Carbon Research Articles

Secondary transformations in the structure of grey cast iron

A nanostructural mechanism of secondary transformations in the structure of gray cast iron is proposed. First, structureforming nanocrystals of austenite, ferrite, cementite and graphite are formed from elementary nanocrystals of iron and graphite, free atoms of iron and carbon. The crystallization centers of microcrystals of phases are formed from them. From these centers, structure‑forming nanocrystals of phases, free iron and carbon atoms, microcrystals of austenite, ferrite, cementite and graphite of binary gray cast irons are formed.

Effects of Different Shade Treatments on the Epidermal Wax Deposition of Hosta Genotypes with Different Glaucousness of Leaf Surface

Epidermal wax is strategically situated at the interface between plants and air; therefore, it plays a key role in plants’ interactions with their surroundings. It is also unstable and susceptible to light intensity. Hosta plants are shade-loving herbs with admirable flowers and leaves. Hosta ‘Halcyon’ and Hosta ensata F. Maek. are two species of Hosta with a glaucous and a glossy appearance, respectively. Light intensity can affect the composition of epicuticular wax on the leaf surface, which influences the leaf color phenotype and ornamental value. In this paper, the crystal micromorphology, content, and components of epicuticular wax on the leaves of two species of Hosta under different light conditions (10%-, 30%-, 50%-, 70%-, and 100%-intensity sunlight, relative light intensity (RLI)) have been studied using pot experiments. The results indicate that the epicuticular wax crystals of H. ‘Halcyon’ and H. ensata are tubular and platelet-like, respectively. The wax crystals of H. ‘Halcyon’ melted and formed a thick crust under 100% RLI, and those of H. ensata melted and formed a thick crust under 70% and 100% RLI conditions. The primary ingredients of the epicuticular wax of the two species of Hosta contained primary alcohols, alkanes, fatty acids, and esters; β-diketones were only detected in H. ‘Halcyon’. The quantity of epicuticular wax of H. ‘Halcyon’ reduced at first and then increased with an RLI increase, achieving its lowest value at 50% RLI, but that of H. ensata declined little by little. The amounts of C28 primary alcohols, C31 alkanes, and C18 fatty acids were significantly higher than those of other carbon atoms in the two genotypes of Hosta. The C31β-diketones content decreased with the increase in light intensity, which caused the white frost phenotype to gradually weaken in H. ‘Halcyon’.

Fluidized-bed OCM reaction: A promising Mn2O3-Na2WO4/TiO2 catalyst and a numerical study

The fluidized-bed reactor with excellent heat and mass transfer features has great appeal for application in the oxidative coupling of methane (FB-OCM), whereas qualified fluid catalysts represent a grand challenge. Herein, we report a high-performance Mn2O3-Na2WO4/TiO2 fluid catalyst (5.4 wt% Mn2O3 and 2 wt% Na2WO4), which was obtained by the incipient-wetness impregnation method and examined in the OCM reaction in an electric-heating quartz fluidized-bed reactor (i.d., 2 cm). The standard normalization method on the basis of carbon atom was used for calculating the CH4 conversion and C2-C3 selectivity. This catalyst achieves 35.5 % CH4 conversion, 66 % C2-C3 selectivity and particularly 15.1 % single-pass yield of C2H4 for a feed of CH4/O2/H2O=3/1/1 with a catalyst dosage of 20 mL at 700 °C and a total GHSV of 7200 h−1. Such catalyst is stable for at least 50 h without signs of deactivation and agglomeration/defluidization. The catalyst particle size is crucial for the FB-OCM reaction with respect to the reaction light-off and catalyst fluidization. The catalyst with preferable particle size of 450–600 μm can not only trigger the OCM reaction at a relatively low temperature of 630 °C but also warrant active bubbling fluidization. Furthermore, thanks to the low amount of Na2WO4 and interpenetrating structure of TiO2-nanorod, such catalyst achieves good anti-aggregation and robust mechanical strength (with a low attrition index of 1.9 %). The effects of water-adding amount in feedstock and catalyst particle size distribution on the hydrodynamics behaviour were investigated in a laboratory-scale fluidized-bed OCM reactor by using numerical simulation method.

