Articles

https://doi.org/10.1038/s41929-018-0164-8

Atomically dispersed manganese catalysts for

oxygen reduction in proton-exchange membrane
fuel cells
Jiazhan Li1,2,11, Mengjie Chen2,11, David A. Cullen3, Sooyeon Hwang4, Maoyu Wang5, Boyang Li6, Kexi Liu6,
Stavros Karakalos   7, Marcos Lucero5, Hanguang Zhang2, Chao Lei8, Hui Xu8, George E. Sterbinsky9,
Zhenxing Feng   5, Dong Su   4, Karren L. More10, Guofeng Wang6, Zhenbo Wang   1* and Gang Wu   2*

Platinum group metal (PGM)-free catalysts that are also iron free are highly desirable for the oxygen reduction reaction (ORR)
in proton-exchange membrane fuel cells, as they avoid possible Fenton reactions. Here we report an efficient ORR catalyst that
consists of atomically dispersed nitrogen-coordinated single Mn sites on partially graphitic carbon (Mn-N-C). Evidence for
the embedding of the atomically dispersed MnN4 moieties within the carbon surface-exposed basal planes was established by
X-ray absorption spectroscopy and their dispersion was confirmed by aberration-corrected electron microscopy with atomic
resolution. The Mn-N-C catalyst exhibited a half-wave potential of 0.80 V versus the reversible hydrogen electrode, approach-
ing that of Fe-N-C catalysts, along with significantly enhanced stability in acidic media. The encouraging performance of the
Mn-N-C catalyst as a PGM-free cathode was demonstrated in fuel cell tests. First-principles calculations further support the
MnN4 sites as the origin of the ORR activity via a 4e− pathway in acidic media.

D
evelopment of cost-effective and high-performance platinum
group metal (PGM)-free catalysts for the sluggish oxygen
reduction reaction (ORR) is key to realizing the large-scale
application of proton-exchange membrane fuel cells (PEMFCs)1–6.
A wide variety of carbon defects, including nitrogen doping and
surface-exposed carbon basal plane edges and steps, are believed to
act as preferred catalytic sites, thus facilitating the ORR by directly
providing adsorption sites and/or by modifying the electronic prop-
erties of carbon7,8. However, the activity of such metal-free active
sites in acidic media is not sufficient because they suffer from large
overpotential, mostly catalysing the ORR via a two-electron path-
way9. In contrast, the co-doped metal and nitrogen in the form of
MNxCy can tune the electronic and geometric properties of carbon
matrix more significantly. The MNxCy moieties themselves are also
believed to be acting as the active sites to directly adsorb O2 and
catalyse the subsequent O–O bond breaking in acidic media, there-
fore significantly improving the ORR catalytic activity6,10,11. The
bonding energies of MNxCy sites with O2 and other ORR interme-
diates are dependent on the nature of the transition metal, which
leads to significantly different activities and stabilities. Among the
studied transition metals, Fe or Co with N-doped carbon form the
M-N-C catalysts, which are recognized to be the most promising
PGM-free catalysts12. They exhibit encouraging ORR activities
and stabilities even in harsh acidic media13. Despite tremendous
efforts to develop Fe-N-C and Co-N-C catalysts, they still suffer
from insufficient durability, especially at the desirable high voltages
(>​0.6 V), which limits their practical applications in PEMFCs14–17.
Kinetic losses primarily result from the dissolution of active metal
sites15,16. These problems may be caused by H2O2 oxidative attack
or by protonation of the doped N neighbouring the active metal
sites followed by anion adsorption14. Carbon corrosion of catalysts
also promotes dissolution of the metal sites18,19 and induces signifi-
cant charge- and mass-transport resistances due to the changes in
the carbon lattice structures and morphologies20. Thus, a relatively
high degree of graphitization is vital for PGM-free catalyst stabil-
ity to enhance the corrosion resistance of the carbon. The Fe-N-C
catalysts are also criticized for their participation in and/or promo-
tion of the Fenton reactions (Fe2+ +​  H2O2), where dissolved Fe ions
combine with H2O2, a byproduct of the two-electron ORR21. As a
result, a significant amount of active oxygen-containing hydroxyl
and hydroperoxyl radicals are generated that can degrade the iono-
mer within the electrode and the polymer membrane in PEMFCs
(Supplementary Note 1). Therefore, high-performance PGM- and
Fe-free catalysts are highly desirable for PEMFC technologies. In
principle, the Co-N-C catalyst is a logical alternative22, but it suf-
fers from substantial generation of H2O2 during the ORR in acidic
media, and is thus likely to participate in Fenton reactions23. The
Co–N coordinated structures are even less stable in acids than
Fe-N-C catalysts24. Unlike Fe and Co, Fenton reactions involving
Mn ions are insignificant because of weak reactivity between Mn
and H2O2 (ref. 23). We discovered that Mn doping promotes the sta-
bility of nanocarbon (NC) catalysts and catalyses graphitic struc-
tures in catalysts25,26. Preliminary density functional theory (DFT)
calculations predicted that MnN4 moieties embedded in carbon

1
MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin
Institute of Technology, Harbin, China. 2Department of Chemical and Biological Engineering, University at Buffalo, The State University of New York,
Buffalo, NY, USA. 3Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN, USA. 4Center for Functional Nanomaterials,
Brookhaven National Laboratory, Upton, NY, USA. 5School of Chemical Biological, and Environmental Engineering, Oregon State University, Corvallis, OR,
USA. 6Department of Mechanical Engineering and Materials Science, University of Pittsburgh, Pittsburgh, PA, USA. 7Department of Chemical Engineering,
University of South Carolina, Columbia, SC, USA. 8Giner Inc, Newton, MA, USA. 9Advanced Photon Source, Argonne National Laboratory, Argonne, IL,
USA. 10Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN, USA. 11These authors contributed equally: Jiazhan Li,
Mengjie Chen *e-mail: wangzhb@hit.edu.cn; gangwu@buffalo.edu

