- Email: [email protected]
Highly active and reusable nanocomposites for hydrogen generation
Highly active and reusable nanocomposites for hydrogen generation
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Betu€l S¸en, Esra Kuyuldar, Buse Demirkan, Aysun S¸avk, Ays¸enur Aygu€n, Fatih S¸en Sen Research Group, Biochemistry Department, Faculty of Arts and Science, Dumlupınar University, K€utahya, Turkey
Chapter Outline 2.1 Introduction 27 2.2 Experimental methods
28
2.2.1 Materials and methods 28 2.2.2 The synthesis of Pd-Ni nanomaterials decorated by AC 28 2.2.3 Reusability examination of Pd-Ni @AC 29
2.3 Results and discussion 2.4 Conclusions 34 Acknowledgments 35 References 35
2.1
29
Introduction
There is a growing interest in alternative novel materials for many types of applications [1–18]. Those applications are fuel cells, organic synthesis, solar cells, electrochemical sensors, fluorescence sensors, drug delivery, dye removal, etc. [7, 19–43]. One of them is also the efficient storage of hydrogen. For this purpose, a variety of materials such as amine-borane are considered leading candidates for chemical hydrogen storage [44–53]. More importantly, recent studies have suggested amine-borane adducts as an alternative energy carrier [54–65]. Of particular interest, the catalytic dehydrogenation of dimethylamine-borane (DMAB) potentially releases 3.5% H2 by weight. Furthermore, it is very easy to generate hydrogen by using DMABs at room temperature if there is an appropriate catalyst. A quick literature survey shows that many materials were tried as catalysts for dehydrocoupling of dimethylamine borane [66–76]. For instance, catalytic activities in the formation of hydrogen from the Pd-Co NPs stabilized by polyvinylpyrolidone (PVP) and dehydrogenation of DMAB at 25 0.1°C have recently been reported [48]. In this paper, instead of PVP, activated carbon (AC) was proposed as a stabilizer for transition metal NPs. In the Nanocarbon and its Composites. https://doi.org/10.1016/B978-0-08-102509-3.00002-X © 2019 Elsevier Ltd. All rights reserved.
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dehydrogenation of DMAB, the high catalytic performance of these Pd-based bimetallic alloy NPs prompted us to test another Pd-based bimetallic nanocatalyst (palladium-nickel nanoparticles, Pd-Ni NPs) in the dehydrogenation of DMAB. For this purpose, we report the production, characterization, and catalytical performance of monodispersed Pd-Ni NPs stabilized by AC in terms of dehydrogenation, kinetic studies, and reusability of DMAB under mild conditions. To get good stability, nanocatalyst production was performed by coreducing both metals, employing the sodium hydroxide-assisted reduction method. Later, ultraviolet-visible (UV–Vis) spectroscopy, X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy were used in order to describe the prepared nanomaterials. Then, one equivalent of H2 per dimethylamine borane was generated with the help of Pd-Ni NPs stabilized by AC. The turnover frequency was found to be 316.41 h1 for dehydrocoupling of dimethylamine borane. Also, the kinetic parameters of dehydrocoupling of dimethylamine borane were examined with the help of different temperatures and catalyst amounts.
2.2 2.2.1
Experimental methods Materials and methods
Aldrich supplied dimethylamine-borane, NiCl2, K2PdCl4, and activated carbon. The C2H5OH and water used during this study were provided by Merck and a Milli Q-pure machine, respectively. Before all glass pieces and other lab materials were washed with large amounts of distilled water, they were cleaned with acetone and then dried. Transmission electron microscopy images was obtained by a JEOL 200 kV. For X-ray photoelectron spectroscopy (XPS) analysis, a Specs spectrometer (Kα lines of Mg (1253.6 eV, 10 mA)) was used. XRD analysis was performed with the help of a Panalytical Empyrean instrument. UV-Vis analyses were taken by a Perkin Elmer Lambda 750. A 200–900 nm was selected to gather the data and 1 cm quartz cell was employed.
2.2.2
The synthesis of Pd-Ni nanomaterials decorated by AC
The Pd-Ni nanoparticles supported by AC were synthesized by a facile sodium hydroxide-assisted reduction method. Typically, 100 mg of activated carbon powder in a two-necked, round-bottomed flask was ultrasonically dispersed in 2.5 mL of ethanol and subsequently mixed with an aqueous solution of NiCl2 and PdCl2 with desired concentrations. The resultant aqueous suspension was further homogenized under sonication for 30 min. Then, 12 mg of NaBH4 dissolved in 1.0 mL of 3.0 M NaOH solution was added into the above-obtained solution with vigorous shaking, resulting in the generation of the catalyst as a dark suspension. Other kinetic and catalytic investigations for the Pd-Ni@AC NPs were given in detail in our previous papers [77–89]. The dehydrogenation of DMAB was performed in a typical jacketed reaction flask connected to the water-filled cylinder glass tube under a dry nitrogen atmosphere.
Highly active and reusable nanocomposites for hydrogen generation
2.2.3
29
Reusability examination of Pd-Ni @AC
For the reusability experiments of Pd-Ni @AC, the solid mixture at the end of the dehydrogenation reaction was precipitated with cold hexane (10 mL, added under N2 atmosphere) and the supernatant solution was removed by filtration. The solid was further washed with hexane (3 20 mL) and dried under vacuum, giving the isolated colloid as a dark brown powder.
2.3
Results and discussion
The monodisperse Pd-Ni @AC nanoparticles were characterized by using UV-VIS, XRD, TEM, HRTEM, and XPS. For this purpose, after the NiCl2 and PdCl2 were reduced together by using the sodium hydroxide-assisted reduction method, the resulting mixture was refluxed for 3 h, then the color of the material was changed. Here, the color implies the reduction of Pd2+ and Ni2+ ions to the zero oxidation state of metals. To see this, a UV–VIS investigation was performed (Fig. 2.1) and the d–d transitions belonging to the Pd2+ and Ni2+ ions exhibited the reduction of all cations. Moreover, TEM analyses were accomplished to determine the size, morphology, and composition of the Pd-Ni @AC NPs (Fig. 2.2). The average particle size was measured as 3.55 0.42 nm. HR-TEM results indicating the morphology of the NPs can be seen in Fig. 2.2. It was shown that the particles were mostly spherical and no agglomerations were seen for the prepared catalyst. It can also be seen from the HRTEM image that monodispersed Pd-Ni @AC NPs had (Fig. 2.2) 0.21 nm atomic lattice fringes, which is a bit smaller than nominal Pd (111) spacing (0.22 nm) and indicates the alloy formation of Pd-Ni @AC [9]. Additionally, an EELS line profile also confirms that Pd-Ni @AC NPs had alloy structures as well as the ratio of Pd:Ni in this
Fig. 2.1 UV-Vis absorption spectra of the aqueous solutions of Pd+2, Ni+2, and Pd-Ni@AC NPs.
