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Surface Modifications of Carbon Nanomaterials

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A special issue of Nanomaterials (ISSN 2079-4991). This special issue belongs to the section "Synthesis, Interfaces and Nanostructures".

Deadline for manuscript submissions: closed (31 December 2020) | Viewed by 29832

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Dr. Manuel J. Pérez-Mendoza

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Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Granada, 18071 Granada, Spain
Interests: functionalization of carbon nanomaterials; plasma functionalization; carbon nanotubes; graphene derivatives; supported nanoparticles

Special Issue Information

Dear Colleagues,

The surface chemistry and morphology of carbon nanomaterials strongly determine many of their distinctive properties, and have recently attracted the interest of the materials research community at the nanoscale level. It is of paramount importance to selectively control the presence of different heteroatoms in the outer layers of nanocarbons, and to know exactly how they influence their morphology and optoelectronic properties, if we want to widen the application possibilities for these nanomaterials, finding proper solutions to new technological demands. This is especially crucial in the case of new graphene derivatives.

The surface modification of carbon nanomaterials is an active and rich research field that includes a wide range of methodologies to tune the material properties. From physical treatments (e.g., plasma surface functionalization or ozonation) to chemical methods with different oxidative agents and other reactive molecules, there are many different strategies to achieve both covalent and non-covalent functionalization, and to modify the structural morphology of the nanocarbons. The modified materials can in this way present new interfacial and electronic properties which can improve their behavior in different application systems. Similarly, the decoration of carbon nanomaterials by anchoring complex molecules or biomolecules, or by supporting metal and non-metal nanoparticles, can open the door to new applications in biomedicine and catalysis.

The present Special Issue aims to comprehensively compile new cutting-edge research that is being performed about the design and preparation of new carbon nanomaterials by surface modification and/or by controlling the factors that determine their surface properties. Therefore, we welcome contributions with novel results that address the present challenges of nanocarbons surface chemistry and morphology (and their characterization), as well as critical review articles which revise the present knowledge of the related hot topics offering new platforms for discussion.

Dr. Manuel J. Pérez-Mendoza
Guest Editor

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Keywords

carbon nanomaterials
graphene
graphene oxide
graphene derivatives
covalent functionalization
non-covalent functionalization
supported nanoparticles
plasma surface functionalization
surface morphology
decoration of carbon nanomaterials

Published Papers (10 papers)

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Research

12 pages, 2806 KiB

Open AccessEditor’s ChoiceArticle

Conversion of Secondary C3-C4 Aliphatic Alcohols on Carbon Nanotubes Consolidated by Spark Plasma Sintering

by Serguei Savilov, Evgeniya Suslova, Vsevolod Epishev, Evgeniya Tveritinova, Yuriy Zhitnev, Alexander Ulyanov, Konstantin Maslakov and Oksana Isaikina

Nanomaterials 2021, 11(2), 352; https://doi.org/10.3390/nano11020352 - 01 Feb 2021

Cited by 13 | Viewed by 2145

Abstract

We analyze how the changes in the dimension of carbon nanomaterial (CNM) affect their catalytic conversion of secondary aliphatic alcohols. Carbon nanotubes (CNTs) consolidated by spark plasma sintering (SPS) were inactive in the conversion of secondary C₃-C₄ aliphatic alcohols because of the «healing» of defects in carbon structure during SPS. Gas-phase treatment of consolidated CNTs with HNO₃ vapors led to their surface oxidation without destruction of the bulk structure of pellets. The oxygen content in consolidated CNTs determined by X-ray photoelectron spectroscopy increased from 11.3 to 14.9 at. % with increasing the oxidation time from 3 to 6 h. Despite the decrease in the specific surface area, the oxidized samples showed enhanced catalytic activity in alcohol conversion because of the increased number of oxygen radicals with unpaired electrons, which was established by electron paramagnetic resonance spectroscopy. We conclude that the structure of CNM determines the content and/or ratio of sp² and sp³-hybridized carbon atoms in the material. The experimental and literature data demonstrated that sp³-hybridized carbon atoms on the surface are probably the preferable site for catalytic conversion of alcohols. Full article

(This article belongs to the Special Issue Surface Modifications of Carbon Nanomaterials)

