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- 저자 : LADISLAV KAVAN (검색결과 2 건)
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SPECTROELECTROCHEMICAL RECOGNITION OF CHEMICAL DOPANTS IN THE INNER SPACE OF CARBON NANOSTRUCTURES
MARTIN KALBÁČ,LADISLAV KAVAN,MARKÉTA ZUKALOVÁ,LOTHAR DUNSCH 성균관대학교(자연과학캠퍼스) 성균나노과학기술원 2006 NANO Vol.1 No.3
By in situ Raman spectroelectrochemistry the state of chemical dopants in the inner space of potassium vapor treated single-walled carbon nanotubes (SWCNT), double-walled carbon nanotubes (DWCNT) and C60 fullerene peapods was followed. We show that the spectroelectrochemistry is a method of choice to locate the dopant within carbon nanostructures. The presence of potassium inside the carbon nanostructures was found to be associated with a characteristic response of the tangential (TG) mode of SWCNT to electrochemical doping after treatment of the sample with the water. Our study confirmed the presence of residual potassium in peapods even after treatment with water. On the other hand, potassium was not found in the interior of the water-treated DWCNT and SWCNT.
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De Angelis, Filippo,Vitillaro, Giuseppe,Kavan, Ladislav,Nazeeruddin, Mohammad. K.,Grä,tzel, Michael American Chemical Society 2012 JOURNAL OF PHYSICAL CHEMISTRY C - Vol.116 No.34
<P>We present a first-principles computational investigation on the adsorption mode and electronic structure of the highly efficient heteroleptic ruthenium dye C101, [NaRu(4,4′-bis(5-hexylthiophene-2-yl)-2,2′-bipyridine)(4-carboxylic acid-4′-carboxylate-2,2′-bipyridine)(NCS)<SUB>2</SUB>], on anatase TiO<SUB>2</SUB> models exposing the (001) and (101) surfaces. The electronic structure of the TiO<SUB>2</SUB> models shows a conduction band energy upshift for the (001)-surface ranging between ∼50 and ∼110 meV compared with the (101) surface, in agreement with previous interfacial impedance and recent spectro-electrochemical data. TDDFT excited-state calculations provided the same optical band gap, within 0.01 eV, for the (001)- and (101) models. Two dominant adsorption modes for C101 dye adsorption on the (001) and (101) surfaces were found, which differ by the binding of the dye carboxylic groups to the TiO<SUB>2</SUB> surfaces (bridged bidentate vs monodentate), leading to sizably different tilting of the anchoring bipyridine plane with respect to the TiO<SUB>2</SUB> surface. The different adsorption mode leads to a smaller dye coverage on the (001) surface, as experimentally found, due to partial contact of the thiophene and alkyl bipyridine substituents with the TiO<SUB>2</SUB> surface. For the energetically favored adsorption modes, we calculate a larger average spatial separation, by 1.3 Å, between the dye-based HOMO and the semiconductor surface in (001) and (101) TiO<SUB>2</SUB> models. In terms of simple nonadiabatic electron-transfer considerations, our model predicts a retardation of the charge recombination kinetics, in agreement with the experimental observations.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/jpccck/2012/jpccck.2012.116.issue-34/jp306186y/production/images/medium/jp-2012-06186y_0008.gif'></P>
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