Design and Preparation of Fe−N5 Catalytic Sites in Single-Atom

Catalysts for Enhancing the Oxygen Reduction Reaction in Fuel Cells

The researchers aims to describe a method to prepare atomically dispersed iron catalysts embedded in nitrogen- and
fluorine-doped porous carbon materials with five-coordinated Fe−N5 sites. The catalyst C@PVI-(DFTPP)Fe-800
exhibited excellent electrocatalytic activity for oxygen reduction reaction with an onset and half-wave potential of
0.99 and 0.88 V versus RHE respectively in alkaline electrolyte.
The catalyst was found to be highly selective for the 4e− reduction of O2 to H2O in both alkaline and acidic
electrolytes. The results suggested that the fluorine substitution introduced by doping into the carbon matrix of the
pyrolyzed composite (C@PVI-(DFTPP)Fe-800) has a positive effect on its catalytic activity for oxygen reduction
reaction.
The study also discussed the characterization of the catalyst, including the presence of various nitrogen species and
the confirmation of a Cl−FeN5 structure. It highlighted the importance of the Fe−N5 center in the catalytic activity of
the prepared catalysts. The analysis included evaluations using cyclic voltammetry in O2- and Ar-saturated KOH
solutions to demonstrate the catalyst's performance.

In summary, the article provides valuable insights into the synthesis, characterization, and electrocatalytic
performance of single-atom catalysts with Fe−N5 sites for enhancing the oxygen reduction reaction in fuel cells.
 Synthesis of C@PVI-(DFTPP)Fe-
800 material designed for use as a catalyst in oxygen reduction reactions (ORR),
C@PVI-(DFTPP)Fe-800 is a complex
which are crucial for the efficiency of fuel cells. The name itself is a shorthand for a carbon material coated with
polyvinylimidazole (PVI), integrated with a dopamine functionalized tetra(pentafluorophenyl)porphyrin (DFTPP)
ligand, and an iron (Fe) center, which has been pyrolyzed at a temperature of 800 degrees Celsius.

The starting materials for the synthesis of C@PVI-(DFTPP)Fe-800 are quite specific and are chosen for their roles in the
formation and functionality of the catalyst:
1.Polyvinylimidazole (PVI): This is a polymer that provides a nitrogen-rich backbone to the catalyst. Nitrogen atoms within PVI
can act as coordination sites for metal centers, which are crucial for the catalytic activity.
2.Dopamine functionalized tetra(pentafluorophenyl)porphyrin (DFTPP): This is a porphyrin-based macrocycle that has been
functionalized with dopamine groups. Porphyrins are known for their ability to coordinate metal atoms at their center; the
modification with dopamine helps to integrate the porphyrin into the polymer framework and may also facilitate electron transfer
processes.
3.Iron Source: An iron source is needed to introduce iron atoms into the catalyst structure. These iron atoms become the active
sites for the ORR after the heat treatment. The iron interacts with the nitrogen atoms from PVI and possibly with the porphyrin to
form catalytically active sites.

The combination of these materials, followed by a controlled pyrolysis process, results in the formation of the final catalyst,
which is a carbon-based material with embedded nitrogen-coordinated iron sites, encapsulated in a porphyrin derivative
structure.
Figure 1 shows typical fabrication strategy for a C@PVI-(DFTPP)Fe-T
composite which involved several steps. First, carbon black was coated with
PVI polymer to produce a C@PVI composite using an immersion method.
Next, an iron porphyrin was assembled on the surface of C@PVI to create a
C@PVI-(DFTPP)Fe composite. This was possible because the PVI-
functionalized carbon black provided sufficient imidazole-N sites for axial
coordination with the iron porphyrin. Finally, the C@PVI-(DFTPP)Fe
composite was carbonized under an inert atmosphere at different
Figure 1. Fabrication of C@PVI-(DFTPP)Fe-T catalysts.
temperatures and then collected.
Formation of precursor composite:Initially, PVI is used to coat carbon black, which provides a support matrix for the
subsequent steps. Then, the iron porphyrin complex (DFTPP)FeCl is introduced, ensuring that the iron is coordinated
with the porphyrin ring and the axial imidazole from the PVI.

