C — Journal of Carbon Research — Open Access Journal

There is currently quite a lot of scientific interest in carbon dioxide (CO₂) capture and valorization with ionic liquids (ILs). In this manuscript, we analyze the influence of the potential applied, the nature of the cathode and the electrolyte using different organic mediators, such as nitro or cyano aromatic derivatives, to promote the electrochemical activation of CO_2. An electrocatalytic process using a homogeneous catalysis is seen when nitroderivatives are used, yielding to oxalate in organic electrolytes and ILs. Turnover frequency (TOF) values and Farafay efficiencies were slightly higher in N,N’-dimethylformamide (DMF) than in ILs probably due to the viscosity of the electrolyte. The use of cyano derivatives allows to tune the electrochemical reactivity in function of the reduction potential value applied from electrocarboxylated products (via a nucleophile-electrophile reaction) to oxalate. These electrochemical reactions were also performed using three different cathodes, organic electrolytes and ionic liquids. The use of copper, as a cathode, and ionic liquids, as electrolytes, would be a cheaper and greener alternative for activating carbon dioxide. Full article

This paper is a review on the application of imidazolium-based ionic liquids tethered to polymer backbones in the electrochemical conversion of CO₂ to carbon monoxide and formic acid. These tethered ionic liquids have been incorporated into novel anion ion exchange membranes for CO₂ electrolysis, as well as for ionomers that have been incorporated into the cathode catalyst layer, providing a co-catalyst for the reduction reaction. In using these tethered ionic liquids in the cathode catalyst composition, the cell operating current increased by a factor of two or more. The Faradaic efficiencies also increased by 20–30%. This paper provides a review of the literature, in addition to providing some new experimental results from Dioxide Materials, in the electrochemical conversion of CO₂ to CO and formic acid. Full article

Porous carbon monoliths can be used as key components in a variety of applications, such as energy storage, adsorption and catalysis. The preparation of porous carbon monoliths suffers from several limitations, e.g., time-consuming synthesis steps, the use of hazardous chemicals, limited porosity or mechanical stability. This paper describes the investigation of a simple synthesis route to produce porous carbon monoliths from sustainable carbon precursors. Mixtures from different kinds of cellulose and starch, respectively, have been used as the carbon precursor. Fundamental features of porous monoliths, i.e., the porosity and the mechanic stability, respectively, have been investigated in dependence on the composition of the precursor mixtures. First attempts to explain the observed behavior have already been made. Full article

This paper examines the effect of incorporating graphene nanoplatelets (GNPs) in an Ni-based/Zeolite-Y catalyst on the hydrocracking of heptane fuel at two temperatures, 350 and 400 °C. Specifically, reduced GNP/NiO-ZY and NiO-ZY catalysts, each with a 5 wt. % Ni loading, were compared in this study. The results show that the reduced GNP/NiO-ZY enhanced the conversion percentage by 31% at 350 °C and by 6% at 400 °C as compared with the reduced NiO-ZY, and the GNP/NiO-ZY also showed superior stability, reporting a less than 2% drop in conversion over 20 h of time-on-stream. The enhancement in performance is linked to the surface and texture characteristics of both catalysts. Although the calcined GNP/NiO-ZY possessed a lower Brunauer–Emmett–Teller (BET) surface area of 458 m²/g compared with 536 m²/g for the calcined NiO-ZY, it showed a more hydrophobic nature, as deduced from the water adsorption profiles, which corroborates the hypothesis that the increased affinity between the catalyst surface and heptane molecules during the reaction leads to an improved catalytic activity. Full article

It has been reported that even if single-walled carbon nanotubes (SWNTs) are coated with the same polymer, the redox characteristics change of each chirality may differ. Particularly, the addition of hydrogen peroxide (H₂O₂) minimally affects the near-infrared (NIR) absorption spectra of the dsDNA-(6,5)-enriched SWNT complex (DNA-SWNT complex). Detecting the redox properties of (6,5) chirality using NIR absorption spectra has been one of the issues to be solved. We hypothesized that an oxidizing agent with high oxidizing power is required to detect the absorption spectra of (6,5) chirality. In this study, we used KMnO₄, which contains atoms with a high oxidation number. A dispersion was prepared by mixing 0.5 mg of (6,5)-enriched SWNT powder with 1 mg/mL of DNA solution. After adding H₂O₂ or KMnO₄ to this dispersion and oxidizing it, catechin solutions were added to reduce the dispersion. The absorption peak of the DNA-SWNT complex decreased by 23.9% following the addition of KMnO₄ (final concentration: 0.5 µM) and recovered 30.7% following the addition of the catechin solution. We revealed that the changes in the absorption spectra change of (6,5) chirality, which could not be detected by H₂O₂, can be detected by using KMnO₄. We also varied the concentration of KMnO₄ and verified whether the adsorption of KMnO₄ can be modeled as a Langmuir adsorption isotherm. Full article

