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Appendix A.
Supplementary Information
Metal-Organic Frameworks Derived Reverse-
Encapsulation Co-NC@Mo2C Complex for
Efficient Overall Water Splitting
Qirui Lianga, Huihui Jina, Zhe Wangb, Yuli Xiong*c, Shuai Yuana, Xianci Zengb, Daping He*a,b
and Shichun Mu*a
a State Key Laboratory of Advanced Technology for Materials Synthesis and Processing,
Wuhan University of Technology, Wuhan 430070, China.
b Hubei Engineering Research Center of RF-Microwave Technology and Application, Wuhan
University of Technology, Wuhan 430070, China.
c School of Electronic and Electrical Engineering, Wuhan Textile University, Wuhan 430200,
China.
*Address corresponding to: [email protected], [email protected], [email protected]
Figure S1 SEM images of ZIF-67.
Figure S2 TEM images of ZIF-67.
Figure S3 SEM images of ZIF-67 after grinding with ammonium molybdate tetrahydrate.
Figure S4 SEM images of Co-NC@Mo2C.
Figure S5 (a) TEM and (b) HAADF-STEM images of Co-NC@Mo2C.
Figure S6 HRTEM image of Co-NC@Mo2C
Figure S7 EDX spectrum of Co-NC@Mo2C.
Figure S8 SEM images of Co-NC.
Figure S9 TEM images of ZIF-8.
Figure S10 TEM images of NC@Mo2C.
Figure S11 XRD patterns of Co-NC@Mo2C and some contrast samples.
Figure S12 Raman spectrum of Co-NC@Mo2C.
Figure S13 XPS spectra of Co-NC@Mo2C: (a) survey, (b) C 1s, (c) N 1s, (d) O 1s.
Figure S14 HER polarization curves of Co-NC@Mo2C at different temperatures in 1.0 M
KOH aqueous solution.
Figure S15 Time-dependent current density curves for Pt/C at constant potentials for 25 h
and corresponding polarization curves before and after 1000 CV cycles in (a) 1.0 M KOH
and (b) 0.5 M H2SO4 aqueous solution.
Figure S16 XPS spectra of Co-NC@Mo2C after HER stability test.
Figure S17 XRD patterns of Co-NC@Mo2C before and after HER stability test.
Figure S18 SEM image of the Co-NC@Mo2C after HER stability test.
Figure S19 (a, b, c) CVs with different rates from 20 to 120 mV s−1 in the region of -0.5 ~ -
0.6 V for Co-NC@Mo2C, Co-NC, NC@Mo2C in 1.0 M KOH aqueous solution respectively.
(d) The capacitive currents at -0.55 V with different scan rates.
Figure S20 Time-dependent current density curves for (a) IrO2 and (b) IrO2-Pt/C at constant
potentials for 20 h and corresponding polarization curves before and after 1000 CV cycles.
Figure S21 Comparison with selected state-of-the-art (a, b) HER and (c) OER electrocatalysts.
Figure S22 Gas collection device of water splitting.
Table S1 Inductively coupled plasma results for Co and Mo contents in Co-NC@Mo2C.
Element W(B)%Co 27.43Mo 62.95
Table S2 The surface element content of Co-NC@Mo2C measured by XPS measurements.
Element Content (at.%)C 19.64N 28.57O 31.45Co 6.94Mo 13.41
Table S3 Tafel slope (mV dec-1) of several catalysts in this experiment.
HER in 1.0 M KOH HER in 0.5 M H2SO4 OER in 1.0 M KOHCo-NC@Mo2C 65 60 61
Co-NC 172 267 121
NC@Mo2C 68 65 176
NC 277 319 228
Commercial Mo2C
122 180 96
Commercial Pt/C 69 34 /
Commercial Ir2O / / 88
Table S4 Comparison of HER performance in acid/alkaline media for Co-NC@Mo2C with
other reported electrocatalysts.
Catalysts Electrolytes η@10mA cm-2(mV)
Catalyst loading (mg cm-2)
Ref.
Co-NC@Mo2C 0.5 M H2SO4
1.0 M KOH14399
0.83 This work
MoCN-3D 0.5 M H2SO4
1.0 M KOH89122
0.26 Asia. Mater. 2016, 8, e293-e293.
Co-C-N 0.5 M H2SO4
1.0 M KOH138178
- J. Am. Chem. Soc. 2015, 137, 15070-15073.
CoP/CC 0.5 M H2SO4
1.0 M KOH67209
0.92 J. Am. Chem. Soc.2014, 136, 7587-7590.
Co, N/3DG-2 0.5 M H2SO4 141 0.28 J. Power Sources 2017, 363, 260-268.
CoP/CNT 0.5 M H2SO4 122 0.285 Angew. Chem. Int. Ed. 2014, 53, 6710-6714.