Nature Catalysis | VOL 1 | DECEMBER 2018 | 935–945 | www.nature.com/natcatal 935

Articles
have comparable activity and enhanced stability relative to FeN4
sites. Inspired by this theoretical prediction, we hypothesized that
Mn-N-C catalysts are probably more stable than Fe-N-C in harsh
acidic media. However, a grand challenge is to increase the density
of MnN4 active sites in catalysts because Mn atoms tend to form
unstable and inactive metallic compounds, oxides and carbides
during the heat treatment when simply increasing the amount of
Mn precursors13,27.
Knowledge gained through our previous studies on Fe and Co
catalysts22,27–31 provides guidelines for the synthesis of Mn-N-C cata-
lysts with atomic dispersion of MnN4 active sites within a porous
three-dimensional (3D) carbon framework. A zinc-containing
zeolitic imidazolate frameworks (ZIF-8), a type of metal–organic
framework with flexible control of the structure and chemistry,
enables the formation of atomically dispersed MN4 active sites for
Fe- or Co-N-C catalysts22,32–34. The unique hydrocarbon networks
in ZIF precursors can be directly converted into N- and M-doped
highly disordered carbon, while maintaining their original poly-
hedral particle shape and porous structure during thermal activa-
tion35. Recently, synthesis based on ZIF-8 precursors with chemical
doping or ion confinement has resulted in atomically dispersed Fe
or Co sites with increased density2,22,27,36. Motivated by these suc-
cesses, we explore the ZIF approach to prepare atomically dispersed
Mn-N-C catalysts. However, unlike Fe and Co ions, Mn ions can-
not easily exchange the original Zn and form complexes with N
in the ZIF-8 precursor. Only a low density of atomic Mn sites are
introduced using a conventional one-step chemical doping. Due to
a wide variety of Mn valences from 0 to +​7, Mn aggregates easily
form during the high-temperature carbonization even at a low con-
tent. Thus, realizing atomically dispersed MnN4 sites with increased
density is very challenging.
Here, we report a catalyst with atomically dispersed MnN4 sites
obtained through a two-step synthesis strategy involving doping
and adsorption processes by leveraging the unique properties of
ZIF-8 precursors, which has been shown to effectively increase the
active-site density. In the first step of synthesis, Mn ions are com-
bined with Zn ions to prepare Mn-doped ZIF-8 precursors. After
carbonization and acid leaching, the derived porous carbon is used
as a host to adsorb additional Mn and N sources followed by a sub-
sequent thermal activation. This atomically dispersed Mn-N-C
catalyst achieves promising activity and excellent stability for the
ORR in aqueous acids.
Results
Atomically dispersed and N-coordinated Mn sites. A continu-
ous two-step doping and adsorption approach as shown in Fig. 1
has proved effective for gradually introducing more MnN4 active
sites in Mn-N-C catalysts. Supplementary Fig. 1 presents the over-
all morphology of the best-performing 20Mn-NC-second catalyst
(where 20 is molar percentage of Mn against the total metals in
solutions durng the synthesis of Mn-doped ZIF-8 precursors; sec-
ond refers to the sample obtained after the second adsorption step)
and shows a homogeneous distribution of polyhedral carbon par-
ticles with a size of about 50 nm, which directly transforms from
the 20Mn-ZIF-8 nanocrystal precursors with slight size reduction.
The dominant diffraction peaks corresponding to carbon in the
X-ray diffraction (XRD) spectra together with the broad D and G
bonds in the Raman spectra (Supplementary Fig. 2) are consistent
with a partially graphitized carbon structures (meso-graphitic),
which is confirmed by high-resolution scanning transmission
electron microscopy (HR-STEM) images (Supplementary Fig. 1h).
Both XRD patterns and STEM images verified the absence of any
crystalline Mn-containing phases or clusters in the catalyst. The
carbon particles exhibit a high degree of microporosity, an essen-
tial characteristic for increasing surface areas available for host-
ing active sites. The morphology (shape and size) and structure
936
Nature Catalysis
(extent of graphitization) of carbon particles can be tuned by vary-
ing the Mn content in the first step. As shown in Supplementary
Fig. 3, the carbon particle size is slightly increased by adding more
Mn content. Large particles with an irregular shape appeared
when the Mn content reached 30at%, indicating that excess Mn
ions in the solution disturb the controlled growth of the ZIF nano-
crystals. Raman results further indicated that the Mn content in
the first step can significantly increase the extent of graphitiza-
tion in the resulting carbon structures (Supplementary Fig. 4 and
Supplementary Table 1). All three of the nMn-NC-first (n =​  10,
20 and 30 at%) samples exhibited much smaller ratios of D and G
peak areas (AreaD/AreaG) relative to the Mn-free 0Mn-NC sample.
The carbon structures remain nearly the same after the second
adsorption step of synthesis.
According to inductively coupled plasma-mass spectrom-
etry (ICP-MS), the Mn content in the 20Mn-NC-second catalyst,
which exhibited the highest catalyst activity, can be up to 3.03 wt%
(Supplementary Table 2), which is comparable to other atomically
dispersed Fe and Co catalysts (Supplementary Table 3). As no sig-
nificant Mn clustering was observed by HR-STEM and XRD analy-
ses, homogeneous dispersion of atomic Mn species is likely, which
was further examined by X-ray absorption spectroscopy (XAS)
measurements. X-ray absorption near edge structure (XANES)
spectroscopy and extended X-ray absorption fine structure (EXAFS)
spectroscopy analyses are based on our established experimental and
theoretical modelling methods22,27,28,37,38. Several standard Mn com-
pounds (for example, MnO, MnO2 and Mn phthalocyanine (Pc))
were included in the XANES/EXAFS studies to compare with the
20Mn-NC-second catalyst. MnPc has a well-defined MnN4 chemical
structure (Supplementary Fig. 5), which provides a baseline for the
bulk catalyst measurements and can be used to identify the possible
active sites in the 20Mn-NC-second catalyst. As shown in Fig. 2a, the
XANFS edge profile of the 20Mn-NC-second catalyst is close to that
of Mn(ii) in MnO but is far from that of Mn(iv) in MnO2, suggest-
ing that the oxidation state of Mn in the 20Mn-NC-second catalyst
is close to 2+​. Figure 2b shows the EXAFS spectrum of the MnPc,
which is well fitted with MnN4 coordination (CNMn–N =​  4  ±​  0.4,
where CN refers to coordination number and Mn–N is the scatter-
ing path). The fit is also plotted in k-space in Supplementary Fig. 5.
As shown in Fig. 2c, the EXAFS of the 20Mn-NC-second catalyst
is well represented by a combination of the Mn–N and Mn–C scat-
tering paths (Supplementary Table 4). The first shell coordination
number of Mn–N is given by CNMn–N =​  3.2  ±​ 1.0, suggesting the
dominant Mn–N structure in the 20Mn-NC-second catalyst is likely
to be MnN4. We also compared the Mn K-edge EXAFS spectra of
20Mn-NC-second to manganese nitride (Mn4N) and metallic man-
ganese (Mn foil) to exclude the formation of nitrides and metallic
Mn (Supplementary Fig. 6). Both Mn4N and Mn foil exhibit peaks at