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Nanocarbon and its Composites
Fig. 2.2 (A) Transition electron micrograph, (B) HR-TEM image, (C) The EELS line profile scanned on the arrow shown in HR-TEM image, (D) Particle size histogram of Pd-Ni@AC NPs.
alloy structure. The ratio of Pd:Ni was found to be 1:1, also confirmed by an ICP analysis (Pd52Ni48). Besides, an XRD analysis was performed to define the crystal morphology of the prepared nanocomposites. As shown in Fig. 2.3A, a face-centered cubic structure was determined for the prepared material. Moreover, slightly shifted diffraction peaks can be seen in Fig. 2.3A; this confirms the alloy formation of Pd-Ni @AC NPs. Furthermore, here the peak at around 25.7 degree was attributed to AC. In the XRD patterns for Pd-Ni, no significant diffraction peaks of Ni species were detected due to relatively strong signals for Pd species. In addition, in Fig. 2.3A, the peaks at 2θ ¼ 40.1, 46.6, 68.1, and 82.1 degrees correspond to the crystal planes of prepared nanomaterials. Moreover, the crystalline particle size was calculated to be 3.72 0.42 nm with the help of the Debye-Scherrer [90–96]. The particle size of Pd-Ni @AC is in good agreement with TEM results. Raman spectroscopy was also used in the present study to discriminate the ordered and disordered carbon structures in the carbonaceous materials. In Fig. 2.3B, the
31
20
40
(A)
36
38 40 2θ (degree)
60
42
44
Pd(311)
34
Pd(200)
Pd@AC PdNi@AC
Pd@AC PdNi@AC
Pd(220)
Intensity (a.u.)
Pd(111)
Intensity (a.u.)
Pd(111)
Highly active and reusable nanocomposites for hydrogen generation
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2q (degree)
AC Pd-Ni@AC
D 1580 cm–1
Intensity (a.u.)
1350 cm–1
G
ID /IG : 0.90
ID /IG : 0.53
1200
(B)
1300
1400 1500 1600 Raman shift (cm–1)
1700
1800
Fig. 2.3 (A) The XRD of Pd@AC and Pd-Ni@AC NPs and (B) The Raman spectra of Pd-Ni@AC.
Raman spectra of AC and Pd-Ni @AC are shown. The peaks at 1350 and 1580 cm1 are the remarkable scattering peaks in this figure. It is known that the ID/IG ratio is the intensity ratio of the D to G band and can be employed to find the degree of modification or defects in the AC. In the present study, the ID/IG values of AC and Pd-Ni @AC were found to be 0.53 and 0.90, respectively, which indicate the increasing disorder in the AC lattice after functionalization with Pd-Ni. The X-ray photoelectron spectroscopy data for Pd and Ni were studied using the Gaussian-Lorentzian method [97–105]. The relative intensity of the species was evaluated by counting each peak’s integral after smoothing and subtracting the Shirleyshaped background. The binding energies (0.3 eV) were determined by referencing
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Nanocarbon and its Composites
Fig. 2.4 Pd 3d (A) and Ni 2p (B) XPS spectra of PdNi@AC NPs.
the C 1s peak at 284.6 eV in the XPS spectra. The XPS results are shown in Fig. 2.4. After comparing the experimental binding energies (Pd-3d5/2 was 335.6 eV and Ni-2p3/2 was 856.3 eV), it was understood that Pd and Ni at the surface were not oxides, but were mostly metallic. For the Ni binding energy, the shift of the 2p3/2 peak to the lower energy indicated an alloying process of Pd-Ni. These findings showed that Ni and Pd existed as elements in the Pd-Ni @AC NPs produced in the present study rather than O2-containing oxide compounds. Some metal oxides in the prepared nanomaterials can be a possible surface oxidation or chemical sorption of oxygen during the fabrication procedures. After the completion of characterization of Pd-Ni @AC with the help of various techniques, the catalytic performances of Pd-Ni @AC were evaluated for DMAB dehydrogenation. The experiments showed that the Pd-Ni @AC NPs are highly efficient catalysts for DMAB dehydrogenation. In Fig. 2.5A, the graph of nH2/nDMAB versus time can be seen, indicating the DMAB dehydrogenation while there were nanocatalysts at different amounts at 25.0 0.1°C. Hydrogen evolution starts rapidly and continues until the reaction is completed. The nuclear magnetic
Highly active and reusable nanocomposites for hydrogen generation
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Fig. 2.5 (A) Plot of nH2/nDMAB vs time for the DMAB dehydrocoupling with the existence of Pd-Ni@AC NPs at different catalyst concentrations at 25 0.1oC; (B) % conversion vs time plots for Pd-Ni@AC NPs (7.5% mol) catalyzed dehydrocoupling of DMAB in THF at different temperatures; (C) Arrhenius plot; and (D) Eyring plot.
resonance analysis showed that the conversion of (CH3)2NHBH3 (δ ’ 12.6 ppm) to [(CH3)2NBH2]2 (δ ’ 5.1 ppm) occurred completely. This indicates that DMAB dehydrocoupling (at 1.0 equiv. H2 generation) can happen at room temperature. Fig. 2.5B was depicted to determine the hydrogen production rate constants throughout the DMAB dehydrogenation. In this figure, the change of conversion percentage at different temperatures (20oC, 25oC, 30oC, and 35oC) was displayed. By using the rate constants and Fig. 2.5C, the Arrhenius plot, the Ea was found to be 46.99 2 kJ mol1. With the help of Fig. 2.5D, the Eyring plot, the Δ H (activation enthalpy) and Δ S (activation entropy) were calculated to be 45.17 kJ mol1 and 68.82 J mol1 K1, respectively. Furthermore, in the DMAB dehydrocoupling’s transition state, an associative mechanism was observed by looking to the activation entropy and the activation enthalpy values. To sum up, in this study, a high catalytic activity was observed when Pd-Ni @AC NPs (316.41 h1) were utilized for the DMAB dehydrocoupling. It should be stated that with the help of Pd-Ni @AC NPs, hydrogen gas (1 mol H2/1 mol DMAB) was completely emitted in the DMAB dehydrogenation within a short time at 25 0.1oC. Pd-Ni @AC NPs can be considered a good nanocatalyst because they are isolable and
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Nanocarbon and its Composites
100
% conversion
100
96
90
85
83
81
80 60 40 20 0 1
2
3
4
5
6
run
Fig. 2.6 Plots % conversion versus time graph for Pd-Ni@AC NPs (7.5 % mol) catalysed dehydrocoupling of DMAB in THF at room temperature for first and sixth catalytic runs.