Formation of the desired catalyst C@PVI-(DFTPP)Fe-800: The precursor undergoes pyrolysis, a high-temperature
process that carbonizes the composite material around 800°C. During this heat treatment, the organic components
decompose and the porphyrin and PVI structure transforms into a nitrogen- and fluorine-doped carbon matrix. The
fluorine atoms from difluorinated porphyrin rings are believed to dope into the carbon matrix during carbonization,
forming semi-ionic and ionic C−F bonds on the carbon surface.
The heat treatment also induces the formation of a mesoporous structure with a significant surface area and hierarchical
pore nanostructure, which facilitates mass transfer and exposes more active sites for the ORR.
 Characterization of the C@PVI-(DFTPP)Fe-800 composite using several
techniques:
Characterization of materials at each step of synthesis can reveal how their properties evolve. Understanding these changes
allows scientists to deduce how the final material's performance or efficiency might be optimized. It is crucial to know exact
compositions to ensure desired elements incorporate properly. This requires confirming dopants like nitrogen or fluorine and
the atomic dispersion of iron.

X-ray Diffraction (XRD): This technique is used to identify the

crystalline structure of the materials. The document mentions that XRD
patterns for C@PVI-800, C@PVI-(DFTPP)Fe-800, and C/(DFTPP)Fe-
800 show characteristic diffraction peaks of carbon but do not show
peaks for metal, metal oxides, or metal carbide. This suggests that the
iron species are atomically dispersed in the carbon matrix and that no
larger particles or clusters of iron are present.

Figure 2. XRD patterns of C/DFTPPFe-800, C@PVI-(DFTPP)Fe-800 and

C@PVI-800
 High-resolution Transmission Electron Microscopy (HR-TEM)
and Elemental Mapping: High-Resolution Transmission Electron
Microscopy (HR-TEM) is an invaluable tool for analyzing the
morphology of the final product in material synthesis, such as the
C@PVI-(DFTPP)Fe-800 catalyst. This technique allows scientists to
visualize the structure of materials at the atomic or molecular level,
providing insights into the arrangement of atoms and any nanoscale
features that may be present.

HR-TEM analysis confirmed the atomic dispersion of Fe species in the

C@PVI-(DFTPP)Fe-800 carbon matrix. No nanoparticles were
observed, suggesting Fe is evenly distributed as individual atoms or
small clusters. This atomic dispersion often enhances catalytic
activity, especially for oxygen reduction reaction in fuel cells.

Morphology revealed by HR-TEM sheds light on porosity and surface

area, critical for catalysis by influencing reactant access to active sites.
Pore size distribution and specific surface area, often studied with HR-
TEM, correlate with catalytic measurements to better understand
performance.
Figure 3. (a,b) HR-TEM images for C@PVI-(DFTPP)Fe-
800
 X-ray Photoelectron Spectroscopy (XPS): X-ray photoelectron spectroscopy (XPS) was conducted to analyze the
chemical composition of the as-prepared catalysts. Peaks for C,N,O, F, and Fe were detected in the XPS spectrum of the
C@PVI-(DFTPP)Fe-T composites. The nitrogen contents of C@PVI-(DFTPP)Fe-800 and C@PVI-(DFTPP)-Fe-900 were
3.61 and 2.38 at%, respectively, implying higher pyrolysis temperatures decrease nitrogen contents due to heteroatom
evaporation. The N 1s XP spectrum of C@PVI-(DFTPP)Fe-800 showed a broad N signal at 400 eV, deconvoluted into
peaks at 398.9, 399.4, 400.1, and 401.1 eV from pyridinic-N, Fe coordinated N, pyrrolic-N, and graphitic-N. The F 1s XP
spectrum of C@PVI-(DFTPP)Fe-800 revealed ionic- and semi-ionic-F peaks at 684.5 and 688.5 eV. C@PVI-(DFTPP)Fe-
900's lower F content (0.03 at% vs 0.40 at%) results from its higher carbonization temperature. C@PVI-(DFTPP)Fe-400's
F content was 1.46 at%. Previous studies indicate heteroatom incorporation induces charge redistribution and spin density
changes, improving electrocatalytic activity. The Fe 2p XP spectrum of C@PVI-(DFTPP)Fe-800 displayed peaks at 711.5
and 725.1 eV for Fe 2p3/2 and Fe 2p1/2.

