scholarly journals Mechanisms of Carbon Nanotubes and Graphene Growth: Kinetics versus Thermodynamics

2020 ◽  
Vol 6 (4) ◽  
pp. 67 ◽  
Author(s):  
Luís Sousa Lobo ◽  
Sónia A. C. Carabineiro
Keyword(s):  
Carbon Nanotubes ◽  
Steady State ◽  
Noble Metals ◽  
Bulk Diffusion ◽  
Catalyst Particle ◽  
Kinetic Studies ◽  
Covalent Radius ◽  
Operating Mechanism ◽  
The Operating Mechanism ◽  
Evidenced Based

Thermodynamics must be favorable for the growth of carbon nanotubes (CNTs) and graphene to take place, but a kinetic study is required to find the operating mechanism. In fact, thermodynamics indicates whether a reaction is possible; however, the route prevailing is not necessarily the most thermodynamically favorable, but the fastest one. Detailed kinetic studies state that there are three alternative routes operating under different temperature and pressure rates. The modes and rates of diffusion of carbon (C) atoms and noble metals have been known since the 1930s, but proof of C bulk diffusion operating in CNT growth came from detailed kinetic studies performed in the early 1970s, when reversible versus irreversible C formation was discussed with examples. The reason for interstitial C bulk diffusion in transition metals is evidenced based on the values of covalent radius. The reason for operating under steady-state conditions (linearity of the weight versus time) when searching for the operating mechanism is discussed herein. The steady-state C formation process operates sometimes with two different solid phases at each side of the catalyst particle (e.g., Ni and Ni3C), with thicknesses proportional to 1/D of the respective C bulk diffusivities when the carbon bulk diffusion step is the rate-determining one.

Insights into the phenomenon of ‘bubble-free’ electrocatalytic oxygen evolution from water

2021 ◽  
Author(s):  
George Tsekouras ◽  
Richard Terrett ◽  
Zheyin Yu ◽  
Zhenxiang Cheng ◽  
Gerhard F. Swiegers ◽  
...  
Keyword(s):  
Water Splitting ◽  
Oxygen Evolution ◽  
Operating Mechanism ◽  
Evolved Gas ◽  
The Operating Mechanism

Understanding of the operating mechanism of a ‘breathable’ water-splitting electrode, which extracts evolved gas without forming bubbles, is advanced.

In Situ Observation of Nucleation and Growth of Carbon Nanotubes from Iron Carbide Nanoparticles

2008 ◽  
Vol 1142 ◽  
Author(s):  
Hideto Yoshida ◽  
Seiji Takeda ◽  
Tetsuya Uchiyama ◽  
Hideo Kohno ◽  
Yoshikazu Homma
Keyword(s):  
Carbon Nanotubes ◽  
Iron Carbide ◽  
Bulk Diffusion ◽  
Chemical Vapor ◽  
Nucleation And Growth ◽  
Atomic Scale ◽  
In Situ Observation ◽  
Transmission Electron ◽  
Cvd Growth

ABSTRACTNucleation and growth processes of carbon nanotubes (CNTs) in iron catalyzed chemical vapor deposition (CVD) have been observed by means of in-situ environmental transmission electron microscopy. Our atomic scale observations demonstrate that solid state iron carbide (Fe3C) nanoparticles act as catalyst for the CVD growth of CNTs. Iron carbide nanoparticles are structurally fluctuated in CVD condition. Growth of CNTs can be simply explained by bulk diffusion of carbon atoms since nanoparticles are carbide.

α-Retaining glucosyl transfer catalysed by trehalose phosphorylase from Schizophyllum commune: mechanistic evidence obtained from steady-state kinetic studies with substrate analogues and inhibitors

2001 ◽  
Vol 360 (3) ◽  
pp. 727-736 ◽  
Author(s):  
Bernd NIDETZKY ◽  
Christian EIS
Keyword(s):  
Steady State ◽  
Transition State ◽  
Schizophyllum Commune ◽  
Catalytic Efficiency ◽  
Kinetic Studies ◽  
Competitive Inhibitor ◽  
Chemical Mechanism ◽  
Steady State Kinetic ◽  
State Kinetic ◽  
Trehalose Phosphorylase

Fungal trehalose phosphorylase is classified as a family 4 glucosyltransferase that catalyses the reversible phosphorolysis of α,α-trehalose with net retention of anomeric configuration. Glucosyl transfer to and from phosphate takes place by the partly rate-limiting interconversion of ternary enzyme–substrate complexes formed from binary enzyme–phosphate and enzyme–α-d-glucopyranosyl phosphate adducts respectively. To advance a model of the chemical mechanism of trehalose phosphorylase, we performed a steady-state kinetic study with the purified enzyme from the basidiomycete fungus Schizophyllum commune by using alternative substrates, inhibitors and combinations thereof in pairs as specific probes of substrate-binding recognition and transition-state structure. Orthovanadate is a competitive inhibitor against phosphate and α-d-glucopyranosyl phosphate, and binds 3×104-fold tighter (Ki≈ 1μM) than phosphate. Structural alterations of d-glucose at C-2 and O-5 are tolerated by the enzyme at subsite +1. They lead to parallel effects of approximately the same magnitude (slope = 1.14; r2 = 0.98) on the reciprocal catalytic efficiency for reverse glucosyl transfer [log (Km/kcat)] and the apparent affinity of orthovanadate determined in the presence of the respective glucosyl acceptor (log Ki). An adduct of orthovanadate and the nucleophile/leaving group bound at subsite +1 is therefore the true inhibitor and displays partial transition state analogy. Isofagomine binds to subsite −1 in the enzyme–phosphate complex with a dissociation constant of 56μM and inhibits trehalose phosphorylase at least 20-fold better than 1-deoxynojirimycin. The specificity of the reversible azasugars inhibitors would be explained if a positive charge developed on C-1 rather than O-5 in the proposed glucosyl cation-like transition state of the reaction. The results are discussed in the context of α-retaining glucosyltransferase mechanisms that occur with and without a β-glucosyl enzyme intermediate.