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10 pages, 1701 KiB

Open AccessArticle

Direct As(V) Determination Using Screen-Printed Electrodes Modified with Silver Nanoparticles

by Karina Torres-Rivero, Clara Pérez-Ràfols, Julio Bastos-Arrieta, Antonio Florido, Vicenç Martí and Núria Serrano

Nanomaterials 2020, 10(7), 1280; https://doi.org/10.3390/nano10071280 - 30 Jun 2020

Cited by 12 | Viewed by 2409

Abstract

Carbon-nanofiber-based screen-printed electrodes modified with silver nanoparticles (Ag-NP-SPCNFEs) were tested in a pioneering manner for the direct determination of As(V) at low μg L⁻¹ levels by means of differential pulse anodic stripping voltammetry. Screen-printed electrodes were modified with two different types of Ag-NPs, nanoseeds (NS), and nanoprisms (NPr) and characterized both microscopically and electrochemically. Furthermore, after optimizing the direct voltammetric determination of As(V), the analytical performance of considered sensors was compared for the direct determination of As(V). These results suggest that Ag-NS offer a better analytical response compared to Ag-NPr, with a detection and quantification limit of 0.6 and 1.9 µg L⁻¹, respectively. The proposed methodology was validated using a spiked tap water sample with a very high reproducibility and good agreement with inductively coupled plasma-mass spectrometry (ICP-MS) measurements. Full article

(This article belongs to the Special Issue Surface Modifications of Carbon Nanomaterials)

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13 pages, 2877 KiB

Open AccessArticle

Organic Functionalized Graphene Oxide Behavior in Water

by Changwoo Kim, Junseok Lee, Will Wang and John Fortner

Nanomaterials 2020, 10(6), 1228; https://doi.org/10.3390/nano10061228 - 24 Jun 2020

Cited by 11 | Viewed by 2733

Abstract

Surface modified graphene oxide (GO) has received broad interest as a potential platform material for sensors, membranes, and sorbents, among other environmental applications. However, compared to parent (unmodified) GO, there is a dearth of information regarding the behavior of subsequently (secondary) modified GO, other than bulk natural organic matter (NOM) coating(s). Here, we systematically explore the critical role of organic functionalization with respect to GO stability in water. Specifically, we synthesized a matrix of GO-based materials considering a carefully chosen range of bound organic molecules (hydrophobic coatings: propylamine, tert-octylamine, and 1-adamantylamine; hydrophilic coatings: 3-amino-1-propanol and 3-amino-1-adamantanol), so that chemical structures and functional groups could be directly compared. GO (without organic functionalization) with varying oxidation extent(s) was also included for comparison. The material matrix was evaluated for aqueous stability by comparing critical coagulation concentration (CCC) as a function of varied ionic strength and type (NaCl, CaCl₂, MgCl₂, and MgSO₄) at pH 7.0. Without surface derivatization (i.e., pristine GO), increased stability was observed with an increase in the GO oxidation state, which is supported by plate–plate Derjaguin, Landau, Verwey and Overbeek (DLVO) energy interaction analyses. For derivatized GO, we observed that hydrophilic additions (phi-GO) are relatively more stable than hydrophobic organic coated GO (pho-GO). We further explored this by altering a single OH group in the adamantane-x structure (3-amino-1-adamantanol vs. 1-adamantylamine). As expected, Ca²⁺ and monovalent co-ions play an important role in the aggregation of highly oxidized GO (HGO) and phi-GO, while the effects of divalent cations and co-ions were less significant for pho-GO. Taken together, this work provides new insight into the intricate dynamics of GO-based material stability in water as it relates to surface functionalization (surface energies) and ionic conditions including type of co- and counter-ion, valence, and concentration. Full article

(This article belongs to the Special Issue Surface Modifications of Carbon Nanomaterials)

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21 pages, 3279 KiB

Open AccessArticle

Tuning the Solubility Parameters of Carbon Nanotubes by Means of Their Adducts with Janus Pyrrole Compounds

by Daniele Locatelli, Vincenzina Barbera, Luigi Brambilla, Chiara Castiglioni, Annalisa Sironi and Maurizio Galimberti

Nanomaterials 2020, 10(6), 1176; https://doi.org/10.3390/nano10061176 - 16 Jun 2020