reusable when utilized in catalytic reactions substantially. The probable reason is the stability of AC and the cooperative and synergistic impact of Pd and Ni in the present study’s catalyst system. Besides, the reusability of the AC-supported Pd-Ni NPs was investigated, as shown in Fig. 2.6. To do that, DMAB was introduced subsequently after the first catalysis reaction in the DMAB dehydrogenation. At the end of the sixth experiment, Pd-Ni @AC NPs maintained 81% of their initial performance. In the DMAB dehydrocoupling, the probable reason for the catalytic activity decrease can be the passivation, as there are increased amounts of nanoparticles on surfaces, and therefore active site accessibility becomes low. The aggregation of NPs was shown after six cycles of the catalytic experiment because, even after six cycles, the catalyst retains its initial content, as found by the ICP analysis (12.95% metals based) study.
2.4
Conclusions
In conclusion, AC-decorated Pd-Ni NPs were shown to be a highly efficient catalyst for DMAB dehydrogenation and the significant steps related to its fabrication, analytical examination, and utilization are as follows: l
l
l
l
l
l
The sodium hydroxide-assisted reduction method was utilized to fabricate Pd-Ni @AC NPs. The results showed that the fabrication method was very operative to distribute Pd-Ni NPs uniformly on the AC material and to prevent the agglomeration problem of Pd-Ni NPs. Pd-Ni @AC NPs had good catalytic performances in DMAB dehydrogenation compared to the literature data. A high TOF (316.41 h1) value was achieved for DMAB dehydrocoupling. 46.99 3 kJ mol1 of Ea was calculated for dehydrocoupling of dimethylamine borane when Pd-Ni @AC nanocatalysts were used. According to these results, Pd-Ni @AC NPs are promising materials and can be used in many catalytic applications as a nanocatalyst.
Highly active and reusable nanocomposites for hydrogen generation
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Acknowledgments The authors would like to thank DPU-BAP (2014-05 and 2015-50) for financial support.
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[66] Friederich A, Drees M, Schneider S. Ruthenium-catalyzed dimethylamine-borane dehydrogenation, stepwise metal-centered dehydrocyclization. Chem Eur J 2009; 15:10339–42. [67] Pun D, Lobkovsky E, Chirik PJ. Amine-borane dehydrogenation promoted by isolable zirconium sandwich, titanium sandwich and N2 complexes. Chem Commun 2007;44:3297. [68] Yao CF, Zhuang L, Cao YL, Hi XP, Yang HX. Hydrogen release from hydrolysis of borazane on Pt- and Ni-based alloy catalysts. Int J Hydrog Energy 2008;33:2462–7. [69] Yang X, Cheng F, Liang J, Tao Z, Chen J. PtxNi1x nanoparticles as catalysts for hydrogen generation from hydrolysis of ammonia borane. Int J Hydrog Energy 2009;34: 8785–91. [70] Dai HB, Gao LL, Liang Y, Kang XD, Wang P. Promoted hydrogen generation from ammonia borane aqueous solution using cobalt–molybdenum–boron/nickel foam catalyst. J Power Sources 2010;195:307–12. [71] Chen Y, Fulton JL, Linehan JC, Autrey T. In situ XAFS and NMR study of rhodiumcatalyzed dehydrogenation of dimethylamine borane. J Am Chem Soc 2005;127:3254–5. [72] Munoz-Olasagasti M, Telleria A, Perez-Miqueo J, Garralda MA, Freixa ZA. A readily accessible ruthenium catalyst for the solvolytic dehydrogenation of amine–borane adducts. Dalton Trans 2014;43:11404–9. [73] Jiang Y, Berke H. Dehydro-coupling of dimethylamine-borane catalysed by rhenium complexes and its application in olefin transfer-hydrogenations. Chem Commun 2007; (34):3571–3. [74] Sloan ME, Clark TJ, Manners I. Homogeneous catalytic dehydrogenation/ dehydro-coupling of amine-borane adducts by the Rh(I) Wilkinson’s complex analogue RhCl(PHCy2)3(Cy ¼ cyclohexyl). Inorg Chem 2009;48:2429–35. [75] Fulton JL, Linehan JC, Autrey T, Balasubramanian M, Chen Y, Szymczak KN. When is a nanoparticle a cluster? An operando exafs study of amine Borane Dehydro-coupling by Rh4-6 Clusters. J Am Chem Soc 2007;129:11936–49. [76] Sen B, Kuzu S, Demir E, Akocak S, Sen F. Highly monodisperse RuCo Nanoparticles decorated on functionalized multiwalled carbon nanotube with the highest observed catalytic activity in the dehydrogenation of dimethylamine borane. Int J Hydrog Energy 2017;42(36):23292–8. [77] Sen B, Kuzu S, Demir E, Akocak S, Sen F. Monodisperse palladium-nickel alloy nanoparticles assembled on graphene oxide with the high catalytic activity and reusability in the dehydrogenation of dimethylamine-borane. Int J Hydrog Energy 2017;42(36): 23276–83. [78] Sen B, Kuzu S, Demir E, Okyay TO, Sen F. Hydrogen liberation from the dehydrocoupling of dimethylamine-borane at room temperature by using novel and highly monodispersed RuPtNi nanocatalysts decorated with graphene oxide. Int J Hydrog Energy 2017;42(36):23299–306. [79] Sen B, Kuzu S, Demir Eea. Polymer-graphene hybride decorated Pt nanoparticles as highly eficient and reusable catalyst for the dehydrogenation of dimethylamine-borane at room temperature. Int J Hydrog Energy 2017;42(36):23284–91. [80] Sen B, Kuzu S, Demir E, Yıldırır E, Sen F. Highly efficient catalytic dehydrogenation of dimethly ammonia borane via monodisperse palladium-nickel alloy nanoparticles assembled on PEDOT. Int J Hydrog Energy 2017;42(36):23307–14. [81] Yildiz Y, Erken E, Pamuk H, Sert H, Sen F. Monodisperse Pt Nanoparticles assembled on reduced graphene oxide: highly efficient and reusable catalyst for Methanol oxidation
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[82]
[83]
[84]
[85]
[86]
[87]
[88]
[89]
[90]
[91]
[92]
[93]
[94]
