Sorokin, Pavel B; Lee, Hoonkyung; Antipina, Lyubov Yu; Singh, Abhishek K; Yakobson, Boris I
Among the carbon allotropes, carbyne chains appear outstandingly accessible for sorption and very light. Hydrogen adsorption on calcium-decorated carbyne chain was studied using ab initio density functional calculations. The estimation of surface area of carbyne gives the value four times larger than that of graphene, which makes carbyne attractive as a storage scaffold medium. Furthermore, calculations show that a Ca-decorated carbyne can adsorb up to 6 H(2) molecules per Ca atom with a binding energy of ∼0.2 eV, desirable for reversible storage, and the hydrogen storage capacity can exceed ∼8 wt %. Unlike recently reported transition metal-decorated carbon nanostructures, which suffer from the metal clustering diminishing the storage capacity, the clustering of Ca atoms on carbyne is energetically unfavorable. Thermodynamics of adsorption of H(2) molecules on the Ca atom was also investigated using equilibrium grand partition function.
Agwa, M. A.; Eltaher, M. A.
This paper presents a comprehensive model to investigate the influence of surface elasticity and residual surface tension on the natural frequency of flexural vibrations of nanomechanical mass sensor using a carbyne resonator. Carbyne is modeled as an equivalent continuum circular cross-section Timoshenko nanobeam including rotary inertia and shear deformation effects. Surface stress and surface elasticity are presented via the Young-Laplace equation. The analytical solution is presented and verified with molecular dynamics solution. The results show that the carbyne resonator can measure a very small mass with weight below 10-3 zg. The effects of surface elasticity, residual surface tension, carbyne length, and mass position on the fundamental frequencies are illustrated. This study is helpful for characterizing the mechanical behavior of high-precision measurement devices such as chemical and biological sensor.
Demyashev, G M; Taube, A L; Siores, E
The aim of this research is to investigate a novel approach to surface engineering of biomaterials that are based on transition metals of the groups IVA-VIA. The approach taken relies on the fact that, during the electropolishing of TiC surfaces, the removal of Ti atoms from the TiC surface surpasses that of C atoms. This leads to enrichment of the TiC surface with carbon. Transmission electron microscopic investigation showed that carbon-based films contain carbynes in the form of nanorod-like clusters with lengths in the range of 5-100 nm. This carbyne-containing layer is 50-100 nm thick. It was generalized that carbyne-containing nanofilms are formed on the carbide surface of transition metals of groups IVA-VIA during electropolishing. Since carbynes, being one-dimensional chain-like structures [(-C identical to C-)n/(=C=C=)n] with sp1 carbon-carbon hybridization, have the highest degree of biocompatibility because of their biological activity, the development of such surface bioengineering with carbynes extends applications of biomaterials based on transition metals of the groups IVA-VIA.
Shi, Lei; Rohringer, Philip; Suenaga, Kazu; Niimi, Yoshiko; Kotakoski, Jani; Meyer, Jannik C.; Peterlik, Herwig; Wanko, Marius; Cahangirov, Seymur; Rubio, Angel; Lapin, Zachary J.; Novotny, Lukas; Ayala, Paola; Pichler, Thomas
Strong chemical activity and extreme instability in ambient conditions characterize carbyne, an infinite sp1 hybridized carbon chain. As a result, much less has been explored about carbyne as compared to other carbon allotropes such as fullerenes, nanotubes and graphene. Although end-capping groups can be used to stabilize carbon chains, length limitations are still a barrier for production, and even more so for application. We report a method for the bulk production of long acetylenic linear carbon chains protected by thin double-walled carbon nanotubes. The synthesis of very long arrangements is confirmed by a combination of transmission electron microscopy, X-ray diffraction and (near-field) resonance Raman spectroscopy. Our results establish a route for the bulk production of exceptionally long and stable chains composed of more than 6,000 carbon atoms, representing an elegant forerunner towards the final goal of carbyne’s bulk production.
Kovriguine, D. A.; Nikitenkova, S. P.
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.
