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Carbon-nanotube-based rhodium nanoparticles as highly-active catalyst for hydrolytic dehydrogenation of dimethylamineborane at room temperature
Accepted Manuscript Carbon-nanotube-based Rhodium Nanoparticles as Highly-active Catalyst for Hydrolytic Dehydrogenation of Dimethylamineborane at Room Temperature Serdar Günbatar, Aysenur Aygun, Yaşar Karataş, Mehmet Gülcan, Fatih Şen PII: DOI: Reference:
S0021-9797(18)30748-3 https://doi.org/10.1016/j.jcis.2018.06.100 YJCIS 23791
To appear in:
Journal of Colloid and Interface Science
Received Date: Revised Date: Accepted Date:
27 April 2018 29 June 2018 30 June 2018
Please cite this article as: S. Günbatar, A. Aygun, Y. Karataş, M. Gülcan, F. Şen, Carbon-nanotube-based Rhodium Nanoparticles as Highly-active Catalyst for Hydrolytic Dehydrogenation of Dimethylamineborane at Room Temperature, Journal of Colloid and Interface Science (2018), doi: https://doi.org/10.1016/j.jcis.2018.06.100
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Carbon-nanotube-based Rhodium Nanoparticles as Highly-active Catalyst for Hydrolytic Dehydrogenation of Dimethylamineborane at Room Temperature
Serdar Günbatara, Aysenur Aygunb, Yaar Karataa, Mehmet Gülcana*, Fatih enb* a
Chemistry Department, Faculty of Science, Van Yüzüncü Yıl University, Zeve Campus 65080 Van, Turkey, bSen Research Group, Biochemistry Department, Faculty of Arts and Science, Dumlupınar University, Evliya Çelebi Campus 43100 Kütahya, Turkey.
Abstract In this study, we present a carbon nanotube-based Rh nanomaterial as a highly active catalyst for the hydrolytic dehydrogenation of dimethylamine – borane (DMAB) at room temperature. The prepared multi-walled carbon nanotube based Rh nanoparticles, called Rh NPs@ MWCNT, was readily prepared, stabilized and effectively used for the hydrolytic dehydrogenation of DMAB under ambient conditions. Monodisperse Rh NPs@ MWCNT nanocatalyst was characterized by using advanced analytical methods such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM) etc. These analytical methods revealed that Rh nanoparticles on the surface of MWCNT were well dispersed and the average particle size was found to be 1.44 ± 0.17 nm. The catalytic experiments revealed that the new Rh NPs@MWCNT nanocatalyst has a high catalytic effect to obtain hydrogen in 3.0 equation from DMAB, and the record catalytic TOF value for the catalytic reaction catalyzed by Rh NPs@MWCNT nanocatalyst was found to be 3010.47 h-1 at room temperature. The current study presents the detailed kinetic studies of the hydrolytic dehydrogenation of DMAB catalyzed by Rh NPs@MWCNT, the results of catalytic experiments were performed at different temperatures, substrate and catalyst concentrations, the Rh NPs@MWCNT nanocatalyst was effectively used in the completion of the hydrolytic dehydrogenation of DMAB, and activation energy, enthalpy and entropy parameters. The experimental results showed that monodisperse Rh NPs@MWCNT nanocatalyst have record
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catalytic activity with TOF value of 3010.47 h-1, and Rh(0) nanoparticles were well dispersed on the multi-walled carbon nanotubes. Keywords:Catalyst, Hydrolytic dehydrogenation, MWCNT, Nanoparticle, Rhodium
Introduction Recently, the one of the most important obstacles to overcome with hydrogen technologies is the safe and efficient storage [1,2]. The need for large mass storage materials is increasing day by day. Because of hydrogen gas has a very low density; the liquefaction and compression of hydrogen gas are very difficult for the transportation at ambient conditions [3]. For this purpose, there are many compounds which have been used as solid hydrogen storage materials such as boron nitrogen (B-N) compounds (NH3BH3, NR3BH3 [4] (R-H or alkyl), chemical containing boron (LiBH4, [5] NaBH4, [6] Ca(BH4)2, [7] Mg(BH4)2 [8], hydrazine (N2H4), mesoporous-microporous materials [9] in recent times. B-N compounds appear to be more advantageous because of their high hydrogen storage capacity and the tendency to hold more hydrogen (with boron and nitrogen) among mentioned materials, this feature of the material allows charging and discharging of the material [10]. When compared to hydride and porous materials for the releasing and up taking of hydrogen, the above-mentioned properties at controllable temperature and pressure make the B-N compounds distinguishable. According to literature [11,12], the hydrolytic dehydrogenation of dimethylamine – borane (CH3)2NHBH3) was carried out by using an appropriate catalyst at room temperature. The hydrolytic dehydrogenation of DMAB has various advantageous. For instance, DMAB has very high water solubility in room temperature [11]. Further, the current solution with DMAB has a stable form across to self-hydrolysis at ambient conditions, and 3 moles of H2 can be obtained from 1 mole of DMAB in aqueous