P(2-VP) supported Ru(II) material as catalyst for H2 production from the methanolysis of NaBH4

Article abstract of DOI:10.1080/24701556.2020.1749077

Existing energy resources are not sufficient to meet the energy needs of the increasing world population so the need for clean and renewable energy systems is increasing day after day. Hydrogen is a good alternative energy source because of its clean by-products and high energy capacity. Studies on hydrogen storage systems that provide instant hydrogen production in the literature are of great interest. In this study, poly-2-vinylpyridine (p(2-VP)) polymer was prepared by photopolymerization method and reacted with 2,6-bis(2-benzimidazolyl)pyridine ligand containing Ru(II) complex to give p(2-VP) supported Ru(II) material. The synthesized Ru(II) complex was characterized by FT-IR, UV-Vis and ¹H-NMR spectroscopic techniques. Also the p(2-VP) polymer was characterized by FT-IR spectroscopy. The obtained p(2-VP) supported Ru(II) material was used as catalyst in hydrogen generation from NaBH₄ metanolysis reaction and the reaction kinetic was investigated.

Full text of DOI:10.1080/24701556.2020.1749077

Inorganic and Nano-Metal Chemistry
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P(2-VP) supported Ru(II) material as catalyst for H2
production from the methanolysis of NaBH4
Melek Tercan, Elif Karacan Yeldir, Osman Dayan & Ayhan Oral
To cite this article: Melek Tercan, Elif Karacan Yeldir, Osman Dayan & Ayhan Oral (2020): P(2-
VP) supported Ru(II) material as catalyst for H2 production from the methanolysis of NaBH4,
Inorganic and Nano-Metal Chemistry, DOI: 10.1080/24701556.2020.1749077
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INORGANIC AND NANO-METAL CHEMISTRY
https://doi.org/10.1080/24701556.2020.1749077
P(2-VP) supported Ru(II) material as catalyst for H2 production from the
methanolysis of NaBH4
Melek Tercan, Elif Karacan Yeldir, Osman Dayan , and Ayhan Oral
Department of Chemistry, Faculty of Arts and Science, Canakkale Onsekiz Mart University, Canakkale, Turkey
ABSTRACT
ARTICLE HISTORY
Received 24 January 2020
Accepted 10 March 2020
Existing energy resources are not sufficient to meet the energy needs of the increasing world
population so the need for clean and renewable energy systems is increasing day after day.
Hydrogen is a good alternative energy source because of its clean by-products and high energy
capacity. Studies on hydrogen storage systems that provide instant hydrogen production in the lit-
erature are of great interest. In this study, poly-2-vinylpyridine (p(2-VP)) polymer was prepared by
photopolymerization method and reacted with 2,6-bis(2-benzimidazolyl)pyridine ligand containing
Ru(II) complex to give p(2-VP) supported Ru(II) material. The synthesized Ru(II) complex was char-
acterized by FT-IR, UV-Vis and 1H-NMR spectroscopic techniques. Also the p(2-VP) polymer was
characterized by FT-IR spectroscopy. The obtained p(2-VP) supported Ru(II) material was used as
catalyst in hydrogen generation from NaBH4 metanolysis reaction and the reaction kinetic was
investigated.
KEYWORDS
Hydrogen energy;
ruthenium; benzimidazole
type ligand; p(2-VP)
polymer; methanolysis
Introduction
Sorbents (C materials, graphene, zeolite, activated C,
metal-organic frameworks, nano structured and nano-por-
ous materials), metal hydrides (NaBH4, LiBH4), chemical
hydrides and B-N compounds (ammonia borane (H3N.BH3),
borazine, polyborazylene) are used in dehydrogenation reac-
tions commonly.[6,12,13] Recently, ammonia boranes are the
most popular storage systems due to their high gravimetric
hydrogen capacities, low molar masses and rechargeabil-
ities.[14–23] But practical H2 formation, suitable reaction con-
ditions with many different methods and different catalysts
makes metal hydrides still remain attractive.[11] Especially
sodium borahyride (NaBH4) is widely studied in the litera-
ture because of its high hydrogen content (10.9% by mass),
generation of four moles of hydrogen per mol of NaBH4,
workability at mild reaction conditions and its relatively low
cost.[24–26] At room temperature self-hydrolysis of NaBH4
occurs in aqueous media but the reaction is very slow.
Alternative solvents have been tried for this catalytic process,
but the fastest reaction kinetics have been observed with
methanol at low temperatures and even in the absence of
catalyst (Eq (1)).[26,27] Also the byproduct of methanolysis,
sodium tetramethoxyborate (NaB(OCH3)4) can be regener-
ated to methanol through hydrolysis (Eq (2)).
The depletion and inadequacy of universal energy resources
led researchers to develop new energy systems.[1]
Considering the limitation of fossil fuels and the atmos-
pheric pollution caused by the emission of greenhouse gases,
the use of renewable energy sources is becoming more and
more important. Hydrogen is a good alternative for renew-
able energy by its source-independent character and high
potential to be a clean energy.[2–5] Also its high energy con-
tent compared to petrolum (44 MJ kgꢀ1 for petroleum and
120 MJ kgꢀ1 for hydrogen) makes it important for indus-
try.[6] However, the efficient storage of hydrogen, safe and
economic distribution systems are still an issue.[7,8] The US
Department of Energy (DOE) has set the system capacity in
vehicles as 62 kg H2/m3 at specified temperature and pres-
sure.[9] Hydrogen can be stored in liquefied form in high
pressured tanks filled with sorbent materials. However, due
to the difficulties in cryogenic hydrogen storage systems, the
development of solid H2 storage systems is essential.[9,10]
There are some features sought in systems to be used in
hydrogen storage:
ꢁ Hydrogen storage capacities of the materials
ꢁ High gravimetric H2 capacities
ꢁ Safety
NaBH4 þ 4CH3OH ! NaBðOCH3Þ4 þ 4H2
NaBðOCH3Þ4 þ 2H2O ! NaBO2 þ 4CH3OH
(1)
(2)
ꢁ Low-cost
ꢁ Systems in which reversible dehydrogenation is thermo-
Besides the advantages of NaBH4 as nontoxic and non-
dynamically favorable. The efficiency of a storage system flammable, hydrogen release via NaBH4 is a controllable
is depend on recyclability.[10,11]
hydrolysis reaction, because the reaction starts with
CONTACT Melek Tercan
melektercan@comu.edu.tr
Department of Chemistry, Faculty of Arts and Science, Canakkale Onsekiz Mart University,
Canakkale, Turkey
ß 2020 Taylor & Francis Group, LLC