~2.3 Å assigned to Mn–Mn distance, corresponding to the metallic
structure. The absence of a Mn–Mn peak in the 20Mn-NC-second
spectra further verifies there is no such Mn clusters in the catalyst.
We note that the peak at around 1.9 Å deviates from the fitted curve
for 20Mn-NC-second catalyst, which may be due to a weak Mn–O
scattering path caused by a very small amounts of O, since MnPc
does not have a Mn–O scattering path. We have attempted to add a
Mn–O scattering path directly from the MnO structure, but this did
not provide us with representative structure information. Compared
with standard MnPc that has a well-defined and uniform MnN4 mol-
ecule structure, the 20Mn-NC-second catalyst exhibits disorganized
structures, especially in terms of the disordered nature and defective
structures that comprise the edges of carbon planes and grain/domain
boundary at the surface of the carbon particles. Due to a low content
of Mn and a more disorganized, defective carbonaceous/meso-gra-
phitic structure, the EXAFS data of the actual catalyst 20Mn-NC-
second exhibits more noise, which could also contribute to the peak
deviation observed at around 1.9 Å. We also compared the Mn
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Nature Catalysis
Carbonization
Adsorption
acid leaching
Mn-ZIF precursor Mn-NC-first (step 1)
C N Mn Cyanamide
Fig. 1 | Schematic of atomically dispersed MnN4 site catalyst synthesis. A two-step doping and adsorption approach can gradually increase the density
of the atomically dispersed and nitrogen-coordinated MnN4 sites into the 3D carbon particles. In the first step, Mn-doped ZIF-8 precursors are carbonized
and then leached with an acid solution to prepare a partially graphitized carbon host with optimal nitrogen doping and microporous structures. In the
second step, additional Mn and N sources were adsorbed into the 3D carbon host followed by a thermal activation to generate increased density of MnN4
active sites.
catalysts at different synthesis stages, which shows the evolution of
the Mn local structures and demonstrates the formation of atomi-
cally dispersed Mn sites instead of Mn clusters. Although we tried
the measurement for 20Mn-NC-first to study the possible structure
changes of the active sites after the adsorption step, due to a very low
Mn concentration (0.68 wt% by ICP-MS) the recorded spectrum was
not sufficient for high-quality data analyses (Supplementary Fig. 7).
The elemental quantifications of different precursors and
Mn-N-C catalysts determined from X-ray photoelectron spectros-
copy (XPS) are summarized in Supplementary Table 5. The content
of N in the 20Mn-ZIF precursor is 31.2 at% and the N 1s spectrum
shows a symmetric and sharp peak at 398.6 eV corresponding to
C=​N of 2-methylimidazole (Fig. 2d)39. After pyrolysis, the hydrocar-
bon networks of the precursors transformed into partially graphi-
tized carbon with a N content of 2.2 at%. The samples obtained at
the different processing steps exhibited nearly identical C 1s spectra
(Fig. 2e and Supplementary Table 6) and carbon content, indicating
that the second adsorption step does not induce any change to the
carbon structure. Although the N content continuously decreased
during processing to a level of 1.3 at% after the second adsorption
step, the amount of N appears to be sufficient to form a significant
fraction of MnN4 coordination relative to the low content of Mn
(approximately half that of N). In addition to two dominant peaks
that correspond to graphitic- and pyridinic-N, respectively, the N 1s
XPS peak at 399.1 eV could be attributed to N atoms bonded to M
sites40, likely MnN4 in the catalyst. The percentage of MnN4 increased
from 5.8% to 11.2% after the second adsorption step (Supplementary
Table 7); the percentage of pyridinic-N decreased by about 10%,
likely due to further coordination with Mn ions as evidenced by the
N 1s peak shift from the original pyridinic-N at 398.4 eV to 399.1 eV.
The XPS Mn 2p peak of 20Mn-NC-first (Fig. 2f) shows a 0.7 eV shift
to a higher bonding energy compared with the sample before acid
leaching (20Mn-NC). It was reported that the interaction between
metallic clusters and MNx could change the charge density of the
central metal ions and lead to a shift in the binding energy12. Thus,
the positive shift may be due to the removal of Mn clusters during
acid leaching. Considering that 20Mn-NC-first and 20Mn-NC-
second exhibit the same Mn 2p peak position, no additional Mn
clusters are produced during the second adsorption step.
Nature Catalysis | VOL 1 | DECEMBER 2018 | 935–945 | www.nature.com/natcatal
Articles
Thermal
activation
Adsorption Mn-NC-second (step 2)
Mn and cyanamide in micropores
Figure 3a–c present typical bright-field and medium-angle
annular dark field (MAADF) STEM images of the carbon particles
in the 20Mn-NC-second catalyst that show highly disordered car-
bon structures with randomly oriented graphitic domains and less
dense, pore-like morphologies (dark contrast in Fig. 3c). Similar
carbon phases were observed in other ZIF-8-derived catalysts22,27,28,
but the Mn-N-C catalyst appears to contain domains with a higher
degree of graphitization. Low voltage, aberration-corrected STEM
imaging coupled with electron energy loss spectroscopy (EELS)
was used to study the atomic dispersion and local environment
of Mn at an atomic resolution. The MAADF detector extends
the range of the collection semi-angle to 54–200 mrad (versus
86–200 mrad for high-angle annular dark field STEM), which can
provide more contrast from lower-scattering, light elements for
example, carbon and nitrogen. Distinguishable signals for C, N, O
and Mn are observed in the EELS maps across the carbon nanopar-
ticles (Fig. 3e–h), respectively, acquired for the particle shown in
Fig. 3d. The bright spots shown in the high-resolution MAADF-
STEM images in Fig. 3i,j correspond to single heavy atoms that are
uniformly dispersed across/within the carbon structure, indicating
a high density of Mn doping. Furthermore, an EEL point spectrum
(Fig. 3k) was obtained by placing the 1 Å electron probe directly
on a single atom (for example, as circled in red in Fig. 3j), which
is near the edge of a single or double graphene layer (basal planes)
that form the graphite domains of the carbon nanoparticles. Based
on the ångström resolution of the electron probe and thin sam-
ple area, the signal that contributes to the EEL point spectrum
(Fig. 3k) originates from the atom and its closest neighbouring
atoms. The co-existence of N and a single Mn within this ångström
region provides strong evidence for a Mn–N coordinate structure,
suggesting that single Mn ions are anchored by N within carbon.
The immediate vicinity of single Mn sites with N is confirmed by
similar EELS analyses acquired from different areas of the catalysts
(Supplementary Fig. 8).
Atomically dispersed Mn sites are also observed in MAADF-
STEM images acquired of the 20Mn-NC-first catalyst and the
EEL point spectra reveal a similar co-existence of Mn and N
(Supplementary Fig. 8). We infer from this result that the state of
Mn in the 20Mn-NC-first is similar to that in the 20Mn-NC-second,
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Articles Nature Catalysis

