Fe,N-Codoped Graphdiyne Displaying Efficient Oxygen Reduction Reaction Activity

Article abstract of DOI:10.1002/cssc.201802170

On account of the high-cost of platinum, researchers are working to develop a new catalyst that is cheaper and has a catalytic effect equivalent to platinum. Herein, owing to the unique acetylenic bonds in graphdiyne, iron, nitrogen co-doped graphdiyne (Fe-N-GDY) is a promising nonprecious metal catalyst, which has been developed with just a small amount of iron precursor with the plan to substitute it for Pt-based catalysts. The as-synthesized Fe-N-GDY composited catalyst shows excellent catalytic performance with the onset potential of 0.94 V versus reversible hydrogen electrode and limited current density of 5.4 mA cm^?2. Moreover, it shows excellent resistance to methanol poisoning and stability in both acidic and alkaline electrolytes, which makes potentially applicable in the oxygen reduction reaction field.

Full text of DOI:10.1002/cssc.201802170

Accepted Article
Title: Fe, N-codoped Graphdiyne Displaying Efficient Oxygen
Reduction Reaction Activity
Authors: Wenyan Si, Ze Yang, Xin Wang, Qing Lv, Fuhua Zhao,
Xiaodong Li, Jianjiang He, Yunze Long, Juan Gao, and
Changshui Huang
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To be cited as: ChemSusChem 10.1002/cssc.201802170
Link to VoR: http://dx.doi.org/10.1002/cssc.201802170
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10.1002/cssc.201802170
ChemSusChem
COMMUNICATION
Fe, N-codoped Graphdiyne Displaying Efficient Oxygen
Reduction Reaction Activity
Wenyan Si,[a,c] Ze Yang,[a] Xin Wang,[a,b] Qing Lv,*[a] Fuhua Zhao,[a] Xiaodong Li,[a,b] Jianjiang He,[a] Ning
Wang,*[a] Yunze Long,[c] Juan Gao,[a] Changshui Huang*[a]
Abstract: On account of the high-cost of platinum, researchers are
working to develop a new catalyst which is cheaper and has a
catalytic effect that is equivalent to platinum. Herein, owing to the
unique acetylenic bonds in the graphdiyne, the iron-nitrogen-doped
graphdiyne (Fe-N-GDY) as a new promising nonprecious metal
catalyst is developed with just a small amount of iron precursor to
substitute for Pt-based catalysts. The as-synthesized Fe-N-GDY
composited catalyst shows excellent catalytic performance with the
onset potential of 0.94V versus RHE and limited current density of
5.4 mA cm-2. Moreover, it shows excellent resistance to methanol
poisoning and stability in both acidic and alkaline electrolytes, which
makes it the potential application in oxygen reduction reaction field.
carbon (M–N–C) catalysts. Many M-N-C catalysts have exhibited
comparable catalytic activity to commercial Pt/C.[6] Among them,
iron-nitrogen-carbon (Fe-N-C) composited catalysts have
emerged as one of the most promising non-precious-metal
catalysts with high catalytic activity, superior methanol tolerance
and low cost.[7] However, despite the great performance, some
problems also existed in these Fe-N-C catalysts. Because of the
low adsorption energy between Fe and C materials, much Fe
precursor is needed to produce Fe-N-C catalysts with only a
small amount of doped Fe. For example, with the mass of Fe in
precursor exceeding that of carbon substrate, the content of Fe
was only 0.81 wt% in the as-synthesized Fe doped carbon
materials after acid leaching.[1b] Moreover, the stabilities of Fe-N-
C catalysts are not high enough, especially in the acidic media.
Therefore, it is urgent to develop a new carbon material to
improve the performance of Fe-N-C catalysts for ORR.
The oxygen reduction reaction (ORR) is an important cathodic
reaction involved in fuel cells and other energy storage and
conversion devices.[1] In this field, the Pt-based material is used
as a high active catalyst. However, with high cost and low
stability, Pt is not so ideal for various energy conversion systems.
