Surface Reactions and Electronic Structure of Carboxylic Acid Porphyrins Adsorbed on TiO2(110)

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11320%2F21%3A10439683" target="_blank" >RIV/00216208:11320/21:10439683 - isvavai.cz</a>

Result on the web

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=ny7lUw5PrD" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=ny7lUw5PrD</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpcc.1c01133" target="_blank" >10.1021/acs.jpcc.1c01133</a>

Result language

angličtina

Original language name

Surface Reactions and Electronic Structure of Carboxylic Acid Porphyrins Adsorbed on TiO2(110)

Original language description

We studied the coverage- and temperature-dependent proton transfer and self-metalation reactions of tetraphenylporphyrin molecules containing a carboxyl functional group (MCTPP) on rutile TiO2(110) surfaces. Furthermore, we also determined changes in the molecular geometric and electronic structures as a function of coverage and temperature. The investigation was carried out by means of synchrotron radiation X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure measurements. We found that at a coverage of 0.2 ML, most MCTPP molecules adsorb with the iminic nitrogen atoms protonated; at 0.5 ML, a decrease in the proportion of protonated molecules is observed; and at a monolayer coverage, most molecules are not protonated. Raising the temperature to above 500 K, where hydroxyl groups recombine to desorb as water, causes a decrease in the number of protonated porphyrin molecules. In roughly the same temperature range, we start to observe the self-metalation of the free-base molecules, which produces flat-lying titanyl porphyrin molecules on the TiO2(110) surface. This reaction is found to be coverage dependent: For 0.2 ML, it starts above 450 K, and for 1.0 ML, temperatures above 650 K are needed. Metalation shifts the surface state located in the semiconductor band gap to lower energies. Our results suggest that protonation and self-metalation depend on the proximity of the macrocycle to the surface and show that metalation modifies the molecular occupied and vacant electronic states.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

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OECD FORD branch

10305 - Fluids and plasma physics (including surface physics)

Project

Result was created during the realization of more than one project. More information in the Projects tab.

Continuities

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Publication year

2021

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Journal of Physical Chemistry C

ISSN

1932-7447

e-ISSN

—

Volume of the periodical

125

Issue of the periodical within the volume

12

Country of publishing house

US - UNITED STATES

Number of pages

8

Pages from-to

6708-6715

UT code for WoS article

000636924700020

EID of the result in the Scopus database

2-s2.0-85104999874