Accepted Manuscript

Short communication

A novel functional material of Co3O4/Fe2O3 nanocubes derived from a MOF

precursor for high-performance electrochemical energy storage and conversion
application

Xijun Wei, Yanhong Li, Huarong Peng, Di Gao, Yingqing Ou, Yibin Yang,
Jingrui Hu, Yunhuai Zhang, Peng Xiao

PII: S1385-8947(18)31476-1
DOI: https://doi.org/10.1016/j.cej.2018.08.009
Reference: CEJ 19623

To appear in: Chemical Engineering Journal

Received Date: 13 June 2018

Revised Date: 26 July 2018
Accepted Date: 2 August 2018

Please cite this article as: X. Wei, Y. Li, H. Peng, D. Gao, Y. Ou, Y. Yang, J. Hu, Y. Zhang, P. Xiao, A novel
functional material of Co3O4/Fe2O3 nanocubes derived from a MOF precursor for high-performance electrochemical
energy storage and conversion application, Chemical Engineering Journal (2018), doi: https://doi.org/10.1016/j.cej.
2018.08.009

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 A novel functional material of Co3O4/Fe2O3 nanocubes derived from a

MOF precursor for high-performance electrochemical energy storage and

conversion application

Xijun Wei,a Yanhong Li, b Huarong Peng,a Di Gao,a Yingqing Ou,a Yibin Yang,b Jingrui Hu, b

Yunhuai Zhang*a and Peng Xiao*a,b

a
College of Chemistry and Chemical Engineering, Chongqing University, Chongqing

400044, China

b
College of Physics, Chongqing University, Chongqing 400044, China
 Abstract

We have successfully developed a MOF-based (Co3[Fe(CN)6]2·10H2O) strategy to

synthesize Co-Fe mixed metal oxide (Co 3O4/Fe2O3) nanocubes (denoted as CFNC).

The obtained CFNC is applied as both anode and cathode for high-performance

symmetric supercapacitors, exhibiting high energy density of 35.15 W h kg-1 at a

power density of 1125 W kg-1 as well as excellent stability. Meanwhile, when CFNC

is used as electrocatalyst for oxygen evolution reaction (OER), it requires a low

overpotential of 310 mV to achieve a current density of 10 mA cm-2 and exhibited

excellent stability.

KEYWORDS: metal-organic framework; Co3O4/Fe2O3; symmetric

supercapacitors; oxygen evolution reaction;

 With the growing energy crisis and environmental problems, more and more

research is focused on sustainable clean energy conversion and storage[1-3]. At present,

the research on new energy field mainly including lithium-ion batteries (Li-ions),

supercapacitors (SCs), fuel cells, oxygen and hydrogen evolution reactions (OERs and

HERs) and oxygen reduction reactions (ORRs)[4-9]. In the field of energy conversion,

electrocatalytic water splitting is recognized as an ideal way to produce hydrogen and

oxygen. However, as one of the half reaction of water splitting, the OER is kinetically

very slow and thus the speed of the whole reaction rate is limited[10]. In recent years,

the commercial catalysts of OER are mainly derived from noble metals and their

oxides, which are very effective, but expensive[11-12]. Therefore, it is necessary and

important to develop non-precious metal based catalysts with low cost and high

catalytic activity to lower the overpotential.

In the field of energy storage, SCs have attracted increasingly attention due to

their high power density, fast charging-discharging and cycling stability[13]. These

features make the SCs bridge the function for the power/energy gap between

traditional dielectric capacitors with high power density and batteries/fuel cells with

high energy density[14].Generally, SCs are divided into symmetric supercapacitors

(SSCs) and asymmetric supercapacitors (ASCs), and most of the research focused on

ASCs because of the wider potential window and higher energy density[15]. Relatively,

less research focused on SSCs. Therefore, in this communication, we are committed

to developing a symmetric supercapacitor with high energy density.

Metal-organic frameworks (MOFs), also known as porous coordination polymers

(PCPs), which are made by linking inorganic and organic units by strong bonds [16].

