One-dimensional sp carbon: Synthesis,properties, and modifications

Carbyne, as the truly one-dimensional carbon allotrope with sp-hybridization, has attracted significant interest in recent years, showing potential applications in next-generation molecular devices due to its ultimate one-atom thinness. Various excellent properties of carbyne have been predicted, however, free-standing carbyne sample is extremely unstable and the corresponding experimental researches and modifications are under-developed compared to other known carbon allotropes. The synthesis of carbyne has been slowly developed for the past decades. Recently, there have been several breakthroughs in in-situ synthesis and measurement of carbyne related materials, as well as the preparation of ultra-long carbon chains toward infinite carbyne. These progresses have aroused widespread discussion in the academic community. In this review, the latest approaches in the synthesis of sp carbon are summarized. We then discuss its extraordinary properties, including mechanical, electronic, magnetic, and optical properties, especially focusing on the regulations of these properties. Finally, we provide a perspective on the development of carbyne.     

Large-scale synthesis of polyynes with commercial laser marking technology

The space-confined synthesis method has been an efficient way for the preparation of linear carbon chains. However, the large-scale preparation of linear carbon chains still faces many challenges due to the lack of methods for the large-scale synthesis of precursors, such as short carbon chains (polyynes), and regulation technology for the transport of reactants in one-dimensional space. Here, we report a facile method for the rapid preparation of polyynes in large quantities using a commercial laser marking machine. Spectroscopic characterizations show that a large number of polyynes, such as C₈H₂, C₁₀H₂, C₁₂H₂, and C₁₄H₂, can be produced by ablating the graphite plate immersed in the organic liquid using a laser marking machine. The results of in situ Raman spectroscopy investigation of C_2nH₂-filled single-walled carbon nanotubes further confirm that a variety of polyyne molecules are synthesized. Meanwhile, in situ Raman spectroscopy also shows that the local heating treatment can accelerate the filling process of C_2nH₂ into one-dimensional channels. This work provides new insights into the study of linear carbon chains and space-confined synthesis methods.     

Raman spectroscopy of isolated carbyne chains confined in carbon nanotubes: Progress and prospects

Carbyne is an infinitely long linear chain of carbon atoms with sp¹ hybridization and the truly one-dimensional allotrope of carbon. While obtaining freestanding carbyne is still an open challenge, the study of confined carbyne, linear chains of carbon encapsulated in carbon nanotubes, provides a pathway to explore carbyne and its remarkable properties in a well-defined environment. In this review, we discuss the basics and recent advances in studying single confined carbyne chains by Raman spectroscopy, which is their primary spectroscopic characterization method. We highlight where single carbyne chain studies are needed to advance our understanding of confined carbyne as a material system and provide an overview of the open questions that need to be addressed and of those aspects currently under debate.     

First-principles study on the mechanics,optical, and phonon properties of carbon chains

Besides graphite, diamond, graphene, carbon nanotubes, and fullerenes, there is another allotrope of carbon, carbyne,existing in the form of a one-dimensional chain of carbon atoms. It has been theoretically predicted that carbyne would be stronger, stiffer, and more exotic than other materials that have been synthesized before. In this article, two kinds of carbyne, i.e., cumulene and polyyne are investigated by the first principles, where the mechanical properties, electronic structure, optical and phonon properties of the carbynes are calculated. The results on the crystal binding energy and the formation energy show that though both are difficult to be synthesized from diamond or graphite, polyyne is more stable and harder than cummulene. The tensile stiffness, bond stiffness, and Young's modulus of cumulene are 94.669 eV/?A,90.334 GPa, and 60.62 GPa, respectively, while the corresponding values of polyyne are 94.939 eV/?A, 101.42 GPa, and60.06 GPa. The supercell calculation shows that carbyne is most stable at N = 5, where N is the supercell number, which indicates that the carbon chain with 10 atoms is most stable. The calculation on the electronic band structure shows that cumulene is a conductor and polyyne is a semiconductor with a band gap of 0.37 eV. The dielectric function of carbynes varies along different directions, consistent with the one-dimensional nature of the carbon chains. In the phonon dispersion of cumulene, there are imaginary frequencies with the lowest value down to-3.817 THz, which indicates that cumulene could be unstable at room temperature and normal pressure.     

