C — Journal of Carbon Research — Open Access Journal

The substitution of petroleum-based polymers with naturally derived biopolymers may be a good alternative for the conservation of natural fossil resources and the alleviation of pollution and waste disposal problems. However, in order to be used in a wide range of applications, some biopolymers’ properties should be enhanced. In this study, biocompatible, non-toxic, and biodegradable chitosan (CS) film and CS reinforced with 10 wt% of cellulose nanocrystals (CN–CS) were coated with amorphous hydrogenated carbon layers (a–C:H) of different thickness. To investigate the effect of the nano-reinforcement on the a–C:H layer applied, mild radio frequency plasma enhanced chemical vapor deposition (RF-PECVD) was used to coat the CS and its CN–CS bio-nanocomposite film. Both the surface characteristics and the chemical composition were analyzed. The surface morphology and wettability were examined by ex-situ atomic force microscopy (AFM) and contact angle measurements (CA), respectively. Hereby, the relationship between sp²/sp³ ratios on a macroscopic scale was also evaluated. For the investigation of the chemical composition, the surface sensitive synchrotron X-ray radiation techniques near edge X-ray absorption fine structure (NEXAFS) and X-ray photoelectron spectroscopy (XPS) as well as diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) were used. Full article

Amorphous carbons are disordered carbons with densities of circa 1.9–3.1 g/cc and a mixture of $s{p}^2$ and $s{p}^3$ hybridization. Using molecular dynamics simulations, we simulate diffusion in amorphous carbons at different densities and temperatures to investigate the transition between amorphous carbon and the liquid state. Arrhenius plots of the self-diffusion coefficient clearly demonstrate that there is a glass transition rather than a melting point. We consider five common carbon potentials (Tersoff, REBO-II, AIREBO, ReaxFF and EDIP) and all exhibit a glass transition. Although the glass-transition temperature ($T_g$) is not significantly affected by density, the choice of potential can vary $T_g$ by up to 40%. Our results suggest that amorphous carbon should be interpreted as a glass rather than a solid. Full article

High anisotropy and the existence of two-dimensional highly conducting interfaces at stacking faults parallel to the graphene planes of the graphite structure influence, in a non-simple way, the transport properties of highly oriented graphite. We report two related effects on the electrical resistance of highly oriented pyrolytic as well as of natural graphite bulk samples, measured with the four points method in the temperature range 300 K $\le T\le$ 410 K. A qualitative and quantitative change in the temperature dependence of the resistance was obtained by simply enlarging the electrodes and contacting the edges of the internal interfaces on the same sample. Additionally, at temperatures $T\gtrsim 350$ K the resistance can change with time. We show that this temperature-dependent annealing effect is related to the stacking faults and can irreversibly change the absolute value of the resistance and its temperature dependence. A partial recovery is obtained after leaving the sample at normal conditions for several days. The overall results stress the importance of the electrodes location on a bulk graphite sample, the contribution of the stacking faults in the interpretation of the measured transport properties and the need of systematic studies on the influence of high temperature annealing on the interfaces properties. Full article

Low-cost carbon-conductive films were screen-printed on a Plexiglas^® substrate, and then, after a standard annealing procedure, subjected to femtosecond (fs) laser treatments at different values of total accumulated laser fluence Φ_A. Four-point probe measurements showed that, if Φ_A > 0.3 kJ/cm², the sheet resistance of laser-treated films can be reduced down to about 15 Ω/sq, which is a value more than 20% lower than that measured on as-annealed untreated films. Furthermore, as pointed out by a comprehensive Raman spectroscopy analysis, it was found that sheet resistance decreases linearly with Φ_A, due to a progressively higher degree of crystallinity and stacking order of the graphitic phase. Results therefore highlight that fs-laser treatment can be profitably used as an additional process for improving the performance of printable carbon electrodes, which have been recently proposed as a valid alternative to metal electrodes for stable and up-scalable perovskite solar cells. Full article

Development of a practicable artificial photosynthesis process has been considered today as one of the top-most research priorities to address the problems related to the global warming and the associated social cost of carbon, and to develop the renewable fuels employable in place of fossil fuels. For this purpose, a simple and inexpensive route has been devised to synthesize a high-purity bmim[BF₄] to employ as a helper catalyst to promote the electrochemical CO₂ reduction (ECR) to CO formation over Sn and MoSi₂ cathodes. The rates of CO₂ reduction over Sn and MoSi₂ cathodes have been determined to be >110 mA/cm² during cyclic voltammetry. The CO formation at a current density of >100 mA/cm² in the ECR reaction is very essential to consider this reaction for industrial practice when the required electricity derived from sunlight is available at an affordable price. The bmim[BF₄] mediated ECR reaction over Sn and MoSi₂ cathodes has been identified to be a revere reaction of CO oxidation in air. The experiments with isotopic ¹³CO₂ confirmed that CO₂ is the only source of CO formation in the ECR reaction. The underlying reaction mechanism in bmim[BF₄] mediated ECR reaction over Sn has been presented and discussed in this article. Full article

