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Title: Infrared Spectroscopic Study of the Adsorption of HCN by gamma-Al2O3: Competition with Triethylenediamine for Adsorption Sites

Abstract

The adsorption and vibrational properties of chemisorbed HCN on Lewis acid sites, Lewis base sites, and Brønsted Al-OH acid sites on a partially hydroxylated [gamma]-Al2O3 surface have been obtained by a combination of FTIR and density functional theory studies. The vibrational modes from the molecular and dissociative adsorption of HCN were assigned by using deuterium and 13C-labeled D13CN molecules at 170 K. In addition, [eta]2(C, N)-HCN bonding is also found from the [nu](CdN) vibrational spectra. Good correlation of the calculated vibrational frequencies for the adsorbed species with experimental data is found. The effect of triethylenediamine (TEDA) (also called 1, 4-diazabicyclo [2.2.2]octane, DABCO) on the adsorption of hydrogen cyanide (HCN) on the high area [gamma]-Al2O3 surface has been investigated using transmission FTIR spectroscopy. During HCN adsorption on TEDA-functionalized surfaces, there is no spectral change or emerging feature in either the TEDA or HCN spectral regions, indicating that no direct interaction occurs between these two molecules. Instead, we found that TEDA competes with HCN for the active sites on [gamma]-Al2O3. The observed [nu](C [identical with] N) mode on a TEDA-precovered surface is due to the HCN adsorption on Lewis base sites (Al-O-Al) which are less affected by TEDA preadsorption.

Authors:
; ;
Publication Date:
Research Org.:
National Energy Technology Laboratory (NETL), Pittsburgh, PA, Morgantown, WV, and Albany, OR (United States)
Sponsoring Org.:
USDOE - Office of Fossil Energy (FE)
OSTI Identifier:
913403
Report Number(s):
DOE/NETL-IR-2007-128
Journal ID: ISSN 1932-7447; TRN: US200802%%645
DOE Contract Number:  
None cited
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry. C; Journal Volume: 111; Journal Issue: 14
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CHEMISORPTION; HYDROCYANIC ACID; LEWIS ACIDS; LEWIS BASES; INFRARED SPECTRA; ALUMINIUM OXIDES; SORPTIVE PROPERTIES; VIBRATIONAL STATES; DENSITY FUNCTIONAL METHOD; AMINES

Citation Formats

Kim, S, Sorescu, D C, and Yates, Jr, J T. Infrared Spectroscopic Study of the Adsorption of HCN by gamma-Al2O3: Competition with Triethylenediamine for Adsorption Sites. United States: N. p., 2007. Web. doi:10.1021/jp065570l.
Kim, S, Sorescu, D C, & Yates, Jr, J T. Infrared Spectroscopic Study of the Adsorption of HCN by gamma-Al2O3: Competition with Triethylenediamine for Adsorption Sites. United States. doi:10.1021/jp065570l.
Kim, S, Sorescu, D C, and Yates, Jr, J T. Thu . "Infrared Spectroscopic Study of the Adsorption of HCN by gamma-Al2O3: Competition with Triethylenediamine for Adsorption Sites". United States. doi:10.1021/jp065570l.
@article{osti_913403,
title = {Infrared Spectroscopic Study of the Adsorption of HCN by gamma-Al2O3: Competition with Triethylenediamine for Adsorption Sites},
author = {Kim, S and Sorescu, D C and Yates, Jr, J T},
abstractNote = {The adsorption and vibrational properties of chemisorbed HCN on Lewis acid sites, Lewis base sites, and Brønsted Al-OH acid sites on a partially hydroxylated [gamma]-Al2O3 surface have been obtained by a combination of FTIR and density functional theory studies. The vibrational modes from the molecular and dissociative adsorption of HCN were assigned by using deuterium and 13C-labeled D13CN molecules at 170 K. In addition, [eta]2(C, N)-HCN bonding is also found from the [nu](CdN) vibrational spectra. Good correlation of the calculated vibrational frequencies for the adsorbed species with experimental data is found. The effect of triethylenediamine (TEDA) (also called 1, 4-diazabicyclo [2.2.2]octane, DABCO) on the adsorption of hydrogen cyanide (HCN) on the high area [gamma]-Al2O3 surface has been investigated using transmission FTIR spectroscopy. During HCN adsorption on TEDA-functionalized surfaces, there is no spectral change or emerging feature in either the TEDA or HCN spectral regions, indicating that no direct interaction occurs between these two molecules. Instead, we found that TEDA competes with HCN for the active sites on [gamma]-Al2O3. The observed [nu](C [identical with] N) mode on a TEDA-precovered surface is due to the HCN adsorption on Lewis base sites (Al-O-Al) which are less affected by TEDA preadsorption.},
doi = {10.1021/jp065570l},
journal = {Journal of Physical Chemistry. C},
number = 14,
volume = 111,
place = {United States},
year = {Thu Apr 12 00:00:00 EDT 2007},
month = {Thu Apr 12 00:00:00 EDT 2007}
}