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Modication of single wall carbon nanotubes (SWNT) for hydrogen storage

A.M. Rashidi a,*, A. Nouralishahi a, A.A. Khodadadi b, Y. Mortazavi b, A. Karimi a, K. Kashe a
a b

Nanotechnology Research Center, Research Institute of petroleum industry (RIPI), Tehran, Iran Chemical engineering Department, University of Tehran, Tehran, Iran

article info
Article history: Received 11 August 2009 Received in revised form 17 February 2010 Accepted 7 March 2010 Available online 1 May 2010 Keywords: Hydrogen Single wall carbon nanotubes Activated carbon Physisorption

abstract
Due to unique structural, mechanical and electrical properties of single wall carbon nanotubes, SWNTs, they have been proposed as promising hydrogen storage materials especially in automotive industries. This research deals with investing of CNTs and some activated carbons hydrogen storage capacity. The CNTs were prepared through natural gas decomposition at a temperature of 900C over cobalt-molybdenum nanoparticles supported by nanoporous magnesium oxide (CoeMo/MgO) during a chemical vapor deposition (CVD) process. The effects of purity of CNT (80e95%wt.) on hydrogen storage were investigated here. The results showed an improvement in the hydrogen adsorption capacity with increasing the purity of CNTs. Maximum adsorption capacity was 0.8%wt. in case of CNTs with 95% purity and it may be raised up with some purication to 1%wt. which was far less than the target specied by DOE (6.5%wt.). Also some activated carbons were manufactured and the results compared to CNTs. There were no considerable H2storage for carbon nanotubes and activated carbons at room-temperature due to insufcient binding between H2 molecules carbon nanostructures. Therefore, hydrogen must be adsorbed via interaction of atomic hydrogen with the storage environment in order to achieve DOE target, because the H atoms have a very stronger interaction with carbon nanostructures. 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.

1.

Introduction

Hydrogen is a sustainable and renewable energy carrier and is the cleanest one. The existing fossil fuels are expected to be replaced by hydrogen energy systems in the future. The concept of hydrogen based systems was born in mid 1970s, against a background of the worldwide oil crisis [1e4]. There are four different technologies for storing hydrogen as follows: (1) Cryogenic liquid hydrogen (LH); (2) compressed gas storage;

(3) metal hydride storage technology; (4) Physisorption methods of hydrogen storage. Hydrogen storage in high-pressure cylinders is the most convenient and industrially approved method among all other storage methods. However hydrogen compression is a considerably power consuming process. Furthermore, Safety is the main problem of hydrogen storage in gas cylinders. On the other hand, there is extremely high power consumption in hydrogen liquefaction and liquid hydrogen

* Corresponding author. E-mail address: rashidiam@ripi.ir (A.M. Rashidi). 0360-3199/$ e see front matter 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.ijhydene.2010.03.038

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storage. Additionally, there are always high evaporation losses in cryogenic liquid H2 technology due to heat penetration from environment [1,2]. Low weight content of hydrogen atoms is the main drawback of low-temperature metal hydrides (MH) methods for hydrogen storage. Although, High temperature metal hydrides processes have larger weight capacity and a smaller price, they should take place at increased temperatures (250e350  C) because of slow hydrogen absorption/desorption kinetics [5]. Physisorption of hydrogen in some porous materials especially carbon nanostructures such as CNT is another method for storage of hydrogen. In this process hydrogen adsorbed by physical methods and H2 molecules lie in adsorbent interspaces with no interaction with the storage medium. In spite of high stability in cycling operation for hydrogen storage (Table 1), the physisorption based storage processes have low hydrogen capacity, due to insufcient binding between H2 molecules and adsorbent surface, [6]. Because of several advantages of Physisorption such as fast hydrogen sorption kinetics, feasible thermodynamics and sorption/desorption cyclic stability [7e9], Hydrogen storage on carbon materials has been of great concern in recent years [10e17]. Erdogan and Kopac studied sorption characteristic of H2 and N2 gases in activated carbon with different particle sizes in a temperature range of 303e473 K using a dynamic technique [18]. They concluded that the interactions between Adsorbent and hydrogen should be enhanced by increasing pore size, surface area and some surface modication studies in order to improve adsorbent capacity. Hydrogen storage capacity of various carbon materials, including activated carbon (AC), single-walled carbon nanohorn, single-walled carbon nanotubes, and graphitic carbon nanobers, was investigated by Xu et al. [19]. They reported all carbon materials adsorbed hydrogen gas physically. Hou et al.[20] investigated hydrogen storage capacity of MWNT with different mean outer diameters in the range of 13e53 nm, and reported that hydrogen storage capacity of MWNT was proportional to their diameter, up to 4.6%wt. at 293 K and 13.5 MPa. Gayathri and her coworkers [21] reported a density functional calculation of the adsorption of molecular hydrogen on the external surface of coiled carbon nanotube (CCNT) and concluded that the binding energy values are larger than linear (5,5) armchair nanotube, which had approximately same diameter as that of coiled carbon nanotube. They proposed that the curvature and topology of CCNT are responsible for this considerable enhancement.