Cited by 16 | Viewed by 2448

Abstract

The solubility parameters of multiwalled carbon nanotubes (CNTs) was tuned via their chemical modification with pyrrole compounds (PyCs), by means of a simple and sustainable methodology. PyCs were synthesized with high atom efficiency through the Paal–Knorr reaction of primary amines with 2,5-hexanedione, in the absence of solvents and catalysts. Methylamine, 1-dodecylamine, 2-amino-1,3-propanediol, and 3-(triethoxysilyl)propan-1-amine were selected. PyCs are characterized by two moieties, the pyrrole ring and the substituent of the nitrogen atom, and can be considered as Janus molecules. The functionalization of CNTs occurred with a high yield by simply heating CNTs and PyC. The whole reaction pathway did not produce any waste and was characterized by a carbon efficiency up to almost 100%. Thanks to the variety of PyC chemical structures, the CNT solubility parameter was modified in a pretty broad range of values, in the expected direction. Stable CNT dispersions were prepared in different solvents. From the aqueous dispersion, coating layers were prepared with high electrical conductivity, larger with respect to a top commercial product. The “pyrrole methodology” reported here is based on one reaction and allows almost infinite variations of the CNT solubility parameter, thus promoting their compatibility with target matrices and allowing the preparation of nanocomposite materials with improved properties. This work thus paves the way for a highly efficient exploitation of CNTs. Full article

(This article belongs to the Special Issue Surface Modifications of Carbon Nanomaterials)

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11 pages, 3335 KiB

Open AccessArticle

Effect of the Fluorination of Graphene Nanoflake on the Dispersion and Mechanical Properties of Polypropylene Nanocomposites

by Min Gyu Lee, Sangwoon Lee, Jaehyun Cho, Seokyoung Bae and Jae Young Jho

Nanomaterials 2020, 10(6), 1171; https://doi.org/10.3390/nano10061171 - 16 Jun 2020

Cited by 8 | Viewed by 2551

Abstract

In order to investigate the effect of fluorination of graphene nanoflake on the dispersibility in polypropylene (PP) composites, fluorinated graphene oxide (FGO) was prepared by solvo-thermal reaction and applied as a filler of the PP nanocomposite. Due to the weakened inter-particle attraction among the graphene nanoflake and reduced surface energy difference between PP and the filler, PP/FGO composites showed better exfoliation and dispersion state of the filler compared with that of PP/graphene oxide (GO) or PP/reduced graphene oxide (RGO) composites. The improved exfoliation and dispersion of graphene nanoflake resulted in a significant reinforcement on the composites. The Young’s modulus and tensile strength of PP composites filled with 2 wt% of FGO increased by 31% and 15%, respectively, compared with those of PP. Full article

(This article belongs to the Special Issue Surface Modifications of Carbon Nanomaterials)

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13 pages, 1487 KiB

Open AccessArticle

Control of pH-Responsiveness in Graphene Oxide Grafted with Poly-DEAEMA via Tailored Functionalization

by Roxana Noriega-Navarro, Jésica Castro-Medina, Martha V. Escárcega-Bobadilla and Gustavo A. Zelada-Guillén

Nanomaterials 2020, 10(4), 614; https://doi.org/10.3390/nano10040614 - 27 Mar 2020

Cited by 2 | Viewed by 2847

Abstract

Polymer-grafted nanomaterials based on carbon allotropes and their derivatives (graphene oxide (GO), etc.) are typically prepared by successive reaction stages that depend upon the initial functionalities in the nanostructure and the polymerization type needed for grafting. However, due to the multiple variables involved in the functionalization steps, it is commonly difficult to predict the properties in the final product and to correlate the material history with its final performance. In this work, we explored the steps needed to graft the carboxylic acid moieties in GO (COOH@GO) with a pH-sensitive polymer, poly[2-(diethylamino)ethyl methacrylate] (poly[DEAEMA]), varying the reactant ratios at each stage prior to polymerization. We studied the combinatorial relationship between these variables and the behavior of the novel grafted material GO-g-poly[DEAEMA], in terms of swelling ratio vs. pH (%Q) in solid specimens and potentiometric response vs. Log[H⁺] in a solid-state sensor format. We first introduced N-hydroxysuccinimide (NHS)-ester moieties at the –COOH groups (GO-g-NHS) by a classical activation with N-ethyl-N′-(3-dimethylaminopropyl)carbodiimide (EDC). Then, we substituted the NHS-ester groups by polymerizable amide-linked acrylic moieties using 2-aminoethyl methacrylate (AEMA) at different ratios to finally introduce the polymer chains via radical polymerization in an excess of DEAEMA monomer. We found correlated trends in swelling pH range, interval of maximum and minimum swelling values, response in potentiometry and potentiometric linear range vs. Log[H⁺] and could establish their relationship with the combinatorial stoichiometries in synthetic stages. Full article