[95]
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and dehydro-coupling of dimethylamine-borane (DMAB). J Nanosci Nanotechnol 2016; (6):5951–8. Erken E, Yildiz Y, Kilbas B, Sen F. Synthesis and characterization of nearly monodisperse Pt nanoparticles for C1 to C3 alcohol oxidation and dehydrogenation of dimethylamine-borane (DMAB). J Nanosci Nanotechnol 2016;16:5944–50. € Erken E, Sen F. Monodisperse Pt (0)/DPA@GO Celik B, Başkaya G, Karatepe O, nanoparticles as highly active catalysts for alcohol oxidation and dehydrogenation of DMAB. Int J Hydrog Energy 2016;41:5661–9. Sen B, Kuzu S, Demir E, Akocak S, Sen F. Polymer-Graphene hybride decorated Pt nanoparticles as highly eficient and reusable catalyst for the dehydrogenation of dimethylamine-borane at room temperature. Int J Hydrog Energy 2017. https://doi. org/10.1016/j.ijhydene.2017.05.112. Sen B, Kuzu S, Demir E, Akocak S, Sen F. Highly monodisperse Ru-Co nanoparticles decorated on functionalized multiwalled carbon nanotube with the highest observed catalytic activity in the dehydrogenation of dimethylamine borane. Int J Hydrog Energy 2017. https://doi.org/10.1016/j.ijhydene.2017.06.032. Celik B, Kuzu S, Erken E, Sert H, Koskun Y, Sen F. Nearly monodisperse carbon nanotube furnished nano catalysts as highly efficient and reusable catalyst for dehydrocoupling of DMAB and C1 to C3 alcohol oxidation. Int J Hydrog Energy 2016;41:3093–101. Sen F, Karatas Y, Gulcan M, Zahmakiran M. Amylamine stabilized platinum (0) nanoparticles: active and reusable nano catalyst in the room temperature dehydrogenation of dimethylamine-borane. RSC Adv 2014;4:1526–31. € Başkaya G, Sert H, Kalfa OM, Sen F. New Pt (0) Erken E, Pamuk H, Karatepe O, nanoparticles as highly active and reusable catalysts in the C1–C3 alcohol oxidation and the room temperature dehydro-coupling of dimethylamine-borane (DMAB). J Clust Sci 2016;27(1):9–23. C¸elik B, Erken E, Eriş S, Yıldız Y, Şahin B, Pamuk H, Sen F. Highly monodisperse Pt (0) @AC NPs as highly efficient and reusable catalysts, the effect of the surfactant on their catalytic activities in room temperature dehydro-coupling of DMAB. Catal Sci Technol 2016;6:1685–92. Karatepe O, Yıldız Y, Pamuk H, Eris S, Dasdelen Z, Sen F. Enhanced electro catalytic activity and durability of highly mono disperse Pt@PPY-PANI nanocomposites as a novel catalyst for electro-oxidation of methanol. RSC Adv 2016;6:50851–7. Yıldız Y, Kuzu S, Sen B, Savk A, Akocak S, Sen F. Different ligand based monodispersed Pt nanoparticles decorated with rGO as highly active and reusable catalysts for the methanol oxidation. Int J Hydrog Energy 2017;42(18):13061–9. Dasdelen Z, Yıldız Y, Eris S, Sen F. Enhanced electrocatalytic activity and durability of Pt nanoparticles decorated on GO-PVP hybride material for methanol oxidation reaction. Appl Catal B Environ 2017;219C:511–6. Eris S, Dasdelen Z, Sen F. Enhanced electrocatalytic activity and stability of monodisperse Pt nanocomposites for direct methanol fuel cells. J Colloid Interface Sci 2018;513:767–73. Eris S, Daşdelen Z, Sen F. Investigation of electrocatalytic activity and stability of Pt@fVC catalyst prepared by in-situ synthesis for Methanol electrooxidation. Int J Hydrog Energy 2018;43(1):385–90. Eris S, Daşdelen Z, Yıldız Y, Sen F. Nanostructured Polyaniline-rGO decorated platinum catalyst with enhanced activity and durability for Methanol oxidation. Int J Hydrog Energy 2018;43(3):1337–43.
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[96] Ozturk Z, Sen F, Sen S, Gokagac G. The preparation and characterization of nano-sized Pt-Pd/C catalysts and comparison of their superior catalytic activities for methanol and ethanol oxidation. J Mater Sci 2012;47:8134–44. [97] Sen B, Akdere EH, Savk A, Gultekin E, Goksu H, Sen F. A novel thiocarbamide functionalized graphene oxide supported bimetallic monodisperse Rh-Pt nanoparticles (RhPt/TC@GO NPs) for Knoevenagel condensation of aryl aldehydes together with malononitrile. Appl Catal B Environ 2018;225(5):148–53. [98] Sen F, Ertan S, Sen S, Gokagac G. Platinum nano-catalysts prepared with different surfactants for C1-C3 alcohol oxidations and their surface morphologies by AFM. J Nanopart Res 2012;14:922–6. [99] Sen F, Sen S, Gokagac¸ G. Efficiency enhancement of methanol/ethanol oxidation reactions on Pt nanoparticles prepared using a new surfactant, 1, 1-dimethyl heptanethiol. Phys Chem Chem Phys 2011;13:1676–84. [100] Sen F, Sen S, Gokagac G. High performance Pt nanoparticles prepared by new surfactants for C1 to C3 alcohol oxidation reactions. J Nanopart Res 2013;15:1979. [101] Sen F, Gokagac G. Different sized platinum nanoparticles supported on carbon: an XPS study on these methanol oxidation catalysts. J Phys Chem C 2007;111:5715–20. [102] Sen F, Gokagac¸ G. Activity of carbon-supported platinum nanoparticles toward methanol oxidation reaction: role of metal precursor and a new surfactant, tert-octanethiol. J Phys Chem C 2007;11:1467–73. [103] Sen F, Gokagac¸ G. Improving catalytic efficiency in the methanol oxidation reaction by inserting Ru in face-centered cubic Pt nanoparticles prepared by a new surfactant, tert-octanethiol. Energy Fuel 2008;22:1858–64. [104] Sen F, Gokagac G. Pt nanoparticles synthesized with new surfactans: improvement in C1-C3 alcohol oxidation catalytic activity. J Appl Electrochem 2014;44(1):199–207. [105] Sen S, Sen F, Gokagac¸ G. Preparation and characterization of nano-sized Pt-Ru/C catalysts and their superior catalytic activities for methanol and ethanol oxidation. Phys Chem Chem Phys 2011;13:6784–92.
