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Supporting Information
An Iodine-treated Metal-Organic Framework with Enhanced Catalytic Activity
for Oxygen Reduction Reaction in Alkaline Electrolyte
Xiaobo He1, 3 ┼, Xuerui Yi2 ┼, Fengxiang Yin1, 3*, Biaohua Chen1, Guoru Li1, Huaqiang
Yin4
1 Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, School of
Petrochemical Engineering, Changzhou University, Changzhou 213164, PR China
2 College of Chemical Engineering, Beijing University of Chemical Technology,
Beijing 100029, PR China
3 Changzhou Institute of Advanced Materials, Beijing University of Chemical
Technology, Changzhou 213164, PR China
4 Key Laboratory of Advanced Reactor Engineering and Safety, Ministry of Education,
Tsinghua University, Beijing 100084, PR China
*Corresponding author
Tel.: +86-519-86330253
E-mail: [email protected] (F. Yin)
┼ These authors contributed equally.
Fig. S1 XRD patterns of the as-prepared ZIF-67 and the simulated one.
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Fig. S2 SEM images of (a, b) I2&ZIF-67(1:1) and (c, d) I2&ZIF-67(4:1).
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Fig. S3 ORR LSV curves at a scan rate of 5 mV s-1 under 1600 rpm in (a) 0.1 M KOH
and (b) 0.5 M H2SO4, respectively, for the resultant catalysts.
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Fig. S4 Images of the electrocatalytic layer deposited on the surface of RRDE.
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Fig. S5 Koutecky-Levich (K-L) curves of the resulting samples at different potentials
vs RHE.
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Fig. S6 CV curves at different scan rates within a potential window of 0.914-0.964 V
in N2 for the resulting samples.
Table S1 Assignment of the Raman bands of ZIF-67, oop refers to out of plane and ar
refers to aromatic a)
Raman Bands / cm-1 Assignment
684 imidazole ring puckering, H oop bend
735 C=N oop bend, δ N-H
831 C-H oop bend (C4-C5)
948 C-H oop bend (C2-H)
1024 C-H oop bend
1144 ν C5-N
1177 ν C-N + N-H wag
1304 ring expansion
1382 δ CH3
1455 C-H wag
S8
1505 C2N3 + C4N3 +ν C5N1 + N-H wag
2927 νsym C-H (methyl) + νasym C-H (methyl)
3113 ν C-H (ar)
3135 ν C-H (ar)
a) Usov P M, McDonnell-Worth C, Zhou F, et al. The Electrochemical Transformation
of the Zeolitic Imidazolate Framework ZIF-67 in Aqueous Electrolytes.
Electrochimica Acta, 2015, 153: 433-438.
Table S2 BET SSAs and pore structures of all samples.
Samples SBET / m2 g-1 Vp / cm3 g-1 a) d / nm b)
I2&ZIF-67(4:1) 17 0.117 0.848
I2&ZIF-67(2:1) 47 0.077 0.689
I2&ZIF-67(1:1) 418 0.220 0.521
ZIF-67 1206 0.538 0.552
a) Vp is the total pore volume for pores at P/P0 = 0.95.
b) d is the micropore size distribution by H-K method.
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Table S3 Comparison of the ORR activity of the recently reported MOFs derived
catalysts.
MOFs Catalyst ElectrolyteEonset vs RHE/V
E1/2 vs RHE/V
Refs.
Co-MOF Co/CoNx/CNT 0.1 M KOH 0.90 0.80 [S1]
Zn/Co-MOF Fe0.3Co0.7/NC 0.1 M KOH N.A. 0.88 [S2]
ZIF-67 Pt-Co/NC 0.1 M KOH N.A. 0.87 [S3]
Co-MOFCo@NC-MOF-2-
9000.1 M KOH 0.92 0.81 [S4]
Co-MOF Co/NPC 0.1 M KOH 0.91 0.74 [S5]
ZIF-67 Co/N-CNTs 0.1 M KOH−0.005(vs
. Ag/AgCl)
0.154 (vs.