Increased interlayer spacing N-doping Ti3C2Tx MXene-based mezzanine heterostructure for enhanced performance lithium/sodium storage

Structure of the electrode materials play a critical role in electrochemical performance for both lithium-ion batteries and sodium ion batteries. Herein, MXene modified by element doping and compositing metal–organic frameworks (MOF)-based Fe2O3@Carbon nanofibers (CNFs) with a mezzanine heterostructure, is constructed to achieve low interfacial impedance, high specific capacity stability in lithium/sodium storage processes. The prepared mezzanine heterostructure Fe2O3@C@N-Ti3C2Tx composite is highly conductive and mesoporous. During the nitrogen-doping thermal treatment process, the interlayer spacing of Ti3C2Tx MXene was increased, providing wider ion transport channels. Additionally, inert carbon atoms were transformed into electrochemically active nitrogen atoms, leading to the construction of more active centers and surface defects. The spatial confinement of N-Ti3C2Tx MXene during the electrochemical process, effectively mitigating volume expansion and maintaining structural stability upon applied as electrode materials. Benefitting from the unique 3D conductive network, the mezzanine heterostructure Fe2O3@C@N-Ti3C2Tx composite nanofibers exhibits excellent Li/Na storage performance. In LIBs, it delivers a capacity of 226 mAh/g at 10 A/g and retains 314 mAh/g after 2800 ultra-long cycles at 5 A/g. For SIBs, it exhibits a capacity of 135 mAh/g at 5 A/g and maintains 209 mAh/g after 3000 cycles at 2 A/g.

Dynamic Deformation in Nuclear Graphite and Underlying Mechanisms.

Time-dependent deformation in nuclear graphite is influenced by the creation and migration of radiation-induced defects in the reactor environment. This study investigates the role of pre-existing defects such as point defect clusters and Mrozowski cracks in nuclear graphite IG-110. Separate specimens were irradiated with a 2.8 MeV Au2+ beam with a fluence of 4.38 × 1014 cm-2 and an 8 MeV C2+ beam with a fluence of 1.24 × 1016 cm-2. Microscopic specimens were either mechanically loaded inside a transmission electron microscope (TEM) or subjected to ex situ indentation-based creep loading. In situ TEM tests showed significant plasticity in regions highly localized around the Mrozowski cracks, resembling slip or ripplocation bands. Slip bands were also seen near regions without pre-existing defects but at very high stresses. Ex situ self-ion irradiation embrittled the specimens and decreased the creep displacement and rate, while heavy ion irradiation resulted in the opposite behavior. We hypothesize that the large-sized gold ions (compared to the carbon atoms) induced interplanar swelling as well as cross-plane channels for increased defect mobility. These findings illustrate the role of pre-existing defects in the dynamic relaxation of stresses during irradiation and the need for more studies into the radiation environment's impact on the mechanical response of nuclear graphite.

Single-Crystal Structure Analysis of Dicarboxamides: Impact of Heteroatoms on Hydrogen Bonding of Carboxamide Groups

This research examines how heteroatoms in a six- or five-membered pyridine, thiophene or furan ring spacer between two carboxamide groups influence the hydrogen bonding for advancements in supramolecular chemistry and drug development. The solvent-free crystal structures of 3,5-pyridinedicarboxamide (PDC), 2,5-thiophenedicarboxamide (TDC) and 2,5-furandicarboxamide (FDC-subl, crystallized by sublimation), and the monohydrate structure of FDC-solv (crystallized from methanol) are described with the hydrogen-bonding analyzed by the Etter graph-set notation. The carbon atoms of the amide groups form an angle of 121° in PDC, 151° in TDC, 137° in FDC-solv and 135° in FDC-subl with the ring centroid. Only in the structure of PDC does the heteroatom act as an H-bond acceptor as part of a C11(6) chain. In TDC and FDC, the heteroatoms do not interact with the amide -NH2 groups.