Table 2 e General characteristic of CNT for hydrogen storage. Advantages

Low density High chemical and mechanical stability Fast kinetic Appropriate thermodynamic High sorption/desorption cyclic stability Strong CeH bond

Disadvantages
Low hydrogen storage capacity at standard condition Low desorption temperature Expensive bulk production Purication problem

Hydrogen storage capacities of various carbon adsorbents have been summarized in several papers [22e24]. General characteristics of CNTs for hydrogen storage are listed in Table 2. The Hydrogen storage densities of different carbon nanostructures after year 2001 are reported in Table 3. It is interesting that the hydrogen storage capacity on CNT varies widely in different studies. This can be caused by the impurity (metal catalysts, amorphous carbon) and the pretreatment processes of the samples before adsorption tests [19]. Generally, carbon nanostructures adsorb hydrogen physically. This can cause some advantage and disadvantage compared to other materials used for hydrogen storage. Some specications of different materials which are used for storage of hydrogen are compared in Table 4. In this paper, we studied the physisorption method for hydrogen storage on single wall carbon nanotubes and activated carbons. Also the effect of purication and physical/ chemical treatment of single wall carbon nanotubes on its adsorption capacity were investigated.

2.

Experimental

We synthesized single wall carbon nanotubes through natural gas decomposition at 900  C over cobalt- molybdenum nanoparticles supported by nanoporous magnesium oxide (CoeMo/ MgO) during a chemical vapor deposition (CVD) process [33]. The reaction of natural gas decomposition was conducted at atmospheric pressure with a holding time of 20e50 min. The as produced CNTs were puried by acid washing and drying steps and characterized by different methods including: BET,

Table 3 e Different carbon nanostructure density. Material Table 1 e Hydrogen storage different cyclic adsorption performance [1,2]. Storage method
Compressed gas storage Cryogenic liquid hydrogen Metal hydride Physisorption

Hydrogen T Pressure storage (K) (Bar) density (%wt.)

1e6 2.3e3.1 1.5 1.2 0.9 0.6 0.55 0.43 0.25 77 298 298 298 294 78 298 298 303 20 100 1e6 48 200 2 18 80 30

Reference

Year

Temperature Pressure Cyclic adsorption (K) (bar) performance (%)

298 20 293e573 77 200e250 1e5 1e60 1e10 80 60 75 90

SWNT Zr-MWNT Pd-CNF SWNT SWNT SWNT MWNT SWNT SWNT

Pradhan [25] Shaijumon [26] Biri [27] Smith [28] Lawrence [29] Zuttel [30] Zacharia [7] Kajiura [31] Takagi [32]

2002 2003 2004 2003 2004 2002 2005 2003 2004

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Table 4 e Comparison of different hydrogen adsorbent. Examples

Metal hydride Chemical hydride MgH2 Mg2NiH4 NaAlH4 LiBH4 Mg (BH4)2 CNTb AC CDC MOFc

Bonding with H
Chemical Chemical

Tdesa
Too high High

Kinetics
Slow Moderate

Advantages
High capacity Very high capacity

Disadvantages
Irreversible Regeneration

Carbon-based materials

Physical

Too low

Fast

Reversible

Low capacity

Metal-organic hybrids

Physical

Too low

Fast

Large surface area

Low capacity

a Hydrogen desorption temperature (Tdes). b Carbon nanotubes (CNT), activated carbon (AC), and carbide-derived carbon (CDC). c Metal-organic framework (MOF).

