Hydrogen adsorption in the series of carbon nanostructures: Graphenes–graphene nanotubes–nanocrystallites

A comparative analysis of hydrogen absorption capability is performed for the first time for three types of carbon nanostructures: graphenes, oriented carbon nanotubes with graphene walls (OCNTGs), and pyrocarbon nanocrystallites (PCNs) synthesized in the pores of TRUMEM ultrafiltration membranes with mean diameters (D_m) of 50 and 90 nm, using methane as the pyrolized gas. The morphology of the carbon nanostructures is studied by means of powder X-ray diffraction, X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and transmission electron microscopy (TEM). Hydrogen adsorption is investigated via thermogravimetric analysis (TGA) in combination with mass-spectrometry. It is shown that only OCNTGs can adsorb and store hydrogen, the desorption of which under atmospheric pressure occurs at a temperature of around 175°C. Hydrogen adsorption by OCNTGs is quantitatively determined and found to be about 1.5% of their mass. Applying certain assumptions, the relationship between the mass of carbon required for the formation of single-wall OCNTGs in membrane pores and the surface area of pores is established. Numerical factor Ψ = m_dep/m_calc, where m_dep is the actual mass of carbon deposited upon the formation of OCNTGs and mcalc is the calculated mass of carbon necessary for the formation of OCNTGs is introduced. It is found that the dependence of specific hydrogen adsorption on the magnitude of the factor has a maximum at Ψ = 1.2, and OCNTGs can adsorb and store hydrogen in the interval 0.4 to 0.6 < Ψ < 1.5 to 1.7. Possible mechanisms of hydrogen adsorption and its relationship to the structure of carbon nanoformations are examined.     

Qualitatively graph-theoretical study on stability and formation of fullerenes and nanotubes

Kekule structures of different carbon species have been determined. On the basis of Kekule structure and C-C bond counts as well as the surface curvature, stability of diverse carbon species, driving force for curling of graphite fragments and formation of fullerenes and nanotubes, have been discussed. Curling of graphite flat fragments, end-capping of nanotubes, and closure of curved structures are driven by a tremendous increase in Kekule structures as terminal carbon atoms couple their dangling bonds into C-C o bonds. The increasing tendency becomes particularly striking for large cages and nanotubes. Resonance among numerous Kekule structures will stabilize the curved structure and dominate formation of closed carbon species. For similar carbon cages with comparable Kekule structure counts in magnitude, the surface curvature of carbon cages, as a measure for the strain energy, also plays an important role in determining their most stable forms.     

Ni-catalyzed carbon–carbon bonds cleavage of mixed polyolefin plastics waste

The inert carbon–carbon(C–C) bonds cleavage is a main bottleneck in the chemical upcycling of recalcitrant polyolefin plastics waste. Here we develop an efficient strategy to catalyze the complete cleavage of C–C bonds in mixed polyolefin plastics over non-noble metal catalysts under mild conditions. The nickelbased catalyst involving Ni₂Al₃ phase enables the direct transformation of mixed polyolefin plastics into natural gas, and the gas carbon yield reaches up to 89.6%. R...     

Metal-free and selective cleavage of unstrained carbon–carbon single bonds: Synthesis of β-ketosulfones from β-chlorohydrins and sodium sulfinates

A metal-free protocol for the selective cleavage of unstrained C–C single bonds was developed. Under the catalysis of KI and in the presence of NaHCO₃, the readily available α-chloro-β-hydroxy ketones underwent bond breaking and sulfonylation smoothly to afford β-ketosulfones with high efficiency and broad substrate scope. Mechanism investigations, both experimental and theoretical, showed that a retro-aldol cleavage/nucleophilic substitution sequence might be involved.     

Synthesis,structure and thermal properties of propylene oxide–carbon dioxide–L-lactide terpolymers

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Combination self-assembly of β-sheet peptides and carbon nanotubes: functionalizing carbon nanotubes with bioactive β-sheet block copolypeptides

Understanding the self-assembly behavior of β-sheet peptides is important, not only in constructing bioactive peptide nanostructures, but also in inhibiting uncontrollable protein aggregation in protein-misfolding diseases. Here, the first systematic investigation of combination self-assembly between β-sheet block copolypeptides and CNTs is presented, demonstrating the presence of several different association modes during the combination self-assembly process. Bioactive β-sheet block copolypeptides can self-assemble by themselves, or can be used to functionalize CNT hybrids depending on the situation. This behavior may be important both for fabricating bioactive peptide/CNT hybrids and for controlling/inhibiting protein-misfolding diseases.     

