C — Journal of Carbon Research

Carbon materials such as graphene, carbon nanotubes, fullerene, and graphene nanoflakes (GNFs) are used for hydrogen storage. The doping of alkali metals to these materials generally increases the accumulation density of molecular hydrogen (H₂). However, the reason why the doping enhances the ability of the H₂ storage of GNF is not clearly known, although there are some explanations. In addition, the information on the storage capacity of GNF is ambiguous. In the present review article, we introduce our recent theoretical studies on the interaction of GNF with H₂ molecules carried out to elucidate the mechanism of hydrogen storage in alkali-doped GNFs. As alkali metals, lithium (Li), sodium (Na), and potassium (K) were examined, and the abilities of hydrogen storage were discussed. Next, the mechanism of Li-diffusion on GNF, which plays a crucial role in Li-battery, was presented. There are several unanswered questions. In particular, does lithium diffuse randomly on GNF? Or is there a specific diffusion path? We present our study, which elucidates the factors governing lithium diffusion on GNF. If the dominant factor is known, it is possible to arbitrarily control the diffusion path of lithium. This will lead to the development of highly functional battery materials. Finally, the molecular design of H adsorption–desorption reversible storage devices based on GNF will be introduced. Elucidating the mechanism of hydrogen storage, Li-diffusion on GNF, and molecular design of storage device is important in understanding the current molecular devices and provide a deeper insight into materials chemistry. Full article

In the past decade, the formulation of spark-desensitized nanothermites has considerably advanced, making them safe to handle. When ignited, these materials reveal impressive properties such as high temperatures (>1000 °C), intense heat releases (>kJ/cm³), and sometimes gas generation. Unfortunately, these energetic systems are systematically characterized by an extreme sensitivity to electrostatic discharges, which can cause accidental ignitions during preparation, handling, and transport. The present study examines the electrostatic discharge sensitivity response of an Al/WO₃ energetic formulation doped with highly conductive carbon nanoparticles (Ketjenblack EC600JD). The results showed an increased threshold from <0.14 mJ to almost 40 mJ with 18.80 vol. % of KB EC600JD in the energetic mixture. The energetic material was also desensitized to friction stress with a threshold greater than 360 N, in contrast to a value of <4.9 N for an un-doped Al/WO₃ energetic composite material. The reactive performance of the system (w/o Ketjenblack additive) was verified in open medium by means of an optical igniter. The heat release was determined by a calorimetric bomb and a decrease of 50% was recorded for the carbon-doped energetic system compared to the pristine Al/WO₃ composition. Full article

A computational approach for creating realistically structured carbon nanotubes is presented to enable more accurate and impactful multi-scale modeling and simulation techniques for nanotube research. Much of the published literature to date involving computational modeling of carbon nanotubes simplifies their structure as being long and straight, and often existing as isolated individual nanotubes. However, imagery of nanotubes has shown over several decades that nanotubes agglomerate together and exhibit looping and curvature due both to inter- and intra-nanotube attraction. The research presented in this paper leverages multi-scale simulations consisting of a simple bead-spring model for initial nanotube relaxation followed by a differential geometry approach to create an atomic representation of carbon nanotubes, and then finalized with molecular dynamics simulations using the Tersoff potential model for carbon that allows dynamic bonding and cleavage. The result is atomically accurate representations of carbon nanotubes that exist as single nanotubes, or as clusters of multiple nanotubes. The presented approach is demonstrated using (5,5) single-walled carbon nanotubes. The synthesized nanotubes are shown to relax into the curving and looping structures observed in transmission or scanning electron microscopy, but also exhibit nano-scale defects due to buckling, crimping, and twisting that are resolved during the molecular dynamics simulations. These features locally compromise the desired strength characteristics of nanotubes and therefore the presented procedure will enable more accurate modeling and simulation of nanotubes in subsequent research by representing them less as the theoretically straight and independent entities, but as realistically imperfect. Full article

Carbon nanofibers are produced from dielectric polymer precursors such as polyacrylonitrile (PAN). Carbonized nanofiber nonwovens show high surface area and good electrical conductivity, rendering these fiber materials interesting for application as electrodes in batteries, fuel cells, and supercapacitors. However, thermal processing is slow and costly, which is why new processing techniques have been explored for carbon fiber tows. Alternatives for the conversion of PAN-precursors into carbon fiber nonwovens are scarce. Here, we utilize an atmospheric pressure plasma jet to conduct carbonization of stabilized PAN nanofiber nonwovens. We explore the influence of various processing parameters on the conductivity and degree of carbonization of the converted nanofiber material. The precursor fibers are converted by plasma-jet treatment to carbon fiber nonwovens within seconds, by which they develop a rough surface making subsequent surface activation processes obsolete. The resulting carbon nanofiber nonwovens are applied as supercapacitor electrodes and examined by cyclic voltammetry and impedance spectroscopy. Nonwovens that are carbonized within 60 s show capacitances of up to 5 F g⁻¹. Full article