The main purpose of this article is to provide a short review of proton exchange membrane electrolyzer (PEMEL) modeling used for power electronics control. So far, three types of PEMEL modeling have been adopted in the literature: resistive load, static load (including an equivalent resistance series-connected with a DC voltage generator representing the reversible voltage), and dynamic load (taking into consideration the dynamics both at the anode and the cathode). The modeling of the load is crucial for control purposes since it may have an impact on the performance of the system. This article aims at providing essential information and comparing the different load modeling. Full article

A semiconductor bonding technique that is mediated by graphene quantum dots is proposed and demonstrated. The mechanical stability, electrical conductivity, and optical activity in the bonded interfaces are experimentally verified. First, the bonding scheme can be used for the formation of double heterostructures with a core material of graphene quantum dots. The Si/graphene quantum dots/Si double heterostructures fabricated in this study can constitute a new basis for next-generation nanophotonic devices with high photon and carrier confinements, earth abundance, environmental friendliness, and excellent optical and electrical controllability via silicon clads. Second, the bonding mediated by the graphene quantum dots can be used as an optical-wavelength-converting semiconductor interface, as experimentally demonstrated in this study. The proposed fabrication method simultaneously realizes bond formation and interfacial function generation and, thereby, can lead to efficient device production. Our bonding scheme might improve the performance of optoelectronic devices, for example, by allowing spectral light incidence suitable for each photovoltaic material in multijunction solar cells and by delivering preferred frequencies to the optical transceiver components in photonic integrated circuits. Full article

The rigid polyurethane foam (PU) is a versatile material, used especially for construction and household applications. The current situation demands a facile, cost-efficient, and greener approach for developing the polyurethanes from bio-derived materials. In this study, we present a novel bio-polyol synthesized using carvone, an extract from caraway, spearmint, or dill seeds via facile thiol-ene reaction. Our one-step reaction uses a UV irradiation to allow the room temperature conversion of the carvone to a high purity bio-polyol, as confirmed from the standard analytical characterizations. The hydroxyl number of 365 mg KOH/g close to its theoretical limit confirms the high conversion yield of the polyol for rigid PU synthesis. To overcome the flammability issues in PU, expandable graphite (EG) powder was used as an additive flame-retardant during the synthesis step. The resulting foams with EG maintained the uniform closed cell structure (>95%) with a high compression strength of 175 kPa. The addition of EG in PU results in the formation of a protective char layer during the flammability test and reduces the weight loss from 40.70% to 3.55% and burning time from 87 to 11 s. Our results confirm that the carvone-based polyol can be a novel alternative to the petroleum polyols for an industrial-scale application. Full article

We report on the lifespan evolution of thermal diffusivity and thermal conductivity in curing epoxy-based thermal interface materials with graphene fillers. The performance and reliability of graphene composites have been investigated in up to 500 power cycling measurements. The tested composites were prepared with an epoxy resin base and randomly oriented fillers consisting of a mixture of few-layer and single-layer graphene. The power cycling treatment procedure was conducted with a custom-built setup, while the thermal characteristics were determined using the “laser flash” method. The thermal conductivity and thermal diffusivity of these composites do not degrade but instead improve with power cycling. Among all tested filled samples with different graphene loading fractions, an enhancement in the thermal conductivity values of 15% to 25% has been observed. The obtained results suggest that epoxy-based thermal interface materials with graphene fillers undergo an interesting and little-studied intrinsic performance enhancement, which can have important implications for the development of next-generation thermal interface materials. Full article

