evolution reaction alloys anchored on graphene for highly ... · metal-organic frameworks derived...

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Supporting Information

Metal-Organic Frameworks Derived Nitrogen-Doped Carbon-RhNi

Alloys Anchored on Graphene for Highly Efficient Hydrogen

Evolution Reaction

Xian-Ming Xia,†a Cheng-ZongYuan,†b Gang Wang,b Cong Ling,b Tan

Zhao,b Wan-Qing Li,a Yuck-Yun Cheang,*c Sheng-Liang Zhong*a and

An-Wu Xu*b

a College of Chemistry and Chemical Engineering, Jiangxi Normal

University, Nanchang 330022, P. R. China. E-mail: slzhong@jxnu.edu.cn

b Division of Nanomaterials and Chemistry, Hefei National Laboratory

for Physical Sciences at the Microscale, The First Affiliated Hospital,

University of Science and Technology of China, Hefei 230026, P. R.

China. E-mail: anwuxu@ustc.edu.cn.

c The First Affiliated hospital of Guangdong Pharmaceutical University,

Guangzhou 510080, China. 13631322559@163.com

Electronic Supplementary Material (ESI) for Inorganic Chemistry Frontiers.This journal is © the Partner Organisations 2020

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Fig. S1 SEM images of (a) NC-Ni, (b) NC-Rh, (c) NC-RhNi and (d) NC-

RhNi/rGO.

3

Fig. S2 SEM images of different ratio of Rh and Ni (a) 1:1, (b) 1:2, (c)

1:3 and (d) 2:1.

4

Fig. S3 (a) XRD patterns for rGO, NC-Ni, NC-Ni/rGO, NC-RhNi, NC-

RhNi/rGO, RhNi-MOF/GO, NC-Rh/rGO and NC-Rh, (b) XRD patterns

of samples with different ratios of Rh to Ni.

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885 880 875 870 865 860 855 850

Sat. Nix+2p1/2

Ni 2p1/2 Sat.

Nix+2p3/2 Ni 2p3/2

Inte

nsity (a.u

.)

Binding Energy (eV)

Ni 2p

298 296 294 292 290 288 286 284 282 280 278

Inte

nsity (a.u

.)

C=O

C-N/C-O

C-C/C=C

C 1s

Binding Energy (eV)

a b

Fig. S4 High-resolution XPS spectra for (a) Ni 2p and (b) C 1s.

Fig. S5 Energy-dispersive spectroscopic (EDS) pattern of NC-RhNi/rGO.

6

200 400 600 800 1000 1200 1400 1600 1800

Inte

nsity

(a.u

.)

900 OC

800 OC

700 OC

ID/IG = 0.98

ID/IG = 1.01G

ID/IG = 0.96

D

Raman shift (cm-1)

Fig. S6 Raman spectra of the samples calcinated at different temperatures.

7

-0.5 -0.4 -0.3 -0.2 -0.1 0.0 0.1-260-240-220-200-180-160-140-120-100-80-60-40-20

0

NC-RhNi NC-RhNi/rGO

E (V vs. RHE)

j (m

A cm

-2)

Fig. S7 Linear sweep polarization curves of NC-RhNi and NC-RhNi/rGO

obtained in 1.0 M KOH at a scan rate of 5 mV s-1.

8

-0.5 -0.4 -0.3 -0.2 -0.1 0.0 0.1-260-240-220-200-180-160-140-120-100-80-60-40-20

0

1:1 1:2 1:3 2:1

E (V vs. RHE)

j (m

A cm

-2)

Fig. S8 Linear sweep polarization curves of NC-RhNi/rGO with different

rate of Rh to Ni obtained in 1.0 M KOH at a scan rate of 5 mV s-1.

9

-0.5 -0.4 -0.3 -0.2 -0.1 0.0 0.1-250

-200

-150

-100

-50

0

700C

900 C 800 C

j (m

A cm

-2)

E (V vs. RHE )

Fig. S9 Linear sweep polarization curves of NC-RhNi/rGO obtained by

different calcinate temperatures at a scan rate of 5 mV s-1 in 1.0 M KOH.

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0.4 0.6 0.8 1.0 1.2 1.40.00

0.02

0.04

0.06

0.08

0.10NC-Rh/rGONC-Rh

20%Pt/CNC-RhNi/rGO

62 mV dec-1

82 mV dec

-1

119 m

V dec

-1

Ove

rpot

entia

l (V)

Log (\j\ (mA cm-2))

54 mV dec-1

20 40 60 80 1000.51.01.52.02.53.03.54.04.55.05.5

18.74 mF cm-1

23.88 mF cm-1

29.54 mF cm-1

NC-Rh NC-Ni/rGO NC-Rh/rGO NC-RhNi/rGO

Scan rate (mV s-1)

50.18 mF cm-1

j 0.