a 1.6 b c
0.6
MnPc MnPc 20Mn-NC-second
1.6 Mn-N
Fit Fit
20Mn-NC-second Mn-N
1.2 MnO
Normalized Xμ (E)

1.2 0.4 Mn-C

MnO2

∣χ (R )∣ (Å–3)

∣χ (R )∣ (Å–3)
0.8 Mn-C
0.8

0.2
0.4 0.4

0.0
6,540 6,550 6,560 0 1 2 3 4 0 1 2 3 4
Energy (eV) Radial distance (Å) Radial distance (Å)

d e f
20Mn-NC-second N 1s 20Mn-NC-second Mn 2p 20Mn-NC-second C 1s
Mn-Nx

20Mn-NC-first 20Mn-NC-first 20Mn-NC-first

Graphitic Pyridinic
C–O
Intensity (a.u.)

Intensity (a.u.)

Intensity (a.u.)
20Mn-NC 20Mn-NC 20Mn-NC

C–C, C–N

20Mn-ZIF precursor 20Mn-ZIF precursor 20Mn-ZIF precursor

C=N
Positive shift C=C
~0.7 eV
Pyrrolic

406 404 402 400 398 396 660 654 648 642 636 296 292 288 284 280
Binding energy (eV) Binding energy (eV) Binding energy (eV)

Fig. 2 | Structural characterization by XANES, EXAFS and XPS. a, The experimental K-edge XANES spectra of 20Mn-NC-second catalyst
and reference samples (MnO, MnO2 and standard MnPc). b,c, Fourier transforms of Mn K-edge EXAFS data (open circle) and model-based
fits (red line) of standard MnPc (b) and the 20Mn-NC-second catalyst (c). d–f, High-resolution N 1s (d), C 1s (e) and Mn 2p (f) XPS data of
materials obtained from different processing steps. The 20Mn-NC was prepared through a pyrolysis of the 20Mn-ZIF-8 precursor. The 20Mn-
NC-first is obtained after an acid leaching and a heat treatment of 20Mn-NC. The 20Mn-NC-second catalyst is the final catalyst after two-step
doping and adsorption processes.

and is likely that of a MnN4 coordinated structure. The primary dif- ORR activity of atomically dispersed Mn-N-C catalysts. The
ference between the two catalysts is that the density of MnN4 active ORR activity and four-electron selectivity (H2O2 yield) of all cata-
sites is significantly increased after the second adsorption step. The lyst samples were evaluated using a rotating ring-disk electrode
signals of both Mn and N become much stronger after the second (RRDE) in a 0.5 M H2SO4 electrolyte. Unlike ZIF-derived Fe and
adsorption step as evidenced in the comparison of the EELS ele- Co catalysts, one-step chemical doping of Mn into ZIFs is not an
mental maps (Supplementary Fig. 9), indicating a higher density of effective method to generate high ORR activity. With Mn doping
MnN4, which is also verified by MAADF-STEM imaging, as shown content ranging from 0 to 30 at%, poor ORR activity is measured
in Supplementary Fig. 8. Although a number of bright spots are uni- for all Mn-NC-first samples exhibiting half-wave potential (E1/2) less
formly dispersed in the MAADF-STEM images for 20Mn-NC-first, than 0.65 V, which is likely due to an insufficient density of active
only a few Mn-N coordinated sites were confirmed by EELS. Many sites (Supplementary Fig. 10). Inspired by the concept of host–guest
of the brighter atoms probed showed N but not Mn by EELS and may strategy41, we introduced more MnN4 active sites into the promising
be residual Zn (0.1 at%, Supplementary Table 5). After the second Mn-NC-first host through the second adsorption step. The adsorp-
adsorption step, the co-existence of Mn and N becomes dominant tion step leads to significantly enhanced activity for all samples;
and is easily verified by EEL spectra acquired for many differ- the 20Mn-NC-second catalyst exhibited the most positive E1/2 up
ent areas, indicating a significant increase in the density of MnN4 to 0.8 V versus the reversible hydrogen electrode (RHE) (Fig. 4a).
sites in the 20Mn-NC-second catalyst. ICP-MS results also verify Note that there is no Fe contamination during this multistep pro-
that the Mn content increases from 0.68 wt% in the 20Mn-NC-first cessing procedure, as evidenced by negligible Fe content in the
to 3.03 wt% in the 20Mn-NC-second. The two-step Mn doping- catalysts determined by ICP-MS and XPS analyses (Supplementary
adsorption method effectively increases the density of MnN4 active Fig. 11) as well as poor activity of the Mn-free control sample after
sites without the concomitant formation of Mn clusters. multiple heating treatments. Considering the comparable carbon

938 Nature Catalysis | VOL 1 | DECEMBER 2018 | 935–945 | www.nature.com/natcatal

Nature Catalysis Articles
a b c

10 nm 5 nm 5 nm

d e C f N

10 nm

g O h Mn i

1 nm

j k
C
Counts (a.u.)

Mn

2 nm
300 400 500 600 700
Energy (eV)

Fig. 3 | Morphology and atomic structure of the 20Mn-NC-second catalyst. a–d, Representative HR-TEM (a,b) and STEM (c,d) images of a carbon
particle in the catalyst. e–h, EELS elemental maps of C (e), N (f), O (g) and Mn (h) of the area in (d). i,j, Aberration-corrected MAADF-STEM images.
k, EEL point spectrum from the atomic sites circled in red in j. Image resolution in i and j is roughly 0.1 nm using an accelerating voltage of 60 kV.

structure and N dopant (Supplementary Tables 1 and 5) before and
after the adsorption step of synthesis, the enhanced performance
originated from the increasing MnN4 concentration. A poison-
ing experiment was performed by employing KSCN to block the
M–Nx sites42. The negative shift of 150 mV of E1/2 (Supplementary
Fig. 12) further verifies that the primary active sites in the
20Mn-NC-second catalyst are metal-based MnN4, instead of
metal-free CNx sites. The adsorption step also leads to an obvious
enhancement of activity for both ketjenblack (KJ-black) and poly-
aniline-derived nanocarbon (PANI-NC) (Fig. 4b), indicating that
the adsorption step is an effective strategy to introduce MnN4 active
sites, regardless of the carbon host. However, an optimal nitrogen
doping level and the pore structure of the carbon host are crucial for
maximum activity during the adsorption step. The adsorption using
distinct Mn salts without N source still leads to an improvement in
the activity (Fig. 4c and Supplementary Fig. 13). This suggests that
Mn ions chemically bonded with the pre-doped N in the carbon
host and form MnN4 active sites through subsequent thermal acti-
vation. Co-adsorption of Mn and N sources yields improved activity
with an increased N content in the final 20Mn-NC-second catalyst.
(Supplementary Table 5). Due to significant reductions of micro-
pores and Brunauer–Emmett–Teller surface areas of the carbon
host after adsorption process (Supplementary Fig. 14), we believe
that N sources can stabilize Mn ions through possible coordination
in the micropores. During the pyrolysis, the N source creates addi-
tional N doping in the carbon host, which can further coordinate

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Articles Nature Catalysis

a 0 b 0 c 0
0Mn-NC KJ-black

Current density (mA cm–2)

Current density (mA cm–2)

Current density (mA cm–2)

Before adsorption
0Mn-NC-second
No N sources
–1 20Mn-NC –1 PANI-NC –1
Cyanamide
20Mn-NC-second
Phenanthroline
0Mn-NC-
–2 –2 second –2 Dipicolylamine
Melamine

KJ-black-
–3 –3 second –3
PANI-NC-
second
0.5 M H2SO4 0.5 M H2SO4 0.5 M H2SO4
–4 –4 –4
0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Potential (V versus RHE) Potential (V versus RHE) Potential (V versus RHE)

d e 10 f 0.8
0 1.0 20Mn-NC-second (oxygen)
20Mn-NC-second 20Mn-NC-second
20Mn-NC-second (air) 0.7
Current density (mA cm–2)

20Co-NC-second 20Co-NC-second

Power density (W cm–2)

8 20Fe-NC-second (oxygen)
20Fe-NC-second 0.8
–1 20Fe-NC-second 20Fe-NC-second (air) 0.6
Pt/C
H2O2 yeild (%)
–2
Pt/C (60 μg cm ), 0.1 M HClO4

Voltage (V)
6 0.5
0.6
–2 0.4
4 0.4 0.3
H2-O2
–3 0.2
2 0.2
H2-air 0.1
0.5 M H2SO4
–4 0 0.0 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 0.0 0.4 0.8 1.2 1.6 2.0 2.4
Potential (V versus RHE) Potential (V versus RHE) Current density (A cm–2)

