HEI5080_proof • 13 December 2014 • 1/10 INTERN A TfON A LJOURNA L Of' HYDROGtN E:NE:RGY XXX ( 2 014) J - I O Available online at www.sclencedirect.com 65 66 1 ScienceDirect 67 2 68 3 69 4 70 5 journal homepage: www.elsevier.com/locate{he 71 6 ELSEVIER 72 7 73 8 74 9 Synthesis and characterization of polymer 75 10 76 11 (sulfonated poly-ether-ether-ketone) based 77 12 78 13 nanocomposite (h-boron nitride) membrane 79 14 80 15 for hydrogen storage 81 16 82 17 83 18 R. Naresh Muthlia .·,J?. Rajashaballl. a,b, R. Kanna'l c 84 19 ~ 1 1 85 20 • School of Physics, Madurai Kamaraj University, Madurai 625021, TamU Nadu, India 86 21 "Department of Chemistry and Biochemistry, Utah State Uniuersity, Logan, UT 84322-0300, USA 87 22 • Department of Physics, Uniuersity College of Engineering, Anna Uniuersity, Dindigul624622, TamU Nadu, India 88 23 89 24 90 25 ARTICLE INFO ABSTRACT 91 26 92 27 Article history: The development of light weight and compact hydrogen storage materials is still prereq­ 93 28 94 29 Received 7 August 2014 uisite to fuel-cell technology to be fully competitive. The present experimental study reports Received in revised form the hydrogen storage capability of sulfonated poly-ether-ether-ketone (SPED<)-hexagonal 95 30 96 20 November 2014 boron nitride (h-BN) (SPEEK-h-BN) nanO<Dmposite membranes. The nanocomposite mem­ 31 97 32 Accepted 27 November 2014 branes are prepared by considering various amount of h-BN (0, 1, 3 and 5 wt. %) by phase 98 33 Available online xxx inversion technique. The degree of sulfonation of the PEEK (SPEEI<) is found to be 65% by 99 34 Proton Nuclear Magnetic Resonance ('H NMR) spectroscopy. Hydrogen adsorption studies 100 35 Keywords: have been carried out using a Seiverts-like hydrogenation setup. The membranes are 101 36 Polymer nanocomposite (SPEEK-h­ characterized by X-ray Diffractometer (XRD), Micro-Raman spectroscopy, Fourier Transform 102 37 BN) membrane Infrared (FTIR) spectroscopy, Scanning Electron Microscopy (SEM), Atomic Force Microscopy 103 38 Phase inversion technique (AFM), CHN-elemental analysis and Thermo Gravimetric Analysis (rGA). It is observed that 104 39 105 40 Seivert's hydrogenation setup the SPED<-5% h-BN membrane performs better than pure SPED< membrane, has maximum Hydrogen storage storage capacity of 2.98 wt.% at 150 •c and the adsorbed hydrogen has an average binding 106 41 107 energy of 0.38 eV. The TGA study shows the dehydrogenation behavior of hydrogenated 42 108 43 SPED< -h-BN nanocomposite membrane and it is found to be in the temperature range of 214 109 - 218 for SPEEK-5% h-BN membrane. 44 •c 110 45 Copyright 0 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights 111 46 reserved. 112 47 113 48 114 49 115 50 116 51 117 52 118 53 sources like wind, solar, super capacitor and fuel cells have Introduction 119 54 ~n developed recently and are used effectively. Nowadays 120 55 hydrogen is considered as the most pr·omising and potential 121 56 The major challenges in the recent years are the reduction of alternative energy carrier lhat can facilitate the transition 122 57 fossil fuels and global warming (1]. Necessity is the driving from fossil fuels to sources of clean energy (2,3]. The devel­ 123 58 force fo r finding innovative technologies. Alternative energy opment of fuel cell power systems has enabled hydrogen as an 124 59 125 60 126 61 • Corresponding author. Tel: +91 7708980409(mobile). 127 62 E-mail address: maresh7708@gmailcom (R. Naresh Muthu). 128 http://dx doi.org/10.1016/j.ijhydene. 2014.11.136 63 129 64 0360-3199/CopyrightO 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ud. All rights reserved. Please cite this article in press as: Naresh Muthu R, eta!., Synthesis and characterization ofpolymE!!' (sulfonated poly-ether­ ether-ketone) based nanocomposite (h-boron nitride) membrane for hydrogen storage, International Journal of Hydrogen .Energy (2014), http://dx.doiorgl10.10161j1jhydene. 2014.11.136 HEI5080_proof • 13 December 2014 • 2/10 2 lNT!RNA TlON A LJOURN A L OF HYDROGEN I:NE:RGY XX X (20 14) I-1 0 1 alternative to conventional systems (4]. Although hydrogen is polymers with platinum (P~ nanoparticles was analyzed and a 66 2 often presented as the fuel of the future, the developmentofa maximum storage capacity of0.21 wt.% at298.15 K and 19 bar 67 3 hydrogen-based fuel is rather difficult Hydrogen has to be was noticed (28]. Hypercrosslinked polystyrene - Pt nano­ 68 4 produced, stored, distributed and used, but each ofthese steps particles display a hydrogen uptake of 0.36 wt.