Samples C (atom%) N (atom%) O (atom%) F (atom%) Fe (atom%)

C@PVI-(DFTPP)Fe- 85.10 6.24 6.75 1.46 0.45
400
C@PVI-(DFTPP)Fe- 90.94 3.61 4.62 0.43 0.40
800
C@PVI-(DFTPP)Fe- 94.25 2.38 3.00 0.03 0.34
900
C@PVI-(TPP)Fe-800 90.93 2.94 5.73 Null 0.40
C/(DFTPP)Fe-800
Table 95.92
1. XPS elements 0.84
analysis of C@PVI-(DFTPP)Fe-800, 2.56 0.33
C@PVI-(DFTPP)Fe-900,C@PVI-(TPP)Fe-800 and 0.35
C/(DFTPP)Fe-800.
 Final Product Analysis(C@PVI-(TPP)Fe-
800)
 X-ray Absorption Spectroscopy (XAS): X-ray absorption
spectroscopy (XAS) was conducted on the C@PVI-(DFTPP)Fe
composite before and after pyrolysis to obtain structural information.
Reference samples included Fe foil, FeO, Fe2O3, and (TPP)FeCl.
C@PVI-(DFTPP)Fe-800 showed higher near-edge absorption energy
than FeO but lower than Fe2O3, indicating its iron valence state was
between Fe2+ and Fe3+. [Figure 4a]After pyrolysis, the Fe edge of
C@PVI-(DFTPP)Fe-800 shifted slightly higher than C@PVI-
(DFTPP)Fe. Compared to (TPP)FeCl, the Fe absorption edge of
C@PVI-(DFTPP)Fe and C@PVI-(DFTPP)Fe-800 shifted lower and
the white line peak intensity decreased, suggesting the Fe oxidation
state was reduced from charge transfer from the fifth N coordination
to iron.
Furthermore, extended X-ray absorption fine structure (EXAFS)
spectroscopy provides detailed information for C@PVI-(DFTPP)Fe-
800 catalyst, EXAFS fitting curves may distinguish between an Fe-N4 Figure 4a :Fe K-edge X-ray absorption near-edge structure spectra of Fe
foil, FeO, Fe2O3, (TPP)FeCl, C@PVI-(DFTPP)Fe, and C@PVI-
or Fe-N5 coordination environment, helping characterize the catalyst's (DFTPP)Fe-800
structure.
  Fourier-transformed extended X-ray absorption spectroscopy: Fine structure
(FT-EXAFS) analysis revealed predominant peaks at 1.65, 1.50, and 1.45 Å
in R space for (TPP)FeCl, C@PVI-(DFTPP)Fe, and C@PVI-(DFTPP)Fe-
800, respectively. These peaks can be associated with Fe−N bonding.
[Figure 4b]
 After heat treatment, the peak relating to Fe−N bonding in C@PVI-
(DFTPP)Fe-800 showed a small shift to a lower value, lower than that of the
Fe−N4 sample (TPP)FeCl. A peak around 2.2 Å, attributed to Fe−Fe
bonding in iron foil, was not detected for C@PVI-(DFTPP)Fe-800. These
results suggest the iron sites in C@PVI-(DFTPP)Fe-800 were atomically
dispersed. Curve-fitting of FT EXAFS spectra using FEFFIT also simulated Figure 4b: Fourier-transformed X-ray absorption fine structure (EXAFS) spectra
the iron atom configuration in the composite. of Fe foil, FeO, Fe2O3, (TPP)FeCl, C@PVI-(DFTPP)Fe, and C@PVI-
 The Figure 4c shows that the unpyrolyzed C@PVI-(DFTPP)Fe composite (DFTPP)Fe-800.

were well fitted with six-coordinate iron. The Fe−N4 center was axially
coordinated with an imidazole and the sixth position was occupied by one
chloride anion, making it a Cl−FeN5 structure. Moreover, the presence of
Cl was also confirmed by elemental mapping[Figure 4d], in which the
simulated structure matched the chemical structure of the molecular
catalyst.