3 v(m

A cm

-2)

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.20

0.25

0.30

0.35

0.40

Log (\j\ (mA cm-2))

162 mV dec

-1

NC-Ni/rGO

Ove

rpot

entia

l (V)

a b

dc

0

50

100

150

200

250

300

350

400

162

373 Overpotential 10 mV Tafel slope (mV dec-1)

NC-Ni/rGO

Fig. S10 (a) the corresponding Tafel plots of NC-Rh/rGO, NC-RhNi/rGO,

NC-Rh and 20% Pt/C. (b) Estimation of electrochemical double-layer

capacitance (Cdl) for various electrocatalysts by plotting the difference in

current densities at 0.3 V versus RHE for NC-Ni/rGO, NC-RhNi/rGO,

NC-Rh/rGO and NC-Rh. (c) The corresponding Tafel plot of NC-Ni/rGO,

and (d) Comparison of overpotential at a current density of 10 mA cm-2

and Tafel slope of NC-Ni/rGO in 1.0 M KOH.

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0.20 0.25 0.30 0.35 0.40

-4

-3

-2

-1

0

1

2

3

E (V vs. RHE)

20 mV s-1

100 mV s-1

80 mV s-1 60 mV s-1 40 mV s-1

NC-RhNi/rGOj (

mA

cm-2)

0.20 0.25 0.30 0.35 0.40

-3

-2

-1

0

1NC-Rh/rGO

20 mV s-1

100 mV s-1 80 mV s-1 60 mV s-1 40 mV s-1

E (V vs. RHE)

j (m

A cm

-2)

0.20 0.25 0.30 0.35 0.40-3

-2

-1

0

1NC-Rh

20mV s-1

100mV s-1

80mV s-1 60mV s-1 40mV s-1

E (V vs. RHE)

j (m

A cm

-2)

0.20 0.25 0.30 0.35 0.40

-3

-2

-1

0

1

2NC-Ni/rGO

20 mV s-1

100 mV s-1 80 mV s-1 60 mV s

-1 40 mV s-1

E (V vs. RHE)

j (m

A cm

-2)

a b

dc

Fig. S11 Cyclic voltammograms (CV) curves of (a) NC-RhNi/rGO, (b)

NC-Rh/rGO, (c) NC-Rh, and (d) NC-Ni/rGO in the region of 0.20-0.40V

vs. RHE in 1.0 M KOH at various scan rates.

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-0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0.0 0.1-600-550-500-450-400-350-300-250-200-150-100-50

0 NC-RhNi NC-RhNi/rGO

E (V vs. RHE)

j (m

A cm

-2)

Fig. S12 Linear sweep polarization curves of NC-RhNi/rGO and NC-

RhNi obtained in 0.5 M H2SO4 at a scan rate of 5 mV s-1.

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0.0 0.2 0.4 0.6 0.8 1.0

0.20

0.25

0.30

0.35

0.40

Log (\j\ (mA cm-2))

NC-Ni/rGO

221 mv d

ec-1

Overp

ote

ntial (V

)

050

100150200250300350400450

NC-Ni/rGO

Overpotential 10 mV Tafel slope (mV dec-1)

415

221

a b

Fig. S13 (a) The corresponding Tafel plot of NC-Ni/rGO and (b)

Comparison of overpotential at a current density of 10 mA cm-2 and Tafel

slope of NC-Ni/rGO in 0.5 M H2SO4.

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Table S1. The atomic ratio of NC-RhNi/rGO obtained from XPS spectra.

Element Rh 3d Ni 2p C 1s N 1s O 1s

NC-RhNi/rGO 0.49% 1.75% 83.92% 5.73% 8.11

%

Table S2. Comparison of HER performance with that of recently

reported alloy electrocatalysts.

Electrocatalysts Electrolyte η10

(mV)Tafel slope(mV dec-1)

References

Cu-Ni nanocages

1 M KOH 140 79 [1]

NixCuy@NG-NC 1 M KOH 122 84.2 [2]IrNi@OC 1 M KOH 27 50 [3]

Pt-Ni hetero 1 M KOH 48 [4]CoRux@N-C 1 M KOH

0.5 M H2SO4

2794

7364

[5]

PtRh ANDs 0.5 M H2SO4 25 32 [6]NiRu@N–C 0.5 M H2SO4 50 36 [7]CoNi@NC 0.1 M H2SO4 142 105 [8]NiCu@C 0.5 M H2SO4

1 M KOH4874

63.294.5

[9]

RuAu SAAs 1 M KOH 24 37 [10]hcp Pt–Ni 1 M KOH 65 78 [11]

NC-RhNi/rGO 1 M KOH0.5 M H2SO4

3734

5422

This work

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