C | March 2021 - Browse Articles

Open AccessArticle

Carbide-Derived Carbons: WAXS and Raman Spectra for Detailed Structural Analysis

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C 2021, 7(1), 29; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010029 - 20 Mar 2021

Viewed by 764

Abstract

Quick characterization methods to determine the structure of carbon materials are sought after for a wide array of technical applications. In this study we present the combined analysis of the structure of carbide-derived carbons (CDCs) with Raman spectroscopy and wide-angle X-ray scattering (WAXS) [...] Read more.

Quick characterization methods to determine the structure of carbon materials are sought after for a wide array of technical applications. In this study we present the combined analysis of the structure of carbide-derived carbons (CDCs) with Raman spectroscopy and wide-angle X-ray scattering (WAXS) methods. We present the optimal deconvolution method to be used for the detailed analysis of Raman spectroscopy data of CDCs and comparison to corresponding WAXS results is made. For a broad set of CDCs both WAXS and Raman spectroscopy data showed that the average graphene layer extent increases with synthesis temperature of CDC, while the coherent domain lengths obtained from Raman spectroscopy higher by an average of 4.4 nm. In addition, the presence of correlations between the parameters (D-band width and the parameter A_∑D/A_∑G) from Raman spectroscopy and the synthesis temperature are established. Based on the WAXS and Raman spectra data analysis the strong influence of the precursor carbide structure on the graphitization pathway is shown. Full article

(This article belongs to the Special Issue Carbide Derived Carbons)

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Open AccessArticle

Impact of Nitrogen, Boron and Phosphorus Impurities on the Electronic Structure of Diamond Probed by X-ray Spectroscopies

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Marie-Amandine Pinault-Thaury

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François Jomard

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Peter Knittel

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Tristan Petit

C 2021, 7(1), 28; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010028 - 09 Mar 2021

Viewed by 939

Abstract

Doping diamond with boron, nitrogen or phosphorus enables a fine tuning of its electronic properties, which is particularly relevant for applications involving electron emission. However, the chemical nature of the doping sites and its correlation with electron emission properties remain to be clarified. [...] Read more.

Doping diamond with boron, nitrogen or phosphorus enables a fine tuning of its electronic properties, which is particularly relevant for applications involving electron emission. However, the chemical nature of the doping sites and its correlation with electron emission properties remain to be clarified. In this work, we applied soft X-ray spectroscopy techniques to probe occupied and unoccupied electronic states in undoped, boron-, phosphorus- and nitrogen-containing single crystal diamonds. X-ray absorption, X-ray emission and X-ray photoemission spectroscopies, performed at the carbon K-edge, provide a full picture of new electronic states created by impurities in diamond. The different probing depths of fluorescence- and electron-based detection techniques enable a comparison between surface and bulk contributions. Full article

(This article belongs to the Collection Feature Papers in the Science and Engineering of Carbons)

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Open AccessArticle

The Role of Surface Chemistry and Polyethylenimine Grafting in the Removal of Cr (VI) by Activated Carbons from Cashew Nut Shells

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Victoria A. Smith

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Juster F. A. Rivera

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Ruby Bello

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Elena Rodríguez-Aguado

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Mohammed R. Elshaer

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Rebecca L. Wodzinski

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Svetlana Bashkova

C 2021, 7(1), 27; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010027 - 27 Feb 2021

Cited by 1 | Viewed by 559

Abstract

Activated carbons prepared from cashew nut shells and modified by grafting polyethylenimine onto the surface were tested for removal of Cr (VI). The removal efficiency of carbons without and with polyethylenimine decreased with an increase in pH, with maximum efficiency found at pH [...] Read more.

Activated carbons prepared from cashew nut shells and modified by grafting polyethylenimine onto the surface were tested for removal of Cr (VI). The removal efficiency of carbons without and with polyethylenimine decreased with an increase in pH, with maximum efficiency found at pH 2. The average maximum adsorption capacities of carbons were calculated to be 340 ± 20 mg/g and 320 ± 20 mg/g for unmodified and modified carbons, respectively. Surface characterization of carbons revealed that C–O functionalities are actively involved in both polyethylenimine grafting and Cr (VI) removal. Moreover, lactone groups and amides, formed by polyethylenimine grafting, seemingly undergo acid hydrolysis with formation of phenol and carboxylic groups. Considering that Cr (III) is the only form of chromium found on the surface of both carbons, the reduction mechanism is deduced as the predominant one. Here Cr (VI), majorly present as HCrO₄¯, is attracted to the positively charged carbon surface, reduced to Cr (III) by phenol groups, and adsorbed inside the pores. The mechanism of Cr (VI) removal appears to be similar for unmodified and modified carbons, where the smaller adsorption capacity of the latter one can be related to steric hindrance and pore inaccessibility. Full article

(This article belongs to the Collection Carbon-Derived Materials from Bioresources for Advanced Applications)

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Open AccessArticle

A New Composite Material on the Base of Carbon Nanotubes and Boron Clusters B12 as the Base for High-Performance Supercapacitor Electrodes

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Dmitry A. Kolosov

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Olga E. Glukhova

C 2021, 7(1), 26; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010026 - 25 Feb 2021

Cited by 1 | Viewed by 573

Abstract

We explore the quantum capacitance, stability, and electronic properties of single-walled carbon nanotubes decorated with B12 icosahedral boron clusters by first-principle calculation methods implemented in the SIESTA code. After the optimization of the built supercells, the B12 clusters formed bonds with the walls [...] Read more.