A novel flexible supercapacitor device was developed from a polyethylene terephthalate substrate, reused from beverage bottles, and a conductive ink based on carbon black (CB) and cellulose acetate (CA). The weight composition of the conductive ink was evaluated to determine the best mass percentage ratio between CB and CA in terms of capacitive behavior. The evaluation was performed by using different electrochemical techniques: cyclic voltammetry, obtaining the highest capacitance value for the device with the 66.7/33.3 wt% CB/CA in a basic H₂SO₄ solution, reaching 135.64 F g⁻¹. The device was applied in potentiostatic charge/discharge measurements, achieving values of 2.45 Wh kg⁻¹ for specific energy and around 1000 W kg⁻¹ for specific power. Therefore, corroborated with electrochemical impedance spectroscopy assays, the relatively low-price proposed device presented a suitable performance for application as supercapacitors, being manufactured from reused materials, contributing to the energy storage field enhancement. Full article

A new purification procedure for carbon nanoforms is proposed. It was tested on multiwall carbon nanotubes (MWCNTs) prepared by arc discharge, which is among the most challenging of cases due to the chemical and structural similarity between the MWCNTs and most of the impurities to be removed. Indeed, the various methods for synthesizing carbon nanoforms lead to a distribution of carbonaceous products, such as carbon shells, carbon spheres, fullerenes, and a variety of other species. Thus, many strategies to purify the desired products have been developed. Among the most successful ones, thermal oxidation (combustion) seems particularly efficient. To be successful while preserving a reasonable amount of MWCNTs, the combustion temperature has to be carefully selected. Moreover, the ideal combustion temperature does not only depend on the material to be treated but also on the overall system used to perform the reaction, including the reactor type and the parameters of the gaseous reactant. Typically, the optimization of the purification relies on multiple experiments and analysis of the products. However, to the best of our knowledge, a strategy to determine a priori the most suitable temperature has not been reported yet. We demonstrate here that a thermogravimetric method, namely the constant decomposition rate thermal analysis (CRTA), is particularly well adapted to answer this question. An isothermal treatment based on the results obtained from a CRTA program allowed arc-MWCNTs to be successfully purified from graphenic shells while optimizing the yield of the MWCNTs. This strategy is believed to be valuable not only for purifying MWCNTs but also for the purification of other carbonaceous forms, including new carbon nanoforms. Full article

Fiber-shaped batteries have attracted much interest in the last few years. However, a major challenge for this type of battery is their relatively low energy density. Here, we present a freestanding, flexible CNT fiber with high electrical conductivity and applied oxygen plasma-functionalization, which was successfully employed to serve as an effective cathode for Li-S batteries. The electrochemical results obtained from the conducted battery tests showed a decent rate capability and cyclic stability. The cathode delivered a capacity of 1019 mAh g⁻¹ at 0.1 C. It accommodated a high sulfur loading of 73% and maintained 47% of the initial capacity after 300 cycles. The demonstrated performance of the fiber cathode provides new insights for the designing and fabrication of high energy density fiber-shaped batteries. Full article

Greenhouse gas emissions to the atmosphere have been a long-standing issue that has existed since the Industrial Revolution. To date, carbon dioxide capture through the carbon capture, utilization, and storage approach has been one of the feasible options to combat the strong release of carbon dioxide into the atmosphere. This review focuses in general on the utilization of activated carbon as a tool when performing the carbon-capture process. Activated carbon possesses a lower isosteric heat of adsorption and a stronger tolerance to humidity as compared to zeolites and metal–organic frameworks, despite the overall gas-separation performance of activated carbon being comparatively lower. In addition, investigations of the activation methods of activated carbon are summarized in this review, together with an illustration of CO₂ adsorption performance, in the context of process simulations and pilot-plant studies. This is followed by providing future research directions in terms of the applicability of activated carbon in real CO₂ adsorption processes. Full article