Due to the ultrahigh porosity and high specific surface areas, the MOFs have been

widely used in gas adsorption/separation, drug delivery, gas storage, heterogeneous

catalysis and sensing[17-22]. Recently, MOFs-based derivatives including carbon,

carbon/metal, and metal oxides have attracted numerous interests in the field of

energy conversion and storage[23-24].

With the aforementioned issues in mind, in this communication, a novel

functional material of Co 3O4/Fe2O3 nanocubes (CFNC) derived from a MOF

precursor (Co3[Fe(CN)6]2·10H2O) are synthesized as anode and cathode for SSC and

electrocatalysts for efficient OER in alkaline solution for the first time. The strategy to

synthesize CFNC is schematically shown in Figure 1 (more synthetic details can be

found in the ESI†). Firstly, uniform Co3[Fe(CN)6]2·10H2O nanocubes are synthesized

by a coprecipitation method. Then the collected precursors are calcinated in an air

atmosphere to prepare CFNC. As a result, unique Co 3O4/Fe2O3 nanocubes composed

of Co-Fe mixed metal oxides are obtained.

The crystallographic structures and phase purity of the as-prepared

Co3[Fe(CN)6]2·10H2O and CFNC were characterized by X-ray diffraction (XRD). As

shown in Figure 2a, the pattern confirms the formation of phase-pure

Co3[Fe(CN)6]2·10H2O nanocubes (JCPDS card No.46-0907), and all diffraction peaks

of CFNC can be indexed to the JCPDS card No.42-1467 and JCPDS card No.33-0604,

respectively, suggesting precursors were completely converted into Co3O4 and Fe2O3.

The X-ray photoelectron spectroscopy (XPS) measurements further confirms the

surface structure of the CFNC. Figure 2b and 2c show the high-resolution XPS

spectra of Co 2p and Fe 2p, respectively. Except for two shakeup satellites at 788.6

eV and 802.5 eV, two peaks in the Co 2p spectrum at 779.1 and 794.5 eV with a

splitting of 15.4 eV can be assigned to Co 2p3/2 and Co 2p1/2[25], respectively,

indicating the coexistence of Co 3+ and Co2+. Similarly, two major peaks observed at

711 eV and 724.6 eV could be assigned to Fe 2p3/2 and Fe 2p1/2, respectively, and the

separation of the 2p doublet was 13.4 eV confirming the presence of Fe3+ [26-27]
. The

O 1s peak can belong to three types of contributions for oxygen species,

corresponding to Co3O4 phase (529.96 eV), Fe2O3 phase (530.5 eV) and absorbed

water (532.9 eV), respectively[25,28], as shown in Figure S1 (a). As for C 1s, a

prominent peak at 284.6 eV suggests the presence of sp2-hybridized carbon (C=C),

and two other peaks at 285.8 eV and 288.5 eV, respectively, can be attributed to the

C-O and C=O bonds in the CFNC[28], shown in Figure S1 (b).

The morphology and detailed structural information of the as-synthesized samples

are characterized by field-emission scanning electron microscopy (FESEM) and

transmission electron microscopy (TEM). As shown in Figure 2d and S2 (a), the

precursors possesses well-defined and uniform size with diameter range of 100 ~ 200

nm without any by-products. After calcination, the size of precursors change slightly.

The oxidation process and the formation of CFNC make the surface become rough as

shown in Figure 3a. As indicated in TEM results in Figure 3b and S2 (c), (d), the

obtained CFNC exhibits very uniform hollow structure and the high-angle annular

dark field TEM and corresponding element mapping figure confirm that CFNC is
composed of Co, Fe, O and C elements, respectively (Figure 3d). Furthermore, the

high-resolution TEM (HRTEM) clearly show lattice fringes 0.47 and 0.24 nm for (111)

and (311) planes of Co 3O4, and 0.36 and 0.27 nm for (012) and (104) planes of Fe2O3,

respectively (Figure 3c). According to the results of TEM and HRTEM that the

particle size (or grain size) of Fe2O3 and Co3O4 in the CFNC are about 15 nm (Figure

S3).