2
Betu€l S¸en, Esra Kuyuldar, Buse Demirkan, Aysun S¸avk, Ays¸enur Aygu€n, Fatih S¸en Sen Research Group, Biochemistry Department, Faculty of Arts and Science, Dumlupınar University, K€utahya, Turkey
Chapter Outline 2.1 Introduction 27 2.2 Experimental methods
28
2.2.1 Materials and methods 28 2.2.2 The synthesis of Pd-Ni nanomaterials decorated by AC 28 2.2.3 Reusability examination of Pd-Ni @AC 29
2.3 Results and discussion 2.4 Conclusions 34 Acknowledgments 35 References 35
2.1
29
Introduction
There is a growing interest in alternative novel materials for many types of applications [1–18]. Those applications are fuel cells, organic synthesis, solar cells, electrochemical sensors, fluorescence sensors, drug delivery, dye removal, etc. [7, 19–43]. One of them is also the efficient storage of hydrogen. For this purpose, a variety of materials such as amine-borane are considered leading candidates for chemical hydrogen storage [44–53]. More importantly, recent studies have suggested amine-borane adducts as an alternative energy carrier [54–65]. Of particular interest, the catalytic dehydrogenation of dimethylamine-borane (DMAB) potentially releases 3.5% H2 by weight. Furthermore, it is very easy to generate hydrogen by using DMABs at room temperature if there is an appropriate catalyst. A quick literature survey shows that many materials were tried as catalysts for dehydrocoupling of dimethylamine borane [66–76]. For instance, catalytic activities in the formation of hydrogen from the Pd-Co NPs stabilized by polyvinylpyrolidone (PVP) and dehydrogenation of DMAB at 25 0.1°C have recently been reported [48]. In this paper, instead of PVP, activated carbon (AC) was proposed as a stabilizer for transition metal NPs. In the Nanocarbon and its Composites. https://doi.org/10.1016/B978-0-08-102509-3.00002-X © 2019 Elsevier Ltd. All rights reserved.
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dehydrogenation of DMAB, the high catalytic performance of these Pd-based bimetallic alloy NPs prompted us to test another Pd-based bimetallic nanocatalyst (palladium-nickel nanoparticles, Pd-Ni NPs) in the dehydrogenation of DMAB. For this purpose, we report the production, characterization, and catalytical performance of monodispersed Pd-Ni NPs stabilized by AC in terms of dehydrogenation, kinetic studies, and reusability of DMAB under mild conditions. To get good stability, nanocatalyst production was performed by coreducing both metals, employing the sodium hydroxide-assisted reduction method. Later, ultraviolet-visible (UV–Vis) spectroscopy, X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy were used in order to describe the prepared nanomaterials. Then, one equivalent of H2 per dimethylamine borane was generated with the help of Pd-Ni NPs stabilized by AC. The turnover frequency was found to be 316.41 h1 for dehydrocoupling of dimethylamine borane. Also, the kinetic parameters of dehydrocoupling of dimethylamine borane were examined with the help of different temperatures and catalyst amounts.
2.2 2.2.1
Experimental methods Materials and methods
Aldrich supplied dimethylamine-borane, NiCl2, K2PdCl4, and activated carbon. The C2H5OH and water used during this study were provided by Merck and a Milli Q-pure machine, respectively. Before all glass pieces and other lab materials were washed with large amounts of distilled water, they were cleaned with acetone and then dried. Transmission electron microscopy images was obtained by a JEOL 200 kV. For X-ray photoelectron spectroscopy (XPS) analysis, a Specs spectrometer (Kα lines of Mg (1253.6 eV, 10 mA)) was used. XRD analysis was performed with the help of a Panalytical Empyrean instrument. UV-Vis analyses were taken by a Perkin Elmer Lambda 750. A 200–900 nm was selected to gather the data and 1 cm quartz cell was employed.
2.2.2
The synthesis of Pd-Ni nanomaterials decorated by AC
The Pd-Ni nanoparticles supported by AC were synthesized by a facile sodium hydroxide-assisted reduction method. Typically, 100 mg of activated carbon powder in a two-necked, round-bottomed flask was ultrasonically dispersed in 2.5 mL of ethanol and subsequently mixed with an aqueous solution of NiCl2 and PdCl2 with desired concentrations. The resultant aqueous suspension was further homogenized under sonication for 30 min. Then, 12 mg of NaBH4 dissolved in 1.0 mL of 3.0 M NaOH solution was added into the above-obtained solution with vigorous shaking, resulting in the generation of the catalyst as a dark suspension. Other kinetic and catalytic investigations for the Pd-Ni@AC NPs were given in detail in our previous papers [77–89]. The dehydrogenation of DMAB was performed in a typical jacketed reaction flask connected to the water-filled cylinder glass tube under a dry nitrogen atmosphere.
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2.2.3
29
Reusability examination of Pd-Ni @AC
For the reusability experiments of Pd-Ni @AC, the solid mixture at the end of the dehydrogenation reaction was precipitated with cold hexane (10 mL, added under N2 atmosphere) and the supernatant solution was removed by filtration. The solid was further washed with hexane (3 20 mL) and dried under vacuum, giving the isolated colloid as a dark brown powder.
2.3
Results and discussion
The monodisperse Pd-Ni @AC nanoparticles were characterized by using UV-VIS, XRD, TEM, HRTEM, and XPS. For this purpose, after the NiCl2 and PdCl2 were reduced together by using the sodium hydroxide-assisted reduction method, the resulting mixture was refluxed for 3 h, then the color of the material was changed. Here, the color implies the reduction of Pd2+ and Ni2+ ions to the zero oxidation state of metals. To see this, a UV–VIS investigation was performed (Fig. 2.1) and the d–d transitions belonging to the Pd2+ and Ni2+ ions exhibited the reduction of all cations. Moreover, TEM analyses were accomplished to determine the size, morphology, and composition of the Pd-Ni @AC NPs (Fig. 2.2). The average particle size was measured as 3.55 0.42 nm. HR-TEM results indicating the morphology of the NPs can be seen in Fig. 2.2. It was shown that the particles were mostly spherical and no agglomerations were seen for the prepared catalyst. It can also be seen from the HRTEM image that monodispersed Pd-Ni @AC NPs had (Fig. 2.2) 0.21 nm atomic lattice fringes, which is a bit smaller than nominal Pd (111) spacing (0.22 nm) and indicates the alloy formation of Pd-Ni @AC [9]. Additionally, an EELS line profile also confirms that Pd-Ni @AC NPs had alloy structures as well as the ratio of Pd:Ni in this
Fig. 2.1 UV-Vis absorption spectra of the aqueous solutions of Pd+2, Ni+2, and Pd-Ni@AC NPs.