Fig. 4 | ORR activity studied by using RRDE and fuel cell tests. a–d, Steady-state ORR polarization plots in 0.5 M H2SO4 electrolytes (Pt/C catalyst
reference was studied in 0.1 M HClO4) to study the effect of synthesis steps (that is, first doping and second adsorption) on Mn-N-C catalyst activity (a),
effect of various carbon hosts used for the second adsorption step on resultant activity (b), effect of different nitrogen sources used for the adsorption step
on final catalyst activity (c), and comparison of catalytic activity of Fe-, Co- and Mn-N-C catalysts prepared from identical procedures (d). e, Four-electron
selectivity (that is, H2O2 yields) of the ORR on Fe-, Co- and Mn-N-C catalysts. f, Fuel cell performance of the best-performing 20Mn-NC-second and 20Fe-
NC-second catalysts in both H2/O2 and H2/air conditions. Error bars represent the standard deviation from at least three independent measurements.

with Mn ions and form MnN4 active sites. Cyanamide exhibited the very low level (<​4%). This further indicates a 4e−​pathway, rather
best performance, compared with other N sources (for example, than the 2e− +​  2e− pathway. A Tafel slope of ~80 mV dec−1 for the
dipicolylamine, phenanthroline and melamine), probably due to its 20Mn-NC-second is comparable to that of Co- or Fe-based catalysts
size and unique C≡​N structures. The C≡​N structures decompose (Supplementary Fig. 22 and Supplementary Table 11), indicating a
at the elevated temperature and easily bond to unsaturated carbon similar rate-determining step involving mixed controls including
atoms to form stable pyridinic-N34. This is favourable for the forma- transfer of the first electron (118 mV dec−1) and the diffusion of
tion of MnN4 active sites. intermediates at catalyst surfaces (59 mV dec−1)44.
The influence of post-treatments on the Mn-NC host before The 20Mn-NC-second catalyst is further studied as a cathode in
adsorption was investigated. When directly using 20Mn-NC without membrane electrode assemblies (MEAs) for fuel cells. The open cir-
an acidic treatment as the host for the second adsorption step, the cuit voltage is 0.95 V using H2 and O2, suggesting a high intrinsic
activity showed an obvious decline (Supplementary Fig. 15). Acid ORR activity in fuel cell environments. The 20Mn-NC-second cath-
leaching effectively removes the MnO clusters from the 20Mn-NC ode is capable of generating current densities of 0.35 and 2.0 A cm−2
host, which likely creates pore structures and increases micropore at 0.6 and 0.2 V, respectively, at a reasonable 1.0 bar partial pressure
sizes (from 1.0 to 1.4 nm) and surface areas (from 699 to 821 m2 g−1) (Fig. 4f). The corresponding power density is up to 0.46 W cm−2. The
(Supplementary Figs. 16 and 17 and Supplementary Table 8), which is achieved performance exceeds the Fe-N-C catalyst derived from
favourable for the subsequent adsorption. As a result, the 20Mn-NC- PANI reported in 2010 (ref. 45); however, the performance is inferior
second catalyst exhibits the highest electrochemically accessible sur- to the 20Fe-NC-second catalyst especially in the kinetic range.
face area of 715 m2 g−1 (Supplementary Fig. 18 and Supplementary
Table 9), corresponding to the highest ORR activity. The correlation Enhanced catalyst stability in acids. The 20Mn-NC-second cata-
between the porous structure of the carbon host and the ORR activ- lyst exhibited excellent stability, as evidenced by a loss of only 17 mV
ity was established (Supplementary Figs. 19 and 20). in E1/2 after 30,000 potential cycles from 0.6 to 1.0 V in O2-saturated
The ORR activity of the best-performing 20Mn-NC-second cat- 0.5 M H2SO4 solution (Fig. 5a). The stability is largely enhanced
alyst, which is higher than that of a 20Co-NC-second catalyst and over traditional Fe-N-C catalysts derived from PANI (loss 80 mV
approaches that of a 20Fe-NC-second catalyst (Fig. 4d), is 60 mV after 5,000 cycles)45, as well as the ZIF-derived 20Fe-NC-second
less than of a Pt/C catalyst (~0.86 V). The atomically dispersed catalyst (29 mV loss) (Fig. 5b). The microstructure and morphology
Mn catalyst represents one of the best PGM- and Fe-free catalysts of carbon in the 20Mn-NC-second catalyst remain nearly the same
(Supplementary Table 10)43. The H2O2 yield of the 20Mn-NC- (Supplementary Fig. 23) after the potential cycling tests. Long-term
second catalyst is less than 2% indicating a four-electron reduction durability tests were conducted by holding at a constant potential of
pathway, which is comparable to that of the 20Fe-NC-second, and 0.7 V for 100 hours during the ORR (Fig. 5c). The 20Mn-NC-second
much lower than that of the 20Co-NC-second catalyst (Fig. 4e). catalyst retains 88% of its initial current density and exhibits a 29 mV
When the catalyst loadings vary within a wide range from 0.2 to loss of E1/2 after 100 hours (Fig. 5d). The identical cyclic voltam-
1.2 mg cm−2, the H2O2 yields (Supplementary Fig. 21) remain at a metry curves during the stability tests (inset of Fig. 5d) indicate

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Nature Catalysis Articles
a b
0 20Mn-NC-second, initial, 0.795 V 0 20Fe-NC-second, initial, 0.822 V
20Mn-NC-second, after 30 K, 0.778 V 20Fe-NC-second, after 30 K, 0.793 V

Current density (mA cm–2)

Current density (mA cm–2)
–1 –1
After 30,000 cycles After 30,000 cycles
17 mV loss 29 mV loss
–2 –2

–3 –3

–4 –4
0.5 M H2SO4, 25 °C 0.5M H2SO4, 25 °C

0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Potential (V versus RHE) Potential (V versus RHE)
c 120 d
20Mn-NC-second 20Mn-NC-second, initial, 0.795 V
0
20Mn-NC-second, after 100 h, 0.766 V
100
Relative current density (%)

87.5%

Current density (mA cm–2)

10
–1 5
80
0 29 mV loss
3% increase
60 –2 –5

–10
40 –15
@ E = 0.7 V versus RHE –3 0.0 0.2 0.4 0.6 0.8 1.0
200 r.p.m., 0.5 M H2SO4, 25 °C
20
–4
0.5 M H2SO4, 25 °C
0
0 10 20 30 40 50 60 70 80 90 100 0.0 0.2 0.4 0.6 0.8 1.0
Time (h) Potential (V versus RHE)
e f
20Mn-NC-second
100 0 20Mn-NC-second, initial, 0.795 V
20Fe-NC-second
Relative current density (%)

20Mn-NC-second, after 100 h, 0.777 V

Current density (mA cm–2)

90.2% 10
80 80.8% –1
78.3% 5
71.8% 18 mV loss
0
28% increase
60
–2 –5
57.2% –10
40 –15
@ E = 0.8 V versus RHE 38.9% –3
0.0 0.2 0.4 0.6 0.8 1.0
200 r.p.m., 0.5 M H2SO4, 25 °C
20
–4
0.5 M H2SO4, 25 °C
0
0 10 20 30 40 50 60 70 80 90 100 0.0 0.2 0.4 0.6 0.8 1.0
Time (h) Potential (V versus RHE)

Fig. 5 | Catalyst stability studied by using potential cycling and constant potentials. a,b, Steady-state ORR polarization plots before and after potential
cycling stability tests (0.6–1.0 V, 30,000 cycles) for the 20Mn-NC-second (a) and 20Fe-NC-second (b) catalysts. c,e, i–t curves (where i is current density
and t is time) at constant potentials of 0.7 V (c) and 0.8 V (e). d,f, Steady-state ORR polarization plots and cyclic voltammetry curves before and after
constant potential tests at 0.7 V (d) and 0.8 V (f) for 100 hours in O2-saturated 0.5 M H2SO4.

