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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/
[email protected] 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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