Role of surface functional groups in the adsorption kinetics of water vapor on microporous activated carbons

Ashleigh J. Fletcher, Yaprak Uygur, K. Mark Thomas

Research output: Contribution to journalArticle

80 Citations (Scopus)

Abstract

Activated carbons have both hydrophilic surface oxygen functional groups, which act as primary adsorption centers for water vapor, and hydrophobic graphene layers on which nonpolar species are primarily adsorbed. The aim of this research was to investigate the effects of oxygen surface functional groups, in activated carbons, on the adsorption characteristics of water vapor. Activated carbon G was oxidized using nitric acid and then heat treated in the range 387-894 K to produce a suite of adsorbents with varying oxygen contents in the range 0.4-21.5 wt % daf, but very similar porous structure characteristics, thereby minimizing effects due to changes in porous structure. The type and concentration of surface oxygen groups present in each sample were assessed using TPD, FTIR, Boehm titration, and analytical methods. Water vapor adsorption at low relative pressure was dramatically enhanced by the presence of functional groups, in particular, carboxylic groups. Kinetic profiles for each pressure increment were modeled using a set of nested kinetic models, which allow the adsorption kinetics to be analyzed in relation to the adsorption mechanism. Relationships between water adsorption kinetics at low surface coverage and the type and concentration of oxygen surface functional groups were observed. A two component double exponential kinetic model was used when carboxylic groups were present in significant amounts with a slow kinetic component associated with adsorption on these groups. In the case of carbons where carboxylic groups were only present in, at most, relatively small amounts, a stretched exponential kinetic model was used and the rate constants in the low-pressure region decreased linearly with increasing Henry's Law constant and oxygen content. The results indicate the importance of adsorbate-adsorbent interactions in water adsorption kinetics and are consistent with a site-to-site hopping mechanism between functional groups.
LanguageEnglish
Pages8349-8359
Number of pages10
JournalJournal of Physical Chemistry C
Volume111
Issue number23
DOIs
Publication statusPublished - 23 May 2007

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Steam
activated carbon
Activated carbon
Water vapor
Functional groups
water vapor
Adsorption
Kinetics
adsorption
kinetics
Oxygen
oxygen
Adsorbents
adsorbents
Nitric Acid
Graphite
Water
Adsorbates
Temperature programmed desorption
Nitric acid

Keywords

  • adsorption
  • kinetics
  • water vapor
  • microporous
  • carbons

Cite this

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abstract = "Activated carbons have both hydrophilic surface oxygen functional groups, which act as primary adsorption centers for water vapor, and hydrophobic graphene layers on which nonpolar species are primarily adsorbed. The aim of this research was to investigate the effects of oxygen surface functional groups, in activated carbons, on the adsorption characteristics of water vapor. Activated carbon G was oxidized using nitric acid and then heat treated in the range 387-894 K to produce a suite of adsorbents with varying oxygen contents in the range 0.4-21.5 wt {\%} daf, but very similar porous structure characteristics, thereby minimizing effects due to changes in porous structure. The type and concentration of surface oxygen groups present in each sample were assessed using TPD, FTIR, Boehm titration, and analytical methods. Water vapor adsorption at low relative pressure was dramatically enhanced by the presence of functional groups, in particular, carboxylic groups. Kinetic profiles for each pressure increment were modeled using a set of nested kinetic models, which allow the adsorption kinetics to be analyzed in relation to the adsorption mechanism. Relationships between water adsorption kinetics at low surface coverage and the type and concentration of oxygen surface functional groups were observed. A two component double exponential kinetic model was used when carboxylic groups were present in significant amounts with a slow kinetic component associated with adsorption on these groups. In the case of carbons where carboxylic groups were only present in, at most, relatively small amounts, a stretched exponential kinetic model was used and the rate constants in the low-pressure region decreased linearly with increasing Henry's Law constant and oxygen content. The results indicate the importance of adsorbate-adsorbent interactions in water adsorption kinetics and are consistent with a site-to-site hopping mechanism between functional groups.",
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Role of surface functional groups in the adsorption kinetics of water vapor on microporous activated carbons. / Fletcher, Ashleigh J.; Uygur, Yaprak; Thomas, K. Mark.

In: Journal of Physical Chemistry C, Vol. 111, No. 23, 23.05.2007, p. 8349-8359.

Research output: Contribution to journalArticle

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AU - Uygur, Yaprak

AU - Thomas, K. Mark

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N2 - Activated carbons have both hydrophilic surface oxygen functional groups, which act as primary adsorption centers for water vapor, and hydrophobic graphene layers on which nonpolar species are primarily adsorbed. The aim of this research was to investigate the effects of oxygen surface functional groups, in activated carbons, on the adsorption characteristics of water vapor. Activated carbon G was oxidized using nitric acid and then heat treated in the range 387-894 K to produce a suite of adsorbents with varying oxygen contents in the range 0.4-21.5 wt % daf, but very similar porous structure characteristics, thereby minimizing effects due to changes in porous structure. The type and concentration of surface oxygen groups present in each sample were assessed using TPD, FTIR, Boehm titration, and analytical methods. Water vapor adsorption at low relative pressure was dramatically enhanced by the presence of functional groups, in particular, carboxylic groups. Kinetic profiles for each pressure increment were modeled using a set of nested kinetic models, which allow the adsorption kinetics to be analyzed in relation to the adsorption mechanism. Relationships between water adsorption kinetics at low surface coverage and the type and concentration of oxygen surface functional groups were observed. A two component double exponential kinetic model was used when carboxylic groups were present in significant amounts with a slow kinetic component associated with adsorption on these groups. In the case of carbons where carboxylic groups were only present in, at most, relatively small amounts, a stretched exponential kinetic model was used and the rate constants in the low-pressure region decreased linearly with increasing Henry's Law constant and oxygen content. The results indicate the importance of adsorbate-adsorbent interactions in water adsorption kinetics and are consistent with a site-to-site hopping mechanism between functional groups.

AB - Activated carbons have both hydrophilic surface oxygen functional groups, which act as primary adsorption centers for water vapor, and hydrophobic graphene layers on which nonpolar species are primarily adsorbed. The aim of this research was to investigate the effects of oxygen surface functional groups, in activated carbons, on the adsorption characteristics of water vapor. Activated carbon G was oxidized using nitric acid and then heat treated in the range 387-894 K to produce a suite of adsorbents with varying oxygen contents in the range 0.4-21.5 wt % daf, but very similar porous structure characteristics, thereby minimizing effects due to changes in porous structure. The type and concentration of surface oxygen groups present in each sample were assessed using TPD, FTIR, Boehm titration, and analytical methods. Water vapor adsorption at low relative pressure was dramatically enhanced by the presence of functional groups, in particular, carboxylic groups. Kinetic profiles for each pressure increment were modeled using a set of nested kinetic models, which allow the adsorption kinetics to be analyzed in relation to the adsorption mechanism. Relationships between water adsorption kinetics at low surface coverage and the type and concentration of oxygen surface functional groups were observed. A two component double exponential kinetic model was used when carboxylic groups were present in significant amounts with a slow kinetic component associated with adsorption on these groups. In the case of carbons where carboxylic groups were only present in, at most, relatively small amounts, a stretched exponential kinetic model was used and the rate constants in the low-pressure region decreased linearly with increasing Henry's Law constant and oxygen content. The results indicate the importance of adsorbate-adsorbent interactions in water adsorption kinetics and are consistent with a site-to-site hopping mechanism between functional groups.

KW - adsorption

KW - kinetics

KW - water vapor

KW - microporous

KW - carbons

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JF - Journal of Physical Chemistry C

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