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I N T E R N AT I O N A L J O U R N A L O F H Y D R O G E N E N E R G Y 33 (2008) 1688– 1692

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journal homepage: www.elsevier.com/locate/ijhydene

Hydrogen adsorption on porous silica

D.A. Sheppard, C.E. Buckley


Department of Imaging and Applied Physics, Curtin University of Technology, GPO Box U 1987, Perth, WA, Australia

ar t ic l e i n f o abs tra ct

Article history: A number of MCM-41 samples were produced with different ageing times and zinc dopant
Received 22 May 2007 levels. Hydrogen adsorption experiments performed at 77 K on pure MCM-41 samples
Received in revised form showed a maximum excess wt% uptake of 2.01%. Samples were doped with Zn in the Si:Zn
10 December 2007 ratio of 50:1, 25:1 and 10:1. These samples showed an increase in d-spacing in their XRD
Accepted 10 December 2007 patterns, suggestive of Zn incorporation into the structure but resulting in a decrease in
Available online 5 March 2008 long range pore ordering and surface area with increasing Zn content. Two of the three
doped samples showed an increase in H2 adsorbed per unit surface area suggestive of
Keywords:
increased interaction strength. However, definitive confirmation is difficult due to
Hydrogen storage material
degradation of the pore structure and surface area. Adsorption at room temperature was
Porous material
minimal, being 0.1 wt% or below.
Silica
& 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights
MCM-41
reserved.
Hydrogen
Zinc
Doping

1. Introduction continue to increase at higher hydrogen pressure. Interest-


ingly, hydrogen uptake at room temperature showed a
maximum adsorption of 0.9 wt% which peaked at 20 bar
Hydrogen storage is currently an intense area of research.
before plateauing. In zeolite research, metal cations including
Numerous materials are being investigated for hydrogen
zinc, nickel and iron [6–8] have been incorporated into zeolite
storage including metal hydrides, various forms of carbon,
structures and have been shown to be active sites for
zeolites and metal-organic frameworks [1]. MCM-41 is a silica-
hydrogen adsorption. Here we present results for H2 adsorp-
based material with a regular hexagonal array of cylindrical
tion of a number of pure MCM-41 samples as well as samples
pores. The pore walls are amorphous but the regular array of
doped with different levels of zinc. These samples reversibly
cylindrical mesopores generates diffraction peaks at low
absorb hydrogen at 77 K and were characterised by X-ray
scattering angles [2]. Nijkamp et al. [3] have examined
diffraction (XRD), N2 adsorption and H2 adsorption.
hydrogen adsorption on MCM-41 at 77 K but only up to a
pressure of 1 bar and measured an adsorption of 0.58 wt%. We
performed a similar experiment but at higher pressure and
showed that for our sample, excess H2 uptake reached a 2. Experimental
maximum of 1.6 wt% at 35 bar [4]. Recently, Jung et al. [5]
measured the hydrogen adsorption of an organic–inorganic Five MCM-41 samples were made from a mixture of sodium
silica hybrid material with a similar pore structure to MCM- silicate, cetyltrimethylammonium bromide (CTAB), sulphuric
41. Measurements at 77 K were only performed up to 0.8 bar acid and water in a similar manner to Edler and White [9]. All
but showed an uptake of 0.6 wt%. The shape of their samples made via this method had the molar ratio
adsorption curve suggests that hydrogen uptake would 1SiO2 : 0:26CTAB: 0:09H2 SO4 : 275:6H2 O. The pH of the solution

Corresponding author. Tel.: +61 8 9266 3532; fax: +61 8 9266 2377.
E-mail address: c.buckley@curtin.edu.au (C.E. Buckley).
0360-3199/$ - see front matter & 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2007.12.021
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was reduced to 10 with the addition of 1 M H2 SO4 before being