So, scientists are looking for a new type of material that can
replace Pt-based materials to solve this problem. Currently,
plenty of carbon materials doped with various non-metallic
elements have been used as catalysts for ORR.[2] Although the
catalytic activities of the most reported carbon-based metal-free
catalysts were much poorer than that of the Pt-based materials,
a series of progress and improvement in the metal-free catalyst
field have been made. Among all these non-metallic elements,
Nitrogen (N) was used most commonly. The electronegativity of
N (3.0) is higher than that of C (2.5), inducing positive charge
density for adjacent C atoms which are favorable for O2
adsorption during the ORR. Moreover, the size of the N atom is
similar to that of C, which makes it easy for N to be doped into
the carbon framework. It is reported that the N doping can
greatly enhance the catalytic performances of the carbon
materials, and drive more reactions toward a four-electron
process.[3]
Graphdiyne (GDY) is
a novel two-dimensional carbon
allotrope, which consists of sp- and sp2- hybridized carbon
atoms, different from graphene and other traditional carbon
materials.[8] On account of the unique structure and stable
chemical properties, GDY exhibits excellent performance in
many aspects, such as lithium storage,[9] supercapacitor,[10] UV
photodetector,[11] DNA detection[12] and oil/water separation.[13]
Recently, the N-doped GDY has been reported to reveal high
activity for ORR.[14] The density functional theory (DFT)
calculations have demonstrated that the adsorption energy
between GDY and many transition metals (such as Fe, Pt, Ru) is
high.[15] Therefore, a large amount of Fe may be doped into GDY
using a small quantity of Fe precursor. Moreover, the stability of
Fe-N-GDY (Fe, N co-doped GDY) may be improved, compared
to other Fe and N co-doped carbon materials.
Herein, Fe-N-GDY catalysts were synthesized with FeCl3 and
melamine as Fe source and N source, respectively. During the
synthesis process, just a small amount of FeCl3 (less than 2 wt%
Fe) was used. Heat-treatment was used to dope Fe and N into
the GDY framework, which can not only develop abundant
active sites for ORR, but also remove small chips and oxygen-
containing groups of GDY. The unstable Fe was removed by
acid leaching. The contents of Fe and N in the Fe-N-GDY were
adjusted by altering the ratio of the added FeCl3 with 0.1 wt%,
0.5 wt%, 1.0 wt%, 1.5 wt% and 2.0 wt% Fe, donated as 0.1%Fe-
N-GDY, 0.5%Fe-N-GDY, 1.0%Fe-N-GDY, 1.5%Fe-N-GDY and
2.0%Fe-N-GDY. Among these Fe-N-GDY catalysts, the 1.5%Fe-
N-GDY exhibited the highest activity for ORR, almost similar with
commercial Pt/C (JM), but higher stability and methanol
tolerance than that of Pt/C. Compared with other M-N-C catalyst
materials, the 1.5%Fe-N-GDY performed catalytic activity more
efficiently.[16]
To further improve the catalytic activity of N doped carbon
materials (N-C), earth-abundant transition metals (such as Fe,[4]
Co and Ni[5]) were doped to obtain nonprecious metal–nitrogen–
[a]
Qingdao Institute of Bioenergy and Bioprocess Technology,
Chinese Academy of Sciences,
No. 189 Songling Road, 266101, Qingdao, China.
E-mail: huangcs@qibebt.ac.cn; lvqing@qibebt.ac.cn.
University of Chinese Academy of Sciences
Beijing 100039, PR China.
[b]
[c]
Qingdao University
308 Ningxia Road, 266071, Qingdao, China.
Supporting information for this article is given via a link at the end of
the document.
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10.1002/cssc.201802170
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Figure 2. (a) XRD pattern of 1.5%Fe-N-GDY. (b) XPS full-scan spectra, (c)
Raman spectra and (d) the ratios of ID/IG in Raman spectra for the initial GDY
and all Fe-N-GDY samples.
Figure 1. (a) Schematic illustration of synthetic procedure for Fe-N-GDY
catalysts. SEM images of (b) 0.1% Fe-N-GDY, (c) 1.5% Fe-N-GDY and (d) 2%
Fe-N-GDY. TEM images of (e) 0.1% Fe-N-GDY, (f) 1.5%Fe-N-GDY and (g)
2.0%Fe-N-GDY.
nanoparticles are γ-Fe2O3. The broad peak at ~23.0°
corresponds to (002) plane of GDY. Figure 2b reveals the XPS
full-scan spectra of all Fe-N-GDY samples. Peaks for carbon,
nitrogen and oxygen can be observed clearly. The occurrence of
N1s peak shows the successful doping of nitrogen into the GDY.