The article presents the test results of the co-firing process of a glycerine fraction derived from the production of liquid biofuels (fatty acid methyl esters) with coal. The test was performed in industrial conditions using a steam boiler with a capacity of approx. 2 MW in one of the building materials manufacturing facilities. The process of co-firing a mixture of a 3% glycerine fraction and eco-pea coal was evaluated. The reference fuel was eco-pea coal. The combustion process, composition and temperature of exhaust gases were analyzed. Incorrect combustion of glycerine fraction may result in the emission of toxic, mutagenic, and carcinogenic substances, including polycyclic aromatic hydrocarbons. During the test of the combustion process of a mixture of glycerine fraction and eco-pea coal, a decrease in the content of O₂, CO, and NO_x was observed as well as an increase in the content of H₂, CO₂, and SO₂ in the fumes and growth of temperature of exhaust gases in relation to the results of combustion to eco-pea coal. Reduced content of carbon monoxide in exhaust gases produced in the combustion could be caused by the high temperature of the grate or by an excessive amount of oxygen in the grate. The higher content of oxygen in glycerine changes the value of excess air coefficient and the combustion process is more effective. The bigger content of sulfur dioxide in burnt fuels containing the glycerine fraction could be caused by the presence of reactive ingredients contained in the glycerine fraction. The reduced content of nitrogen oxides in exhaust gases originating from the combustion of a fuel mixture containing a fraction of glycerine could be caused by lower content of nitrogen in the glycerine fraction submitted to co-firing with coal and also higher combustion temperature and amount of air in the combustion chamber. The increased content of carbon dioxide in exhaust gases originating from the combustion of fuel mixture containing glycerine fraction could be caused by the influence of glycerine on the combustion process. The increase of hydrogen in the glycerine fraction causes the flame temperature to grow and makes the combustion process more efficient. Full article

The chemical exfoliation of graphite to produce graphene and its oxide is undoubtedly an economical method for scalable production. Carbon researchers have dedicated significant resources to developing new exfoliation methods leads to graphene oxides with high quality. However, only a few studies have been dedicated to the effect of the starting graphite material on the resulting GO. Herein, we have prepared two different GOs through chemical exfoliation of graphite materials having different textural and structural characteristics. All samples have been subjected to structural investigations and comprehensive characterizations using Raman, X-ray diffraction, scanning electron microscopy, TGA, N₂ physisorption, and FTIR spectroscopy. Our results provide direct evidence of how the crystallite size of the raw graphite affects the oxidation degree, surface functionality, and sheet size of the resulting GO. Building on these significant understandings, the optimized GO achieves a highly specific capacitance of 191 F·g⁻¹ at the specific current of 0.25 A·g⁻¹ in an aqueous electrolyte. This superior electrochemical performance was attributed to several factors, among which the specific surface area was accessible to the electrolyte ions and oxygenated functional groups on the surface, which can significantly modify the electronic structure of graphene and further enhance the surface energy. Full article

Capacitive proximity sensors (CPSs) have recently been a focus of increased attention because of their widespread applications, simplicity of design, low cost, and low power consumption. This mini review article provides a comprehensive overview of various applications of CPSs, as well as current advancements in CPS construction approaches. We begin by outlining the major technologies utilized in proximity sensing, highlighting their characteristics and applications, and discussing their advantages and disadvantages, with a heavy emphasis on capacitive sensors. Evaluating various nanocomposites for proximity sensing and corresponding detecting approaches ranging from physical to chemical detection are emphasized. The matrix and active ingredients used in such sensors, as well as the measured ranges, will also be discussed. A good understanding of CPSs is not only essential for resolving issues, but is also one of the primary forces propelling CPS technology ahead. We aim to examine the impediments and possible solutions to the development of CPSs. Furthermore, we illustrate how nanocomposite fusion may be used to improve the detection range and accuracy of a CPS while also broadening the application scenarios. Finally, the impact of conductance on sensor performance and other variables that impact the sensitivity distribution of CPSs are presented. Full article

In the present study, the concept of Ionic Liquid (IL)-mediated formation of carbon was applied to derive composite membranes bearing a nanoporous carbon phase within their separation layer. Thermolytic carbonization of the supported ionic liquid membranes, prepared by infiltration of the IL 1-methyl-3-butylimidazolium tricyanomethanide into the porous network of Vycor^® porous glass tubes, was applied to derive the precursor Carbon/Vycor^® composites. All precursors underwent a second cycle of IL infiltration/pyrolysis with the target to finetune the pore structural characteristics of the carbonaceous matter nesting inside the separation layer. The pore structural assets and evolution of the gas permeation properties and separation efficiency of the as-derived composite membranes were investigated with reference to the duration of the second infiltration step. The transport mechanisms of the permeating gases were elucidated and correlated to the structural characteristics of the supported carbon phase and the analysis of LN₂ adsorption isotherms. Regarding the gas separation efficiency of the fabricated Carbon/Vycor^® composite membranes, He/CO₂ ideal selectivity values as high as 4.31 at 1 bar and 25 °C and 4.64 at 0.3 bar and 90 °C were achieved. In addition, the CO₂/N₂ ideal selectivity becomes slightly improved for longer second-impregnation times. Full article

