Supramolecular bimetallogels: A nanofiber network for bimetal/nitrogen co-doped carbon electrocatalysts

Article abstract of DOI:10.1039/c8ta01898g

This paper reports a rational strategy using 'supramolecular bimetallogel' as a template to synthesize a series of bimetal (Fe-Co, Fe-Ni or Fe-Mn)/nitrogen co-doped carbon electrocatalysts for ORR with excellent performance. The bimetallogel nanofiber network serves as both bimetal and N sources as well as host matrix for the commercially available carbon. Thermal treatment of the bimetallogels enables homogenous in situ doping of the bimetal and N, affording bimetal/N co-doped carbon catalysts.

Full text of DOI:10.1039/c8ta01898g

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PAPER
Kun Chang, Zhaorong Chang et al.
Bubble-template-assisted synthesis of hollow fullerene-like
MoS nanocages as a lithium ion battery anode material
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DOI: 10.1039/C8TA01898G
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Supramolecular Bimetallogels: A Nanofiber Network for
Bimetal/Nitrogen Co-Doped Carbon Electrocatalysts
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
a
a
a
a
a
Minli Tan, Ting He, Jian Liu, Huiqiong Wu, Qiang Li, Jun Zheng, Yong Wang, Zhifang Sun,*
b
a
Shuangyin Wang and Yi Zhang*
DOI: 10.1039/x0xx00000x
www.rsc.org/
This paper report a rational strategy, using ‘supramolecular structures, can exert great effect on the composition and
2
4-26
bimetallogel’ as template, to synthesize a series of bimetal (Fe-Co, catalytic activity of the final products.
So far, despite of
Fe-Ni or Fe-Mn)/nitrogen co-doped carbon electrocatalysts for their great practical potential, it is still challenging to rational
ORR with excellent performance. The bimetallogel nanofiber design and synthesis of highly active nonprecious metal-
network serves as both bimetal and N sources, as well as host nitrogen-carbon nanocomposites for ORR.
matrix for the commercially available carbon. Thermal treatment
In the previous work, we have reported that a
of the bimetallogels enables a homogenous in-situ doping of the supramolecular metallogelator, ferrocenoyl-phenylalanine (Fc-
bimetal and N, affording bimetal/N co-doped carbon catalysts.
F), could undergo hierarchical self-assembly to form
supramolecular hydrogel composed of well-defined three-
dimensional nanofibers. These nanofibers contain large
Rational design and synthesis of highly efficient and durable
catalysts for oxygen reduction reactions (ORR) have exhibited
considerable practical value for clean energy conversion
systems, such as metal-air batteries and fuel cells.1 Though
precious metals, such as Pt-based materials, possess high
electrocatalytic activity,5 the prohibitive cost, scarcity and
low stability greatly hinder their large-scale practical
applications.8 Recently, nonprecious metal-nitrogen-carbon
nanocomposites (MNCs) show great potential as alternatives
to Pt-based catalysts, but only rare examples exhibit superior
27
amount of Fe and N as the metallogelator Fc-F was synthesized
by condensation of ferrocene and amino acid moieties. In the
present study, we found that the Fc-F, containing -COOH and -
CO-NH- groups, could further coordinate with other transition
metal ions (Co, Ni or Mn) and self-assembled into
bimetallogels (their corresponding bimetallogels are denoted
as Fc-F/Co, Fc-F/Ni and Fc-F/Mn, respectively). The
bimetallogel nanofiber network could serve as bimetal and
nitrogen sources, as well as host matrix to accommodate the
commercially available carbon, Ketjenblack EC 600J, to form a
hybrid hydrogel (denoted as Fc-F/Co@C, Fc-F/Ni@C and Fc-
F/Mn@C, respectively). Using this hybrid bimetallogel as
template, we were able to obtained a series of bimetal
-4
-7
-10
11-14
activity and better durability than the Pt/C.