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Nanocarbon and its Composites
Fig. 2.2 (A) Transition electron micrograph, (B) HR-TEM image, (C) The EELS line profile scanned on the arrow shown in HR-TEM image, (D) Particle size histogram of Pd-Ni@AC NPs.
alloy structure. The ratio of Pd:Ni was found to be 1:1, also confirmed by an ICP analysis (Pd52Ni48). Besides, an XRD analysis was performed to define the crystal morphology of the prepared nanocomposites. As shown in Fig. 2.3A, a face-centered cubic structure was determined for the prepared material. Moreover, slightly shifted diffraction peaks can be seen in Fig. 2.3A; this confirms the alloy formation of Pd-Ni @AC NPs. Furthermore, here the peak at around 25.7 degree was attributed to AC. In the XRD patterns for Pd-Ni, no significant diffraction peaks of Ni species were detected due to relatively strong signals for Pd species. In addition, in Fig. 2.3A, the peaks at 2θ ¼ 40.1, 46.6, 68.1, and 82.1 degrees correspond to the crystal planes of prepared nanomaterials. Moreover, the crystalline particle size was calculated to be 3.72 0.42 nm with the help of the Debye-Scherrer [90–96]. The particle size of Pd-Ni @AC is in good agreement with TEM results. Raman spectroscopy was also used in the present study to discriminate the ordered and disordered carbon structures in the carbonaceous materials. In Fig. 2.3B, the
31
20
40
(A)
36
38 40 2θ (degree)
60
42
44
Pd(311)
34
Pd(200)
Pd@AC PdNi@AC
Pd@AC PdNi@AC
Pd(220)
Intensity (a.u.)
Pd(111)
Intensity (a.u.)
Pd(111)
Highly active and reusable nanocomposites for hydrogen generation
80
2q (degree)
AC Pd-Ni@AC
D 1580 cm–1
Intensity (a.u.)
1350 cm–1
G
ID /IG : 0.90
ID /IG : 0.53
1200
(B)
1300
1400 1500 1600 Raman shift (cm–1)
1700
1800
Fig. 2.3 (A) The XRD of Pd@AC and Pd-Ni@AC NPs and (B) The Raman spectra of Pd-Ni@AC.
Raman spectra of AC and Pd-Ni @AC are shown. The peaks at 1350 and 1580 cm1 are the remarkable scattering peaks in this figure. It is known that the ID/IG ratio is the intensity ratio of the D to G band and can be employed to find the degree of modification or defects in the AC. In the present study, the ID/IG values of AC and Pd-Ni @AC were found to be 0.53 and 0.90, respectively, which indicate the increasing disorder in the AC lattice after functionalization with Pd-Ni. The X-ray photoelectron spectroscopy data for Pd and Ni were studied using the Gaussian-Lorentzian method [97–105]. The relative intensity of the species was evaluated by counting each peak’s integral after smoothing and subtracting the Shirleyshaped background. The binding energies (0.3 eV) were determined by referencing
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Nanocarbon and its Composites
Fig. 2.4 Pd 3d (A) and Ni 2p (B) XPS spectra of PdNi@AC NPs.
the C 1s peak at 284.6 eV in the XPS spectra. The XPS results are shown in Fig. 2.4. After comparing the experimental binding energies (Pd-3d5/2 was 335.6 eV and Ni-2p3/2 was 856.3 eV), it was understood that Pd and Ni at the surface were not oxides, but were mostly metallic. For the Ni binding energy, the shift of the 2p3/2 peak to the lower energy indicated an alloying process of Pd-Ni. These findings showed that Ni and Pd existed as elements in the Pd-Ni @AC NPs produced in the present study rather than O2-containing oxide compounds. Some metal oxides in the prepared nanomaterials can be a possible surface oxidation or chemical sorption of oxygen during the fabrication procedures. After the completion of characterization of Pd-Ni @AC with the help of various techniques, the catalytic performances of Pd-Ni @AC were evaluated for DMAB dehydrogenation. The experiments showed that the Pd-Ni @AC NPs are highly efficient catalysts for DMAB dehydrogenation. In Fig. 2.5A, the graph of nH2/nDMAB versus time can be seen, indicating the DMAB dehydrogenation while there were nanocatalysts at different amounts at 25.0 0.1°C. Hydrogen evolution starts rapidly and continues until the reaction is completed. The nuclear magnetic
Highly active and reusable nanocomposites for hydrogen generation
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Fig. 2.5 (A) Plot of nH2/nDMAB vs time for the DMAB dehydrocoupling with the existence of Pd-Ni@AC NPs at different catalyst concentrations at 25 0.1oC; (B) % conversion vs time plots for Pd-Ni@AC NPs (7.5% mol) catalyzed dehydrocoupling of DMAB in THF at different temperatures; (C) Arrhenius plot; and (D) Eyring plot.
resonance analysis showed that the conversion of (CH3)2NHBH3 (δ ’ 12.6 ppm) to [(CH3)2NBH2]2 (δ ’ 5.1 ppm) occurred completely. This indicates that DMAB dehydrocoupling (at 1.0 equiv. H2 generation) can happen at room temperature. Fig. 2.5B was depicted to determine the hydrogen production rate constants throughout the DMAB dehydrogenation. In this figure, the change of conversion percentage at different temperatures (20oC, 25oC, 30oC, and 35oC) was displayed. By using the rate constants and Fig. 2.5C, the Arrhenius plot, the Ea was found to be 46.99 2 kJ mol1. With the help of Fig. 2.5D, the Eyring plot, the Δ H (activation enthalpy) and Δ S (activation entropy) were calculated to be 45.17 kJ mol1 and 68.82 J mol1 K1, respectively. Furthermore, in the DMAB dehydrocoupling’s transition state, an associative mechanism was observed by looking to the activation entropy and the activation enthalpy values. To sum up, in this study, a high catalytic activity was observed when Pd-Ni @AC NPs (316.41 h1) were utilized for the DMAB dehydrocoupling. It should be stated that with the help of Pd-Ni @AC NPs, hydrogen gas (1 mol H2/1 mol DMAB) was completely emitted in the DMAB dehydrogenation within a short time at 25 0.1oC. Pd-Ni @AC NPs can be considered a good nanocatalyst because they are isolable and
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Nanocarbon and its Composites
100
% conversion
100
96
90
85
83
81
80 60 40 20 0 1
2
3
4
5
6
run
Fig. 2.6 Plots % conversion versus time graph for Pd-Ni@AC NPs (7.5 % mol) catalysed dehydrocoupling of DMAB in THF at room temperature for first and sixth catalytic runs.
reusable when utilized in catalytic reactions substantially. The probable reason is the stability of AC and the cooperative and synergistic impact of Pd and Ni in the present study’s catalyst system. Besides, the reusability of the AC-supported Pd-Ni NPs was investigated, as shown in Fig. 2.6. To do that, DMAB was introduced subsequently after the first catalysis reaction in the DMAB dehydrogenation. At the end of the sixth experiment, Pd-Ni @AC NPs maintained 81% of their initial performance. In the DMAB dehydrocoupling, the probable reason for the catalytic activity decrease can be the passivation, as there are increased amounts of nanoparticles on surfaces, and therefore active site accessibility becomes low. The aggregation of NPs was shown after six cycles of the catalytic experiment because, even after six cycles, the catalyst retains its initial content, as found by the ICP analysis (12.95% metals based) study.