We explore the quantum capacitance, stability, and electronic properties of single-walled carbon nanotubes decorated with B12 icosahedral boron clusters by first-principle calculation methods implemented in the SIESTA code. After the optimization of the built supercells, the B12 clusters formed bonds with the walls of the carbon nanotubes and demonstrated metallic properties in all cases. The network of carbon nanotubes with its large area and branched surface is able to increase the capacity of the electric double-layer capacity, but the low quantum capacity of each nanotube in this network limits its application in supercapacitors. We found that the addition of boron clusters to both the outer and inner walls increased the quantum capacitance of carbon nanotubes. The calculation of the transmission function near the Fermi energy showed an increase in the conductivity of supercells. It was also found that an increase in the concentration of boron clusters in the structure led to a decrease in the heat of formation that positively affects the stability of supercells. The calculation of the specific charge density showed that with an increase in the boron concentration, the considered material demonstrated the properties of an asymmetric electrode. Full article

(This article belongs to the Special Issue Carbon-Rich Compounds: From Molecules to Materials)

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Open AccessArticle

Selection of Mixed Amines in the CO₂ Capture Process

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C 2021, 7(1), 25; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010025 - 24 Feb 2021

Viewed by 739

Abstract

In order to select the best mixed amines in the CO₂ capture process, the absorption of CO₂ in mixed amines was explored at the required concentrations by using monoethanolamine (MEA) as a basic solvent, mixed with diisopropanolamine (DIPA), triethanolamine [...] Read more.

In order to select the best mixed amines in the CO₂ capture process, the absorption of CO₂ in mixed amines was explored at the required concentrations by using monoethanolamine (MEA) as a basic solvent, mixed with diisopropanolamine (DIPA), triethanolamine (TEA), 2-amino-2-methyl-1-propanol (AMP), and piperazine (PZ). Here, a bubble column was used as the scrubber, and a continuous operation was adopted. The Taguchi method was used for the experimental design. The conditional factors included the type of mixed amine (A), the ratio of the mixed amines (B), the liquid feed flow (C), the gas-flow rate (D), and the concentration of mixed amines (E). There were four levels, respectively, and a total of 16 experiments. The absorption efficiency (E_F), absorption rate (R_A), overall mass transfer coefficient (K_Ga), and scrubbing factor (

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) were used as indicators and were determined in a steady-state by the mass balance and two-film models. According to the Taguchi analysis, the importance of the parameters and the optimum conditions were obtained. In terms of the absorption efficiency (E_F), the absorption rate (absorption factor) (R_A/

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), and the overall mass transfer coefficient (K_Ga), the order of importance is D > E > A > B > C, D > E > C > B > A, and D > E > C > A > B, respectively, and the optimum conditions are A1B4C4D3E3, A1B3C4D4E2, A4B2C3D4E4, and A1B1C1D4E1. The optimum condition validation results showed that the optimal values of E_F, R_A, and K_Ga are 100%, 30.69 × 10⁻⁴ mol/s·L, 1.540 l/s, and 0.269, respectively. With regard to the selection of mixed amine, it was found that the mixed amine (MEA + AMP) performed the best in the CO₂ capture process. Full article

(This article belongs to the Special Issue CO2 Capture and Valorization)

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Open AccessEditorial

C—Journal of Carbon Research: 300th Publications Milestone

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Craig E. Banks

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Jandro L. Abot

C 2021, 7(1), 24; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010024 - 20 Feb 2021

Viewed by 535

Abstract

The C—Journal of Carbon Research (ISSN 2311-5629) is quite pleased to announce the publication of its 300th article [...] Full article

Open AccessArticle

Removal of Lead by Oxidized Graphite

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Namasivayam Selvanantharajah

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Poobalasuntharam Iyngaran

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Poobalasingam Abiman

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Navaratnarajah Kuganathan

C 2021, 7(1), 23; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010023 - 20 Feb 2021

Viewed by 549

Abstract

Lead ion adsorption on the surfaces of pristine and oxidized graphite is studied quantitatively using X-ray photoelectron spectroscopy (XPS) and standard electrochemical measurements. The XPS analysis confirmed the oxidation of graphite, yielding a final composite consisting of 15.97% of oxygen and 84.03% of [...] Read more.

Lead ion adsorption on the surfaces of pristine and oxidized graphite is studied quantitatively using X-ray photoelectron spectroscopy (XPS) and standard electrochemical measurements. The XPS analysis confirmed the oxidation of graphite, yielding a final composite consisting of 15.97% of oxygen and 84.03% of carbon in comparison with the pristine graphite powder consisting of 6.13% oxygen and 93.87% carbon. The adsorption of lead (II) ion was confirmed by the peaks observed at 138 eV and 143.8 eV, associated with the emissions from Pb4f 7/2 and Pb4f 5/2, respectively. The effective concentration of Pb²⁺ ion and the optimum dosage of oxidized graphite were calculated to be 400 µM and 200 mg, respectively. Adsorption capacity of bare graphite was 41.18%, whereas that of oxidized graphite was 73.3%. The present results show that graphite oxide is a candidate material for the adsorption of Pb²⁺ ion from water. Full article

(This article belongs to the Special Issue Carbon-Related Nanomaterials in Analytical Nanoscience and Nanotechnology)

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Open AccessFeature PaperArticle

Anisotropic Magnetism in Gradient Porous Carbon Composite Aerogels

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Jochen Bahner

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Nicolas Hug

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Sebastian Polarz

C 2021, 7(1), 22; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010022 - 13 Feb 2021

Viewed by 842

Abstract

Porosity is of high importance for functional materials, as it allows for high surface areas and the accessibility of materials. While the fundamental interplay between different pore sizes and functionalities is quite well understood, few studies on gradually changing properties in a material [...] Read more.