Castelli, Ivano E.; Salvestrini, Paolo; Manini, Nicola
As sp carbon chains (carbynes) are relatively rigid molecular objects, can we exploit them as construction elements in nanomechanics? To answer this question, we investigate their remarkable mechanical properties by ab initio total-energy simulations. In particular, we evaluate their linear...... response to small longitudinal and bending deformations and their failure limits for longitudinal compression and elongation....
Valyaev, Dmitry A; Bastin, Stéphanie; Utegenov, Kamil I; Lugan, Noël; Lavigne, Guy; Ustynyuk, Nikolai A
Easily available carbyne complexes of manganese were used as a source of carbyne fragments in an unconventional synthesis of backbone-substituted diphosphinomethanes and cyclic P-ylides upon coupling with secondary or tertiary phosphines, respectively, followed by demetalation under mild conditions.
Wang, Mingchao; Lin, Shangchao
The elastic modulus of carbyne, a one-dimensional carbon chain, was recently predicted to be much higher than graphene. Inspired by this discovery and the fundamental correlation between elastic modulus and thermal conductivity, we investigate the intrinsic thermal transport in two carbon allotropes: carbyne and cumulene. Using molecular dynamics simulations, we discover that thermal conductivities of carbyne and cumulene at the quantum-corrected room temperature can exceed 54 and 148 kW/m/K, respectively, much higher than that for graphene. Such conductivity is attributed to high phonon energies and group velocities, as well as reduced scattering from non-overlapped acoustic and optical phonon modes. The prolonged spectral acoustic phonon lifetime of 30-110 ps and mean free path of 0.5-2.5 μm exceed those for graphene, and allow ballistic phonon transport along micron-length carbon chains. Tensile extensions can enhance the thermal conductivity of carbyne due to the increased phonon density of states in the acoustic modes and the increased phonon lifetime from phonon bandgap opening. These findings provide fundamental insights into phonon transport and band structure engineering through tensile deformation in low-dimensional materials, and will inspire studies on carbyne, cumulene, and boron nitride chains for their practical deployments in nano-devices.
The activity of silica-supported tungsten carbyne complexes (≡SiO)xW(≡CH)(Me)y (x = 1, y = 2; x = 2, y = 1) toward alkynes is reported. We found that they are efficient precatalysts for terminal alkyne cyclotrimerization with high TONs. We also demonstrate that this catalyst species is active for alkyne cyclotrimerization without the formation of significant alkyne metathesis products. Additional DFT calculations highlight the importance of the W coordination sphere in supporting this experimental behavior.
Sadykov, N. R.; Aporoski, A. V.
Electron properties of semiconducting zigzag carbon nanotubes (CNTs) can be described by two uncoupled Dirac equations of dimension (1+1) for the particle with nonzero mass. The solutions of these equations are two charge-neutral Majorana fields. An analogous equation is obtained for the carbon chains. We use the approach, wherein wavefunction of charged particle is represented as the production of a rapidly oscillating exponent and the slowly varying function amplitude depending on the longitudinal coordinate.
Designing supported well-defined bis(carbene) complexes remains a key challenge in heterogeneous catalysis. The reaction of W(CtBu)(CH(2)tBu)(3) with amine-modified mesoporous SBA15 silica, which has vicinal silanol/silylamine pairs [(SiOH)(SiNH2)], leads to [(SiNH2-)(SiO-)W(CHtBu)(CH(2)tBu)(2)] and [(SiNH2-)(SiO-)W(=CHtBu)(2)(CH(2)tBu). Variable temperature, H-1-H-1 2D double-quantum, H-1-C-13 HETCOR, and HETCOR with spin diffusion solid-state NMR spectroscopy demonstrate tautomerization between the alkyl alkylidyne and the bis(alkylidene) on the SBA15 surface. Such equilibrium is possible through the coordination of W to the surface [(Si-OH)(Si-NH2)] groups, which act as a [N,O] pincer ligand. DFT calculations provide a rationalization for the surface-complex tautomerization and support the experimental results. This direct observation of such a process shows the strong similarity between molecular mechanisms in homogeneous and heterogeneous catalysis. In propane metathesis (at 150 degrees C), the tungsten bis(carbene) tautomer is favorable, with a turnover number (TON) of 262. It is the highest TON among all the tungsten alkyl-supported catalysts.
