Polymer-graphene hybrid stabilized ruthenium nanocatalysts for the dimethylamine-borane dehydrogenation at ambient conditions

Article abstract of DOI:10.1016/j.molliq.2019.02.003

In this work, we reported a new catalyst consistent of graphene oxide (GO) – poly(N-vinyl-2-pyrrolidone) (PVP) hybrid supported ruthenium nanoparticles and called as Ru@GO-PVP. The GO-coupled PVP nanosheets were prepared with a new and straightforward pathway. The prepared Ru@GO-PVP nanocatalysts were characterized using some advanced analytic measurements such as XPS (X-ray photoelectron spectroscopy), XRD (X-ray diffraction), TEM/HRTEM (Transmission electron microscopy/high resolution transmission electron microscopy), Raman and ICP (Inductively coupled plasma). The mean particle size of the catalyst was found to be 2.09 nm, and this catalyst having small particle size showed one of the highest catalytic activities with a very high TOF value of 896.54 h^?1 in dehydrogenation of DMAB at room temperature. Therefore, the proposed hybrid and supported catalyst offer a new pathway to enhance the catalytic dehydrogenation of DMAB greatly, and this study presents a universal and powerful technique for such applications.

Full text of DOI:10.1016/j.molliq.2019.02.003

Accepted Manuscript
Polymer-graphene hybrid stabilized ruthenium nanocatalysts for
the dimethylamine-borane dehydrogenation at ambient conditions
Betül Şen, Ayşenur Aygün, Aysun Şavk, Sibel Duman, Mehmet
Harbi Calimli, Ela Bulut, Fatih Şen
PII:
S0167-7322(18)36896-X
DOI:
https://doi.org/10.1016/j.molliq.2019.02.003
MOLLIQ 10403
Reference:
To appear in:
Journal of Molecular Liquids
Received date:
Revised date:
Accepted date:
31 December 2018
25 January 2019
1 February 2019
Please cite this article as: B. Şen, A. Aygün, A. Şavk, et al., Polymer-graphene hybrid
stabilized ruthenium nanocatalysts for the dimethylamine-borane dehydrogenation at
ambient conditions, Journal of Molecular Liquids, https://doi.org/10.1016/
j.molliq.2019.02.003
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ACCEPTED MANUSCRIPT
Polymer-Graphene Hybrid Stabilized Ruthenium Nanocatalysts for the
Dimethylamine -Borane Dehydrogenation at Ambient Conditions
1
,£
1,£
1
2
1,3
Betül Şen , Ayşenur Aygün , Aysun Şavk , Sibel Duman , Mehmet Harbi Calimli ,
1
,4
1*
Ela Bulut , Fatih Şen
1
Sen Research Group, Department of Biochemistry, Faculty of Arts and Science, Dumlupınar
University, Evliya Çelebi Campus, 43100 Kütahya, Turkey
2
Department of Chemistry, Faculty of Arts and Science, Bingol University, Bingöl, Turkey
3
Department of Environmental Engineering, Faculty of Engineering, University of Igdir, Igdir, Turkey
4
Department of Electrical and Electronics Engineering, Faculty of Engineering, University of Hitit,
Çorum, Turkey
*Corresponding authors: fatihsen1980@gmail.com
£
These authors equally contributed this work.
Abstract
In this work, we reported a new catalyst consistent of graphene oxide (GO) – poly(N-vinyl-
2
-pyrrolidone) (PVP) hybrid supported ruthenium nanoparticles and called as Ru@GO-PVP.
The GO-coupled PVP nanosheets were prepared with a new and straightforward pathway.
The prepared Ru@GO-PVP nanocatalysts were characterized using some advanced analytic
measurements such as XPS (X-ray photoelectron spectroscopy), XRD (X-ray diffraction),
TEM/HRTEM (Transmission electron microscopy/high resolution transmission electron
microscopy), Raman and ICP (Inductively coupled plasma). The mean particle size of the
catalyst was found to be 2.09 nm, and this catalyst having small particle size showed one of
-1
the highest catalytic activities with a very high TOF value of 896.54 h in dehydrogenation
of DMAB at room temperature. Therefore, the proposed hybrid and supported catalyst offer
a new pathway to enhance the catalytic dehydrogenation of DMAB greatly, and this study
presents a universal and powerful technique for such applications.
Keywords: Dehydrogenation; DMAB; GO-coupled PVP Nanosheets; Polymer-Graphene
Hybrid; Nanocatalyst.
1

