Metal-free N–S- and N–P-doped nanocarbon (SCNP and PCNP) electrocatalysts prepared through sustainable microwaveassisted synthesis using hemigraphis alternata plant leaves. The prepared heteroatom-doped nanocarbon materials are active catalysts for the two-electron oxygen reduction reaction (ORR) to produce 65–70% of hydrogen peroxide. As evidenced from the XPS, most proportion of the doped heteroatoms contain the oxygen functional groups in the nanocarbons. These attributes are the critical factors to see the selective two-electron transfer ORR for the PCNP and SCNP. This approach shed light on the critical role of dual heteroatoms doping and the oxygen functionalities in nanocarbon towards the selectivity of ORR. We believe that this method would allow the preparation of heteroatom that contains oxygen functionalities. Our work paves a sustainable way of preparation of nanocarbon based ORR catalysts that are only selective for two-electron transfer process.
The detailed understanding of fluorescence emission processes is still unclear. This study demonstrates Aegle marmelos derived luminescent heteroatoms (N, Ca, K) doped carbon quantum dots (CQDs) using an economically and ecologically sustainable synthesis process without the necessity for any doping precursors due to its phytochemical, vitamin and mineral content. Carboxyl functionalization was done by adding lemon juice to the fruit extract. The morphological, physiochemical, compositional, crystallinity, and surface functional groups having heteroatom doped CQDs were analysed by HRTEM, EDX, XPS, XRD, FTIR etc. Besides, CQDs exhibited pH and solvent-dependent tuneable fluorescence characteristics. In fact, beyond pH 7.77, a protonation-deprotonation-driven red-shift was observed together with a decrease in the contribution of prominent peaks. Meanwhile, the features of solvatochromic fluorescence were examined in a range of aprotic and protic solvents with low and high polarity. Based on the studied Kamlet–Taft parameters and the obtained spectroscopic characterizations, a suitable fluorescence emission mechanism is provided. The observed solvatochromic fluorescence is thought to be caused by a combination of dipole moment polarisation, intramolecular charge transfer processes with or without H-bond stabilisation via the interaction of heteroatoms doped CQDs with solvent mediated by electron donation and acceptance from various surface functional groups such as hydroxyl, carboxyl with solvent molecules. Hence, this study is believed to promote the development of eco-tuneable fluorescent heteroatom doped CQDs and provide further insights into the fundamental fluorescence mechanisms, which include the relationship between morphology, surface properties and plausible quantum effects between CQDs and solvents.
The surface of carbon films deposited with inverted plasma fireballs is analysed in this paper. Measurements were conducted with Raman spectroscopy, atomic force microscopy and nanoindentation. The latter was used to obtain Young’s modulus as well as Martens and Vickers hardness. The roughness of the film was measured by atomic force microscopy and its thickness was measured. It was shown with Raman spectroscopy that the films are homogeneous in terms of atomic composition and layer thickness over an area of about 125 × 125 mm. Furthermore, it was demonstrated that inverted plasma fireballs are a viable tool for obtaining homogeneous, large area carbon films with rapid growth and very little energy consumption. The obtained films show very low roughness.
Lead sulfide ( PbS ) nanocrystals anchored on nitrogen-doped multiwalled carbon nanotubes ( CNx ) have been synthesized employing an environmentally friendly and inexpensive wet chemistry process. CNx∕PbS composites have been examined by scanning electron microscopy, X-ray diffraction and Raman spectroscopy. Theorical ab initio calculations have been developed to determine the samples structural, morphological and optical properties to explain the experimental evidences. The PbS nanoparticles exhibit of 4 nm to 27 nm particle size with a face-centered cubic crystal structure and are homogeneously distributed along the carbon nanotubes. The nitrogen-doped CNTs acts as binding sites for the PbS clusters as ab initio theoretical study suggests.