Figure 4d: SEM and EDS mapping of elemental C, N,

F, Cl and Fe in the C@PVI-(DFTPP)Fe composite.

Figure 4c: Corresponding EXAFS fitting curves of the C@PVI-(DFTPP)Fe

 The FT EXAFS spectra of the pyrolyzed composite C@PVI-
(DFTPP)Fe-800 [Figure 4e] was best fitted with a five-
coordinate iron center, forming an Fe−N5 structure. This
indicates that chlorine was likely removed as HCl during
pyrolysis.

Figure 4e: Corresponding EXAFS fitting curves of C@PVI-

(DFTPP)Fe-800 with the Fe−N5 and Fe−N4 model.

 The absence of chlorine in C@PVI-(DFTPP)Fe-800 was also

verified by XPS analysis and SEM elemental mapping in
Figure 4f.

Figure 4f: SEM and EDS mapping of elemental C, N, F and Fe in the C@PVI-
(DFTPP)Fe-800 composite.
 ICP-AES: Inductively coupled plasma atomic emission spectroscopy, was used to measure the iron content in the
final product, C@PVI-(DFTPP)Fe-800 , precisely, which was found to be 0.50 wt %. This level of detail is crucial
because the iron content can significantly affect the catalytic activity and stability. Knowing the exact amount of
iron helps in the optimization process of the catalyst and ensures reproducibility in research and applications.

 N2 adsorption−desorption isotherms: N2 adsorption-desorption

experiments were conducted to examine the surface properties of the
C@PVI-(DFTPP)Fe-T composites. Product catalysts pyrolyzed at 700,
800, and 900 °C were tested and labeled C@PVI-(DFTPP)Fe-700,
C@PVI-(DFTPP)Fe-800, and C@PVI-(DFTPP)Fe-900, respectively.
[Figure 5] The Brunauer-Emmett-Teller (BET) specific surface area of
the C@PVI-(DFTPP)Fe-800 composite (868.0 m2/g) was found to be
comparable to that of C@PVI-(DFTPP)Fe-900 (885.2 m2/g). Both
surface areas are significantly larger than that of C@PVI-(DFTPP)Fe-
400 (398.0 m2/g) and C@PVI-(DFTPP)Fe-700 (520.1 m2/g).

Figure 5: N2 adsorption−desorption isotherms of

C@PVI-(DFTPP)Fe-400, C@PVI-(DFTPP)Fe-700,
C@PVI-(DFTPP)Fe-800, and C@PVI- (DFTPP)Fe-
900
 Pore size distribution : The catalyst C@PVI-(DFTPP)Fe-800
exhibited a hierarchical pore nanostructure with the pore size
distribution primarily centered around approximately 3.7 and 32
nanometers, revealing the existence of a mesoporous structure. This
porous architecture with abundant mesopores exposes more
accessible active sites, facilitates the mass transfer of reactants
during electrochemical reactions, and maximizes atom utilization
efficiency. The result is an improvement in the catalytic activity of
the catalyst for the oxygen reduction reaction.