excellent resistance to carbon corrosion. To test the 20Mn-MC- 20Fe-NC-second catalyst (60%), suggesting an enhanced carbon
second catalyst under harsher conditions, we performed the dura- oxidation resistance. The catalyst degradation may be dependent on
bility test at 0.8 V (Fig. 5e). A larger decline of the current density total number of electrons passing through catalysts during the ORR.
of 57% after 100 hours is observed, relative to 0.7 V. The loss of cur- Therefore, we calculated the degradation rates against the total
rent density during the test can be partially recovered by potential electric charge (Supplementary Table 12). The degradation of E1/2
cycling between 0 to 1.0 V. For the first 20 hours, nearly 90% of the at 0.8 V is 0.237 mV C−1 for the 20Mn-NC-second catalyst, much
activity can be restored. However, the irreversible loss accumulates less than that for the 20Fe-NC-second catalyst (0.716 mV C−1).
and the current density only recovers 70% after 80 hours, indicating Stability tests at a constant current density (1.42 mA cm−2) further
that the activity loss is due to multiple factors. The reversible activ- verified that the 20Mn-NC-second catalyst is more stable than
ity loss may be associated with deactivation of active sites by anion the 20Fe-NC-second catalyst (Supplementary Fig. 25). Corrosion
binding or reversible adsorption of oxygen-containing functional resistance of carbon in catalysts was further assessed by cycling at
groups on local carbon atoms adjacent to MnN4 sites, which are a high potential range (1.0–-1.5 V) in N2-saturated 0.5 M H2SO4
considered to be part of the active site46. After the 100 hour test at (Supplementary Fig. 26). After 5,000 cycles, the capacitance of the
0.8 V, E1/2 showed a loss of 18 mV for the 20Mn-NC-second catalyst 20Mn-NC-second and 30Mn-NC-second increase 52% and 34%,
(Fig. 5f). In comparison, the 20Fe-NC-second catalyst only retains respectively, suggesting carbon oxidation in catalysts. However,
39% of its activity and a loss of E1/2 is up to 48 mV (Supplementary these values are much lower than those of 0Mn-NC-second (70%)
Fig. 24). The increase of capacitance for the 20Mn-NC-second cat- and the 20Fe-NC-second catalyst (94%) (Supplementary Table 9),
alyst (inset of Fig. 5f) is around 30%, much less than that of the indicating significantly enhanced carbon stability due to Mn doping

