Communications
gases on the porous material (PN1=22or O2 > 500 Torr) as well as
the third component of the CO experimental adsorption
isotherm curve. Another key feature is the selectivity of the
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CO adsorption compared to those of O2 and N2. Indeed, these
O2 or N2
1
values, which are calculated from (P1/2
)
/(P1/2)
CO, are
1
about 470 and 5600 for CO/O2 and CO/N2 respectively. These
significant values represent the adsorption phenomenon at a
very low partial pressure of CO and therefore at a very low
CO content. However, from a chemical point of view, the CO/
O2 and CO/N2 selectivities are infinite as O2 and N2 cannot
bind to the CoIII ion.[27] Such an attribute is significant for a
CO gas detector to be used under ambient conditions.
The adsorption of CO by M1(3H) (Table 1 and the
Supporting Information) is very low and results only from
physisorption on the solid. This is not surprising as M1(3H)
incorporates a free-base corrole, therefore no chemisorption
of CO can occur. Furthermore, it is clear that the introduction
of pyridine during the gelation process significantly increases
the accessibility of the CoIII sites as demonstrated by the
[12] R. J. P. Corriu, F. Embert, Y. Guari, C. Reyꢁ, R. Guilard, Chem.
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higher V1 and lower (P1/2
)
values for M1Co(py) and
[20] A. Walcarius, C. Delacote, S. Sayen, Electrochim. Acta 2004, 49,
3775.
[21] S. Bourg, J.-C. Broudic, O. Conocar, J. J. E. Moreau, D. Meyer,
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[26] E. S. Ribeiro, Y. Gushikem, J. C. Biazzotto, O. S. Serra, J.
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1
M2Co(py) compared with M1Co (see Table 1). Moreover,
the use of MTEOS instead of TEOS induces an important
decrease in the physisorption of CO, which is reflected by a
lower K3 value (Table 1) while maintaining a high accessibility
of the metallocorroles, as shown by the low V2 value with
respect to V1. Thus, a large surface area is not a prerequisite
for a material that is very reactive towards CO.
In conclusion, very high affinities for CO compared with
O2 and N2 were obtained for CoIII corroles incorporated into
silica matrices. The sol–gel process led to new organic–
inorganic hybrid composite materials. By this flexible process,
devices with different shapes might be prepared, such as thin
films coated on a solid support through a gelation reaction.
This development facilitates the elaboration of a gas sensor
and enhances the long-term stability of the device.
[28] R. Corriu, C. Reye, A. Mehdi, G. Dubois, C. Chuit, F. Denat, B.
Roux-Fouillet, R. Guilard, G. Lagrange, S. Brandꢀs, WO Pat.
9937656, 1999; J. Goulon, C. Goulon-Ginet, A. Rogalev, F.
Wilhelm, N. Jaouen, D. Cabaret, Y. Joly, G. Dubois, R. J. P.
Corriu, G. David, S. Brandꢀs, R. Guilard, Eur. J. Inorg. Chem., in
press.
Received: December 21, 2004
Published online: April 14, 2005
[29] B. Boury, R. J. P. Corriu, Chem. Commun. 2002, 795.
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[31] Abbreviations: compound 1: 5,15-dimesityl-10-(4-aminophe-
nyl)corrole; compound 2: 5,15-dimesityl-10-{4-phenyl-[3-(3-trie-
thoxysilyl)propyl]urea}corrole; compound 3: [5,15-dimesityl-10-
{4-phenyl-[3-(3-triethoxysilyl)propyl]urea}corrolato] cobalt(iii);
acac: acetylacetonate; TEOS: tetraethoxysilane; MTEOS:
methyltriethoxysilane; TBAF: tetrabutylammonium fluoride.
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Keywords: carbon monoxide sensors · cobalt ·
organic–inorganic hybrid composites ·
porphyrinoids · sol–gel processes
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