Supplementary Information

Electronic Supplementary Material (ESI) for RSC Advances.
This journal is © The Royal Society of Chemistry 2022
Supplementary Information
Electrocatalytic Hydrogen Generation using Tripod Containing

tris(Pyrazolyl) borate-based Copper(II), Nickel(II), and Iron(III)
Complexes Loaded on Glassy Carbon Electrode
Mohamed M. Ibrahim1, G. A. M. Mersal1, Ahmed M. Fallatah1, Khaled Althubeiti1, Hamdy S.

El-Sheshtawy2, Manal F. Abou Taleb3,4, Manash R. Das5,6, Rabah Boukherroub7, Mohamed S.
Attia8*, Mohammed A. Amin1*
1Department of chemistry, College of Science, Taif University, P.O. Box 11099, Taif 21944,
Saudi Arabia
2Chemistry Department, Faculty of Science, Kafrelsheikh University, Kafr El Sheikh 33516,
Egypt
3Department of Chemistry, College of Science and Humanities in Al-Kharj, Prince Sattam
Bin Abdulaziz University, Al-Kharj, Saudi Arabia
4Polymer Chemistry Department, National Center for Radiation Research and Technology
(NCRRT), Egyptian Atomic Energy Authority, Cairo, Egypt
5Advanced Materials Group, Materials Sciences and Technology Division, CSIR-North East
Institute of Science and Technology, Jorhat 785006, Assam, India
6Academy of Scientific and Innovative Research (AcSIR), Ghaziabad 201002, India
7Univ. Lille, CNRS, Centrale Lille, Univ. Polytechnique Hauts-de-France, UMR 8520 -
IEMN, F59000 Lille, France
*To whom correspondence should be addressed: mohamed@tu.edu.sa (Mohammed A. Amin);

Mohd_mostafa@sci.asu.edu.eg (Mohamed S. Attia).
1
S1. Instrumentation and general procedure for the synthesis of the model complexes 1-3
S1.1. Instrumentation
The IR spectra were recorded using Alpha-Atunated FT-IR spectrophotometer (Bruker) in the
400–4000 cm−1 frequency range. UV-visible absorption was measured using UV-Lambda 25
Perkin Elmer. Thermogravimetric (TG) and differential thermogravimetric (DTG) analyses of
all complexes were performed on Netzsch STA 449F3 with system interface device. All the
samples were placed in alumina crucibles. Experiments were performed using 6.0 ± 0.3 mg of
the samples under nitrogen as the purge gas and a flow rate of 50 mL/min in the 30 - 1000 oC
temperature range at a heating rate of 10 oC/min. Scanning electron microscopy (SEM) imaging
was recorded using a JEOL-840 Electron probe micro analyzer with an accelerating voltage of
30 kV at a magnification of 1500X.
S1.2. General procedure for the synthesis of the model complexes 1-3
A solution of 336 mg (1.0 mmol) of the ligand KTpMeMe in absolute MeOH (10 mL) was added
dropwise (30 min) to a solution of 1.0 mmol of CuCl26H2O, NiCl26H2O or FeCl36H2O
previously dissolved in absolute MeOH (10 mL) under magnetic stirring. The resulting solution
was stirred for additional 4 h at room temperature. The volume of the solution was reduced to
10 mL in vacuo, the precipitate was filtered off, and the filtrate was evaporated to dryness. The
residue was redispersed in 10 mL of CH2Cl2, filtered, and evaporated to dryness again. Complex
1, [TpMeMeCuCl(H2O)]: Anal. For C15H24BClN6OCu (414.20): Calcd. C, 43.50; H, 5.84; N,
20.29; Cl, 8.56; Cu, 16.04. Found. C, 43.98; H, 5.55; N, 20.13; Cl, 8.63; Cu, 16.32. IR (KBr):
(cm-1): 2441 (B-H). Complex 2, [TpMeMeNiCl]: Anal. For C15H22BClN6Ni (391.35): Calcd.
C, 46.04; H, 5.67; N, 21.47; Cl, 9.06; Ni, 15.00. Found. C, 46.54; H, 5.43; N, 21.62; Cl, 8.74;
Ni, 15.32. IR (KBr): (cm-1): 2438 (B-H). Complex 3, [TpMeMeFeCl2(H2O)]: Anal. For
C15H24BCl2N6OFe (442.04): Calcd. C, 40.76; H, 5.47; N, 19.01; Cl, 16.04; Fe, 12.65. Found.
C, 40.21; H, 5.11; N, 19.12; Cl, 16.11; Fe, 13.46. IR (KBr): (cm-1): 2443 (W, B-H).
S2. Electrochemical Techniques
All electrochemical measurements were performed in an aqueous (deaerated) solution of KOH