The electrochemical performance of novel nano-silicon/biogas-derived carbon nanofibers composites (nSi/BCNFs) as anodes in lithium-ion batteries was investigated, focusing on composition and galvanostatic cycling conditions. The optimization of these variables contributes to reduce the stress associated with silicon lithiation/delithiation by accommodating/controlling the volume changes, thus preventing anode degradation and therefore improving its performance regarding capacity and stability. Specific capacities up to 520 mAh g⁻¹ with coulombic efficiency > 95% and 94% of capacity retention are achieved for nSi/BCNFs anodes at electric current density of 100/200 mA g⁻¹ and low cutoff voltage of 80 mV. Among the BCNFs, those no-graphitized with fishbone microstructure, which have a great number of active sites to interact with nSi particles, are the best carbon matrices. Specifically, a nSi:BCNFs 1:1 weight ratio in the composite is the optimal, since it allows a compromise between a suitable specific capacity, which is higher than that of graphitic materials currently commercialized for LIBs, and an acceptable capacity retention along cycling. Low cutoff voltage in the 80–100 mV range is the most suitable for the cycling of nSi/BCNFs anodes because it avoids formation of the highest lithiated phase (Li₁₅Si₄) and therefore the complete silicon lithiation, which leads to electrode damage. Full article

Methane is the second most important greenhouse gas. Natural methane emissions represent 35–50% of the global emissions budget. They are identified, measured and categorized, but, in stark contrast to anthropogenic emissions, research on their mitigation is largely absent. To explain this, 18 problems are identified and presented. This includes problems related to the emission characteristics, technological and economic challenges, as well as problems resulting from a missing framework. Consequently, strategies, methods and solutions to solve or circumvent the identified problems are proposed. The framework covers definitions for methane source categorization and for categories of emission types and mitigation approaches. Business cases for methane mitigation are discussed and promising mitigation technologies briefly assessed. The importance to get started with methane mitigation in the different areas is highlighted and avenues for doing so are presented. Full article

The combined effects of geometrical structure and chemical composition on the diamond surface electronic structures have been investigated in the present study by using high-level theoretical calculations. The effects of diamond surface planes [(111) vs. (100)], surface terminations (H, F, OH, O_ontop, O_bridge, vs. NH₂), and substitutional doping (B, N vs. P), were of the largest interest to study. As a measure of different electronic structures, the bandgaps, work functions, and electron affinities have been used. In addition to the effects by the doping elements, the different diamond surface planes [(111) vs. (100)] were also observed to cause large differences in the electronic structures. With few exceptions, this was also the case for the surface termination species. For example, O_ontop-termination was found to induce surface electron conductivities for all systems in the present study (except for a non-doped (100) surface). The other types of surface terminating species induced a reduction in bandgap values. The calculated bandgap ranges for the (111) surface were 3.4–5.7 (non-doping), and 0.9–5.3 (B-doping). For the (100) surface, the ranges were 0.9–5.3 (undoping) and 3.2–4.3 (B-doping). For almost all systems in the present investigation, it was found that photo-induced electron emission cannot take place. The only exception is the non-doped NH₂-terminated diamond (111) surface, for which a direct photo-induced electron emission is possible. Full article

Thermo-catalytic decomposition is well-suited for the generation of hydrogen from natural gas. In a decarbonization process for fossil fuel—pre-combustion—solid carbon is produced, with potential commercial uses including energy storage. Metal catalysts have the disadvantages of coking and deactivation, whereas carbon materials as catalysts offer resistance to deactivation and poisoning. Many forms of carbon have been tested with varied characterization techniques providing insights into the catalyzed carbon deposition. The breadth of studies testing carbon materials motivated this review. Thermocatalytic decomposition (TCD) rates and active duration vary widely across carbons tested. Regeneration remains rarely investigated but does appear necessary in a cyclic TCD–partial oxidation sequence. Presently, studies making fundamental connections between active sites and deposit nanostructures are few. Full article

This study reviews the most relevant results on the synthesis, characterization, and applications of activated carbons obtained by novel chemical activation with FeCl₃. The text includes a description of the activation mechanism, which compromises three different stages: (1) intense de-polymerization of the carbon precursor (up to 300 °C), (2) devolatilization and formation of the inner porosity (between 300 and 700 °C), and (3) dehydrogenation of the fixed carbon structure (>700 °C). Among the different synthesis conditions, the activation temperature, and, to a lesser extent, the impregnation ratio (i.e., mass ratio of FeCl₃ to carbon precursor), are the most relevant parameters controlling the final properties of the resulting activated carbons. The characteristics of the carbons in terms of porosity, surface chemistry, and magnetic properties are analyzed in detail. These carbons showed a well-developed porous texture mainly in the micropore size range, an acidic surface with an abundance of oxygen surface groups, and a superparamagnetic character due to the presence of well-distributed iron species. These properties convert these carbons into promising candidates for different applications. They are widely analyzed as adsorbents in aqueous phase applications due to their porosity, surface acidity, and ease of separation. The presence of stable and well-distributed iron species on the carbons’ surface makes them promising catalysts for different applications. Finally, the presence of iron compounds has been shown to improve the graphitization degree and conductivity of the carbons; these are consequently being analyzed in energy storage applications. Full article