Synthesis and properties of zinc–nickel–carbon nanotube composite coatings

Composite electrochemical coatings modified with carbon nanotubes were produced on the basis of the zinc–nickel alloy. The functional properties (friction coefficient, protective capacity) of the composite coatings were studied in comparison with zinc–nickel alloys without a dispersed phase. It was found that, upon inclusion of carbon nanotubes particles into zinc–nickel deposits, their sliding friction coefficient decreases by a factor of 1.3–1.4 and the range of passive-state potentials becomes two times wider.     

Effect of the functionalizing of carbon nanotubes on the electrodeposited catalysts’ structure and catalytic properties

The structure and hydrophilic-hydrophobic properties of functionalized single-wall carbon nanotubes are studied by the standard porosimetry method. It is shown that the functionalized nanotubes have highly hydrophilic surface; at that the summary surface area measured “by octane” decreased, as a result of the functionalizing, due to the blocking of the nanotubes’ inner channels by the functional groups located at the nanotubes’ ends. The nanotubes’ capacitive properties are studied; their charging-discharging curves appeared being highly reversible, unlike those of other carbonaceous materials. Catalytic properties of the functionalized nanotubes are studied, with particular tendency toward their using as a carrier of platinum catalysts for the methanol oxidation and oxygen electroreduction reactions. When minor amounts (5–10 μg cm⁻²) of platinum or platinum-ruthenium alloy are deposited onto the nanotubes’ hydrophilic surface, uniform layer of the catalyst is formed, with specific surface area up to 150–300 m² g⁻¹; high current of the methanol oxidation or oxygen electroreduction is observed at these catalysts. When the catalyst deposit mass increased, its specific surface area decreased, as well as the specific current of the reactions occurring thereon. When the current is related to the electrochemically active unit surface, the catalytic activity is nearly the same both for different catalyst mass deposited onto the nanotubes and the same catalyst mass at different carbonaceous carriers.     

Syntheses,structures and properties of four organic–inorganic hybrid nicotinate-bridging rare-earth-containing phosphotungstates

Four novel organic–inorganic hybrid nicotinate-bridging dimeric rare-earth (RE)-containing phosphotungstates [H₂N(CH₃)₂]₈[RE(H₂O)(NA)(α-HPW₁₁O₃₉)]₂·24H₂O (RE = Ho^III for 1, Er^III for 2, Tb^III for 3, Dy^III for 4; HNA = nicotinic acid) have been synthesized from the reaction of trivacant Keggin precursor Na₉[α-PW₉O₃₄]∙16H₂O, RE(NO₃)₃·6H₂O, HNA by employing dimethylamine hydrochloride as organic solubilizing agent in the conventional aqueous solution system, which have been further characterized by elemental analyses, IR spectra, thermogravimetric analyses and single-crystal X-ray diffraction. Structural analysis indicates that the hybrid dimeric {[RE(H₂O)(NA)(α-HPW₁₁O₃₉)]₂}⁸⁻ polyoxoanion in 1–4 can be considered as two head-to-head mono-RE-containing Keggin [RE(H₂O)(NA)(α-HPW₁₁O₃₉)]⁴⁻ subunits bridged by two (η²,μ-1,1)-nicotinate linkers, which stands for the first organic–inorganic hybrid RE-containing phosphotungstates functionalized by nicotinate ligands. What's more, the solid-state photoluminescence properties and lifetime decay behaviors of 1–4 have been measured at room temperature and their photoluminescence spectra display the characteristic emission bands of corresponding trivalent RE cations.     

Elastic properties and electronic structures of typical Al–Ce structures from first-principles calculations

The elastic property and electronic structure of three typical Al–Ce structures have been studied by means of first-principles calculations within GGA approximation. The optimized structural parameters for these precipitates agree very well with experimental data. The obtained negative cohesive energy and formation enthalpy show that all of these precipitates have strong structural stability. Elastic constants as well as other mechanical parameters such as bulk modulus B, shear modulus G, Young’s modulus E and Poisson’s ratio ν for these phases are computed and discussed. The calculated electronic densities of state and charge distribution show the covalent features of Ce–Ce and Al–Ce bonding in three phases, which reveals the underlying mechanism for the elastic properties of these Al–Ce structures.     

