SYN-GAS PRODUCTION FROM ELECTROCHEMICAL REDUCTION …
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SYN-GAS PRODUCTION FROM ELECTROCHEMICAL REDUCTION OF CO 2 Daniel Torres Jurado Carlos Larrea Castro Juan Ramón Avilés Moreno Pilar Ocón Esteban Universidad Autónoma de Madrid Proyecto BIOTRES Departamento de Química Física Aplicada 17 December 2020 Workshop “Innovative technologies for sustainable management of urban and industrial waste streams”
Transcript of SYN-GAS PRODUCTION FROM ELECTROCHEMICAL REDUCTION …
SYN-GAS PRODUCTION FROM ELECTROCHEMICAL REDUCTION OF
CO2
Daniel Torres Jurado
Carlos Larrea Castro
Juan Ramón Avilés Moreno
Pilar Ocón Esteban
Universidad Autónoma de Madrid
Proyecto BIOTRES
Departamento de Química Física Aplicada
17 December 2020
Workshop “Innovative technologies for sustainable management of urban and
industrial waste streams”
Introduction Method 1 Method 2 Conclusions Future
Carbon Dioxide
Source: https://www.climate.gov/news-features/understanding-climate/climate-change-atmospheric-carbon-dioxide
420
410
400
390
380
370
360
350
340
330
320
310
300
Car
bo
nD
ioxid
eA
bundan
ce(p
pm
)
1970 1975 1980 1985 1990 1995 2000 2005 2010 2015 2020 2025 2030Year
CO2 Emissions
22%
Workshop “Innovative technologies for sustainable management of urban and industrial waste streams”
Workshop “Innovative technologies for sustainable management of urban and industrial waste streams”
Introduction Method 1 Method 2 Conclusions Future
Carbon
Dioxide
ElectrochemicalPhotocatalytic
Biological Chemical
Catalyst
Transformation ways
- Electricity from renowable source
- Electrolyte can be recycled
- ECR are cotrolled by electrodes and temperature
Selectivity Durability Profitability
Workshop “Innovative technologies for sustainable management of urban and industrial waste streams”
Introduction Method 1 Method 2 Conclusions Future
Experimental Scheme: Liquid phase
AgNPs or CuNps on GDL
Ni FoamH2O
O2+4H++4e-
CO2+ xH++ xe-
CO2
Gas
Mass Flow
100mL/min
Peristaltic
Pump
5mL/minKHCO3
0,5M
+
EDTA
0,02M
Nafion 117 Membrane
Gas Chromatograph Mass Spectrometer
KHCO3
0,5M
+
EDTA
0,02M
Peristaltic
Pump
5mL/min
Previously we work:- Copper foil and Silver thread in three electrode cell
- Raman such as Products Analyzer in three electrode cell
Syn-Gas
(CO, H2)
CO2 + 2H++2e- CO + H2O
2H++2e- H2
Workshop “Innovative technologies for sustainable management of urban and industrial waste streams”
Introduction Method 1 Method 2 Conclusions Future
m/z 12m/z 28
110 120 130 140 150 160 170 180
0,0
2,0x10-10
4,0x10-10
6,0x10-10
8,0x10-10
1,0x10-9
To
tal Io
n C
urr
ent
(u.a
.)
Retention time (sec)
CG+Masas -10mA/cm2 AgNps
CG+Masas -5mA/cm2 CuNps 80nm
110 120 130 140 150 160 170 180-1x10
-11
0
1x10-11
2x10-11
3x10-11
4x10-11
5x10-11
6x10-11
Rela
tive
Inte
nsi
ty (
u.a
)
Retention Time (sec)
110 120 130 140 150 160 170 180
0,0
5,0x10-13
1,0x10-12
1,5x10-12
2,0x10-12
2,5x10-12
Rela
tive
Inte
nsi
ty (
u.a
)
Retention Time (sec)
0 1000 2000 3000 4000 5000 6000-2,6
-2,5
-2,4
-2,3
-2,2
-2,1
-2,0
-5mA/cm2 CuNps 80 nm
Po
tenti
al (V
)
Time (sec)
-10mA/cm2 AgNps
Catalyst
1mg/cm2
[KHCO3] (M)
Supported on Carbon
Current density applied on ECR (mA/cm2)
Potential (V)
Rate CO (ppm/min)
Rate H2
(ppm/min)CO : H2
AgNps 100nm 0.5 No
-5 -2.29 <DL 949 -
-10 -2.50 99 1331 0.07
-25 -3.05 <DL 2654 -
AgNps 100nm 3 No
-25 -2.77 181 3712 0.05
-50 -3.10 124 6222 0.02
-100 -3.42 55 11104 0.005
CuNps 80nm 0.5 No
-5 -2.27 6 1045 0.01
-10 -2.55 - 2019 -
-25 -2.95 - 2551 -
CuNps 22nm 0.5 Yes-10 -3.12 - 889 -
-25 -3.18 - 1810 -
Workshop “Innovative technologies for sustainable management of urban and industrial waste streams”
Introduction Method 1 Method 2 Conclusions Future
Experimental Scheme: Gas phase
Ni FoamMass Flow
100mL/minH2O
Humidifier
Peristaltic
Pump
5mL/minKHCO3
0,5M
+
EDTA
0,02M
Nafion 117 Membrane
Gas Chromatograph Mass Spectrometer