(1.0 M) at room temperature. All potentials were corrected for uncompensated resistance (R)
and were given in the text relative to the reversible hydrogen electrode (RHE) using the formula
(ERHE = EHg/HgO + 0.059 pH + 0.165− iR), where ERHE is the potential calibrated against RHE,
EHg/HgO is the potential measured against the Hg/HgO reference electrode, and i is the current.
2
The reproducibility of electrochemical measurements was verified by repeating each run at least
three times, obtaining statistically respectable results. The arithmetical mean and standard
deviation were determined for each recorded value.
S2.1. HER Catalytic Activity Studies
Linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) were
conducted to evaluate the investigated catalysts’ HER electrocatalytic activity. An LSV run was
operated through sweeping the WE’s potential cathodically from the corrosion potential (Ecorr)
to a cathodic potential of -2.0 V vs. RHE at a scan rate of 5.0 mV s-1. A steady cathodic
overpotential was applied to the catalyst/KOH interface using 5 mV peak-to-peak AC signals
covering the frequency range from 100 kHz to 10 mHz to conduct EIS measurements.
S2.2. Long-term Stability and Durability Tests
Continuous cathodic potential cycling was applied to the catalyst/KOH interface to assess the
catalyst’s long-term stability and durability. Using a scan rate of 5.0 mV s-1, the potential was
swept linearly from the starting potential (Ecorr) to the cathodic direction until a cathodic
potential of -2.0 V vs. RHE was reached, and then reversed with the same scan rate to reach
Ecorr again forming a complete loop. Without withdrawing the electrode from the solution and
without delay in time, the cycling process was repeated 10000 times.
S2.3. HER’s Faradaic efficiency measurements
The quantity of H2 released (expressed in µmol) during a controlled galvanostatic electrolysis

(CGE) was collected using a gas chromatography (GC) to calculate the HER Faradaic
efficiency values of the investigated catalysts. The measurements were performed in a custom-
made airtight electrolysis cell. The H2 gas evolved during the performed CGE was quantified
by a GC conducted on an Agilent 7890A gas chromatograph with a pneumatically controlled
automatic gas sampling valve. The electrolysis cell was connected to the GC device via bespoke
airtight glass-to-metal adapters and copper tubing with an internal diameter of 1/8 in. The
temperature of the furnace was set at 45 °C and the carrier gas was Ar at a flow rate of about 3
mL min-1.
The working electrode (WE) was subjected to a cathodic current density of -10 mA cm-2 for 1.0
h in 1.0 M KOH at room temperature. The volume of H2 gas measured by GC is symbolized
here as Vm, Eq. (1).
3
Vm = mol gas (GC) (1)
The volume of H2 theoretically estimated during the performed CGE run from the charge passed
(assuming 100% Faradaic efficiency) through the WE is designated here as Vc, and calculated
based on Eq. (2) [1]:
Vc = Q(CGE) / nF (2)
where F is the Faraday's constant (F = 96485 C) and Q(CGE) is the charge passed through the
WE during the controlled process of controlled galvanostatic electrolysis (CGE). The factor n
represents the number of electrons transferred during the HER (2H+ + 2e- = H2, n = 2). The
value of FE is then calculated via dividing Vm by Vc. Finally, the tested electrocatalyst’s FE%
value is calculated via multiplying the quotient of the ratio (Vm/Vc) by 100, Eq. (3) [1]:
Faradaic efficiency (%) = [F × n × mol gas (GC) × 100] / Q(CGE) (3)
S2.4. Electrochemical active surface area determination
The double-layer capacitance measurements using cyclic voltammetry (CV) were employed to
determine the electrochemically-active surface area [2]. First, CV measurements were used to
estimate the potential range where a non-Faradaic current response exists. These measurements
were made in static solution by sweeping the potential across the nonfaradaic area from a more
positive to a more negative potential and back at different potential sweep rates (ca. 20 – 120
mV s-1). Before starting the next sweep, the working electrode was kept at each potential vertex
for 10 seconds [3], the cathodic and anodic charging currents were measured at 0.35 V vs RHE
plotted as a function of scan rate. The determined double-layer capacitance of the system is
taken as the average of the absolute value of the slope of the linear fits to the data.
4
(a)
GC-FeC (0.2 mg cm-2)
j / mA cm-2 2
-2 120 mV s-1
scan rate
20 mV s-1
0.30 0.32 0.34 0.36 0.38 0.40