medium, but in only 1 mole H2 is obtained from 1 mole DMAB in an organic solution [13,14]. So far, polymer nanogel-supported Ni particles [15], RuNPs [12], Pd/C [14], NiSO4/Na2MoO4 [16,17], NiSO4/KReO4 [17] and NiSO4/Na2WO4 [17] have been tested as catalysts for the hydrolytic dehydrogenation of DMAB. Generally, all these catalysts are heterogeneous catalysts and their surface contain a few active atoms. So, the catalytic activity is restricted by the limited surface area in mentioned heterogeneous catalysts. Besides, the literature contains some semi-heterogeneous (metal nanoparticles) catalysts [18] which have been also used for the hydrolytic dehydrogenation of DMAB. Generally, metal nanoparticles can be dispersible in water to enhance catalyst surface. Such a pathway appears very promising way for rapid hydrogen
generation and high catalytic activity [19]. [ Therefore, it is necessary cessary to develop a metal nanocatalyst which is water-dispersible, dispersible, and which can be used in the hydrolyti hydrolytic dehydrogenation of DMAB. For this purpose, in this study, we present the preparation, characterization and the detailed kinetic studies of of Rh NPs@MWCNT nanocatalyst for the hydrolytic dehydrogenation of DMAB. Rh (0) nanoparticles were well-dispersed dispersed on multi walled carbon nanotube surface, and Rh NPs@MWCNT nanocatalyst was as obtained by reduction of Rh (III) to Rh(0) in an aqueous medium. medium The prepared Rh NPs@MWCNT nanocatalyst was used for the hydrolytic dehydrogenation of DMAB as shown in Scheme 1. The resulting Rh NPs@MWCNT nanocatalyst was characterized by using some advanced analytic methods such as TEM, XPS, XRD etc.
Scheme 1: The hydrolytic dehydrogenation of DMAB catalyzed by Rh NPs at room temperature
After catalytic experiments, a record turn over frequency fre y value (TOF) of 3010.47 h-1 was obtained for the hydrolytic dehydrogenation dehydro of DMAB catalyzed ed by Rh NPs@MWCNT nanocatalyst.
Experimental methods The preparation of Rh NPs@MWCNT nanocatalyst The preparation of Rh NPs@MWCNT nanocatalyst has been performed by using a facile impregnation method [20]. To prepare Rh NPs@MWCNT nanocatalyst,, briefly, 6.22 mg of rhodium (III) chloride and 150 mg of multi-walled multi walled carbon nanotube (previously functionalized according to our previous works, works as given in supporting information [21]) were added to 5.0 mL H2O, and the resulting solution was stirred at 600 rpm rpm for 2 hours. Then, 17.21 mg NaBH4 have been used to reduce Rh+3@MWCNT and to obtain the Rh NPs@MWCNT nanocatalyst.. The obtained NPs were washed with 3 x 10 mL H2O and dried in 150 oC for 45 min.
The catalytic experiments, kinetic and activation parameters of the hydrolytic dehydrogenation of DMAB catalyzed Rh NPs@MWCNT nanocatalyst In order to determine the effect of Rh nanocatalyst concentration on the hydrolytic dehydrogenation of DMAB catalyzed Rh NPs@MWCNT nanocatalyst, a serious experiment with various Rh concentration (0.685, 1.370, 2.055, 2.740 mM) were carried out at 1 mM of DMAB (10 mL). Another set of experiments with various DMAB concentrations (50, 100, 150, 200 mM) were performed at 2.74 mM of Rh at room temperature. Besides, the hydrolytic dehydrogenation of DMAB at 20, 25, 30, 35 °C with solution of 10 mL containing 200 mM of DMAB, 2.74 mM of Rh NPs. Activation parameters (Ea, S, H) were detected using various temperatures experiment data, and Arrhenius-Eyring plots [21].
Results and discussion The characterization of Rh NPs@MWCNT nanocatalyst Monodisperse Rh NPs@MWCNT was obtained by the reduction Rh (III) in the presence of NaBH4 medium containing multi-walled carbon nanotubes at mild conditions. Formation of an agglomerate and precipitate in the solution containing NaBH4 and Rh (0) nanoparticles was seen without using multi-walled carbon nanotubes. Because of this situation, it can be said that only chloride anion cannot be stabilize the solution medium of metal without carbon nanotube. In presence of multi-walled carbon nanotube nanomaterials in the solution, no participate or agglomeration occurs, and the resulting nanoparticles form a very stable structure [22]. This result shows that the stabilization of Rh nanoparticles was provided by multi-walled carbon nanotubes. Towards the end of the catalytic reaction, the light brown color turns into dark brown because of the reduction of Rh (III) to Rh (0). The formation of Rh NPs@MWCNT nanocatalyst can be seen in Fig. 1a by the help of TEM images. The related EDS diagram also indicates the existence of Rh in prepared nanoparticles as shown in Fig. 1b. The particle size of Rh NPs@MWCNT were investigated by using the TEM image and NIH image program [23]. More than 200 particles were counted and the results showed in Fig. 1c. The average particle size of Rh NPs@MWCNT nanocatalyst was found to be 1.44 ± 0.17 nm, and this size is in good agreement with Rh (0) nanoparticles [24].