Porosity is of high importance for functional materials, as it allows for high surface areas and the accessibility of materials. While the fundamental interplay between different pore sizes and functionalities is quite well understood, few studies on gradually changing properties in a material exist. To date, only a few examples of such materials have been synthesized successfully. Herein, we present a facile method for synthesizing macroscopic carbon aerogels with locally changing pore sizes and functionalities. We used ultracentrifugation to fractionate differently functionalized and sized polystyrene nanoparticles. The assembly into gradient templates was conducted in a resorcinol–formaldehyde (RF) sol, which acted as a liquid phase and carbon precursor. We show that the modification of nanoparticles and a sol–gel precursor is a powerful tool for introducing dopants (sulfur and phosphorous) and metal nanoparticles (e.g., Ni) into gradient porous carbons formed during the carbonization of the RF sol. Understanding the underlying interactions between particles and precursors will lead to a plethora of possibilities in the material design of complex functionally graded materials. We showed this by exchanging parts of the template with magnetite–polystyrene composites as templating nanoparticles. This led to the incorporation of magnetite nanoparticles in the formed gradient porous carbon aerogels. Finally, gradually increasing concentrations of magnetite were obtained, ultimately leading to macroscopic carbon aerogels with locally changing magnetic properties, while the graded porosity was maintained. Full article

(This article belongs to the Special Issue Carbon-Rich Compounds: From Molecules to Materials)

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Open AccessFeature PaperArticle

A Comparative Study of Aromatization Catalysts: The Advantage of Hybrid Oxy/Carbides and Platinum-Catalysts Based on Carbon Gels

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Luisa M. Pastrana-Martínez

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Sergio Morales-Torres

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Francisco J. Maldonado-Hódar

C 2021, 7(1), 21; https://doi.org/10.3390/c7010021 - 12 Feb 2021

Viewed by 560

Abstract

This manuscript is focused on the relationship between sol-gel synthesis processes and the development of new active phases with fitted morphology, porosity and surface chemistry. The influence of the above parameters on the catalytic performance of the prepared materials for the aromatization of [...] Read more.

This manuscript is focused on the relationship between sol-gel synthesis processes and the development of new active phases with fitted morphology, porosity and surface chemistry. The influence of the above parameters on the catalytic performance of the prepared materials for the aromatization of n-hexane to benzene is also evaluated. Different series of catalysts were prepared, either using noble metals (i.e., Pt) or metal oxides (i.e., Mo, W), as active phases. In both cases, the catalytic performance and stability of classical aromatization catalysts was significantly improved. Interesting one-pot carboreduction process of the metal oxide during carbonization is suggested as a real alternative for the preparation of high-performance aromatization catalysts, leading to the formation of less acidic and non-stoichiometric oxides and carbides. Full article

(This article belongs to the Collection Carbon-Derived Materials from Bioresources for Advanced Applications)

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Open AccessReview

Preparation and Applications of Fluorinated Graphenes

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C 2021, 7(1), 20; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010020 - 07 Feb 2021

Cited by 1 | Viewed by 878

Abstract

The present review focuses on the numerous routes for the preparation of fluorinated graphene (FG) according to the starting materials. Two strategies are considered: (i) addition of fluorine atoms on graphenes of various nature and quality and (ii) exfoliation of graphite fluoride. Chemical [...] Read more.

The present review focuses on the numerous routes for the preparation of fluorinated graphene (FG) according to the starting materials. Two strategies are considered: (i) addition of fluorine atoms on graphenes of various nature and quality and (ii) exfoliation of graphite fluoride. Chemical bonding in fluorinated graphene, related properties and a selection of applications for lubrication, energy storage, and gas sensing will then be discussed. Full article

(This article belongs to the Special Issue 2D Ultrathin Carbon Films)

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Open AccessReview

Carbon-Based Nanomaterials for Delivery of Biologicals and Therapeutics: A Cutting-Edge Technology

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C 2021, 7(1), 19; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010019 - 05 Feb 2021

Cited by 2 | Viewed by 1031

Abstract

After hydrogen and oxygen, carbon is the third most abundant component present in the cosmos with excellent characteristic features of binding to itself and nearly all elements. Since ancient times, carbon-based materials such as graphite, charcoal, and carbon black have been utilized for [...] Read more.

After hydrogen and oxygen, carbon is the third most abundant component present in the cosmos with excellent characteristic features of binding to itself and nearly all elements. Since ancient times, carbon-based materials such as graphite, charcoal, and carbon black have been utilized for writing and drawing materials. As these materials possess excellent chemical, mechanical, electrical, and thermal features, they have been readily engineered into carbon-based nanomaterials (CNMs) such as carbon nanotubes, graphene oxide, graphene quantum dots, nanodiamonds, fullerenes, carbon nano-onions, and so forth. These materials are now widely explored in biomedical applications. Thus, the emergence of CNMs has opened up a gateway for the detection, delivery, and treatment of a multitude of diseases. They are being actively researched for applications within tissue engineering, as vaccine vectors, and for the delivery of therapeutics to the immune system. This review focuses on the recent advances in various types of CNMs, their fabrication techniques, and their application in the delivery of therapeutics both in vitro and in vivo. The review also focuses on the toxicity concern of the CNMs and the possible remedies to tackle the toxicity issues. Concluding remarks emphasize all the CNMs discussed in the review over their possible biomedical applications, while the future perspectives section discusses the approaches to bring CNMs into the mainstream of clinical trials and their therapeutic applications. Full article

(This article belongs to the Special Issue Functional Carbons and Carbides: Bioapplications and Beyond)

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Open AccessArticle

Carbon Nanotubes Transform Soft Gellan Gum Hydrogels into Hybrid Organic–Inorganic Coatings with Excellent Cell Growth Capability

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C 2021, 7(1), 18; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010018 - 04 Feb 2021

Cited by 1 | Viewed by 631

Abstract

Carbone nanotubes (CNTs) possess distinct properties, for example, hardness, which is very complementary to biologically relevant soft polymeric and protein materials. Combining CNTs with bio-interfaces leads to obtaining new materials with advanced properties. In this work, we have designed novel organic-inorganic hybrid coatings [...] Read more.