physisorption, X-ray diffraction, SEM, TEM and Raman spectroscopy. The results showed bundle of SWNTs with an aspect ratio of 10,000 and the diameter of 0.8e1.1 nm (Fig. 1). To investigate the CNTs hydrogen storage capacity some experiments were designed and a setup (Fig. 2) was established. At rst, 1 g of a sample was loaded in the adsorption reactor and attached to the system. Second, the existing gas inside the system was swept out with helium. After opening all of the valves except 2, 7 and 9 the system was vacuumed and then the valve 5 was closed and He owed into the system through valve 2 and 4 and the pressure of the system raised up to 1 bar. After opening the valves 3, 4 and 7 the HP vessel loaded an appropriate pressure, then these valves were closed and the system was vacuumed again. The hydrogen was adsorbed by opening the valves 3, 1 and closing all other valves. The pressure of HP vessel decreased due to some dead volume in reactor (including hollow space and the connected tubes) and some adsorption. By measuring the dead volumes, one could calculate the exact pressure decrease because of hydrogen adsorption.

3.

Results and discussions

The CNTs prepared by a chemical vapor deposition (CVD) were tested by hydrogen adsorption experiments. At the rst step, Hydrogen adsorbed on CNTs with 80% purity and the results were plotted in Fig. 3. As shown in graph 3, the maximum hydrogen adsorption was 0.4%wt. which was far less than the target of DOE. This can be due to metal particles closing the opening of the CNTs which is clearly showed in Fig. 4. In order to increase the adsorption capacity of CNTs, some additional steps consist of drying at 100  C, oxidation with H2O2 for 3 h and reux with hydrochloric acid for 18 h were done. The resulted carbon nanotubes had a purity of 90% according to TGA results [33] and were tested again (Fig. 5). Fig. 5 shows a high dependency of adsorption capacity and amount of purity. In fact, elimination of metal particles from CNT opening can cause more adsorption capacity, because the inner space of carbon nanotubes has the highest potential for hydrogen adsorption. That is why purication and acid washing can improve CNTs performance. Besides, oxidation with different agent such as H2O2 eliminates carbon amorphous

and other carbon structures which results in higher purity and capacity. Elimination of metal nanoparticles from CNT opening and shorten of carbon nanotubes by cutting them can expose more space for adsorption. Therefore, the CNTs with the purity of 90% were treated by annealing under hydrogen atmosphere at 1200  C and Then they were cut by following steps; rst, 1 g of SWNT with purity of 90% was stirred in sulfuric acid at ambient temperature for half of an hour. Then 180 cc of concentrated nitric acid was added to the solution and temperature raised to 60  C for 3 h. Finally, the resulted solution was washed, ltered and dried at 120  C. CNTs had 95% purity after above treatments and its surface area increased to 700 m2/g from 550 m2/g for 90% pure CNTs and 480 for 80% pure CNTs. The hydrogen capacity of these CNTs are plotted in Fig. 6. As it can be seen in Fig. 6, more purication step consisting of Cutting and annealing caused a growth in carbon nanotubes capacity with maximum of 0.8%wt. this is because of increase in surface area and elimination of defects in crystal structures and probably removal of metal nanoparticles from CNTs opening. However, it can achieve to 1%wt., when the purication steps continue. We manufactured and characterized different activated carbon samples in order to compare their hydrogen capacity with the carbon nanotubes samples. First activated carbon made from nut shell as the precursor and phosphoric acid as the oxidant with an acid/precursor ratio of 1.15 (AC3-NNS). This sample was rewashed with a solution of concentrated hydrochloric acid acid and water with a ratio of 1:1 and then was placed in a quartz reactor and heated up to 900  C for 5 h under an atmosphere of 5% CO2 and 95% N2 (AC3-NNS-DW). In order to make two other samples, the above procedures were repeated with ZnCl2 as an oxidant with the ratio of 0.82 (AC2-NNS) and the CO2 activation process was exactly the same for sample AC2NNS-DW, the detailed information is explained elsewhere [34]. It is very interesting to note that the surface area of activated carbon samples is much higher than carbon nanotubes but their hydrogen capacity is lower (Table 5). Although, the BET surface area is a very important parameter in adsorption phenomenon, there are still some other factors inuencing the storage capacity. For instance the instinct radial curved structure of carbon nanotubes causes the p electrons in sp2 hybrid orbital to arrange asymmetrically around carbon

