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Pyrolysis-free Fe–PIPhen catalyzes alkaline ORR

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An Fe2+ coordination polymer of a nitrogen-rich phenanthroline ligand on carbon reduces O2 near 0.85 V with a four-electron pathway.

Source

Supramolecular Iron Complex Formed Between Nitrogen Riched Phenanthroline Derivative and Iron With Improved Oxygen Reduction Activity in Alkaline Electrolyte

Gu L, Chu Y, Du H, et al. · Frontiers in chemistry · 2019

doi.org/10.3389/fchem.2019.00622Read the full paper ↗4 citationscc by

What they did

Authors condensed phenanthroline-dione with bipyridyl-dialdehyde to PIPhen, coordinated Fe2+, loaded Vulcan XC-72 without pyrolysis, and ran RRDE/XPS/XRD.

What they found

Onset ~0.85 V; average electron number 3.94 at 1600 rpm; H2O2 yield 1.6–3.1%; k1 ≫ k2 ≈ k3 (k1/k2 = 30–50). XPS: 0.748 at% Fe.

The limits

What it doesn't show

No PEMFC device data; alkaline-only; Fe loading is low and part of the polymer is microcrystalline.

Key terms

ORR
Oxygen reduction reaction, ideally O2 + 4H+ + 4e– → 2H2O (or alkaline analogue).
PIPhen
Nitrogen-rich phenanthroline–imidazole ligand made by condensation.
RRDE
Rotating ring–disk electrode used to quantify H2O2 and electron number.
Four-electron pathway
Direct reduction of O2 to water rather than peroxide.
Pyrolysis-free M–N–C
ORR catalyst that keeps a molecular Fe–N coordination polymer instead of high-T carbonization.

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Fe-PIPhen/C is made:

Common questions

Was the catalyst pyrolyzed?

No—Fe-PIPhen was loaded on carbon powder only.

Onset potential?

About 0.85 V, slightly below Pt/C.

Electron number?

Average n = 3.94.

Main kinetic path?

k1 (4e– to water) is 30–50× k2 (peroxide).

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