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Author:Repo, Eveliina
Title:Kuparibentsoaattikompleksien sähkökemiallinen karakterisointi
Electrochemical characteristics of copper bentzoate complexes
Publication type:Licentiate thesis
Publication year:2010
Pages:ix + 81 s. + liitt.      Language:   fin
Department/School:Kemian laitos
Main subject:Fysikaalinen kemia   (Kem-31)
Supervisor:Kontturi, Kyösti
Instructor:Murtomäki, Lasse
OEVS:
Electronic archive copy is available via Aalto Thesis Database.
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Location:P1 Ark Aalto  3711   | Archive
Keywords:cyclic voltammetry
surface grafting
Cu(II)-benzoate
simulations of voltammograms
syklinen voltammetria
pinnan modifiointi
Cu(II)-bentsoaatti
voltammogrammit
Abstract (eng): In this work electrochemistry of immobilized and free Cu(II) benzoate compexes were studied.

The literature part included an introduction of the grafting technique of electrode surface by reduction of diazonium salts, the properties of the grafted layers and the parameters that affect their properties, the properties of Cu(II) benzoate complexes in the solution and solid phase, and the effects of amine ligands on the properties of Cu(II) benzoates.

In the experimental part the properties of the grafted electrodes as well as free Cu(II)-benzoate complexes were studied.
At first, the blocking effect of benzoate groups immobilized on the gassy carbon and gold electrodes was investigated.
The blocking was much more significant in the case of glassy carbon than gold.
This was attributed to the lateral orientation of benzoate groups on the gold surface.
In addition, the electrochemical properties of immobilized Cu(II) benzoate complexes were studied using cyclic voltammetry.
Complexes formed on the god surface were unstable.

The reaction mechanism of the Cu(II) benzoates grafted on the glassy carbon electrode was best described by the ECEC mechanism.
Cu(II) centres were presented to locate in different environments on the layer and the large values of the peak widths observed in cyclic voltammograms were explained by the deviation of formal potential of Cu(II).
Finally, the properties of free Cu(II) benzoate complexes with different amine ligands were studied.
Amine ligands affected the stability of the complexes.
The complex with pyridine ligands was found to be unstable.
The characteristics of cyclic voltammograms of Cu(II) benzoate with bipyridine ligands indicated on the disproportionation reaction mechanism.
Abstract (fin): Tässä työssä tutkittiin pintaan sidottujen ja vapaiden Cu(ll)-bentsoaattikompleksien sähkökemiaa.

Teoriaosiossa tarkasteltiin aryyliryhmien sitomista elektrodin pintaan diatsoniumsuolan pelkistysreaktiolla, kerroksen rakennetta ja ominaisuuksia sekä niihin vaikuttavia tekijöitä.
Lisäksi tarkastettiin vapaiden Cu(II)-bentsoaattikompleksien ominaisuuksia ja erilaisten amiiniligandien vaikutusta kompleksien ominaisuuksiin.

Kokeellisessa osassa tutkittiin sekä modifioitujen elektrodien että vapaiden Cu(II)bentsoaattikompleksien sähkökemiallisia ominaisuuksia.
Aluksi tarkastettiin pintaan sidottujen bentsoaattiryhmien vaikutusta elektrodin passivoitumiseen sekä lasihiilielektrodilla että kultaelektrodilla.
Lasihiilielektrodi passivoitui tehokkaammin kuin kultaelektrodi.
Tämän esitettiin johtuvan bentsoaattiryhmien asettumisesta kultaelektrodin pinnan suuntaisesti.
Lisäksi tutkittiin pintaan sidottujen Cu(ll)-bentsoaattikompleksien ominaisuuksia syklisellä voltammetrialla.

Kultaelektrodin pinnalle muodostetut kompleksit havaittiin epästabiileiksi.
Lasihiilielektrodin pinnalla kompleksien reaktiomekanismia kuvasi parhaiten ECEC-mekanismi, jossa Cu(II)-keskukset sijaitsivat erilaisissa ympäristöissä.
Voltammogrammeissa havaitut leventyneet piikit pystyttiin selittämään Cu(II):n formaalipotentiaalin jakautumisella.
Lopuksi tutkittiin Cu(II)-bentsoaattiliuoskompleksien sähkökemiaa.
Komplekseissa oli ligandeina erilaisia amiiniryhmiä.
Amiiniryhmän havaittiin vaikuttavan kompleksin stabiilisuuteen.
Yksihampaiset pyridiiniligandit muodostivat epästabiileja komplekseja.
Kompleksin, jossa amiiniligandina oli bipyridiini, voltammogrammien piirteet viittasivat disproportioitumismekanismiin.
ED:2010-10-11
INSSI record number: 41025
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