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Catalysis Science & Technology
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Journal Name
ARTICLE
There are no conflicts to declare.
Cyclic Voltammetry. Cyclic voltammograms (CVs) were
recorded in a home-made three neck cell with a gas inlet. The
working electrode was a 3 mm-diameter glassy carbon (CH
Instrument) disk carefully polished using decreasing size of
diamond paste (from 15 to 1 µm), ultrasonically cleaned in
ultrapure water and dried before use. The counter-electrode
was a graphite rod and the reference electrode was a KCl-
saturated calomel electrode (SCE). All experiments were carried
out under argon atmosphere at room temperature, CVs were
obtained with a SP 150 (Bio-Logic) potentiostat. The CVs were
recorded at 100 mV s-1. Unless specified, the ohmic drop was
uncompensated. Catalytic onset potentials (Eonset) were
DOI: 10.1039/C8CY02164C
Acknowledgements
CNRS, Université de Rennes 1, Rennes Métropole and Institut
des Sciences Chimiques de Rennes (“Projet inter-Equipe“) are
acknowledged for financial support. S.K. acknowledges Foun-
dation Rennes 1, French Embassy in Thailand and Campus
France for a Mastership grant. Dr. J. Rault-Berthelot is
acknowledged for valuable discussions and C. Valter-Potier for
making the Hoffman cell.
determined at the beginning of the HER curve (i = 5
concentration of proton source of 10 mM.
µA) at a
Notes and references
4.4. Bulk electrolysis and faradaic efficiency
Bulk Electrolysis. The experiments were carried out in a
Hoffman cell with a glassy carbon rod (the active surface area
was 5 cm2) as the working electrode, SCE as the reference
electrode, and graphite as a counter electrode, respectively.
The cell contained 20 mL of 0.5 mM iron porphyrin, 15 mM
Et3NHCl, and 0.1 M Bu4NPF6 in DMF. The electrolysis solution
was purged with argon for 30 minutes, prior to electrolysis
measurements. The solution resistance was compensated by
the potentiostat (measured as the impedance at high
frequency). A CV was first recorded, and the controlled-
potential electrolysis was performed at a potential slightly more
negative than the catalytic onset potential. After 1 hour, the
electrolysis was stopped and the volume of produced gas was
measured.
1
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5
Faradaic Efficiency Calculation. The HER Faradaic efficiency (
was calculated by dividing the measured number of moles of H2
produced (nH2exp) by the theoretical amount of H2 (nH2th
η)
)
expected on the basis of the charge (Q) consumed during the
6
7
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,
,
controlled-potential electrolysis measurements, calculated
following equation (1):
ꢔ
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ꢏꢐ ꢄ ꢊꢋ
ꢑ ꢒꢓ
The experimental number of moles of hydrogen was determined
using the measured volume of produced gas in the cathodic
compartment of the Hoffman cell, that was converted in number of
moles using the perfect gas law.
8
9
4.5. UV-vis titration studies of 1-4 and 2’-4’ with Et3NHCl.
General procedure for UV-vis titrations. Host-guest interactions in
solution were studied by UV-vis spectroscopy. Solution of each
molecule (10-6 M except 10-5 M for 4) was prepared using N,N-
dimethylformamide as a solvent. Increasing number of Et3NHCl
equivalents were added to the solution of each molecule (1.5 mL in
a 1 cm-pathlength quartz cell). The host concentration was kept
constant. This study enabled us to qualitatively evidence the
interaction between the molecule and ammonium salt (Et3NHCl).
Note that the data was not accurate enough to determine binding
constants probably due to the presence of traces of water.
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Conflicts of interest
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