Figure 6: Pore size distribution of C@PVI-(DFTPP)Fe-400, C@PVI-

(DFTPP)Fe-700, C@PVI-(DFTPP)Fe-800, and C@PVI-(DFTPP)Fe-
900.
 Electrocatalytic ORR performance of prepared
material
 Cyclic voltammetry: the ORR catalytic activity of the prepared catalysts
was evaluated using cyclic voltammetry conducted in O 2- and Ar-
saturated 0.1 M KOH solutions. No reduction peak was observed for
C@PVI-(DFTPP)Fe-800 in an Ar-saturated solution. However, in an O 2-
saturated solution a cathodic ORR peak was detected at 0.88 V (vs
RHE) for C@PVI-(DFTPP)Fe-800, 50 mV more positive than the
control sample C/(DFTPP)Fe-800. Additionally, C@PVI-(TPP)Fe-800
displayed a significant positive shift of approximately 70 mV relative to
C@PVI-800, indicating the introduction of iron into the carbon
materials to form Fe-Nx active sites promoted ORR performance. Figure 7a: Cyclic voltammogram curves of C@PVI-800, C/(DFTPP)Fe-
800, C@PVI-(TPP)Fe-800, and C@PVI-(DFTPP)Fe-800 in an O2- or
Ar-saturated 0.1 M KOH solution

 Linear sweep voltammetry: The ORR catalytic activities of the C@PVI-

(DFTPP)Fe-T catalysts were observed in an O2-saturated 0.1 M KOH
solution using linear sweep voltammetry with a rotating ring-disk
electrode at room temperature. The ORR polarization curves revealed
that the ORR onset and half-wave potential positively shifted from
approximately 0.83 to 0.88 V versus RHE with catalyst pyrolyzed from
300 to 800°C, followed by a decline with catalyst pyrolyzed at higher
temperatures.

Figure 7b: ORR polarization curves of C@PVI-(DFTPP)Fe-T (T =

300−900) catalysts at 1600 rpm in an O2-saturated 0.1 M KOH solution
 In Figure 7c the catalyst C@PVI-(DFTPP)Fe-800 showed the highest ORR catalytic
activity with onset and E1/2 values comparable to 20 wt % Pt/C (Eonset = 1.05 V, E1/2 =
0.87 V). Its E1/2 value was 0.88V and onset of 0.99V versus RHE.

 C@PVI-(DFTPP)Fe-800(0.48) also showed a much higher TOF than C/(DFTPP)Fe-

800(0.10) . This clearly suggests that the C@PVI-(DFTPP)Fe-800 catalyst with axial
imidazole-coordinated iron porphyrin exhibited superior ORR performance compared to
the composite without axial coordination. The ORR half-wave potential of C@PVI-
(DFTPP)Fe-400 was 40 mV lower than C@PVI-(DFTPP)Fe-800, although it had higher
N and F contents. However, its specific surface area of 398.0 m2 g−1 was remarkably
lower than C@PVI-(DFTPP)Fe-800's 868.0 m2 g−1, indicating the vital impact of
pyrolysis temperature on catalyst performance. Figure 7c: ORR polarization curves of C@PVI-800,
C/(DFTPP)Fe-800, C@PVI-(DFTPP)Fe-800, and commercial 20
wt % Pt/C catalysts (0.3mg cm−2, JM) in an O2-saturated 0.1 M
KOH solution
 The RRDE measurements were employed to probe the ORR pathways of the catalysts
obtained. Figure 7d illustrates that significantly less hydrogen peroxide was generated
with the C@PVI-(DFTPP)Fe-800 catalyst compared to C/(DFTPP)Fe-800 over the
potential range from 0.2 to 0.7 V. For example, at a potential of 0.6V versus RHE, the
electron transfer number and yield of HO2 production using C@PVI-(DFTPP)Fe-800
were calculated to be 3.98 and 0.80% respectively, similar to the commercial Pt/C
catalyst. This indicates that the C@PVI-(DFTPP)Fe-800 catalyst could directly promote
the four-electron reduction of O2 to H2O.