However, the XPS peak of metal Fe is not obvious, owing to its
low contents in the samples. As shown in Figure 2c, the Raman
spectra of all prepared samples display three peaks. Two
prominent peaks around 1335.7 and 1586.6cm-1 were typical
peaks, which corresponded to the D band and G band. Raman
spectra showed that the calcined Fe-N-GDY catalysts exhibited
higher ID/IG ratios (Figure 2d) compared to the initial GDY,
indicating that more defects and edge sites were created after
the doping of Fe and N. The small peak at 1975 cm-1 can be
ascribed to carbon-carbon triple bond of GDY.[8d]
Figure 1a is a schematic illustration of synthesis process of
the Fe-N-GDY catalysts. Melamine and ferric trichloride
hexahydrate were used as N and Fe source, respectively, to
dope N and Fe into the GDY. During the synthesis procedure,
only a small amount of FeCl3 was used (the contents of Fe
varied from 0.1 wt% to 2 wt%). The morphology of the Fe-N-
GDY samples was detected by SEM and TEM. As shown in the
Figure 1b, 1c and S1 collected by SEM, there are many
nanoparticles existed in the 0.1%Fe-N-GDY and 1.5%Fe-N-GDY
samples, similar to that of the original GDY.[17] With the content
increase of iron, the surface of GDY was destroyed and many
holes were produced when the content of iron approaching 2%
(Figure 1d). The pictures of the Figure 1 (e, f, g) are the TEM
images of the 0.1%Fe-N-GDY, 1.5%Fe-N-GDY and 2.0%Fe-N-
GDY. It can be observed that compared to the original GDY,[14]
abundant micropores were produced for these Fe-N-GDY
samples, which should be caused by the removal of small GDY
pieces and the oxygen-containing functional groups at high
temperature. It can be seen from Figure S3, with the increase of
Fe, the average size of the micropores was enhanced as well.
The doped Fe can be observed as the black particles in the TEM
images. And the Fe nanoparticles and the interlayer stripes of
GDY can be observed clearly from HRTEM (Figure S2). With
more FeCl3 used in the synthesis procedure, both the number
and the size of Fe particles were increased. For 2.0%Fe-N-GDY
sample, some Fe particles with diameter as large as ~50 nm can
be seen, which should have little effect on improving its catalytic
activity for ORR.[15a]
Figure 2a shows the XRD pattern of 1.5%Fe-N-GDY sample.
The XRD pattern can be well indexed to a cubic cell of γ-Fe2O3
with a = b = c = 8.351 Å, in good agreement with the standard
data (JCPDS39-1346). It indicates that the large Fe
Figure 3. (a) XPS full-scan spectra of 1.5%Fe-N-GDY. XPS narrow-scan
spectra for N 1s (b), C1s (c) and Fe2p (d) regions of 1.5%Fe-N-GDY,
respectively.
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Surface Fe and
N
contents of 1.5%Fe-N-GDY were
element is introduced in this catalyst, providing another active
site, Fe-Nx.[21] Another possible active site in Fe-N-GDY is
carbon layers encapsulated iron (Fe@GDY), which can also
improve its catalytic activity for ORR.[22] In addition, the large
diameter Fe nanoparticles should have little effect on improving
the catalytic properties.[15a] Therefore, N, Fe-Nx and Fe@GDY
should be the active sites for Fe-N-GDY. On the other hand, the
strong interaction between iron and GDY made the catalyst
more stable in the reaction process.
determined by XPS, which is 3.2 wt% and 5.2 wt%, respectively.