This dilemma
comes with the methodology for the synthesis of MNCs, where
high temperature annealing process is always required to
pyrolyze a mixture of carbon sources, metal salts and nitrogen
precursors.1
5-17
During thermal treatment, these metal salts
/nitrogen co-doped carbon electrocatalysts for ORR. To test
and nitrogen precursors easily agglomerate and resulted in
this strategy, we chosen the Fc-F/Co@C gel as a model
material for further investigation and elucidated the structure-
inhomogeneous doping of metal and nitrogen into carbon
matrix.1
8-20
Traditionally, methodologies are overwhelmingly
focusing on different combinations of mixtures containing
2
1-
carbon sources, metal ions and nitrogen-enriched molecules,
23
however, an important but often ignored aspect is that the
structure and distribution of precursors, such as the geometric
a.Hunan Provincial Key Laboratory of Efficient and Clean Untilization of Manganse
Resources, College of Chemistry and Chemical Engineering, Central South
University, Changsha 410083, China. E-mail: allensune@gmail.com (Z. Sun);
yzhangcsu@csu.edu.cn (Y. Zhang)
b.
State Key Laboratory of Chem/Bio-Sensing and Chemometrics, Hunan University,
Changsha 410082, China
†
Footnotes relating to the title and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
Scheme 1. Schematic representation for the synthesis of Fc-F/Co@N-C800 as efficient
ORR catalysts.
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properties relationship of the final catalysts. Scheme 1
illustrates the procedure for the synthesis of the
bimetal/nitrogen co-doped catalysts. First, Fc-F/Co@C gel was
treated by hydrothermal reaction at 150 °C for 12 h, which
resulted in uniform raspberry-like nanostructures (designated
as Fc-F/Co@N-C150). Subsequent pyrolysis at 800 °C
generated the final bimetal and nitrogen co-doped catalysts,
here denoted as Fc-F/Co@N-C800. As the precursor structure
exerts great effect on the composition and activity of the final
catalysts, we characterized the precursors, intermediates and
final products in detail and showed as below.
View Article Online
DOI: 10.1039/C8TA01898G
Before the encapsulation of carbon, we first confirmed
the formation of the Fc-F/Co bimetallogel, and further
elucidated the gelation mechanism. As shown in Fig. S1, the
scanning electron microscopy (SEM) reveals that both Fc-F and
Fc-F/Co hydrogels are composed of nanofiber networks.
However, compared with Fc-F, fibrils in the Fc-F/Co
bimetallogel are much denser and thinner, suggesting that the
2+
Co ions can further cross-link with Fc-F to form interwoven
D networks. This is in agreement with the circular dichroism
CD) spectra, where a slight red shift can be observed as a
3
(
2+
result of coordination between Fc-F nanofibers and Co ions
(Fig. S2). In addition, fourier transform infrared spectroscopy
(
FT-IR) spectra were carried out to provide direct evidence for
-
1
the coordination. As shown in Fig. S3, a peak at 3420 cm
(
attributable to Fc-F υOH and υNH absorptions) is shifted to 3411
-
1
cm , confirming the coordination between the Fc-F and the
Co . Furthermore, both carboxyl group at 1726 cm and
amide group at 1530 cm−1 undergo a red shift, indicating that hydrogel; (b) SEM (inset is TEM) image of the raspberry-like Fc-F/Co@N-C150 hybrids
2+
−1
Fig. 1 (a) The SEM image (inset is the digital photograph) of the Fc-F/Co@C hybrid
after hydrothermal reaction at 150 °C for 12 h; (c)-(d) TEM images, (e) HAADF-STEM
both -COOH and -CO-NH- groups from Fc-F participate in the
image and HAADF-STEM-EDS mapping of the resultant catalyst Fc-F/Co@N-C800; (f)
coordination with Co2+ ions. Therefore, it can be concluded
28
HRTEM images of the Fc-F/Co@N-C800. The lattice distance and crystal plane angle
indicate the coexistence of FeCo and CoFe O nanoparticles.
2 4
2+
that the efficient complexation of Co ions with -COOH and -
CO-NH- groups in Fc-F promotes the gel-network formation.
Surprisingly, unlike other supramolecular gel systems,
as Fc-F, which are disassembled at high temperature, the Fc-
F/Co bimetallogel could endure temperature over 100 °C, even
boiling, without notable change (Fig. S4), indicative of its
excellent thermostability. This is attributed to the strong
coordination between metal cations and the Fc-F nanofibers,
and consistent with our previous work on metal-biopolymer
hydrogels, which also exhibit good thermal stability.32
2
9-31
such
with hydrothermal reaction at 150 °C for 12 h. As a result,
uniform raspberry-like nanospheres (denoted as Fc-F/Co@N-
C150) with a diameter of about 220 nm were generated (Fig.