Fig. 1 (a) TEM image; (b) EDS diagram (c) associated size histogram of of RhNPs@MWCNT nanocatalyst during the DMAB catalytic reaction at ambient conditions. condi
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Multi-walled carbon nanotubes-supported supported Rh (0) nanoparticles, obtained by the red reduction of Rh (III)/ multi walled carbon nanotubes precursor by b the help of NaBH4 at mild conditions, and were characterized terized using some other advanced analytical methods methods and isolated from the
reaction medium. XRD patterns of multi-walled carbon nanotubes (MWCNT) and multiwalled carbon nanotubes-supported Rh (0) nanoparticles (Rh NPs@MWCNT) in Fig. 2 (a-b) show the characteristic diffraction peaks of Rh at 25o, 44o, 47o, 70o, 78o assigned to the C (002), Rh (111), Rh (200), Rh (220), Rh (311) reflections [25,26]. This indicates that MWCNT maintains its crystallinity after the preparation of Rh (III)/ MWCNT and the formation of Rh (0) in the presence of NaBH4. The crystallite size of Rh NPs@MWCNT nanocatalyst was calculated using Debye-Scherrer equation to be 1.9 nm.
Fig. 2 XRD spectra of multi-walled carbon nanotubes (MWCNT) and; multi-walled carbon nanotubes-supported Rh (0) nanoparticles (Rh NPs@MWCNT) (theoretical Rh loading on multiwalled carbon nanotubes is 5.0% wt)
The oxidation state and surface composition of Rh NPs@MWCNT nanocatalyst were investigated by X-ray photoelectron spectroscopy (XPS) analysis. The survey and high resolution Rh 3d XPS spectra of Rh NPs@MWCNT nanocatalyst together with its deconvoluted chemical states are seen in Fig. 3 (a-b). Fig. 3 (a) shows the photopics of Rh with C and O atoms forming the carbon nanotube. Fig. 3 (b) contains two distinctive peaks for Rh 3d3/2 and 3d5/2 feature give two distinct peaks at 311.8 and 306.9 eV, corresponding to the Rh (0) 3d5/2 (metallic Rh NPs) and Rh (IV) 3d3/2 [27]. These two peaks occur during getting XPS analyze due to the formation Rh (IV) oxide on surface the catalyst [28].
Fig. 3 Survey (a) and Rh 3d region high-resolution (b) XPS spectra of Rh NPs@MWCNT nanocatalyst
The hydrolytic dehydrogenation reaction of DMAB catalyzed Rh NPs@MWCNT nanocatalyst was shown in Scheme 1. The 11B-NMR spectra of DMAB were taken at the end of catalytic reaction in order to characterize the products. The
11
B-NMR spectra of DMAB
and the reaction solution obtained at the end of the hydrolytic dehydrogenation of DMAB are given in Fig. 4, showing that the quartet signal of DMAB at −16.50 ppm is completely converted to the singlet of the borate anion at 4.88 ppm [12,29].
Fig. 4 11B-NMR spectra of aqueous DMAB (down) and the reaction solution obtained at the end of the Rh NPs@MWCNT catalyzed hydrolytic dehydrogenation of DMAB (up).
The detailed kinetic studies of the hydrolytic dehydrogenation of DMAB catalyzed by Rh NPs@MWCNT The H2 production from the hydrolytic dehydrogenation of DMAB with various Rh NPs@MWCNT nanocatalyst concentrations at room temperatures are seen in Fig. 5. The catalytic reaction of DMAB using Rh NPs@MWCNT nanocatalyst was completed shortly (average in 7 minutes) and 3 moles of H2 were obtained at room temperature. As seen in Fig.
3, the amount of H2 released increases almost linearly with the increase in the amount of catalyst (Fig. S1). A graphic for a rate versus Rh NPs@MWCNT nanocatalyst concentration between ln(k) and ln(cat.) forms a straight line with a slope of 1.055 (Fig. S2). The result revealed that the rate of catalytic reaction of DMAB catalysed by Rh NPs@MWCNT nanocatalyst was corresponded with the first-order equation. A set of different experiments were carried out to determine the effect of DMAB concentration on the catalytic reaction with the same catalyst concentration at room temperature. The results at different DMAB concentrations are given in Fig. 6. A plot for a rate versus for different DMAB concentrations between ln(k) and ln(DMAB) forms a slope of 0.196 (as shown in Fig. S3). This result indicates that the catalytic reaction of DMAB using Rh NPs@MWCNT nanocatalyst is compatible with zero-order dependence. The results of reactions were also conducted at different temperatures (20, 25, 30, 35 °C) for the hydrolytic dehydrogenation of DMAB catalysed by Rh NPs@MWCNT nanocatalyst is given in Fig. 7. As seen in the Fig. 7 the volume of H2 released increases with the increasing temperature. The results of catalytic reaction showed that Rh NPs@MWCNT nanocatalyst highly catalyzed the hydrolytic dehydrogenation of DMAB at room temperature with a record turnover frequency value of 3010.47 h-1 and 3 moles of H2.