2.4
Conclusions
In conclusion, AC-decorated Pd-Ni NPs were shown to be a highly efficient catalyst for DMAB dehydrogenation and the significant steps related to its fabrication, analytical examination, and utilization are as follows: l
l
l
l
l
l
The sodium hydroxide-assisted reduction method was utilized to fabricate Pd-Ni @AC NPs. The results showed that the fabrication method was very operative to distribute Pd-Ni NPs uniformly on the AC material and to prevent the agglomeration problem of Pd-Ni NPs. Pd-Ni @AC NPs had good catalytic performances in DMAB dehydrogenation compared to the literature data. A high TOF (316.41 h1) value was achieved for DMAB dehydrocoupling. 46.99 3 kJ mol1 of Ea was calculated for dehydrocoupling of dimethylamine borane when Pd-Ni @AC nanocatalysts were used. According to these results, Pd-Ni @AC NPs are promising materials and can be used in many catalytic applications as a nanocatalyst.
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35
Acknowledgments The authors would like to thank DPU-BAP (2014-05 and 2015-50) for financial support.
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[15] Sahin B, Demir E, Aygun A, Gunduz H, Sen F. Investigation of the effect of pomegranate extract and monodisperse silver nanoparticle combination on MCF-7 cell line. J Biotechnol 2017;260C:79–83. [16] Rand DAJ, Dell RM. The hydrogen economy a threat or an opportunity for lead–acid batteries. J Power Sources 2005;144:568–78. [17] Baskaya G, Yıldız Y, Savk A, Okyay TO, Eris S, Sen F. Rapid, sensitive, and reusable detection of glucose by highly monodisperse nickel nanoparticles decorated functionalized multi-walled carbon nanotubes. Biosens Bioelectron 2017;91:728–33. [18] Demir E, Savk A, Sen B, Sen F. A novel monodisperse metal nanoparticles anchored graphene oxide as counter electrode for dye-sensitized solar cells. Nano-Struct NanoObjects 2017;12:41–5. [19] Demir E, Sen B, Sen F. Highly efficient nanoparticles and f-MWCNT nanocomposites based counter electrodes for dye-sensitized solar cells. Nano-Struct Nano-Objects 2017;11:39–45. [20] Gezer B, Okyay TO, Bozkurt S, Baskaya G, Sahin B, Uluturk C, et al. Reduced graphene oxide (rGO) as highly effective material for the ultrasound assisted boric acid extraction from ulexite ore. Chem Eng Res Des 2017;117C:542–8. [21] Goksu H, Kilbas B, Sen F. Recent advances in the reduction of nitro compounds by heterogenous catalysts. Curr Org Chem 2017;21:27. [22] Sen F, Ulissi ZW, Gong X, Sen S, Iverson N, Boghossian AA, et al. Spatiotemporal intracellular nitric oxide signaling captured using internalized, near-infrared fluorescent carbon nanotube nanosensors. Nano Lett 2014;14(8):4887–94. [23] Sert H, Yıldız Y, Okyay TO, Gezer B, Dasdelen Z, Sen B, Sen F. Monodisperse Mw-Pt NPs@VC as highly efficient and reusable adsorbents for methylene blue removal. J Clust Sci 2016. https://doi.org/10.1007/s10876-016-1054-3. [24] Sen S, Sen F, Boghossian AA, Zhang J, The SMS. effect of reductive dithiothreitol and trolox on nitric oxide quenching of single walled carbon nanotubes. J Phys Chem C 2013;117(1):593–602. [25] Pamuk H, Aday B, Sen F, Kaya M. Pt NPs@GO as a highly efficient and reusable catalyst for one-pot synthesis of acridinedione derivatives. RSC Adv 2015;5:49295–300. [26] Goksu H, Yıldız Y, Celik B, Yazıcı M, Kilbas B, Sen F. Highly efficient and monodisperse graphene oxide furnished Ru/Pd nanoparticles for the de- halogenation of aryl halides via ammonia borane. Chem Select 2016;(5):953–8. [27] Erken E, Esirden I, Kaya M, Sen F. A rapid and novel method for the synthesis of 5-substituted 1H-tetrazole catalyzed by exceptional reusable monodisperse Pt NPs@AC under the microwave irradiation. RSC Adv 2015;5:68558–64. [28] Erken E, Esirden ˙I, Kaya M, Sen F. Monodisperse Pt NPs@rGO as highly efficient and reusable heterogeneous catalyst for the synthesis of 5-substituted 1H-tetrazole derivatives. Catal Sci Technol 2015;5:4452–7. [29] Yıldız Y, Okyay TO, Sen B, Gezer B, Kuzu S, Savk A, Demir E, Dasdelen Z, Sert H, Sen F. Highly monodisperse Pt/Rh nanoparticles confined in the graphene oxide for highly efficient and reusable sorbents for methylene blue removal from aqueous solutions. Chem Select 2017;2:697–701. [30] Demirci T, C ¸ elik B, Yıldız Y, Eriş S, Arslan M, Sen F, Kilbas B. One-pot synthesis of Hantzsch dihydropyridines using a highly efficient and stable PdRuNi@GO catalyst. RSC Adv 2016;6:76948–56. [31] Yıldız Y, Okyay TO, Sen B, Gezer B, Bozkurt S, Baskaya G, et al. Activated carbon furnished monodisperse Pt nanocomposites as a superior adsorbent for methylene blue removal from aqueous solutions. J Nanosci Nanotechnol 2017;17:4799–804.