1
b and S5). Transmission electron microscopy (TEM) reveals
that these raspberry-like spheres are composed of small
polycrystalline nanoparticles (inset of Fig. 1b and S6). Energy
dispersive X-ray spectra (EDS) and high-angle annular dark field
scanning TEM (HAADF-STEM) reveal that all the elements are
homogeneously distributed over the entire architecture (Fig.
S7 and S8), indicating that agglomerations of metal and
nitrogen can be efficiently suppressed by the supramolecular
bimetallogel templates.
Previous reports have shown that aromatic gelators can
co-assemble with carbon materials to form hybrid gel, due to
strong π-π interaction.3
3-35
As the Fc-F is one of the most
efficient aromatic gelators,2
7, 36
we employed the Fc-F based
bimetallogel as host matrix to accommodate the commercially
available carbon, Ketjenblack EC 600J, which resulted in self-
supporting hybrid hydrogel Fc-F/Co@C (inset of Fig. 1a). The
SEM revealed that the Fc-F/Co@C bimetallogel was composed
of nanofiber network, with carbon nanoparticles
homogeneously attached on the nanofibers (Fig. 1a). Due to
the excellent thermal stability of the Fc-F/Co@C bimetallogel,
we conjectured that relatively mild thermal treatment of the
gel, such as hydrothermal reaction, would allow slow
decomposition of the nanofibers, leading to homogenous
distribution of metal and nitrogen species within the carbon
matrix. Accordingly, the Fc-F/Co@C bimetallogel was treated
To dope metals and nitrogen into carbon matrix, the Fc-
F/Co@N-C150 was further pyrolyzed at 800 °C (denoted as Fc-
F/Co@N-C800). As shown in Fig. 1c and 1d, nanoparticles with
an average size of 28 nm were anchored homogeneously
within the carbon matrix. The HAADF-STEM images in Fig. 1e
shows the elemental distributions of C, N, O, Fe and Co, and a
typical core-shell structure can be observed, where the
elemental of Fe and Co locate in the core. This indicates the
nanoparticles are encapsulated in the carbon shells, and
consistent with the core-shell structures in the Fig. 1d. In
addition, high-resolution TEM (HRTEM) images (Fig. 1f and S9)
2
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of the encapsulated nanoparticles reveal that the lattice onding to active sites is calculated (Table S1). InteVrieewstAirnticglelyO,nFlince-
fringes of 0.296 and 0.252 nm can be assigned well to the F/Co@N-C800 with bimetal nanoparticlDesOI:a1n0d.10t3h9e/Cm8ToAd01e8r9a8tGe
2 4
(220) and (311) planes of cubic CoFe O , while 0.285 and 0.202 amount of active N exhibits the highest activity. This result
nm can be indexed to the (111) and (100) planes of cubic FeCo indicates that the ORR performance cannot be simply
alloy. Recently, some reports have reported that the spinel- correlated to the type of nitrogen, or the active nitrogen
type transition metal oxides (AB
high activity and good durability for electrocatalysis.
In contrast with the bimetallogel, samples with neither Co
2 4
O ) and alloys could display content, or any single factor. However, the introduction of
25, 26, 37-39
metals into N-doped carbon system exerts an indispensable
effect on the substantial improvement of the ORR activity,
2+
nor Fc-F only resulted in serious agglomeration (Fig. S10), which could generate different intrinsic active sites, like M-N.
further signifying that the bimetallogel plays a critical role on Subsequently, we evaluated the ORR performance of the
the homogeneous doping. In addition, we also checked the resulted catalysts Fc-F/Co@N-C800. For comparison, we also
temperature effect during the pyrolysis process. It was found prepared the Fc-F@N-C800 (without Co), Co@N-C800 (without
that samples annealed at 700 °C or 900 °C produces faint or Fc-F), Fe/Co@N-C800 (replaced Fc-F with FeCl ) and C800
3
agglomerated nanoparticles in the carbon matrix (Fig. S11). (simply pyrolyzed the carbon) by using the similar procedure
Together with the electrocatalytic performances (Fig. S12), we to Fc-F/Co@N-C800 (see Experimental Section in SI). We first
choose 800 °C as the optimized condition hereafter.