To evaluate the electrochemical performance of the CFNC, it was employed as

both positive and negative electrode materials for SSC. The main reasons are as

follows: (1) Co3O4 is a common positive electrode material because of its high

theoretical specific capacitance; (2) Fe2O3 is emerging as one of promising negative

electrode with respect to its large theoretical capacity and more negative working

potential in alkaline electrolytes; (3) combining the two materials into a single

material, different active components in CFNC will play different roles as positive

and negative electrode. The related three-electrode and two-electrode electrochemical

tests were performed in a 3 M KOH aqueous electrolyte. To prove the feasibility of

this idea, a full cyclic voltammetry (CV) scan of CFNC were performed in the

potential range of -1.1 ~ 0.5 V at 40 mV s-1, as shown in Figure S4. Obviously, the

characteristic response peaks of Co3O4 and Fe2O3 can be observed at positive and

negative potential, respectively. Figure 4a and b show the CV curves of the CFNC as

positive and negative electrode at various scan rates from 5 to 100 mV s -1 in

three-electrode system, respectively. As shown in Figure 4a, all the CV curves

exhibited distinct redox peaks, indicating that the capacitance characteristics are
determined by both redox reactions and electric double-layer capacitance, and the

strong redox peaks observed in the CV curves, which comes from the reversible

Faradaic reaction processes between Co2+/Co3+/Co4+[29]. The CV curves in Figure 4b

is consistent with the most reported results of Fe2O3, where the pseudocapacitance

performance is attributed to a redox reaction between Fe2+ and Fe3+[30]. The shape of

all the CV curves almost stayed unchanged and the integrated area enlarged as the

scan rates increased, demonstrating fast and reversible Faradaic redox reaction of

CFNC as positive and negative electrodes materials. To better understand the reaction

kinetic of CFNC as positive and negative electrodes, current contributions of diffusion

and surface controlled process are separated using Dunn’s method[31]. As shown in

Figure 4d and e, the diffusion-controlled contribution is represented by the purple

shaded region in the CV curve. Figure S5 (a) and (b) show the surface capacitive and

diffusion controlled contributions to the total charge stored of the CFNC as positive

and negative electrodes at various scan rates. The estimated surface-controlled

capacitive contribution is about 84.12 % and 43.18 % of the total charge storage at a

scan rate of 1 mV s-1 for positive and negative electrode, respectively. Therefore, as a

positive material, CFNC is dominated by surface process, while as a negative material,

it is mainly controlled by diffusion process. The charge-discharge curves of CFNC as

positive and negative electrodes at different current densities were highly symmetric,

and possessed slight IR drop, suggesting its perfect reversibility and small internal

resistance, as shown in Figure 3c and f. According to the discharge curves, the

calculated specific capacitance of positive and negative electrodes are 312 and 267 F
g-1 at a current density of 1 A g-1, respectively.

For practical application, the symmetric supercapacitor device was assembled

using CFNC as both positive and negative electrodes, respectively (denoted as

CFNC//CFNC), as schematically illustrated in Figure 5a. Figure 5b shows the CV

curves of the CFNC as positive and negative electrodes in separated potential

windows at a scan rate of 40 mV s-1 and the integrated area of them are similar, which

demonstrates that they have matchable capacitance and it will be beneficial to

construct highly efficient SSCs. As shown in Figure S6, the operating voltage of the

CFNC//CFNC can be extended to 1.5 V, which is higher than that of most reported

symmetric supercapacitors in aqueous electrolytes (0.8 ~ 1.0 V). The increased

potential window is in favor of improving the energy density of SSC. Figure 5c and d

show the CV and GCD curves of the CFNC//CFNC at various scan rates and current

densities, respectively. The CFNC//CFNC device can achieve a large energy density

of 35.15 W h kg-1 at a power density of 1125 W kg-1, and even at a high power density

of 10.61 kW kg-1, the energy density remain at 20.58 W h kg-1, which is much larger

than the values of previously reported SSCs, such as AZ-SGHs SSC (18.2 W h kg-1 at

