Supporting Information

Electrospinning High-dispersed Ru Nanoparticles Embedded Carbon

Nanofiber Boosts CO2 Reduction in a H2/CO2 Fuel Cell

Ting Qu,† Jixiang Hu,† Xin Dai,† Qiang Tan,† Yan Liu,† Yuanzhen Chen,† Shengwu

Guo,† and Yongning Liu*,†

†State Key Laboratory for Mechanical Behavior of Materials, Xi’an Jiaotong University,

Xi’an, 710049, PR China.

*Correspondence Authors: ynliu@xjtu.edu.cn

Calculations details

Figures S1 to S19

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Calculations details

Calculations for voltage of H2/CO2 fuel cell

The following electrode processes are assumed to occur when the H2/CO2 fuel cell

discharges:

Anode: H2 → 2H+ + 2e– (1)

Cathode: CO2 + 8H+ + 8e– → CH4 + 2H2O (2)

2H+ + 2e– → H2 (3)

Overall fuel cell reaction: CO2 + 4H2 → CH4 + 2H2O (4)

Thus, for an isothermal process, the Gibbs free energy for this reaction is defined as:

∆g = ∆h0 – T∆s0 (5)

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

H2O are given in the table below.

Chemical Species ∆h0 (kJ/mol) ∆s0 [J/(mol·K)]

CO2 -393.51 213.8

H2 0 130.68

CH4 -74.80 186.25

H2O(g) -241.83 188.84

Following Equation (6), ∆h0 is calculated as

∆h0 = [∆h0(CH4) + 2∆h0(H2O)] – [∆h0(CO2) + 4∆h0(H2)]

= [(–74.8) + 2×(-241.83)] – [(–393.51) + 4×(0)]

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 = –164.95 kJ/mol (6)

Similarly, ∆s0 is calculated as

∆s0 = [∆s0(CH4) + 2∆s0(H2O)] – [∆s0(CO2) + 4∆s0(H2)]

= [186.25 + 2×188.84] – [213.8 + 4×130.68]

= –172.59 J/(mol·K) (7)

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

n is number of moles of electrons transferred and F is Faraday’s constant. Thus, the

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.

Calculations of the cathodic CO2RR and HER selectivity

To determine the selectivity for CO2RR and HER in this H2/CO2 fuel cell, the electron

transfer moles of CO2RR and HER were given as:

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

imax (mA)  t (h)  3.6 (C / mAh)

ntotal  (12)
ec (C)  N A (mol-1 )

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

time, CCH 4 ( CH 2 ) is the concentration of CH4 (H2) generated by the reaction,  CH 4 (  H 2 ) is

the density of CH4 (H2), and M CH 4 ( M H 2 ) is the molar mass of CH4 (H2).

According to above calculations, the selectivity was defined as:

nCH 4
CO RR  100% (13)
2
ntotal

nH 2
HER  100% (14)
ntotal

Calculation of the CH4 production rate

The gas products were sampled after a continuous electrolysis of ~10 min under each

condition. The CH4 production rates ( CH 4 ) was calculated as below:

VCO 2 (mL / min)  60 (min / h)  CCH 4 (ppm)   CH 4 (mg / mL)

 CH  (15)
4
M CH 4 (g / mol)  LCat. (mg)

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).

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Supplementary Figures

Figure S1. Photos of different stages of Ru-CNF preparation process.

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

elemental maps of N, C and Ru.

Figure S6. Schematic diagram of a H2/CO2 fuel cell assembly process.

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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.

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Figure S10. The image of the membrane electrode assembly after this test when the

operation temperature at 200 °C.

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

re-oxidation of the CO2 reductant in the ~0.2-0.9 V vs. RHE.)

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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.

Figure S19. Dependence of the apparent activation energy on cell voltage.

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Table S1. Comparative table on CO2RR performances of various Ru-based and carbon
nitride-based materials.

Catalysts Reaction System Temperature CH4 Production Rate Reference

Ru-CNF H2/CO2 Fuel Cell 170 °C 308.46 μmol gcat–1 h–1 This Work

RuO2/CNTs H2/CO2 Fuel Cell 170 °C 66.25 μmol gcat–1 h–1 1

Ru/NaTaO3 Photocatalysis 25 °C 51.8 μmol gcat–1 h–1 2

Ru-TNAs Photocatalysis 25 °C 26.37 μmol gcat–1 h–1 3

Ni/g-CN Photocatalysis 150 °C 28 μmol gcat–1 h–1 4

g-C3N4 Photocatalysis 25 °C 3.26 μmol gcat–1 h–1 5

Pt/CN Photocatalysis 25 °C 13.02 μmol gcat–1 h–1 6

m-CN Photocatalysis 25 °C 33 μmol gcat–1 h–1 7

Ru/TiO2 CO2 Hydrogenation 200 °C 154.2 μmol gcat–1 h–1 8

Ru/γ-Al2O3 CO2 Hydrogenation 190 °C 162 μmol gcat–1 h–1 9

Ru-CaO/Al2O3 CO2 Hydrogenation 400 °C 414 μmol gcat–1 h–1 10

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