performed the electrical impedance spectroscopy (EIS) to
To probe the fine structure of the Fc-F/Co@N-C800, X-ray measure the electrical conductivity of these materials. As
diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) shown in Fig. 3a, S15 and Table S2, the catalyst Fc-F/Co@N-
were performed. As shown in the Fig. 2a and S13, XRD pattern C800 shows the lowest charge-transfer resistance, indicating
shows that a broad diffraction peak at 26° can be observed in that it exhibits the best electrical conductivity and will
all samples, which attribute to the (002) planes of the graphitic contribute to the fastest acceleration of electron transfer. This
carbon. We also noticed a slight shift of the peak with the is possibly due to the existence of bimetal Fe and Co, which
addition of metal sources, possibly caused by metal doping in facilitates the graphitization of the carbon during the pyrolysis
the carbon matrix. XPS spectra (Fig. S14 and Table S1) reveal process. We then carried out the cyclic voltammetry (CV) to
that Fc-F can increase the contents of the metal and nitrogen assess the ORR performance of the catalysts (Fig. 3b and S16).
residues, which may be ascribed to the effective adsorption of As expected, C800 barely exhibited obvious catalytic activity.
metal complex on the carbon surface. In the high-resolution After the introduction of bimetal Fe and Co (using metal salts
XPS spectra (Fig. 2b), the peaks of 712.4 eV (Fe 2p3/2), 724.9 eV instead of bimetallogel), the catalytic activity of Fe/Co@N-
(
Fe 2p1/2) and the shake-up satellite of 719.0 eV confirmed the C800 increased to some extent, signifying the effective role of
3+
presence of Fe species. Meanwhile, the peaks around 709.5 the doped bimetals. Noticeably, Fc-F/Co@N-C800 derived
and 722.0 eV were assigned to FeCo phase. An additional peak from the bimetallogel displays an extraordinary ORR activity
at 710.9 eV is ascribed to the Fe-N coordination. The existence with the peak potential (Epeak) at 0.85 V. To confirm the role of
2 4
of M-N coordination could also be seen from the Co 2p (Fig. bimetal nanoparticles (CoFe O /FeCo) on boosting ORR
2
c) and N 1s spectra (Fig. 2d). Thus, we can conclude that both catalytic activity, we examine the ORR activity of the Fc-
4
0
Fe and Co are co-doped into the carbon from these F/Co@N-C800 after an acid leaching treatment. The results
measurements. Since the pyridinic N, graphitic N and M-N of TEM and EDS (Fig. S17) confirm that metal nanoparticles are
have been interpreted as the active sites toward ORR in successfully removed and the nitrogen is still retained. As can
5
, 13, 22, 40
considerable studies,
the amount of nitrogen corresp-
be seen from Fig. S18, the acid-leached Fc-F/Co@N-C800
displays clearly inferior ORR activity with a significant peak
potential shift by 51 mV. The above results reveal that the
upgrade of ORR activity is attributed to the existence of the
2 4
bimetal centre (CoFe O /FeCo). Furthermore, the Fc-F/Co@N-
C800 shows better ORR property than Fc/Co@N-C800 (replac-
Fig. 3 (a) Nyquist plots of the as-prepared Fc-F/Co@N-C800 catalysts and the
equivalent electrical circuit used for fitting impedance spectra. R
electrolyte resistance, charge-transfer resistance and the constant phase element,
respectively. Cdl is the double-layer capacitance, and C is the limit capacitance; (b) CV
curves of different catalysts in O –saturated (solid line) and N –saturated (dash line) 0.1
s
, Rct and Q are the
L
Fig. 2 (a) XRD pattern of Fc-F/Co@N-C800; High-resolution (b) Fe 2p, (c) Co 2p and (d) N
s XPS spectra of Fc-F/Co@N-C800.
1
2
2
-
1
M KOH at a scan rate of 50 mV s .
