydrophobic properties, and a Young's modulus that is more than 200 times larger than that of pure rGO aerogel. Variation of the polymer content makes it possible to tune the electro-conductive properties of the aerogel in the range from 4.8 × 10-6 to 4.9 × 10-1 S/m and adjust its hydrophobic properties. The developed approach would make it possible to create composite materials with highly developed nanostructural morphology and advanced properties controlled by the thickness of the polymer layer on the surface of graphene sheets.

Manifesting Epoxide and Hydroxyl Groups in XPS Spectra and Valence Band of Graphene Derivatives.

The derivatization of graphene to engineer its band structure is a subject of significant attention nowadays, extending the frames of graphene material applications in the fields of catalysis, sensing, and energy harvesting. Yet, the accurate identification of a certain group and its effect on graphene's electronic structure is an intricate question. Herein, we propose the advanced fingerprinting of the epoxide and hydroxyl groups on the graphene layers via core-level methods and reveal the modification of their valence band (VB) upon the introduction of these oxygen functionalities. The distinctive contribution of epoxide and hydroxyl groups to the C 1s X-ray photoelectron spectra was indicated experimentally, allowing the quantitative characterization of each group, not just their sum. The appearance of a set of localized states in graphene's VB related to the molecular orbitals of the introduced functionalities was signified both experimentally and theoretically. Applying the density functional theory calculations, the impact of the localized states corresponding to the molecular orbitals of the hydroxyl and epoxide groups was decomposed. Altogether, these findings unveiled the particular contribution of the epoxide and hydroxyl groups to the core-level spectra and band structure of graphene derivatives, advancing graphene functionalization as a tool to engineer its physical properties.

Valence Band Structure Engineering in Graphene Derivatives.

Engineering of the 2D materials' electronic structure is at the forefront of nanomaterials research nowadays, giving an advance in the development of next-generation photonic devices, e-sensing technologies, and smart materials. Herein, employing core-level spectroscopy methods combined with density functional theory (DFT) modeling, the modification of the graphenes' valence band (VB) upon its derivatization by carboxyls and ketones is revealed. The appearance of a set of localized states in the VB of graphene related to molecular orbitals of the introduced functionalities is signified both experimentally and theoretically. Applying the DFT calculations of the density of states projected on the functional groups, their contributions to the VB structure are decomposed. An empirical approach, allowing one to analyze and predict the impact of a certain functional group on the graphenes' electronic structure in terms of examination of the model molecules, mimicking the introduced functionality, is proposed and validated. The interpretation of the arising states origin is made and their designation, pointing out their symmetry type, is proposed. Taken together, these results guide the band structure engineering of graphene derivatives and give a hint on the mechanisms underlying the alteration of the VB structure of 2D materials upon their derivatization.

Aminated Graphene-Graft-Oligo(Glutamic Acid) /Poly(ε-Caprolactone) Composites: Preparation, Characterization and Biological Evaluation.

Biodegradable and biocompatible composites are of great interest as biomedical materials for various regeneration processes such as the regeneration of bones, cartilage and soft tissues. Modification of the filler surface can improve its compatibility with the polymer matrix, and, as a result, the characteristics and properties of composite materials. This work is devoted to the synthesis and modification of aminated graphene with oligomers of glutamic acid and their use for the preparation of composite materials based on poly(ε-caprolactone). Ring-opening polymerization of N-carboxyanhydride of glutamic acid γ-benzyl ester was used to graft oligomers of glutamic acid from the surface of aminated graphene. The success of the modification was confirmed by Fourier-transform infrared and X-ray photoelectron spectroscopy as well as thermogravimetric analysis. In addition, the dispersions of neat and modified aminated graphene were analyzed by dynamic and electrophoretic light scattering to monitor changes in the characteristics due to modification. The poly(ε-caprolactone) films filled with neat and modified aminated graphene were manufactured and carefully characterized for their mechanical and biological properties. Grafting of glutamic acid oligomers from the surface of aminated graphene improved the distribution of the filler in the polymer matrix that, in turn, positively affected the mechanical properties of composite materials in comparison to ones containing the unmodified filler. Moreover, the modification improved the biocompatibility of the filler with human MG-63 osteoblast-like cells.

Decoupling the Positive and Negative Aging Processes of Perovskite Light-Emitting Diodes Using a Thin Interlayer of Ionic Liquid.