700 W kg-1)[32], Co3O4// Co3O4 (8 W h kg-1 at 200 W kg-1)[33], CuCo2O4// CuCo2O4

(16.82 W h kg-1 at 8200 W kg-1)[34], Fe3O4/graphene//Fe3O4/graphene (9 W h kg-1 at

3000 W kg-1)[35] and Ni–Co oxide//Ni–Co oxide (11.5 W h kg-1 at 158 W kg-1)[36]. The

corresponding comparison Ragone plots are shown in Figure 5e. Furthermore, the

CFNC//CFNC exhibits good cycling stability with 89.4 % capacitance retention after

10000 cycles at the current density of 10 A g-1, as shown in Figure 5f. Three red light
emitting diodes (LEDs) can be lit up using two CFNC//CFNC connected in series,

confirming its practicability intuitively (inset in Figure 4 f). These results indicate

that CFNC//CFNC have great potential in the future smart devices application.

In addition to the excellent energy storage performance above, the as-prepared

CFNC had excellent electrocatalytic activity for OER and electrochemical tests were

conducted in 1.0 M KOH solution in a standard three-electrode system. Figure 6a

displays the polarization curve of the electrocatalyst CFNC and RuO2 with IR

correction. The results indicate that CFNC exhibits comparable onset potential to that

of RuO2, moreover, the CFNC electrode can deliver a current density of 10 mA cm-2

(a metric associated with solar fuel synthesis) at 1.54 V (correlated to an overpotential

of 310 mV), lower than that of RuO2 at 1.56 V (330 mV) and superior to the

performance of many other non-precious metal-based electrocatalysts (Table S1). The

oxidation peak at around 1.35 V observed in the LSV curves for CFNC is

characteristic of the reaction of Co3O4 with OH- in the electrolyte[37]. The Tafel plots

of the CFNC and RuO2 are shown in Figure 6b and the Tafel slope of CFNC (67mV

dec-1) is lower than RuO2 (87mV dec-1). Stability is also critical for catalyst

application in energy conversion systems. Therefore, the catalytic stability of the

CFNC is investigated at a constant current density of 10 mA cm-2, as shown in Figure

6c. Obviously, CFNC has excellent long-term electrochemical stability and delivere a

very stable voltage during 20 h with little change.

In summary, we have developed a facile MOF-based strategy to prepare CFNC as

electrode material for symmetry supercapacitor and oxygen evolution reaction . With
their compositional and structure advantages, the CFNC//CFNC exhibited high energy

density of 35.15 W h kg-1 at a power density of 1125 W kg -1. Moreover, CFNC

showed excellent OER performance with an overpotential of 310 mV to attain a

current density of 10 mA cm-2 which lower than RuO2 (330 mV). In addition, the

CFNC exhibited perfect long-term stability with almost no attenuation after 20 h

duration test. We believe that this work not only represents an important addition to

the family of MOF-based functional materials but also highlights the potential

application of composite materials for energy conversion and storage.

Acknowledgements

This work was supported by the fundamental research funds for the Central

Universities (Project No. 106112015CDJZR305501)

Notes and references

[1] L. Li, Z. Wu, S. Yuan, X. B. Zhang, Energy Environ. Sci., 2014, 7, 2101.

[2] K. Zhang, X. P. Han, Z. Hu, X. L. Zhang, Z. L. Tao, J. Chen, Chem. Soc. Rev.,

2015, 44, 699.

[3] K. Y. Xie, B. Q. Wei, Adv. Mater., 2014, 26, 3592–3617.

[4] L. Zhang, H. B. Wu, S. Madhavi, H. H. Hng, X. W. Lou, J. Am. Chem. Soc.,

2012, 134, 17388−17391.

[5] D. Sheberla, J. C. Bachman, J. S. Elias, C. J. Sun, Y. S. Horn, M. Dinca, Nat.

Mater., 2017, 16, 220–224.