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Articles
a b
2 U = 1.23 V
Free energy (eV)
0
–1
Fig. 6 | Fundamental understanding of possible Mn active sites by using DFT calculations. a, Atomistic structure of MnN4C12 active site in the 20Mn-
NC-second catalyst. b, Calculated free-energy evolution diagram for ORR through a 4e− associative pathway on the MnN4C12 active site under electrode
potential of U =​ 1.23 V and U =​ 0.80 V. c, Atomistic structure of initial state (left panel, that is, state *OOH in b), transition state (middle panel) and final
state (right panel, that is, state *O +​ *OH in b) for OOH dissociation reaction on MnN4C12 active site. Grey, blue, purple, red and white balls represent C, N,
Mn, O and H atoms, respectively.
into ZIF-8 precursors. Thus, the enhanced stability of the Mn-N-C
catalyst likely results from the improved corrosion resistance of the
carbon in the catalysts.
To evaluate catalyst stability under real fuel cell operating condi-
tions, we conducted 100 hour life tests at a challenging high volt-
age of 0.7 V for MEAs made with the 20Mn-NC-second catalyst
(Supplementary Fig. 27). Although an initial degradation occurred
at 0.7 V, enhanced durability of the Mn-N-C cathode was observed,
compared with Co- and Fe-based catalysts15,22. The Mn-N-C catalyst
prepared from the two-step doping and adsorption approach repre-
sents one of the most stable PGM-free catalysts in acidic electrolytes
(Supplementary Table 10). In addition to the intrinsic stability of the
20Mn-NC-second catalyst, non-electrochemical factors including
degradation of the catalyst/ionomer interfaces and water flooding
also influence the performance durability of PGM-free cathodes.
DFT calculations. We identified a variety of possible MnNxCy
active sites and predicted their adsorption energies, free-energy
evolution and activation energies for the ORR in acids. As shown
in Supplementary Fig. 28, nine possible active sites (denoted as
MnN2C12, MnN3C9, MnN3C11, MnN4C8, MnN4C10, MnN4C12,
MnN5C10, Mn2N5C12 and Mn2N6C14) are carefully examined in the
computational study. The predicted adsorption energy of O2, OOH,
O, OH and H2O on each of these potential MnNxCy active sites are
presented in Supplementary Table 13. The DFT adsorption energy
results indicate that MnN2C12 and MnN3C9 sites, which have fewer
chelated N atoms around the central metal atom than the other
sites, bind the final product H2O too strongly to be good active sites.
Moreover, MnN3C11, MnN4C8, and Mn2N5C12 sites were predicted to
bind the intermediate OH too strongly, which are not good active
sites as well. Computational screening identified that MnN4C10,
MnN4C12, MnN5C10, and Mn2N6C14 sites have an appropriate
binding strength with the ORR species and can be active sites for
the 4e− pathway.
XAS analyses suggest that MnN4 structures are likely. Among
studied MnN4Cy sites, the MnN4C12 site (a Mn–N4 moiety bridging
over two adjacent zigzag graphitic edges, as shown in Fig. 6a) was
further predicted as the most optimal active sites (Supplementary
Table 13). Its free-energy evolution for the ORR (Fig. 6b) and the
transition state for an OOH dissociation on the active site were also
942
Nature Catalysis
O2 *OOH
U = 0.80 V
*O + *OH
*O + H2O *OH + H O 2H O
2 2
Reaction coordinates
calculated (Fig. 6c). We assumed a 4e− pathway, in which an O2 mol-
ecule will first adsorb on the top of central Mn and then O2 will be
protonated to form OOH. Next, the OOH will dissociate into O and
OH, and finally both O and OH will be protonated to form the final
product H2O. We employed the computational hydrogen electrode
method developed by Nørskov et al.47 and computed the free ener-
gies of all elementary steps as a function of electrode potential U
with reference to the RHE. Figure 6b shows that, under the standard
potentials of the ORR, U =​ 1.23 V, that is, zero overpotential, some
of the elementary reactions along the 4e− ORR associative pathway
are endergonic and thus thermodynamically unfavourable on the
MnN4C12 site. However, the free-energy change for these elemen-
tary reactions involving charge transfer will become negative (that
is, exergonic reaction) when the electrode potential U is lower than
a limiting potential of 0.80 V. Moreover, our computational results
(Fig. 6b) show that both the free-energy differences between O2*
and OOH* as well as between OH* and H2O* (* represents the
adsorption of the molecule on the active site) are close to zero under
the limiting potential, suggesting that the MnN4C12 site could have
an optimal activity for the ORR48. We performed the climbing image
nudged elastic band (CI-NEB) calculation to locate the transition
state and predict the activation energies for the OOH dissociation
reaction49, which is the crucial step of breaking the O–O bond for
the 4e− ORR associative pathway on the MnN4C12 site. Figure 6c
shows the atomic details of this reaction. In the initial state, OOH
is adsorbed on the central Mn atom; in the final state, both the dis-
sociated O and OH are co-adsorbed on the central Mn atom. The
reaction process from the initial state to the final state requires pass-
ing a transition state and overcoming an energy barrier of 0.49 eV,
which is surmountable. Consequently, the DFT results predict that
it is both thermodynamically and kinetically favourable for the 4e−
ORR to occur on the MnN4C12 site. According to the XANES and
EXAFS analysis (Fig. 2), the atomic Mn sites in the catalysts have
an oxidation state of 2+​ and coordinate with N mainly in the form
of MnN4. The MAADF-STEM images (Fig. 3) further proved the
atomic dispersion and N was detected in the immediate vicinity
of the single Mn sites by EEL point spectrum. Hence, the compu-
tational model explains well our experimental findings. Although
multiple possible sites in nanocarbon are able to coordinate with
single metals sites50, their ORR activities and stabilities in acids are
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Nature Catalysis
not sufficient. In contrast, the MnN4 structure therefore is the most
stable and the most active sites for the ORR in acids, likely due to the
lone pair electrons in pyridinic-N, which can form strong coordina-
tion bonds with transition metals.
We also performed DFT calculations to specifically examine the
influence of water solvent on the ORR in Mn-N-C catalysts, sug-
gesting that the water solvent effect is not significant enough to
alter the reaction mechanism for the ORR on the Mn-N-C cata-
lysts (Supplementary Fig. 29). The MnN4 sites with surrounding
graphitic-N dopants would also be active to promote the 4e− ORR
following the same OOH dissociation pathway (Supplementary
Fig. 30). The MnN4 site with immediately adjacent graphitic-N
dopants could have a lower limiting potential and lower activa-
tion energy for O–O bond breaking than the MnN4 site without
graphitic-N dopants.
Conclusion
An atomically dispersed and nitrogen-coordinated Mn-N-C cata-
lyst has been developed through a two-step doping and adsorption
approach, which is effective to significantly increase the density of
active sites. Atomically dispersed MnN4 sites were verified using
XAS experiments to determine their possible coordination as well
as directly observed at the atomic scale using low voltage, aberra-
tion-corrected STEM imaging coupled with EELS analysis. The
high activity of the Mn-N-C catalyst was evidenced by a commend-
able E1/2 of 0.80 V versus RHE in acids, which results from intrinsic
activity of atomically dispersed MnN4 sites with increased density
within a 3D porous ZIF-derived carbon. The remarkable stability is
due to the robust MnN4 sites and the enhanced corrosion resistance
of adjacent carbon derived from Mn doping. DFT calculations also
further confirmed that the MnN4C12 site has a favourable binding
energy with O2, OOH and H2O during the ORR as well as a sur-
mountable energy barrier to break O–O bonds for complete 4e−
reduction. Therefore, the reported atomically dispersed Mn-N-C
catalyst demonstrates an alternative concept to develop robust and
highly active PGM-free catalysts as replacements for Fe catalysts in
future PEMFC technologies.
Methods
Catalysts synthesis. In the first doping step, Mn-doped ZIF-8 precursors
were synthesized in a dimethylformamide (DMF) solution. The precursors are
designated as nMn-ZIF, where n is the molar percentage of Mn against total
metals (Mn and Zn) in the solutions. In this work, the n value varied from 0
(Mn free) to 30 at% and the concentration of 2-methylimidazle and Zn2+ were
controlled at 80 and 40 mmol l−1, respectively. Typically, a controlled amount
of zinc(ii) nitrate hexahydrate and manganese(iii) acetate dihydrate were
dissolved into DMF to form a uniform solution in a round-bottom flask (A).
2-Methylimidazole was dissolved in a conical-flask with DMF solution (B).
After mixing solutions A and B, the reaction temperature was increased to
120 °C, holding for 24 h to allow Mn-doped ZIF-8 nanocrystals to grow. After
cooling down to room temperature, the Mn-ZIF-8 nanocrystals were collected by
centrifugation, washed at least three times with ethanol, and then dried at 60 °C
in a vacuum oven for 5 h. The Mn-ZIF-8 precursors were subsequently heated at a
temperature of 1,100 °C in a tube furnace under N2 flow for 1 h to obtain the Mn
and N co-doped nanocarbon (NC). The samples were labelled as nMn-NC, where
n is atomic percent of Mn against total metal (for example, 20Mn-NC). Next,
acid leaching treatment in 0.5 M H2SO4 solution at 80 °C for 5 h was carried out to
remove Mn clusters and open porous structures of nMn-NC samples. Typically,
100 ml acid solution was used for 100 mg sample. An additional heat treatment
at 900 °C under N2 flow for 3 h is necessary to repair the carbon structure.