Co-NCNT/CC 0.5 M H2SO4
1.0 M KOH78180
3.4 ChemSusChem2015, 8, 1850-1855.
CoNC/GD 0.5 M H2SO4
1.0 M KOH340284
- ACS. Appl. Mater. Inter.2016, 8, 31083-31091.
Zn0.30Co2.70S4 0.5 M H2SO4
1.0 M KOH8085
0.285 J. Am. Chem. Soc. 2016, 138, 1359-1365.
MoCx/C 0.5 M H2SO4
1.0 M KOH135150
0.45 Small Methods2018, 2, 1700353.
Mo2C/GCSs 0.5 M H2SO4 200 0.36 ACS. Catal.2014, 4, 2658-2661.
Mo2CTx 0.5 M H2SO4 283 0.1 ACS. Energy. Lett.2016, 1, 589-594.
Mo2C@2D-NPCs
0.5 M H2SO4
1.0 M KOH8645
- ACS. Nano2017, 11, 3933-3942.
Mo2C@NC 0.5 M H2SO4
1.0 M KOH12460
0.28 Angew. Chem. Int. Ed. 2015, 54, 10752-10757.
uf-Mo2C/CF 0.5 M H2SO4
1.0 M KOH184185
0.25 Small Methods 2018, 2, 1700396.
Mo2C QD/NGCL
0.5 M H2SO4
1.0 M KOH136111
2.0 Chem. Commun.2016, 52, 12753-12756.
Co-P/NC 1.0 M KOH 154 0.283 Chem. Mater.2015, 27, 7636-7642.
Co-P 1.0 M KOH 94 - Angew. Chem. Int. Ed.2015, 54, 6251-6254.
Table S5 The surface elemental content of Co-NC@Mo2C after HER stability test measured
by XPS measurements.
Element Content (at.%)C 18.16N 10.76O 55.72Co 5.29Mo 10.07
Table S6 Comparison of OER performance in alkaline media for Co-NC@Mo2C with other
reported electrocatalysts.
Catalysts Electrolytes η@10mA cm-2(mV)
Catalyst loading(mg cm-2)
Ref.
Co-NC@Mo2C 1.0 M KOH 347 0.83 This work
Co-P/NC 1.0 M KOH 319 0.283 Chem. Mater. 2015, 27, 7636-7642.
Co-P 1.0 M KOH 345 - Angew. Chem. Int. Ed. 2015, 54, 6251-6254.
NiCoP/C 1.0 M KOH 330 0.25 Angew. Chem. Int. Ed. 2017, 56, 3897-3900.
Co NPs 0.1 M KOH 390 0.2 J. Am. Chem. Soc. 2015, 137, 7071-7074.
ZnCo2O4 1.0 M KOH 390 - J. Phys. Chem. Lett. 2014, 5, 2370-2374.
Co3O4 0.1 M KOH 300 - Angew. Chem. Int. Ed. 2016, 55, 5277-5281.
NCO–HNSs 1.0 M NaOH 340 - Adv. Energy. Mater. 2015, 5, 1500091.
Co3O4_EC_0.50 1.0 M NaOH 377 - ACS. Appl. Mater. Inter.
2015, 7, 24550-24555.
HFC Co3O4 2.0 M KOH 409 0.14 ACS. Appl. Mater. Inter. 2015, 7, 20322-
20331.
Ni-Co2-O HNSs 0.1 M KOH 362 0.2 Chem. Commun. 2015, 51, 7851-7854.
Co-S/Ti mesh 1.0 M KOH 361 - Electrochem.Commun. 2015, 60, 92-96.
CFO/rGO 1.0 M KOH 340 - ChemSusChem 2015, 8, 659-664.
CeO2/Co3O4-2 0.3 M KOH 386 - J. Mater. Sci-Mater. El. 2016, 27, 5294-
5302.
Fe1Co1-ONS 0.1 M KOH 308 0.36 Adv. Mater. 2017, 29. 1703614.
NiCo2O4 0.1 M KOH 340 0.25 Dalton Trans. 2015, 44, 4148-4154.
Ni-Fe-Co 0.1 M KOH 310 0.25 ACS. Catal. 2015, 6, 155-161.
BCFSn-721 0.1 M KOH 450 - Adv. Sci. 2016, 3, 1500187.
Table S7 Comparison of catalytic performance (mV) at the current density of 10 mA cm–2 in
1.0 M KOH aqueous solution for Co-NC@Mo2C with other relevant bifunctional
electrocatalysts reported in recent years.
Catalysts HER(mV)
OER(mV)
Water Splitting(V)
Ref.
Co-NC@Mo2C
Cu@CoFe LDH
Fe-Co
PO-Ni/Ni-N-CNFs
Co/NBC
N-NiMoO4/NiS2
Ni–Co–P HNBs
99
171
163
262
117
99
107
347
240
283
420
302
283
270
1.685
1.681
1.68
1.69
1.68
1.60
1.62
This work
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