Fig. 5 The rate of [H2]/[DMAB] versus time for the hydrolytic dehydrogenation of DMAB catalysed different Rh NPs@MWCNT nanocatalyst with a solution containing 100 mM (CH3)2NHBH3 in various Rh NPs@MWCNT nanocatalyst concentrations corresponding to [Rh]= 0.69, 1.37, 2.06, 2.74, 1.5 mM at 25 ± 0.5 oC.
Fig. 6 The rate of [H2]/[DMAB] versus time for the hydrolytic dehydrogenation of DMAB catalyzed Rh NPs@MWCNT nanocatalyst with different DMAB concentrations at room temperature.
Fig. 7 The rate of [H2]/[DMAB] versus time for the hydrolytic dehydrogenation of DMAB catalyzed RhNPs@MWCNT nanocatalyst at various temperatures.
Activation energy (Ea = 96.83 kJ.mol-1), enthalpy (H = 93.69 kJ mol−1) and entropy (S = 90.68 J mol-1K-1) values were calculated using Fig. 7. Arrhenius [30] and Eyring [31] equations (Fig. S5) have been used for those calculations of the hydrolytic dehydrogenation of DMAB catalysed by Rh NPs@MWCNT nanocatalyst. The reaction rate constant was obtained from the almost linear portion of the generation H2 versus time plot in the range of
temperature 20-35 oC. Monodisperse Rh NPs@MWCNT nanocatalyst has been found to be heterogeneous catalyst by the help of the mercury m poison experiments as shown in Figure S6 [32,33]. The decreasing catalytic activity with adding mercury mercury shows that Rh NPs@MWCNT nanocatalyst is heterogeneous. For the reusability experiements, the obtained Rh NPs@MWCNT nanocatalyst was precipitated and formed colorless solution. The isolated bulk Rh had noo activity on the catalytic ca activity of DMAB (Fig. 8), ), but well dispersed Rh NPs@MWCNT nanocatalyst maintained its catalytic activity at 68 % at even 8th cycle at the same time. As a result, ult, the obtained Rh NPs@MWCNT nanocatalyst is a complementary factor for the catalytic reaction of DMAB in water. The TO TOF value (3010.47 h-11) found is the highest value among previous studies such as polymer nanogel-supported supported Ni particles (TOF = 376 h-1) [15], RuNPs NPs (TOF = 500 h-1) [12], NiSO4/Na2MoO4 (TOF = 2.8 h−1) [16 16,17]; NiSO4/ KReO4 (TOF = 3.6 h−1) [17]; carbon arbon supported Pd (TOF = 30 h−1) [14]; NiSO4/Na2WO4 (TOF = 4.2 h−1) [17]. ;ĂͿ
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ZƵŶ Fig. 8 The volume of H2 versus time for Rh NPs@MWCNT nanocatalyst (in 1st ( ) and 2nd ( ) runs 3rd ( ) 4th ( ) 5th ( ) 6th ( ) 7th ( ) 8th ( ) catalyzed hydrolytic dehydrogenation of DMAB at rroom temperature.
Conclusions The findings and results about the hydrolytic dehydrogenation dehyd of DMAB catalyzed by Rh NPs@MWCNT nanocatalyst obtained in this study can be summarized as follows follows:
Rh NPs@MWCNT nanocatalyst was prepared in a stable form using RhCl3H2O and multi-walled carbon nanotubes at mild conditions by using a facile impregnation method. A set of advanced analytic methods such as TEM, XPS,
11
B-NMR, XRD etc. were
used to characterize the formation of well-dispersed Rh NPs@MWCNT nanocatalyst of 1.44 ± 0.17 nm size (as Rh (0) stabilized by multi-walled carbon nanotubes). The hydrolytic dehydrogenation of DMAB with Rh NPs@MWCNT nanocatalyst was occurred even at low (20 °C) temperature with 3 moles of H2. The resultant Rh NPs@MWCNT nanocatalyst was determined for the completion catalytic reaction of DMAB with a highest catalytic activity (TOFinitial = 3010.47 h−1) for the hydrolytic dehydrogenation of DMAB under mild conditions. The kinetic studies, the activation energy (Ea = 96.83 kJ mol−1), enthalpy and entropy values (H = 93.69 kJ mol−1; S = 90.68 J mol-1K-1) were calculated for the hydrolytic dehydrogenation of DMAB catalyzed by monodisperse rhodium nanoparticles using Arrhenius and Eyring plots. Besides, the restricted catalytic activity by adding mercury can be apparent evidence for heterogeneity of the catalysis. Thanks to the ultra-small sizes, monodispersity and high Rh (0) % surface of novel catalyst The prepared Rh NPs@MWCNT nanocatalyst can have a great potential in both fuel cells and other catalysis reactions in near future in terms of high catalytic activity and stability by the help of carbon nanotube.
Acknowledgements The authors would like to thank to Yuzuncu Yil University and Dumlupinar University BAP for financial support (2014-05).
