Supporting Information acids for the sustainable ...
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Supporting Information Electrocatalytic cross-coupling of biogenic di- acids for the sustainable production of fuels F. Joschka Holzhäuser, a Guido Creusen, b Gilles Moos, Manuel Dahmen, c Andrea König, d Jens Artz, a Stefan Palkovits a and Regina Palkovits a ,* a Institut für Technische und Makromolekulare Chemie, RWTH Aachen University, Aachen, Germany. [*[email protected]] b Institut für Makromolekulare Chemie, Albert-Ludwigs-Universität Freiburg, Freiburg, Germany. c Institut für Energie- und Klimaforschung Modellierung von Energiesystemen, Forschungszentrum Jülich, Jülich, Germany d Aachener Verfahrenstechnik - Process Systems Engineering, RWTH Aachen University, Aachen, Germany 1. Calculations 2. Experimental photographs 3. NMR spectra 4. Additional charts 5. Total faradaic efficiency charts Electronic Supplementary Material (ESI) for Green Chemistry. This journal is © The Royal Society of Chemistry 2019
Transcript of Supporting Information acids for the sustainable ...
Supporting Information
Electrocatalytic cross-coupling of biogenic di-acids for the sustainable production of fuels
F. Joschka Holzhäuser,a Guido Creusen,b Gilles Moos, Manuel Dahmen,c Andrea König,d Jens
Artz,a Stefan Palkovitsa and Regina Palkovitsa,*
a Institut für Technische und Makromolekulare Chemie, RWTH Aachen University, Aachen, Germany. [*[email protected]]
b Institut für Makromolekulare Chemie, Albert-Ludwigs-Universität Freiburg, Freiburg, Germany.
c Institut für Energie- und Klimaforschung Modellierung von Energiesystemen, Forschungszentrum Jülich, Jülich, Germany
d Aachener Verfahrenstechnik - Process Systems Engineering, RWTH Aachen University, Aachen, Germany
1. Calculations2. Experimental photographs3. NMR spectra4. Additional charts5. Total faradaic efficiency charts
Electronic Supplementary Material (ESI) for Green Chemistry.This journal is © The Royal Society of Chemistry 2019
1. Calculations
Calculation of charge chronoamperometry (Q = charge, I = current, t = time):
𝑄 =𝑦
∫𝑥
𝐼 𝑑𝑡
Calculation of charge potentiometry:
𝑄 = 𝐼𝑡
Caclulation of the faradiac efficiency (nmol = amount of total product amount in mol, n = number of electrons transferred, F = Faraday constant):
𝐹𝑒𝑓𝑓 =𝑛𝑚𝑜𝑙𝑛𝐹
𝑄∙ 100%
For 1 faradaic equivalent the equation becomes (nmol-spl = simplified factor [dimensionless]):
𝐹𝑒𝑓𝑓 = 𝑛𝑚𝑜𝑙 ‒ 𝑠𝑝𝑙 ∙ 100%
2. Experimental pictures
3. NMR spectra
1H-NMR: Tertbutyl-isovalerate
1H-NMR: mono-Methyl hydrogen methylsuccinic acid (MMSA)
1H-NMR: mono-Ethyl hydrogen succinate (HESA)
1H-NMR: Ethyl 5-methylhexanoate
1H-NMR: Dimethyl 2,5-dimethyladipiate
1H-NMR: Methyl 2,5-dimethylhexanoate
1H-NMR: 2,9-Dimethyldecane
4. Additional charts
1:1 1:2 1:4 1:8 1:160
10
20
30
40
50
60
DH DDH MDH
MMSA:IVA
Yie
ld [%
]
Figure 1a: Variation of different ratios of MMSA with IVA. Conditions: 0 °C, MeOH:H2O 80:20, 1 farad equivalent, 0.1 M NEt3, 100 mAcm-2, WE: Pt, CE: Ti. Yield of MDH/ DDH related to MMSA, DH related to IVA (total Volume 5 mL).