Figure 7d: H2O2 % yields of C@PVI-800,

C/(DFTPP)Fe-800, C@PVI-(DFTPP)Fe-800 and Pt/C
 Durability of the catalyst prepared

In Basic medium:
 The catalyst C@PVI-(DFTPP)Fe-800 demonstrated strong durability for
oxygen reduction reaction (ORR) in O2 saturated 0.1 M KOH electrolyte.
In Figure 8a Chronoamperometric analysis showed the catalyst maintained
approximately 97% of its initial current after 25 hours of continuous
operation at 0.55 V. Additionally, cycling the potential between 0.6 and 1.0
V at 50 mV/s in O2-saturated 0.1 M KOH electrolyte for 5000 cycles
resulted in a negative shift of half-wave potential of only -16 mV, Figure 8a: ORR polarization plots for C@PVI-
(DFTPP)Fe-800 after 0 and 5000 potential cycles in O2-
indicating strong stability. saturated 0.1 M KOH (inset, current−time
chronoamperometric responses of C@PVI-(DFTPP)-Fe-
800)
 The chronoamperometric method was carried out in O2-saturated 0.1 M
KOH solution to investigate the effects of methanol crossover on C@PVI-
(DFTPP)Fe-800 (Figure 8b). When 2.0 M methanol was added to the
alkaline electrolyte, C@PVI-(DFTPP)Fe-800 showed a stable
amperometric response with little loss in current density, indicating
tolerance for methanol crossover. In contrast, Pt/C showed an intense
decrease in current density after methanol addition. These results suggest
C@PVI-(DFTPP)Fe-800 could be used as a methanol-tolerant cathode
catalyst in direct methanol fuel cells.
Figure 8b: Tolerance tests to methanol for C@PVI-
(DFTPP)Fe-800 and Pt/C.
In Acidic medium:

Featureless voltametric currents were detected for C@PVI-

(DFTPP)-Fe-800 in 0.1 M HClO4 under Ar. A pronounced
cathodic ORR peak appeared at 0.69 V when saturated with O2,
indicating good ORR electrocatalytic activity.

Figure 9a: Cyclic voltammograms curves of C/(DFTPP)Fe-

800, C@PVI-(TPP)Fe-800,C@PVI-(DFTPP)Fe-800 in an O2
or Ar-saturated 0.1 M HClO4 solution.

The LSV results for C@PVI-(DFTPP)Fe-800 showed ORR

onset and half-wave potential values of 0.86 V and 0.70 V,
respectively. These values were approximately 30 mV and 130
mV higher than the control composite C/(DFTPP)Fe-800,
which had values of 0.83 V and 0.57 V.

Figure 9b: ORR polarization curves of C/(DFTPP)Fe-

800, C@PVI-(DFTPP)Fe-800, Pt/C catalysts at 1600
rpm in an O2-saturated 0.1 M HClO4 solution.
 Anion Exchange Membrane Fuel Cell (AEMFC) test

Figure 10b : AEMFC performance while using C@PVI-(DFTPP)Fe-400 (2.0 mg cm−2,

Figure 10a: Schematic of an anion-exchange membrane H2−O2 fuel cell. black), C@PVI-(DFTPP)Fe-800 (2.0 mg cm−2, red), and Pt/C (2.0 mg cm−2, blue) as the
cathode catalysts at 60 °C (Conditions: anode catalyst, 20 wt % Pt/C (2.0 mg cm−2); flow
rate: O2, 200 mL min−1; H2, 200 mL min−1; no back pressure was applied).

The synthesized catalysts were utilized as the cathode catalyst in an anion-exchange membrane fuel cell
(AEMFC) to further examine their electrocatalytic activity. C@PVI-(DFTPP)Fe-400 was also assembled as
the cathode catalyst for comparison. The membrane electrode assembly (MEA) with commercial Pt/C as the
anode catalyst and C@PVI-(DFTPP)Fe-T as the cathode catalyst was prepared. The maximum power density
of AEMFC with C@PVI-(DFTPP)Fe-400 was 0.036 W/cm2 at 60°C and 0.2V without back pressure, with
an open cell voltage (OCV) of 0.88V. AEMFC with C@PVI-(DFTPP)Fe-800 achieved a maximum power
density of 0.104 W/cm2 at 0.33V with an OCV of 0.93V. While the maximum power density was lower than
AEMFCs with Pt/C cathode, the OCV was still comparable to commercial Pt/C under similar conditions.