2 research outputs found
Efficient Chemisorption of Organophosphorous Redox Probes on Indium Tin Oxide Surfaces under Mild Conditions
We report a mild and straightforward
one-step chemical surface
functionalization of indium tin oxide (ITO) electrodes by redox-active
molecules bearing an organophosphoryl anchoring group (i.e., alkyl
phosphate or alkyl phosphonate group). The method takes advantage
of simple passive adsorption in an aqueous solution at room temperature.
We show that organophosphorus compounds can adsorb much more strongly
and stably on an ITO surface than analogous redox-active molecules
bearing a carboxylate or a boronate moiety. We provide evidence, through
quantitative electrochemical characterization (i.e., by cyclic voltammetry)
of the adsorbed organophosphoryl redox-active molecules, of the occurrence
of three different adsorbate fractions on ITO, exhibiting different
stabilities on the surface. Among these three fractions, one is observed
to be strongly chemisorbed, exhibiting high stability and resistance
to desorption/hydrolysis in a free-redox probe aqueous buffer. We
attribute this remarkable stability to the formation of chemical bonds
between the organophosphorus anchoring group and the metal oxide surface,
likely occurring through a heterocondensation reaction in water. From
XPS analysis, we also demonstrate that the surface coverage of the
chemisorbed molecules is highly affected by the degree of surface
hydroxylation, a parameter that can be tuned by simply preconditioning
the freshly cleaned ITO surfaces in water. The lower the relative
surface hydroxide density on ITO, the higher was the surface coverage
of the chemisorbed species. This behavior is in line with a chemisorption
mechanism involving coordination of a deprotonated phosphoryl oxygen
atom to the non-hydroxylated acidic metal sites of ITO
Synthesis and Reactivity of Tripodal Complexes Containing Pendant Bases
The
synthesis of a new tripodal ligand family that contains tertiary amine
groups in the second-coordination sphere is reported. The ligands
are trisĀ(amido)Āamine derivatives, with the pendant amines attached
via a peptide coupling strategy. They were designed to function as
new molecular catalysts for the oxygen reduction reaction (ORR), in
which the pendant acid/base group could improve the catalyst performance.
Two members of the ligand family were each metalated with cobaltĀ(II)
and zincĀ(II) to afford trigonal-monopyramidal complexes. The reaction
of the cobalt complexes <b>[CoĀ(L)]</b><sup><b>ā</b></sup> with dioxygen reversibly generates a small amount of a cobaltĀ(III)
superoxo species, which was characterized by electron paramagnetic
resonance (EPR) spectroscopy. Protonation of the zinc complex ZnĀ[NĀ{CH<sub>2</sub>CH<sub>2</sub>NCĀ(O)ĀCH<sub>2</sub>NĀ(CH<sub>2</sub>Ph)<sub>2</sub>}<sub>3</sub>)]<sup>ā</sup> (<b>[ZnĀ(TN</b><sup><b>Bn</b></sup><b>)]</b><sup><b>ā</b></sup>) with
1 equiv of acid occurs at a primary-coordination-sphere amide moiety
rather than at a pendant basic site. The addition of excess acid to
any of the complexes <b>[MĀ(L)]</b><sup><b>ā</b></sup> results in complete proteolysis and formation of the ligands <b>H</b><sub><b>3</b></sub><b>L</b>. These undesired
reactions limit the use of these complexes as catalysts for the ORR.
An alternative ligand with two pyridyl arms was also prepared but
could not be metalated. These studies highlight the importance of
the stability of the primary-coordination sphere of ORR electrocatalysts
to both oxidative <i>and</i> acidic conditions