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Furthermore, we measure the chronoamperometry of the
View Article Online
DOI: 10.1039/C8TA01898G
2
Fc-F/Co@N-C800 catalyst in 0.1 M KOH saturated with O to
check the durability. As shown in Fig. 4e, even operated at
.678 V for 40000 s, the catalyst still retains a high relative
0
current of 86.82%, and shows higher stability than the Pt/C.
This is consistent with the CV results under continuous
potentiodynamic sweeps (Fig. S23). The fuel crossover effect
was also examined (Fig. 4f). In the presence of 1M methanol,
the CV curves of the Fc-F/Co@N-C800 catalyst is identical to
that of without methanol, showing good tolerance to
methanol. However, the Pt/C presents an obvious inverse
methanol oxidation peak. Because of the high activity of the
as-obtained Fc-F/Co@N-C800, we further integrated the
catalyst into the Al-air battery device. As shown in Fig. S24,
-2
after discharging at a constant density of 20 mA cm for 16 h,
the battery still preserves ~90 % of its activity, indicating that
the Fc-F/Co@N-C800 catalyst has great potential in the Al-air
batteries. Apart from the Fc-F/Co, Fc-F/Mn and Fc-F/Ni
bimetallogels were also used as templates to synthesis bimetal
and nitrogen co-doped carbon catalysts. Likewise, the
resultant catalysts show high ORR performance in terms of
E
peak (0.84 and 0.81 V, respectively, Fig. S25), large limited
-2
diffusion current density (6.07 and 5.77 mA cm , respectively,
Fig. 4 (a) ORR polarization curves at 1600 rpm in O
2
-sarturated 0.1 M KOH; (b) J
K
at 0.80 Fig. 4a and S26) as well as high mass activity (0.80 and 0.72 A
V and E1/2, (c) H
O
2 2
yield and (d) Corresponding electron transfer number of C800, mgTM-1
,
respectively, Fig. S20). In addition, all the
bimetal/nitrogen co-doped carbon electrocatalysts Fc-F/M@N-
C800 (M=Co, Mn, Ni) show good ORR activities in 0.1 M HClO
Fig. S27), further confirming that the ‘supramolecular
Fe/Co@N-C800, Fc-F/Co@N-C800 and 20 wt% Pt/C; (e) Chronoamperometry
measurements for Fc-F/Co@N-C800 and 20 wt% Pt/C at 0.678 V, 1600 rpm; (f) CV
curves of Fc-F/Co@N-C800 and 20 wt% Pt/C with or without 1 M methanol.
4
(
ed Fc-F gel with Fc powder), indicating that the supramolecular
bimetallogel template is beneficial for higher electrocatalytic
performance. Thus it can be concluded that the synergistic
effect of the doped bimetals and nitrogen species, which they
bimetallogel’ can be an outstanding template for the in-situ
synthesis of MNCs materials with excellent ORR performance.
are distributed homogeneously within the carbon matrix, Conclusions
exerts great effect on boosting the activity of the catalysts.
In summary, we provide a rational strategy to synthesize
A detailed study of the electrochemical activity and the
mass-transfer kinetics was investigated by using rotating disk
electrode (RDE) and rotating ring-disk electrode (RRDE)
techniques. As shown in Fig. 4a, compared with C800 (0.86 V)
and Fe/Co@N-C800 (0.92 V), the Fc-F/Co@N-C800 catalyst
manifests an exceptionally high onset potential with 1.01 V,
which is superior to the commercial Pt/C catalyst (0.98 V), and
outperforming most of the reported MNCs catalysts (Table S3).
bimetal/N co-doped carbon catalysts, using bimetallogel
nanofiber network as template. Thermal treatment of the
bimetallogel, hybridized with commercially available carbon,
enables bimetals and nitrogen simultaneously doped into
carbon matrix. Remarkably, our materials possess superior
performance to commercial Pt/C benchmark for the ORR in
alkaline solution, and also deliver satisfactory activity in acidic
environment. Detailed electrochemical characterizations,
together with XRD and XPS analysis, prove that the
simultaneous doping of both bimetal and nitrogen into the
carbon has a synergistic effect to boost the ORR activity. The
high onset potential, large kinetic current density, high mass
activity, good methanol tolerance, and long-term stability
altogether make the bimetal/N-doped carbon one of the best
nonprecious metal catalysts toward ORR. We believe the
successful demonstration of this supramolecular bimetallogel
would provide useful archetypical template for the design of
other advanced electrocatalysts in energy conversion and
storage systems.