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€ Dasdelen Z, Sen F. Carbon black hybride material [32] Yıldız Y, Pamuk H, Karatepe O, furnished monodisperse Platinum nanoparticles as highly efficient and reusable electrocatalysts for formic acid electro-oxidation. RSC Adv 2016;6:32858–62. [33] Koskun Y, Savk A, Sen B, Sen F. Highly sensitive glucose sensor based on monodisperse palladium nickel/activated carbon nanocomposites. Anal Chim Acta 2018. https://doi. org/10.1016/j.aca.2018.01.035. [34] Yıldız Y, Ulus R, Eris S, Aday B, Kaya M, Sen F. Functionalized multi-walled carbon nanotubes (f-MWCNT) as highly efficient and reusable heterogeneous catalysts for the synthesis of acridinedione derivatives. Chem Select 2016;1(13):3861–5. [35] Kang K, Godin K, Kim YD, Fu S, Jang W, Hone J, Yang EH. Graphene-assisted antioxidation of tungsten disulfide monolayers substrate and electric field effect. Adv Mater 2017. https://doi.org/10.1002/adma.201603898. [36] Malgras V, Ataee-Esfahani H, Wang H, Jiang B, Li C, Wu KCW, Kim JH, Yamauchi Y. Nanoarchitectures for mesoporous metals. Adv Mater 2016;28(6):993–1010. [37] Ding J, Fisher FT, Yang EH. Direct transfer of corrugated graphene sheets for stretchable electrodes. J Vac Sci Technol B 2016;5(34):2166. [38] Ayranci R, Baskaya G, Guzel M, Bozkurt S, Ak M, Savk A, Sen F. Enhanced optical and electrical properties of PEDOT via nanostructured carbon materials: a comparative investigation. Nano-Struct Nano-Objects 2017. https://doi.org/10.1016/j .nanoso.2017.05.008. [39] Goksu H, Celik B, Yıldız Y, Kılbas B, Sen F. Superior monodisperse CNT-supported Co-Pd (CoPd @CNT) nanoparticles for selective reduction of nitro compounds to primary amines with NaBH4 in aqueous medium. Chem Select 2016;1(10):2366–72. [40] Jiang B, Li C, Malgras V, Imura M, Tominaka S, Yamauchi Y. Mesoporous Pt nanospheres with designed pore surface as highly active electrocatalyst. Chem Sci 2016;7(2):1575–81. [41] Li Y, Bastakoti BP, Malgras V, Li C, Tang J, Kim JH, Yamauchi Y. Polymeric micelle assembly for the smart synthesis of mesoporous platinum nanospheres with tunable pore sizes. Angew Chem Int Ed 2015;54:1073–11077. [42] Ayranci R, Baskaya G, Guzel M, Bozkurt S, Ak M, Savk A, Sen F. Carbon based nanomaterials for high performance opto-electrochemical systems. Chem Select 2017; 2(4):1548–55. [43] Goksu H, Yıldız Y, Celik B, Yazıcı M, Kılbas B, Sen F. Eco-friendly hydrogenation of aromatic aldehyde compounds by tandem dehydrogenation of dimethylamine-borane in the presence of a reduced graphene oxide furnished platinum nano catalyst. Catal Sci Technol 2016;6:2318–24. [44] Zhang Q, Smith GM, Wu Y. Catalytic hydrolysis of sodium borohydride in an integrated reactor for hydrogen generation. Int J Hydrog Energy 2007;32:4731–5. [45] Amendola SC, Janjua JM, Spencer NC, Kelly MT, Petillo PJ, Sharp –GSL, Binder M. A safe, portable, hydrogen gas generator using aqueous borohydride solution and Ru catalyst. Int J Hydrog Energy 2000;25:969–75. [46] Mohajeri N, T-Raissi A, Adebiyi O. Hydrolytic cleavage of ammonia-borane complex for hydrogen production. J Power Sources 2007;167:482–5. [47] Ramachandran PV, Gagare PD. Preparation of ammonia borane in high yield and purity, methanolysis, and regeneration. Inorg Chem 2007;46:7810–7. [48] C ¸ elik B, Yıldız Y, Sert H, Erken E, Koskun Y, Sen F. Monodispersed palladium–cobalt alloy nanoparticles assembled on poly(N-vinyl-pyrrolidone) (PVP) as a highly effective catalyst for dimethylamine borane (DMAB) dehydro-coupling. RSC Adv 2016;6: 24097–102.
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[96] Ozturk Z, Sen F, Sen S, Gokagac G. The preparation and characterization of nano-sized Pt-Pd/C catalysts and comparison of their superior catalytic activities for methanol and ethanol oxidation. J Mater Sci 2012;47:8134–44. [97] Sen B, Akdere EH, Savk A, Gultekin E, Goksu H, Sen F. A novel thiocarbamide functionalized graphene oxide supported bimetallic monodisperse Rh-Pt nanoparticles (RhPt/TC@GO NPs) for Knoevenagel condensation of aryl aldehydes together with malononitrile. Appl Catal B Environ 2018;225(5):148–53. [98] Sen F, Ertan S, Sen S, Gokagac G. Platinum nano-catalysts prepared with different surfactants for C1-C3 alcohol oxidations and their surface morphologies by AFM. J Nanopart Res 2012;14:922–6. [99] Sen F, Sen S, Gokagac¸ G. Efficiency enhancement of methanol/ethanol oxidation reactions on Pt nanoparticles prepared using a new surfactant, 1, 1-dimethyl heptanethiol. Phys Chem Chem Phys 2011;13:1676–84. [100] Sen F, Sen S, Gokagac G. High performance Pt nanoparticles prepared by new surfactants for C1 to C3 alcohol oxidation reactions. J Nanopart Res 2013;15:1979. [101] Sen F, Gokagac G. Different sized platinum nanoparticles supported on carbon: an XPS study on these methanol oxidation catalysts. J Phys Chem C 2007;111:5715–20. [102] Sen F, Gokagac¸ G. Activity of carbon-supported platinum nanoparticles toward methanol oxidation reaction: role of metal precursor and a new surfactant, tert-octanethiol. J Phys Chem C 2007;11:1467–73. [103] Sen F, Gokagac¸ G. Improving catalytic efficiency in the methanol oxidation reaction by inserting Ru in face-centered cubic Pt nanoparticles prepared by a new surfactant, tert-octanethiol. Energy Fuel 2008;22:1858–64. [104] Sen F, Gokagac G. Pt nanoparticles synthesized with new surfactans: improvement in C1-C3 alcohol oxidation catalytic activity. J Appl Electrochem 2014;44(1):199–207. [105] Sen S, Sen F, Gokagac¸ G. Preparation and characterization of nano-sized Pt-Ru/C catalysts and their superior catalytic activities for methanol and ethanol oxidation. Phys Chem Chem Phys 2011;13:6784–92.