Potential (V vs. RHE)
1.6
(b)
1.2
Slope = 12.32 mF cm-2
0.8
j / mA cm-2
0.4
0.0
-0.4
-0.8 Slope = -10.2 mF cm-2
-1.2
0 20 40 60 80 100 120
Scan rate / mV s-1

Figure S1. (a) Cyclic voltammograms recorded for the GC-FeC (0.2 mg cm-2) electrocatalyst
at various potential scan rates (20-120 mV s-1) measured in a non-Faradaic region of the
voltammograms. Measurements were conducted in deaerated KOH solution (0.1 M) at room
temperature. (b) Double-layer capacitance measurements for determining the catalyst’s
electrochemically-active surface area.
5
6
(a)
-2
4 GC-FeC (0.4 mg cm )
2
j / mA cm-2
-2
120 mV s-1
-4 scan rate
20 mV s-1
-6
0.30 0.32 0.34 0.36 0.38 0.40
3
(b)
2 GC-FeC (0.4 mg cm-2)
j / mA cm-2
-1
Slope = -18.89 mF cm-2
-2
0 20 40 60 80 100 120
Scan rate / mV s-1

6
10
(a)
8
6
4
j / mA cm-2
2
0
-2
-4
120 mV s-1
-6
scan rate
-8 20 mV s-1
-10
0.30 0.32 0.34 0.36 0.38 0.40
4 (b)
3
2
j / mA cm-2
-1
-2
-3
-4
0 20 40 60 80 100 120
-1
Scan rate / mV s
7
(a)
4
GC-NiC (0.2 mg cm-2)
2
j / mA cm-2
-2
120 mV s-1
scan rate
-4 20 mV s-1
0.30 0.32 0.34 0.36 0.38 0.40

2.0 GC-NiC (0.2 mg cm-2)
1.5 (b)
1.0
j / mA cm-2
0.5
0.0
-0.5
-1.0
-1.5
-2.0
0 20 40 60 80 100 120
-1
Scan rate / mV s
Figure S4. (a) Cyclic voltammograms recorded for the GC-NiC (0.2 mg cm-2) electrocatalyst
8
(a)
6
4
j / mA cm-2
-2
120 mV s-1
-4 scan rate
20 mV s-1
-6
0.30 0.32 0.34 0.36 0.38 0.40
4
(b)
3 GC-NiC (0.4 mg cm-2)
2
j / mA cm-2
-1
-2 Slope = -27.06 mF cm-2

-3
-4
0 20 40 60 80 100 120
Scan rate / mV s-1

9
10 (a)
8
6
j / mA cm-2
4
2
0
-2
-4 120 mV s-1
-6 scan rate
-8 20 mV s-1
0.30 0.32 0.34 0.36 0.38 0.40