A positive aging phenomenon, that is, enhancement of the electroluminescence performance at the beginning of electrical aging, is commonly observed for the state-of-the-art perovskite light-emitting diodes (PeLEDs). The origins of positive aging could fundamentally interfere with those of the operational deterioration processes of PeLEDs (namely negative aging), bringing difficulty in analyzing the degradation mechanisms. This work decouples the positive and negative aging processes of PeLEDs by inserting a thin ionic liquid interlayer between the hole-injection layer and the perovskite layer. This interlayer inhibits ions migration by passivating the halogen vacancies of perovskite films and suppresses interfacial exciton quenching, enabling us to decouple the positive and negative aging processes of PeLEDs while increasing the device efficiency. Inserting an ionic liquid interlayer is also demonstrated to be effective for iodide-based PeLEDs and applicable with the use of other ionic liquids. Our work provides an ideal system for fundamental studies on the degradation mechanisms of PeLEDs.

Graphene Oxide Chemistry Management via the Use of KMnO4/K2Cr2O7 Oxidizing Agents.

In this paper, we propose a facile approach to the management of graphene oxide (GO) chemistry via its synthesis using KMnO4/K2Cr2O7 oxidizing agents at different ratios. Using Fourier Transformed Infrared Spectroscopy, X-ray Photoelectron Spectroscopy, and X-ray Absorption Spectroscopy, we show that the number of basal-plane and edge-located oxygenic groups can be controllably tuned by altering the KMnO4/K2Cr2O7 ratio. The linear two-fold reduction in the number of the hydroxyls and epoxides with the simultaneous three-fold rise in the content of carbonyls and carboxyls is indicated upon the transition from KMnO4 to K2Cr2O7 as a predominant oxidizing agent. The effect of the oxidation mixture's composition on the structure of the synthesized GOs is also comprehensively studied by means of X-ray diffraction, Raman spectroscopy, transmission electron microscopy, atomic-force microscopy, optical microscopy, and the laser diffraction method. The nanoscale corrugation of the GO platelets with the increase of the K2Cr2O7 content is signified, whereas the 10-100 µm lateral size, lamellar, and defect-free structure is demonstrated for all of the synthesized GOs regardless of the KMnO4/K2Cr2O7 ratio. The proposed method for the synthesis of GO with the desired chemistry opens up new horizons for the development of graphene-based materials with tunable functional properties.

A Blueprint for the Synthesis and Characterization of Thiolated Graphene.

Graphene derivatization to either engineer its physical and chemical properties or overcome the problem of the facile synthesis of nanographenes is a subject of significant attention in the nanomaterials research community. In this paper, we propose a facile and scalable method for the synthesis of thiolated graphene via a two-step liquid-phase treatment of graphene oxide (GO). Employing the core-level methods, the introduction of up to 5.1 at.% of thiols is indicated with the simultaneous rise of the C/O ratio to 16.8. The crumpling of the graphene layer upon thiolation without its perforation is pointed out by microscopic and Raman studies. The conductance of thiolated graphene is revealed to be driven by the Mott hopping mechanism with the sheet resistance values of 2.15 kΩ/sq and dependable on the environment. The preliminary results on the chemiresistive effect of these films upon exposure to ethanol vapors in the mix with dry and humid air are shown. Finally, the work function value and valence band structure of thiolated graphene are analyzed. Taken together, the developed method and findings of the morphology and physics of the thiolated graphene guide the further application of this derivative in energy storage, sensing devices, and smart materials.

Segregated Network Polymer Composites with High Electrical Conductivity and Well Mechanical Properties based on PVC, P(VDF-TFE), UHMWPE, and rGO.

The formation of a segregated network structure (wittingly uneven distribution of a filler) is one of the most promising strategies for the fabrication of electrically conductive polymer composites at present. However, the simultaneous achievement of high values of electrical conductivity with the retention of well mechanical properties within this approach remains a great challenge. Here, by means of X-ray photoelectron spectra (XPS), near-edge X-ray absorption fine structure (NEXAFS) spectra, scanning electron microscopy (SEM), dielectric spectroscopy, and compression engineering stress-strain curve analysis, we have studied the effect of a segregated network structure on the electrical conductivity and mechanical properties of a set of polymer composites. The composites were prepared by applying graphene oxide (GO) with ultralarge basal plane size (up to 150 µm) onto the surface of polymer powder particles, namely, poly(vinyl chloride) (PVC), poly(vinylidene fluoride-co-tetrafluoroethylene) (P(VDF-TFE)), and ultrahigh-molecular-weight poly(ethylene) (UHMWPE) with the subsequent GO reduction and composite hot pressing. A strong dependence of the segregated network polymer composites' physical properties on the polymer matrix was demonstrated. Particularly, 12 orders of magnitude rise of the polymers' electrical conductivity up to 0.7 S/m was found upon the incorporation of the reduced GO (rGO). A 17% increase in the P(VDF-TFE) elastic modulus filled by 1 wt % of rGO was observed. Fracture strength of PVC/rGO at 0.5 wt % content of the filler was demonstrated to decrease by fourfold. At the same time, the change in strength was not significant for P(VDF-TFE) and UHMWPE composites in comparison with pure polymers. Our results show a promise to accelerate the development of new composites for energy applications, such as metal-free supercapacitor plates and current collectors of lithium-ion batteries, bipolar plates of proton-exchange membrane fuel cells, antistatic elements of various electronic devices, etc.