Ag/AgCl)
[S6]
MIL-100(Fe) +
ZIF-81MIL/40ZIF-1000 0.1 M KOH 0.91 0.88 [S7]
Bio-MOF-11
Co-N/PC@CNT 0.1 M KOH 0.92 0.79 [S8]
ZIF-67 CNF@Zn/CoNC 0.1 M KOH 0.91 0.82 [S9]
ZIF-8 NLPC 0.1 M KOH 0.92 N.A.[S10
]
ZIF-67 I2&ZIF-67(2:1) 0.1 M KOH 0.91 0.83 This
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work
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Table S4 The atomic percentage (at. %) of the resulting samples determined by XPS.
Samples C/at. % N/at. % Co/at. % I /at. %
I2&ZIF-67(4:1) 75.67 17.38 2.97 3.98
I2&ZIF-67(2:1) 74.32 17.12 5.59 2.96
I2&ZIF-67(1:1) 77.78 14.04 5.33 2.85
ZIF-67 83.19 13.66 3.15 --
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(
B
Table S5 The binding energy and surface concentration of N 1s, Co 2p2/3 and I 3d2/5 determined by XPS.
N 1s Co 2p2/3 I 3d2/5
Samples Pyridinic-N Co-N Pyrrolic-N Graphitic-N Co3+ Co2+ I3- I5
-
Binding energy / eV
I2&ZIF-67(4:1) 398.4 399.2 400.3 401.2 780.5 782.5 620.7 618.6
I2&ZIF-67(2:1) 398.4 399.2 400.3 401.4 780.6 782.6 620.7 618.6
I2&ZIF-67(1:1) 398.4 399.1 400.2 401.2 780.8 782.6 620.8 618.7
ZIF-67 -- 399 -- -- 781.0 782.9 -- --
Surface concentration / at. %
I2&ZIF-67(4:1) 6.9 5.86 4.62 3.03 1.11 1.07 1.44 2.54
I2&ZIF-67(2:1) 7.48 4.11 3.51 2.02 1.94 2.01 2.34 0.62
I2&ZIF-67(1:1) 4.44 6.08 2.43 1.09 1.74 1.9 1.41 1.44
ZIF-67 -- 13.66 -- -- 1.09 0.93 -- --
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Supplementary References
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their derivatives for electrochemical energy conversion and storage, Chem.
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Alloy/Nitrogen-Doped Carbon Cages Synthesized via Pyrolysis of Complex
Metal-Organic Framework Hybrids for Oxygen Reduction, Adv. Funct. Mater.,
28 (2018) 1706738.
[S3] L.-L. Ling, W.-J. Liu, S.-Q. Chen, X. Hu, H. Jiang, MOF Templated Nitrogen
Doped Carbon Stabilized Pt-Co Bimetallic Nanoparticles: Low Pt Content and
Robust Activity toward Electrocatalytic Oxygen Reduction Reaction, ACS
Appl. Nano Mater., 1 (2018) 3331-3338.
[S4] S.G. Peera, J. Balamurugan, N.H. Kim, J.H. Lee, Sustainable Synthesis of
Co@NC Core Shell Nanostructures from Metal Organic Frameworks via
Mechanochemical Coordination Self-Assembly: An Efficient Electrocatalyst
for Oxygen Reduction Reaction, Small, 14 (2018) 1800441.
[S5] T. Zhan, S. Lu, H. Rong, W. Hou, H. Teng, Y. Wen, Metal-organic-framework-
derived Co/nitrogen-doped porous carbon composite as an effective oxygen
reduction electrocatalyst, J. Mater. Sci., 53 (2018) 6774-6784.
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[S6] H. Zhou, D. He, A.I. Saana, J. Yang, Z. Wang, J. Zhang, Q. Liang, S. Yuan, J.
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H.Q. Yin, Engineering Fe-Fe3C@ Fe-N-C Active Sites and Hybrid Structures
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[S8] J. Ban, G. Xu, L. Zhang, G. Xu, L. Yang, Z. Sun, D. Jia, Efficient
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