hydrogen evolution in alkaline medium interfaces ... · s-1 supporting information niag0.4 3d...
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S-1
Supporting Information
NiAg0.4 3D porous nanoclusters with epitaxial
interfaces exhibiting Pt like activity towards
hydrogen evolution in alkaline medium
Chidanand Hegde,‡a Xiaoli Sun,‡b Hao Ren,c Aijian Huang,d Daobin Liu,c Bing Li,e Raksha
Dangol,c Chuntai Liu,f Shuiqing Li,*b Hua Li*a and Qingyu Yan*c
aSingapore Center for 3D Printing, Department of Mechanical and Aerospace Engineering, Nanyang Technological University, Singapore 639798, Singapore
bDepartment of Energy and Power Engineering, Tsinghua University, Beijing, 100084, China
cDepartment of Materials Science and Engineering, Nanyang Technological University, Singapore 639798, Singapore
dSchool of Electronics Science and Engineering, University of Electronic Science and Technology of China, Chengdu, 610054, P.R. China
eInstitute of Materials Research and Engineering, A*STAR (Agency for Science, Technology, and Research), 2 Fusionopolis Way Innovis #08-03, Singapore 138634, Singapore
fKey Laboratory of Materials Processing and Mold, Ministry of Education, Zhengzhou University, Zhengzhou 450002, China
*Corresponding authors.
E-mail addresses: [email protected] (Q. Yan), [email protected] (S. Li), [email protected] (H. Li).
‡These authors contributed equally.
Electronic Supplementary Material (ESI) for Nanoscale.This journal is © The Royal Society of Chemistry 2020
S-2
30 40 50 60 70 80
Inte
nsity
(a.u
.) NiAg0.13 3DPNC
2(degree)
Ni
Ag
NiAg0.25 3DPNC
NiAg0.34 3DPNC
PDF #01-087-0720
NiAg0.4 3DPNCPDF #01-071-4654
30 40 50 60 70 80
NiAg0.44 3DPNC
NiAg0.6 3DPNC
PDF #01-087-0720)PDF #01-071-4654)
NiAg0.95 3DPNC
NiAg2.75 3DPNC
Ag
Inte
nsity
(a.u
.)
2(degree)
Ni
(a) (b)
Fig. S1 XRD patterns of (a) NiAg0.13 3DPNC, NiAg0.25 3DPNC, NiAg0.34 3DPNC, and NiAg0.4 3DPNC, and (b) NiAg0.44 3DPNC, NiAg0.6 3DPNC, NiAg0.95 3DPNC, and NiAg2.75 3DPNC.
1000 800 600 400 200 0
Ni 2p
Ag 3s
Ag 3pO 1s
Ag 3d
C 1s
Cou
nts
/s
Binding Energy (eV)
Ni 3p
Fig. S2 XPS survey spectrum of NiAg0.4 3DPNC.
S-3
100 nm 1 µm
(a) (b)
Fig. S3 FESEM images of (a) Ag NPs, (b) Ni 3DPNC.
S-4
Fig. S4 HRTEM image of (a) NiAg0.4 3DPNC, (b) FFT analyzed image of NiAg0.4 3DPNC, and (c) HRTEM image of Ag/Ni(OH)2.2/3H2O precursor.
S-5
(a)
(d)(c)
(b)
0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.02
0.00
0.02
0.04
0.06
0.08
45.3 mV dec-1
47.4 mV dec-1
46.5 mV dec-1
50.42 mV dec-1
Ove
rpot
entia
l (V)
log j
NiAg0.13 3DPNC
55.7 mV dec-1
NiAg0.25 3DPNC
NiAg0.4 3DPNC
NiAg0.34 3DPNC
NiAg0.44 3DPNC
0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.02
0.00
0.02
0.04
0.06
0.08
0.10
0.12
O
verp
oten
tial (
V)
log j
NiAg0.6 3DPNC
91.5 mV dec-1
71.3 mV dec-1
46.4 mV dec-1
46.2 mV dec-1
NiAg0.95 3DPNC
NiAg4.42 3DPNC
NiAg2.75 3DPNC
-0.3 -0.2 -0.1 0.0-100
-80
-60
-40
-20
0
Cur
rent
Den
sity
(mA
cm-2)
Evs RHE (V)
NiAg0.13 3DPNC NiAg0.25 3DPNC NiAg0.34 3DPNC NiAg0.4 3DPNC NiAg0.44 3DPNC NiAg0.6 3DPNC NiAg0.95 3DPNC NiAg2.75 3DPNC NiAg4.42 3DPNC
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00
50
100
150
200
250
300
350
400
Ove
rpot
entia
l (m
V)
Mass loading (mg cm-2)
NiAg0.4 3DPNC Pt/C Ni 3DPNC Ag NPs
Fig. S5 (a) Variation of overpotential with catalyst loading for Ni 3DPNC, Ag NPs, NiAg0.4 3DPNC, and Pt/C catalysts. (b) HER polarization curves of NiAgx 3DPNC with varying Ni to Ag ratios without iR correction and their corresponding (c-d) Tafel plots.