Carbone nanotubes (CNTs) possess distinct properties, for example, hardness, which is very complementary to biologically relevant soft polymeric and protein materials. Combining CNTs with bio-interfaces leads to obtaining new materials with advanced properties. In this work, we have designed novel organic-inorganic hybrid coatings by combining CNTs with gellan gum (GG) hydrogels. The surface topography of the samples is investigated using scanning electron microscopy and atomic force microscopy. Mechanical properties of synthesized hybrid materials are both assessed at the macro-scale and mapped at the nanoscale. A clear correlation between the CNT concentration and the hardness of the coatings is revealed. Cell culture studies show that effective cell growth is achieved at the CNT concentration of 15 mg/mL. The presented materials can open new perspectives for hybrid bio-interfaces and can serve as a platform for advanced cell culture. Full article

(This article belongs to the Section Carbon Materials and Carbon Allotropes)

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Open AccessReview

Fully Hydrogenated and Fluorinated Bigraphenes–Diamanes: Theoretical and Experimental Studies

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Leonid A. Chernozatonskii

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Victor A. Demin

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Dmitry G. Kvashnin

C 2021, 7(1), 17; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010017 - 02 Feb 2021

Cited by 1 | Viewed by 702

Abstract

Diamanes are 2D diamond-like films that are nanometers in thickness. Diamanes can exist as bilayer or multilayer graphene with various modes of stacking and interlayer covalent sp³ bonds. The term “diamane” is used broadly for a variety of diamond-like materials at the [...] Read more.

Diamanes are 2D diamond-like films that are nanometers in thickness. Diamanes can exist as bilayer or multilayer graphene with various modes of stacking and interlayer covalent sp³ bonds. The term “diamane” is used broadly for a variety of diamond-like materials at the nanoscale, from individual diamond clusters to nanocrystal films. A short overview of recent progress in the investigation of diamanes, starting from the first theoretical predictions to practical realization, is presented. The results of both theoretical and experimental studies on diamanes with various atomic structures and types of functionalization are considered. It is shown that diamanes are stronger than graphene and graphane and have wide bandgaps ranging from 3.1 to 4.5 eV depending on the structure. Diamane-like structures have been obtained using different experimental techniques, and their structures have been determined by Raman spectroscopy. The potential applications of these carbon nanostructures are briefly reviewed. Full article

(This article belongs to the Special Issue 2D Ultrathin Carbon Films)

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Open AccessFeature PaperArticle

Energy Absorption in Carbon Fiber Composites with Holes under Quasi-Static Loading

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Omar Alhyari

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Golam Newaz

C 2021, 7(1), 16; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010016 - 01 Feb 2021

Cited by 1 | Viewed by 516

Abstract

Composite tubular structures have shown promise as energy absorbers in the automobile industry. This paper investigates the energy absorption characteristics of carbon fiber reinforced plastic (CFRP) tubes with pre-existing holes. Holes may represent an extreme case of impact damage that perforates the tube, [...] Read more.

Composite tubular structures have shown promise as energy absorbers in the automobile industry. This paper investigates the energy absorption characteristics of carbon fiber reinforced plastic (CFRP) tubes with pre-existing holes. Holes may represent an extreme case of impact damage that perforates the tube, e.g., stones from road surface impacting the tubes. Tubes with holes represent more conservative performance characteristics, since impact damage of the same size will have residual material, which may carry some load. Tubes with holes can provide the lower limit of CFRP tube performance under axial crushing relative to impact damaged tubes with perforation diameter close to the hole diameter. In this study, tubes with lay-up of [05/902/04] with one and two holes in defined locations and different diameters are experimentally studied under quasi-static loading. It was found that specific energy absorption (SEA) reduces by 50% with one or two holes of 15 mm size, 100 mm from top of the tube. The SEA reduction is about 60% lower than the regular tube when the diameter of the hole is 20 mm located at 100 mm from top. The most severe reduction occurs if the location of single or double holes are 75 mm from the top. In this case, a SEA reduction of 75% can be expected. Results indicate that holes can significantly alter the energy absorption capability of the tubes. It is also clear that in axial crushing of composite tubes, the location of the hole (100 to 75 mm) appears to create more pronounced effect than the size of the hole itself (15 vs. 20 mm) for the cases investigated. The failure modes for tubes with holes seem to preserve similar damage modes with delamination, frond creation, and brittle fracture, which is typically observed in regular composite tubes under axial crushing load. This is due to primarily front end crushing, which dominates the failure modes, while hole induced damage occurs later. Full article

(This article belongs to the Special Issue Nanocarbon-Based Composites and Their Thermal, Electrical, and Mechanical Properties)

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Open AccessArticle

Design of Porous Carbons for Supercapacitor Applications for Different Organic Solvent-Electrolytes

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C 2021, 7(1), 15; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010015 - 29 Jan 2021

Cited by 1 | Viewed by 675

Abstract

The challenge of optimizing the pore size distribution of porous electrodes for different electrolytes is encountered in supercapacitors, lithium-ion capacitors and hybridized battery-supercapacitor devices. A volume-averaged continuum model of ion transport, taking into account the pore size distribution, is employed for the design [...] Read more.