Notes and references
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;DĞϮE,ϮͿϮ Monodisperse Rh NPs@MWCNT catalyst showed excellent catalytic activity and the shortest reaction time for the hydrolytic dehydrocoupling of DMAB [(CH3)2NHBH3)].
S0021-9797(18)30748-3 https://doi.org/10.1016/j.jcis.2018.06.100 YJCIS 23791
To appear in:
Journal of Colloid and Interface Science
Received Date: Revised Date: Accepted Date:
27 April 2018 29 June 2018 30 June 2018
Please cite this article as: S. Günbatar, A. Aygun, Y. Karataş, M. Gülcan, F. Şen, Carbon-nanotube-based Rhodium Nanoparticles as Highly-active Catalyst for Hydrolytic Dehydrogenation of Dimethylamineborane at Room Temperature, Journal of Colloid and Interface Science (2018), doi: https://doi.org/10.1016/j.jcis.2018.06.100
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Carbon-nanotube-based Rhodium Nanoparticles as Highly-active Catalyst for Hydrolytic Dehydrogenation of Dimethylamineborane at Room Temperature
Serdar Günbatara, Aysenur Aygunb, Yaar Karataa, Mehmet Gülcana*, Fatih enb* a
Chemistry Department, Faculty of Science, Van Yüzüncü Yıl University, Zeve Campus 65080 Van, Turkey, bSen Research Group, Biochemistry Department, Faculty of Arts and Science, Dumlupınar University, Evliya Çelebi Campus 43100 Kütahya, Turkey.
Abstract In this study, we present a carbon nanotube-based Rh nanomaterial as a highly active catalyst for the hydrolytic dehydrogenation of dimethylamine – borane (DMAB) at room temperature. The prepared multi-walled carbon nanotube based Rh nanoparticles, called Rh NPs@ MWCNT, was readily prepared, stabilized and effectively used for the hydrolytic dehydrogenation of DMAB under ambient conditions. Monodisperse Rh NPs@ MWCNT nanocatalyst was characterized by using advanced analytical methods such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM) etc. These analytical methods revealed that Rh nanoparticles on the surface of MWCNT were well dispersed and the average particle size was found to be 1.44 ± 0.17 nm. The catalytic experiments revealed that the new Rh NPs@MWCNT nanocatalyst has a high catalytic effect to obtain hydrogen in 3.0 equation from DMAB, and the record catalytic TOF value for the catalytic reaction catalyzed by Rh NPs@MWCNT nanocatalyst was found to be 3010.47 h-1 at room temperature. The current study presents the detailed kinetic studies of the hydrolytic dehydrogenation of DMAB catalyzed by Rh NPs@MWCNT, the results of catalytic experiments were performed at different temperatures, substrate and catalyst concentrations, the Rh NPs@MWCNT nanocatalyst was effectively used in the completion of the hydrolytic dehydrogenation of DMAB, and activation energy, enthalpy and entropy parameters. The experimental results showed that monodisperse Rh NPs@MWCNT nanocatalyst have record
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catalytic activity with TOF value of 3010.47 h-1, and Rh(0) nanoparticles were well dispersed on the multi-walled carbon nanotubes. Keywords:Catalyst, Hydrolytic dehydrogenation, MWCNT, Nanoparticle, Rhodium
Introduction Recently, the one of the most important obstacles to overcome with hydrogen technologies is the safe and efficient storage [1,2]. The need for large mass storage materials is increasing day by day. Because of hydrogen gas has a very low density; the liquefaction and compression of hydrogen gas are very difficult for the transportation at ambient conditions [3]. For this purpose, there are many compounds which have been used as solid hydrogen storage materials such as boron nitrogen (B-N) compounds (NH3BH3, NR3BH3 [4] (R-H or alkyl), chemical containing boron (LiBH4, [5] NaBH4, [6] Ca(BH4)2, [7] Mg(BH4)2 [8], hydrazine (N2H4), mesoporous-microporous materials [9] in recent times. B-N compounds appear to be more advantageous because of their high hydrogen storage capacity and the tendency to hold more hydrogen (with boron and nitrogen) among mentioned materials, this feature of the material allows charging and discharging of the material [10]. When compared to hydride and porous materials for the releasing and up taking of hydrogen, the above-mentioned properties at controllable temperature and pressure make the B-N compounds distinguishable. According to literature [11,12], the hydrolytic dehydrogenation of dimethylamine – borane (CH3)2NHBH3) was carried out by using an appropriate catalyst at room temperature. The hydrolytic dehydrogenation of DMAB has various advantageous. For instance, DMAB has very high water solubility in room temperature [11]. Further, the current solution with DMAB has a stable form across to self-hydrolysis at ambient conditions, and 3 moles of H2 can be obtained from 1 mole of DMAB in aqueous medium, but in only 1 mole H2 is obtained from 1 mole DMAB in an organic solution [13,14]. So far, polymer nanogel-supported Ni particles [15], RuNPs [12], Pd/C [14], NiSO4/Na2MoO4 [16,17], NiSO4/KReO4 [17] and NiSO4/Na2WO4 [17] have been tested as catalysts for the hydrolytic dehydrogenation of DMAB. Generally, all these catalysts are heterogeneous catalysts and their surface contain a few active atoms. So, the catalytic activity is restricted by the limited surface area in mentioned heterogeneous catalysts. Besides, the literature contains some semi-heterogeneous (metal nanoparticles) catalysts [18] which have been also used for the hydrolytic dehydrogenation of DMAB. Generally, metal nanoparticles can be dispersible in water to enhance catalyst surface. Such a pathway appears very promising way for rapid hydrogen
generation and high catalytic activity [19]. [ Therefore, it is necessary cessary to develop a metal nanocatalyst which is water-dispersible, dispersible, and which can be used in the hydrolyti hydrolytic dehydrogenation of DMAB. For this purpose, in this study, we present the preparation, characterization and the detailed kinetic studies of of Rh NPs@MWCNT nanocatalyst for the hydrolytic dehydrogenation of DMAB. Rh (0) nanoparticles were well-dispersed dispersed on multi walled carbon nanotube surface, and Rh NPs@MWCNT nanocatalyst was as obtained by reduction of Rh (III) to Rh(0) in an aqueous medium. medium The prepared Rh NPs@MWCNT nanocatalyst was used for the hydrolytic dehydrogenation of DMAB as shown in Scheme 1. The resulting Rh NPs@MWCNT nanocatalyst was characterized by using some advanced analytic methods such as TEM, XPS, XRD etc.
