Reinterpreting the role of the catalyst formal potential. the case of thiocyanate electrooxidation catalyzed by CoN4-l

C. Linares-Flores, D. Mac-Leod Carey, A. Muñoz-Castro, J. H. Zagal, J. Pavez, D. Pino-Riffo, R. Arratia-Pérez

Resultado de la investigación: Review article

8 Citas (Scopus)

Resumen

We report on the interaction of the thiocyanate ion (SCN -) with Co macrocyclics. In order to modulate the electron density located on the metal center, we used several phthalocyanine and macrocyclic molecules with electron-donating or electron-withdrawing groups located on the phthalocyanine ligand. We studied the following substituted Cobalt-macrocycles (CoPcâ's): cobalt-tetraamino-phthalocyanine (4β(NH 2)CoPc), cobalt-phthalocyanine (CoPc), cobalt-octahydroxyethylthio-phthalocyanine (8β(SC 2H 4OH)CoPc), cobalt-tetrapentylopyrrol- phthalocyanine (4β(PenPyr)CoPc), cobalt-tetrapyridino-phorphyrazine (4β(Pyr)CoPc), cobalt-octaethylhexyloxy-phthalocyanine (8β(EH)CoPc), cobalt-octamethoxyphthalocyanine (8β(OCH 3)CoPc), and cobalt-hexadecafluorophthalocyanine (16(F)CoPc). Our results for the formation of a CoPc-SCN adduct indicate that the electron-withdrawing groups favors the formation of an adduct between thiocyanate and the Co center, with an increase of the thiocyanate-binding energy. When the adducts are formed, they exhibit an increasing chemical potential, thus indicating the feasibility to produce the catalysis once the adducts are formed. The molecular hardness values suggest that the CoPc's with electron-withdrawing substituents will show low catalytic activity while those with electron-donor substituents will show an enhanced catalytic activity. The functionalized Co-phthalocyanine shows the highest catalytic activity for the thiocyanate electroxidation, which presents an appropriate energy gap (HOMOSCN --LUMO CoPc's) for the adduct formation and the subsequent electronic transfer.

Idioma originalEnglish
Páginas (desde-hasta)7091-7098
Número de páginas8
PublicaciónJournal of Physical Chemistry C
Volumen116
N.º12
DOI
EstadoPublished - 29 mar 2012

Huella dactilar

Electrooxidation
Cobalt
cobalt
catalysts
Catalysts
adducts
Electrons
Catalyst activity
catalytic activity
cobalt phthalocyanine
thiocyanate
electrons
Chemical potential
Binding energy
Catalysis
Carrier concentration
Energy gap
Metals
Hardness
Ligands

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Citar esto

Linares-Flores, C. ; Mac-Leod Carey, D. ; Muñoz-Castro, A. ; Zagal, J. H. ; Pavez, J. ; Pino-Riffo, D. ; Arratia-Pérez, R. / Reinterpreting the role of the catalyst formal potential. the case of thiocyanate electrooxidation catalyzed by CoN4-l. En: Journal of Physical Chemistry C. 2012 ; Vol. 116, N.º 12. pp. 7091-7098.
@article{bf552e26fc244a0995984fc183107933,
title = "Reinterpreting the role of the catalyst formal potential. the case of thiocyanate electrooxidation catalyzed by CoN4-l",
abstract = "We report on the interaction of the thiocyanate ion (SCN -) with Co macrocyclics. In order to modulate the electron density located on the metal center, we used several phthalocyanine and macrocyclic molecules with electron-donating or electron-withdrawing groups located on the phthalocyanine ligand. We studied the following substituted Cobalt-macrocycles (CoPc{\^a}'s): cobalt-tetraamino-phthalocyanine (4β(NH 2)CoPc), cobalt-phthalocyanine (CoPc), cobalt-octahydroxyethylthio-phthalocyanine (8β(SC 2H 4OH)CoPc), cobalt-tetrapentylopyrrol- phthalocyanine (4β(PenPyr)CoPc), cobalt-tetrapyridino-phorphyrazine (4β(Pyr)CoPc), cobalt-octaethylhexyloxy-phthalocyanine (8β(EH)CoPc), cobalt-octamethoxyphthalocyanine (8β(OCH 3)CoPc), and cobalt-hexadecafluorophthalocyanine (16(F)CoPc). Our results for the formation of a CoPc-SCN adduct indicate that the electron-withdrawing groups favors the formation of an adduct between thiocyanate and the Co center, with an increase of the thiocyanate-binding energy. When the adducts are formed, they exhibit an increasing chemical potential, thus indicating the feasibility to produce the catalysis once the adducts are formed. The molecular hardness values suggest that the CoPc's with electron-withdrawing substituents will show low catalytic activity while those with electron-donor substituents will show an enhanced catalytic activity. The functionalized Co-phthalocyanine shows the highest catalytic activity for the thiocyanate electroxidation, which presents an appropriate energy gap (HOMOSCN --LUMO CoPc's) for the adduct formation and the subsequent electronic transfer.",
author = "C. Linares-Flores and {Mac-Leod Carey}, D. and A. Mu{\~n}oz-Castro and Zagal, {J. H.} and J. Pavez and D. Pino-Riffo and R. Arratia-P{\'e}rez",
year = "2012",
month = "3",
day = "29",
doi = "10.1021/jp300764n",
language = "English",
volume = "116",
pages = "7091--7098",
journal = "Journal of Physical Chemistry C",
issn = "1932-7447",
publisher = "American Chemical Society",
number = "12",

}

Linares-Flores, C, Mac-Leod Carey, D, Muñoz-Castro, A, Zagal, JH, Pavez, J, Pino-Riffo, D & Arratia-Pérez, R 2012, 'Reinterpreting the role of the catalyst formal potential. the case of thiocyanate electrooxidation catalyzed by CoN4-l', Journal of Physical Chemistry C, vol. 116, n.º 12, pp. 7091-7098. https://doi.org/10.1021/jp300764n

Reinterpreting the role of the catalyst formal potential. the case of thiocyanate electrooxidation catalyzed by CoN4-l. / Linares-Flores, C.; Mac-Leod Carey, D.; Muñoz-Castro, A.; Zagal, J. H.; Pavez, J.; Pino-Riffo, D.; Arratia-Pérez, R.