Previously we work:- Pt and IrO2 such as anode
- Synthetized Copper and Silver Nanoparticles
- Controlled Conditions: Temperature and Pressure
CO2
Gas
AgNPs or CuNps on GDL
H2O
O2+4H++4e-
CO2+ xH++ xe-
Syn-Gas
(CO, H2)
CO2 + 2H++2e- CO + H2O
2H++2e- H2
Workshop “Innovative technologies for sustainable management of urban and industrial waste streams”
Introduction Method 1 Method 2 Conclusions Future
m/z 12m/z 28
Catalyst
1mg/cm2
CO2 Flow
(mL/min)
Degree of
wetting
Supported on
Carbon
Current density applied on
ECR (mA/cm2)
Potential
(V)
Rate CO
(ppm/min)
Rate H2
(ppm/min)CO:H2
AgNps 100nm 100 Low No
-5 -2.34 132 644 0.20
-10 -2.58 310 573 0.54
-25 -3.12 1782 815 2.19
AgNps 100nm 100 High No-10 -2.15 - 1430 -
-25 -2.64 336 2102 0.16
CuNps 80nm 100 Low No-1 -1.75 - 571 -
-5 -2.66 - 1275 -
CuNps 22nm 100 Low Yes-5 -2.68 - 941 -
-10 -3.07 - 1598 -
110 120 130 140 150 160 170 180 190 200
-1x10-11
0
1x10-11
2x10-11
3x10-11
4x10-11
5x10-11
6x10-11
7x10-11
8x10-11
To
tal Io
n C
urr
ent
(u.a
)
Time (sec)
CG +Masas -25mA/cm2 AgNps
CG + Masas -5mA/cm2 CuNps 80 nm
-500 0 500 1000 1500 2000 2500 3000 3500 4000
-3,2
-3,0
-2,8
-2,6
-2,4
-2,2
-25mA/cm2 AgNps
Po
tenti
al (V
)
Time (sec)
-5mA/cm2 CuNps 80 nm
110 120 130 140 150 160 170 180 190 200-1x10
-11
0
1x10-11
2x10-11
3x10-11
4x10-11
5x10-11
6x10-11
7x10-11
Rela
tive
Inte
nsi
ty (
u.a
)
Retention Time (sec)
110 120 130 140 150 160 170 180 190 200
-5,0x10-13
0,0
5,0x10-13
1,0x10-12
1,5x10-12
2,0x10-12
2,5x10-12
Rela
tive
Inte
nsi
ty (
u.a
.)
Retention Time (sec)
Workshop “Innovative technologies for sustainable management of urban and industrial waste streams”
Introduction Method 2 Conclusions FutureMethod 1
Experimental Results: Gas phase
Experimental Results: Liquid phase
Syn-Gas (CO:H2) >1
Catalyst
1mg/cm2
CO2 Flow
(mL/min)
Degree of
wetting
Supported on
Carbon
Current density applied on
ECR (mA/cm2)
Potential
(V)
Rate CO
(ppm/min)
Rate H2
(ppm/min)CO:H2
AgNps 100nm 100 Low No
-5 -2.34 132 644 0.20
-10 -2.58 310 573 0.54
-25 -3.12 1782 815 2.19
AgNps 100nm 100 High No-10 -2.15 - 1430 -
-25 -2.64 336 2102 0.16
CuNps 80nm 100 Low No-1 -1.75 - 571 -
-5 -2.66 - 1275 -
CuNps 22nm 100 Low Yes-5 -2.68 - 941 -
-10 -3.07 - 1598 -
Catalyst
1mg/cm2
[KHCO3] (M)
Supported on Carbon
Current density applied on ECR (mA/cm2)
Potential (V)
Rate CO (ppm/min)
Rate H2
(ppm/min)CO : H2
AgNps 100nm 0.5 No
-5 -2.29 <DL 949 -
-10 -2.50 99 1331 0.07
-25 -3.05 <DL 2654 -
AgNps 100nm 3 No
-25 -2.77 181 3712 0.05
-50 -3.10 124 6222 0.02
-100 -3.42 55 11104 0.005
CuNps 80nm 0.5 No
-5 -2.27 6 1045 0.01
-10 -2.55 - 2019 -
-25 -2.95 - 2551 -
CuNps 22nm 0.5 Yes-10 -3.12 - 889 -
-25 -3.18 - 1810 -
Workshop “Innovative technologies for sustainable management of urban and industrial waste streams”
Introduction Method 2 Conclusions FutureMethod 1
Two CO2 electroreduction methods have been developed in presence of silver and
copper nanoparticles catalysts.The first one in liquid phase and the second in gas phase.
The silver catalyst is more efficient for syn-gas production than copper catalyst.
One of the objectives is to achieve a high CO: H2 ratio. In this way, ECR in the gas phase
seems more efficient than the liquid phase.
Workshop “Innovative technologies for sustainable management of urban and industrial waste streams”
Introduction FutureMethod 1 Method 2 Conclusions
Gas phase
Liquid phase
Work under: controlled pressure
and temperature
Eliminateimpurities on
copper (EDTA isnot a goodmethod).
Improvementsin both methods
Applydifferent current density
Use othercatalystssuch as
bimetallicSn-Cu
Study theinfluence of the amountof catalyst
Formation of C1-C2
Hydrocarbonswith copper
catalyst
Workshop “Innovative technologies for sustainable management of urban and industrial waste streams”
SYN-GAS PRODUCTION FROM ELECTROCHEMICAL REDUCTION OF
CO2
ACKNOWLEDGEMENT:
17 December 2020
BIOTRES-CM (P2018/EMT-4344) ELECTROCHEMISTRY GROUP (UAM)