The biocarbon (SKPH) was obtained from Sargassum spp., and it was evaluated electrochemically as support for the CO2 reduction. The biocarbon was synthesized and activated with KOH, obtaining a high surface area (1600 m2 g− 1) due to the activation process. Graphitic carbon formation after pyrolysis was confirmed by Raman spectroscopy. The XRD results show that SKPH has an amorphous structure with peaks corresponding to typical amorphous carbonaceous materials. FTIR was used to determine the chemical structure of SKPH. The bands at 3426, 2981, 2851, and 1604 cm− 1 correspond to O–H, C-H, and C-O stretching vibrations, respectively. Then, it compares SKPH films with different carbon films using two electrolytic systems with and without charge transfer. The SKPH film showed a capacitive behavior in the KOH, H2SO4, and, KCl systems; in the acid medium, the presence of a redox couple associated with carbon functional groups was shown. Likewise, in the [Fe(CN)6]−3 and Cu(II) systems, the charge transfer process coupled with a capacitive behavior was described, and this effect is more noticeable in the [Fe(CN)6]−3 system. Electrodeposition of copper on SKPH film showed two stages Cu(NH 3)2+ 4 /Cu(NH 3)+ 2 and Cu(NH 3)+ 2 ∕Cu in ammonia media. Hydrogen formation and the activity of CO2 are observed on SKPH film and are favored by the carbon’s surface chemistry. Cu/SKPH electrocatalyst has a catalytic effect on electrochemical reduction of CO2 and inhibition of hydrogen formation. This study showed that the SKPH film electrode responds as a capacitive material that can be used as an electrode for energy storage or as metal support.
We report the behaviour of carbon black (CB) nanoparticles (spherical carbon shells), subjected to external pressure, using diamond anvil cell at synchrotron facility. CB nanoparticles have been synthesized by lamp black method using olive oil as combustion precursor and ferrocene as an organometallic additive. The catalyst-assisted CB has an iron oxide (γ-Fe2O3) core and amorphous carbon shell (i.e. core–shell structure). Our present study suggests that the carbon shells are partially transparent to the applied high pressure, and result in the reduction of effective pressure that gets transferred to the iron oxide core. High-pressure Raman spectroscopy results indicate that the surrounding carbon shells get compressed with pressure and this change is reversible. However, no structural transformation was observed till the highest applied pressure (25 GPa). The Raman spectroscopy results also suggests that the carbon shells are less pressure sensitive as their pressure coefficients (dω/dP) of G-peak were calculated (3.79 cm− 1/GPa) to be less than that for other carbon allotropes.
Individual multi-walled carbon nanotubes (MWCNTs) were exposed to the electron beam of 200 kV energy and high resolution transmission electron micrographs were recorded at several time intervals. Interestingly, the nucleation of diamond nanoparticles with in the highly disordered MWCNT matrix upon electron-irradiation is observed. This happens without any assistance of high pressures and temperatures. High pressure X-ray diffraction experiments were performed on core/shell structures which suggest that even the closed structures of carbon resist any inward pressure, thereby ruling out the possibility of a hypothetical internal pressure under the electron irradiation conditions. Our experiments suggest that the transformation of graphitic carbon into diamond in the size window of a few nanometers is possible due to the stability of the diamond and a selective dissolution effect of 200 kV electrons on graphite. A mechanism for the same is proposed.
The bituminous coal was extracted with different industrial solvents like coal tar (CT), heavy cycle oil (HCO) and with their blends to determine the influence of solvent type on the extract yield, composition, thermal behavior, properties such as solubility to toluene and quinoline. The extracts obtained at 380 °C represented pitch-like solid matter with the softening points of 72–127 °C depending on the solvent used. They were characterized using the elemental and group analysis, FTIR spectroscopy, TG-DTG thermogravimetry and liquid chromatography for benzo(a)pyrene concentration. Also, maltene fractions of some extracts were studied by GC–MS. The results showed coal dissolution and the properties of the extracts to differ greatly depending on the solvent used. Coal tar was more favorable solvent for coal dissolution than HCO. Good correlation between the extract aromaticity and the content of the toluene insolubles was observed. The maltene fractions of the extracts obtained with CT and CT blended with HCO consisted mainly of polycyclic aromatics, and that obtained with the HCO contained also large amount of aliphatic compounds. It was found that the amount of the carcinogenic benzo(a) pyrene (BaP) in the toluene soluble fractions of the extracts were different depending on the solvents used for extraction. The remarkable result was that the BaP concentrations in all extracts were much lower than in the solvents used.
By polymerizing acrylonitrile in the presence of ammonium persulfate as an initiator and Pterocladia capillacea-activated carbon (P-AC) as a filler, a composite material polyacrylonitrile/Pterocladia capillacea-activated carbon (PAN/P- AC) was developed. By reacting hydroxylamine with the composite's nitrile groups, the prepared composite was functionalized by amidoximation. FTIR spectrometry, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and Brunauer–Emmett–Teller (BET) analysis were all applied to thoroughly characterize the fabricated adsorbent. For the treatment of Cr(VI) ions from synthetic solutions, the adsorption properties of amidoximated polyacrylonitrile/Pterocladia capillacea-activated carbon (PAO/P-AC) were investigated. The pH effect, uptake kinetics, adsorption isotherms, and thermodynamics studies were used to characterize adsorption properties. As a kinetic model analysis, the data confirmed that the pseudo-second-order rate equation matched well the adsorption process. With coefficients of determination (R2) of 0.9998, the Tempkin isotherm model had the lowest error, suggesting that it is the best fitted model to describe this adsorption mechanism. Thermodynamic parameters demonstrated that Cr(VI) adsorption was endothermic.