Equilibrium distribution of the wave energy in a carbyne chain

The steady-state energy distribution of thermal vibrations at a given ambient temperature has been investigated based on a simple mathematical model that takes into account central and noncentral interactions between carbon atoms in a one-dimensional carbyne chain. The investigation has been performed using standard asymptotic methods of nonlinear dynamics in terms of the classical mechanics. In the first-order nonlinear approximation, there have been revealed resonant wave triads that are formed at a typical nonlinearity of the system under phase matching conditions. Each resonant triad consists of one longitudinal and two transverse vibration modes. In the general case, the chain is characterized by a superposition of similar resonant triplets of different spectral scales. It has been found that the energy equipartition of nonlinear stationary waves in the carbyne chain at a given temperature completely obeys the standard Rayleigh–Jeans law due to the proportional amplitude dispersion. The possibility of spontaneous formation of three-frequency envelope solitons in carbyne has been demonstrated. Heat in the form of such solitons can propagate in a chain of carbon atoms without diffusion, like localized waves.     

Energetic barrier reduction at the carbyne film interface

An abnormal injection current density through SiO₂ has been observed recently for both signs of charge carriers in experiments with an oriented carbyne film grown on a SiO₂ layer. The absence of a surface leakage current and the insulating property of SiO₂ were experimentally proved. The temperature dependence of the current through SiO₂ showed low activation energy and confirmed the model of thermally activated injection. A strong influence of the electric field applied transverse to the carbon chains on the current through SiO₂ was observed. A model of energetic barrier reduction at the carbyne interface based on the hypothesis of transverse inter-chain hopping in the electric field was proposed. It was shown that a transverse electric field can be induced in a carbyne film as in one-dimensional media. The first organic light emitting device with a carbyne-based effective injector was fabricated.     

Length and temperature dependence of the mechanical properties of finite-size carbyne

Carbyne is an ideal one-dimensional conductor and the thinnest interconnection in an ultimate nano-device and it requires an understanding of the mechanical properties that affect device performance and reliability. Here, we report the mechanical properties of finite-size carbyne, obtained by a molecular dynamics simulation study based on the adaptive intermolecular reactive empirical bond order potential. To avoid confusion in assigning the effective cross-sectional area of carbyne, the value of the effective cross-sectional area of carbyne (4.148 Å²) was deduced via experiment and adopted in our study. Ends-constraints effects on the ultimate stress (maximum force) of the carbyne chains are investigated, revealing that the molecular dynamics simulation results agree very well with the experimental results. The ultimate strength, Young's Modulus and maximum strain of carbyne are rather sensitive to the temperature and all decrease with the temperature. Opposite tendencies of the length dependence of the overall ultimate strength and maximum strain of carbyne at room temperature and very low temperature have been found, and analyses show that this originates in the ends effect of carbyne.     

Thermal conduction of one-dimensional carbon nanomaterials and nanoarchitectures

This review summarizes the current studies of the thermal transport properties of one-dimensional(1D) carbon nanomaterials and nanoarchitectures. Considering different hybridization states of carbon, emphases are laid on a variety of 1D carbon nanomaterials, such as diamond nanothreads, penta-graphene nanotubes, supernanotubes, and carbyne. Based on experimental measurements and simulation/calculation results, we discuss the dependence of the thermal conductivity of these 1D carbon nanomaterials on a wide range of factors, including the size effect, temperature influence, strain effect, and others. This review provides an overall understanding of the thermal transport properties of 1D carbon nanomaterials and nanoarchitectures, which paves the way for effective thermal management at nanoscale.     

The influence of hydrogen impurities on the atomic and electronic structures of carbyne crystals

An ab initio DFT study of atomic and electronic structure of carbyne crystals was carried out. The influence of hydrogen impurities on carbyne structure was investigated. Calculations with atomic relaxations showed that carbon chains in the carbyne crystal structure are bow-like curved; free-energy calculations showed that the most probable lengths of those chains are four and six atoms, which is in a good agreement with experiments. Carbyne-crystal electronic-structure analysis showed that there is a small gap of 0.09 eV near the Fermi level in four-atomic carbyne, while there is no such gap in six-atomic carbyne. In studying of the hydrogen impurity influence on the atomic and electronic structure of carbyne crystals, hydrogen atoms were embedded in two directions: across and along carbon chains in the crystal. As a result we found that the crystal structure is not distorted in the case of hydrogen embedded across the chains, while the type of bonding between carbon atoms in carbon chains in the carbyne crystal structure depended on the impurity concentration. The crystal structure was distorted when hydrogen was embedded along the chains. The concentration of impurities influences the conductivity of a carbyne crystal.     