6 (b)
4 Slope = 46.82 mF cm-2
j / mA cm-2
-2

-4
0 20 40 60 80 100 120
-1
Scan rate / mV s
10
6
(a)
GC-CuC (0.2 mg cm-2)
j / mA cm-2 4
-2 120 mV s-1
scan rate
-4 20 mV s-1
0.30 0.32 0.34 0.36 0.38 0.40

3
(b)
2 Slope = 22.79 mF cm-2
j / mA cm-2
-1

-2
0 20 40 60 80 100 120
-1
Scan rate / mV s
Figure S7. (a) Cyclic voltammograms recorded for the GC-CuC (0.2 mg cm-2) electrocatalyst
11
6 (a)
4
j / mA cm-2
-2
-4 120 mV s-1
scan rate
-6 20 mV s-1
0.30 0.32 0.34 0.36 0.38 0.40

5 (b)
4 GC-CuC (0.4 mg cm-2)
3 Slope = 36.52 mF cm-2
2
j / mA cm-2
1
0
-1
-2
-3 Slope = -36.89 mF cm-2
-4
-5
0 20 40 60 80 100 120
-1
Scan rate / mV s
12
10 (a)
-2
8 GC-CuC (0.8 mg cm )
6
4
j / mA cm-2
2
0
-2
-4
-6 120 mV s-1
-8 scan rate
-10 20 mV s-1
0.30 0.32 0.34 0.36 0.38 0.40

(b)
6 GC-CuC (0.8 mg cm-2)
4 Slope = 52.43 mF cm-2
j / mA cm-2
-2
-4 Slope = -53.61 mF cm-2

-6
0 20 40 60 80 100 120
-1
Scan rate / mV s
13
14
15
Figure S10. Phase plots recorded for the HER on the surfaces of
(a) GC-FeC (0.4 mg cm-2), (b) GC-NiC (0.4 mg cm-2), and (c) GC-CuC (0.4 mg cm-2).
Measurements were conducted in deaerated 0.1 M KOH solution at various overpotentials at
room temperature. (1)
16
17
Figure S11 – Complex-plane EIS plots for the bare GCE electrode (a) and Pt/C (b).
Measurements were conducted in 0.1 M KOH at 500 mV at room temperature.
Figure S12. The equivalent circuit adopted to fit the experimental impedance data.
18
Table S1: Comparison of HER catalytic activity of our best electrocatalyst, namely GC-CuC
(0.8 mg cm-2) with the highly efficient electrocatalysts reported in the literature.
Samples Electrolyte Onset Potential Tafel TOF @ Ref.

