Journal Review

Versatile Strategy for Tuning ORR Activity of a Single Fe‑N4 Site by Controlling
Electron-Withdrawing/Donating Properties of a Carbon Plane

Yeunhee Lee
Graduate School of Nanoscience and Technology, KAIST, Daejeon 34141,
Korea
2019. 05. 29.
The proton exchange membrane fuel cells (PEMFCs)

• Anode : Hydrogen oxidation reaction

• Cathode : Oxygen reduction reaction
M/N/C (metals and N-doped carbon)

• Non-precious metal catalyst (low

cost)
• Active site : transition metal ion

• Main research topic : Active site

characterization and appropriate
nanostructure
• Lack of the study on controlling
kinetic activity
ACS Catal. 2018, 88, 7517-7525
 Intermolecular hardness factor (ηDA)

Electrochim. Acta 2001, 46, 3227.

Large carbon plane

→ High electron density of the π-band (high degree of delocalization)
→ Increase of the d-orbital energy level of the Fe-N4 sites
→ Large intermolecular hardness factor (ηDA) of the bond between the ORR intermediates
and the Fe-N4 sites
→ Strong adsorption of the ORR intermediates
Decrease carbon plane size in Fe/N/C catalyst to increase ORR activity
→ Lower the stability due to the increased number of carbon edge sites,
which can be oxidized

↓
To control and enhance the ORR activity of the single Fe-N 4 site in the catalyst
→ Incorporate the electron-withdrawing/donating functionalities on the
carbon plane by S-doping
MSU-F-C (Mesocellular carbon foam)
→ S-doping
→ Formation of the Fe-N4 active site

Figure S3
Figure S4 Figure S5

Amount of S-doping ↑ →Thiophene-like S ↑

ORR activity is mainly due to the
incorporation of Fe-N4 sites.

Fe exists in the same geometric

state in all the catalysts.
Figure S6
XRD and RAMAN

The thickness of carbon crystallite

(Lc size) and the d-spacing value
were almost independent of S-
doping.

The change in carbon plane size is

not a reason for the change in
ORR activity of the Fe-N4 sites.s
D to G band ratio (ID/IG) value ↑ → sp2-domain size ↓