The reverse-DADI method: Computation of frequency-dependent atomic polarizabilities for carbon and hydrogen atoms in hydrocarbon structures

A specific method, combining some ingredients of the well-known DDA and PDI approaches, has been developed in our group since many years to calculate the absorption cross-sections of carbonaceous nanoparticles based on their atomistic details. This method, here named the Dynamic Atomic Dipole Interaction (DADI) model, requires the knowledge of the position and frequency-dependent polarizability of each atom constituting the nanoparticles. While the atomic positions can be quite easily obtained, for example as the results of molecular dynamics simulations, obtaining the frequency-dependent atomic polarizabilities is a trickier task. Here, a fitting procedure, named the reverse-DADI method, has been applied to calculate the frequency-dependent atomic polarizability values for carbon and hydrogen atoms involved in aromatic cycles or in aliphatic chains, on the basis of frequency-dependent molecular polarizabilities of various PAH and alkane molecules, calculated with the TD-DFT theory, in the UV–Visible range. Then, using these frequency-dependent atomic polarizabilities as input parameters in the DADI model has been shown to lead to an accurate representation of the absorption cross-sections of various PAH and alkane molecules with respect to the corresponding values obtained at the TD-DFT level, with however the great advantage of a much shorter time of calculations. Furthermore, these results are indications of a good transferability of the frequency-dependent atomic polarizability values obtained here to any C or H atom of any PAH or alkane molecule. This opens the way for building large databases of optical properties for carbonaceous species of atmospheric or astrophysical interests.

Synthesis of Hexabenzocoronene‐Cored Graphdiyne Nanosheets through Dehydrogenative Coupling on Au(111) Surface

AbstractThermally‐induced dehydrogenative coupling of polyphenylenes on metal surfaces is an important technique to synthesize ‐conjugated carbon nanostructures with atomic precision. However, this protocol has rarely been utilized to fabricate structurally defined carbon nanosheets composed of sp‐ and sp2‐hybridized carbon atoms. Here, we present the synthesis of butadiyne‐linked hexabenzocoronenes (HBCs) on Au(111) surfaces as core‐expanded graphdiynes. The reaction started from hexa(4‐ethylphenyl)benzene, which undergoes dehydrogenation toward hexa(4‐vinylphenyl)benzene, followed by planarization to hexabenzocoronene, coupling between the vinyl groups, and further dehydrogenation. In addition to butadiyne linkages, benzene groups were also found as another type of linker. The reaction sequences were monitored by scanning tunneling microscopy and bond‐resolved non‐contact atomic force microscopy, which disclose the structures of intermediates and final products. In combination with density functional theory simulations, the key steps from ethyl substituents to butadiyne and benzene linkers were elucidated. This is a new on‐surface synthesis of core‐expanded graphdiynes with unprecedented electronic properties.

Thermoelectric properties of pristine and defective α-graphyne nanoribbons with vacancies present in different positions

In the present work, first-principle thermoelectric property investigations of pristine and defective α-graphyne nanoribbons (α-GYNRs) are conducted. Investigations have also been extended toward variation in temperature affecting the thermoelectric properties. Other objectives of the work presented are to investigate the thermoelectric properties at three temperatures, 300K, 500K, and 700K, of a single vacancy defect in a carbon atom removed from α-GYNRs. Pristine α-GYNRs is an intrinsic band gap semiconductor since defects occur naturally during synthesis, and the band gap significantly increases due to single vacancies and removal of carbon atoms at different positions. It results in a change of electrical conductivity Seebeck coefficient, and thermal conductivity. For some defective structures, with increasing temperature, the Seebeck coefficient increases compared with that of the pure structure and decreases. Also, the total thermal conductivity increases with increasing temperature. The obtained results show that the figure-of-merit value of defective α-GYNRs is much better than pristine α-GYNRs. In addition, ZT decreases in different structures by increasing temperature. Among all the considered structures, the Seebeck coefficient values and the ZT of some defective structures reach about 1.18 and 2.5 times that of the pristine structures at room temperature, respectively.

Porous Silicon-Supported Catalytic Materials for Energy Conversion and Storage.

Porous silicon (Si) has a tetrahedral structure similar to that of sp3- hybridized carbon atoms in a typical diamond structure, which affords it unique chemical and physical properties including an adjustable intrinsic bandgap, a high-speed carrier transfer efficiency. It has shown great potential in photocatalysis, rechargeable batteries, solar cells, detectors, and electrocatalysis. This review introduces various porous Si-supported electrocatalysts and analyzes the reasons why porous Si is used as a new carrier/active sites from the perspectives of its molecular structure, electronic properties, synthesis methods, etc. The electrochemical applications of porous Si-based electrocatalysts in energy conversion reactions such as hydrogen evolution reaction, oxygen evolution reaction, oxygen reduction reaction, and total water decomposition together with lithium-ion batteries (LIBs) and supercapacitors in energy storage are summarized. The challenges and future research directions for porous Si are also discussed. This review aims to deepen the understanding of porous Si and promote the development and applications of this new type of Si material.