The high content of the doped Fe with small amount of Fe
precursor should derive from the strong interaction between Fe
and GDY. GDY consists of special sp- hybridized carbon atoms,
different from graphene (only sp2) and other traditional carbon
materials. The special carbon-carbon triple bond in GDY can
supply stable binding sites for metal atoms.[18] Thus, high
content of iron can be doped into GDY with just a small amount
of iron precursor. Besides, the stability of Fe-N-GDY should also
be improved. The N1s spectrum of 1.5%Fe-N-GDY was further
analyzed in Figure 3b. It can be deconvoluted into four peaks at
398.3, 399.4, 401, and 402.7 eV. The peak at 399.4eV
corresponds to the characteristic peak of Fe-N bond. The
appearance of other peaks centred at 398.3, 401, and 402.7eV
can be assignable to pyridinic-N, graphitic-N, and oxidized
nitrogen compounds.[7, 19] The C1s XPS spectrum of 1.5%Fe-N-
GDY was showed in Figure 3c, which can be deconvoluted into
four peaks with binding energy of 284.4, 284.8, 285.9, and 288.1
eV, which can be corresponded to C-C (sp2), C-C (sp), C=N,
and C=O, respectively.[3] The Figure 3d is the Fe2p XPS
spectrum of 1.5%Fe-N-GDY. The Fe2p XPS spectrum of
1.5%Fe-N-GDY (Figure 3d) was deconvoluted into two peaks
centred at 707.5, 708.1 and 711.5 eV, corresponding to the Fe-
N, Fe-C and Fe 2p3/2 of Fe3+, respectively.[5a]
The catalytic performance of the prepared samples for ORR
was tested in the alkaline electrolyte (0.1 M KOH) by the rotating
ring disk electrode (RRDE) method. All samples with different
iron contents exhibited similar onset potential at about 0.94 V
versus RHE (Figure 4a), which was equivalent to commercial
Pt/C. Especially, the 1.5%Fe-N-GDY expressed the most
superior limited current density, closed to commercial Pt/C
(Figure 4b), whereas other Fe-N-GDY catalysts performed lower
limited current densities than that of the Pt/C. And then, the
resistance of methanol poisoning and stability have been
measured. After the normal LSV test completed, 4 mL of
methanol was injected into the KOH electrolyte and the
performance was tested again. As shown in Figure 4c and 4d,
the catalytic activity of 1.5%Fe-N-GDY changed a little after the
injection of methanol. However, there was an obvious peak for
methanol electrooxidation in the LSV curves of Pt/C after the
injection of methanol. It indicates that 1.5%Fe-N-GDY is much
better than the commercial Pt/C in the resistance to methanol
toxicity aspect. The stability of 1.5%Fe-N-GDY was also tested
and compared with that of Pt/C. In 0.1 M KOH, the sample of
1.5%Fe-N-GDY shows an 18 mV negative shift of half-wave
potential in the LSV curves (Figure 4f) after continuous 5000
cycles CV of the accelerating aging test, smaller than the
commercial Pt/C with negative half-wave potential shift of 35 mV
(Figure 4e). Therefore, the stability of 1.5%Fe-N-GDY is better
than that of commercial Pt/C. Due to the introduction of iron,
more effective catalytic sites were produced in catalysts, which
induced the high catalytic activity of 1.5%Fe-N-GDY. Fe-N-GDY
catalyst was obtained by pyrolysis iron, nitrogen-contained
precursor and GDY powder. There should be many kinds of
active sites in this catalyst, such as Fe, Fe-Nx, N, etc. Among
these reaction sites, nitrogen is demonstrated the most
commonly doped and efficient non-metallic element for carbon-
based catalysts on ORR field.[20] On the base of N doping, Fe
Figure 4. (a) LSV curves of all the Fe-N-GDY samples at 1600 rpm in O2-
saturated 0.1M KOH. (b) Schematic diagram for the catalytic process for ORR
with 1.5%Fe-N-GDY in 0.1M KOH. LSVs of (c) commercial 20wt% Pt/C and
(d) 1.5%Fe-N-GDY at a scan rate of 5 mV s-1 before and after injecting
methanol in O2-saturated 0.1 M KOH at 1600 rpm. LSVs of (e) commercial
20wt% Pt/C and (f) 1.5%Fe-N-GDY at a scan rate of 5 mV s-1 before and after
5000 potential cycles in O2-saturated 0.1 M KOH solution at 1600 rpm.
Moreover, to prove that both Fe and N play an essential role
in the catalyst, the catalysts of only N-doped GDY and only Fe-
doped GDY have been fabricated. The limited current densities
of N-GDY and 1.5%Fe-GDY are both smaller than that of Fe and
N co-doped GDY (Figure 5a). In order to verify the important role
of GDY in this composite catalyst, other carbon materials (Super
P and Graphene) have been used to perform the same
pretreatment as GDY to obtain 1.5%Fe-N-Graphene, and
1.5%Fe-N-Super P. In the same test conditions, the catalytic
activities of 1.5%Fe-N-Super P and 1.5%Fe-N-Graphene are
much worse than that of Fe-N-GDY (Figure 5a). Therefore, the
Fe, N and GDY are all essential for the excellent performance of
this composite catalyst.
