Product distribution profiling of the carbon dioxide electrocatalytic reduction process in varying

applied voltages
Jomari Angel JACINTO[1], Armando QUITAIN, Nathaniel DUGOS, Mitsuru SASAKI, Tetsuya KIDA, Lawrence BELO
[1] De La Salle University, jomari_jacinto@dlsu.edu.ph
THE PRODUCT DISTRIBUTION PROFILE AT DIFFERENT APPLIED VOLTAGES
INTRODUCTION METHODOLOGY
H+ Electrocatalyst Product Carbon Monoxide Formic Acid Acetic Acid Methanol Ethanol
Electrolysis
Synthesis Characterization Analysis
Anode: Platinum
100%
Figure 7. Copper catalyst profile ✓ Copper catalysts tend to be
Hydrogen Source (Physical (XRD, SEM) Gas and Liquid
Electrical Deposition) Ref: Ag/AgCl 10090% more selective to producing
Chromatography alcohols at more negative
Carbon Dioxide Energy 80%
potentials (-0.8 V vs. Ag/AgCl and

Current Density, mA / sq. cm

80 0
2.89
70%
ELECTROCATALYSTS 12.54 below).

Faradaic Efficiency
Reduced Graphene Oxide (rGO) Based Catalysts EXPERIMENT Figures 3 and 4 show the
SEM analysis of the metal
6060% -1
Copper NPs
2.33
N - supported
56.40 43.20
15.67
14.22
✓ Tin catalyst tend to increase
production of formic acid. At
50% -2 Tin NPs0.00 rGO 0.00
4.56
and nitrogen supported 0.00
CATHODIC REACTION CATHODIC REACTION Fig. IV 4040% 18.97 moderate potentials, acetic acid
Fig. III -3 34.21 18.23
PATHWAY: PATHWAY: catalysts. 22.30 formation is achieved at high
2030% -4 45.23 34.00 selectivity.
CO2 + 2H+ + 2e− → CO + H2O CO2 + 2H+ + 2e− → HCOOH
(Eo = −0.61 V vs. SHE) ✓ Presence of 20% -5 7.89 17.45 21.56 ✓ High yield of products with two
(Eo = −0.53 V vs. SHE) 23.77 2.37 34.24
crystals and 0010% 24.11 12.91 23.11 carbons in the chain are more
20 -6 40 60 80 100
3.11
5.61 10.43 12.34 likely to be produced by nitrogen
defects confirms 0% 3.41
0.00 -7 4.51 5.61 3.41 4.99
supported catalyst due to the C –
Formic Acid successful 0 -0.2 -0.4 -0.6 -0.8 -1 -1.2 -1.4 -1.6 -1.8 -2
-2 -1.6 -1.2 -0.8 -0.4 0 C coupling induced by the high
Carbon Monoxide deposition. Potential, V vs. Ag/AgCl affinity of Nitrogen sites with
carbon.

Other Hydrocarbons and

Current Density, mA / sq. cm

Carbon Monoxide Formic Acid Acetic Acid Methanol Ethanol
0 100%
Oxygenates 100 Figure 8. Tin catalyst profile
✓ Catalysts show a stabilized current
-1
Copper NPs N - supported density at applied voltage ranges -0.4
8080%
90%
4.55 CONCLUSION
Ethanol -2 Tin NPs rGO to -1.5 V vs. Ag/ AgCl. 0.54 0.67
2.51 Potential Range