(This article belongs to the Special Issue Surface Modifications of Carbon Nanomaterials)

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16 pages, 8879 KiB

Open AccessArticle

Bioelectronic Nose Based on Single-Stranded DNA and Single-Walled Carbon Nanotube to Identify a Major Plant Volatile Organic Compound (p-Ethylphenol) Released by Phytophthora Cactorum Infected Strawberries

by Hui Wang, Yue Wang, Xiaopeng Hou and Benhai Xiong

Nanomaterials 2020, 10(3), 479; https://doi.org/10.3390/nano10030479 - 07 Mar 2020

Cited by 24 | Viewed by 3912

Abstract

The metabolic activity in plants or fruits is associated with volatile organic compounds (VOCs), which can help identify the different diseases. P-ethylphenol has been demonstrated as one of the most important VOCs released by the Phytophthora cactorum (P. cactorum) infected strawberries. In this study, a bioelectronic nose based on a gas biosensor array and signal processing model was developed for the noninvasive diagnostics of the P. cactorum infected strawberries, which could overcome the limitations of the traditional spectral analysis methods. The gas biosensor array was fabricated using the single-wall carbon nanotubes (SWNTs) immobilized on the surface of field-effect transistor, and then non-covalently functionalized with different single-strand DNAs (ssDNA) through π–π interaction. The characteristics of ssDNA-SWNTs were investigated using scanning electron microscope, atomic force microscopy, Raman, UV spectroscopy, and electrical measurements, indicating that ssDNA-SWNTs revealed excellent stability and repeatability. By comparing the responses of different ssDNA-SWNTs, the sensitivity to P-ethylphenol was significantly higher for the s6DNA-SWNTs than other ssDNA-SWNTs, in which the limit of detection reached 0.13% saturated vapor of P-ethylphenol. However, s6DNA-SWNTs can still be interfered with by other VOCs emitted by the strawberries in the view of poor selectivity. The bioelectronic nose took advantage of the different sensitivities of different gas biosensors to different VOCs. To improve measure precision, all ssDNA-SWNTs as a gas biosensor array were applied to monitor the different VOCs released by the strawberries, and the detecting data were processed by neural network fitting (NNF) and Gaussian process regression (GPR) with high accuracy. Full article

(This article belongs to the Special Issue Surface Modifications of Carbon Nanomaterials)

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12 pages, 18523 KiB

Open AccessArticle

Bacterial Nanocellulose Nitrates

by Vera V. Budaeva, Yulia A. Gismatulina, Galina F. Mironova, Ekaterina A. Skiba, Evgenia K. Gladysheva, Ekaterina I. Kashcheyeva, Olga V. Baibakova, Anna A. Korchagina, Nadezhda A. Shavyrkina, Dmitry S. Golubev, Nikolay V. Bychin, Igor N. Pavlov and Gennady V. Sakovich

Nanomaterials 2019, 9(12), 1694; https://doi.org/10.3390/nano9121694 - 27 Nov 2019

Cited by 24 | Viewed by 3846

Abstract

Bacterial nanocellulose (BNC) whose biosynthesis fully conforms to green chemistry principles arouses much interest of specialists in technical chemistry and materials science because of its specific properties, such as nanostructure, purity, thermal stability, reactivity, high crystallinity, etc. The functionalization of the BNC surface remains a priority research area of polymers. The present study was aimed at scaled production of an enlarged BNC sample and at synthesizing cellulose nitrate (CN) therefrom. Cyclic biosynthesis of BNC was run in a semisynthetic glucose medium of 10−72 L in volume by using the Medusomyces gisevii Sa-12 symbiont. The most representative BNC sample weighing 6800 g and having an α-cellulose content of 99% and a polymerization degree of 4000 was nitrated. The nitration of freeze-dried BNC was performed with sulfuric-nitric mixed acid. BNC was examined by scanning electron microscopy (SEM) and infrared spectroscopy (IR), and CN was explored to a fuller extent by SEM, IR, thermogravimetric analysis/differential scanning analysis (TGA/DTA) and ¹³C nuclear magnetic resonance (NMR) spectroscopy. The three-cycle biosynthesis of BNC with an increasing volume of the nutrient medium from 10 to 72 L was successfully scaled up in nonsterile conditions to afford 9432 g of BNC gel-films. CNs with a nitrogen content of 10.96% and a viscosity of 916 cP were synthesized. It was found by the SEM technique that the CN preserved the 3D reticulate structure of initial BNC fibers a marginal thickening of the nanofibers themselves. Different analytical techniques reliably proved the resultant nitration product to be CN. When dissolved in acetone, the CN was found to form a clear high-viscosity organogel whose further studies will broaden application fields of the modified BNC. Full article