The production of macroalgae-derived adsorbent is of great importance to realize the idea of treating pollutants with invaluable renewable materials. Herein, a novel meso-micro porous nano-activated carbon was prepared from green alga Ulava lactuca in a facile way via chemical activation with zinc chloride. The resultant activated carbon possesses a significant specific surface area 1486.3 m2/ g. The resulting activated carbon was characterized and investigated for the adsorption of Direct Red 23 (DR23) dye from an aqueous environment. Batch method was conducted to study the effects of different adsorption processes on the DR23 dye adsorption from water. Isotherms and kinetics models were investigated for the adsorption process of DR23 dye. It was found that the adsorption data were well fitted by Langmuir model showing a monolayer adsorption capacity 149.26 mg/g. Kinetic experiments revealed that the adsorptions of DR23 dye can be described with pseudo-secondorder model showing a good correlation (R2 > 0.997). The prepared activated carbon from Ulava lactuca was exposed to a total of six regeneration experiments. The regeneration result proved that the fabricated activated carbon only loses 19% of its adsorption capacity after six cycles. These results clearly demonstrated the high ability of the obtained active carbon to absorb anionic dyes from the aqueous environment.
The use of recycled materials, such as the fine recycled aggregate made from concrete waste and carbon fiber (CF) product of industrial waste, for the manufacture of conductive recycled mortars (CRM), transforms the mortar base cement normally made with cement:sand in a sustainable multifunctional material, conferring satisfactory mechanical and electrical properties for non-structural uses. This action provides ecological benefits, reducing the use of natural fine aggregates from rivers and the amount of concrete waste deposited in landfills resulting from construction waste. In this investigation the effect of the addition of CF on electrical properties in hardened, wet and dry state, electric percolation in dry state and fluidity of the wet mixture of a cement based CRM was evaluated: fine recycled aggregate: graphite powder, CRM specimens with dimensions of 4 × 4 × 16 cm. were manufactured for 3, 7 and 28 days of age and sand/cement ratios = 1.00, graphite/cement = 1.00, water/cement = 0.60 and CF = 0.1, 0.3, 0.5, 1.0, 1.5, 2.0, 2.5 and 3.0% compared to the weight of cement. The results demonstrated the effect of the addition of CF in CRM, reducing fluidity of the mixtures due to the opposition generated by its physical interaction of CF with recycled sand or recycled fine aggregate and graphite powder (GP), in its case, placing the electric percolation percolation at 0.30% and 0.45% of CF for CRM with and without GP, respectively. Increases in electrical conductivity (EC) without the presence of GP are defined by the contact between the CF and the conductive paths formed. In contrast, with the presence of GP, the EC is defined by the contact between the CF and the GP simultaneously, forming conductive routes with greater performance in its EC.
One- and two-dimensional carbon nanomaterials were tested as adsorbents for the elimination of two anionic dyes, reactive red 2 and methyl orange, and the cationic dye methylene blue from aqueous solutions under the same conditions. Carbon nanomaterials performed well in the removal of dyes. Surface oxygenated groups in the nanomaterials improved the cationic dyes’ adsorption, but not the adsorption of the anionic dye. The interactions between nanomaterials and dyes were verified by infrared and Raman spectroscopy. The pseudo-second order kinetic model was better fitted to the kinetic experimental data than the Elovich and pseudo-first order models. The equilibrium adsorption data were best fitted by the Langmuir model. The dimensions and morphology of the carbon nanomaterials play an important role in the adsorption of the three dyes. The main mechanism of adsorption of anionic dyes is by the interactions of the aromatic rings of the dye structures and π delocalized electrons on carbon nanostructures; the adsorption of cationic dye is mainly due to electrostatic interactions.
We present the analysis of KMT-2016-BLG-0212, a low flux-variation (Iflux−var ∼ 20 mag) microlensing event, which is in a high-cadence (Γ = 4hr −1) field of the three-telescope Korea Microlensing Telescope Network (KMTNet) survey. The event shows a short anomaly that is incompletely covered due to the brief visibility intervals that characterize the early microlensing season when the anomaly occurred. We show that the data are consistent with two classes of solutions, characterized respectively by low-mass brown-dwarf (q = 0.037) and sub-Neptune (q < 10−4) companions. Future high-resolution imaging should easily distinguish between these solutions.