Scheme 1: The hydrolytic dehydrogenation of DMAB catalyzed by Rh NPs at room temperature
After catalytic experiments, a record turn over frequency fre y value (TOF) of 3010.47 h-1 was obtained for the hydrolytic dehydrogenation dehydro of DMAB catalyzed ed by Rh NPs@MWCNT nanocatalyst.
Experimental methods The preparation of Rh NPs@MWCNT nanocatalyst The preparation of Rh NPs@MWCNT nanocatalyst has been performed by using a facile impregnation method [20]. To prepare Rh NPs@MWCNT nanocatalyst,, briefly, 6.22 mg of rhodium (III) chloride and 150 mg of multi-walled multi walled carbon nanotube (previously functionalized according to our previous works, works as given in supporting information [21]) were added to 5.0 mL H2O, and the resulting solution was stirred at 600 rpm rpm for 2 hours. Then, 17.21 mg NaBH4 have been used to reduce Rh+3@MWCNT and to obtain the Rh NPs@MWCNT nanocatalyst.. The obtained NPs were washed with 3 x 10 mL H2O and dried in 150 oC for 45 min.
The catalytic experiments, kinetic and activation parameters of the hydrolytic dehydrogenation of DMAB catalyzed Rh NPs@MWCNT nanocatalyst In order to determine the effect of Rh nanocatalyst concentration on the hydrolytic dehydrogenation of DMAB catalyzed Rh NPs@MWCNT nanocatalyst, a serious experiment with various Rh concentration (0.685, 1.370, 2.055, 2.740 mM) were carried out at 1 mM of DMAB (10 mL). Another set of experiments with various DMAB concentrations (50, 100, 150, 200 mM) were performed at 2.74 mM of Rh at room temperature. Besides, the hydrolytic dehydrogenation of DMAB at 20, 25, 30, 35 °C with solution of 10 mL containing 200 mM of DMAB, 2.74 mM of Rh NPs. Activation parameters (Ea, S, H) were detected using various temperatures experiment data, and Arrhenius-Eyring plots [21].
Results and discussion The characterization of Rh NPs@MWCNT nanocatalyst Monodisperse Rh NPs@MWCNT was obtained by the reduction Rh (III) in the presence of NaBH4 medium containing multi-walled carbon nanotubes at mild conditions. Formation of an agglomerate and precipitate in the solution containing NaBH4 and Rh (0) nanoparticles was seen without using multi-walled carbon nanotubes. Because of this situation, it can be said that only chloride anion cannot be stabilize the solution medium of metal without carbon nanotube. In presence of multi-walled carbon nanotube nanomaterials in the solution, no participate or agglomeration occurs, and the resulting nanoparticles form a very stable structure [22]. This result shows that the stabilization of Rh nanoparticles was provided by multi-walled carbon nanotubes. Towards the end of the catalytic reaction, the light brown color turns into dark brown because of the reduction of Rh (III) to Rh (0). The formation of Rh NPs@MWCNT nanocatalyst can be seen in Fig. 1a by the help of TEM images. The related EDS diagram also indicates the existence of Rh in prepared nanoparticles as shown in Fig. 1b. The particle size of Rh NPs@MWCNT were investigated by using the TEM image and NIH image program [23]. More than 200 particles were counted and the results showed in Fig. 1c. The average particle size of Rh NPs@MWCNT nanocatalyst was found to be 1.44 ± 0.17 nm, and this size is in good agreement with Rh (0) nanoparticles [24].
