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21-Electrospinning Ru Carbon Nanofibers Boost CO2 Reduction in A H2 CO2 Fuel Cell Si
21-Electrospinning Ru Carbon Nanofibers Boost CO2 Reduction in A H2 CO2 Fuel Cell Si
Ting Qu,† Jixiang Hu,† Xin Dai,† Qiang Tan,† Yan Liu,† Yuanzhen Chen,† Shengwu
†State Key Laboratory for Mechanical Behavior of Materials, Xi’an Jiaotong University,
Calculations details
Figures S1 to S19
S-1
Calculations details
The following electrode processes are assumed to occur when the H2/CO2 fuel cell
discharges:
Thus, for an isothermal process, the Gibbs free energy for this reaction is defined as:
To get an approximate answer, we assume that ∆h0 and ∆s0 are independent of temperature
(heat capacity effects are ignored). In this case, the ∆h0 and ∆s0 values for CO2, H2, CH4 and
H2 0 130.68
S-2
= –164.95 kJ/mol (6)
This gives ∆g = –164.95 kJ/mol – 298.15 K × [–172.59 J/(mol·K)] = –113.49 KJ/mol (8)
Besides, the relationship between Gibbs free energy (∆g) and voltage (E) is ∆g = -nFE, where
theoretical reversible voltage (E0) generated by a H2/CO2 fuel cell under normal pressure and
temperature is:
g 113490 J / mol
E0
0.147 V (9)
nF (8 mol e / mol reactant) (96485 C / mol)
As seen, the calculated theoretical voltage is very close to the measured open-circuit voltage
Eocv = 0.121 V.
To determine the selectivity for CO2RR and HER in this H2/CO2 fuel cell, the electron
VCO 2 (mL / min) t (min) CCH 4 (ppm) CH 4 (mg / mL) 8 (mol e / mol reactant)
nCH 4 (10)
M CH 4 (g / mol) 103
VCO 2 (mL / min) t (min) CH 2 (ppm) H 2 (mg / mL) 2 (mol e / mol reactant)
nH 2 (11)
M H 2 (g / mol) 103
where CO2RR is issued from a 8 e– reduction and HER is formed upon 2e–/2H+ reduction.
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Similarly, VCO 2 is the flow rate of CO2 at the cathode outlet, t is the galvanostatic discharge
the density of CH4 (H2), and M CH 4 ( M H 2 ) is the molar mass of CH4 (H2).
nCH 4
CO RR 100% (13)
2
ntotal
nH 2
HER 100% (14)
ntotal
The gas products were sampled after a continuous electrolysis of ~10 min under each
where VCO 2 is the flow rate of CO2 at the cathode outlet, CCH 4 is the concentration of CH4
generated by the reaction, CH 4 is the density of CH4, M CH 4 is the molar mass of CH4, and
LCat. is the material loading of cathode catalysts (Pt/C, Ru/CNT, Ru-CNF or CNF).
S-4
Supplementary Figures
Figure S2. SEM image and map scanning EDS analysis results of Ru-CNF.
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Figure S3. SEM image and spot scanning EDS analysis results of Ru-CNF.
Figure S4. TGA curve of the Ru–CNF from 100 to 600 °C at a heating rate of 10 °C min−1 in
air atmosphere.
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Figure S5. High-resolution HAADF-STEM image of Ru-CNF and the corresponding EDX
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Figure S7. Changes in OCV as different gases are supplied into the cell at room temperature.
Figure S8. Gas chromatograms obtained by TCD before the cell performances test.
Figure S9. Open circuit voltage of the H2/CO2 fuel cell under normal pressure and
temperature.
S-8
Figure S10. The image of the membrane electrode assembly after this test when the
Figure S11. (a) Gas chromatograms obtained using FID when the cell is operating at
different temperatures from 80 °C to 200 °C with CO2 flow rate of 20 mL min−1. (b) The
corresponding production concentration for CH4. (c) Gas chromatograms obtained using
TCD when the cell is operating at different temperatures from 80 °C to 200 °C with CO2 flow
rate of 100 mL min−1. (d) The corresponding production concentration for H2.
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Figure S12. (a) XRD pattern of Ru/CNT. (b) SEM image of Ru/CNT.
Figure S13. (a) XRD pattern of Ru/CNF. (b) SEM image of Ru/CNF.
Figure S14. (a) XRD pattern of CNF. (b) SEM image of CNF.
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Figure S15. (a) Gas chromatograms obtained using FID when the cell is operating with Pt/C,
Ru/CNT, Ru/CNF, Ru-CNF and CNF cathode catalysts at 170 °C (CO2: 20 mL min−1). (b)
The corresponding production concentration for CH4. (c) Gas chromatograms obtained using
TCD when the cell is operating with Pt/C, Ru/CNT, Ru/CNF, Ru-CNF and CNF cathode
catalysts at 170 °C (CO2: 100 mL min−1). (d) The corresponding production concentration for
H2.
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Figure S16. Cyclic voltammograms of commercial Pt/C, Ru/CNT, Ru/CNF, Ru-CNF and
CNF catalysts in N2- or CO2-saturated 0.5 M H2SO4 solution at a scan rate of 20 mV s−1.
(“A”: the H adsorption below 0.3 V vs. RHE; “B”: H desorption at ~ 0.1 V vs. RHE; “C”: the
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Figure S17. Dependence of the peak power density on operating temperature for H2/CO2 fuel
cell.
Figure S18. Arrhenius plots of the H2/CO2 fuel cell at various voltages.
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Table S1. Comparative table on CO2RR performances of various Ru-based and carbon
nitride-based materials.
Ru-CNF H2/CO2 Fuel Cell 170 °C 308.46 μmol gcat–1 h–1 This Work
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