Pd nanocubes and PdAg enclosed within (100)

planes as electrocatalysts for the ethylene glycol

electro-oxidation
Andrés López-Coronel,1, 4 E. Ortiz-Ortega,1 L. Torres-Pacheco,1 Minerva Guerra-Balcázar,2 Luis Gerardo Arriaga,1 Lorena Álvarez-Contreras,3 and Noé Arjona1**

1 Centro de Investigación y Desarrollo Tecnológico en Electroquímica S. C., Sanfandila, Pedro Escobedo, Querétaro, C. P. 76703, México
2 Facultad de Ingeniería, División de Investigación y Posgrado, Universidad Autónoma de Querétaro, Querétaro, C. P. 76010, México
3 Centro de Investigación en Materiales Avanzados S. C., Complejo Industrial Chihuahua, Chihuahua, C. P. 31136, México.4
*noe.arjona@yahoo.com.mx & wvelazquez@cideteq.mx. Tel: +52 (442) 211 60 00 ext. 7874

ABSTRACT
The ethylene glycol electro-oxidation reaction (EGOR) is a surface-sensitive electrochemical reaction of high interest for fuel cells applications. In this work, Pd and
PdAg with a well-defined form of nanocubes were synthesized with the aim of investigate the effect of silver incorporation within Pd nanocubes on the electrocatalytic
properties of PdAg nanocubes toward EGOR. .

INTRODUCTION EXPERIMENTAL
In this work, we succeed in developing a sub-5nm PdAg
catalyst with abundance of {100} facets, and a sub-10 nm Allow the solution to
Pd nanocubes which also contains abundance of {100} PVP and AA
NaBr and Na2PdCl4 cool and proceed with the
in water add Vulcan carbon washes.
facets as the reference material. ethylene glycol (EG) is a In wáter
promising fuel due to it is less volatile than methanol and
ethanol, and it displays a higher electron rate (almost 80%)
than the ethanol electro-oxidation reaction (EOR, 33%)
due to EOR promotes the formation of acetates, while EG
tends to form oxalates [2]. react at a temperature of 80 ° C react for 3 hours. react for 30 minutes.
Figure 1. Schematic diagram of a PEMFC [1] in magnetic stirring.
Figure 2. Description of the synthesis by a chemical reduction in aqueous medium.

RESULTS AND DISCUSSION

a) 100
1M

a) b) c) a)

-2
80

Current density / mA cm
Ag 3d +
Ag 3d5/2
0.5 M

60
Ag+ 3d3/2
0.3 M
Counts/ a.u.

40

0.1 M
20

200 nm 100 nm 100 nm 0

4.1 ± 0.45 nm 375 370 365
40

c) 35 d) e) Binding energy / eV -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6

b)
30
Potential / V vs. NHE
25 Br 3d
Counts

b) 140
20
Br 3d5/2
15

10 1M
Figure 7. Cyclic voltammograms of PdAg/C
Counts/ a.u.

5
(111)
120

-2
0 Br 3d3/2 0.5 M
and Pd nanocubes/C in a deaerated 0.5 M KOH

Current density / mA cm
2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0
Particle size / nm
(220)
(220)
solution. Scan rate: 50 mV s-1. 100
(311)
a) 80

1M 60 0.3 M
50 nm 10 nm 1/10 nm
80
0.5 M 40
-2

9.9 ± 0.53 nm 72 70 68 66 64
70
2M
Current density / mA cm

f) 60 g) h) Binding energy / eV
20
0.1 M
50 c) 60 0.3 M
Counts

40 Pd 3d
Pd0 3d5/2 0
30
-0.6 -0.4 -0.2 0.0 0.2 0.4 0.6
20 (111)
40 Potential / V vs. NHE
10
Pd0 3d3/2

c) 140
Counts/ a.u.

0
8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 0.1 M
Particle size / nm
(311)
20 PdAg
(200) 120
-2

Pd nanocubes
Current density / mA cm

(220) Pd2+ 3d5/2 Ei=-0.34 V @1M

Pd4+ 3d5/2 100
0
50 nm 20 nm 1/10 nm 80
-0.6 -0.4 -0.2 0.0 0.2 0.4 0.6
344 342 340 338 336 334 332
Binding energy / eV
Potential / V vs. NHE 60
Figure 3. a, b) TEM micrographs of unsupported PdAg nanoparticles and c) electron
Figure 5. Deconvolved XPS spectra of 40
pattern. d, e) TEM micrographs of unsupported Pd nanocubes and f) electron pattern.
3d core-levels of Pd, Ag, and Br
Histogram of particle size distribution of PdAg and Pd nanocubes are inset in Figs. a and 20
presented in the PdAg catalyst.
d, respectively. 0
-0.6 -0.4 -0.2 0.0 0.2 0.4 0.6
Potential / V vs. NHE
a) b) g) a)
1.97 Å * (111) d) 210
(200)
2.26 Å
1.96 Å
2.0 Å
180 200%
2.23 Å
*
Activity loss (i/i0) / %

2.26 Å (220)

(200) 150
Intensity / a.u.