Solvent effect in sonochemical synthesis of metal-alloy nanoparticles for use as electrocatalysts

Nanomaterials are now widely used in the fabrication of electrodes and electrocatalysts. Herein, we report a sonochemical study of the synthesis of molybdenum and palladium alloy nanomaterials supported on functionalized carbon material in various solvents: hexadecane, ethanol, ethylene glycol, polyethylene glycol (PEG 400) and Ionic liquids (ILs). The objective was to identify simple and more environmentally friendly design and fabrication methods for nanomaterial synthesis that are suitable as electrocatalysts in electrochemical applications. The particles size and distribution of nanomaterials were compared on two different carbons as supports: activated carbon and multiwall carbon nanotubes (MWCNTs). The results show that carbon materials functionalized with ILs in ethanol/deionized water mixture solvent produced smaller particles sizes (3.00 ± 0.05 nm) with uniform distribution while in PEG 400, functionalized materials produced 4.00 ± 1 nm sized particles with uneven distribution (range). In hexadecane solvents with Polyvinylpyrrolidone (PVP) as capping ligands, large particle sizes (14.00 ± 1 nm) were produced with wide particle size distribution. The metal alloy nanoparticles produced in ILs without any external reducing agent have potential to exhibit a higher catalytic activity due to smaller particle size and uniform distribution.     

Raman spectral features of longer polyynes HC2 nH ({\sf n=4}–8) in SWNTs

Size-selected linear hydrocarbon molecules, polyynes HC_2nH, were contacted in solutions with single-wall carbon nanotubes (SWNTs) prepared from laser-ablated metal/carbon composite rods (Rh/Pt/C) to produce polyyne-encapsulating SWNTs, HC_2nH@SWNT(RhPt). New Raman spectral features were observed at 2120, 2061, 2017, 1982, and 1963 cm^-1 for five polyynes of n=4–8, respectively, and identified as the vibrational excitation of symmetric stretching modes of the molecules inside the SWNTs. The Raman spectra were compared with those observed for polyynes on Ag islands (SERS) and in solutions. The filling factor was investigated from the concentration dependence of the Raman intensity for HC₁₀H@SWNT(NiCo) to give an estimate of one polyyne molecule per ~350 carbon atoms of SWNTs, providing a picture for head-to-tale filling of aligned C₁₀H₂ molecules inside the SWNTs.     

Electronic structure of carbyne studied by X-ray photoelectron spectroscopy and X-ray emission spectroscopy

The electronic structure of amorphous carbyne has been investigated by X-ray photoelectron spectroscopy and X-ray emission spectroscopy. Carbyne band structure has been calculated semiempirically and the experimental data have been interpreted on the basis of the calculation results. The valence band width was found to be about 20 eV which is the same as that in all other condensed carbon structures. The fine satellite structure near the 1s line of carbon has been studied. It is shown that the energy bands in carbyne are arranged in a mirror-like way relative to the Fermi level. The real carbyne structure is susceptible to conformations which affect primarily the π-subband structure.     

DFT approach on stability and conductance of nine different polyyne and cumulene molecules

Cumulene molecules are one of the main candidates for the use as molecular wires. Low bond length alternation (BLA) values are one of the main attractive property of cumulene molecules as it leads to high conductivity, whereas stability under normal conditions is the main problem. The study is aimed at achieving stable molecules with low BLA values by forcing cumulene structure in polyynes through substitution. Hence, we considered symmetric LCC molecules of n core carbon atoms (n?=?4–12) with nine different terminal groups substitution such as hydrogen terminated polyynes (H[n]), phenyl terminated polyynes (Ph[n]), pyridine-capped polyynes Py[n], 3, 5-diphenyl pyridyl terminated polyynes (Py*[n]) their hydrogenated forms (H-Py[n] and H-Py*[n]), oxygen substituted phenyl terminated polyynes (O=Ph[n]) and 2, 4, 6-trimethylphenyl capped cumulenes (Mes[n]). The BLA values, transport barrier, excitation energy, reorganisation energy, energy gap and vertical and adiabatic ionisation energy were analysed to find the suitable molecule for molecular wires.     