Extensive solid-state NMR analyses unambiguously determine the formation of silica supported W bis-methylidene methyl species by reaction of the corresponding methyl carbyne with trimethylphosphine or a cyclic olefin. © 2014 the Partner Organisations.
Xiao, Xiao; Zeng, Zigao; Xiao, Songwen
The mechano-chemical (MC) dechlorination of polyvinyl chloride (PVC) and polyvinylidene chloride (PVDC) was performed by mechanical milling PVC/PVDC powder with zinc powder in a planetary ball mill, and the products of dechlorination were characterized by Infrared spectra (IR), X-ray diffraction (XRD), Raman spectroscopy, gas chromatography-mass spectrometry (GC-MS), and 13C solid-state nuclear magnetic resonance (NMR). The experimental results show that PVC/PVDC can be easily dechlorinated by milling with zinc powder, and formed various kinds of inorganic and organic products. Inorganic compounds included Zn2OCl(2).2H2O, Zn5(OH)8Cl2.H2O etc., and organic products involved diamond-like carbon, carbyne fragment, polyacetylene etc. Organic products formed following the paths of dechlorination, dehydrochlorination, crosslink, and oxidation. The mechano-chemical dechlorination process of PVC/PVDC may be an effective approach for carbyne synthesizing in the appropriate condition.
Full Text Available Linear strings of sp1-hybridized carbon atoms are considered as a possible phase of carbon since decades. Whereas the debate about the stability of the corresponding bulk phase carbyne continues until today, the existence of isolated chains of carbon atoms has meanwhile been corroborated experimentally. Since graphene, as the two-dimensional sp2-bonded allotrope of carbon, has become a vast field, the question about the importance of one-dimensional carbon became of renewed interest. The present article gives an overview of the work that has been carried out on chains of carbon atoms in the past one or two decades. The review concentrates on isolated chains of carbon atoms and summarizes the experimental observations to date. While the experimental information is still very limited, many calculations of the physical and chemical properties have been published in the past years. Some of the most important theoretical studies and their importance in the present experimental situation are reviewed.
Valsecchi, R; Pansera, B; Rossi, A; Cainelli, T
Pigmentation troubles have been associated in the past years with contact dermatitis and patch-testing. Contact allergy and increase of pigmentation has been associated with Tinopal; on the other hand contact allergy and depigmentation have been associated with many substances such as DNCB, squaric acid dibutylester (SADBE), carbyne, alstroemeria. Leukoderma can also be produced by irritant compound such as phenols, catechols and mercaptoamines. During 1978 and 1984 we have treated 132 patients suffering from alopecia areata with DNCB or SADBE: 51 patients have been treated by DNCB and 81 by SADBE. During the treatment 10 patients developed a leukoderma vitiligo-like localized to the areas of topical application of the allergens and to the flare-up site; one patient had an increase of pigmentation. Lesions vitiligo-like appeared 10-15 weeks after the onset of treatment. Among the patients who developed leukoderma, 4 had a personal history of vitiligo. The possible pathogenetic mechanisms are discussed.
Zhu, Congqing; Yang, Yuhui; Luo, Ming; Yang, Caixia; Wu, Jingjing; Chen, Lina; Liu, Gang; Wen, Tingbin; Zhu, Jun; Xia, Haiping
Antiaromatic species are substantially less thermodynamically stable than aromatic moieties. Herein, we report the stabilization of two classical antiaromatic frameworks, cyclobutadiene and pentalene, by introducing one metal fragment through the first [2+2] cycloaddition reaction of a late-transition-metal carbyne with alkynes. Experimental observations and theoretical calculations reveal that the metal fragment decreases the antiaromaticity in cyclobutadiene and pentalene simultaneously, leading to air- and moisture-stable products. These molecules show broad absorption from the UV to the near-IR region, resulting in photoacoustic and photothermal effects for metalla-aromatic compounds for the first time. These results will encourage further efforts into the exploration of organometallic compounds for photoacoustic-imaging-guided photothermal therapy.