[6] D. Sebastian, A. Serovb, K. Artyushkova, P. Atanassov , A. S. Arico, V. Baglio,

J. Power Sources., 2016, 319, 235-246.

[7] I. S. Amiinu, Z. H. Pu, X. B. Liu, K. A. Owusu, H. G. R. Monestel, F. O. Boakye,

H. N. Zhang, S. C. Mu, Adv. Funct. Mater., 2017, 27, 1702300.

[8] Z. P. Shi, Y. X. Wang, H. L. Lin, H. B. Zhang, M. K. Shen, S. H. Xie, Y. H.

Zhang, Q. S. Gao, Y. Tang, J. Mater. Chem. A., 2016, 4, 6006.

[9] C. Z. Zhu, H. Li, S. F. Fu, D. Du, Y. H. Lin, Chem. Soc. Rev., 2016, 45, 517.

[10] M. X. Chen, J. Qi, D. Y. Guo, H. T. Lei, W. Zhang, R. Cao, Chem. Commun.,

2017, 53, 9566.

[11] J. W. Wan, W. X. Chen, C. Chen, Q. Peng, D. S. Wang, Y. D. Li, Chem.

Commun., 2017, 53, 12177.

[12] J. J. Qian, T. T. Li, Y. Hua, S. M. Huang, Chem. Commun., 2017, 53, 13027.

[13] G. P. Wang, L. Zhang, J. J. Zhang, Chem. Soc. Rev. 2012, 41, 797–828.

[14] Z. Tang, C. H. Tang, H. Gong, Adv. Funct. Mater., 2012, 2, 1272–1278.

[15] M. Salanne, B. Rotenberg, K. Naoi, K. Kaneko, P.-L. Taberna, C.P. Grey, B.

Dunn, P. Simon, Nat. Energy., 2016, 1, 16070.

[16] Q.L. Zhu, Q. Xu, Chem. Soc. Rev., 2014, 43, 5468–5512.

[17] M. S. Yao, X. J. Lv, Z. H. Fu, W. H. Li, W. H. Deng, G. D. Wu, and G. Xu, Angew.

Chem. Int. Ed. 56 (2017) 16510 –16514.

[18] B. Ghalei and E. Sivaniah et al., Nat. Energy. 2 (2017) 17086.

[19] M. S. Yao, W. X. Tang, G. E. Wang, B. Nath and G. Xu, Adv. Mater. 28 (2016)

5229–5234.

[20] C. Sapsanis, H. Omran, V. Chernikova, O. Shekhah, Y. Belmabkhout, U. Buttner,

M. Eddaoudi, K. N. Salama, Sensors. 15 (2015) 18153-18166.

[21] X. C. Gao, M. J. Zhai, W. H. Guan, J. J. Liu, Z. L. Liu, A. Damirin, ACS Appl.

Mater. Interfaces. 9 (2017) 3455-3462.

[22] V. Stavila, A. A. Talin, M. D. Allendorf, Chem. Soc. Rev. 43 (2014) 5994-6010.

[23] P. P. He, X. Y. Yu, X. W. Lou, Angew. Chem. Int. Ed., 2017, 56, 3897 –3900.

[24] X. J. Wei, Y. H. Li, H. R. Peng, M. Zhou, Y. Q. Ou, Y. B. Yang, Y. H. Zhang, P.

Xiao, Chem. Eng. J., 2018, 341, 618–627.

[25] S. E. Moosavifard, S. Fani, M. Rahmanianc, Chem. Commun., 2016, 52, 4517.

[26] H. A. Bandal, A. R. Jadhav, A. A. Chaugule, W. J. Chung, H. Kim,

Electrochimica Acta., 2016, 222, 1316–1325.

[27] M. Wang, M. Pyeon, Y. Gonullu, A. Kaouk, S. H. Shen, L. J. Guo, S. Mathur,

Nanoscale., 2015, 7, 10094.

[28] C. Zhang, J. Xiao, X. L. Lv, L. H. Qian, S. L. Yuan, S. Wang, P. X. Lei, J. Mater.

Chem. A., 2016, 4, 16516.