Faradaic Efficiency
In this work, we Product Catalyst Support

Current Density, mA / sq. cm

70% 5.65
-3 60 0 (vs. Ag/AgCl)
Acetic Acid Methanol answer these ✓ Decline of current densities at higher
60% 45.12
voltages may show evidence that the -1 2.31 Carbon
N -1.6 V to -2.0 V
questions through -4 catalyst had changed.
4050% Copper NPs
15.24
N 36.11
- supported Monoxide
PROBLEM: For a specific product; -2 Tin NPs rGO
PRODUCT -5 20 40% Formic Sn -1.4 V to -2.0 V
-3
i.) Which is the best catalyst in producing the DISTRIBUTION ✓ Highly electroconductive materials 63.10 67.12
54.12
Acid other catalysts less than -0.8 V
30%
highest efficiency? -6 tend to sustain a specific current -4
PROFILING 0020% 20
43.23
60 35.68 8032.33 100 39.11 Ethanol Cu -1.0 V to -1.4 V
ii.) How much energy is needed to attain high density at different levels of energy -540 36.79
-7 application no catalyst is selective -0.8 V to -2.0 V
selectivity? 10% 15.68
-6 Methanol
-2 -1.6 -1.2 -0.8 -0.4 0 3.56
2.87 2.66 2.71 5.31 4.51 1.72 2.36 1.16 4.56 1.57
to methanol (Cu)
0%
Potential, V vs. Ag/AgCl ✓ Thus, profiling at ranges -1.6 to -0.4 -0.2
-7
-0.4 -0.6 -0.8 -1 -1.2 -1.4 -1.6 -1.8 -2 Acetic
N -0.8 V to -1.4 V
CATALYSTS b.) Tin (Sn) Supported rGO Figure 5. Effects of different Applied
V vs. Ag/AgCl applied voltage will
show unbiased results. 100
-2 -1.6 -1.2 -0.8 -0.4
Potential, V vs. Ag/AgCl
0 Acid

a.) Copper (Cu) Supported rGO Potentials on the catalysts

✓ Highly selective to catalyst – 100% Carbon Monoxide Formic Acid Acetic Acid Methanol Ethanol
✓ Iron nanocatalysts are known to be 80

Current Density, mA / sq.cm

selective in producing C2 products
induced formate production. (see
Fig. III).
✓ All catalysts are stable up to nine
– hour bulk electrolysis. Thus
90% Figure 9. Nitrogen supported catalyst profile FUTURE WORK

Faradaic Efficiency
or chains with two carbons. -4

Current Density, mA / sq. cm

4.23
the amount of time applied to 6080% 0
-NH2 c.) Nitrogen Supported the multiple electrolytic 3.38 ✓ Test other types of catalysts.
e- e- rGO process. -5
70%
-1 ✓ Life cycle analyses.
VOLTAGE 4060% Copper NPs N - supported
✓ Increased affinity with carbon ✓ Mechanism and Process
SOURCE FARADAIC EFFICIENCY WAS THE -2
dioxide and reaction Tin NPs 2.43 rGO
PARAMETER USED TO HAVE A 12.51 Design
intermediates (see Fig. IV) -6 50% 56.77 45.01
STANDARDIZED QUANTIFICATION OF 20 -3 33.67 12.45
PRODUCT: 40% 34.65
Copper NPs Tin NPs -4
-7 N - supported rGO
4.11 ACKNOWLEDGEMENTS
Reduction H+ H2O 030%
0 20 40 60 80 100 7.89
products H+ -5 9.65 Thank you very much!
Membrane

17.23
0 1 2 3
4 5 6 7 8 9 34.82
✓ Japan
Nafion

Where: 20% 32.12 Student Services

H+ moli = amount of product i produced in mol Time, h -624.11 11.11 12.11
8.70 23.21
CO2 O2 10% 24.56 Organization (JASSO), Tokyo
ni = number of electron equivalents of product i Figure 6. Chronoamperometric 11.59
F = Faraday’s constant
3.40 -74.51 11.23 5.69 7.61 Japan
CO2 CO2 H+ Figure. 2. Reduced Measurements 0% 2.33
✓ Sakura Science Club, Japan
H+ I = applied current -0.2 -2-0.4 -1.6 -0.8 -1.2
-0.6 -1 -0.8-1.4 -0.4
-1.2 -1.6 -1.8 0 -2
Graphene Oxide (rGO) t = time
Figure 1. Electrocatalytic reduction setup catalyst base Potential, V vs. Ag/AgCl