Basharin, A. Yu.; Dozhdikov, V. S.; Dubinchuk, V. T.; Kirillin, A. V.; Lysenko, I. Yu.; Turchaninov, M. A.
Pulsed laser action upon a sample of highly oriented pyrolytic graphite (HOPG) in a gasostat filled with helium at a pressure above that corresponding to the triple point of carbon, followed by rapid quenching of the liquid phase at a rate of about 106 K/s leads to the formation of a crater with a periodic spatial structure at the surface. The composition and structure of nongraphite carbon phases in the near-surface region of the crater have been studied using the Raman scattering spectroscopy, electron microdiffraction, and energy-dispersive X-ray analysis. It is established that rapidly quenched carbon possesses predominantly a hybrid structure of glassy carbon formed as a result of the high-temperature treatment, with inclusions of crystalline carbyne, chaoite, and a hybrid cubic phase of ultradense carbon (C8). The hybrid phases of glassy carbon and C8 had not been reported until now as possible products of solidification of liquid carbon.
[WMe6] (1) supported on the surface of SiO2-Al2O3(500) (2) has been extensively characterized by solid-state NMR spectroscopy, elemental analysis, and gas quantification, which clearly reveal the formation of a mixture of monopodal and bipodal species with the migration of methyl from W to Al. The supported species SiO2-Al2O3(500) (2) transformed at 120°C into two types of carbynic centers, one of which is cationic and the other neutral. These species are very efficient for the metathesis of n-decane. Comparison with already-synthesized neutral bipodal tungsten indicates that the high increase in activity is due to the cationic character of the grafted tungsten.
Casillas García, Gilberto; Zhang, Weijia; José-Yacamán, Miguel
Carbyne is a linear allotrope of carbon. It is formed by a linear arrangement of carbon atoms with sp-hybridization. We present a reliable and reproducible experiment to obtain these carbon atomic chains using few-layer-graphene (FLG) sheets and a HRTEM. First the FLG sheets were synthesized from worm-like exfoliated graphite and then drop-casted on a lacey-carbon copper grid. Once in the TEM, two holes are opened near each other in a FLG sheet by focusing the electron beam into a small spot. Due to the radiation, the carbon atoms rearrange themselves between the two holes and form carbon fibers. The beam is concentrated on the carbon fibers in order excite the atoms and induce a tension until multi wall carbon nanotube (MWCNT) is formed. As the radiation continues the MWCNT breaks down until there is only a single wall carbon nanotube (SWCNT). Then, when the SWCNT breaks, an atomic carbon chain is formed, lasts for several seconds under the radiation and finally breaks. This demonstrates the stability of this carbon structure.
The study results on highly functional carbon related materials are reported as a part of the leading research in fiscal 1996. Synthesis of these novel materials is outlined, and R & D results on the following materials are described: diamond, hetero-diamond, graphite, amorphous carbon, carbyne, fullerences, carbon nitride and chemically modified carbon materials. Their issues, future possibility and market in 2010 are also described. The markets are predicted of such electronic materials as electronic emitter, sensor, solid device and heat sink, such optical materials as X-ray lithography, and such chemical materials as electrode and catalyst. Promising characteristics of light-weight and high-hardness machine materials are presented, and some issues such as material synthesis, and intensive machining and application technologies are described. The future markets are predicted of their applications to tools, dies, information equipment, glass, automobiles, aircraft, spacecraft and industrial machines. Problems and their break through techniques of these novel materials are also presented. 220 refs., 68 figs., 16 tabs.