2
M. TERCAN ET AL.
Figure 1. Schematical show of the preparation of p(2-VP) supported Ru(II) material.
catalyst.[28–30] Various catalyst systems, generally metal cata- bis(dichloro(p-cymene)ruthenium (II)) dimer used in the
lysts, were used to produce hydrogen from NaBH4 hydroly-
sis and metanolysis reactions.[31–37] Hydrogen obtained in
hydrogen storage systems should be transported by surface
diffusion. That is, hydrogen is obtained on the first surface
and adsorbs on another surface. The first surface is usually a
metal center, the second surface is a support material in
which the metal is doped.[9] Therefore, the choose of the
catalyst and the support material to immobilize the catalyst
are important. The use of active and stable transition metals
such as Ru, Pt in catalytic applications requires effective
reduction of the metal. By using a low amount of metal by
weight, more surface area per unit weight is obtained and
metal aggregation is prevented. For this purpose, various
support materials are used as alumina, silica, MOFs etc.
However, during the contact of metal hydride with water,
formation of B-O-based compounds and borates besides
hydrogen causes an increase in the alkalinity and catalytic
efficiency decreases as a result.[7] So, the chemical stability
of the support material is as important as the surface area,
porosity etc. and a polymer supported catalyst system can be
a good option for catalysis.[37–40]
complexation reaction was taken from Alfa Aesar. The ben-
zoin used as initiator in the preparation of p(2-VP) polymer
and the 2-VP used as monomer were obtained from Sigma
Aldrich and Alfa Aesar. Tetrahydrofuran (THF), N,N-dime-
thylformamide (DMF), ortho-phosphoric acid that used as
reaction solvents, and all solvents used in the separation-
purification processes were obtained from Merck. Sodium
tetrahydridoborate (NaBH4) and methanol that used in
hydrogen generation reactions were purchased from Merck.
Infrared spectra of the ligand, polymer and the material
were recorded with Perkin Elmer Spectrum One FT-IR sys-
1
tem using ATR sampling accessory. The H-NMR spectrum
of the 2,6-bis(2-benzimidazolyl)pyridine ligand was recorded
with a JEOL NMR – 400 MHz. The SEM image of the pre-
pared polymer supported Ru(II) material was taken with
JEOL – SEM – 7100 – EDX, while the XRD pattern of the
material was recorded by Panalytical Empyrean X-Ray
diffractometer.
Synthesis of 2,6-bis(2-benzimidazolyl)pyridine
In this study, polypyridine type ligand bearing
ruthenium(II) complex was chosen as catalysts and poly-2-
vinylpyridine (p(2-VP)) polymer as a support material.
2-Vinylpyridine (2-VP) as a polymer template was polymer-
ized by photopolymerization method, characterized by FT-
IR spectroscopy. The p-(2-VP) polymer and Ru(II) complex
were reacted in a certain ratio to obtain Ru metal-contain-
ing polymeric material and the metal content of the mater-
ial was determined by SEM-EDX analysis. The obtained
p(2-VP) supported Ru(II) material was used as catalyst in
hydrogen generation from NaBH4 metanolysis reaction
(Figure 1).
The tri-dentate NN’N’’ ligand, 2,6-bis(2-benzimidazolyl)pyr-
idine, was synthesized according to the related litera-
ture.[41,42] Pyridine-2,6-dicarboxylic acid (20 mmol, 3.35 g)
was added to 1,2-phenylenediamine (44 mmol, 4.7 g) in
phosphoric acid (40 mL). The reaction mixture was stirred
during 4 hours under Ar atmosphere. The obtained blue
colored melt was poured into ice and after reaching room
temperature, filtered off. Then sodium carbonate (10%,
100 mL) solution was added to the filtrate. The obtained
pink-purple melt was washed with methanol numbers of
times. And the solid was crystallized from MeOH. The
orange crystals were purified by adding activated carbon.
After recrystallization from methanol white-beige crystals
were obtained.
Experimental
FT-IR (ATR/cmꢀ1): 3181, 3064, 1681, 1603, 1576, 1490,
1457, 1434, 1409, 1386, 1317, 1277, 1230, 1144, 1112, 1012,
958, 926, 845, 815, 738, 729, 693. 1H–NMR (400 MHz,
DMSO–d6) d ppm 8.34 (d, J ¼ 7.37 Hz, 2 H), 8.17 (t,
J ¼ 8.14 Hz, 1 H), 7.77 (d, J ¼ 7.74 Hz, 2 H), 7.74 (d,
J ¼ 8.34 Hz, 2 H), 7.35 (t, J ¼ 7.69 Hz, 2 H), 7.28 (t,
Materials
Materials and apparatus
1,2-phenylenediamine (Alfa Aesar) and 2,6-pyridinedicar-
boxylic acid (Acros Organics) that used in the synthesis of
2,6-bis(2-benzimidazolyl)pyridine ligand were obtained
commercially. RuCl3.3H2O used in the preparation of J ¼ 7.46 Hz, 2 H).

