Designed synthesis of three-dimensional callistemon-like networks

structural multifunctional electrocatalyst: graphitic-carbon-

encapsulated Co Nanoparticles/N-doped carbon nanotubes@carbon

nanofibers for Zn-air batteries application

Xiuyun Yao, Jiajia Li, Yajing Zhu, Ling Li*, Wenming Zhang*

National-Local Joint Engineering Laboratory of New Energy Photoelectric Devices,

College of Physics Science and Technology, Hebei University, Baoding 071002,

China

1

Figures Captions:

Fig. S1. (a) ZIF-8@PAN fibers. (b) NC@CNF, (c) ZIF 67@PAN fibers. (d)

CoNC@CNF electrocatalysts.

Fig. S2. H2-TPR profiles of CoNC/NCNTs@CNF catalyst.

Fig. S3. Pore size distribution for NC@CNF, CoNC@CNF and CoNC/CNTs@CNF

electrocatalysts.

Fig. S4. LSV curves of CoNC/CNTs@CNF at different rotation rates in O2-saturated

0.1 M KOH.

Fig. S5. Rotating ring-disk electrode (RRDE) voltammograms for

CoNC/CNTs@CNF in O2-saturated 0.1 M KOH at 1600 rpm.

Fig. S6. Typical SEM images of CoNC/NCNTs@CNF before (a) and after (b)

stability test.

Fig. S7. (a-c) CVs measured in 1 M KOH at scan rates from 20 to 80 mV s -1 for

NC@CNF, CoNC@CNF and CoNC/CNTs@CNF.

Fig. S8. (a-c) CVs measured in 1 M KOH at scan rates from 20 to 80 mV s -1 for

NC@CNF, CoNC@CNF and CoNC/CNTs@CNF.

Fig. S9. The particle size distribution of CoNC/CNTs@CNF calculated by the TEM.

Tables Captions:

Table S1. Performance of important non-precious metal based electrocatalysts for

ORR, OER, HER in alkaline environment. η is the over potentials to deliver a -10 mA

cm-2 current density for OER, HER. All of the catalytic electrodes for OER, HER in 1

M KOH, and 0.1M KOH for ORR. 0.1M represents 0.1M KOH solution.

Table S2. BET surface area, total pore volume, micropore volume and adsorption

2

average pore width of NC@CNF, CoNC@CNF and CoNC/CNTs@CNF.

3

Fig. S1. (a) ZIF-8@PAN fibers. (b) NC@CNF, (c) ZIF 67@PAN fibers. (d)

CoNC@CNF electrocatalysts.

4

Fig. S2. H2-TPR profiles of CoNC/NCNTs@CNF catalyst.

5

Fig. S3. Pore size distribution for NC@CNF, CoNC@CNF and CoNC/CNTs@CNF

electrocatalysts.

6

Fig. S4. LSV curves of CoNC/CNTs@CNF at different rotation rates in O2-saturated

0.1 M KOH

7

Fig. S5. Rotating ring-disk electrode (RRDE) voltammograms for

CoNC/CNTs@CNF in O2-saturated 0.1 M KOH at 1600 rpm.

8

Fig. S6. Typical SEM images of CoNC/NCNTs@CNF before (a) and after (b)

stability test.

9

Fig. S7. (a-c) CVs measured in 1 M KOH at scan rates from 20 to 80 mV s -1 for

NC@CNF, CoNC@CNF and CoNC/CNTs@CNF.

10

Fig. S8. (a-c) CVs measured in 1 M KOH at scan rates from 20 to 80 mV s -1 for

NC@CNF, CoNC@CNF and CoNC/CNTs@CNF.

11

Fig. S9. The particle size distribution of CoNC/CNTs@CNF calculated by the TEM.

12

Table S1. Performance of important non-precious metal based electrocatalysts for

ORR, OER, HER in alkaline environment. η is the over potentials to deliver a -10 mA

cm-2 current density for OER, HER. All of the catalytic electrodes for OER, HER in 1

M KOH, and 0.1M KOH for ORR. 0.1M represents 0.1M KOH solution.

Catalysts

ORR OER HER

Reference

Diffusion-

limiting

current

density

(mA cm-2)

Tafel

slope

(mV

dec-1)

η

(mV)

Tafel

slope

(mV

dec-1)

η

(mV)

Tafel

slope

(mV

dec-1)

CoNC/NCNTs@CNF -5.6 92 390 82 190 117 This work

NC@CNF -3.5 248 580 167 373 203 This work

CoNC @CNF -4.5 160 490 104 235 173 This work

Pt/C -5.6 112 - - 40 106 This work

RuO2 - - 320 73 - - This work

NC@GC -4.4 - 340 - - - S1

Co@N-PCFs -5.09 - - - - - S2

CoSAs@CNTs - 99 410 85 - - S3

CNF@Zn/CoNC -5.8 43.3470

(0.1M)

124

(0.1M)- - S4

Co@NC-3/1 -4.7 - 370 90 - - S5

NC@Co-NGC

DSNC-5 51

410

(0.1M)

91

(0.1M)- - S6

13

Co–Nx/C NRA -5 74300

(6M)

62.3

(6M)- - S7

Mo–N/C@MoS2 -5 -390

(0.1M)