Carbon materials have proven to be a suitable choice for hydrogen storage and, recently, for hydrogen compression. Their developed textural properties, such as large surface area and high microporosity, are essential features for hydrogen adsorption. In this work, we first review recent advances in the physisorption characterization of nanoporous carbon materials. Among them, approaches based on the density functional theory are considered now standard methods for obtaining a reliable assessment of the pore size distribution (PSD) over the whole range from narrow micropores to mesopores. Both a high surface area and ultramicropores (pore width < 0.7 nm) are needed to achieve significant hydrogen adsorption at pressures below 1 MPa and 77 K. However, due to the wide PSD typical of activated carbons, it follows from an extensive literature review that pressures above 3 MP are needed to reach maximum excess uptakes in the range of ca. 7 wt.%. Finally, we present the adsorption–desorption compression technology, allowing hydrogen to be compressed at 70 MPa by cooling/heating cycles between 77 and 298 K, and being an alternative to mechanical compressors. The cyclic, thermally driven hydrogen compression might open a new scenario within the vast field of hydrogen applications. Full article

Polymerization of furfuryl alcohol carried out using ZnCl₂ or CuCl₂ as Lewis acid activators was investigated by exploring various synthesis parameters in order to produce activated carbons with different porosity and metal load. The temperature of polymerization was changed according to Lewis acidity strength of the two metal chlorides: 0 °C for CuCl₂ and 80 °C for ZnCl₂. The polymer obtained was pyrolyzed under pure He flow or under 1000 ppm O₂/He flow at 600 or 850 °C in order to produce activated carbons with specific textural features. The load and nature of the residual metal after pyrolysis were determined by ICP and XRD analyses, respectively. Copper was mostly preserved even at high pyrolysis temperature in contrast to zinc, which was almost totally lost at 850 °C. A foamy structure was detected by SEM analysis for all samples. Textural properties were determined by both N₂ and CO₂ physisorption; surface areas and pore size distributions were evaluated according to BET, DFT and DR models. The polymerization activated by ZnCl₂ produced carbons with larger surface areas were also related to the presence of some mesopores, whereas CuCl₂ promoted the prevailing formation of narrow micropores, making these materials particularly suited to H₂ storage applications. Full article

This study presents for the first time the synthesis and characterization of GO (graphene oxide), PFSiC (polyferric silicate chloride), and hybrid GO-PFSiC derivatives, aiming to enhance synergistically the performance of coagulation, when applied for the treatment of water. The structure and the morphology of composite GO-PFSiC coagulants were studied in detail by the application of FTIR, XRD, and SEM characterization techniques. Furthermore, the proposed coagulants were applied for the treatment of simulated turbid surface water. The effects of the reagent’s dosage, pH value, and experimental/operational conditions on the coagulation efficiency, applied mainly for the removal of turbidity, were examined. The results, obtained from the FTIR and XRD measurements, showed the presence of a bond between the PFSiC and the GO surface, indicating that the PFSiC particles are distributed uniformly on the surface of graphene, which was also confirmed by the SEM images. Especially, the composite compound GO-PFSiC_1.5-15-0.5 presents the most uniform distribution of iron on the surface of graphene oxide and exhibits the optimum coagulation efficiency, while it significantly reduces the turbidity for doses above 3–5 mg/L, i.e., achieving the respective legislation limit as proposed by WHO. Specifically, at the alkaline pH values (>7.9), the removal of turbidity reaches 96%. Consequently, the results of this study render these materials as potential coagulant agents for further research and applications, aiming to also achieve the co-removal of other water components. Full article