INORGANIC AND NANO-METAL CHEMISTRY
3
Figure 2. The prepation of p(2-VP) by photopolymerization.
Synthesis of poly(2-vinylpyridine), p(2-VP)
Ru(II) material catalysts. A series of methanolysis tests were
Benzoin was used as a type I photoinitiator and tetrahydro- carried out for various temperatures (0 ꢂC, 15 ꢂC, 25 ꢂC,
35 ꢂC, 45 ꢂC) to examine the kinetics.
furan (THF) was used as solvent in the polymerization of 2-
VP. Initiator an amount of 1% of by mass of the monomer
was placed into quartz tube and degassed with nitrogen.
Than, THF and the monomer, 2-VP, were added into tube
Results and discussion
under N2 atmosphere. Photopolymerization occured at
310 nm for benzoin. The contains of tube was dissolved in
methanol after specified time (1.5, 3, 6, 9, 12 and 24 h). The
polymer was precipitated with diethyl ether, than filtered
and washed with diethyl ether for three times.
Characterization of p(2-VP) and p(2-VP) supported Ru(II)
material catalyst
P(2-VP) polymer was prepared by photopolymerization
method (Figure 2). Then p(2-VP) supported Ru(II) material
was prepared according to the procedure at 2.4. The morph-
ology and the distribution of metal in the synthesized p(2-
VP) supported Ru(II) material was examined by SEM
coupled EDX, the images at different magnifications are
given in Figure 3.
Synthesis of p(2-VP) supported Ru(II) material
The tridentate 2,6-bis(2-benzimidazolyl)pyridine ligand
(100 mg, 0.321 mmol) was dissolved in DMF (10 mL) and
As shown in Figure 3, it is possible to say that the
obtained p(2-VP) supported Ru(II) material is homoge-
neous. In addition, as a result of EDX measurements taken
from different sections of the spectra, Ru composition is
observed in the range of 0.4-0.5% and supports homogen-
eity. The overlapped XRD spectra of p(2-VP) polymer and
the p(2-VP) supported Ru(II) material is given in Figure 4.
With the extension of the p(2-VP) polymer chain, the
amount of Ru per chain is reduced. Therefore, the Ru peak
was suppressed and could not be observed in the XRD pat-
tern. In addition, the peaks of the p(2-VP) polymer were
sharper, while the p(2-VP) supported Ru(II) material peaks
showed spreading and this indicates amorphous structure.
The overlapped FT-IR spectra of p(2-VP), tri-dentated
ligand, (2,6-bis(2-benzimidazolyl)pyridine), and p(2-VP)
supported Ru(II) material are given in Figure 5. When the
FT-IR spectrum of p(2-VP) supported Ru(II) material was
examined, aromatic C-H stretching peaks were observed at
3056 and 3005 cmꢀ1. The peaks monitored at 2927 and
2851 cmꢀ1 are belong to aliphatic CH2 and CH stretching
peaks of p(2-VP) and prove that the material contains the p
(2-VP) polymer. The C ¼ N double bond stretching peak of
(2,6-bis(2-benzimidazolyl)pyridine) ligand at 1681 cmꢀ1 was
dichloro(p-cymene)ruthenium
(II)
dimer
(98 mg,
0.161 mmol) was added. The reaction mixture was stirred at
50 ꢂC until the color turned brown-cherry. Then p(2-VP)
(337 mg, 3.21 mmol) was added to the media and stirred at
80 ꢂC over night. The reaction solvent was removed, the
residue was washed with diethyl ether and allowed to dry.
p(2-VP) supported Ru(II) material was obtained as
brown solid.
FT-IR (ATR/cmꢀ1): 3388, 3056, 3005, 2927, 2851, 1709,
1623, 1589, 1568, 1473, 1433, 1359, 1318, 1222, 1148, 1085,
1049, 994, 914, 857, 748.
The catalytic tests
The H2 generation reactions via NaBH4 hydrolysis were car-
ried out by water displacement method. 20 mL of deionized
water (or methanol) was placed into a 50 mL two-necked
flask, NaBH4 (125 mM) was added and H2 generation was
investigated at 1000 rpm mixing rate at 25 ꢂC. H2 generation
from the self-hydrolysis/methanolysis of NaBH4 were tested
first without catalyst. Then, the catalytic performance of
p(2-VP) supported Ru(II) material as catalyst was deter-
mined. H2 generation was investigated in the presence of
different amounts (10, 25, 50, 100 mg) of p(2-VP) supported shifted to 1709 cmꢀ1 in the spectrum of Ru(II) material.