5 10 15 200
10
20
30
40
50
60
DH DDH MDH
Electrolyte [mol %]
Yie
ld [%
]
Figure 2a: Variation of the electrolyte concentration. Conditions: 0 °C, MeOH:H2O 80:20, 1 farad equivalent, 100 mAcm-2, WE: Pt, CE: Ti, 0.33 M MMSA, 1.3 M IVA. Yield of MDH/ DDH related to MMSA, DH related to IVA (total Volume 5 mL).
100:0 80:20 50:50 20:80 10:90 0:1000
10
20
30
40
50
60
DH DDH MDH
H2O: MeOH
Yie
ld [%
]
Figure 3a: Variation of the solvent mixture. Conditions: 0 °C, 1 farad equivalent, 100 mAcm-2, WE: Pt, CE: Ti, 0.33 M MMSA, 1.3 M IVA, 0.1 M NEt3 (for 100% Water: 0.1 M MMSA, 0.4 M IVA). Yield of MDH/ DDH related to MMSA, DH related to IVA (total Volume 5 mL).
Ru100 Ru75 Ru50 Ru500
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40
45
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DH DDH MDH Isovaleric acid
Working
Yield[%]
Figure 4a: Screening of (RuxTi1-x)O2 on titanium plates in comparison with Pt. Conditions: 0 °C, 1 farad equivalent, 100 mAcm-
2, MeOH as solvent, CE: Ti, 0.33 M MMSA, 1.3 M IVA, 0.1 M NEt3. Yield of MDH/ DDH related to MMSA, DH related to IVA (total Volume 2 mL).
5. Total faradaic efficiency charts (Complete new Section!)
1:1 1:2 1:4 1:8 1:160
5
10
15
20
25
30
35HESA + IVA MMSA + IVA
Faradaicefficiency[%]
HESA or
For Figure 1(left) + Figure 1a: Variation of different ratios of MMSA/HESA with IVA. Conditions: 0 °C, MeOH:H2O 80:20, after 1 farad equivalent, 0.1 M NEt3, 100 mAcm-2, WE: Pt, CE: Ti.
5 10 15 200
5
10
15
20
25
30
35
HESA + IVA MMSA + IVA
Faradaicefficiency[%]
Triethylamine
For Figure 1(right) + Figure 2a: Variation of the electrolyte concentration. Conditions: 0 °C, MeOH:H2O 80:20, after 1 farad equivalent, 100 mAcm-2, WE: Pt, CE: Ti, 0.33 M MMSA/HESA, 1.3 M IVA.
100:0 80:20 50:50 20:80 10:90 0:1000
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10
15
20
25
30
35
40
45
50
HESA + IVA MMSA + IVA
Faradaicefficiency[%]
Water/MeOH
For Figure 2 + Figure 3a: Variation of the solvent mixture. Conditions: 0 °C, after 1 farad equivalent, 100 mAcm-2, WE: Pt, CE: Ti, 0.33 M MMSA/HESA, 1.3 M IVA, 0.1 M NEt3 (for 100% Water: 0.1 M MMSA/HESA, 0.4 M IVA).
For Figure 3 + Figure 4a: Screening of (RuxTi1-x)O2 on titanium plates in comparison with Pt. Conditions: 0 °C, after 1 farad equivalent, 100 mAcm-2, MeOH as solvent, CE: Ti, 0.33 M MMSA/HESA, 1.3 M IVA, 0.1 M NEt3.
For Figure 4: Screening of (RuxTi1-x)O2 on Ti and Pt plates with different electrolytes. Left: Using 0.1 M NEt3 as electrolyte and base. Right: Using 0.1 M KOH as electrolyte and base. General conditions: 0 °C, after 1 farad equivalent, 100 mAcm-2, MeOH as solvent, CE: Ti, 0.33 M MHO, 1.3 M IVA.
For Figure 5: Screening of (RuxTi1-x)O2 on Ti and Pt plates with different electrolytes. General conditions: 0 °C, after 1 farad equivalent, 100 mAcm-2, MeOH as solvent, CE: Ti, 1 M MHO.
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