Koo, Jahyun; Bae, Hyeonhu; Kang, Lei; Huang, Bing; Lee, Hoonkyung
The development of advanced materials for CO2 capture is of great importance for mitigating climate change. In this paper, we outline our discovery that calcium-decorated carbon nanostructures, i.e., zigzag graphene nanoribbons (ZGNRs), carbyne, and graphyne, have great potential for selective CO2 capture, as demonstrated via first-principles calculations. Our findings show that Ca-decorated ZGNRs can bind up to three CO2 molecules at each Ca atom site with an adsorption energy of ∼-0.8 eV per CO2, making them suitable for reversible CO2 capture. They adsorb CO2 molecules preferentially, compared with other gas molecules such as H2, N2, and CH4. Moreover, based on equilibrium thermodynamical simulations, we confirm that Ca-decorated ZGNRs can capture CO2 selectively from a gas mixture with a capacity of ∼4.5 mmol g(-1) under ambient conditions. Similar results have been found in other carbon nanomaterials, indicating the generality of carbon based nanostructures for selective CO2 capture under ambient conditions.
LICHTENBERGER, DENNIS L.
This research program is directed at obtaining detailed experimental information on the electronic interactions between metals and organic molecules. These interactions provide low energy pathways for many important chemical and catalytic processes. A major feature of the program is the continued development and application of our special high-resolution valence photoelectron spectroscopy (UPS), and high-precision X-ray core photoelectron spectroscopy (XPS) instrumentation for study of organometallic molecules in the gas phase. The study involves a systematic approach towards understanding the interactions and activation of bound carbonyls, C-H bonds, methylenes, vinylidenes, acetylides, alkenes, alkynes, carbenes, carbynes, alkylidenes, alkylidynes, and others with various monometal, dimetal, and cluster metal species. Supporting ligands include -aryls, alkoxides, oxides, and phosphines. We are expanding our studies of both early and late transition metal species and electron-rich and electron-poor environments in order to more completely understand the electronic factors that serve to stabilize particular organic fragments and intermediates on metals. Additional new directions for this program are being taken in ultra-high vacuum surface UPS, XPS, scanning tunneling microscopy (STM) and atomic force microscopy (AFM) experiments on both physisorbed and chemisorbed organometallic thin films. The combination of these methods provides additional electronic structure information on surface-molecule and molecule-molecule interactions. A very important general result emerging from this program is the identification of a close relationship between the ionization energies of the species and the thermodynamics of the chemical and catalytic reactions of these systems.
Bolaño, Tamara; Castarlenas, Ricardo; Esteruelas, Miguel A; Oñate, Enrique
Treatment in acetonitrile at -30 C of the hydride-alkenylcarbyne complex [OsH([triple bond]CCH=CPh2)(CH3CN)2(P(i)Pr3)2][BF4]2 (1) with (t)BuOK produces the selective deprotonation of the alkenyl substituent of the carbyne and the formation of the bis-solvento hydride-allenylidene derivative [OsH(=C=C=CPh2)(CH3CN)2(P(i)Pr3)2]BF4 (2), which under carbon monoxide atmosphere is converted into [Os(CH=C=CPh2)(CO)(CH3CN)2(P(i)Pr3)2]BF4 (3). When the treatment of 1 with (t)BuOK is carried out in dichloromethane at room temperature, the fluoro-alkenylcarbyne [OsHF([triple bond]CCH=CPh2)(CH3CN)(P(i)Pr3)2]BF4 (4) is isolated. Complex 2 reacts with terminal alkynes. The reactions with phenylacetylene and cyclohexylacetylene afford [Os[(E)-CH=CHR](=C=C=CPh2)(CH3CN)2(P(i)Pr3)2]BF4 (R = Ph (5), Cy (6)), containing an alkenyl ligand beside the allenylidene, while the reaction with acetylene in dichloromethane at -20 degrees C gives the hydride-allenylidene-pi-alkyne [OsH(=C=C=CPh2)(eta2-HC[triple bond]CH)(P(i)Pr3)2]BF4 (7), with the alkyne acting as a four-electron donor ligand. In acetonitrile under reflux, complexes 5 and 6 are transformed into the osmacyclopentapyrrole compounds [Os[C=C(CPh2CR=CH)CMe=NH](CH3CN)2]BF4 (R = Ph (8), Cy (9)), as a result of the assembly of the allenylidene ligand, the alkenyl group, and an acetonitrile molecule. The X-ray structures of 2, 5, and 8 are also reported.