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1.
Introduction
Hydrogen gas is generally considered as clean, renewable, environmental energy source and
used in electricity generation. But, a big problem for a hydrogen economy is unable to store
hydrogen. Among the available hydrogen sources, ammonia borane derivations have
increasing attention because of their high hydrogen content, availability, stability, ease of
use and non-flammability [1-2]. However, they cannot be used as a hydrogen source without
a suitable catalyst. A presence of a suitable catalyst in a dehydrogenation reaction of
ammonia borane derivatives at ambient conditions can easily produce hydrogen. So far, for
this purpose, several types of catalysts have been used in hydrogen generation from
ammonia borane derivations. Generally, nanocatalysts have been used for the hydrogen
generation from ammonia borane derivations due to their high catalytic activity and small
particle size [3-20]. The usage of dimethylamine borane (DMAB, (CH ) NHBH )) which is
3
2
3
one of the ammonia borane derivatives has received significant attention because of its
advantages such as stability, non - toxicity and environmentally-friendly. So far, the studies
conducted for the hydrogen generation from dimethylamine borane have revealed that
DMAB is a one of the best hydrogen sources compared to the other ammonia borane
5
derivations as shown in Scheme 1 [21-30]. For dehydrogenation of DMAB, [ C H -
5
3
1
,3(SiMe ) ) Ti] has shown one of the best catalytic activity [31] in the hydrogen
3 2 2 2
generation from DMAB as a homogenous catalyst. In prepared catalysts, mostly Ru based
nanomaterials have great catalytic activity compared to the others as shown in Table 1. For
this purpose, in this study, we have prepared a new Ru based nanocatalyst having some
significant advantages such as high reusability, recovery and catalytic activity. Further, the
scientist has also used many supporting agent such as carbon and polymer derivatives. [7,
1
4, 30]
Scheme 1. The catalytic dehydrocoupling of DMAB.
Hitherto, several studies have arisen dealing with graphene oxide as a support material due to
its high electrical conductivity, stability and specific surface area for the preparing catalyst [6-
7
]. Metal nanocatalyst composed of graphene oxide as supporting materials have shown high
catalytic activity, stability and synergistic effect for hydrogen generation and hydrogen
applications [10, 26, 27]. However, there are some critical issues with graphite oxide as a
2

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supporting material: (1) Irreversibly restacking of GO sheets resulting from their strong
interactions causes most catalyst nanoparticles to be embedded between GO layers and
unavailable to reactants [32]. (2) Due to the high surface energy and poor interaction on the
GO surface, the dissolution and sintering of the nanoparticles reduce nanocatalyst activity in
fuel cells [33]. (3) Due to the carbon corrosion of the graphene oxide, the structural integrity
of the nanocatalyst is dissipated so that the nanoparticles are dispersed [34-36] and thus
reduce the usage of nanocatalyst. To solve the mentioned above problems, various strategies
have been tested such as making spaces between the graphene oxide layers, surface
applications of GO for preventing carbon corrosion and spontaneously stabilize nanoparticles
on the GO [37, 38]. It is extremely difficult to develop a nanocatalyst based graphene oxide
that can address all the above problems. In this study, we report preparation of Ru @GO-PVP
(poly(N-vinyl-2-pyrrolidone)) nanocatalyst and a one-step preparation method prevention
interaction between graphene oxide sheets. The mentioned method gives a new aspect for
solving the main problems. To accomplish this at the beginning, the nanoparticles facilitate
the mass transfer that allowing more contact with the active site in the catalyst, that allows the
catalyst to be used in an efficient manner [39, 40]. In the second stage PVP particles having
stable manner are stacked between the GO layers that give a stable structure to GO, hence the
corrosion of GO is prevented [39, 40]. At the last stage, compared to GO, PVP is more
compatible with inorganic materials and a conductive material. At the same time, PVP, which
contains more nitrogen atoms, provides a controllable structure with metal nanoparticles, and
that enhance anchor effects [14]. The PVP coupled GO nanoparticles prepared according to
the described methods both have acquired a more stable structure and can be used effectively.
So, prepared PVP-GO systems can be used actively in hydrogen applications. For this reason,
in this work, the preparation of PVP-GO decorated Ru nanoparticles (Ru@GO-PVP), its
outstanding catalytic activity in the dehydrogenation of DMAB and its characterization were
investigated. In the study, the preparation of the catalyst was carried out by the ultrasonic
reduction method (given later); hence the stability of the Ru@GO-PVP catalyst was ensured.
The characterization of Ru@GO-PVP catalyst was investigated using advanced analytical
techniques such as TEM, HRTEM, ICP, XPS, and Raman.
Experimental methods
The preparation of Ru@GO-PVP Nanocatalysts
3

