Carbon nanotubes catalysis in liquid-phase aerobic oxidation of hydrocarbons: Influence of nanotube impurities

Eldar Zeynalov, Norman S. Allen, Nazilya Salmanova, Vladimir Vishnyakov

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Pure carbon nanotubes (CNTs) have a high electron affinity and as such are able to actively absorb free radicals. This functional feature of CNTs leads to a linear chain breakage with the formation of inert spin adducts and effective inhibition of the oxidation process. However, there is a clear contradiction in this issue in the literature with the analysis of research results indicating that CNTs exhibit antioxidant activity mainly in polymeric materials, under conditions of diffusional restrictions for oxygen access. While, in the liquid-phase oxidation of hydrocarbons by CNTs (CNTs synthesised by the thermal catalytic pyrolysis of carbon-containing raw materials (CVD-process)), the CNTs enhance catalytic processes. In this study the aerobic liquid phase oxidation of cumene and initiated (by azobisisobutyronitrile) at low-temperature (333 K) in the presence of multi-walled carbon nanotubes (MWCNTs) obtained by thermal catalytic pyrolysis of cyclohexane (catalyst-ferrocene) has been undertaken. Kinetic analysis establishes that the catalysis of the oxidation process is associated with the presence of metal compounds in the structure of the MWCNTs. These metals are residues of metal catalysts remaining in the synthesis and in the process of pyrolysis. The metals are converted, as a rule, into metal carbides and are not easily removable by treatment with mineral acids. Thus, in the presence of metals in the composition of MWCNTs, interfering parallel reactions are observed with two processes running in parallel — MWCNTs + R• (RO2 •) → •MWCNTs-R (RO2) and ROOH + M @ MWCNTs → RO• radicals (RO2•). The branching of the chain processes involving hydroperoxides suppresses the route of attachment of alkyl and peroxide radicals to the carbon cage structure of the nanotubes and the reaction proceeds in an autocatalytic mode. Contradictory conclusions regarding the effect of CNTs on the chain processes in the oxidation of organic substances (hydrocarbons, polymers) that exist in the literature are attributed to the lack of control over the presence and nature of the metal containing impurities in the CNTs.

LanguageEnglish
Pages245-251
Number of pages7
JournalJournal of Physics and Chemistry of Solids
Volume127
Early online date26 Dec 2018
DOIs
Publication statusPublished - 1 Apr 2019

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Carbon Nanotubes
Hydrocarbons
Nanotubes
Catalysis
catalysis
Carbon nanotubes
nanotubes
liquid phases
hydrocarbons
carbon nanotubes
Impurities
impurities
Oxidation
oxidation
Liquids
Metals
metals
pyrolysis
Pyrolysis
Carbon

Cite this

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title = "Carbon nanotubes catalysis in liquid-phase aerobic oxidation of hydrocarbons: Influence of nanotube impurities",
abstract = "Pure carbon nanotubes (CNTs) have a high electron affinity and as such are able to actively absorb free radicals. This functional feature of CNTs leads to a linear chain breakage with the formation of inert spin adducts and effective inhibition of the oxidation process. However, there is a clear contradiction in this issue in the literature with the analysis of research results indicating that CNTs exhibit antioxidant activity mainly in polymeric materials, under conditions of diffusional restrictions for oxygen access. While, in the liquid-phase oxidation of hydrocarbons by CNTs (CNTs synthesised by the thermal catalytic pyrolysis of carbon-containing raw materials (CVD-process)), the CNTs enhance catalytic processes. In this study the aerobic liquid phase oxidation of cumene and initiated (by azobisisobutyronitrile) at low-temperature (333 K) in the presence of multi-walled carbon nanotubes (MWCNTs) obtained by thermal catalytic pyrolysis of cyclohexane (catalyst-ferrocene) has been undertaken. Kinetic analysis establishes that the catalysis of the oxidation process is associated with the presence of metal compounds in the structure of the MWCNTs. These metals are residues of metal catalysts remaining in the synthesis and in the process of pyrolysis. The metals are converted, as a rule, into metal carbides and are not easily removable by treatment with mineral acids. Thus, in the presence of metals in the composition of MWCNTs, interfering parallel reactions are observed with two processes running in parallel — MWCNTs + R• (RO2 •) → •MWCNTs-R (RO2) and ROOH + M @ MWCNTs → RO• radicals (RO2•). The branching of the chain processes involving hydroperoxides suppresses the route of attachment of alkyl and peroxide radicals to the carbon cage structure of the nanotubes and the reaction proceeds in an autocatalytic mode. Contradictory conclusions regarding the effect of CNTs on the chain processes in the oxidation of organic substances (hydrocarbons, polymers) that exist in the literature are attributed to the lack of control over the presence and nature of the metal containing impurities in the CNTs.",
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Carbon nanotubes catalysis in liquid-phase aerobic oxidation of hydrocarbons : Influence of nanotube impurities. / Zeynalov, Eldar; Allen, Norman S.; Salmanova, Nazilya; Vishnyakov, Vladimir.