72

(0.1M)117 64.3 S8

NiMo3S4 - - - - 257 98 S9

(CoSx/N, S-CNT)700 -4.8 67.9 574 88.1 - - S10

3D-CNTA -4.2 - 360 89 185 135 S11

Co-N,B-CSs -5.66 64470

(0.1M)- - - S12

FeNx/C-700-20 - 93770

(0.1M)219 - - S13

CuCo@NC -5.5 80 - -163

(0.1M)- S14

Fe0.3Co0.7/NC cages -6 79 - - - - S15

CoZn-NC-800 -5.36 126480

(0.1M)

94

(0.1M)- - S16

Co@N-Carbon - - 400 61 - - S17

MCO@NCNTs -6 96510

(0.1M)- - - S18

CoP hollow

polyhedron- - 400 57 159 59 S19

Ni2P - - 290 - 220 - S20

β-Ni(OH)2 - - 444 111 - - S21

Co3O4@Co/NCNT -5.2 61 380 58.7 - - S22

14

NGO/Ni7S6 - -380

(0.1M)

45.4

(0.1

M)

370 145.5 S23

FeCo-N/C -5 52370

(0.1M)

74

(0.1M)- - S24

PO-Ni/Ni-N-CNFs - - 420 113.10 262 97.42 S25

BNPC-1100 4.73 -320

(6M)117 - - S26

NiCo2S4/N-CNT -3 - 370 - - - S27

APBCCF-H -5.8 - 410 99 240 42 S28

Co@Co3O4/NC-2 -4 - 435 - - - S29

Co-N-MoO2 -5.39 60 - -258

(0.1M)

126.8

(0.1M)S30

D-Co@CNG -4.6 83 360 - 205 95 S31

FeNx-embedded PNC -6 -395

(0.1M)

80

(0.1M)- - S32

CoFe LDH-F - - 270 47 255 95 S33

MNG-CoFe -5.5 - 390 - 240 - S34

15

Table S2. BET surface area, total pore volume, micropore volume and adsorption

average pore width of NC@CNF, CoNC@CNF and CoNC/CNTs@CNF.

Catalysts

BET surface

area

(m2 g-1)

Pore volume (cm3 g-1) Adsorption

average pore

width (nm)

total pore

volume

micropore

volume

NC@CNF 140 0.08 0.05 2.34

CoNC@CNF 103 0.11 0.01 4.06

CoNC/CNTs@CNF 261 0.19 0.07 2.95

16

Table S3. Comparison of the metal loadings, mass activity and estimated turn-over

frequency (TOF) of our catalyst with those reported previously.

Catalysts

Metal

loading

(wt.%)a

Mass activity (A g-1)TOF × 10-3

(s-1)

Referenceη = 300

mV (OER)

η =25 mV

(HER)

V =700

m

V（ORR

）

η = 300

mV

(OER)

η =25

mV

(HER)

V =700

mV

（ORR）

CoNC/CNTs@CNF 6.93 4.02 0.003 0.011 8.86 6.54 24.30 This work

CoNC@CNF 5.26 0.97 0.002 0.006 2.82 5.17 16.84 This work

RuO2 0.76 8.12 - - 2.80 - - This work

Pt/C 0.2 - 0.013 0.011 - 33.02 27.22 This work

Fe-N-C-950 0.32 - - 6.6 - - 1.71 S35

Fe-N-C - - - 3.2 - - 0.4 S36

FePhenMOF-

ArNH3

0.5 - - 7.78 - - 2.4 S37

(Fe,Fe)1 + N2/H2 2.4 - - 1.23 - - 0.06 S38

0.5Fe-950 1.2 - - 3.42 - - 0.33 S39

Co(OH)X -NCNT 17 - - - 2.3 - - S40

S,S′-CNT1000 °C 148 - - 5.87 - - S41

PtNi/C - - - - 3.6 - - S42

HI-CoP/CNT - - - - - 0.175 - S43

17

N-doped Ni3S2 - - - - - 2.4 - S44

PPy@NiCo HNTAs - - - - - 0.625 - S45

Co/G NSs - 583.3 - - 0.089 - - S46

SSUCo-900 - - - - 0.034 - - S47

Co3O4@CoOSC - 234.0 - - 0.0487 - - S48

Y2Ru2O7-δ - - - - 67.7 - - S49

18

Table S4. Co dispersion in different catalysts prepared by different methods.

Catalysts

H2 pulse adsorption TEM XRD

Dispers

ion

(%)a

Crystallite

Size (nm)

a

Co

particle

size

(nm)b

Dispe

rsion

(%)b

Diffrac

tion

Peak

2The

ta (°)

FW

HM

(nm

)

Cryst

allite

size

(nm)c

Disper

sion

(%)c

CoNC/

CNTs@CNF4.11 22.41 26.70 8.49

(111)44.3

6

0.33

6

25.55 3.76

(200)51.7

4

0.29

5

29.95 3.21

(220)75.9

0

0.26

8

37.62 2.55

CoNC@CNF 2.08 43.46 - -

(111)44.0

1

0.33

1

25.91 3.71

(200)51.2

6

0.22

3

39.54 2.43

a Calculated from H2 pulse adsorption

b Calculated in HRTEM analysis.

c Determined from the XRD patterns.

19

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