% at 294 K and 69 5 is hindered due to several factors (5]. Multiple challenges must 100 atrn (29]. The PANl impregnated with tin oxide, multiwall 70 6 71 be overcome to achieve the vision of secure, abundant, inex­ carbon nanotubes (MWCNTs) and aluminum powder (AI) 7 72 pensive, and clean hydrogen production with low carbon exhibit 0.31, 0.38, 0.5 wt. %of hydrogen adsorption at 115 •c 8 73 9 emissions (4,6,7]. and 70 bar (30]. Hydrogen storage capacity of halloysite 74 10 In the prospect of a hydrogen-based economy, the major nanotubes (HNT) - PANl nanocomposite was examined by 75 11 issue is to address how to reversibly store hydrogen while Attia et al. (31] and noticed 0.78 wt% of hydrogen was stored 76 12 minimizing energy consumption. Three major approaches at room temperature and a pressure of0.5 MPa. The hydrogen 77 13 (8,9], compression for storage in tank, storage by purely storage capacity of poly (ether-ether-ketone) functionalized in 78 14 physical absorption and storage via chemical reaction or situ by manganese oxide formation, showed a hydrogen 79 15 chemical storage are in the forefront of current research ef­ storage capacity of 1.2 wt.% at 77 K (6]. The hydrogen storage 80 16 forts. Direct use ofcompressed hydrogen as a fuel encounters capacity of acid treated water-soluble polymers such as 81 17 major constraints due to large tank volumes, short lifetimes of polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP) doped 82 18 83 the storage system and stringent safety measures, in addition single-walled carbon nanotubes (SWCNTs) has shown to be 19 84 20 to high investment costs and portability. 1.2 and 1.5 wt. %, respectively at 50 •c (32]. Kim et el (33]. re­ 85 21 A lot of research works have been carried out on hydrogen ported that the PAN! - vanadium oxide nanocomposites 86 22 rich materials like chemical hydrides (10], complex hydrides (VON C) showed storage capacity of1.8 wt.% at 77 K and 70 bar. 87 23 (11] and metal hydrides (12] that store hydrogen by chemi­ The activated rectangular PANl-based carbon tubes (ARP-CTs) 88 24 sorption. In the last two decades, over 350 distinct materials exhibited the hydrogen adsorption of 5.2 wt. % at 77 K and 89 25 have been investigated experimentally (13] and more than 70% 5 MPa and 0.62 wt.% at 293 K and 7.5 MPa respectively (34]. 90 26 have been discontinued as potential candidates for hydrogen­ Makridis et al. (4] studied Mg doped polymethylmethacrylate 91 27 fuel cells. Although some complex metal hydrides (such as, (PMMA) which exhibited 6 wt. % at 250 •c. The Li-conjugated 92 28 93 MgH , NaBH , Ca(BH,}.,, AlH , K,LiAIH , etc.) have advantages of microporous polymers could able to store more than 6 wt % 29 2 4 3 6 94 high gravimetric density (-15- 20 wt. % of H.) and high volu­ of hydrogen at 77.3 K and at 1 bar (35]. 30 95 31 metric density (about 150 g H,/IJ, major disadvantages were Up to date, none of the proposed hydrogen storage systems 96 32 found to be high desorption energy, slow kinetics and toxic appears able to match US-DOE targets. Recent studies showed 97 33 byproducts, besides cyclability as a major issue. that the polymer nanocomposites could be an attractive ma­ 98 34 Large specific surface area materials such as carbon terial for hydrogen storage. The present work is aimed at the 99 35 nanotubes (14], metalorganic frameworks (15,16] and zeolites synthesis and characterization of light weight and compact 100 36 (15,17] store hydrogen by physisorption and in most of these hydrogen storage material based on polymer nanocomposite 101 37 cases hydrogen uptake are not so high. Recent reports have using sulfonated poly (ether-ether-ketone) (SPEEK) and hex­ 102 38 demonstrated that boron nitride (BN) nanomaterial can be agonal boron nitride (h-BN) nanoparticles, where the PEEK has 103 39 used as a potential hydrogen storage medium (18- 22]. Hex­ excellent mechanical and chemical properties and thermal 104 40 105 agonal boron nitride (h-BN) is an analoL of graphite, has stability (36,37]. The dipolar nature of B~bonds in hexagonal 41 106 unique physical and chemical properties, including high boron nitride (h-BN) can have stronger absorption of hydrogen 42 107 43 specific surface area, low density, high mechanical strength from hydrocarbons. where phase inversion technique is 108 44 and oxidation resistance (22- 24]. Weng et al. (18] reported the employed for the preparation of microporous SPEEK-h-BN 109 45 ability of BN porous microbelts to exhibit high and reversible nanocomposite membranes. So it is expected that the light 110 46 hydrogenuptakeof23wt.% at n Kand 1 MPa. Wangetal. (19] weight and more micro porous nature of SPEEK could accom­ 111 47 reported a hydrogen storage capacity of 2.6 wt % in h-BN modate more h-BN nanoparticles which in tum can adsorb 112 48 powders under the hydrogen pressure of 1.0 MPa.