S-6
6052 50 45
5161
69
110
140
0
25
50
75
100
125
150
NiAg0.25 NiAg0.34 NiAg0.4NiAg0.44
NiAg0.6 NiAg0.95 NiAg4.42NiAg2.75
Ove
rpot
entia
l (m
V)
CatalystNiAg0.13
(a) (b)
2840
132
280
0
50
100
150
200
250
300
Ag NPsNiAg0.4 3DPNC Ni 3DPNC
Catalyst
@10
mA
cm
-2 (m
V)
Pt/C
Fig. S6 Variation of overpotential at 10 mA cm-2 for (a) synthesized catalysts with varying Ag composition, (b) Pt/C, NiAg0.4 3DPNC, Ni 3DPNC and Ag NPs.
-0.4 -0.3 -0.2 -0.1 0.0
-120
-100
-80
-60
-40
-20
0
Cur
rent
Den
sity
(mA
cm-2)
Evs RHE (V)
NiAg0.4 3DPNC Pt/C
Fig. S7 HER polarization curves for NiAg0.4 3DPNC and Pt/C in 0.5 M H2SO4.
S-7
0.675 0.700 0.725 0.750 0.775
-0.4
-0.2
0.0
0.2
0.4
NiAg0.4
j (m
A cm
-2)
E vs RHE (V)
10 mV/s 20 mV/s 50 mV/s
40 mV/s 60 mV/s
30 mV/s
0.675 0.700 0.725 0.750 0.775-0.75
-0.50
-0.25
0.00
0.25
0.50
0.75
j (m
A cm
-2)
E vs RHE (V)
10 mV/s 20 mV/s 30 mV/s
50 mV/s
Ni
40 mV/s
0.675 0.700 0.725 0.750 0.775
-1.2
-0.8
-0.4
0.0
0.4
0.8
1.2
j (m
A cm
-2)
E vs RHE (V)
5 mV/s 10 mV/s 20 mV/s 50 mV/s
Ag
30 mV/s 40 mV/s
0.00 0.25 0.50 0.75 1.00 1.25
-10
-5
0
5
10
j (m
A cm
-2)
E vs RHE (V)
50 mV/s
(a)
(d)(c)
(b)
Fig. S8 Cyclic voltagram (CV) curves for (a) NiAg0.4 3DPNC, (b) Ni 3DPNC, (c) Ag NPs, and (d) CV curve for underpotential deposition for Pt/C 20% wt. catalyst.
S-8
S2S1 S3 Fo
rmin
g en
ergy
(eV
)
-2.73
-2.02
-2.72
S1S2S3
S1S2
S3S1
S2
S3
S1S2
S3
-1.80
-2.11 -2.12
S2S1 S3
Form
ing
ener
gy (
eV)
(e)
(d)(c)(b)(a)
(f)
Ni Ag
Fig. S9 The top and side view of crystal structures of: (a) pristine Ni (111) surface, (b) Ag/Ni (111) surface where the adsorption sites: top of Ni (S1), the Ni fcc sites (S2) and Ni hcp sites (S3); the top and side view of crystal structures of (c) pristine Ag (111) surface, (b) Ni/Ag (111) surface where the adsorption sites: top of Ag (S1), the Ag fcc sites (S2) and Ag hcp sites (S3); (e) the forming energy of Ag adsorbed on Ni (111) surface; (f) the forming energy of Ni adsorbed on Ag(111) surface.
S-9
0.4 0.6 0.8 1.0 1.2 1.4 1.60.00
0.02
0.04
0.06
Ove
rpot
entia
l (V)
Log j
Equation y = a + b*x
Weight No Weighting
Residual Sum of Squares
1.21983E-6
Pearson's r 0.99965Adj. R-Square 0.99915
Value Standard Erro
OverpotentialIntercept -0.06192 0.00112Slope 0.07785 9.24844E-4
Fig. S10 Tafel plot of NiAg0.4 3DPNC to evaluate the exchange current density. Exchange current density was computed from the Tafel equation.
The exchange current density of the NiAg0.4 3DPNC based on the geometric surface area was computed from the Tafel equation as shown below:
η = -0.062 + 0.077 log j
0 = -0.062 + 0.077 log j
Log j = 0.8052
j0geometric = 6.3856 mA cm-2geometric
j0 (ECSA) = 6.3856/125 mA cm-2(ECSA)
j0 (ECSA) = 5.10 * 10-5 A cm-2(ECSA)
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-0.3 -0.2 -0.1 0.0-100
-80
-60
-40
-20
0
Cur
rent
Den
sity
(mA
cm
-2)
Evs RHE (V)
NiAg0.4 3DPNC before stability test NiAg0.4 3DPNC post stability test
Fig. S11 Comparison of HER polarization curve of NiAg0.4 3DPNC after 80 hours chronoamperometry test with the initial catalyst.