The challenge of optimizing the pore size distribution of porous electrodes for different electrolytes is encountered in supercapacitors, lithium-ion capacitors and hybridized battery-supercapacitor devices. A volume-averaged continuum model of ion transport, taking into account the pore size distribution, is employed for the design of porous electrodes for electrochemical double-layer capacitors (EDLCs) in this study. After validation against experimental data, computer simulations investigate two types of porous electrodes, an activated carbon coating and an activated carbon fabric, and three electrolytes: 1.5 M TEABF₄ in acetonitrile (AN), 1.5 M TEABF₄ in propylene carbonate (PC), and 1 M LiPF₆ in ethylene carbonate:ethyl methyl carbonate (EC:EMC) 1:1 v/v. The design exercise concluded that it is important that the porous electrode has a large specific area in terms of micropores larger than the largest desolvated ion, to achieve high specific capacity, and a good proportion of mesopores larger than the largest solvated ion to ensure fast ion transport and accessibility of the micropores. Full article

(This article belongs to the Special Issue Carbon Based Electrochemical Devices)

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Open AccessEditorial

Acknowledgment to Reviewers of C in 2020

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C Editorial Office

C 2021, 7(1), 14; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010014 - 28 Jan 2021

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Abstract

Peer review is the driving force of journal development, and reviewers are gatekeepers who ensure that C maintains its standards for the high quality of its published papers [...] Full article

Open AccessArticle

Symmetrical Derivative of Anthrone as a Novel Receptor for Mercury Ions: Enhanced Performance of Modified Screen-Printed Electrode

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C 2021, 7(1), 13; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010013 - 27 Jan 2021

Viewed by 576

Abstract

Voltammetric sensor using a symmetrical derivative of anthrone3 (1,7-diamino-3,9-dibutyl benzo[1,2,3-de:4,5,6-d’e’]diquinoline-2,8(3H,9H)-dione) (SPE-A) has been developed as a probe for Hg(II) ions. Performance of the probe as screen-printed electrode modified with the receptor (SPE-A) has been compared with anthrone3 in solution phase, using 1:1 water-acetonitrile [...] Read more.

Voltammetric sensor using a symmetrical derivative of anthrone3 (1,7-diamino-3,9-dibutyl benzo[1,2,3-de:4,5,6-d’e’]diquinoline-2,8(3H,9H)-dione) (SPE-A) has been developed as a probe for Hg(II) ions. Performance of the probe as screen-printed electrode modified with the receptor (SPE-A) has been compared with anthrone3 in solution phase, using 1:1 water-acetonitrile solvent system. Anthrone3 displayed an electrochemically quasi-reversible nature in voltammograms with both the systems and is presented as a novel disposable voltammetric sensor for mercury ions. Upon interaction with cations, both the electrode systems showed sensitivity towards Hg²⁺ ions with a lower detection limit of 0.61 µM. The magnitude of the voltammetric current with the SPE-A exhibited three times the current obtained with a bare glassy carbon electrode (GC). Kinetic performance of the SPE-A electrode is better than the GC electrode. The morphological studies indicate reusability of the electrodes. Full article

(This article belongs to the Special Issue Carbon Based Electrochemical Devices)

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Open AccessArticle

Stabilization and Carbonization of PAN Nanofiber Mats Electrospun on Metal Substrates

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C 2021, 7(1), 12; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010012 - 27 Jan 2021

Viewed by 689

Abstract

Polyacrylonitrile (PAN) nanofiber mats are typical precursors for carbon nanofibers. They can be fixed or even elongated during stabilization and subsequent carbonization to gain straight, mechanically robust carbon nanofibers. These processes necessitate additional equipment or are—if the nanofiber mats are just fixed at [...] Read more.

Polyacrylonitrile (PAN) nanofiber mats are typical precursors for carbon nanofibers. They can be fixed or even elongated during stabilization and subsequent carbonization to gain straight, mechanically robust carbon nanofibers. These processes necessitate additional equipment or are—if the nanofiber mats are just fixed at the edges—prone to resulting in the specimens breaking, due to an uneven force distribution. Hence, we showed in a previous study that electrospinning PAN on aluminum foils and stabilizing them fixed on these substrates, is a suitable solution to keep the desired morphology after stabilization and incipient carbonization. Here, we report on the influence of different metallic and semiconductor substrates on the physical and chemical properties of the nanofiber mats after stabilization and carbonization at temperatures up to 1200 °C. For stabilization on a metal substrate, an optimum stabilization temperature of slightly above 240 °C was found, approached with a heating rate of 0.25 K/min. Independent from the substrate material, SEM images revealed less defect fibers in the nanofiber mats stabilized and incipiently carbonized on a metal foil. Finally, high-temperature carbonization on different substrates is shown to allow for producing metal/carbon nano-composites. Full article

(This article belongs to the Collection Feature Papers in the Science and Engineering of Carbons)

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Open AccessArticle

Surface Charge Effects on Adsorption of Solutes by Poplar and Elm Biochars

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Steven C. Peterson

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Sanghoon Kim

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Jason Adkins

C 2021, 7(1), 11; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010011 - 26 Jan 2021

Viewed by 497

Abstract

Elm and poplar are two tree species that can provide a large amount of low-value feedstock for biochar production due to their rapid growth rate (poplar), and susceptibility to disease and/or infestation (both elm and poplar). Biochar has been studied recently as filtration [...] Read more.

Elm and poplar are two tree species that can provide a large amount of low-value feedstock for biochar production due to their rapid growth rate (poplar), and susceptibility to disease and/or infestation (both elm and poplar). Biochar has been studied recently as filtration medium for water purification, as it provides a renewable alternative to activated carbon. In this work, the adsorption efficiency of biochars made from elm and poplar as a function of pyrolysis temperature were studied by ultraviolet (UV) adsorption of dyes with positive, neutral, and negative charges to determine what factors had the greatest effect on adsorption of these dyes. It was found that conductivity of the biochars increased with pyrolysis temperature, and that this factor was more important than surface area in terms of adsorbing charged dyes. Both elm and poplar biochars were not effective in adsorbing neutral dyes. This research demonstrates that elm and poplar biochars adsorb charged (either positively or negatively) solutes more efficiently than uncharged ones because they carry both charges themselves. Therefore, these biochars would make excellent candidates as renewable filtration media for charged contaminants. Full article

(This article belongs to the Collection Feature Papers in the Science and Engineering of Carbons)