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Fig. 1 e TEM (a), SEM (b) and Raman spectroscopy (c, d) of the produced SWNTs.

atoms. This in turn, can affect inter molecular eld forces between adsorbent structure and hydrogen molecules and may cause an improvement in hydrogen capacity. It should be noted that post treatment on carbon nanotubes increases the

defects on SWNT wall structure which make different type curvatures. On the other hand, it should be noted that since the size of activated carbon grains are remarkably higher than the

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Fig. 2 e Setup for sorption/desorption capacity test.

nanopore diameters, therefore high portion of its surface area cannot be reachable by the hydrogen molecules, properly. Also, the carbon surfaces functional groups play an important role in physisorption on several molecules because of their key function in the determination of force elds. Since the SWNT samples were acid washed with stronger oxidizing agents (i.e., H2SO4, HNO3, H2O2, HCl), the concentration of oxyfunctional groups are much higher than activated carbon samples, therefore the interaction of carbon nanotubes and hydrogen molecules may be much stronger than in case of activated carbon and their capacity increase. The obtained results are far less than DOE targets. It is because hydrogen adsorbed on carbon nanostructures by physical attractions and H2 molecules lie in CNT interspaces without a strong interaction with storage medium, therefore, to achieve a high capacity by physisorption method at

ambient temperature is impossible. Although, simultaneous cooling down during physisorption process can rise up the hydrogen storage capacity, it is not applicable for several reasons. Since hydrogen atoms have stronger interaction with CNT structures, it is believed that in order to improve CNTs adsorption capacity and to achieve the DOE targets, hydrogen must be adsorbed via interaction of atomic hydrogen with the adsorbent surface.

Fig. 3 e Hydrogen adsorption capacity of SWNTs with 80% purity.

Fig. 4 e TEM image of open ended SWNT with 90% purity.

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4.

Conclusion

Fig. 5 e Hydrogen adsorption capacity of SWNTs with 90% purity.

However, investment of hydrogen sorption properties of different well dened carbon nanostructures is very interesting from the fundamental point of view, and growing research activities will result in better understanding of different gasesolid interaction mechanisms.

This research studied hydrogen physisorption on carbon nanostructures (i.e., SWNTs and activated carbons). The SWNTs were prepared by a chemical vapor deposition (CVD) method. The effects of SWNT purity (80e95%wt.) on hydrogen storage were investigated and compared to activated carbons results. On SWNTs, it was shown an improvement in the hydrogen adsorption storage with increasing the purity with maximum capacity of 0.8%wt. for 95% purity which may be raised up to 1%wt. with some more purications. Also different activated carbons were manufactured and the results compared to CNTs. The best activated carbon just adsorbed almost 0.2%wt. which was far less than the target specied by DOE (6.5%wt.). There were no considerable hydrogen physisorption carbon nanostructures at roomtemperature due to insufcient binding between H2 molecules and carbon nanostructures. Therefore, adsorption of hydrogen via interaction of atomic hydrogen with the carbon adsorbent structure can result in better capacity, because the H atoms have very stronger interactions with carbon nanostructures.

references

Fig. 6 e Hydrogen adsorption tests on the SWNT after annealing and cutting.

Table 5 e Hydrogen adsorption data on different carbon nanostructures. Sample names

AC3-NNSa AC3-NNS-DWb AC2-NNSc AC2-NNS-DWb SWNT 80% SWNT 90% SWNT 95%

Amount of hydrogen adsorption (%wt.)

0.13 0.19 0.12 0.14 0.39 0.53 0.8

BET surface area (m2/g)

1212 1650 321 512 480 550 700

a Activated carbon synthesized by phosphoric acid. b DW: double washing with physical treatment. c Activated carbon synthesized by ZnCl2.

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