Fig. 1 (a) TEM image; (b) EDS diagram (c) associated size histogram of of RhNPs@MWCNT nanocatalyst during the DMAB catalytic reaction at ambient conditions. condi
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Multi-walled carbon nanotubes-supported supported Rh (0) nanoparticles, obtained by the red reduction of Rh (III)/ multi walled carbon nanotubes precursor by b the help of NaBH4 at mild conditions, and were characterized terized using some other advanced analytical methods methods and isolated from the
reaction medium. XRD patterns of multi-walled carbon nanotubes (MWCNT) and multiwalled carbon nanotubes-supported Rh (0) nanoparticles (Rh NPs@MWCNT) in Fig. 2 (a-b) show the characteristic diffraction peaks of Rh at 25o, 44o, 47o, 70o, 78o assigned to the C (002), Rh (111), Rh (200), Rh (220), Rh (311) reflections [25,26]. This indicates that MWCNT maintains its crystallinity after the preparation of Rh (III)/ MWCNT and the formation of Rh (0) in the presence of NaBH4. The crystallite size of Rh NPs@MWCNT nanocatalyst was calculated using Debye-Scherrer equation to be 1.9 nm.
Fig. 2 XRD spectra of multi-walled carbon nanotubes (MWCNT) and; multi-walled carbon nanotubes-supported Rh (0) nanoparticles (Rh NPs@MWCNT) (theoretical Rh loading on multiwalled carbon nanotubes is 5.0% wt)
The oxidation state and surface composition of Rh NPs@MWCNT nanocatalyst were investigated by X-ray photoelectron spectroscopy (XPS) analysis. The survey and high resolution Rh 3d XPS spectra of Rh NPs@MWCNT nanocatalyst together with its deconvoluted chemical states are seen in Fig. 3 (a-b). Fig. 3 (a) shows the photopics of Rh with C and O atoms forming the carbon nanotube. Fig. 3 (b) contains two distinctive peaks for Rh 3d3/2 and 3d5/2 feature give two distinct peaks at 311.8 and 306.9 eV, corresponding to the Rh (0) 3d5/2 (metallic Rh NPs) and Rh (IV) 3d3/2 [27]. These two peaks occur during getting XPS analyze due to the formation Rh (IV) oxide on surface the catalyst [28].
Fig. 3 Survey (a) and Rh 3d region high-resolution (b) XPS spectra of Rh NPs@MWCNT nanocatalyst
The hydrolytic dehydrogenation reaction of DMAB catalyzed Rh NPs@MWCNT nanocatalyst was shown in Scheme 1. The 11B-NMR spectra of DMAB were taken at the end of catalytic reaction in order to characterize the products. The
11
B-NMR spectra of DMAB
and the reaction solution obtained at the end of the hydrolytic dehydrogenation of DMAB are given in Fig. 4, showing that the quartet signal of DMAB at −16.50 ppm is completely converted to the singlet of the borate anion at 4.88 ppm [12,29].
Fig. 4 11B-NMR spectra of aqueous DMAB (down) and the reaction solution obtained at the end of the Rh NPs@MWCNT catalyzed hydrolytic dehydrogenation of DMAB (up).
The detailed kinetic studies of the hydrolytic dehydrogenation of DMAB catalyzed by Rh NPs@MWCNT The H2 production from the hydrolytic dehydrogenation of DMAB with various Rh NPs@MWCNT nanocatalyst concentrations at room temperatures are seen in Fig. 5. The catalytic reaction of DMAB using Rh NPs@MWCNT nanocatalyst was completed shortly (average in 7 minutes) and 3 moles of H2 were obtained at room temperature. As seen in Fig.
3, the amount of H2 released increases almost linearly with the increase in the amount of catalyst (Fig. S1). A graphic for a rate versus Rh NPs@MWCNT nanocatalyst concentration between ln(k) and ln(cat.) forms a straight line with a slope of 1.055 (Fig. S2). The result revealed that the rate of catalytic reaction of DMAB catalysed by Rh NPs@MWCNT nanocatalyst was corresponded with the first-order equation. A set of different experiments were carried out to determine the effect of DMAB concentration on the catalytic reaction with the same catalyst concentration at room temperature. The results at different DMAB concentrations are given in Fig. 6. A plot for a rate versus for different DMAB concentrations between ln(k) and ln(DMAB) forms a slope of 0.196 (as shown in Fig. S3). This result indicates that the catalytic reaction of DMAB using Rh NPs@MWCNT nanocatalyst is compatible with zero-order dependence. The results of reactions were also conducted at different temperatures (20, 25, 30, 35 °C) for the hydrolytic dehydrogenation of DMAB catalysed by Rh NPs@MWCNT nanocatalyst is given in Fig. 7. As seen in the Fig. 7 the volume of H2 released increases with the increasing temperature. The results of catalytic reaction showed that Rh NPs@MWCNT nanocatalyst highly catalyzed the hydrolytic dehydrogenation of DMAB at room temperature with a record turnover frequency value of 3010.47 h-1 and 3 moles of H2.
