Molecular Design of Intercalation-Based Sensors. 2. Sensing of Carbon Dioxide in Functionalized Thin Films of Copper Octanediylbis(phosphonate)

Louis C. Brousseau, David Jeffrey Aurentz, Alan J. Benesi, Thomas E. Mallouk

Research output: Contribution to journalArticle

51 Citations (Scopus)

Abstract

Self-assembled thin films of layered copper alkanediylbis-(phosphonates) retain the amine-specific intercalation chemistry of the corresponding microcrystalline solids. Aliphatic and aromatic amines bind in a 1:1 ratio to coordinatively unsaturated copper ions in anhydrous Cu2(O3P(CH2)8PO3); and by selecting an amine with an appropriate functional tail group, a chemically and sterically well-defined interlamellar binding site for CO2 is created. Powder X-ray diffraction, Fourier transform infrared spectroscopy, and solid-state NMR experiments were used to study the intercalation of 3-aminopropanol, (3-aminopropyl)methyldihydroxysilane, and p-xylylenediamine, and their reversible reaction with CO2 to form carbonates and carbamates, respectively. By growing these films on the electrodes of a quartz crystal microbalance device, a sensor can be fabricated for monitoring CO2 in gas streams at concentrations of 0.5-19% (v/v). A Henrian response (frequency change directly proportional to CO2 partial pressure) was observed, and the time required for equilibration of these devices with CO2, using 5-layer films, was 3-4 min. Effective diffusion coefficients for CO2 in the films were determined using a dual-transport model and were found to be in the range (6-9) × 10-9 cm2/s.

Original languageEnglish (US)
Pages (from-to)688-694
Number of pages7
JournalAnalytical Chemistry
Volume69
Issue number4
DOIs
StatePublished - Jan 1 1997

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Organophosphonates
Intercalation
Carbon Dioxide
Amines
Copper
Thin films
Propanolamines
Sensors
Carbamates
Quartz crystal microbalances
Carbonates
Film growth
Partial pressure
X ray powder diffraction
Frequency response
Gases
Binding Sites
Nuclear magnetic resonance
Ions
Electrodes

All Science Journal Classification (ASJC) codes

  • Analytical Chemistry

Cite this

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title = "Molecular Design of Intercalation-Based Sensors. 2. Sensing of Carbon Dioxide in Functionalized Thin Films of Copper Octanediylbis(phosphonate)",
abstract = "Self-assembled thin films of layered copper alkanediylbis-(phosphonates) retain the amine-specific intercalation chemistry of the corresponding microcrystalline solids. Aliphatic and aromatic amines bind in a 1:1 ratio to coordinatively unsaturated copper ions in anhydrous Cu2(O3P(CH2)8PO3); and by selecting an amine with an appropriate functional tail group, a chemically and sterically well-defined interlamellar binding site for CO2 is created. Powder X-ray diffraction, Fourier transform infrared spectroscopy, and solid-state NMR experiments were used to study the intercalation of 3-aminopropanol, (3-aminopropyl)methyldihydroxysilane, and p-xylylenediamine, and their reversible reaction with CO2 to form carbonates and carbamates, respectively. By growing these films on the electrodes of a quartz crystal microbalance device, a sensor can be fabricated for monitoring CO2 in gas streams at concentrations of 0.5-19{\%} (v/v). A Henrian response (frequency change directly proportional to CO2 partial pressure) was observed, and the time required for equilibration of these devices with CO2, using 5-layer films, was 3-4 min. Effective diffusion coefficients for CO2 in the films were determined using a dual-transport model and were found to be in the range (6-9) × 10-9 cm2/s.",
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Molecular Design of Intercalation-Based Sensors. 2. Sensing of Carbon Dioxide in Functionalized Thin Films of Copper Octanediylbis(phosphonate). / Brousseau, Louis C.; Aurentz, David Jeffrey; Benesi, Alan J.; Mallouk, Thomas E.

In: Analytical Chemistry, Vol. 69, No. 4, 01.01.1997, p. 688-694.

Research output: Contribution to journalArticle

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