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The preparation route for Ru@GO–PVP nanocatalysts is explained as below. The synthes of
graphene oxide from graphite powder was performed according to Hummer’s method as
shown in Supporting Information. For this purpose, a required amount of GO obtained from
powder graphite powder was mixed in pure water using ultrasonic method for 2 h, then the
same amount of water and PVP were transferred into the GO mixture, at last, the resulting
slurry was stirred for another 2 h. At the end of this time, a solution containing 148 mg
DMAB and 2 ml 0.01 M RuCl was added into the above mixture under the same condition.
3
o
The resulting solution was stirred in reflux at 90 C temperature for 2 h. The obtained solid
Ru@GO–PVP nanocatalysts was centrifugated, washed with distilled water and ethanol. The
o
catalyst was dried in a vacuum oven at 25 C. Ruthenium nanocatalysts decorated with
graphene oxides or poly(N-vinyl-2-pyrrolidone) were also prepared according to the
procedure given above, the prepared catalyst system was indicated as Ru@GO and Ru@PVP
nanocatalysts, respectively.
Results and discussion
The analytical techniques and characterization of Ru@GO-PVP Nanocatalysts
Analytical investigations of catalytic performances of the prepared Ru@GO-PVP
nanocatalysts and reusability of Ru@GO-PVP nanocatalysts have examined after fully
characterization of prepared nanomaterials. For this purpose, firstly, the Ru@GO-PVP
nanocatalysts have been characterized using TEM, HRTEM, ICP, XPS, and Raman
techniques. The chemical composition and particle size of Ru@GO-PVP nanocatalysts were
also investigated using TEM analysis, given in Fig. 1a. HR-TEM (high-resolution
transmission electron microscopy) analysis was conducted to reveal the composition and
morphology of Ru@GO-PVP nanocatalysts in more detail; the results are given in Fig. 1b.
According to the data of HR-TEM, whole particles of the prepared catalyst have a spherical
shape, and any agglomeration wasn’t observed in the preparation of the catalyst. And again,
thanks to HR-TEM analysis, the atomic lattice fringes on the catalyst have been revealed in
Fig. 1b. Further, the mean particle size of Ru@GO-PVP nanocatalysts was found to be 2.09 ±
0
.23 nm as shown in Figure 1c. The calculated fringes for Ru (111) were found to be 0.21 nm
which is the same as nominal Ru (111) space of 0.21nm [9, 27]. The EELS line profile also
indicates the existence of the Ruthenium in prepared nanomaterials as shown in Figure 1d.
4