Template-based synthesis of nanomaterials

The large interest in nanostructures results from their numerous potential applications in various areas such as materials and biomedical sciences, electronics, optics, magnetism, energy storage, and electrochemistry. Ultrasmall building blocks have been found to exhibit a broad range of enhanced mechanical, optical, magnetic, and electronic properties compared to coarser-grained matter of the same chemical composition. In this paper various template techniques suitable for nanotechnology applications with emphasis on characterization of created arrays of tailored nanomaterials have been reviewed. These methods involve the fabrication of the desired material within the pores or channels of a nanoporous template. Track-etch membranes, porous alumina, and other nanoporous structures have been characterized as templates. They have been used to prepare nanometer-sized fibrils, rods, and tubules of conductive polymers, metals, semiconductors, carbons, and other solid matter. Electrochemical and electroless depositions, chemical polymerization, sol-gel deposition, and chemical vapour deposition have been presented as major template synthetic strategies. In particular, the template-based synthesis of carbon nanotubes has been demonstrated as this is the most promising class of new carbon-based materials for electronic and optic nanodevices as well as reinforcement nanocomposites. Received: 27 May 1999 / Accepted: 27 October 1999 / Published online: 8 March 2000     

Hard carbons derived from pine nut shells as anode materials for Na-ion batteries

Hard carbons as promising anode materials for Na-ion batteries(NIBs) have captured extensive attention because of their low operation voltage, easy synthesis process, and competitive specific capacity. However, there are still several disadvantages, such as high cost and low initial coulombic efficiency, which limit their large-scale commercial applications.Herein, pine nut shells(PNSs), a low-cost biomass waste, are used as precursors to prepare hard carbon materials. Via a series of washing and heat treatment procedures, a pine nut shell hard carbon(PNSHC)-1400 sample has been obtained and delivers a reversible capacity of around 300 mAh/g, a high initial coulombic efficiency of 84%, and good cycling performance. These excellent Na storage properties indicate that PNSHC is one of the most promising candidates of hard carbon anodes for NIBs.     

聚1，1-二氯乙烯（PVDC）热解产物的拉曼光谱

碳炔是一类新型的功能材料。本工作以PVDC为原料采用直接加热脱氯化氢的方法探索制备碳块的可能性,经热重分析（TGA）及拉曼光谱分析表明,加热产物中存在碳炔的结构。     

Smallest nanotube: breaking the symmetry of sp(3) bonds in tubular geometries

We describe how sp(2) carbon, threefold coordinated by other carbons, can be replaced by sp(3) carbon, also threefold carbon coordinated, to produce extremely small-diameter ( approximately 0.4 nm) carbon nanowires with only minimal bond-angle distortion. Under a naming convention analogous to that for ordinary carbon nanotubes, the smallest sp(3) tubes have wrapping indices (3,0) and (2,2). These systems have large band gaps and a stiffness larger even than that of traditional sp(2)-bonded carbon nanotubes. They therefore form the stiffest one-dimensional systems known.     

Extraordinary mechanical performance in charged carbyne

Carbyne, the linear chain of carbon, promises the strongest and toughest material but possesses a Peierls instability (alternating single-bonds and triple-bonds) that reduces its strength and toughness. Herein, we computationally found that the gravimetric strength, strain-to-failure, and gravimetric toughness can be improved from 74 GPa·g^-1·cm³, 18%, and 9.4 kJ·g^-1 for pristine carbyne to the highest values of 106 GPa·g^-1·cm³, 26%, and 19.0 kJ·g^-1 for carbyne upon hole injection of +0.07 e/atom, indicating the charged carbyne with record-breaking mechanical performance. Based on the analyses of the atomic and electronic structures, the underlying mechanism behind the record-breaking mechanical performance was revealed as the suppressed and even eliminated bond alternation of carbyne upon charge injection.     

Fabrication of nanowires and nanostructures: combining template synthesis with patterning methods

We report on different approaches that we have adopted and developed for the fabrication of nanowires and nanostructures. Methods based on template synthesis and on self organization seem to be the most promising for the fabrication of nanomaterials and nanostructures due to their easiness and low cost. The development of a supported nanoporous alumina template and the possibility of using this template to combine electrochemical synthesis with lithographic methods open new ways for the fabrication of complex nanostructures. The numerous advantages of the supported template and its compatibility with microelectronic processes make it an ideal candidate for further integration into large-scale fabrication of various nanowire-based devices.