In this paper, we report the results of hydrogen adsorption properties of a new 2D carbon-based material, consisting of pentagons and octagons (Penta-Octa-Penta-graphene or POP-graphene), based on the Grand-Canonical Monte Carlo simulations. The new material exhibits a moderately higher gravimetric uptake at cryogenic temperatures (77 K), as compared to the regular graphene. We discuss the origin of the enhanced uptake of POP-graphene and offer a consistent explanation. Full article

Metal borohydrides have very high hydrogen densities but their poor thermodynamic and kinetic properties hinder their use as solid hydrogen stores. An interesting approach to improve their functionality is nano-sizing by confinement in mesoporous materials. In this respect, we used the 0.725 LiBH₄–0.275 KBH₄ eutectic mixture, and by exploiting its very low melting temperature (378 K) it was possible to successfully melt infiltrate the borohydrides in a mesoporous CMK-3 type carbon (pore diameter ~5 nm). The obtained carbon–borohydride composite appears to partially alleviate the irreversibility of the dehydrogenation reaction when compared with the bulk LiBH₄-KBH₄, and shows a constant hydrogen uptake of 2.5 wt%–3 wt% for at least five absorption–desorption cycles. Moreover, pore infiltration resulted in a drastic decrease of the decomposition temperature (more than 100 K) compared to the bulk eutectic mixture. The increased reversibility and the improved kinetics may be a combined result of several phenomena such as the catalytic action of the carbon surface, the nano-sizing of the borohydride particles or the reduction of irreversible side-reactions. Full article

The mechanism of bamboo-like growth behavior of carbon fibers is discussed. We propose that there is a requirement to have this type of growth: operation above the Tammann temperature of the catalyst (defined as half of the melting point). The metal nanoparticle shape can then change during reaction (sintering-like behavior) facilitating carbon nanotube (CNT) growth, adjusting geometry. Using metal nanoparticles with a diameter below 20 nm, some reduction of the melting point (mp) and Tammann temperature (T_Ta) is observed. Fick’s laws still apply at nano scale. In that range, distances are short and so bulk diffusion of carbon (C) atoms through metal nanoparticles is quick. Growth occurs under catalytic and hybrid carbon formation routes. Better knowledge of the mechanism is an important basis to optimize growth rates and the shape of bamboo-like C fibers. Bamboo-like growth, occurring under pyrolytic carbon formation, is excluded: the nano-catalyst surface in contact with the gas gets quickly “poisoned”, covered by graphene layers. The bamboo-like growth of boron nitride (BN) nanotubes is also briefly discussed. Full article

Viscose fibers were impregnated with different concentrations of diammonium hydrogen phosphate (DAHP), carbonized, activated, and tested as high-performance electrode materials for supercapacitors. The yield of these activated carbon fibers (ACFs) could be increased by a factor of 14 by using DAHP compared to ACF without impregnation. These specific activation procedures yielded a high specific surface area of more than 2700 m²·g⁻¹ with a pore size distribution (PSD) suitable for use as a supercapacitor electrode. The electrode materials were implemented in symmetric supercapacitors using TEMA BF₄ as electrolyte and cyclic voltammetry measurements showed high specific capacitances of up to 167 F·g⁻¹. Furthermore, the devices showed high energy densities of up to 21.4 W·h·kg⁻¹ and high-power densities of up to 8.7 kW·kg⁻¹. The supercapacitors featured high capacity retention (96%) after 10,000 cycles. These results show that ACFs made of viscose fibers, previously impregnated with DAHP, can be used as high-performance electrodes in supercapacitors for energy storage applications. Full article

On a long path of finding appropriate materials to store hydrogen, graphene and carbon nanotubes have drawn a lot of attention as potential storage materials. Their advantages lie at hand since those materials provide a large surface area (which can be used for physisorption), are cheap compared to metal hydrides, are abundant nearly everywhere, and most importantly, can increase safety to existing storage solutions. Therefore, a great variety of theoretical studies were employed to study those materials. After a benchmark study of different van-der-Waals corrections to Generalized Gradient Approximation (GGA), the present Density Functional Theory (DFT) study employs Tkatchenko–Scheffler (TS) correction to study the influence of vacancy and Stone–Wales defects in graphene on the physisorption of the hydrogen molecule. Furthermore, we investigate a large-angle (1,0) grain boundary as well as the adsorption behaviour of Penta-Octa-Penta (POP)-graphene. Full article