(This article belongs to the Special Issue Surface Modifications of Carbon Nanomaterials)

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18 pages, 10536 KiB

Open AccessArticle

Graphene Nanoplatelets Modified with Amino-Groups by Ultrasonic Radiation of Variable Frequency for Potential Adsorption of Uremic Toxins

by C. Cabello-Alvarado, M. Andrade-Guel, M. Pérez-Alvarez, G. Cadenas-Pliego, Dora A. Cortés-Hernández, P. Bartolo-Pérez, C.A. Ávila-Orta, V.J. Cruz-Delgado and A. Zepeda-Pedreguera

Nanomaterials 2019, 9(9), 1261; https://doi.org/10.3390/nano9091261 - 05 Sep 2019

Cited by 20 | Viewed by 3228

Abstract

Chronic kidney disease (CKD) is a worldwide public health problem. In stages III and IV of CKD, uremic toxins must be removed from the patient by absorption, through a treatment commonly called hemodialysis. Aiming to improve the absorption of uremic toxins, we have studied its absorption in chemically modified graphene nanoplatelets (GNPs). This study involved the reaction between GNPs and diamines with reaction times of 30, 45 and 60 min using ultrasound waves of different amplitudes and frequencies. Functionalized GNPs were analyzed by Fourier Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), Scanning electron microscopy and energy dispersitive spectroscopy (SEM-EDS), and Thermogravimetric analysis (TGA). The analysis of the functional groups confirmed the presence of amide and hydroxyl groups on the surface of the GNPs by reactions of diamines with carboxylic acids and epoxides. Adsorption of uremic toxins was determined using equilibrium isotherms, where the maximum percentage of removal of uremic toxins was 97%. Dispersion of modified graphene nanoplatelets was evaluated in water, ethanol and hexane, as a result of this treatment was achieved a good and effective dispersion of diamines-modified graphene nanoplatelets in ethanol and hexane. Finally, the results of hemolysis assays of the modified graphene with amine demonstrated that it was not cytotoxic when using 500 mg/mL. The samples of modified graphene demonstrated low degree of hemolysis (<2%), so this material can be used for in vivo applications such as hemodialysis. Full article

(This article belongs to the Special Issue Surface Modifications of Carbon Nanomaterials)

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13 pages, 2917 KiB

Open AccessArticle

Modification of Graphene Oxide Membranes by the Incorporation of Nafion Macromolecules and Conductive Scaffolds

by Maria O. Concha-Guzmán, Oscar A. Jaramillo-Quintero and Marina E. Rincón

Nanomaterials 2019, 9(4), 556; https://doi.org/10.3390/nano9040556 - 05 Apr 2019

Viewed by 2884

Abstract

Stable, reproducible and low-cost graphene oxide (GO)/Nafion (N) membranes were fabricated using electronically conductive carbon paper (CP) matts as a scaffold. The presence of polar groups in the Nafion molecule facilitates the strong interaction with functional groups in the GO, which increases GO dispersion and aids the retention of the composite into the CP scaffold. Distribution of GO/N was carefully characterized by X-ray diffraction work function measurements, Raman and scanning electron microscopy analyses. The performance of these membranes was tested with 1 M NaCl at standard conditions, finding 85% ion removal in the best membranes by a mixed ion rejection/retention mechanism. The Nafion provided mechanical stability and fixed negative charge to the membranes, and its micellar organization, segregation and confinement favored ion rejection in Nafion-rich areas. The good electronic conductivity of these membranes was also demonstrated, allowing for the application of a small potential bias to enhance membrane performance in future studies. Full article

(This article belongs to the Special Issue Surface Modifications of Carbon Nanomaterials)

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