Pd nanocubes
1.93 Å 2.24 Å *
(222) (311) PdAg
(220) *
(420)
(222) 120

PdAg
Figure 8. LSV curves of a) Pd nanocubes/C and b) 90 80%
c) d)
PdAg/C in deaerated KOH solutions changing the
KOH concentration from 0.1 to 2 M, using 0.5 M 60
0 200 400 600 800 1000
EG as a set concentration. Scan rate: 20 mV s-1.
2.23 Å 1.92 Å Cycle number
Figure 9. LSV curves of a) Pd nanocubes/C and b)
2.21 Å

1.85 Å
1.86 Å PdAg/C in deaerated 1 M KOH solutions changing the
1.85 Å
EG concentration from 0.1 to 1 M. Scan rate: 20 mV s-
1.86 Å 1. c) Activity comparison between Pd nanocubes/C and
1.83 Å Pd nanocubes
30 40 50 60 70 80 90 PdAg/C at 1 M EG and 1 M KOH. d) Stability tests
2 / Degrees through cyclic voltammetry at several cycles (scan
e) b)
f) Spectrum O Si Br Pd Ag 100 Pd nanocubes/C
PdAg/C
rate: 100 mV s-1), the current obtained through cycling
I
CONCLUSIONS is normalized by the measured current at cycle 10.
Spectrum 55.67 16.46 3.97 2.30 21.60 II
1 80 the current density increased 3.3‒fold from 0.1 to 1 M EG, achieving the highest value of 97.59 mA cm-2. PdAg/C also displayed an improvement of the
Weight loss / %

Spectrum 56.31 19.28 11.24 0.00 13.17 III current density with the increase of EG concentration; this material presented the highest value of 138.21 mA cm-2 at 1 M EG in 1 M KOH. Moreover, in the
2 figure is observed that PdAg/C is greatly influenced by the EG concentration, lower concentrations (0.1 and 0.3 M EG) limited both the Eonset and the
60
Spectrum 65.02 30.93 2.66 1.39 maximum current density. The activity comparison between Pd nanocubes/C and PdAg/C indicated that silver incorporation boosted the electrocatalytic
3 properties of Pd, enhancing both the Eonset and the peak current density. In addition, PdAg/C displayed a lower oxidation peak potential than Pd
nanocubes/C (150 mV lower), corroborating the improvement of the reaction kinetics for EGOR.
40 IV
Max. 65.02 30.93 11.24 2.66 21.60 A stability test was performed by cyclic voltammetry at 1000 cycles . Pd nanocubes/C displayed 100% of its activity after 400 cycles, but its activity falls
Min. 55.67 16.46 3.97 0.00 1.39 until an 80% at cycle 1000. The activity of PdAg/C increased until 400 probably by an “electrochemical activation” which could be the reason of activities
upper than 100%, and it remained almost constant until cycle 1000, finding a i/i0 ratio of 200 %.
20
0 100 200 300 400 500 600 700 800
Figure 4. a, c) Dark-field HR-TEM micrographs of unsupported PdAg and Pd Temperature / °C
Acknowledgments
The authors express their gratitude to CONACYT for the financial support granted for the development of this research. CONACyT SENER-Energy
nanocubes, respectively. b, d) bright-field HR-TEM micrographs of unsupported PdAg Figure 6. a) X-ray diffraction Sustainability- INNOVATE UK Grant no. 269546. Acknowledgments to the laboratories of other institutions that contribute with CIMAV NANOTECH,
and Pd nanocubes, their respective dark-field images are found inset the figures. e) EDX patterns, and b) Thermogravimetric LABMyN
analysis of PdAg material. curves of PdAg/C and Pd References
nanocubes/C. 1 [1] L. Yan, Y. Hu, Z. Xiaoming y Y. Baohua, «Chapter Three - Applications of NMR Techniques in the Development and Operation of Proton Exchange Membrane Fuel
] Cells,» Annual Reports on NMR Spectroscopy, vol. 88, nº 4, pp. 149-213, 2016.
[2] [2] C. Bianchini, P. K. Shen, Palladium-Based Electrocatalysts for Alcohol Oxidation in Half Cells and in Direct Alcohol Fuel Cells, Chem. Rev. 109 (2009) 4183-4206.