From graphene oxide towards aminated graphene: facile synthesis, its structure and electronic properties.

In this paper we present a facile method for the synthesis of aminated graphene derivative through simultaneous reduction and amination of graphene oxide via two-step liquid phase treatment with hydrobromic acid and ammonia solution in mild conditions. The amination degree of the obtained aminated reduced graphene oxide is of about 4 at.%, whereas C/O ratio is up to 8.8 as determined by means of X-ray photoelectron spectroscopy. The chemical reactivity of the introduced amine groups is further verified by successful test covalent bonding of the obtained aminated graphene with 3-Chlorobenzoyl chloride. The morphological features and electronic properties, namely conductivity, valence band structure and work function are studied as well, illustrating the influence of amine groups on graphene structure and physical properties. Particularly, the increase of the electrical conductivity, reduction of the work function value and tendency to form wrinkled and corrugated graphene layers are observed in the aminated graphene derivative compared to the pristine reduced graphene oxide. As obtained aminated graphene could be used for photovoltaic, biosensing and catalysis application as well as a starting material for further chemical modifications.

Fluorescence enhancement of monodisperse carbon nanodots treated with aqueous ammonia and hydrogen peroxide.

The treatment of monodisperse carbon nanodots (MCNDs) with a combination of aqueous ammonia and hydrogen peroxide is found to result in a prominent enhancement of their fluorescence efficiency. Depending on the hydrogen peroxide concentration, an increase of the MCNDs quantum yield of up to seven-fold has been achieved. Considering the absence of prominent changes in fluorescence lifetime and fluorescence spectra upon the treatment it is suggested that the observed rise of fluorescence efficiency originates from additional formation of new isolated sp2 domains surrounded by defect sites. The structural modification of MCNDs induced by their treatment with combination of aqueous ammonia and hydrogen peroxide is indicated by both transmission electron microscopy images and infrared spectra. The applied method has insignificant effect on the aggregation properties and size distribution of the studied MCNDs. Taking into account the proposed mechanism, the applied treatment procedure can serve as a basis for a facile approach for modification of emissive properties of various nanocarbon structures.

Facile reduction of graphene oxide suspensions and films using glass wafers.

This paper reports a facile and green method for conversion of graphene oxide (GO) into graphene by low-temperature heating (80 °C) in the presence of a glass wafer. Compared to conventional GO chemical reduction methods, the presented approach is easy-scalable, operationally simple, and based on the use of a non-toxic recyclable deoxygenation agent. The efficiency of the proposed method is further expanded by the fact that it can be applied for reducing both GO suspensions and large-scale thin films formed on various substrates prior to the reduction process. The quality of the obtained reduced graphene oxide (rGO) strongly depends on the type of the used glass wafer, and, particularly, magnesium silicate glass can provide rGO with the C/O ratio of 7.4 and conductivity of up to 33000 S*cm-1. Based on the data obtained, we have suggested a mechanism of the observed reduction process in terms of the hydrolysis of the glass wafer with subsequent interaction of the leached alkali and alkali earth cations and silicate anions with graphene oxide, resulting in elimination of the oxygen-containing groups from the latter one. The proposed approach can be efficiently used for low-cost bulk-quantity production of graphene and graphene-based materials for a wide field of applications.

Controllable spherical aggregation of monodisperse carbon nanodots.

Monodisperse carbon nanodots (MCNDs) having an identical composition, structure, shape and size possess identical chemical and physical properties, making them highly promising for various technical and medical applications. Herein, we report a facile and effective route to obtain monodisperse carbon nanodots 3.5 ± 0.9 nm in size by thermal decomposition of organosilane within the pores of monodisperse mesoporous silica particles with subsequent removal of the silica template. Structural studies demonstrated that the MCNDs we synthesized consist of ∼7-10 defective graphene layers that are misoriented with respect to each other and contain various oxygen-containing functional groups. It was demonstrated that, owing to their identical size and chemical composition, the MCNDs are formed via coagulation primary aggregates ∼10-30 nm in size, which are, in turn, combined into secondary porous spherical aggregates ∼100-200 nm in diameter. The processes of coagulation of MCNDs and peptization of their hierarchical aggregates are fully reversible and can be controlled by varying the MCND concentration or the pH value of the hydrosols. Submicrometer spherical aggregates of MCNDs are not disintegrated as the hydrosol is dried. The thus obtained porous spherical aggregates of MCNDs are promising for drug delivery as a self-disassembling container for medicinal preparations.