Carbon-based materials (CBMs) such as graphene, carbon nanotubes (CNT), highly ordered pyrolytic graphite (HOPG), and pyrolytic carbon (PyC) have received a great deal of attention in recent years due to their unique electronic, optical, thermal, and mechanical properties. CBMs have been grown using a variety of processes, including mechanical exfoliation, pulsed laser deposition (PLD), and chemical vapor deposition (CVD). Mechanical exfoliation creates materials that are irregularly formed and tiny in size. On the other hand, the practicality of the PLD approach for large-area high-quality CMB deposition is quite difficult. Thus, CVD is considered as the most effective method for growing CBMs. In this paper, a novel pulsed laser-assisted chemical vapor deposition (LCVD) technique was explored to determine ways to reduce the energy requirements to produce high quality CBMs. Different growth parameters, such as gas flow rate, temperature, laser energy, and deposition time were considered and studied thoroughly to analyze the growth pattern. CBMs are grown on Si and Cu substrates, where we find better quality CBM films on Cu as it aids the surface solubility of carbon. Raman spectroscopy confirms the presence of high-quality PyC which is grown at a temperature of 750 °C, CH₄ gas flow rate of 20 sccm, a laser frequency of 10 Hz, and an energy density of 0.116 J/cm² per pulse. It is found that the local pulsed-laser bombardment helps in breaking the carbon-hydrogen bonds of CH₄ at a much lower substrate temperature than its thermal decomposition temperature. There is no significant change in the 2D peak intensity in the Raman spectrum with the further increase in temperature which is the indicator of the number of the graphene layer. The intertwined graphene flakes of the PyC are observed due to the surface roughness, which is responsible for the quenching in the Raman 2D signal. These results will provide the platform to fabricate a large area single layer of graphene, including the other 2D materials, on different substrates using the LCVD technique. Full article

This article is devoted to some fundamental aspects of “super” storage in graphite nanofibers (GNF) of “reversible” (~20–30 wt.%) and “irreversible” hydrogen (~7–10 wt.%). Extraordinary results for hydrogen “super” storage were previously published by the group of Rodriguez and Baker at the turn of the century, which been unable to be reproduced or explained in terms of physics by other researchers. For the first time, using an efficient method of processing and analysis of hydrogen thermal desorption spectra, the characteristics of the main desorption peak of “irreversible” hydrogen in GNF were determined: the temperature of the highest desorption rate (T_max = 914–923 K), the activation energy of the desorption process (Q ≈ 40 kJ mol⁻¹), the pre-exponential rate constant factor (K₀ ≈ 2 × 10⁻¹ s⁻¹), and the amount of hydrogen released (~8 wt.%). The physics of hydrogen “super” sorption includes hydrogen diffusion, accompanied by the “reversible” capture of the diffusant by certain sorption “centers”; the hydrogen spillover effect, which provides local atomization of gaseous H₂ during GNF hydrogenation; and the Kurdjumov phenomenon on thermoelastic phase equilibrium. It is shown that the above-mentioned extraordinary data on the hydrogen “super” storage in GNFs are neither a mistake nor a mystification, as most researchers believe. Full article

This paper aims to discuss the importance of the climate crisis and embodied carbon in the landscape architecture sector. The study was carried out in a multiprofessional team with the collaboration of the Landscape Institute (LI) Chartered Body of Landscape Architecture, UK, and experts in the field. Using the expertise and knowledge of professionals as well as existing landscape examples and pioneering tools on carbon, this review paper focuses on the importance of low/net-zero carbon landscapes for our cities and regions and the ways in which these can contribute to the broader health and wellbeing of our communities. Examining the current situation on carbon methodologies and the latest knowledge on carbon calculations through a landscape lens, the paper explores why embodied carbon is important for open spaces/landscapes and the necessary policies to support a more efficient implementation of these concepts. The intensity of recent environmental challenges demands action. This review highlights the need for holistic approaches that integrate embodied carbon calculations on large-scale landscape design. Using the innovative example of the Pathfinder App, a carbon calculation tool, as well as other similar software, this paper argues that more steps are needed towards the calculation and adaptation of CO₂ emissions resulting from design, construction and materials in landscape schemes. The low availability of carbon calculation tools, specially developed for landscape schemes, is a major concern for the profession as it creates several issues with the sustainable development of the landscape projects as well as fragmented policies that exclude spatial and open spaces. Even though carbon calculation and embodied carbon are being calculated in buildings or materials, it is a relatively new area when it comes to land, the landscape and open and green space, and therefore, this study will present and discuss some of the pioneering carbon calculation tools focusing on landscape projects. Full article