3, 26, 41-43
In addition, the Fc-F/Co@N-C800 catalyst also shows
-
2
very larger kinetic current density (J
K
) with 12.71 mA cm at
0
.80 V and high mass activity (ampere per milligram of total
-1
-1
metal) with 0.69 A mgTM at 0.86 V (20 mV s , Fig. 4b, S19, S20
and Table S4) , which again confirms the excellent catalytic
performance of the Fc-F/Co@N-C800. RRDE tests (Fig. S21)
2 2
show that the H O yield of Fc-F/Co@N-C800 remains less than
1
0.39 % at all potentials (Fig. 4c), corresponding to a high
average electron-transfer number (n) of 3.83 (Fig. 4d), close to
that of Pt/C (3.95). The good kinetic process of Fc-F/Co@N-
C800 was also confirmed by the Tafel slope in two regions
(
65.1 mV dec-1 at low overpotentials and 117.7 mV dec-1 at
high overpotentials), closing to those of Pt/C (59.3 and 118.3
-1
mV dec , respectively) (Fig. S22).
Conflicts of interest
4
| J. Name., 2012, 00, 1-3
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There are no conflicts to declare.
19. B. Bayatsarmadi, Y. Zheng, A. Vasileff and S. ZV. ieQwiAaroti,cleSOmnalinlle,
017, 13, 1700191-1700209.
2
DOI: 10.1039/C8TA01898G
2
2
2
0. T. He, H. Xue, X. J. Wang, S. H. He, Y. L. Lei, Y. Y. Zhang, R. J.
Shen, Y. Zhang and J. Xiang, Nanoscale, 2017, 9, 8341-8348.
1. J. Masa, W. Xia, M. Muhler and W. Schuhmann, Angew. Chem.
Int. Ed., 2015, 54, 10102-10120.
2. G. Wu, A. Santandreu, W. Kellogg, S. Gupta, O. Ogoke, H. G.
Zhang, H. L. Wang and L. M. Dai, Nano Energy, 2016, 29, 83-110.
Acknowledgements
This work was supported by National Nature Science
Foundation of China (21473257, 21773311), the National High
Technology Research and Development Program of China
(
2015AA020502), the Hunan Provincial Science and 23. Y. Zheng, Y. Jiao, Y. Zhu, Q. Cai, A. Vasileff, L. H. Li, Y. Han, Y.
Technology Plan Project of China (2016TP1007), the Special
Program for Applied Research on Super Computation of the
NSFC-Guangdong Joint Fund (the second phase) under Grant
Chen and S. Z. Qiao, J. Am. Chem. Soc., 2017, 139, 3336-3339.
4. S. L. Zhao, H. J. Yin, L. Du, L. C. He, K. Zhao, L. Chang, G. P. Yin, H.
J. Zhao, S. Q. Liu and Z. Y. Tang, Acs Nano, 2014, 8, 12660-
2
1
2668.
5. W. H. He, Y. Wang, C. H. Jiang and L. H. Lu, Chem. Soc. Rev.,
016, 45, 2396-2409.
6. G. P. Wu, J. Wang, W. Ding, Y. Nie, L. Li, X. Q. Qi, S. G. Chen and
Z. D. Wei, Angew. Chem. Int. Ed., 2016, 55, 1340-1344.
7. Z. F. Sun, Z. Y. Li, Y. H. He, R. J. Shen, L. Deng, M. H. Yang, Y. Z.
Liang and Y. Zhang, J. Am. Chem. Soc., 2013, 135, 13379-13386.
8. S. Fleming and R. V. Ulijn, Chem. Soc. Rev., 2014, 43, 8150-8177.
9. C. H. Ren, J. W. Zhang, M. S. Chen and Z. M. Yang, Chem. Soc.
Rev., 2014, 43, 7257-7266.