Anaerobic digestion is an established technological option for the treatment of agricultural residues and livestock wastes beneficially producing renewable energy and digestate as biofertilizer. This technology also has significant potential for becoming an essential component of biorefineries for valorizing lignocellulosic biomass due to its great versatility in assimilating a wide spectrum of carbonaceous materials. The integration of anaerobic digestion and pyrolysis of its digestates for enhanced waste treatment was studied. A theoretical analysis was performed for three scenarios based on the thermal needs of the process: The treatment of swine manure (scenario 1), co-digestion with crop wastes (scenario 2), and addition of residual glycerine (scenario 3). The selected plant design basis was to produce biochar and electricity via combined heat and power units. For electricity production, the best performing scenario was scenario 3 (producing three times more electricity than scenario 1), with scenario 2 resulting in the highest production of biochar (double the biochar production and 1.7 times more electricity than scenario 1), but being highly penalized by the great thermal demand associated with digestate dewatering. Sensitivity analysis was performed using a central composite design, predominantly to evaluate the bio-oil yield and its high heating value, as well as digestate dewatering. Results demonstrated the effect of these parameters on electricity production and on the global thermal demand of the plant. The main significant factor was the solid content attained in the dewatering process, which excessively penalized the global process for values lower than 25% TS. Full article

New methods in lowering energy consumption costs for evaporation and concentration are needed in many commercial chemical processes. Pervaporation is an underutilized, low-energy processing method that has a potential capability in achieving lower energy processing costs. A recently developed new electrochemical process that can generate a 5–25 wt% pure formic acid (FA) from the electrochemical reduction of CO₂ requires a low-energy process for producing a more concentrated FA product for use in both on-site and commercial plant applications. In order to accomplish this, a 25 cm² membrane area pervaporation test cell was constructed to evaluate the FA-H₂O system separation performance of three distinct types of membrane candidates at various FA feed concentrations and temperatures. The selection included one cation ion exchange, two anion ion exchange, and two microporous hydrophobic membranes. The permeation flux rates of FA and H₂O were measured for FA feed concentrations of 10, 20, 40, and 60 wt% at corresponding temperatures of 22, 40, and 60 °C. The separation performance results for these particular membranes appeared to follow the vapor liquid equilibrium (VLE) characteristics of the vapor phase in the FA-H₂O system as a function of temperature. A Targray microporous hydrophobic high-density polyethylene (HDPE) membrane and a Chemours Nafion^® N324 membrane showed the best permeation selectivities and mass flux rates FA feed concentrations, ranging from 10 to 40 wt%. The cation and anion ion exchange membranes evaluated were found not to show any significant enhancements in blocking or promoting the transport of the formate ion or FA through the membranes. An extended permeation cell run concentrated a 10.12% FA solution to 25.38% FA at 40 °C. Azeotropic distillation simulations for the FA-H₂O system using ChemCad 6.0 were used to determine the energy requirement using steam costs in processing FA feed concentrations ranging from 5 to 30 wt%. These experimental results indicate that pervaporation is a potentially useful unit process step with the new electrochemical process in producing higher concentration FA product solutions economically and at lower capital costs. One major application identified is in on-site production of FA for bioreactors employing new types of microbes that can assimilate FA in producing various chemicals and bio-products. Full article

The role of the oxidation state of carbon on the early stages of growth of metal oxides was studied for the particular case of ZnO deposition on graphene and graphene oxide on SiO₂ (G/SiO₂ and GO/SiO₂, respectively) substrates. The growth was carried out by thermal evaporation of metallic Zn under an oxygen atmosphere at room temperature. This technique permits quasi-equilibrium conditions during the oxide growth, allowing the characterization of the fundamental interaction between ZnO and the graphene-based substrates. Although in both cases ZnO follows a Volmer–Weber growth mode controlled by nucleation at defects, the details are different. In the case of the GO/SiO₂ substrate, the nucleation process acts as a bottleneck, limiting the coverage of the complete surface and allowing the growth of very large ZnO structures in comparison to G/SiO₂. Moreover, by studying the Zn-LMM Auger spectra, it is shown how the initial nature of the substrate influences the composition of the ZnO deposit during the very early stages of growth in terms of Zn/O atomic ratio. These results are compared to those previously reported regarding ZnO growth on graphite and graphene on Cu (G/Cu). This comparison allows us to understand the role of different characteristics of graphene-based substrates in terms of number of defects, oxidation state, graphene support substrate and number of graphene layers. Full article

A new flower-like hybrid structure consisting of nitrogen-doped 3-dimensional (3D) graphene and vertically aligned graphene has been synthesized using a combination of low-pressure chemical vapor deposition (LPCVD) and plasma-enhanced chemical vapor deposition (PECVD) techniques. Active nitrogen (N) species were found to be essential for the growth of the flower-like morphology. N-doping was responsible for enhanced electrical conductivity and wettability of the obtained nano-carbon hybrid structure. Based on the conducted studies a growth mechanism has been proposed. The high specific surface area, low resistance to charge transfer and enhanced specific capacitance of this nitrogen-doped hybrid structure, makes it an excellent candidate material for supercapacitors. Full article