Ni/CNT/Zeolite-Y composite catalyst for efficient heptane hydrocracking: Steady-state and transient kinetic studies

2021 ◽  
pp. 118437
Author(s):  
Roba Saab ◽  
Constantinos. M. Damaskinos ◽  
Kyriaki Polychronopoulou ◽  
Angelos M. Efstathiou ◽  
Nikolaos Charisiou ◽  
...  
Keyword(s):  
Steady State ◽  
Zeolite Y ◽  
Kinetic Studies ◽  
Composite Catalyst

Temperature profiles in endothermic and exothermic reactions and the interpretation of experimental rate data

1970 ◽  
Vol 320 (1540) ◽  
pp. 71-100 ◽  
Keyword(s):  
Steady State ◽  
Correction Factor ◽  
Exothermic Reaction ◽  
Kinetic Studies ◽  
Activation Energies ◽  
Uniform Temperature ◽  
Exothermic Reactions ◽  
Arrhenius Function ◽  
Point To Point ◽  
Reacting Systems

Any endothermic or exothermic reaction is accompanied by self-cooling or self-heating. In reacting systems in which heat transfer is controlled by conduction, non-uniform temperature-position profiles are established. Examples of this situation are the exothermic decomposition of gaseous diethyl peroxide and the endothermic decomposition of nitrosyl chloride at low pressures (when convection is unimportant). In kinetic studies, allowance must be made for the non-uniform temperature to derive accurate isothermal velocity constants and Arrhenius parameters. In the present paper, the necessary corrections have been derived for a reactant in the steady state whose reaction rate varies exponentially with temperature and in which the temperature excess varies from point to point, being zero at the boundary (Frank-Kamenetskii’s conditions). The geometries considered are the slab, cylinder and sphere. The temperature gradient at the surface in the steady state ( Г ) occupies a key position, and this is exploited to find the correction factor required to convert 'observed’ rate constants to isothermal conditions, and thence to correct ‘observed’ activation energies and pre-exponential factors. The correction factor is found to be simply related to Frank- Kamenetskii’s δ (a dimensionless measure of heat-release rate). A similar analysis is given for systems hotter or cooler than their surroundings but uniform in temperature—such as well stirred fluid systems or small solid crystals (Semenov’s conditions). In these circumstances, systems of arbitrary geometry may be studied, and no approximation need be made to the Arrhenius function. For either type of boundary condition, uncorrected activation energies are overestimates in exothermic reactions and underestimates in endothermic reactions. Explicit relations are derived for making corrections. Boundary conditions intermediate between the two extremes investigated can also be treated though the resulting expressions are more cumbersome. In an appendix, an alternative ‘experimental’ approach is made to the elimination of errors from measured reaction velocities. This approach identifies the measured velocities with a temperature intermediate between those at centre and surface. The optimum choice, which weights the central and surface temperatures in the ratios 2:1 (slab), 1:1 (cylinder) and 2:3 (sphere), gives exactly correct results for the cylinder and acceptable precision for the slab and sphere even to within 5 K of the explosion limit. Other correction methods are also discussed.

scholarly journals Nanostructures and their application in antimicrobial drug delivery system

2017 ◽  
Vol 4 (1-4) ◽  
pp. 81-90
Keyword(s):  
Carbon Nanotubes ◽  
Noble Metals ◽  
Antimicrobial Properties ◽  
High Reactivity ◽  
Great Promise ◽  
Antimicrobial Drugs ◽  
Microbial Inhibition ◽  
Carbon Based Nanomaterials ◽  
Walled Carbon Nanotubes

As multiresistant and pan-resistant infections continue to emerge, and because the development of novel antimicrobial drugs is a slow process, nanotechnology offers valuable alternatives for fighting resistant bugs, mainly by improving the therapeutic effect of current antimicrobials. Antibiotic resistance is one of the greatest global health threats of the 21st century, but nanotechnology is offering new solutions to the problem. Nanostructured biomaterials, nanoparticles in particular, have unique physicochemical properties such as ultra small and controllable size, large surface area to mass ratio, high reactivity, and functionalizable structure. These properties can be applied to facilitate the administration of antimicrobial drugs, thereby overcoming some of the limitations in traditional antimicrobial therapeutics. Carbon-based nanomaterials such as fullerenes, carbon nanotubes (CNTs) (especially single-walled carbon nanotubes (SWCNTs)) and graphene oxide (GO) nanoparticles) show potent antimicrobial properties. Nanocoating and shuttle systems have shown great promise in vitro and animal models. Noble metals nanostructures, particularly silver, have attracted much attention in the fields of medicine due to their unique properties which are strongly dependent on the size and shape of metal nanomaterials. Recent development of nanocarriers, improved the drug therapy of different diseases, together with the mechanisms of microbial inhibition.

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