Synthesis of Hexabenzocoronene-Cored Graphdiyne Nanosheets through Dehydrogenative Coupling on Au(111) Surface.

Thermally-induced dehydrogenative coupling of polyphenylenes on metal surfaces is an important technique to synthesize -conjugated carbon nanostructures with atomic precision. However, this protocol has rarely been utilized to fabricate structurally defined carbon nanosheets composed of sp- and sp2-hybridized carbon atoms. Here, we present the synthesis of butadiyne-linked hexabenzocoronenes (HBCs) on Au(111) surfaces as core-expanded graphdiynes. The reaction started from hexa(4-ethylphenyl)benzene, which undergoes dehydrogenation toward hexa(4-vinylphenyl)benzene, followed by planarization to hexabenzocoronene, coupling between the vinyl groups, and further dehydrogenation. In addition to butadiyne linkages, benzene groups were also found as another type of linker. The reaction sequences were monitored by scanning tunneling microscopy and bond-resolved non-contact atomic force microscopy, which disclose the structures of intermediates and final products. In combination with density functional theory simulations, the key steps from ethyl substituents to butadiyne and benzene linkers were elucidated. This is a new on-surface synthesis of core-expanded graphdiynes with unprecedented electronic properties.

Decomposition of PFAS and Synthesis of BC8 Super-Diamond: Rotations of Electromagnetic Waves for Novel Chemical Dynamics

A new theory is given for the decomposition of PFAS and the formation of BC8 Super-diamond with 13C isotope by application of RBL’s rotating magnetic field, neutrinos and/or antineutrinos and static magnetic field for stimulating nuclei having nonzero nuclear magnetic moments (NMMs). The induced NMMs are proposed more readily in the 19F of PFAS due to the large mass defect of 19F and the many C-F bonds per molecule. The super-diamond with 13C isotope is reasoned to form with its body center cubic lattice with central 13-carbon atom per cube due to the rotating magnetic field, neutrinos and/or antineutrinos and resulting internal induced sp3 hybridization with more efficiency for the applied external pressure and internal pressure by 13C isotope to be better used to compress the resulting sp3 carbon atoms to BC8 super-diamond. The author invented the use of rotating electromagnetic, neutrino and/or antineutrino and magnetic fields to affect chemical dynamics in 2000-07. The author (RBL) thereby here reports the theory and discovery of unusual and large interactions of highly, energetic dynamical hydrogen bonds with neutrinos and antineutrinos.

Fabrication of a novel microflower BiOCl composite incorporated with rosemary powder for enhanced oxygen vacancies and visible-light photocatalytic efficiency

Incorporating metallic or nonmetallic compounds is a promising method for enhancing the oxygen vacancies (OVs), charge transport, and visible light absorption of a bismuth oxychloride (BiOCl) semiconductor. This research aims to improve the properties of BiOCl by incorporating rosemary powder (RPC). BiOCl photocatalysts with enhanced OVs were synthesized through the addition of 1–4 wt% of RPC using a one-pot solvothermal process. The addition of 3 % RPC resulted in the formation of very small particles on the BiOCl lamellar structures, which were aligned with the (002) plane of carbon quantum dots (CQDs). The uniformly distributed CQDs transformed the BiOCl microstructure from a two-dimensional lamellar structure to a three-dimensional floral structure, leading to an increased surface area and pore volume. The incorporation of RPC enhanced the visible light absorption capacity of BiOCl. The carbon atoms in RPC readily attach to oxygen atoms in the Bi-O bond, disrupting the Bi-O lattice bond and forming OVs. The addition of RPC contributed to a higher number of OVs, which impacted both the energy difference between the valence and conduction bands and their locations. This resulted in better charge transfer and enhanced active species formation. The 3 %-RPC-BOC photocatalyst had the highest efficiency, achieving a 98 % degradation of rhodamine B (RhB) and a 45 % removal of organic carbon within 48 min under visible light. This composite also had excellent stability and reusability, as its crystal structure remained unaltered even after conducting 7 cycles. The primary active species of 3 %-RPC-BOC system is the superoxide radical (·O2-), while the hydroxyl radical (·OH) and hole (h+) operate as minor active species. Additionally, the 3 %-RPC-BOC achieved a high tetracycline (TC) removal rate of 82.1 %, which is 2.21 times higher than that of pure BiOCl.