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(Figure 6c and 6d). The stability of the catalyst in acidic
condition is also measured by comparing the catalytic activity
before and after an accelerating aging test. The half-wave
potential of 1.5%Fe-N-GDY shifted 52 mV negatively after 5000
cycles CV, whereas Pt/C showed a negative shift of 71mV after
the accelerating aging test. It indicated that the stability of
1.5%Fe-N-GDY is better than that of Pt/C (Figure 6e and 6f).
The test results showed that the catalyst has great activity and
stability under acidic conditions.
Figure 5. (a) LSVs of 1.5%Fe-N-Graphene, 1.5%Fe-N-Super
P N-GDY,
1.5%Fe-GDY and 1.5%Fe-N-GDY in O2-saturated 0.1 M KOH at 1600 rpm. (b)
The K–L plots of 1.5%Fe-N-GDY. (c) The Tafel slopes for Fe-N-GDY and Pt/C.
LSVs for (d) Electron-transfer number and peroxide yield of the 1.5%Fe-N-
GDY calculated from the RRDE in O2-saturated 0.1 M KOH.
The Tafel slope for the 1.5%Fe-N-GDY (89.1mV/dec) was
close to Pt/C (87.6mV/dec) (Figure 5c). That explained the first
electron transfer is the rate-determining step for 1.5%Fe-N-GDY,
similar to Pt/C. The electron transfer number of commercial Pt/C
and 1.5%Fe-N-GDY in ORR not only calculated by K-L equation
stemmed from the LSV curves at various rotation speeds (Figure
S4, S5 and Figure 5b), but also measured by RRDE linear
sweep voltammogram (Figure 5d). Both tests showed that the
electron transfer number of 1.5%Fe-N-GDY was above 3.87,
indicating that the ORR on 1.5%Fe-N-GDY was mainly through
a four-electron process and the production of H2O2 was below
6% (Figure 5f). The low production rate of H2O2 means that the
Fe-N-GDY catalyst is environmentally friendly.
Figure S6 shows the electron transfer number of 0.1%Fe-N-
GDY, 0.5%Fe-N-GDY, 1.0%Fe-N-GDY and 2.0%Fe-N-GDY
tested by RRDE. The electron transfer numbers were 3.79, 3.48,
3.71 and 3.66, respectively. Comparing to Figure 5d, the catalyst
of 1.5%Fe-N-GDY’s electron transfer process was most tended
to the four-electron process. The peroxide yields of 0.1%Fe-N-
GDY, 0.5%Fe-N-GDY, 1.0%Fe-N-GDY and 2.0%Fe-N-GDY
were 10.41%, 25.89%, 14.68% and 16.37%, while peroxide yield
of 1.5% Fe-N-GDY was below 6% (Figure 5d). 1.5%Fe-N-GDY
has the lowest yield of peroxide tested by RRDE, indicating that
the two-electrons process is the least in the reaction process,
and this catalyst is the most efficient.
The LSVs of all the Fe-N-GDY samples (Figure 6a) were
also used as electrocatalysts for ORR in the acidic electrolyte
(0.1M HClO4). Figure 6a shows that 1.5%Fe-N-GDY exhibited
the best catalytic comprehensive activity for ORR among all the
Fe-N-GDY catalysts, comparable to that of commercial Pt/C
(Figure 6b). Moreover, the 1.5%Fe-N-GDY hold better methanol
tolerance than that of Pt/C. Under acidic conditions, the
commercial Pt/C was still emerged an obvious oxidation peak of
methanol in LSV test after the 4 mL methanol injected in 0.1M
HClO4, while no oxidation peak existed for 1.5%Fe-N-GDY
Figure 6. (a) LSV curves of all the Fe-N-GDY samples and commercial Pt/C at
1600 rpm in O2-saturated 0.1M HClO4. (b) Schematic diagram for the catalytic
process for ORR with 1.5%Fe-N-GDY in 0.1M HClO4. LSVs of (c) commercial
20 wt% Pt/C and (d) 1.5%Fe-N-GDY at a scan rate of 5 mV s-1 before and
after injecting methanol in O2-saturated 0.1M HClO4 at 1600 rpm. LSVs of (e)
commercial 20wt% Pt/C and (f) 1.5%Fe-N-GDY at a scan rate of 5 mV s-1
before and after 5000 potential cycles in O2-saturated 0.1 M HClO4 solution at
1600 rpm.