[29] Y. Z. Zhang, Y. Wang, Y. L. Xie, T. Cheng, W. Y. Lai, H. Pang, W. Huang,

Nanoscale., 2014, 6, 14354.

[30] T. Li, H. Yu, L. Zhi, W. L. Zhang, L. Q. Dang, Z. H. Liu, Z. B. Lei, J. Phys.

Chem. C., 2017, 121, 18982−18991.

[31] T. Brezesinski, J. Wang, S. H. Tolbert, B. Dunn, Nat. Mater., 2010, 9, 146.

[32] N. An, Y. F. An, Z. G. Hu, B. S. Guo, Y. Y. Yang, Z. Q. Lei, J. Mater. Chem. A.,

2015, 3, 22239.

[33] R. R. Salunkhe, J. Tang, Y. Kamachi, T. Nakato, J. H. Kim, Y. Yamauchi, ACS

Nano., 2015, 9, 6288-6296.

[34] L. J. Liao, H. C. Zhang, W. Y. Li, X. J. Huang, Z. Y. Xiao, K. B. Xu, J. M. Yang,

R. J. Zou, J. Q. Hu, Journal of Alloys and Compounds, 2017, 695, 3503-3510.

[35] K. Karthikeyan, D. Kalpana, S. Amaresh and Y. S. Lee, RSC Adv., 2012, 2,

12322.

[36] X. Lu, X. Huang, S. Xie, T. Zhai, C. Wang, P. Zhang, M. Yu, W. Li, C. Liang and

Y. Tong, J. Mater. Chem. A, 2012, 22, 13357.

[37] C. Guan, X. M. Liu, A. M. Elshahawy, H. Zhang, H. J. Wu, S. J. Pennycook, J.

Wang, NanoscaleHoriz., 2017, 2, 342.

 A novel functional material of Co3O4/Fe2O3 nanocubes derived from a

MOF precursor for high-performance electrochemical energy storage and

conversion application

Xijun Wei,a Yanhong Li, b Huarong Peng,a Di Gao,a Yingqing Ou,a Yibin Yang,b Jingrui Hu, b

Yunhuai Zhang*a and Peng Xiao*a,b

a
College of Chemistry and Chemical Engineering, Chongqing University, Chongqing

400044, China

b
College of Physics, Chongqing University, Chongqing 400044, China

AUTHOR INFORMATION

Corresponding author:
Name: Peng Xiao, Yunhuai Zhang
Tel: +86 15823038874; Fax: +86 023 65102031.
E-mail: xiaopeng@cqu.edu.cn; xp2031@163.com

Notes

The authors declare no competing financial interest.

Figure captions
Fig. 1. Schematic illustration of the fabrication processes of CFNC: (Ⅰ) formation of

Co3[Fe(CN)6]2•10H2O nanocubes; (Ⅱ) calcinated in an air atmosphere to prepare

CFNC.

Fig.2. (a) Powder XRD patterns of Co3[Fe(CN)6]2•10H2O and CFNC; (b), (c) XPS

spectra of Co 2p and Fe 2p of the CFNC, respectively; (d) FESEM image of the

Co3[Fe(CN)6]2•10H2O (inset shows a high-magnification image).

Fig.3. (a) FESEM image of the CFNC; (b) TEM image of the CFNC (inset shows a

high-magnification image); (c) high-resolution TEM (HRTEM) image of the CFNC;

(d) annual dark-field TEM image of the CFNC and the corresponding EDX elemental

mapping images of the elements Co, Fe, O and C, respectively.

Fig. 4. (a) CV curves of CFNC as positive electrode at the scan rate between 5 and

100 mV s-1 measured between 0 to 0.55 V; (b) CV curves of CFNC as negative

electrode at the scan rate between 5 and 100 mV s-1 measured between -1.1 to 0 V; (c)

Galvanostatic charge-discharge curves of CFNC as positive electrode at the current

densities between 1 and 10 A g-1 ; (d), (e) the contribution of surface-controlled

process (the white area) and diffusion-controlled process (the purple area) for the
charge storage of CFNC as positive and negative electrode at a scan rate of 1 mV s -1,

respectively; (f) Galvanostatic charge-discharge curves of CFNC as negative electrode

at the current densities between 1 and 10 A g -1.