Constructing a hierarchical graphene–carbon nanotube architecture for enhancing exposure of graphene and electrochemical activity of Pt nanoclusters

Stacking of individual graphene sheets (GS) is effectively inhibited by introducing one-dimensional carbon nanotubes to form a 3-D hierarchical structure which enhances the utilization of GS-based composites. From SEM images, CNTs are useful nanospacers for diminishing the face-to-face aggregation of GS. The specific electrochemically active surface area (SECSA) and specific double-layer capacitance (C_S,DL) of Pt/GS–CNTs (127.9 m²/g, 171.3 F/g) is much higher than that of Pt/GS (105.4 m²/g, 104.7 F/g) and Pt/CNTs (51.5 m²/g, 37.1 F/g), revealing the synergistic effects between GS and CNTs on enhancing the electrochemical activity of Pt nanoparticles and electrolyte-accessible surface area.     

Construction of hierarchical porous graphene–carbon nanotubes hybrid with high surface area for high performance supercapacitor applications

Journal of Solid State Electrochemistry - Unlike activated carbon, graphene sheets are lack of ion pathways on their basal planes and prone to agglomerate or restack unfortunately for their strong...     

Electrochemical oxidation behavior of guanosine-5��-monophosphate on a glassy carbon electrode modified with a composite film of graphene and multi-walled carbon nanotubes, and its amperometric determination

The electrochemical oxidation of guanosine-5??-monophosphate (GMP) was studied with a glassy carbon electrode modified with a composite made from graphene and multi-walled carbon nanotubes. GMP undergoes an irreversible oxidation process at an oxidation peak potential of 987?mV in phosphate buffer solution. Compared to other electrodes, the oxidation peak current of GMP with this electrode was significantly increased, and the corresponding oxidation peak potential negatively shifted, thereby indicating that the modified material exhibited electrochemical catalytic activity towards GMP. Chronocoulometry demonstrates that the material also effectively increases the surface area of the electrode and increases the amount of GMP adsorbed. Under the optimum conditions, the oxidation current is proportional to the GMP concentration in the range from 0.1 to 59.7???M with a correlation coefficient of 0.9991. The detection limit is 0.025???M (at S/N?=?3).

A series of 3d–4f heterometallic MOFs: syntheses,structures, optical,and electrochemical properties

Abstract

A series of heterometallic metal-organic frameworks (MOFs) employing pyridine-2,6-dicarboxylate and 1,10-phenanthroline as ligands have been synthesized hydrothermally. In isostructural compounds 1–3 [Ln(pydc)₃Cu₂(phen)₄]·I·× H₂O (Ln?=?La (1), Nd (2), Dy (3); x?=?6, 5, 5), the metalloligand [Ln(pydc)₃] assembles with [Cu(phen)₂] units to construct a dodecanuclear cluster via Cu–O bonds and π–π interactions. The clusters are further stacked into three-dimensional supramolecular frameworks with nano-sized cavities. In [La(Hpydc)(pydc)₂Zn(phen)₃]·3H₂O (4), the metalloligand [Ln(Hpydc)(pydc)₂] assembles with [Zn(phen)₃] units to construct a tetranuclear cluster via electrostatic interaction and π–π interaction. This work reveals that the changes of lanthanide metalloligands and the coordination pattern of 3d transition centers would result in significant variation in the final structures. The thermal, optical, and electrochemical properties have been well investigated.     

Synthesis of a novel gelatin–carbon nanotubes hybrid hydrogel

This letter focuses on the first result the preparation and its swelling behavior of a novel hybrid gelatin hydrogel with carbon nanotubes. A novel hybrid gelatin hydrogel with carbon nanotubes was synthesized by physical mixing method. The structure of the novel hydorgel obtained was characterized by SEM. Besides, the swelling behavior of the hydrogel synthesized was measured at different temperature. The results indicated that carbon nanotubes added could maintain the stability of the hybrid hydrogel at 37 °C. This suggests that the hybrid gelatin hydrogel with carbon nanotubes could be used in biomedical field. Besides, its application in protein concentrating has been discussed.     

Numerical Kekulé structures of fullerenes and partitioning of pi-electrons to pentagonal and hexagonal rings

We calculated the partitioning of pi-electrons within individual pentagonal and hexagonal rings of fullerenes for a collection of fullerenes from C20 to C72 by constructing their Kekulé valence structures and averaging the pi-electron content of individual rings over all Kekulé valence structures. The resulting information is collected in Table 2, which when combined with the Schlegel diagram of fullerenes (illustrated in Figure 7) uniquely characterizes each of the 19 fullerenes considered. The results are interpreted as the basic information on the distributions (variation) of the local (ring) pi-electron density.