4
M. TERCAN ET AL.
Figure 3. (a,b) SEM images of p(2-VP) supported Ru(II) material (c) EDX of p(2-VP) supported Ru(II) material.
region. On the other hand, the signals at 1.30-1.90 ppm are
assigned to aliphatic protons. Also, the -Hx,y protons of
p(2-VP) supported Ru(II) material are monitored at 7.50 –
8.00 ppm region. The other hydrogen peaks belong to benzi-
midazole ring maybe overlapped with p(2-VP) aromatic
hydrogens peaks.
Also, p(2-VP) and p(2-VP) supported Ru(II) complex
were studied by thermogravimetric analysis from ambient
temperature to 1000 ꢂC in a nitrogen atmosphere (Figure 7).
According to Figure 7, both compounds decompose in two
steps between 50 and 1000 ꢂC while p(2-VP) supported
Ru(II) complex is more stable.
Catalytic performance of p(2-VP) supported Ru(II)
material H2 generation via NaBH4 methanolysis
P(2-VP) supported Ru(II) material was used as catalyst in
H2 generation from NaBH4. For this purpose, hydrolysis
and methanolysis reactions of NaBH4 were compared in
catalyst-free medium and it is observed that the methanoly-
sis of NaBH4 reaction is faster. The generated volume of H2
by the hydrolysis reaction was 82 mL after 2 hours, while
after 10 minutes by methanolysis the reaction was almost
complete and about 165 mL of H2 was collected. Therefore,
Figure 4. XRD patterns of p(2-VP) (red line) and p(2-VP) supported Ru(II) mater-
ial (blue line).
Also, the aromatic C ¼ C double bond stretching peaks were
observed in the range of 1589-1433 cmꢀ1 and support
the structure.
1H-NMR spectra of p(2-VP) and p(2-VP) supported
Ru(II) material are very similar. As shown in Figure 6, the
aromatic protons are observed around 6.00 – 8.50 ppm methanolysis of NaBH4 reactions were used in all catalytic