Fig. 5. (a) An abstract illustration of the CFNC as positive and negative electrodes,

respectively; (b) CV curves of the CFNC as positive and negative electrodes

performed in a three-electrode system in 3M KOH electrolyte at a scan rate of 40 mV

s-1; (b) CV curves of CFNC//CFNC at 0-1.5 V at various scan rates from 5 to 100 mV

s-1; (d) galvanostatic charge-discharge curves of the device at the current densities

between 1 and 10 A g -1; (e) Ragone plots of CFNC//CFNC compared with those of the

previous symmetric supercapacitors; (f) cycling performance of our device with a

voltage of 1.5 V at a current density of 10 A g-1 (inset are photograph of lighting up

three LED).

Fig. 6. (a) Polarization curves of CFNC and RuO2, respectively; (b) Tafel plots of

CFNC and RuO2, respectively; (c) stability tests of CFNC with 20 h in 1.0 M KOH

solution.
Fig. 1. Schematic illustration of the fabrication processes of CFNC: (Ⅰ) formation of

Co3[Fe(CN)6]2•10H2O nanocubes; (Ⅱ) calcinated in an air atmosphere to prepare

CFNC.
Fig.2. (a) Powder XRD patterns of Co3[Fe(CN)6]2•10H2O and CFNC; (b), (c) XPS

spectra of Co 2p and Fe 2p of the CFNC, respectively; (d) FESEM image of the

Co3[Fe(CN)6]2•10H2O (inset shows a high-magnification image).

Fig.3. (a) FESEM image of the CFNC; (b) TEM image of the CFNC; (c)

high-resolution TEM (HRTEM) image of the CFNC; (d) annual dark-field TEM

image of the CFNC and the corresponding EDX elemental mapping images of the

elements Co, Fe, O and C, respectively.

Fig. 4. (a) CV curves of CFNC as positive electrode at the scan rate between 5 and

100 mV s-1 measured between 0 to 0.55 V; (b) CV curves of CFNC as negative

electrode at the scan rate between 5 and 100 mV s-1 measured between -1.1 to 0 V; (c)

Galvanostatic charge-discharge curves of CFNC as positive electrode at the current

densities between 1 and 10 A g-1 ; (d), (e) the contribution of surface-controlled

process (the white area) and diffusion-controlled process (the purple area) for the

charge storage of CFNC as positive and negative electrode at a scan rate of 1 mV s -1,

respectively; (f) Galvanostatic charge-discharge curves of CFNC as negative electrode

at the current densities between 1 and 10 A g -1.

Fig. 5. (a) An abstract illustration of the CFNC as positive and negative electrodes,

respectively; (b) CV curves of the CFNC as positive and negative electrodes

performed in a three-electrode system in 3M KOH electrolyte at a scan rate of 40 mV

s-1; (b) CV curves of CFNC//CFNC at 0-1.5 V at various scan rates from 5 to 100 mV

s-1; (d) galvanostatic charge-discharge curves of the device at the current densities

between 1 and 10 A g -1; (e) Ragone plots of CFNC//CFNC compared with those of the

previous symmetric supercapacitors; (f) cycling performance of our device with a

voltage of 1.5 V at a current density of 10 A g-1 (inset are photograph of lighting up

three LED).
Fig.6. (a) Polarization curves of CFNC and RuO2, respectively; (b) Tafel plots of

CFNC and RuO2, respectively; (c) stability tests of CFNC with 20 h in 1.0 M KOH

solution.
Highlights：
1、 Successfully developed a MOF-based strategy to synthesize Co3O4/Fe2O3

nanocubes.

2、 The obtained CFNC is applied as anode and cathode for symmetric

supercapacitor.

3、 The prepared symmetric supercapacitor have high energy density of 35.15 Wh

kg-1.

4、 The CFNC exhibit excellent OER performance with lower overpotential.