(U1501501), the Fundamental Research Funds for the Central
2
2
2
Universities of Central South University (2017zzts343) and
Programs of Innovation and Entrepreneurship for
Undergraduates (201710533507, 201710533070).
2
Notes and references
2
2
1
2
3
. Z. W. Seh, J. Kibsgaard, C. F. Dickens, I. Chorkendorff, J. K.
Norskov and T. F. Jaramillo, Science, 2017, 355, 146-157.
. D. F. Yan, Y. X. Li, J. Huo, R. Chen, L. M. Dai and S. Y. Wang, Adv.
Mater., 2017, 29, 1606459-1606478.
. A. Aijaz, J. Masa, C. Rösler, W. Xia, P. Weide, A. J. R. Botz, R. A.
Fischer, W. Schuhmann and M. Muhler, Angew. Chem. Int. Ed.,
3
0. Z. A. Arnon, A. Vitalis, A. Levin, T. C. T. Michaels, A. Caflisch, T. P.
J. Knowles, L. Adler-Abramovich and E. Gazit, Nat. Commun.,
2
016, 7, 13190-13196.
3
1. N. Zhou, X. Y. Cao, X. W. Du, H. M. Wang, M. Wang, S. Liu, K.
Nguyen, S. Klaus, Q. B. Xu, G. L. Liang and B. Xu, Angew. Chem.
Int. Ed., 2017, 56, 2623-2627.
2
016, 55, 4087-4091.
4
. Y. Jia, L. Z. Zhang, G. P. Gao, H. Chen, B. Wang, J. Z. Zhou, M. T.
Soo, M. Hong, X. C. Yan, G. R. Qian, J. Zou, A. J. Du and X. D. Yao,
Adv. Mater., 2017, 29, 1700017-1700024.
3
3
3
3
3
2. Z. F. Sun, F. C. Lv, L. J. Cao, L. Liu, Y. Zhang and Z. G. Lu, Angew.
Chem. Int. Ed., 2015, 54, 7944-7948.
3. B. G. Cousins, A. K. Das, R. Sharma, Y. N. Li, J. P. McNamara, I. H.
Hillier, I. A. Kinloch and R. V. Ulijn, Small, 2009, 5, 587-590.
4. X. W. Du, J. Zhou, J. F. Shi and B. Xu, Chem. Rev., 2015, 115,
5
6
. X. M. Ge, A. Sumboja, D. Wuu, T. An, B. Li, F. W. T. Goh, T. S. A.
Hor, Y. Zong and Z. L. Liu, ACS Catal., 2015, 5, 4643-4667.
. H. B. Yang, J. W. Miao, S. F. Hung, J. Z. Chen, H. B. Tao, X. Z.
Wang, L. P. Zhang, R. Chen, J. J. Gao, H. M. Chen, L. M. Dai and
B. Liu, Sci. Adv., 2016, 2, e1501122.
1
3165-13307.
5. Y. Shi, J. Zhang, L. J. Pan, Y. Shi and G. H. Yu, Nano Today, 2016,
1, 738-762.
1
7
. X. Wan, R. Wu, J. Deng, Y. Nie, S. Chen, W. Ding, X. Huang and Z.
Wei, J. Mater. Chem. A, 2018, 6, 3386-3390.
6. K. Tao, A. Levin, L. Adler-Abramovich and E. Gazit, Chem. Soc.
Rev., 2016, 45, 3935-3953.
8
9
. Y. Shi and G. H. Yu, Chem. Mater., 2016, 28, 2466-2477.
. T. He, X. J. Wang, H. Q. Wu, H. Xue, P. Xue, J. Ma, M. L. Tan, S. H.
He, R. J. Shen, L. Z. Yi, Y. Zhang and J. Xiang, ACS Appl. Mater.
Interfaces, 2017, 9, 22490-22501.
3
3
7. G. Q. Zhang and X. W. Lou, Adv. Mater., 2013, 25, 976-979.
8. L. B. Ma, X. P. Shen, G. X. Zhu, Z. Y. Ji and H. Zhou, Carbon, 2014,
7
7, 255-265.