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Figure 1. (a) The TEM (b) HR-TEM image (c) the mean particle size (d) the EELS line profile
scanned on the arrow shown in HRTEM for ruthenium elements of Ru@ GO-PVP nanocatalysts.
The electronic structure for ruthenium on the catalyst, its surface distribution on Ru@GO-
PVP nanocatalysts were investigated by XPS analysis. Fig 2a shows XPS data of Ru 3p
region on Ru@GO-PVP nanocatalysts. As shown in this figure, two apparent peaks are seen
for Ru (3p) at 483.5 eV and 487.4 eV which can be ascribed to metallic ruthenium and
ruthenium oxy and/or hydroxyl species, respectively [41]. These results revealed that
ruthenium atoms present on the catalysts are in mostly metallic state.
5

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Figure 2. (a) Ru (3p) XPS spectra (b) The Raman spectra of Ru@GO-PVP nanocatalysts.
In addition to the analytical techniques given above, Raman spectroscopy was also conducted
for understanding the ordered and disordered carbon in the catalyst, data in Raman
spectroscopy for GO, GO-PVP and Ru@GO-PVP are given in Fig. 2b. Two distinct peaks in
-1
the range 1348, and 1599 cm can be associated with D band and G-band of the carbon atom
for GO, GO-PVP, and Ru@ GO-PVP, respectively. The degrees of defect for GO-PVP could
be determined by using the intensity ratio of D/G (ID/IG) for GO, GO-PVP, and Ru@GO-
PVP, and ID/IG were found to be 0.92, 1.03 and 1.05 for GO, GO-PVP, and Ru@GO-PVP,
respectively. This data proves the formation of Ru@GO-PVP.
The catalytic performance of monodisperse Ru@GO-PVP nanocatalysts
After fully characterization of prepared nanomaterials, the catalytic experiments related to the
dehydrogenation of DMAB were performed with the help of Ru@GO-PVP nanocatalysts and
the results showed that Ru@GO-PVP nanoparticles have very high catalytic activity and
efficiency. In those experiements, the hydrogen generation began linearly and continued until
6

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the end of the catalytic reaction of dehydrogenation of DMAB. After the dehydrogenation
reaction of DMAB, the complete conversion of DMAB (CH ) NHBH (δ= ~-12.7 ppm) to
3
2
3
[
(CH ) NBH ] (δ= ~5 ppm) were shown with the help of NMR. The results of experiments
3 2 2 2
conducted for dehydrogenation of DMAB with Ru@GO-PVP nanocatalysts at different
o
temperatures in the range of 20- 35 C are given in Fig. 3a. Furthermore, Fig. 3b (Arrhenius
plot) and Fig. 3c (Eyring plot) were used to determine the activation energy (E as 11.45 ± 2
a
#
-1
#
kJ/mol), activation enthalpy (∆H = 8.96 kJ mol ) and activation entropy (∆S = -194.02 J mol-
-1
1
K ) for dehydrogenation of DMAB catalyzed Ru@GO-PVP nanocatalysts. It can be stated
that the high negative value of entropy indicate that a associative mechanism in the
conversion process of DMAB with Ru@GO-PVP nanocatalysts. The recycle performance for
dehydrogenation of DMAB catalyzed by Ru@GO-PVP nanoparticles were performed after
the fifth run of catalytic reaction by adding the same amount of DMAB. The intial catalytic
th
performance of Ru@GO-PVP nanocatalysts was found to be 78 % even after the 5 run (Fig.
S1) for dehydrogenation of DMAB. The decrease in the catalytic activity occurring in the
catalyst may be related to the decreasing active sites of catalyst due to the covering of the
th
active zones of catalysts with the resulting products at the end of the 5 cycle. Besides, ICP
analysis revealed that there were no leaching problems, which means that the catalyst
maintained its initial content.
7

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Figure 3. (a) % conversion/Time (b) In k/(1/T) (c) In (k/t)/(1/T) plots for dehydrogenation of DMAB
catalyzed by Ru@PVP-GO nanocatalysts at various temperatures.
8