En: Journal of Physical Chemistry C, Vol. 116, N.º 12, 29.03.2012, p. 7091-7098.

Resultado de la investigación: Review article

TY - JOUR

T1 - Reinterpreting the role of the catalyst formal potential. the case of thiocyanate electrooxidation catalyzed by CoN4-l

AU - Linares-Flores, C.

AU - Mac-Leod Carey, D.

AU - Muñoz-Castro, A.

AU - Zagal, J. H.

AU - Pavez, J.

AU - Pino-Riffo, D.

AU - Arratia-Pérez, R.

PY - 2012/3/29

Y1 - 2012/3/29

N2 - We report on the interaction of the thiocyanate ion (SCN -) with Co macrocyclics. In order to modulate the electron density located on the metal center, we used several phthalocyanine and macrocyclic molecules with electron-donating or electron-withdrawing groups located on the phthalocyanine ligand. We studied the following substituted Cobalt-macrocycles (CoPcâ's): cobalt-tetraamino-phthalocyanine (4β(NH 2)CoPc), cobalt-phthalocyanine (CoPc), cobalt-octahydroxyethylthio-phthalocyanine (8β(SC 2H 4OH)CoPc), cobalt-tetrapentylopyrrol- phthalocyanine (4β(PenPyr)CoPc), cobalt-tetrapyridino-phorphyrazine (4β(Pyr)CoPc), cobalt-octaethylhexyloxy-phthalocyanine (8β(EH)CoPc), cobalt-octamethoxyphthalocyanine (8β(OCH 3)CoPc), and cobalt-hexadecafluorophthalocyanine (16(F)CoPc). Our results for the formation of a CoPc-SCN adduct indicate that the electron-withdrawing groups favors the formation of an adduct between thiocyanate and the Co center, with an increase of the thiocyanate-binding energy. When the adducts are formed, they exhibit an increasing chemical potential, thus indicating the feasibility to produce the catalysis once the adducts are formed. The molecular hardness values suggest that the CoPc's with electron-withdrawing substituents will show low catalytic activity while those with electron-donor substituents will show an enhanced catalytic activity. The functionalized Co-phthalocyanine shows the highest catalytic activity for the thiocyanate electroxidation, which presents an appropriate energy gap (HOMOSCN --LUMO CoPc's) for the adduct formation and the subsequent electronic transfer.

AB - We report on the interaction of the thiocyanate ion (SCN -) with Co macrocyclics. In order to modulate the electron density located on the metal center, we used several phthalocyanine and macrocyclic molecules with electron-donating or electron-withdrawing groups located on the phthalocyanine ligand. We studied the following substituted Cobalt-macrocycles (CoPcâ's): cobalt-tetraamino-phthalocyanine (4β(NH 2)CoPc), cobalt-phthalocyanine (CoPc), cobalt-octahydroxyethylthio-phthalocyanine (8β(SC 2H 4OH)CoPc), cobalt-tetrapentylopyrrol- phthalocyanine (4β(PenPyr)CoPc), cobalt-tetrapyridino-phorphyrazine (4β(Pyr)CoPc), cobalt-octaethylhexyloxy-phthalocyanine (8β(EH)CoPc), cobalt-octamethoxyphthalocyanine (8β(OCH 3)CoPc), and cobalt-hexadecafluorophthalocyanine (16(F)CoPc). Our results for the formation of a CoPc-SCN adduct indicate that the electron-withdrawing groups favors the formation of an adduct between thiocyanate and the Co center, with an increase of the thiocyanate-binding energy. When the adducts are formed, they exhibit an increasing chemical potential, thus indicating the feasibility to produce the catalysis once the adducts are formed. The molecular hardness values suggest that the CoPc's with electron-withdrawing substituents will show low catalytic activity while those with electron-donor substituents will show an enhanced catalytic activity. The functionalized Co-phthalocyanine shows the highest catalytic activity for the thiocyanate electroxidation, which presents an appropriate energy gap (HOMOSCN --LUMO CoPc's) for the adduct formation and the subsequent electronic transfer.

UR - http://www.scopus.com/inward/record.url?scp=84859319984&partnerID=8YFLogxK

U2 - 10.1021/jp300764n

DO - 10.1021/jp300764n

M3 - Review article

VL - 116

SP - 7091

EP - 7098

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

SN - 1932-7447

IS - 12

ER -

Linares-Flores C, Mac-Leod Carey D, Muñoz-Castro A, Zagal JH, Pavez J, Pino-Riffo D y otros. Reinterpreting the role of the catalyst formal potential. the case of thiocyanate electrooxidation catalyzed by CoN4-l. Journal of Physical Chemistry C. 2012 mar 29;116(12):7091-7098. https://doi.org/10.1021/jp300764n