In: Journal of Physics and Chemistry of Solids, Vol. 127, 01.04.2019, p. 245-251.

Research output: Contribution to journalArticle

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T1 - Carbon nanotubes catalysis in liquid-phase aerobic oxidation of hydrocarbons

T2 - Journal of Physics and Chemistry of Solids

AU - Zeynalov, Eldar

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AU - Salmanova, Nazilya

AU - Vishnyakov, Vladimir

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N2 - Pure carbon nanotubes (CNTs) have a high electron affinity and as such are able to actively absorb free radicals. This functional feature of CNTs leads to a linear chain breakage with the formation of inert spin adducts and effective inhibition of the oxidation process. However, there is a clear contradiction in this issue in the literature with the analysis of research results indicating that CNTs exhibit antioxidant activity mainly in polymeric materials, under conditions of diffusional restrictions for oxygen access. While, in the liquid-phase oxidation of hydrocarbons by CNTs (CNTs synthesised by the thermal catalytic pyrolysis of carbon-containing raw materials (CVD-process)), the CNTs enhance catalytic processes. In this study the aerobic liquid phase oxidation of cumene and initiated (by azobisisobutyronitrile) at low-temperature (333 K) in the presence of multi-walled carbon nanotubes (MWCNTs) obtained by thermal catalytic pyrolysis of cyclohexane (catalyst-ferrocene) has been undertaken. Kinetic analysis establishes that the catalysis of the oxidation process is associated with the presence of metal compounds in the structure of the MWCNTs. These metals are residues of metal catalysts remaining in the synthesis and in the process of pyrolysis. The metals are converted, as a rule, into metal carbides and are not easily removable by treatment with mineral acids. Thus, in the presence of metals in the composition of MWCNTs, interfering parallel reactions are observed with two processes running in parallel — MWCNTs + R• (RO2 •) → •MWCNTs-R (RO2) and ROOH + M @ MWCNTs → RO• radicals (RO2•). The branching of the chain processes involving hydroperoxides suppresses the route of attachment of alkyl and peroxide radicals to the carbon cage structure of the nanotubes and the reaction proceeds in an autocatalytic mode. Contradictory conclusions regarding the effect of CNTs on the chain processes in the oxidation of organic substances (hydrocarbons, polymers) that exist in the literature are attributed to the lack of control over the presence and nature of the metal containing impurities in the CNTs.

AB - Pure carbon nanotubes (CNTs) have a high electron affinity and as such are able to actively absorb free radicals. This functional feature of CNTs leads to a linear chain breakage with the formation of inert spin adducts and effective inhibition of the oxidation process. However, there is a clear contradiction in this issue in the literature with the analysis of research results indicating that CNTs exhibit antioxidant activity mainly in polymeric materials, under conditions of diffusional restrictions for oxygen access. While, in the liquid-phase oxidation of hydrocarbons by CNTs (CNTs synthesised by the thermal catalytic pyrolysis of carbon-containing raw materials (CVD-process)), the CNTs enhance catalytic processes. In this study the aerobic liquid phase oxidation of cumene and initiated (by azobisisobutyronitrile) at low-temperature (333 K) in the presence of multi-walled carbon nanotubes (MWCNTs) obtained by thermal catalytic pyrolysis of cyclohexane (catalyst-ferrocene) has been undertaken. Kinetic analysis establishes that the catalysis of the oxidation process is associated with the presence of metal compounds in the structure of the MWCNTs. These metals are residues of metal catalysts remaining in the synthesis and in the process of pyrolysis. The metals are converted, as a rule, into metal carbides and are not easily removable by treatment with mineral acids. Thus, in the presence of metals in the composition of MWCNTs, interfering parallel reactions are observed with two processes running in parallel — MWCNTs + R• (RO2 •) → •MWCNTs-R (RO2) and ROOH + M @ MWCNTs → RO• radicals (RO2•). The branching of the chain processes involving hydroperoxides suppresses the route of attachment of alkyl and peroxide radicals to the carbon cage structure of the nanotubes and the reaction proceeds in an autocatalytic mode. Contradictory conclusions regarding the effect of CNTs on the chain processes in the oxidation of organic substances (hydrocarbons, polymers) that exist in the literature are attributed to the lack of control over the presence and nature of the metal containing impurities in the CNTs.

KW - Aerobic oxidation of hydrocarbons

KW - Carbon nanotubes

KW - Catalysis

KW - Chain branching

KW - CVD process

KW - Electron affinity

KW - Line breakage

KW - Oxidation inhibition

KW - Oxygen absorption

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