3
9. K. W. Liu, C. L. Zhang, Y. D. Sun, G. H. Zhang, X. C. Shen, F. Zou,
H. C. Zhang, Z. W. Wu, E. C. Wegener, C. J. Taubert, J. T. Miller,
Z. M. Peng and Y. Zhu, ACS Nano, 2018, 12, 158-167.
1
0. C. L. Zhang, B. W. Wang, X. C. Shen, J. W. Liu, X. K. Kong, S. S. C.
Chuang, D. Yang, A. G. Dong and Z. M. Peng, Nano Energy, 2016,
3
0, 503-510.
4
0. W. J. Jiang, L. Gu, L. Li, Y. Zhang, X. Zhang, L. J. Zhang, J. Q.
Wang, J. S. Hu, Z. D. Wei and L. J. Wan, J. Am. Chem. Soc., 2016,
1
1
1. R. Bashyam and P. Zelenay, Nature, 2006, 443, 63-66.
2. B. Cai, D. Wen, W. Liu, A. K. Herrmann, A. Benad and A.
Eychmüller, Angew. Chem. Int. Ed., 2015, 54, 13101-13105.
3. Y. Y. Liu, H. L. Jiang, Y. H. Zhu, X. L. Yang and C. Z. Li, J. Mater.
Chem. A, 2016, 4, 1694-1701.
4. L. Z. Zhang, Y. Jia, G. P. Gao, X. C. Yan, N. Chen, J. Chen, M. T.
Soo, B. Wood, D. J. Yang, A. J. Du and X. D. Yao, Chem, 2018, 4,
1
38, 3570-3578.
4
4
4
1. Z. H. Li, M. F. Shao, L. Zhou, R. K. Zhang, C. Zhang, M. Wei, D. G.
Evans and X. Duan, Adv. Mater., 2016, 28, 2337-2344.
2. Y. Tong, P. Z. Chen, T. P. Zhou, K. Xu, W. S. Chu, C. Z. Wu and Y.
Xie, Angew. Chem. Int. Ed., 2017, 56, 7121-7125.
3. P. Z. Chen, T. P. Zhou, L. L. Xing, K. Xu, Y. Tong, H. Xie, L. D.
Zhang, W. S. Yan, W. S. Chu, C. Z. Wu and Y. Xie, Angew. Chem.
Int. Ed., 2017, 56, 610-614.
1
1
2
85-297.
1
5. J. Wei, Y. Liang, Y. X. Hu, B. Kong, J. Zhang, Q. F. Gu, Y. P. Tong,
X. B. Wang, S. P. Jiang and H. T. Wang, Angew. Chem. Int. Ed.,
2
016, 55, 12470-12474.
6. B. Y. Guan, L. Yu and X. W. Lou, Adv. Sci., 2017, 4, 1700247-
700252.
1
1
1
7. J. Ma, X. J. Wang, T. He, M. L. Tan, J. Zheng, H. Q. Wu, M. Y.
Yuan, R. J. Shen, Y. Zhang and J. Xiang, Dalton Trans., 2017, 46,
6
163-6167.
8. G. Wu, K. L. More, C. M. Johnston and P. Zelenay, Science, 2011,
32, 443-447.
1
3
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Journal of Materials Chemistry A
Page 6 of 6
View Article Online
DOI: 10.1039/C8TA01898G
Table of Content (TOC)
Supramolecular Bimetallogels: A Nanofiber Network for
Bimetal/Nitrogen Co-Doped Carbon Electrocatalysts
a
a
a
a
a
a
a
a
Minli Tan, Ting He, Jian Liu, Huiqiong Wu, Qiang Li, Jun Zheng, Yong Wang, Zhifang Sun,*
b
a
Shuangyin Wang, and Yi Zhang*
a.
Hunan Provincial Key Laboratory of Efficient and Clean Untilization of Manganse Resources,
College of Chemistry and Chemical Engineering, Central South University, Changsha 410083,
China. E-mail: allensune@gmail.com (Z. Sun); yzhangcsu@csu.edu.cn (Y. Zhang)
b.
State Key Laboratory of Chem/Bio-Sensing and Chemometrics, Hunan University, Changsha
4
10082, China
As the first example, a type of bimetal/N co-doped carbon electrocatalysts are synthesized by
using ‘supramolecular bimetallogel’ as templates.