Recent works in the development of nanostructured catalysts for bromate reduction in drinking water under hydrogen have highlighted the importance of the properties of the metallic phase support in their overall performance. Since most works in catalyst development are carried out in powder form, there is an overlooked gap in the correlation between catalyst support properties and performance in typical continuous applications such as fixed bed reactors. In this work, it is shown that the mechanical modification of commercially available carbon nanotubes, one of the most promising supports, can significantly enhance the activity of the catalytic system when tested in a stirred tank reactor, but upon transition to a fixed bed reactor, the formation of preferential pathways for the liquid flow and high pressure drops were observed. This effect could be minimized by the addition of an inert filler to increase the bed porosity; however, the improvement in catalytic performance when compared with the as-received support material was not retained. The operation of the continuous catalytic system was then optimized using a 1 wt.% Pd catalyst supported on the as-received carbon nanotubes. Effluent and hydrogen flow rates as well as catalyst loadings were systematically optimized to find an efficient set of parameters for the operation of the system, regarding its catalytic performance, capacity to treat large effluent flows, and minimization of catalyst and hydrogen requirements. Experiments carried out in the presence of distilled water as a reaction medium demonstrate that bromate can be efficiently removed from the liquid phase, whereas when using a real water matrix, a tendency for the deactivation of the catalyst over time was more apparent throughout 200 flow passages over the catalytic bed, which was mostly attributed to the competitive adsorption of inorganic matter on the catalyst active centers, or the formation of mineral deposits blocking access to the catalyst. Full article

The efficiency of two wet chemical processes based on hydroiodic acid (HI) and sodium borohydride (NaBH₄) used to reduce graphene oxide (GO) have been studied. At this aim, the oxygen abundance of reduced graphene oxide (rGO) was studied as a function of the reductant concentration. A number of rGO samples were produced and their chemical compositions were studied using X-ray photoelectron spectroscopy. The analyses show that the reduction of the oxygen concentration proceeds non-linearly. At the beginning, when pristine GO is utilized a higher extent of reduction is obtained. The oxygen concentration decreases from ~32% to 10.5% by increasing the HI concentration to 0.24 M. A steeper reduction was observed for NaBH₄, where the oxygen concentration lowers to ~13.6% using just 50 mg of NaBH₄. Next, reduction reactions performed with increasing amounts of reductants in aqueous suspensions show a progressive saturation effect, indicating a limit in the final oxygen concentration. We obtained a residual oxygen concentration of 5.3% using 7.58 M of HI and 8.6% with 1200 mg of NaBH_4. The chemical analysis highlights that the reduction of the oxygen concentration in rGO samples is mainly derived from the cleavage of C-OH bonds and the next reconstruction of C-C bonds. Full article

The specific branches of industry utilize needle coke, a carbon form with a highly anisotropic structure. Searching for novel raw materials for its production is now rigorously studied. In the present work, we use low-sulfur gasoil for this purpose, namely its high-boiling fractions. We study their chemical and physicochemical parameters with the set of physicochemical and spectral methods. The data of FT-IR and UV-Vis spectroscopies with a phenomenological method (that allows assessing average electronic structure parameters) indicate that the gas oil of the West Siberian origin contains polycyclic aromatic hydrocarbons (PAHs) with 3–5 condensed benzene rings. The maximum amount of PAHs with molecular masses of 400–600 a.u. is contained in the fractions with boiling points higher than 450 °C. According to the data of polarized-light optical microscopy, the higher boiling point of the gasoil fraction the higher anisotropy of the produced coke. This occurs as a result of an increase in the amount of PAHs capable of condensation with the formation of a mesophase. Thus, low-sulfur gas oils from thermally processed West Siberian oil are promising raw materials for the production of needle coke in delayed coking processes. Full article

The present human population is more than three times what it was in 1950. With that, there is an increasing demand for the consumption of fossil fuels for various anthropogenic activities. This consumption is the major source of carbon dioxide emission causing greenhouse effects leading to global warming. The dependency on fossil fuels around the globe is such that it would be hard to move away from it any time soon. Hence, we must work on strategies to improve carbon dioxide fixation as we are making advancements in clean energy technology. This review explores the natural carbon dioxide fixation pathways in plants and various microorganisms and discusses their limitations and alternative strategies. It explains what necessitates the exploration of synthetic pathways and discusses strategies and matrices to consider while evaluating various pathways. This review also discusses the recent breakthroughs in the field of nanosciences that could accelerate chemical methods of carbon dioxide fixation. Full article