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Open AccessReview

Raman Spectroscopy of Twisted Bilayer Graphene

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Marcus V. O. Moutinho

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Pedro Venezuela

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Marcos A. Pimenta

C 2021, 7(1), 10; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010010 - 26 Jan 2021

Cited by 1 | Viewed by 850

Abstract

When two periodic two-dimensional structures are superposed, any mismatch rotation angle between the layers generates a Moiré pattern superlattice, whose size depends on the twisting angle

θ

. If the layers are composed by different materials, this effect is also dependent on the lattice parameters of each layer. Moiré superlattices are commonly observed in bilayer graphene, where the mismatch angle between layers can be produced by growing twisted bilayer graphene (TBG) samples by CVD or folding the monolayer back upon itself. In TBG, it was shown that the coupling between the Dirac cones of the two layers gives rise to van Hove singularities (vHs) in the density of electronic states, whose energies vary with

θ

. The understanding of the behavior of electrons and their interactions with phonons in atomically thin heterostructures is crucial for the engineering of novel 2D devices. Raman spectroscopy has been often used to characterize twisted bilayer graphene and graphene heterostructures. Here, we review the main important effects in the Raman spectra of TBG discussing firstly the appearance of new peaks in the spectra associated with phonons with wavevectors within the interior of the Brillouin zone of graphene corresponding to the reciprocal unit vectors of the Moiré superlattice, and that are folded to the center of the reduced Brillouin Zone (BZ) becoming Raman active. Another important effect is the giant enhancement of G band intensity of TBG that occurs only in a narrow range of laser excitation energies and for a given twisting angle. Results show that the vHs in the density of states is not only related to the folding of the commensurate BZ, but mainly associated with the Moiré pattern that does not necessarily have a translational symmetry. Finally, we show that there are two different resonance mechanisms that activate the appearance of the extra peaks: the intralayer and interlayer electron–phonon processes, involving electrons of the same layer or from different layers, respectively. Both effects are observed for twisted bilayer graphene, but Raman spectroscopy can also be used to probe the intralayer process in any kind of graphene-based heterostructure, like in the graphene/h-BN junctions. Full article

(This article belongs to the Special Issue 2D Ultrathin Carbon Films)

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Open AccessReview

Progress on Diamane and Diamanoid Thin Film Pressureless Synthesis

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C 2021, 7(1), 9; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010009 - 23 Jan 2021

Cited by 2 | Viewed by 1203

Abstract

Nanometer-thick and crystalline sp³-bonded carbon sheets are promising new wide band-gap semiconducting materials for electronics, photonics, and medical devices. Diamane was prepared from the exposure of bi-layer graphene to hydrogen radicals produced by the hot-filament process at low pressure and temperature. [...] Read more.

Nanometer-thick and crystalline sp³-bonded carbon sheets are promising new wide band-gap semiconducting materials for electronics, photonics, and medical devices. Diamane was prepared from the exposure of bi-layer graphene to hydrogen radicals produced by the hot-filament process at low pressure and temperature. A sharp sp³-bonded carbon stretching mode was observed in ultraviolet Raman spectra at around 1344–1367 cm⁻¹ while no sp²-bonded carbon peak was simultaneously detected. By replacing bi-layer graphene with few-layer graphene, diamanoid/graphene hybrids were formed from the partial conversion of few-layer graphene, due to the prevalent Bernal stacking sequence. Raman spectroscopy, electron diffraction, and Density Functional Theory calculations show that partial conversion generates twisted bi-layer graphene located at the interface between the upper diamanoid domain and the non-converted graphenic domain underneath. Carbon-hydrogen bonding in the basal plane of hydrogenated few-layer graphene, where carbon is bonded to a single hydrogen over an area of 150 μm², was directly evidenced by Fourier transform infrared microscopy and the actual full hydrogenation of diamane was supported by first-principle calculations. Those results open the door to large-scale production of diamane, diamanoids, and diamanoid/graphene hybrids. Full article

(This article belongs to the Special Issue 2D Ultrathin Carbon Films)

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Open AccessArticle

Modifying Electronic and Elastic Properties of 2-Dimensional [110] Diamond by Nitrogen Substitution

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Teerachote Pakornchote

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Annop Ektarawong

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Udomsilp Pinsook

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Thiti Bovornratanaraks

C 2021, 7(1), 8; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010008 - 21 Jan 2021

Cited by 2 | Viewed by 562

Abstract

One type of two-dimensional diamonds that are derived from [111] direction, so-called diamane, has been previously shown to be stabilized by N-substitution, where the passivation of dangling bonds is no longer needed. In the present work, we theoretically demonstrated that another type of [...] Read more.

One type of two-dimensional diamonds that are derived from [111] direction, so-called diamane, has been previously shown to be stabilized by N-substitution, where the passivation of dangling bonds is no longer needed. In the present work, we theoretically demonstrated that another type of two-dimensional diamonds derived from [110] direction exhibiting a washboard conformation can also be stabilized by N-substitution. Three structural models of washboard-like carbon nitrides with compositions of C₆N₂, C₅N₃, and C₄N₄ are studied together with the fully hydrogenated washboard-like diamane (C₈H₄). The result shows that the band gap of this type structure is only open the dangling bonds that are entirely diminished through N-substitution. By increasing the N content, the C₁₁ and C₂₂ are softer and the C₃₃ is stiffer where their bulk modulus are in the same order, which is approximately 550 GPa. When comparing with the hydrogenated phase, the N-substituted phases have higher elastic constants and bulk modulus, suggesting that they are possibly harder than the fully hydrogenated diamane. Full article

(This article belongs to the Special Issue 2D Ultrathin Carbon Films)

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Open AccessArticle

Asymmetric Supercapacitors: Optical and Thermal Effects When Active Carbon Electrodes Are Embedded with Nano-Scale Semiconductor Dots

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Haim Grebel

C 2021, 7(1), 7; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010007 - 15 Jan 2021

Cited by 2 | Viewed by 600

Abstract

Optical and thermal effects in asymmetric supercapacitors, whose active-carbon (AC) electrodes were embedded with nano-Si (n-Si) quantum dots (QD), are reported. We describe two structures: (1) p-n-like, obtained by using a polyethylimine (PEI) binder for the “n” electrode and a polyvinylpyrrolidone (PVP) binder [...] Read more.