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Fig. 4 (a) Graph of nH /nDMAB versus time for the dehydrogenation of DMAB with different amount
2
of Ru@GO-PVP nanocatalysts at room temperature. (b) Graph of nH /nDMAB versus time for the
2
dehydrogenation of DMAB with different amount of substrate concentrations at room temperature.
Besides, the results of a set of experiments with different nanocatalyst concentration in the
range of 2.25-9.00 mM at room temperature are given in Figure 4a. As shown in the inset plot
of this figure, the logarithmic function of H production rate is nearly first (0.8066) order with
2
respect to the catalyst concentration. Further, as shown in the inset plot of Figure 4b, the
logarithmic function of hydrogen production rate is also nearly first (0.9059) order depending
upon the substrate concentration (75, 100, 125, 150 mM). It can be stated that, the rate law for
this reaction can be written by;
ꢉ
ꢉ
ꢉ ꢉ
ꢉ
ꢂꢁꢃꢄꢅꢆꢇꢈ ꢆꢊꢋꢆꢇꢌ
ꢂꢃꢄꢄꢅꢆꢇꢈ ꢊꢋꢆ ꢈ ꢌ
ꢂꢍ
ꢃꢆ ꢌ
0
.8066
0.9059
ꢀ
ꢁ
ꢎꢏꢁ
ꢎꢏ ꢂꢍ ꢁꢎꢃꢐꢑꢒꢌ
.[DMAB]
ꢂꢍ
The hydrogen evaluation (1.0 mol H /mol DMAB) from the dehydrogenation reaction of
2
-
DMAB catalyzed by Ru@GO-PVP nanoparticles was completed with TOF value of 896.54 h
1
at room temperature. This current study showed that Ru@GO-PVP nanocatalyst has showed
-1
very good catalytic activity (896.54 h ) for catalytic dehydrogenation of DMAB. Table 1
shows a comparison of different catalyst TOF values for catalytic dehydrogenation of DMAB.
Compared to the TOF values of the catalysts given in this table, it is clear that the obtained
9

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-1
value (896.54 h ) for the Ru@GO-PVP catalyst is really high compared to the others. Thus,
the obtained Ru@GO-PVP catalyst stabilized with GO-PVP is the catalyst showing very good
stability and activity for the catalytic dehydrogenation of DMAB. Additionally, the catalytic
activities of Ru@PVP, Ru@GO, and Ru@GO-PVP nanoparticles were tested, compared for
dehydrogenation of DMAB, and their results are also given in Table 1. It is easy to see that
the catalytic activity of Ru@GO-PVP nanocatalyst is very high compared to other prepared
catalysts in this study. This is mainly due to the large surface area provided by GO-PVP and
the synergistic effect of GO-PVP with the monodisperse distribution of Ru metal. The method
used to prepare the obtained catalyst is very effective, easy, controllable, understandable, and
this method can be used to prepare very high catalytic activity materials for fuel cells. The
materials used in the preparation of catalysts have porous structures that enable a large surface
area and homogeneous distribution of metal nanoparticles for dehydrogenation of DMAB.
Table 1. The comparison of TOF values for dehydrocoupling of DMAB.
-
Catalysts
Conversion TOF (h Reference
1
(
%)
)
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
Ru@GO-PVP
Ru@GO
100
100
100
90
896.54
361.66
403.67
7.9
This study
This study
Ru@PVP
This study
RhCl₃
8
Pd/C
95
2.8
8
trans-RuMe₂(PMe₃)₄
Cp₂Ti
100
100
95
12.4
12.3
0.7
8
10
8
[Ir(1,5-cod)m-Cl]₂
[Rh(1,5-cod)(dmpe)]PF₆
[Rh(1,5-cod)m-Cl]₂
[Rh(1,5-cod)₂]Otf
[RuH(PMe₃)(NC2H4PPr₂)₂]
IrCl₃
95
1.7
8
0
1
2
3
4
5
6
7
8
9
100
95
12.5
12.0
1.5
8
8
100
25
9
0.3
8
[Cr(CO)₅(thf)]
Rh(0)/[Noct₄]Cl
[RhCl(PHCy₂)₃]
RhCl(PPh₃)₃
97
13.4
8.2
11
8
90
100
100
100
100
2.6
12
8
4.3
(Idipp)CuCl
0.3
15
13
Ni(skeletal)
3.2
1
0

