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C, Volume 6, Issue 2 (June 2020) – 27 articles

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Open AccessArticle
Biochar and Energy Production: Valorizing Swine Manure through Coupling Co-Digestion and Pyrolysis
C 2020, 6(2), 43; https://doi.org/10.3390/c6020043 - 24 Jun 2020
Viewed by 205
Abstract
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 [...] Read more.
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
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Open AccessArticle
Investigating Pervaporation as a Process Method for Concentrating Formic Acid Produced from Carbon Dioxide
C 2020, 6(2), 42; https://doi.org/10.3390/c6020042 - 20 Jun 2020
Viewed by 265
Abstract
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 [...] Read more.
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
(This article belongs to the Special Issue Ionic liquids for CO2 Capture and Reduction)
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Open AccessArticle
A Comparative Study of the ZnO Growth on Graphene and Graphene Oxide: The Role of the Initial Oxidation State of Carbon
C 2020, 6(2), 41; https://doi.org/10.3390/c6020041 - 20 Jun 2020
Viewed by 238
Abstract
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 [...] Read more.
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
(This article belongs to the Special Issue Surface Modification of Carbons)
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Open AccessArticle
Nitrogen-Doped Flower-Like Hybrid Structure Based on Three-Dimensional Graphene
C 2020, 6(2), 40; https://doi.org/10.3390/c6020040 - 19 Jun 2020
Viewed by 189
Abstract
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 [...] Read more.
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 article belongs to the Special Issue Characterization and Standardization of Graphene Materials)
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Open AccessArticle
Why the Carbon-Neutral Energy Transition Will Imply the Use of Lots of Carbon
C 2020, 6(2), 39; https://doi.org/10.3390/c6020039 - 10 Jun 2020
Viewed by 763
Abstract
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 [...] Read more.
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
(This article belongs to the Special Issue CO2 Capture and Valorization)
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Open AccessArticle
In Situ Formation of Metal Hydrides Inside Carbon Aerogel Frameworks for Hydrogen Storage Applications
C 2020, 6(2), 38; https://doi.org/10.3390/c6020038 - 09 Jun 2020
Viewed by 307
Abstract
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 [...] Read more.
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
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Open AccessArticle
Plasma Treatments and Light Extraction from Fluorinated CVD-Grown (400) Single Crystal Diamond Nanopillars
C 2020, 6(2), 37; https://doi.org/10.3390/c6020037 - 03 Jun 2020
Viewed by 309
Abstract
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) [...] Read more.
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
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Open AccessEditorial
Optical and Electronic Properties of Carbon-Based Nanomaterials and Composites
C 2020, 6(2), 36; https://doi.org/10.3390/c6020036 - 29 May 2020
Viewed by 213
Abstract
Dear Colleagues, [...] Full article
Open AccessArticle
The Effect of Hydrogen on the Electrical Properties of the Graphene Nanomeshes
C 2020, 6(2), 35; https://doi.org/10.3390/c6020035 - 26 May 2020
Viewed by 247
Abstract
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 [...] Read more.
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
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Open AccessArticle
Electrochemical Tuning of CO2 Reactivity in Ionic Liquids Using Different Cathodes: From Oxalate to Carboxylation Products
C 2020, 6(2), 34; https://doi.org/10.3390/c6020034 - 26 May 2020
Viewed by 294
Abstract
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 [...] Read more.
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 CO2. 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 article belongs to the Special Issue Ionic liquids for CO2 Capture and Reduction)
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Open AccessReview
A Review of the Use of Immobilized Ionic Liquids in the Electrochemical Conversion of CO2
C 2020, 6(2), 33; https://doi.org/10.3390/c6020033 - 24 May 2020
Viewed by 443
Abstract
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 [...] Read more.
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
(This article belongs to the Special Issue Ionic liquids for CO2 Capture and Reduction)
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Open AccessCommunication
Porous Carbon Monoliths Made from Cellulose and Starch
C 2020, 6(2), 32; https://doi.org/10.3390/c6020032 - 19 May 2020
Cited by 1 | Viewed by 260
Abstract
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 [...] Read more.
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 article belongs to the Special Issue Porous Carbon: Synthesis, Modification and Applications)
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Open AccessArticle
Graphene Nanoplatelets-Based Ni-Zeolite Composite Catalysts for Heptane Hydrocracking
C 2020, 6(2), 31; https://doi.org/10.3390/c6020031 - 18 May 2020
Viewed by 288
Abstract
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 [...] Read more.