Such-prepared carbon samples labelled as nMn-NC-first are ready for the
second adsorption step.
In the second adsorption step, the nMn-NC-first powder was dispersed into a
mixed solution (isopropanol: water =​ 1:1) containing Mn(ii) chloride and nitrogen
sources (for example, dipicolylamine, cyanamide, phenanthroline or melamine).
After 2 h ultrasonication along with and 5 h magnetic stirring, the mixture was
collected by centrifugation (13,552g) and then dried at 60 °C in a vacuum oven
for 5 h. A subsequent thermal activation at temperature of 1,100 °C under N2
atmosphere for 1 h was conducted to synthesize the final catalysts, labelled as nMn-
NC-second. As control samples, 20Co-NC-second and 20Fe-NC-second samples
were prepared through similar procedures.
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Articles
Physical characterization. The overall particle size and distribution of the
catalysts’ morphologies were analysed using scanning electron microscopy on
a Hitachi SU 70 microscope at a working voltage of 5 kV. The crystal phases
in catalyst samples were studied by using powder XRD on a Rigaku Ultima IV
diffractometer with Cu Kα​X-rays. XPS was carried out using a Kratos AXIS
Ultra DLD XPS system equipped with a hemispherical energy analyser and a
monochromatic Al Kα​source operated at 15 keV and 150 W. Pass energy was fixed
at 40 eV for all of high-resolution scans. The N2 isothermal adsorption/desorption
was recorded at 77 K on a Micromeritics TriStar II. Before measurements, samples
were degassed at 150 °C for 5 h under vacuum. Atomic-resolution MAADF
images of atomically dispersed Mn sties were captured in a Nion Ultra STEM
U100 operated at 60 keV and equipped with a Gatan Enfina electron energy loss
spectrometer at Oak Ridge National Laboratory. HR-TEM and high-angle annular
dark field STEM were performed on JEOL JEM-2100F and Hitachi HD2700C
with a probe-corrector, respectively, at Brookhaven National Laboratory. Mn
K-edge EXAFS experiments were carried out at beamline 9BM-C at Advanced
Photon Sources at Argonne National Laboratory. The EXAFS data were collected
in fluorescence mode due to low Mn concentration by using a Vertox ME4 silicon
drift diode detector. Data analysis and EXAFS fitting were performed with the
Athena, Artemis, and IFEFFIT software packages.
Electrochemical measurements. An electrochemical workstation (CHI760b)
was employed to perform electrochemical measurements in a three-electrode
cell, in which an Hg/HgSO4 (K2SO4-saturated) electrode and a graphite rod
were used as the reference and counter electrodes, respectively. A RRDE (Pine,
AFMSRCE 3005) with a disk diameter of 5.6 mm was used as working electrode.
The reference electrode was calibrated to a RHE in the same electrolyte before
each measurement. The calibration of reference electrode was performed in
a two-electrode system. In the studied electrolyte (that is, 0.5 M H2SO4), a Pt
wire coated with Pt black was used for the RHE. The Pt electrode is purged and
saturated with high purity H2 during calibrating. A two-probe multi-meter was
employed to measure the potential difference between the reference electrode and
the Pt electrode, which is relative to RHE. The catalyst ink for the RRDE tests was
prepared by ultrasonically dispersing 5.0 mg catalysts and 30 µ​l Nafion (5 wt%) into
2.0 ml isopropanol solution. The ink was drop-casted on the disk electrode with a
controlled loading of 0.8 mg cm−2 and dried at room temperature to yield a thin-
film electrode. The electrocatalytic activity for the ORR was tested by steady-state
measurement using staircase potential control with a step of 0.05 V at an interval
of 30 s from 1.0 to 0 V versus RHE in O2-saturated 0.5 M H2SO4 solution at 25 °C
and a rotation rate of 900 r.p.m. Before recording the steady-state ORR polarization
plots, cyclic voltammetry in O2-saturated 0.5 M H2SO4 at a scan rate of 50 mV s−1
was performed to activate the catalysts until repeatable capacitance of catalyst
samples is achieved. Four-electron selectivity during the ORR was determined by
measuring the ring current for calculating H2O2 yield. Catalyst stability was studied
by cycling potentials from 0.6 to 1.0 V in O2-saturated 0.5 M H2SO4 at a scanning
rate of 50 mV s−1. To determine the carbon corrosion of catalysts, potential cycling
was conducted at high potentials from 1.0 to 1.5 V in N2-saturated 0.5 M H2SO4 at a
scanning rate of 500 mV s−1. In addition, holding at constant potential (for example,
0.7 and 0.8 V) or constant current density for 100 h during the ORR was carried
out. Pt/Vulcan XC-72 (20 wt% Pt) was used as the Pt/C reference, which was tested
in 0.1 M HClO4 solution with a Pt loading of 60 µ​g  cm−2.
Fuel cell tests. The best-performing Mn-N-C catalyst was used to prepare
cathodes for MEA tests in real fuel cell environments. The cathode catalyst inks
were dispersed by ball mixing the catalyst in 1-proponal, de-ionized water, and
Nafion suspension for 2 d. The inks were brush painted on one side of a Nafion
212 membrane until the cathode catalyst loading reached ~4.0 mg cm−2. An in-
house-made Pt electrode decal (0.25 mg Pt cm−2) was used as the anode, and it was
transferred onto the other side of brush painted Nafion 212 membrane at ~150 °C
for 3 min. The full catalyst-coated membrane, which had an active geometric area
of 5.0 cm2, was inserted between two Toray H30 gas diffusion layers and assembled
into a single cell with single-serpentine flow channels. The single cell was then
evaluated in a fuel cell test station (100 W, Scribner 850e, Scribner Associates). The
cells were conditioned at 0.3 V, 100% relative humidity and 80 °C for at least 3 h
and until the steady-state current was reached. Air/oxygen flowing at 200 ml min−1
and H2 (purity 99.999%) flowing at 200 ml min−1 were used as the cathode and
anode reactants, respectively. The back pressures during the fuel cell tests are based
on US Department of Energy protocols, that is 1.0 bar reactant gas. Because of
100% relative humidity, vapour pressure is around 0.5 bar. Thus, the total pressure
applied to MEAs is around 1.5 bar (150 KPa). Fuel cell polarization curves were
recorded in a current control mode. All the cathode catalyst layers contain 35 wt%
of Nafion.
Computational methods. All the first-principles DFT calculations in this work
were performed using the Vienna ab initio simulation package. The projector
augmented wave pseudopotential was used to describe the core electrons of
the elements. The energy cut-off was set as 400 eV to expand wave function.
The electronic exchange-correlation was described by generalized gradient
approximation with the Perdew, Burke and Ernzernhof functional. The brillouin
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zone was sampled with Monkhorst-pack 4 ×​  4  ×​  1 k-point mesh for active sites
MnN2C12, MnN3C9, MnN3C11, MnN4C10, MnN5C10, Mn2N6C14 and Mn2N5C12,
3 ×​  3  ×​  1 k-point mesh for site MnN4C12, and 4 ×​  3  ×​  1 k-point mesh for site
MnN4C8. A vacuum region of 14 Å thick was added in the direction normal to the
carbon layer to ensure negligible interaction between the slab and its images. In
the DFT structure optimization calculations, the atomic positions were allowed
to relax until the force on each ion was below 0.01 eV Å−1. The transition states of
chemical reaction were located using the CI-NEB method, in which the force along
and perpendicular to the reaction path were relaxed to less than 0.05 eV Å−1. Zero-
point energy correction has been included in all the reported energies.
Data availability
The data that support the findings of this study are available from the primary
corresponding author (G.Wu) upon reasonable request.
Received: 16 May 2018; Accepted: 17 September 2018;
Published online: 29 October 2018
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Acknowledgements
G.Wu thanks the Research and Education in eNergy, Environment and Water (RENEW)
program at the University at Buffalo, SUNY and National Science Foundation (CBET-
1604392, 1804326) for partial financial support. G.Wu, G.Wang and H.X. acknowledge
support from the US Department of Energy (DOE), Energy Efficiency and Renewable
Energy, Fuel Cell Technologies Office (DE-EE0008075). Electron microscopy research
was conducted at Oak Ridge National Laboratory’s Center for Nanophase Materials
Sciences of (D.A.C. and K.L.M) and the Center for Functional Nanomaterials at
Brookhaven National Laboratory (S.H. and D.S., under contract No. DE-SC0012704),
which both are US DOE Office of Science User Facilities. XAS measurements were
performed at beamline 9-BM at the Advanced Photon Source, a User Facility operated
for the US DOE Office of Science by Argonne National Laboratory under Contract
No. DE-AC02-06CH11357 (Z.F. and G.E.S.). Z.W. and J.L. thank the National Natural
Science Foundation of China (Grant No. 21273058 and 21673064) for support.
Author contributions
G.Wu, Z.W. and J. L. designed the experiments, analysed the experimental data, and
wrote the manuscript. J.L., M.C. and H.Z. synthesized catalyst samples and carried
Nature Catalysis | VOL 1 | DECEMBER 2018 | 935–945 | www.nature.com/natcatal
Articles
out electrochemical measurements. D.A.C., K.L.M, S.H. and D.S performed electron
microscopy analyses and data interpretation. S.K. conducted XPS analysis. M.W., M.L.,
G.E.S. and Z.F. recorded and analysed XAS data. C.L. and H.X. carried out fuel cell tests.
B.L., K.L. and G.Wang conducted computational studies.
Competing interests
The authors declare no competing interests.
Additional information
Supplementary information is available for this paper at https://doi.org/10.1038/
s41929-018-0164-8.
Reprints and permissions information is available at www.nature.com/reprints.
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