S-11
20 30 40 50 60 70 80
Ag (PDF # 01-087-0720)
In
tens
ity (a
.u.)
2 Theta (degree)
carbon cloth
Ni (PDF # 01-071-4654) (b)(a)
(d)(c)
880 875 870 865 860 855 850 845
Cou
nts
/s
Binding Energy (eV)
sat.Ni2+ 2p1/2
Ni 2p1/2
sat. Ni2+ 2p3/2
Ni 2p3/2
378 376 374 372 370 368 366 364 362
Cou
nts
/s
Binding Energy (eV)
Ag 3d5/2
Ag 3d3/2
Fig. S12 (a) XRD pattern of NiAg0.4 3DPNC after 80 hours chronoamperometry test. (b) FESEM image of the NiAg0.4 3DPNC after chronoamperometry test. XPS spectra of NiAg0.4 3DPNC after 80 hours chronoamperometry test in the (c) Ni 2p region, (d) Ag 3d region.
S-12
Table S1. Inductive couple plasma- atomic emission spectroscopy results for the synthesized samples with different Ni/Ag ratios.
Ni : Ag ratio in the precursor solution
Expected molar
concentration from synthesis
Measured molar
concentration from ICP-
OES
Expected molar
concentration from
synthesis
Measured molar
concentration from ICP-
OES
Sample name in the report
Ni (%) Ni (%) Ag (%) Ag (%)
1 : 0.1 90.9 88.43019 9.1 11.56981 NiAg0.13 3DPNC
1 : 0.2 83 80.20356 17 19.79644 NiAg0.25 3DPNC
1 : 0.3 76.9 74.63433 23.1 25.36567 NiAg0.34 3DPNC
1 : 0.4 71.5 71.89 28.5 28.11 NiAg0.4 3DPNC
1 : 0.5 66.67 69.57572 33.33 30.42428 NiAg0.44 3DPNC
1 : 0.6 62.5 62.55256 37.5 37.44744 NiAg0.6 3DPNC
1 : 0.8 55.55 51.37111 44.45 48.62889 NiAg0.95 3DPNC
1 : 2 33.33 26.63245 66.67 73.36755 NiAg2.75 3DPNC
1 : 3 25 18.4579 75 81.5421 NiAg4.42 3DPNC
68.5 31.5
NiAg0.4 3DPNC Post chronoamperometr
y test
Table S2. Roughness factor values for different catalysts which was evaluated from the double layer capacitance.
Catalyst Cdl (mF cm-2 ) Roughness factor (cm2 per cm2
(geometric))
Ni 3DPNC 7 175
Ag NPs 12.8 320
Pt/C 20.4738 mC cm-2
97.5
NiAg0.4 3DPNC 4.9 125
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Table S3. HER activity of the NiAg0.4 3DPNC in comparison with other recently reported catalysts with good activity.
Catalyst HER
overpotential
(mV@mA
cm-2)
Tafel
slope
(mV
dec-1)
Electrolyte Stability Reference
Boron doped
RhFe alloy
25 mV @ 10
mA cm-2
32 0.5 M H2SO4 8 hours 1
Ni20Fe20Mo10Co
35Cr15 high
entropy alloy
172 mV @ 10
mA cm-2
41 1 M KOH 8 hours 2
Pt3Ni3 NWs 70 mV @
19.8 mA cm-2
NA 1 M KOH 3 hours 3
Micro-nano
MoS2 spheres
214 mV @ 10
mA cm-2
74 0.5 M H2SO4 24 hours 4
Pt3Co
nanoparticles
32.6 mV @
10 mA cm-2
28.6 0.5 M H2SO4 5000
CV
cycles
5
np-CoP3 on Ti
mesh
76 mV @ 10
mA cm-2
50 1 M KOH 60 hours 6
PtCo–Co/TiM 70 mV @
46.5 mA cm-2
35 1 M KOH 50 hours 7
Fe1.89Mo4.11O7/
MoO2
197 mV @10
mA cm-2
79 1 M KOH 1000
CV
cycles
8
V-doped Ni3S2
Nanowires on Ni
foam
68 mV @ 10
mA cm-2
112 1 M KOH 7000
cycles
9
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CrOx/Ni–Cu 48 mV @ 10
mA cm-2
64 KH2PO4 +
K2HPO4
buffer (pH =
7)
24 hours 10
FeP
nanoparticles
154 mV @ 10
mA cm-2
65 0.5 M H2SO4 1.66
hours
11
IrAg nanotubes 20 mV @ 10
mA cm-2
61.1 0.5 M H2SO4 6 hours 12
NiAg0.4 3DPNC 40 mV @ 10
mA cm-2
39.1 1 M KOH 80
hours
and
5000
CV
cycles
This work
S-15
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