We synthesized a new type of non-precious-metal catalyst
using novel GDY materials for ORR. Due to the bonding effect
between GDY and metal, plentiful Fe was doped into GDY with
just a very small amount of precursor. As shown in Table S1, the
catalytic activity of 1.5%Fe-N-GDY is equivalent to commercial
Pt/C under alkaline condition, better than those of most of the
reported M-N-C, and also excellent under acidic condition. In
addition, the resistance of methanol poisoning and stability
performance are better than commercial Pt/C. The Fe, N and
GDY express powerful synergistic effect, which is all essential to
improving the catalytic activity and stability of the Fe-N-GDY
catalysts. These Fe and N co-doped GDY catalysts will have
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potential applications in fuel cells and other energy storage
devices.
Keywords: graphdiyne • oxygen reduction reaction • iron-
nitrogen doped • full cells • electrochemistry
[1] a) L. M. Dai, Y. H. Xue, L.T. Qu, H. J. Choi, J. B. Baek, Chem. Rev. 2015,
115, 4823-4892; b) M. L. Xiao, J. B. Zhu, L. G. Feng, C. P. Liu, W. Xing,
Adv. Mater. 2015, 27, 2521-2527; c) Y. G. Guo, J. S. Hu, L. J. Wan, Adv.
Mater. 2008, 20, 2878-2887.
Experimental Section
[2]S. S. Zhang, Y. J. Cai, H. Y. He, Y. Q. Zhang, R. J. Liu, H. B. Cao, M. Wang,
J. J. Liu, G. J. Zhang, Y. L. Li, H. B. Liu, B. Li, J. Mater. Chem. A 2016, 4,
4738-4744.
Preparation of ORR catalysts
Firstly, GDY and 100 mg melamine were dispersed in 100 mL ethyl
alcohol， and the mixture was sonicated for 30 min. Then, a small
amount of FeCl3·6H2O was added into above suspension with stirring for
24 hours at RT. The total mass of iron and GDY was 15 mg. The
contents of Fe from FeCl3·6H2O were 0.1 wt%, 0.5 wt%, 1.0 wt%, 1.5
wt% and 2.0 wt%, respectively. Next, the above suspension was dried in
vacuum. After these preprocessing, the mixture of GDY, melamine and
FeCl3·6H2O was pretreated at 400 oC, and then the temperature went up
to 900 oC under an Ar flow for 1 hour. The black powder of Fe-N-GDY
catalysts was obtained via the calcination. Then, the powder was
leaching in 1.0 M HCl solution for 2 h at 80 oC. All electrochemical results
of samples were tested after acid leaching.
[3]R. J. Liu, H. B. Liu, Y. L. Li, Y. P. Yi, X. K. Shang, S. S. Zhang, X. L. Yu, S. J.
Zhang, H. B. Cao, G. J. Zhang, Nanoscale 2014, 6, 11336-11343.
[4] F. L. Meng, Z. L. Wang, H. X. Zhong, J. Wang, J. M. Yan, X. B. Zhang, Adv.
Mater. 2016, 28, 7948-7955.
[5] a) Y. J. Ai, M. Q. He, Q. R. Lv, L. Liu, H. B. Sun, M. Y. Ding, Q. L. Liang,
Chem-Asian J 2018, 13, 89-98; b) T. Chen, S. Q. Guo, J. Yang, Y. D. Xu, J.
Sun, D. L. Wei, Z. X. Chen, B. Zhao, W. P. Ding, Chemphyschem 2017, 18,
3454-3461; c) X. Z. Fang, L. Jiao, S. H. Yu, H. L. Jiang, ChemSusChem
2017, 10, 3019-3024.
[6] a) F. S. Farahani, B. Mecheri, M. R. Majidi, M. A. C. de Oliveira, A.
D'Epifanio, F. Zurlo, E. Placidi, F. Arciprete, S. Licoccia, J. Power Sources
2018, 390, 45-53; b) C. Q. Li, F. Z. Sun, Y. Q. Lin, J. Power Sources 2018,
384, 48-57.