Fig. 5 The rate of [H2]/[DMAB] versus time for the hydrolytic dehydrogenation of DMAB catalysed different Rh NPs@MWCNT nanocatalyst with a solution containing 100 mM (CH3)2NHBH3 in various Rh NPs@MWCNT nanocatalyst concentrations corresponding to [Rh]= 0.69, 1.37, 2.06, 2.74, 1.5 mM at 25 ± 0.5 oC.
Fig. 6 The rate of [H2]/[DMAB] versus time for the hydrolytic dehydrogenation of DMAB catalyzed Rh NPs@MWCNT nanocatalyst with different DMAB concentrations at room temperature.
Fig. 7 The rate of [H2]/[DMAB] versus time for the hydrolytic dehydrogenation of DMAB catalyzed RhNPs@MWCNT nanocatalyst at various temperatures.
Activation energy (Ea = 96.83 kJ.mol-1), enthalpy (H = 93.69 kJ mol−1) and entropy (S = 90.68 J mol-1K-1) values were calculated using Fig. 7. Arrhenius [30] and Eyring [31] equations (Fig. S5) have been used for those calculations of the hydrolytic dehydrogenation of DMAB catalysed by Rh NPs@MWCNT nanocatalyst. The reaction rate constant was obtained from the almost linear portion of the generation H2 versus time plot in the range of
temperature 20-35 oC. Monodisperse Rh NPs@MWCNT nanocatalyst has been found to be heterogeneous catalyst by the help of the mercury m poison experiments as shown in Figure S6 [32,33]. The decreasing catalytic activity with adding mercury mercury shows that Rh NPs@MWCNT nanocatalyst is heterogeneous. For the reusability experiements, the obtained Rh NPs@MWCNT nanocatalyst was precipitated and formed colorless solution. The isolated bulk Rh had noo activity on the catalytic ca activity of DMAB (Fig. 8), ), but well dispersed Rh NPs@MWCNT nanocatalyst maintained its catalytic activity at 68 % at even 8th cycle at the same time. As a result, ult, the obtained Rh NPs@MWCNT nanocatalyst is a complementary factor for the catalytic reaction of DMAB in water. The TO TOF value (3010.47 h-11) found is the highest value among previous studies such as polymer nanogel-supported supported Ni particles (TOF = 376 h-1) [15], RuNPs NPs (TOF = 500 h-1) [12], NiSO4/Na2MoO4 (TOF = 2.8 h−1) [16 16,17]; NiSO4/ KReO4 (TOF = 3.6 h−1) [17]; carbon arbon supported Pd (TOF = 30 h−1) [14]; NiSO4/Na2WO4 (TOF = 4.2 h−1) [17]. ;ĂͿ
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ZƵŶ Fig. 8 The volume of H2 versus time for Rh NPs@MWCNT nanocatalyst (in 1st ( ) and 2nd ( ) runs 3rd ( ) 4th ( ) 5th ( ) 6th ( ) 7th ( ) 8th ( ) catalyzed hydrolytic dehydrogenation of DMAB at rroom temperature.
Conclusions The findings and results about the hydrolytic dehydrogenation dehyd of DMAB catalyzed by Rh NPs@MWCNT nanocatalyst obtained in this study can be summarized as follows follows:
Rh NPs@MWCNT nanocatalyst was prepared in a stable form using RhCl3H2O and multi-walled carbon nanotubes at mild conditions by using a facile impregnation method. A set of advanced analytic methods such as TEM, XPS,
11
B-NMR, XRD etc. were
used to characterize the formation of well-dispersed Rh NPs@MWCNT nanocatalyst of 1.44 ± 0.17 nm size (as Rh (0) stabilized by multi-walled carbon nanotubes). The hydrolytic dehydrogenation of DMAB with Rh NPs@MWCNT nanocatalyst was occurred even at low (20 °C) temperature with 3 moles of H2. The resultant Rh NPs@MWCNT nanocatalyst was determined for the completion catalytic reaction of DMAB with a highest catalytic activity (TOFinitial = 3010.47 h−1) for the hydrolytic dehydrogenation of DMAB under mild conditions. The kinetic studies, the activation energy (Ea = 96.83 kJ mol−1), enthalpy and entropy values (H = 93.69 kJ mol−1; S = 90.68 J mol-1K-1) were calculated for the hydrolytic dehydrogenation of DMAB catalyzed by monodisperse rhodium nanoparticles using Arrhenius and Eyring plots. Besides, the restricted catalytic activity by adding mercury can be apparent evidence for heterogeneity of the catalysis. Thanks to the ultra-small sizes, monodispersity and high Rh (0) % surface of novel catalyst The prepared Rh NPs@MWCNT nanocatalyst can have a great potential in both fuel cells and other catalysis reactions in near future in terms of high catalytic activity and stability by the help of carbon nanotube.
Acknowledgements The authors would like to thank to Yuzuncu Yil University and Dumlupinar University BAP for financial support (2014-05).
Notes and references
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ZŚEWƐΛDtEd
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;DĞϮE,ϮͿϮ Monodisperse Rh NPs@MWCNT catalyst showed excellent catalytic activity and the shortest reaction time for the hydrolytic dehydrocoupling of DMAB [(CH3)2NHBH3)].