Oxygen assisted butanol conversion on bifunctional carbon nanotube catalysts: Activity of oxygen functionalities

Li, Fan; Yan, Pengqiang; Herold, Felix; Drochner, Alfons; Wang, Haihua; Cao, Tianlong; Liu, Weijie; Dai, Xueya; Zhang, Bingsen; Etzold, Bastian J. M.; Qi, Wei

doi:10.1016/j.carbon.2020.08.053

Cited by 24 publications

(31 citation statements)

References 59 publications

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“…The main products of the propanol-2 conversion were propene, acetone and ether. The propene yield increased with temperature ( Figure 6 a) because of the different activation energies of two reaction pathways—dehydration and dehydrogenation [ 14 , 54 ].…”

Section: Resultsmentioning

confidence: 99%

“…Primary alcohols are converted at higher temperatures. For example, 100% conversion of n -butanol-1 was observed only at 330 °C and the products were propion and butyr aldehydes, butane and butyl butyrate [ 14 ]. This can be probably explained by the different alcohol polarization and, therefore, different sorption mechanism [ 59 ].…”

Section: Resultsmentioning

confidence: 99%

“…And other molecules on the surface as it was shown in [ 5 , 18 ]. At the same time, onion-like carbon nanoparticles with the same zero dimension and sp 2 -hibridized C atoms are less active and selective in the butalol-1 conversion [ 14 ].…”

Section: Discussionmentioning

confidence: 99%

“…This makes them attractive for application as catalyst supports [ 1 , 2 ]. Even raw (unmodified) CNMs can catalyze several reactions [ 3 , 4 ]: oxidative dehydrogenation of ethylbenzene [ 5 ] and light alkanes [ 6 , 7 , 8 , 9 ], conversion of aliphatic alcohol [ 10 , 11 , 12 , 13 , 14 ] and so forth.…”

Section: Introductionmentioning

confidence: 99%

“…Secondary alcohol conversion is used in industry including fine chemical synthesis and can be considered as a test reaction for basic and/or acidic sites on the surface of carbon materials [ 15 , 16 ]. A wide range of carbon nanomaterials were tested as catalysts including nanodiamonds (NDs) and their oxidized and reduced forms [ 10 , 17 , 18 ], carbon nanofibers [ 12 ], carbon nanotubes (CNTs) with different morphology [ 12 , 13 , 14 ], oxidized CNTs [ 11 , 13 ], carbon nanoflakes (CNFs) and its nitrogen-doped derivatives [ 11 , 18 ], graphene oxide [ 19 ] and activated carbon [ 15 , 16 , 20 , 21 ].…”

Section: Introductionmentioning

confidence: 99%

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Conversion of Secondary C3-C4 Aliphatic Alcohols on Carbon Nanotubes Consolidated by Spark Plasma Sintering

et al. 2021

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We analyze how the changes in the dimension of carbon nanomaterial (CNM) affect their catalytic conversion of secondary aliphatic alcohols. Carbon nanotubes (CNTs) consolidated by spark plasma sintering (SPS) were inactive in the conversion of secondary C3-C4 aliphatic alcohols because of the «healing» of defects in carbon structure during SPS. Gas-phase treatment of consolidated CNTs with HNO3 vapors led to their surface oxidation without destruction of the bulk structure of pellets. The oxygen content in consolidated CNTs determined by X-ray photoelectron spectroscopy increased from 11.3 to 14.9 at. % with increasing the oxidation time from 3 to 6 h. Despite the decrease in the specific surface area, the oxidized samples showed enhanced catalytic activity in alcohol conversion because of the increased number of oxygen radicals with unpaired electrons, which was established by electron paramagnetic resonance spectroscopy. We conclude that the structure of CNM determines the content and/or ratio of sp2 and sp3-hybridized carbon atoms in the material. The experimental and literature data demonstrated that sp3-hybridized carbon atoms on the surface are probably the preferable site for catalytic conversion of alcohols.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Conversion of Secondary C3-C4 Aliphatic Alcohols on Carbon Nanotubes Consolidated by Spark Plasma Sintering

et al. 2021

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Efficient Non‐Precious Metal Catalyst for Propane Dehydrogenation: Atomically Dispersed Cobalt‐nitrogen Compounds on Carbon Nanotubes

et al. 2021

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A hybrid catalyst comprising atomically dispersed cobalt-nitrogen compounds anchoring on oxidized carbon nanotubes (OCNTs) is prepared and applied in propane dehydrogenation (PDH) reactions. The proposed non-precious catalyst exhibits high initial conversion (~20 %) and excellent selectivity of propene (> 95 %), which is superior to those of metal-free nanocarbon and some metal-based catalysts. The chemical composition and structure of the proposed hybrid catalysts are elucidated by a series of characterizations and control experiments with a single component. These characterization results combined with the kinetic analysis indicate that the catalytic activity mainly originates from the cobalt-nitrogen (CoÀ N) species supported on the OCNT surface. The present work sheds light on the structure-function relationships of CoN catalysts, paving the way to develop nonprecious catalysts for PDH reactions.

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The High‐Temperature Acidity Paradox of Oxidized Carbon: An in situ DRIFTS Study

et al. 2022

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Until now, oxygen functionalized carbon materials were not considered to exhibit significant acidity at high temperatures, since carboxylic acids, the most prominent acidic functionality, are prone to decarboxylation at temperatures exceeding 250 °C. Paradoxically, we could show that oxidized carbon materials can act as highly active high-temperature solid acid catalysts in the dehydration of methanol at 300 °C, showing an attractive selectivity to dimethyl ether (DME) of up to 92 % at a conversion of 47 %. Building on a tailor-made carbon model material, we developed a strategy to utilize in situ DRIFT spectroscopy for the analysis of carbon surface species under process conditions, which until now proofed to be highly challenging due to the high intrinsic absorbance of carbon. By correlating the catalytic behavior with a comprehensive in situ DRIFTS study and extensive post mortem analysis we could attribute the hightemperature acidity of oxidized carbons to the interaction of thermally stable carboxylic anhydrides and lactones with nucleophilic constituents of the reaction atmosphere e. g. methanol and H 2 O. Dynamic equilibria of surface oxides depending on reaction atmosphere and temperature were observed, and a methyl ester, formed by methanolysis of anhydrides and lactones, was identified as key intermediate for DME generation on oxidized carbon catalysts.

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Oxygen assisted butanol conversion on bifunctional carbon nanotube catalysts: Activity of oxygen functionalities

Cited by 24 publications

References 59 publications

Conversion of Secondary C3-C4 Aliphatic Alcohols on Carbon Nanotubes Consolidated by Spark Plasma Sintering

Conversion of Secondary C3-C4 Aliphatic Alcohols on Carbon Nanotubes Consolidated by Spark Plasma Sintering

Efficient Non‐Precious Metal Catalyst for Propane Dehydrogenation: Atomically Dispersed Cobalt‐nitrogen Compounds on Carbon Nanotubes

The High‐Temperature Acidity Paradox of Oxidized Carbon: An in situ DRIFTS Study

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