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
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Open AccessArticle
Detection of Redox Properties of (6,5)-Enriched Single-Walled Carbon Nanotubes Using Potassium Permanganate (KMnO4)
C 2020, 6(2), 30; https://doi.org/10.3390/c6020030 - 11 May 2020
Viewed by 286
Abstract
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 [...] Read more.
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
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Open AccessReview
Proton Exchange Membrane Electrolyzer Modeling for Power Electronics Control: A Short Review
C 2020, 6(2), 29; https://doi.org/10.3390/c6020029 - 09 May 2020
Viewed by 510
Abstract
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 [...] Read more.
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
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Open AccessCommunication
Graphene-Quantum-Dot-Mediated Semiconductor Bonding: A Route to Optoelectronic Double Heterostructures and Wavelength-Converting Interfaces
C 2020, 6(2), 28; https://doi.org/10.3390/c6020028 - 09 May 2020
Viewed by 355
Abstract
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 [...] Read more.
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
(This article belongs to the Special Issue Graphene and Carbon Quantum Dots, and Related 2D Quantum Dots)
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Open AccessArticle
Expendable Graphite as an Efficient Flame-Retardant for Novel Partial Bio-Based Rigid Polyurethane Foams
C 2020, 6(2), 27; https://doi.org/10.3390/c6020027 - 01 May 2020
Viewed by 287
Abstract
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 [...] Read more.
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
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Open AccessArticle
Power Cycling and Reliability Testing of Epoxy-Based Graphene Thermal Interface Materials
C 2020, 6(2), 26; https://doi.org/10.3390/c6020026 - 25 Apr 2020
Cited by 1 | Viewed by 453
Abstract
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 [...] Read more.
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
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Open AccessArticle
Silicon/Biogas-Derived Carbon Nanofibers Composites for Anodes of Lithium-Ion Batteries
C 2020, 6(2), 25; https://doi.org/10.3390/c6020025 - 24 Apr 2020
Viewed by 289
Abstract
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, [...] Read more.
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
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Open AccessArticle
A Structured Approach for the Mitigation of Natural Methane Emissions—Lessons Learned from Anthropogenic Emissions
C 2020, 6(2), 24; https://doi.org/10.3390/c6020024 - 22 Apr 2020
Viewed by 458
Abstract
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 [...] Read more.
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
(This article belongs to the Special Issue CO2 Capture and Valorization)
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Open AccessReview
The Combined Influence of Dopant Species and Surface Termination on the Electronic Properties of Diamond Surfaces
C 2020, 6(2), 22; https://doi.org/10.3390/c6020022 - 15 Apr 2020
Viewed by 375
Abstract
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, Oontop [...] Read more.
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, Oontop, Obridge, 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, Oontop-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
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Open AccessReview
Carbons as Catalysts in Thermo-Catalytic Hydrocarbon Decomposition: A Review
C 2020, 6(2), 23; https://doi.org/10.3390/c6020023 - 14 Apr 2020
Viewed by 345
Abstract
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 [...] Read more.
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
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Open AccessFeature PaperReview
Review on Activated Carbons by Chemical Activation with FeCl3
C 2020, 6(2), 21; https://doi.org/10.3390/c6020021 - 10 Apr 2020
Cited by 2 | Viewed by 457
Abstract
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 [...] Read more.
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
(This article belongs to the Special Issue Porous Carbon: Synthesis, Modification and Applications)
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Open AccessArticle
Adsorption of H2 on Penta-Octa-Penta Graphene: Grand Canonical Monte Carlo Study
C 2020, 6(2), 20; https://doi.org/10.3390/c6020020 - 01 Apr 2020
Viewed by 386
Abstract
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 [...] Read more.
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
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Open AccessFeature PaperArticle
Hydrogen Sorption and Reversibility of the LiBH4-KBH4 Eutectic System Confined in a CMK-3 Type Carbon via Melt Infiltration
C 2020, 6(2), 19; https://doi.org/10.3390/c6020019 - 31 Mar 2020
Viewed by 376
Abstract
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 LiBH [...] Read more.
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
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Open AccessReview
Explaining Bamboo-Like Carbon Fiber Growth Mechanism: Catalyst Shape Adjustments above Tammann Temperature
C 2020, 6(2), 18; https://doi.org/10.3390/c6020018 - 30 Mar 2020
Viewed by 334
Abstract
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 [...] Read more.
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 (TTa) 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
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Open AccessArticle
Supercapacitor Electrodes from Viscose-Based Activated Carbon Fibers: Significant Yield and Performance Improvement Using Diammonium Hydrogen Phosphate as Impregnating Agent
C 2020, 6(2), 17; https://doi.org/10.3390/c6020017 - 27 Mar 2020
Viewed by 358
Abstract
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 [...] Read more.
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
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