Optical and thermal effects in asymmetric supercapacitors, whose active-carbon (AC) electrodes were embedded with nano-Si (n-Si) quantum dots (QD), are reported. We describe two structures: (1) p-n-like, obtained by using a polyethylimine (PEI) binder for the “n” electrode and a polyvinylpyrrolidone (PVP) binder for the “p” electrode; (2) a single component binder—poly(methyl methacrylate) (PMMA). In general, AC appears black to the naked eye and one may assume that it indiscriminately absorbs all light spectra. However, on top of a flat lossy spectrum, AC (from two manufacturers) exhibited two distinct absorption bands: one in the blue (~400 nm) and the other one in the near IR (~840 nm). The n-Si material accentuated the absorption in the blue and bleached the IR absorption. Both bands contributed to capacitance increase: (a) when using aqueous solution and a PMMA binder, the optical-related increased capacitance was 20% for low n-Si concentration and more than 100% for a high-concentration dose; (b) when using ion liquid (IL) electrolyte, the large, thermal capacitance increase (of ca. 40%) was comparable to the optical effect (of ca. 42%) and hence was assigned as an optically induced thermal effect. The experimental data point to an optically induced capacitance increase even in the absence of the n-Si dots. Overall, the experimental data suggest intriguing possibilities for optically controlled supercapacitors. Full article

(This article belongs to the Collection Feature Papers in the Science and Engineering of Carbons)

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Open AccessEditorial

Ionic Liquids for CO₂ Capture and Reduction

by

Małgorzata E. Zakrzewska

C 2021, 7(1), 6; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010006 - 13 Jan 2021

Viewed by 538

Abstract

As pointed out in the description of this thematic issue of C, with the current atmospheric levels of carbon dioxide being above 400 ppm, there is a growing interest in recycling this greenhouse gas in the form of valuable compounds [...] Full article

(This article belongs to the Special Issue Ionic liquids for CO2 Capture and Reduction)

Open AccessArticle

First-Principles Study of the Electronic Properties and Thermal Expansivity of a Hybrid 2D Carbon and Boron Nitride Material

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Okikiola Olaniyan

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Lyudmila V. Moskaleva

C 2021, 7(1), 5; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010005 - 12 Jan 2021

Viewed by 625

Abstract

In an attempt to push the boundary of miniaturization, there has been a rising interest in two-dimensional (2D) semiconductors with superior electronic, mechanical, and thermal properties as alternatives for silicon-based devices. Due to their fascinating properties resulting from lowering dimensionality, hexagonal boron nitride [...] Read more.

In an attempt to push the boundary of miniaturization, there has been a rising interest in two-dimensional (2D) semiconductors with superior electronic, mechanical, and thermal properties as alternatives for silicon-based devices. Due to their fascinating properties resulting from lowering dimensionality, hexagonal boron nitride (h-BN) and graphene are considered promising candidates to be used in the next generation of high-performance devices. However, neither h-BN nor graphene is a semiconductor due to a zero bandgap in the one case and a too large bandgap in the other case. Here, we demonstrate from first-principles calculations that a hybrid 2D material formed by cross-linking alternating chains of carbon and boron nitride (HCBN) shows promising characteristics combining the thermal merits of graphene and h-BN while possessing the electronic structure characteristic of a semiconductor. Our calculations demonstrate that the thermal properties of HCBN are comparable to those of h-BN and graphene (parent systems). HCBN is dynamically stable and has a bandgap of 2.43 eV. At low temperatures, it exhibits smaller thermal contraction than the parent systems. However, beyond room temperature, in contrast to the parent systems, it has a positive but finitely small linear-thermal expansion coefficient. The calculated isothermal bulk modulus indicates that at high temperatures, HCBN is less compressible, whereas at low temperatures it is more compressible relative to the parent systems. The results of our study are important for the rational design of a 2D semiconductor with good thermal properties. Full article

(This article belongs to the Collection Feature Papers in the Science and Engineering of Carbons)

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Open AccessArticle

Functionalized Graphene Quantum Dots Modulate Malignancy of Glioblastoma Multiforme by Downregulating Neurospheres Formation

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C 2021, 7(1), 4; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010004 - 05 Jan 2021

Viewed by 610

Abstract

Glioblastoma multiforme (GBM) is the most aggressive brain cancer. We previously demonstrated the effect of biocompatible surface functionalized graphene quantum dots (GQDs) on GBM cells as chemotherapy enhancers in combination with the antitumor drug doxorubicin (Dox). However, traditional two-dimensional cultures could not represent [...] Read more.

Glioblastoma multiforme (GBM) is the most aggressive brain cancer. We previously demonstrated the effect of biocompatible surface functionalized graphene quantum dots (GQDs) on GBM cells as chemotherapy enhancers in combination with the antitumor drug doxorubicin (Dox). However, traditional two-dimensional cultures could not represent a reliable model of tumor behavior. In this work, we investigated the effect of carboxylated (COOH-GQDs), aminated (NH₂-GQDs) and unfunctionalized GQDs on a three-dimensional model of neurospheres. Neurospheres are clusters of GBM cells, which formation is driven by the presence of a stem subpopulation involved in cancer malignancy. Tumor recurrence after surgical resection, chemotherapy and radiotherapy indeed depends on the presence of cancer cells with stem properties. We measured a significant reduction in number and size of neurospheres after two weeks of monitoring in the presence of COOH-GQDs and GQDs. Previous works pointed out how variations of membrane fluidity could affect membrane stability and cell-to-cell interactions, thus influencing cell clustering. Therefore, we measured changes in membrane fluidity after administration of GQDs. We found that COOH-GQDs and GQDs significantly increased membrane fluidity with respect to the treatment with NH₂-GQDs or compared to untreated cells. Shifts in the phase of phospholipid bilayer were in accordance with the negative surface net charge of GQDs. We depicted a strong correlation between negatively charged GQDs-induced increase in membrane fluidity and the downregulation of neurospheres formation. Our results indicate that COOH-GQDs and GQDs significantly modulate tumor malignancy by increasing fluidity of cell membrane, with a consequent inhibition of cell-to-cell interaction. Full article