INORGANIC AND NANO-METAL CHEMISTRY
5
Figure 5. Overlapped FT-IR spectra of p(2-VP), NN’N’’ ligand (2,6-bis(2-benzimidazolyl)pyridine) and p(2-VP) supported Ru(II) material.
studies to investigate the catalytic performance of the p(2- chemistry because of their environmental friendliness. To
VP) supported Ru(II) material.
determine the effect of catalyst amount, p(2-VP) supported
Ru(II) material weighing in the range of 10–100 mg were
used as catalyst in methanolysis of NaBH4 (125 mM, 20 mL)
at room temperature (25 ꢂC) with 1000 rpm mixing rate. All
catalytic trials were performed in triplicate using 10, 25, 50
and 100 mg of catalyst, respectively. In the experiments, it
was observed that all methanolysis reactions were completed
in about 5 minutes, after this time no significant changes
were observed and the generated H2 volumes were almost
The effect of amount of catalyst on H2 generation
In order to investigate the effectiveness of the prepared
material in H2 generation reactions via methanolysis of
NaBH4, some parameters such as catalyst amount and tem-
perature were changed in the catalytic experiments. The pre-
pared p(2-VP) supported Ru(II) material has a very low
metal content of about 0.4% (Figure 3), and supported cata- constant until the end of 20 minutes. The average volume of
lysts with low metal content are important for catalyst hydrogen collected at the end of 5 min for the methanolysis

6
M. TERCAN ET AL.
Figure 6. 1H-NMR spectra of p(2-VP) (a) and p(2-VP) supported Ru(II) material (b).
generation reactions via methanolysis of NaBH4 was investi-
gated (Table 1).
ð
Þ
H2generation rate ¼ ðgenerated H2volume mL
À
Á
ð
Þ
= time min ꢃ catalyst amount ðgÞ
(3)
The effect of temperature on H2 generation via
methanolysis of NaBH4
Catalytic experiments were carried out at varying tempera-
tures (0 to 45 ꢂC) using 50 mg catalyst under the same con-
ditions (125 mM, 20 mL NaBH4, 1000 rpm mixing rate) and
activation energies were calculated for different tempera-
tures. The methanolysis reaction of NaBH4 was completed
at 0 ꢂC at the end of 20 min, and at 12, 8, 5 and 4 min at 15,
25, 35 and 45 ꢂC, respectively. As the temperature increased,
both the reaction time was shortened and the collected
hydrogen volume increased. The time-generated H2 volume
graph by variation of the temperature is shown in Figure 9a.
The generated H2 volume was observed as 161 3 mL,
178 2 mL, 173 5 mL, 188 3 mL and 201 0.4 mL for 0,
15, 25, 35 and 45 ꢂC, respectively. The activation energy of
the reaction was calculated by using Arrhenius equation (Eq
(4)) where, k is the rate constant, Ea is the activation energy,
Figure 7. TG curves of p(2-VP) and p(2-VP) supported Ru(II) complex.
reaction that 10 mg of catalyst used was 149 7 mL, while
148 5 mL, 167 0.4 mL and 170 6 mL were observed for
25 mg, 50 mg and 100 mg, respectively (Figure 8a). An
inverse proportion was observed between H2 generation
rates (HGR) and the amount of catalyst used. The HGR val-
ues were calculated up to 5 min of the methanolysis reaction
time as 2980 71, 1192 11, 669 2, 339 13 mL minꢀ1
ꢀ1
R is the ideal gas constant (8.314 j molꢀ1
K
ꢀ1) and T is
gcatalyst
for 10, 25, 50 and 100 mg p(2-VP) supported
Ru(II) material, respectively (Figure 8b). Since increasing the
amount of catalyst above 50 mg practically results in an
increase of only 2 mL of generated H2 volume (Figure 8c),
this amount was not exceeded and the optimum amount of
catalyst was determined as 50 mg. For this reason, the
amount of catalyst was determined as 50 mg in the experi-
temperature (K). To calculate the reaction constant values (k
values), the times required to collect the same amount of H2
at different temperature values are recorded. The reaction is
the first order (R ¼ k. [A]0), so k values are equal to 1/t
(sꢀ1) values. Thus, the k values of the methanolysis reactions
of NaBH4 at different temperatures were determined, then
ments in which the effect of temperature on the H2 the Ea of the reaction was calculated as 53.9 2 kj molꢀ1 by