This paper argues that electrification and gasification go hand in hand and are crucial on our pathway to a carbon-neutral energy transition. Hydrogen made from renewable electricity will be crucial on this path but is not sufficient, mainly due to its challenges related to its transport and storage. Thus, other ‘molecules’ will be needed on the pathway to a carbon-neutral energy transition. What at first sight seems a contradiction, this paper argues that carbon (C) will be an important and required chemical element in many of these molecules to achieve our carbon neutrality goal. Therefore, on top of the “Hydrogen Economy” we should work also towards a “Synthetic Hydrocarbon Economy”, implying the needs for lots of carbon as a carrier for hydrogen and embedded in products as a form of sequestration. It is crucial that this carbon is taken from the biosphere or recycled from biomass/biogas and not from fossil resources. Due to efficiency losses in capturing and converting atmospheric CO₂, the production of renewable molecules will increase the overall demand for renewable energy drastically. Full article

Nano-confined chemical reactions bear great promise for a wide range of important applications in the near-to-medium term, e.g., within the emerging area of chemical storage of renewable energy. To explore this important trend, in the present work, resorcinol-/formaldehyde-based carbon aerogels were prepared by sol-gel polymerisation of resorcinol, with furfural catalysed by a sodium-carbonate solution using ambient-pressure drying. These aerogels were further carbonised in nitrogen to obtain their corresponding carbon aerogels. Through this study, the synthesis parameters were selected in a way to obtain minimum shrinkage during the drying step. The microstructure of the product was observed using Scanning Electron Microscopy (SEM) and Field Emission Scanning Electron Microscopy (FESEM) imaging techniques. The optimised carbon aerogels were found to have pore sizes of ~21 nm with a specific accessible surface area equal to 854.0 m²/g. Physical activation of the carbon aerogel with CO₂ generates activated carbon aerogels with a surface area of 1756 m²/g and a total porosity volume up to 3.23 cm³/g. The product was then used as a scaffold for magnesium/cobalt-hydride formation. At first, cobalt nanoparticles were formed inside the scaffold, by reducing the confined cobalt oxide, then MgH₂ was synthesised as the second required component in the scaffold, by infiltrating the solution of dibutyl magnesium (MgBu₂) precursor, followed by a hydrogenation reaction. Further hydrogenation at higher temperature leads to the formation of Mg₂CoH₅. In situ synchrotron X-ray diffraction was employed to study the mechanism of hydride formation during the heating process. Full article

We investigate the possibilities to realize light extraction from single crystal diamond (SCD) nanopillars. This was achieved by dedicated 519 nm laser-induced spin-state initiation of negatively charged nitrogen vacancies (NV⁻). We focus on the naturally-generated by chemical vapor deposition (CVD) growth of NV⁻. Applied diamond was neither implanted with ¹⁴N⁺, nor was the CVD synthesized SCD annealed. To investigate the possibility of light extraction by the utilization of NV⁻’s bright photoluminescence at room temperature and ambient conditions with the waveguiding effect, we have performed a top-down nanofabrication of SCD by electron beam lithography (EBL) and dry inductively-coupled plasma/reactive ion etching (ICP-RIE) to generate light focusing nanopillars. In addition, we have fluorinated the diamond’s surface by dedicated 0 V SF₆ ICP plasma. Light extraction and spin manipulations were performed with photoluminescence (PL) spectroscopy and optically detected magnetic resonance (ODMR) at room temperature. We have observed a remarkable effect based on the selective 0 V SF₆ plasma etching and surprisingly, in contrast to literature findings, deactivation of NV⁻ centers. We discuss the possible deactivation mechanism in detail. Full article

This paper is devoted to the in silico study of the electronic properties and electrical conductivity of hydrogenated graphene nanomesh (GNM). It is found that the conductivity of GNM can be controlled by varying the type of hydrogenation. Due to the hydrogenation of the nanohole edges by one or two hydrogen atoms, the energy gap can be changed, the anisotropy of the electrical conductivity can be enhanced, and the electron work function can be controlled. By varying the type of hydrogenation, it is possible to form conductive and insulating paths on 2D GNM. Thus, a certain combination of the sp²- and sp³-topologies of the GNM edge atoms allows one to fully “turn off” the electronic conductivity in all directions or, conversely, “turn on” the desired direction for current transfer. Full article

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