aged statically at 70  C for periods ranging from 1 h to 4 days.
Every 24 h period the solution was readjusted to a pH of 10
hereafter referred to as Method 1. Initial experiments showed
that calcined samples of high quality with up to five
diffraction peaks [4], as seen with small angle X-ray scatter-
ing, could be produced using substantially more dilute
surfactant as compared to the literature [9]. This had the
benefit of removing gelation during the addition of
sodium silicate to the CTAB surfactant solution. Conse-
quently, a sample with very dilute surfactant content was
tried with the starting chemical composition 1SiO2 : 0:17CTAB:
0:09H2 SO4 : 275:6H2 O and aged for 4 days using the above
method of pH adjustment, hereafter referred to as Method 2.
Zinc has been shown to act as an adsorption site for hydrogen
at low temperatures. To investigate if it would perform a
similar role in MCM-41, three samples were doped with zinc
in the silicon to zinc ratios of 50:1, 25:1 and 10:1, respectively. Fig. 1 – XRD patterns of six calcined samples made with
This was achieved by adding ZnSO4  7H2 O during the initial different ageing periods. Each pattern is offset for clarity.
mixing of reagents and ageing was performed for 2 days, (a) Sample made via Method 1 and aged for 1 h. (b) Sample
hereafter referred to as Method 3. The final samples were made via Method 1 and aged for 8 h. (c) Sample made via
filtered and calcined at 500  C for 8 h to remove the CTAB. XRD Method 1 and aged for 24 h. (d) Sample made via Method 1
patterns were collected on a Siemens D500 using a step size of and aged for 48 h. (e) Sample made via Method 1 and aged
0.041 2y and a wavelength, l, of 0.154056 nm. Nitrogen for 96 h. (f) Sample made via Method 2 and aged for 96 h.
adsorption/desorption isotherms were collected at the
Australian Nuclear Science and Technology Organisation
(ANSTO) on a Micromeritics ASAP 2400. Pore size analysis The excess wt% of H2 adsorption curves obtained at 77 K are
of N2 adsorption/desorption curves were done using a shown in Fig. 2. The desorption curves followed the adsorp-
modified BJH method [10] specifically tailored for MCM-41. tion curves and so have been excluded for clarity. The result
Hydrogen adsorption experiments were performed at 77 K at from the sample made via Method 1 and aged for 24 h has also
Curtin using a volumetric/Sieverts type apparatus. The been excluded as the sample mass used was too low for the
compressibility of hydrogen was accounted for by using resolution of the Sieverts apparatus. At 77 K, the kinetics of
two different equations. For ambient temperatures, the adsorption is similar for all the samples with equilibrium
Hemmes equation of state [11] was used following the being reached within a minute. Excess hydrogen adsorption
method of McLennan and Gray [12]. For 77 K, the NIST for the pure MCM-41 samples ranged between 1.68 and
Standard Reference Database Number 69 was used [13]. 2.01 wt%. Peak adsorption for these samples generally
The excess weight percent of hydrogen adsorbed was occurred between 30 and 45 bar, a similar pressure range to
calculated where excess is defined as the hydrogen adsorbed that previously reported for activated carbons [15,16]. The
on the surface of the sample in excess of what would be uncertainties displayed in Fig. 2 are influenced by a number of
there due to the applied hydrogen pressure alone. This factors. The primary factor is the uncertainty in the volume of
method can be misleading as to the true effectiveness of an the sample cell maintained at 77 K. The second factor is the
adsorbate [14], but is the most common used in the literature bulk density of the MCM-41 (which does vary from sample to
for reporting hydrogen uptake by porous materials. Samples sample) and consequently the mass of sample that can fit
were evacuated at 200  C overnight prior to hydrogen adsorp- into the sample cell while the third factor is how much
tion experiments and the pore wall density was taken to hydrogen the sample adsorbs.
be 2:2 g=cm3 . If we consider dispersion forces to be the basis for hydrogen
adsorption at low temperatures, then there are two main
factors which dictate how much a sample will adsorb. The
3. Results and discussion first factor is surface area and the second factor is pore size.
Wang and Johnson [17] have shown that, at least for a slit pore
Fig. 1 depicts the XRD patterns on the calcined MCM-41 geometry, pores of between 9 and 12 Å in size show the best
samples made via Method 1. Each pattern has been offset by storage in terms of optimising both the gravimetric (total
11 in 2y and 20,000 counts for clarity. As can be seen, an hydrogen contained in a pore accounting for both excess
increase in ageing time results in a decrease in the FWHM of adsorption and compression) and volumetric (mass of
the main (1 0 0) diffraction peak. The intensity of the (1 1 0) hydrogen per unit of storage volume) storage of hydrogen.
and (2 1 0) peaks increase and the FWHM also decreases with Their results for cylindrical pores were more mixed [18].
ageing time suggesting an increase in the ordering of the Decreasing pore size means that the interaction potential of
long-range pore structure. BET analysis of the N2 adsorption/ the walls may overlap and thus increase the interaction
desorption curves show that the pure MCM-41 samples had strength with the adsorbate. But this also results in a decrease
surface areas between 916 and 1060 m2 =g. in the total amount of hydrogen contained within the sample
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1690 I N T E R N AT I O N A L J O U R N A L O F H Y D R O G E N E N E R G Y 33 (2008) 1688 – 1692

Fig. 2 – Excess wt% of H2 adsorbed on MCM-41 samples measured at 77 K.