(This article belongs to the Special Issue Graphene and Carbon Quantum Dots, and Related 2D Quantum Dots)

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Open AccessReview

Carbon Nanohorns as Effective Nanotherapeutics in Cancer Therapy

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Fiore Pasquale Nicoletta

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Orazio Vittorio

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Silke Hampel

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Francesca Iemma

C 2021, 7(1), 3; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010003 - 27 Dec 2020

Cited by 1 | Viewed by 955

Abstract

Different carbon nanostructures have been explored as functional materials for the development of effective nanomaterials in cancer treatment applications. This review mainly aims to discuss the features, either strength or weakness, of carbon nanohorn (CNH), carbon conical horn-shaped nanostructures of sp2 carbon atoms. [...] Read more.

Different carbon nanostructures have been explored as functional materials for the development of effective nanomaterials in cancer treatment applications. This review mainly aims to discuss the features, either strength or weakness, of carbon nanohorn (CNH), carbon conical horn-shaped nanostructures of sp2 carbon atoms. The interest for these materials arises from their ability to couple the clinically relevant properties of carbon nanomaterials as drug carriers with the negligible toxicity described in vivo. Here, we offer a comprehensive overview of the recent advances in the use of CNH in cancer treatments, underlining the benefits of each functionalization route and approach, as well as the biological performances of either loaded and unloaded materials, while discussing the importance of delivery devices. Full article

(This article belongs to the Special Issue Functional Carbons and Carbides: Bioapplications and Beyond)

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Open AccessFeature PaperReview

Citric Acid Derived Carbon Dots, the Challenge of Understanding the Synthesis-Structure Relationship

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Junkai Ren

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Luca Malfatti

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Plinio Innocenzi

C 2021, 7(1), 2; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010002 - 22 Dec 2020

Cited by 1 | Viewed by 1102

Abstract

Carbon dots (CDs) are highly-emissive nanoparticles obtained through fast and cheap syntheses. The understanding of CDs’ luminescence, however, is still far from being comprehensive. The intense photoluminescence can have different origins: molecular mechanisms, oxidation of polyaromatic graphene-like layers, and core-shell interactions of carbonaceous [...] Read more.

Carbon dots (CDs) are highly-emissive nanoparticles obtained through fast and cheap syntheses. The understanding of CDs’ luminescence, however, is still far from being comprehensive. The intense photoluminescence can have different origins: molecular mechanisms, oxidation of polyaromatic graphene-like layers, and core-shell interactions of carbonaceous nanoparticles. The citric acid (CA) is one of the most common precursors for CD preparation because of its high biocompatibility, and this review is mainly focused on CA-based CDs. The different parameters that control the synthesis, such as the temperature, the reaction time, and the choice of solvents, were critically described. Particular attention was devoted to the CDs’ optical properties, such as tunable emission and quantum yields, in light of functional applications. The survey of the literature allowed correlating the preparation methods with the structures and the properties of CA-based CDs. Some basic rules to fabricate highly luminescent nanoparticles were selected by the metanalysis of the current literature in the field. In some cases, these findings can be generalized to other types of CDs prepared via liquid phase. Full article

(This article belongs to the Special Issue Graphene and Carbon Quantum Dots, and Related 2D Quantum Dots)

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Open AccessArticle

Effect of Molybdenum Content on Mechanical and Tribological Properties of Diamond-Like Carbon Coatings over Titanium β-21S Alloy

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Dilli Babu Padmanaban

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C 2021, 7(1), 1; https://0-doi-org.brum.beds.ac.uk/10.3390/c7010001 - 22 Dec 2020

Viewed by 706

Abstract

Molybdenum-doped diamond-like carbon (Mo-DLC) coatings have been deposited on titanium β-21S alloy (Ti–15Mo–3Nb–3Al–0.2Si) using plasma-enhanced chemical vapor deposition (PECVD) equipped with pulsed-DC magnetron sputtering. Mo contents in the deposited coatings have been controlled with an applied sputtering pulse duty cycle. Chemical composition, structure, [...] Read more.

Molybdenum-doped diamond-like carbon (Mo-DLC) coatings have been deposited on titanium β-21S alloy (Ti–15Mo–3Nb–3Al–0.2Si) using plasma-enhanced chemical vapor deposition (PECVD) equipped with pulsed-DC magnetron sputtering. Mo contents in the deposited coatings have been controlled with an applied sputtering pulse duty cycle. Chemical composition, structure, morphology, and topography have been studied using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and atomic force microscopy (AFM), respectively. XRD pattern of the coating with highest Mo content shows the presence of carbide phase. Smooth features with low roughness values are observed in low Mo content coating, whereas high Mo content coating shows granular characteristics with a high roughness value. Raman spectra reveal the increased graphitic content for the highest metal concentration in the coatings, wherein the nanohardness is also determined to be highest, at about ~18–19 GPa. Furthermore, the ball-on-disk tribometry test on Mo-DLC coating with highest nanohardness shows a low coefficient of friction (COF) of 0.2 with low wear loss compared to that of the substrate (0.62). Full article

(This article belongs to the Special Issue Carbon-Based Composites for Energy and Biomedical Applications)

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