potential @ 10 mA slope overpotential
(V) cm-2 (mV
(V) dec-1)
GC-CuC (0.8 mg cm-2) 0.1 M KOH -0.025 0.12 112 1820 @ 0.5 V This
work
Chlorobis(2- Phosphare -0.14 0.242 145 1722 @ 0.5 V [4]
aminomethylbenzimidazole) buffer (pH
zinc(II) perchlorate complex 7)
(loading density 0.8 mg cm-
2)
cobalt(III) complex with ----- ----- ----- ----- 1800 @ 0.5 V [5]
Schiff base ligand
molybdenum-oxo complex ----- ----- ----- ----- 1600 @ 0.642 [6]
V
dinickel complex ----- ----- ----- ----- 160 @ 0.82 V [7]
cobalt complex ----- ----- ----- ----- 300 @ 0.98 V [8]
copper complex ----- ----- ----- ----- 457 @ 0.817 V [9]
molybdenum complex ----- ----- ----- ----- 678 @ 0.70 V [10]
N, S co‐doped graphitic 0.1 M KOH 0.23 0.31 112 [11]
sheets with stereoscopic
holes (SHG)
N-rich holey graphene 0.1 M KOH 0.30 0.51 157 [12]
monoliths (N-G)
N, P co-doped nanoporous 0.1 M KOH 0.35 > 0.6 --- [13]
graphene (N, P-G)
N, P Co-doped carbon 0.1 M KOH 0.29 0.47 --- [14]
networks (N, P-C)
N, O, P tri-doped porous 1.0 M KOH 0.28 0.45 154 [15]
carbon (N, O, P-G)
g-C3N4@N-doped graphene 0.1 M KOH 0.35 > 0.6 --- [16]
(C3N4@N-G)
g-C3N4–S, Se co-doped 0.1 M KOH 0.45 1.1 93 [17]
graphene
(C3N4@S,Se-G)
g-C3N4–N, P co-doped 0.1 M KOH 0.45 0.58 129 [18]
graphene
(C3N4@N, P-G)
19
References
1. Beyene, B. B., Mane, S. B., Hung, C.-H. Highly efficient electrocatalytic hydrogen
evolution from neutral aqueous solution by a water-soluble anionic cobalt(II) porphyrin.
Chem. Commun., 2015, 51, 15067-15070.
[2] Trasatti, S.; Petrii, O. A. Real surface area measurements in electrochemistry, Pure Appl.
Chem. 1991, 63, 711−734.
[3] Benck, J. D.; Chen, Z.; Kuritzky, L. Y.; Forman, A. J.; Jaramillo, T. F. ACS Catalysis 2012,
2, 1916−1923.]. Following McCrory et al. [J. Am. Chem. Soc. 2013, 135, 45, 16977–16987,
https://doi.org/10.1021/ja407115p.
4. Amin, M. A., Ibrahim, M. M., Gobouri, A. A., Mersal, G. A.M., Mostafa, N. Y., Altalhi, T.,
Al-Juaid, S. A newly synthesized single crystal zinc complex as molecular electrocatalyst for
efficient hydrogen generation from neutral aqueous solutions. Int. J. Hydrogen Energy, 2017,
42, 25980 - 25995.
5. Fanga, T., Fua, L.-Z., Zhoua, L.-L., Zhana, S.-Z., Chen, S. Electrochemical-driven water
reduction catalyzed by a water soluble cobalt(III) complex with Schiff base ligand. Electrochim.
Acta, 2015, 178, 368-373.
6. Karunadasa, H.I., Chang, C.J., Long, A molecular molybdenum-oxo catalyst for generating
hydrogen from water. Nature, 2010, 464, 1329–1333.
7. Collin, J., Jouaiti, A., Sauvage, J.P. Electrocatalytic properties of (tetraazacyclotetradecane)
nickel(2+) and Ni2(biscyclam)4+ with respect to carbon dioxide and water reduction. Inorg.
Chem. 1988, 27, 1986–1990.
8. Singh, W.M., Baine, T., Kudo, S., Tian, S., Ma, X.A.N., Zhou, H., DeYonker, N.J.,
Pham, T.C., Bollinger, J.C., Baker, D.L., Yan, B., Webster, C.E., Zhao, X. Electrocatalytic
and photocatalytic hydrogen production in aqueous solution by a molecular cobalt complex.
Angew. Chem. Int. Ed., 2012, 51, 5941–5944.
9. Cao, J.P., Fang, T., Fu, L.Z., Zhou, L.L., Zhan, S.Z. First mononuclear copper(II)
electro-catalyst for catalyzing hydrogen evolution from acetic acid and water. Int. J. Hydrogen
Energy, 2014, 39, 13972–13978.
10. Fang, T., Lu, H.X., Zhao, J.X., Zhan, S.Z. Synthesis and studies of a molecular
molybdenum–Schiff base electrocatalyst for generating hydrogen from organic acid or water.
Inorg. Chem. Commun., 2015, 51, 66–70.
11. Hu, C., Dai, L. Multifunctional carbon-based metal-free electrocatalysts for simultaneous
oxygen reduction, oxygen evolution, and hydrogen evolution. Adv. Mater., 2017, 29, 1604942.
20
12. Ge, J. M., Zhang, B., Lv, L. B., Wang, H. H., Ye, T. N., Wei, X., Su, J., Wang, K. X., Lin,
X. H., Chen, J. S. Constructing Holey Graphene Monoliths via Supramolecular Assembly:
Enriching Nitrogen Heteroatoms up to the Theoretical Limit for Hydrogen Evolution Reaction.
Nano Energy, 2015, 15, 567-575.
13. Zheng, Y., Jiao, Y., Li, L. H., Xing, T., Chen, Y., Jaroniec, M., Qiao, S. Z. Toward design
of synergistically active carbon-based catalysts for electrocatalytic hydrogen evolution. ACS
Nano, 2014, 8, 5290-5296.
14. Zhang, J. T., Qu, L. T., Shi, G. Q., Liu, J. Y., Chen, J. F., Dai, L. M. N,P‐Codoped Carbon
Networks as Efficient Metal‐free Bifunctional Catalysts for Oxygen Reduction and Hydrogen
Evolution Reactions. Angew. Chem. Int. Ed., 2016, 55, 2230-2234.
15. Lai, J. P., Li, S. P., Wu, F. X., Saqib, M., Luque, R., Xu, G. B. Unprecedented Metal-free
3D Porous Carbonaceous Electrodes for Full Water Splitting. Energy Environ. Sci., 2016, 9,
1210-1214.
16. Zheng, Y., Jiao, Y., Zhu, Y., Li, L. H., Han, Y., Chen, Y., Du, A., Jaroniec, M., Qiao, S. Z.
Hydrogen Evolution by a Metal-free Electrocatalyst. Nature Commun., 2014, 5, 3783
17. Shinde, S. S., Sami, A., Lee, J. H. Electrocatalytic Hydrogen Evolution Using Graphitic
Carbon Nitride Coupled with Nanoporous Graphene co-doped by S and Se. J. Mater. Chem. A,
2015, 3, 12810-12819.
18. Shinde, S. S., Sami, A., Lee, J. H. Nitrogen‐ and Phosphorus‐Doped Nanoporous
Graphene/Graphitic Carbon Nitride Hybrids as Efficient Electrocatalysts for Hydrogen
Evolution. ChemCatChem, 2015, 7, 873-3880.
21