[7] Y. Y. Li, C. Z. Guo, J. Q. Li, W. L. Liao, Z. B. Li, J. Zhang, C. G. Chen,
Carbon 2017, 119, 201-210.
[8] a) J. Y. Zhou, X. Gao, R. Liu, Z. Q. Xie, J. Yang, S. Q. Zhang, G. M. Zhang,
H. B. Liu, Y. L. Li, J. Zhang, Z. F. Liu, J. Am. Chem. Soc. 2015, 137, 7596-
7599; b) Z. Y. Jia, Y. J. Li, Z. C. Zuo, H. B. Liu, C. S. Huang, Y. L. Li, Acc.
Chem. Res. 2017, 50, 2470-2478; c) Y. J. Li, L. Xu, H. B. Liu, Y. L. Li,
Chem. Soc. Rev. 2014, 43, 2572-2586; d) G. X. Li, Y. L. Li, H. B. Liu, Y. B.
Guo, Y. J. Li, D. B. Zhu, Chem. Commun. 2010, 46, 3256-3258.
[9] a) C. S. Huang, S. L. Zhang, H. B. Liu, Y. J. Li, G. L. Cui, Y. L. Li, Nano
Energy 2015, 11, 481-489; b) C.-S. Huang, Y.-L. Li, Acta Phys. Chim. Sin.
2016, 32, 1314-1329; c) J. J. He, N. Wang, Z. Yang, X. Y. Shen, K. Wang,
C. S. Huang, Y. P. Yi, Z. Y. Tu, Y. L. Li, Energy Environ. Sci. 2018, 11, 2893-
2903.
[10]K. Krishnamoorthy, S. Thangavel, J. C. Veetil, N. Raju, G. Venugopal, S. J.
Kim, Int. J. Hydrogen Energy 2016, 41, 1672-1678.
[11] Z. W. Jin, Q. Zhou, Y. H. Chen, P. Mao, H. Li, H. Liu, J. Z. Wang, Y. L. Li,
Adv. Mater. 2016, 28, 3697-3702.
[12] N. Parvin, Q. Jin, Y. Z. Wei, R. B. Yu, B. Zheng, L. Huang, Y. Zhang, L. H.
Wang, H. Zhang, M. Y. Gao, H. J. Zhao, W. P. Hu, Y. L. Li, D. Wang, Adv.
Mater. 2017, 29, 1606755.
[13]X. Gao, J. Y. Zhou, R. Du, Z. Q. Xie, S. B. Deng, R. Liu, Z. F. Liu, J. Zhang,
Adv. Mater. 2016, 28, 168-173.
[14] Q. Lv, W. Y. Si, Z. Yang, N. Wang, Z. Y. Tu, Y. P. Yi, C. S. Huang, L. Jiang,
M. J. Zhang, J. J. He, Y. Z. Long, ACS Appl. Mater. Inter. 2017, 9, 29744-
29752.
[15] a) Y. J. Chen, S. F. Ji, Y. G. Wang, J. C. Dong, W. X. Chen, Z. Li, R. A.
Shen, L. R. Zheng, Z. B. Zhuang, D. S. Wang, Y. D. Li, Angew. Chem.
2017, 129, 7041-7045; Angew. Chem. Int. Edit. 2017, 56, 6937-6941; b) Z.
Z. Lin, Carbon 2015, 86, 301-309; c) D. W. Ma, T. X. Li, Q. G. Wang, G.
Yang, C. Z. He, B. Y. Ma, Z. S. Lu, Carbon 2015, 95, 756-765.
[16] Z. Q. Xu, J. H. Ma, M. H. Shi, Y. H. Xie, C. Feng, J. Colloid Interf. Sci.
2018, 523, 144-150.
