Oxygen reduction catalysis by [Cu(cyclen)Cl]Cl·H 2 O: The relationship of selectivity to proton in nonaqueous solution and aqueous solution
The reaction of 1,4,7,10‐tetraazacyclododecane (cyclen) with CuCl 2 ·2H 2 O results in a novel five‐coordinated mononuclear copper complex, [Cu(cyclen)Cl]Cl·H 2 O, which has been characterized using physicochemical and spectroscopic methods. This copper complex can serve as a catalyst for oxygen red...
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| Published in | Applied organometallic chemistry Vol. 38; no. 1 |
|---|---|
| Main Authors | , , , , |
| Format | Journal Article |
| Language | English |
| Published |
01.01.2024
|
| Online Access | Get full text |
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| Summary: | The reaction of 1,4,7,10‐tetraazacyclododecane (cyclen) with CuCl
2
·2H
2
O results in a novel five‐coordinated mononuclear copper complex, [Cu(cyclen)Cl]Cl·H
2
O, which has been characterized using physicochemical and spectroscopic methods. This copper complex can serve as a catalyst for oxygen reduction reactions (ORRs). The selectivity for 4e
−
/4H
+
reduction to H
2
O νersus 2e
−
/2H
+
reduction to H
2
O
2
is determined by the relationship of the pKa value of the proton donor in nonaqueous solutions. The dissociation of Cl
−
from [Cu(cyclen)Cl]Cl·H
2
O creates an empty position on the copper centre, enabling to binding of dioxygen (O
2
) to form Cu(II)‐superoxo intermediate, which further reacts with a strong acid as a proton donor to form H
2
O and with a weak acid as a proton donor to form H
2
O
2
. Moreover, the faradaic efficiency for H
2
O
2
production increases in an aqueous environment with the increase of pH. |
|---|---|
| ISSN: | 0268-2605 1099-0739 |
| DOI: | 10.1002/aoc.7319 |