Supplementary Information

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Supplementary Information

Uploaded by

Copyright:

Available Formats

Electronic Supplementary Material (ESI) for RSC Advances.

This journal is © The Royal Society of Chemistry 2022

Electrocatalytic Hydrogen Generation using Tripod Containing

Mohamed M. Ibrahim1, G. A. M. Mersal1, Ahmed M. Fallatah1, Khaled Althubeiti1, Hamdy S.

*To whom correspondence should be addressed: mohamed@tu.edu.sa (Mohammed A. Amin);

S2. Electrochemical Techniques

All electrochemical measurements were performed in an aqueous (deaerated) solution of KOH

S2.1. HER Catalytic Activity Studies

S2.2. Long-term Stability and Durability Tests

S2.3. HER’s Faradaic efficiency measurements

The quantity of H2 released (expressed in µmol) during a controlled galvanostatic electrolysis

Faradaic efficiency (%) = [F × n × mol gas (GC) × 100] / Q(CGE) (3)

S2.4. Electrochemical active surface area determination

0.30 0.32 0.34 0.36 0.38 0.40

-0.8 Slope = -10.2 mF cm-2

Scan rate / mV s-1

Scan rate / mV s-1

0.30 0.32 0.34 0.36 0.38 0.40

-2 Slope = -27.06 mF cm-2

Scan rate / mV s-1

0.30 0.32 0.34 0.36 0.38 0.40

Slope = -42.04 mF cm-2

0.30 0.32 0.34 0.36 0.38 0.40

Slope = -19.62 mF cm-2

0.30 0.32 0.34 0.36 0.38 0.40

0.30 0.32 0.34 0.36 0.38 0.40

-4 Slope = -53.61 mF cm-2

Samples Electrolyte Onset Potential Tafel TOF @ Ref.

You might also like