Functionalized Amorphous Carbon Materials via Reactive Molecular Dynamics Simulations.

We derive a database of atomistic structural models of amorphous carbon materials endowed with exohedral functional groups. We start from phases previously derived using the DynReaxMas method for reactive molecular dynamics simulations, which exhibit atomistic and medium-length-scale features in excellent agreement with available experimental data. Given a generic input structure/phase, we develop postprocessing simulation algorithms mimicking experimental preparation protocols aimed at: (1) "curing" the phase to decrease the defect concentration; (2) automatically selecting the most reactive carbon atoms via interaction with a probe molecular species, and (3) stabilizing the phase by saturating the valence of carbon atoms with single-bond functional groups. Although we focus on oxygen-bearing functionalities, they can be replaced with other monovalent groups, such as -H, -COOH, -CHO, so that the protocol is quite general. We finally classify reactive sites in terms of their location within the structural framework and coordination environment (edges, tunnels, rings, aromatic carbons becoming aliphatic) and try to single out descriptors that correlate with tendency to functionalization.

Updating Reaction Mechanistic Domains for Skin Sensitization: 1. Nucleophilic Skin Sensitizers.

It has long been recognized that skin sensitizers either are electrophilic or can be activated to electrophilic species. Several nonanimal assays for skin sensitization are based on this premise. In the course of a project to update dermal sensitization thresholds (DST), we found a substantial number of sensitizers, with no electrophilic or pro-electrophilic alerts, that could be simply explained in terms of the sensitizer acting as a nucleophile. In some cases, the nucleophilic center is a sulfur or phosphorus atom, while in others, it is an aromatic carbon atom. For carbon-centered nucleophiles, a quantitative mechanistic model based on a combination of Hammett σ+ and logP values has been derived. This has been applied to rationalize several groups of known sensitizers with no electrophilic or pro-electrophilic alerts, including anacardic acids and cardols, which are known human sensitizers associated with, inter alia, cashew nut oil, mango, and Ginkgo biloba. The possibility of nucleophilic sensitization needs to be considered when evaluating new chemicals for skin sensitization potential and potency by nonanimal assays, particularly those based on the premise that skin sensitization is dependent upon reactions of electrophiles with skin protein-based nucleophiles.

Atmospheric oxidation pathways of CF3CH2CFCl2 (HCFC-234fb) with OH-radicals and Cl-atoms: insights into the mechanism, thermodynamics, and kinetics.

The atmospheric oxidation of 1,1-dichloro-1,3,3,3-tetrafluoropropane, HCFC-234fb (DTP), leads to the formation of harmful radicals, contributing to stratospheric ozone depletion. Thus, a detailed study of the gas-phase oxidation of the first-generation chlorofluorocarbon alternative HCFC-234fb by a reaction with hydroxyl radicals and chlorine atoms is important to understand its harmful effects on the environment. In this work, we have performed quantum chemical calculations to investigate the thermodynamic and kinetic aspects of the titled reaction. The potential energy profile calculated at the CCSD(T)/aug-cc-pVTZ//MP2/cc-pVTZ level of theory shows that the major reaction pathway involves the abstraction of the H-atom from the central carbon atom, C2, giving rise to the product radical CF3C˙HCCl2F. The calculated rate-coefficients for the reaction with ˙OH and Cl-atoms are 3.89 × 10-15 and 2.54 × 10-17 cm3 molecule-1 s-1, respectively, at 298 K and are in accordance with the experimental rate coefficients. The results suggest that the rate-coefficient for the reaction of DTP with ˙OH is two orders of magnitude higher than that with Cl-atoms, indicating greater significance of the former reaction in the atmosphere. With the rate-coefficient values, the lifetime and the radiative efficiency were calculated to be 8.2 years and 0.246 W m-2 ppb-1, respectively. A 100-year global warming potential (GWP) of 712 was also estimated using the lifetime corrected radiative efficiency value.

