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: yinfx@cczu.edu.cn (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

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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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