Electrochemical measurements
All electrochemical data were obtained on an electrochemical
biopotentiostat (760E, CH Instrument) with a routine three electrodes
system. A saturated calomel electrode (SCE) was used as the reference
electrode, a Pt foil as the counter electrode and the catalyst film coated
rotating ring-disk electrode (RRDE, 4 mm in diameter) as the working
electrode. 5 mg of the as-synthesized Fe-N-GDY catalyst was well-
dispersed in a solution incorporating 50 µL Nafion (5 wt%) and 950 µL
ethanol as catalyst ink. A commercial Pt/C catalyst (20 wt% Pt, Johnson
Matthey, JM) ink was prepared in the same method. The catalyst
loadings on RRDE were 0.4 mg cm-2 for Fe-N-GDY catalysts and 20 μgPt
cm-2 for commercial Pt/C catalyst. All potentials in this study were versus
the reversible hydrogen electrode (RHE). The ORR measurements were
tested under the acidic (0.1 M HClO4) and alkaline (0.1 M KOH)
conditions. Linear sweep voltammetry (LSV) tests were measured at RT
over the potential range of 0 V to 1.2 V vs RHE with a scan rate of 5 mV
s-1. Before each experiment, the electrolyte was guaranteed to be
saturated with Ar/O2 by means of bubbling Ar/O2 for 20 min. The anti-
methanol experiment was conducted by comparing the change of the
LSV curves before and after injection of 4 mL methanol. The methanol
concentration is above 99.5%. The measurement of stability was tested
by comparing the negative shift of the half-wave potential in the LSV
curves before and after 5000 cycles continuous cyclic voltammetry (CV)
in O2-saturated electrolyte. The scanned potential range of stability
testing was 0.6 V~1.2 V vs RHE.
[17]M. J. Zhang, X. X. Wang, H. J. Sun, N. Wang, Q. Lv, W. W. Cui, Y. Z. Long,
C. S. Huang, Sci. Rep. 2017, 7, 11535.
[18] C. S. Huang, Y. J. Li, N. Wang, Y. R. Xue, Z. C. Zuo, H. B. Liu, Y. L. Li,
Chem. Rev. 2018, 118, 7744-7803.
[19] W. Ding, Z. D. Wei, S. G. Chen, X. Q. Qi, T. Yang, J. S. Hu, D. Wang, L. J.
Wan, S. F. Alvi, L. Li, Angew. Chem. 2013, 125, 11971-11975; Angew.
Chem. Int. Edit. 2013, 52, 11755-11759.
[20] Q. Lv, W. Y. Si, J. J. He, L. Sun, C. F. Zhang, N. Wang, Z. Yang, X. D. Li,
X. Wang, W. Q. Deng, Y. Z. Long, C. S. Huang, Y. L. Li, Nat. Commun.
2018, 9, 3376.
Acknowledgements
[21] L. Jiao, G. Wan, R. Zhang, H. Zhou, S. H. Yu, H. L. Jiang, Angew. Chem.
2018, 130, 8661-8665; Angew. Chem. Int. Edit. 2018, 57, 8525-8529.
[22] D. H. Deng, L. Yu, X. Q. Chen, G. X. Wang, L. Jin, X. L. Pan, J. Deng, G.
Q. Sun, X. H. Bao, Angew. Chem. 2013, 125, 389-393; Angew. Chem. Int.
Edit. 2013, 52, 371-375.
This study was supported by the National Natural Science
Foundation of China (21790050, 21790051, 21771187,
21603250), the Natural Science Foundation of Shandong
Province (China) for Distinguished Young Scholars (JQ201610),
the Natural Science Foundation of Shandong Province
(ZR2016BB24), and Project funded by China Postdoctoral
Science Foundation (2016M592261).
This article is protected by copyright. All rights reserved.

10.1002/cssc.201802170
ChemSusChem
COMMUNICATION
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COMMUNICATION
An efficient non-precious-metal
Wenyan Si,[a,c] Ze Yang,[a] Xin Wang,[a,b]
Qing Lv,*[a] Fuhua Zhao,[a] Xiaodong
Li,[a,b]Jianjiang He,[a] Yunze Long,[c] Juan
Gao,[a] Changshui Huang*[a]
electrocatalyst is synthesized using
novel graphdiyne (GDY) materials for
oxygen reduction reaction. Due to the
powerful synergistic effect between
Fe. N and GDY, the Fe-N co-doped
GDY (Fe-N-GDY) catalyst performs
excellent catalytic activity in both
alkaline and acidic media, comparable
to Pt/C. Moreover, the stability and
methanol tolerance of Fe-N-GDY are
better than those of Pt/C.
Page No. – Page No.
Title: Fe, N-codoped Graphdiyne
Displaying Efficient Oxygen
Reduction Reaction Activity
This article is protected by copyright. All rights reserved.