Graphene with suitable-size nitrogen-doped cavity being an excellent photocatalyst for proton-coupled electron transfer in water splitting

Aiming to attain porous carbon nitride photocatalysts with high specific surface area, abundant active sites, broad absorption range and effective electron-hole separation, we remove carbon rings from graphene and replace all the edge carbon atoms of the cavity with nitrogen atoms. The accurate electronic structures and exciton properties of the proposed materials are revealed by the ab initio many-body Green's function theory. Computational results show that the absorption of the designed materials can cover both the visible and the near-infrared light region. The exciton binding energies of the materials are one order of magnitude lower than those of the typical two-dimensional photocatalyst graphitic carbon nitride. Due to the formation of hydrogen bonds between pyridinic nitrogen atoms and water molecules during water splitting, the key excited-state proton-coupled electron transfer reactions are barrierless. These findings could serve as guidelines for the realization of high-performance metal-free two-dimensional photocatalysts.

Dark NO2 Reduction on a Graphene Surface with Implications for Soot Aging and HONO Formation.

Soot, primarily composed of elemental carbon (EC) and organic carbon (OC), is ubiquitous in PM2.5. In the atmosphere, the heterogeneous interaction between NO2 and soot is not only an important pathway driving soot aging but also of central importance to nitrous acid (HONO) formation. It is commonly believed that the surface redox reaction between reductive OC and NO2 dominates the night aging of soot and the conversion of NO2 to HONO. However, completely differing from the currently popular explanation, we find here that the redox reaction between EC and NO2 can also drive the conversion of NO2 to HONO during soot aging. By combining in situ experiments with density functional theory (DFT) calculations, we proposed that the surface carbon vacancy defects on graphite/graphene-like EC should be a type of potential primary adsorption and reactive sites inducing the heterogeneous reduction of NO2. We suggested a new mechanism that NO2 is reduced to form HONO on surface vacancy defects through the splitting of H2O molecules, and the carbon atoms adjacent to surface vacancy are simultaneously oxidized to form hydroxyl-functionalized EC. This novel finding provides insights into the chemical mechanism driving the NO2-to-HONO conversion and rapid soot aging, which expands our knowledge of the heterogeneous chemistry of soot in the atmosphere.

Reactions of Electrophilic Allenoates [and Isocyanates/Isothiocyanates] with a 2-Alkynylpyridine via a Free Carbene Intermediate.

A pyridine containing a 2-alkynyl substituent armed with a carbene reporter group [R1 = C(Me)2OAc] is shown to engage electrophilic allenes to generate intermediate free carbenes. Depending on the electron density at the carbene carbon atom, a feature that is modulated by the substituents on the allene substrate, the carbene will either rearrange or eject an acetate leaving group, leading to various types of indolizine-containing products. Iso(thio)cyanates react in an analogous fashion.

Hexa-Penta nanobelt: a novel stable structure with potential optical application

ABSTRACT We report a theoretical investigation of a new carbon nanobelt called Hexa-Penta-belt with molecular formula C 42 H 18 . Hexa-Penta-belt is a variation of the synthesised Methylene-bridged[6]cycloparaphenylene (M-b[6]CPP) with molecular formula C 42 H 24 . Hexa-Penta-belt consists of carbon pentagon and hexagon rings and was inspired by the Penta-belt (theoretically derived from the penta-graphene sheet), the [12]cyclophenacene, and the M-b[6]CPP synthesised by Itami and Segawa [1]. Using Density Functional Theory (DFT), we calculated Hexa-Penta-belt electronic, optical, and thermodynamic properties and their vibrational frequencies. Hexa-Penta-belt is a structurally and thermally stable molecule, as Quantum Molecular Dynamics (QMD) showed. The results exhibited that the Hexa-Penta-belt has excellent electronic stability comparable to C 60 , and it behaves as a semiconductor with a gap estimated at 0.89 eV. It absorbs in the ultraviolet and the visible region (corresponding to the violet, green, and red colours) presenting an absorption more consistent in the visible region than M-b[6]CPP, which could indicate application, for example, as an optical nanosensor. We verified through the carbon atom binding energy that Hexa-Penta-belt is an intermediate molecule between Penta-belt and [12]cyclophenacene.