INORGANIC AND NANO-METAL CHEMISTRY
7
Figure 8. The effect of catalyst amount on methanolysis of NaBH4 (a), the comparison of H2 generation rates (b) and the comparison of reaction rates (c) (up to
5 min of reaction time).
Table 1. The effect of catalyst amount on generated H2 volume and H2 generation rate.
ꢀ1
Catalyst amount (mg)
aGenerated H2 volume (mL)
bH2 generation rate (mL minꢀ1 gcatalyst
)
10
25
149
148
7
5
2980 71
1192 11
50
100
167 0.4
669
339 13
2
170
6
aAverage values of generated H2 volume at the end of the 5 minutes in the methanolysis of NaBH4 (125 mM, 20 mL) at room
temperature (25 ꢂC) with 1000 rpm mixing rate with different amount of catalyst (10, 25, 50 and 100 mg).
bH2 generation rates were calculated by using Eq. (4).
plotting ln k versus 1/T graph (Figure 9b). Ea value for Ru(II) material, which has low metal content, was investi-
gated in H2 generation reactions via methanolysis of NaBH4.
All catalytic measurements were made for the methanolysis
reaction, since the amount of hydrogen generated was
greater and the reaction was completed in a shorter time
comparing with hydrolysis. Catalytic experiments were per-
formed for different amounts of catalyst (10, 25, 50 and
100 mg) and best results were obtained as 167 0.4 mL of
generated hydrogen volume for 50 mg catalyst and
170 7 mL for 100 mg catalyst at the end of 5 min for the
methanolysis reaction. Subsequently, catalytic experiments
were carried out at different temperature values (0, 15, 25,
35 and 45 ꢂC) with 50 mg of catalyst under the same reac-
non-catalyst methanolysis reaction of NaBH4 is reported as
62.99 kj molꢀ1 in the literature.[43] This result shows that
the p(2-VP) supported Ru(II) catalyst material is comparable
to expensive catalyst systems (Table 2).
lnk ¼ lnA – ðEa=RTÞ
(4)
Conclusions
In this study, p(2-VP) polymer was first synthesized by pho-
topolymerization method. Then polymer supported Ru(II)
material was prepared using the tri-dentate benzimidazole-
type ligand 2,6-bis(2-benzimidazolyl)pyridine ligand and tion conditions and the highest volume of genereated hydro-
p(2-VP) polymer. The catalytic performance of supported gen was observed as 201 0.4 mL for 45 ꢂC. The activation

8
M. TERCAN ET AL.
Figure 9. The effect of temperature on methanolysis of NaBH4 (a) Arrhenius equation (lnk versus 1/T graph) (b).
Table 2. The completion times of the NaBH4 methanolysis reaction and the
maximum generated H2 volumes at different temperature values.
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