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2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
[Cp*Rh(m-Cl)Cl]₂
100
97
0.9
16
11
8
1
[Cr(CO)₅(ɳ -BH3NMe₃)]
19.9
1.6
Ru(cod)(cot)
40
RuCl₃.3H2O
77
2.7
8
[(C₅H₃-1,3(SiMe₃)₂)₂Ti]₂
[Ru(1,5-cod)Cl₂]n
HRh(CO)(PPh₃)₃
trans-PdCl₂(P(o-tolyl)₃)₂
Pt(0)/BA
100
70
420.0
2.5
31
8
5
0.1
8
20
0.2
8
100
100
100
100
100
100
100
100
100
100
100
100
24.88
31.24
15.0
34.14
330
17
17
22
19
14
42
43
44
45
46
47
48
Pt(0)/TBA
Pt(0)/AA
Pt(0)/TPA@AC
PdCo@PVP
RuPtNi@GO
727
RuCo@ƒ-MWCNT
PdNi@PEDOT
Pt@PANI-rGO
PdNi@GO
775.28
451.28
42.94
271.90
38.02
70.28
Pd@GO
Pt NPs@CBH
Conclusions
In this study, we have shown the preparation GO, PVP and GO-PVP nanocatalysts decorated
ruthenium nanomaterials using an efficient, controllable, understandable process in
dehydrogenation reaction of DMAB. With this method, a uniform distribution of the
ruthenium metal nanoparticles on the GO-PVP materials having stable structure was achieved
using a reduction of ruthenium with one step stage. The characterization of Ru@GO-PVP
nanocatalyst was performed by advanced analytic techniques such as XPS, XRD, TEM-
HRTEM, ICP, and Raman spectroscopy. The mean particle size of monodisperse Ru@GO–
PVP nanocatalyst was found to be 2.09±0.23 nm. The obtained TOF value for Ru@GO–PVP
in the catalytic reaction of DMAB was compared to the previous studies (Table 1) and the
catalytic reactions and the analytical techniques revealed that Ru@GO-PVP nanocatalyst has
-1
a very high catalytic activity with a unique TOF value of 896.54 h at room temperature. The
investigation of kinetic studies was performed to find activation parameters such as activation
1
1

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#
-1
energy (E as 11.45 ± 2 kJ/mol), activation enthalpy (∆H = 8.96 kJ mol ) and activation
a
#
-1
-1
entropy (∆S = -194.02 J mol K ) for dehydrogenation of DMAB catalyzed by Ru@GO-
PVP nanocatalysts. As a result of an investigation of the kinetic studies, we have reached that
the very high negative value of entropy indicate that an associative mechanism in the
conversion process of DMAB with the help of Ru@GO-PVP nanocatalysts. The reusability
experiments revealed that Ru@GO-PVP nanocatalysts have a heterogeneous and isolable
th
structure in dehydrogenation reaction even after 5 runs, it remained the initial catalytic
o
activity of 79 % with complete conversion DMAB at 25 C. Besides, H production rate
2
showed that it is first (0.8066) order with respect to both the catalyst and substrate
concentration. Analytic techniques used in the study showed that GO-PVP has a large surface
area and a great enhanced monodisperse distribution of Ru nanometals with a synergistic
effect for the dehydrogenation of DMAB. In summary, the method used in the study offers a
new, effective and easy way to prepare nanomaterials for fuel cells and extensive applications
in other catalytic reactions with high activities.
Acknowledgments
The authors would like to thank DPU-BAP (2015-50 and 2014-05) for the financial support.
The authors would like to thank to Dr. Mehmet Kahraman for Raman measurements.
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Graphical abstract
Highlights


The synthesis and characterization of Ru NPs @GO-PVP for hydrogen evolution
reaction
Ru NPs decorated on Graphene Oxide- Polyvinylpyrrolidone as highly efficient and
stable catalysts


Monodisperse Ru@GO-PVP provides one of the record catalytic performances
Ru@GO-PVP catalysed dehydrocoupling of DMAB depending upon catalyst and
substrate concentration.
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