as the skeletal density of the adsorbent increases [18]. The


path to increase adsorption would then seem to be reducing
the pore size while increasing the available surface area.
However, with MCM-41 a decrease in the pore size results in
an increase in the wall thickness [10] and the overall effect is
to reduce the surface area. To compound this, steric effects
between the curved pore wall and hydrogen reduce the
effective surface area further as the pore size decreases [17]
and the increased adsorption potential is not enough to
overcome this loss in surface area.
For ambient hydrogen storage conditions, the enthalpy of
adsorption required has been determined to be 15.1 kJ/mol H2
[19]. For adsorption of hydrogen on high surface area carbons,
presumably due to dispersion forces alone, the enthalpy of
adsorption has been measured as being between 3.9 and Fig. 3 – (a) XRD patterns of three samples made with
6.5 kJ/mol H2 [20,21]. Recently, experiments with zeolites [6–8] different Zn dopant levels each aged for 48 h. Patterns are
have shown that co-ordinately unsaturated metal sites have offset for clarity. Si:Zn ratio of (a) 10:1; (b) 25:1; (c) 50:1.
increased interaction strength with hydrogen. Simulations of
negatively charged single-walled carbon nanotubes have also
shown an increased affinity for hydrogen [22] Based on these peak are indistinct in the sample doped at a 50:1 Si:Zn ratio
results, a number of groups [23,24] have incorporated co- and are practically absent at higher loadings. The position of
ordinately unsaturated metal sites in Metal Organic Frame- the (1 0 0) peak also shifts to lower 2y (Table 1) indicating an
work materials [25] and have observed enthalpies of adsorp- increase in the average distance between pore centres. BJH
tion of around 10 kJ/mol H2 . Zinc incorporation into MCM-41 analysis of the N2 adsorption/desorption curves shows that
is believed to create a negative charge on the pore wall [26] the pore size stays relatively constant though there is a
and so it is of interest to see if this charge creates any broadening in the pore size distribution as compared to pure
increased strength of interaction with hydrogen. MCM-41. The consequent increase in wall thickness suggests
The samples doped with Zn show a marked deterioration in that the Zn is being incorporated into the bulk since the Zn–O
the long ranged ordering of the pore structure (see Fig. 3). The bond is longer than the Si–O bond [27].
sample with the lowest zinc loading ðSi: Zn ¼ 50 : 1Þ had only a Excess hydrogen adsorption at 77 K yielded for the samples
slightly reduced surface area of 860 m2 =g while the sample doped at Si: Zn ¼ 50 : 1, 25:1 and 10 : 1 values of 1.83, 1.18 and
with Si: Zn ¼ 25 : 1 had a surface area of 717 m2 =g and the 1.07 wt%, respectively. If we consider the excess hydrogen
sample with the highest zinc loading ðSi: Zn ¼ 10 : 1Þ had a adsorption per unit area, then the pure MCM-41 samples
surface area of only 516 m2 =g. In the XRD patterns for the Zn adsorbed between 1.78 and 1.90 wt% of H2 per 1000 m2 =g. The
doped samples, higher order reflections beyond the (1 0 0) sample with Si : Zn ¼ 25 : 1 adsorbed 1.65 wt% per 1000 m2 =g
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Table 1 – Summary of N2 adsorption/desorption and XRD peak position analysis

Method Ageing (1 0 0) peak Repeat Surface area ðm2 =gÞ BJH pore Wall
time (h) position (Å) distance (Å) ðp=po ¼ 0:0120:1Þ size (Å) thickness
(Å)

1 1 33.7 38.9 994 31.4 7.5


1 8 35.1 40.5 991 32.6 7.9
1 24 36.8 42.5 1032 34.0 8.5
1 48 36.2 41.8 982 33.4 8.4
1 96 36.2 41.8 916 34.0 7.8

2 96 36.5 42.1 1060 34.0 8.1

3—Si:Zn ¼ 50:1 48 35.9 41.5 875 34.0 7.5


3—Si:Zn ¼ 25:1 48 40.2 46.4 717 32.8 13.6
3—Si:Zn ¼ 10:1 48 52.6 60.7 516 35.6 25.1

while the Si: Zn ¼ 50 : 1 and Si: Zn ¼ 10 : 1 showed hydrogen and Engineering for the granting of an Australian Post
uptake of 2.09 and 2.07 wt% per 1000 m2 =g, respectively. The Graduate Research Award (PGRA).
relatively poor hydrogen adsorption of the sample doped at
Si: Zn ¼ 25 : 1 cannot be readily explained. At pressures below R E F E R E N C E S
15 bar, this sample behaves as may be expected for a surface
area that is between the other two doping levels but plateaus
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