Eid, Ahmed A.
Catalysis, which is primarily a molecular phenomenon, is an important field of chemistry because it requires the chemical conversion of molecules into other molecules. It also has an effect on many fields, including, but not limited to, industry, environment and life Science. Surface Organometallic Chemistry is an effective methodology for Catalysis as it imports the concept and mechanism of organometallic chemistry, to surface science and heterogeneous catalysis. So, it bridges the gap between homogenous and heterogeneous catalysis. The aim of the present research work is to study the effect of Nitrogen surface ligands on the activity of Alkane, Propane in particular, metathesis. Our approach is based on the preparation of selectively well-defined group (VI) transition metal complexes supported onto mesoporous materials, SBA15 and bearing amido and/or imido ligands. We choose nitrogen ligands because, according to the literature, they showed in some cases better catalytic properties in homogenous catalysis in comparison with their oxygen counterparts. The first section covers the modification of a highly dehydroxylated SBA15 surface using a controlled ammonia treatment. These will result in the preparation of two kind of Nitrogen surface ligands: -\\tOne with vicinal silylamine/silanol, (≡SiNH2)(≡SiOH), noted [N,O]SBA15 and, -\\tAnother\\tone\\twith\\tvicinal\\tbis-silylamine moieties (≡SiNH2)2, noted [N,N]SBA15. The second section covers the reaction of Schrock type Tungsten Carbyne [W(≡C- tBu)(CH2-tBu)3] with those N-surface ligands and their characterizations by FT-IR, multiple quantum solid state NMR (1H, 13C), elemental analysis and gas phase analysis. The third section covers the generation of the active site, tungsten hydride species. Their performance toward propane metathesis reaction using the dynamic reactor technique PID compared toward previous well-known catalysts supported on silica oxide or mesoporous materials. A fairly good
Verchovsky, A. B.; Russell, S. S.; Pillinger, C. T.; Fisenko, A. V.; Shukolyukov, Yu. A.
contain a carbon phase combusting at 600-800 degrees C with delta^13C in the range from -20o/oo to +20o/oo. The abundance of the phase is relatively low (~1000 ppm in the residue) though noble gas concentrations in this minor phase are higher than for those in Cdelta. A high resolution TEM investigation of separates from Murchison has demonstrated (Gilkes et al., 1992) the presence of minor components other than diamond including carbynes, which could be regarded as candidates for the carrier of H-Cdelta Xe. With a better knowledge of the carbon abundance and delta^13C characteristics of the potential carrier of H-Cdelta Xe we have reconsidered data both published and unpublished for diamond-rich samples produced in our laboratory and have selected a number of candidate residues that may help in its characterisation. In particular, samples isolated from Allende and Krymka seem most promising. A diamond-rich separate from Krymka (Fisenko et al., 1992) indeed contains the carbon phase combusting at 600-800 degrees C with delta^13C ~ +10o/oo in particularly high abundance. Noble gas data for the candidate samples are being acquired. References: Fisenko A.V., Russell S.S., Ash R.D., Semjonova L.F., Verchovsky A.B. and Pillinger C.T. (1992) Lunar Planet. Sci. (abstract) 23, 365; Gilkes K.W.R., Gaskell P.H., Pillinger C.T., Russell S.S. and Arden J.W. (1992) Meteoritics, this volume; Lewis R.S. and Anders E. (1988) Lunar Planet. Sci. (abstract) 19, 679; Nichols R.H. Jr., Hohenberg C.M., Alexander C.M.O'D., Olinger C.T. and Arden J.W. (1991) Geochim. Cosmochim. Acta 55, 2921; Verchovsky A.B., Ott U., Russell S.S. and Pillinger C.T. (1992) Meteoritics 26, 402.