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New sorbents for hydrogen storage by hydrogen spillover – a review

Lifeng Wang and Ralph T. Yang*
Received 9th May 2008, Accepted 12th June 2008
First published as an Advance Article on the web 24th June 2008
DOI: 10.1039/b807957a

The utilization of hydrogen as an energy source or carrier for fuel-cell powered vehicles is limited by the
lack of a safe and effective hydrogen storage system. Recent advances in the application of hydrogen
spillover for hydrogen storage have provided a promising route for hydrogen storage. An overview of
the progress made on hydrogen storage by spillover at ambient temperature on various adsorbents,
including carbons, metal organic frameworks (MOFs) and other nanostructured materials, is given in
this review. New techniques for facilitating hydrogen spillover that were developed in our laboratory
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are discussed, along with future directions.

1. Introduction cells, as well as for non-automobile transportation applications

Hydrogen storage is the crucially missing link to a future
‘‘hydrogen economy.’’ Hydrogen can be stored in compressed
tanks, in liquefied form, and in compressed tanks filled with
sorbent materials. The most promising technique is the sorbent
approach.1–3 The sorbent approach includes metal hydrides and
adsorbents.4 For transportation applications, the US Depart-
ment of Energy (DOE) has set 6.5 wt% and 62 kg H2 m
3 as the
system capacity targets for on-board hydrogen storage in fuel cell
applications in vehicles, at ambient temperature.3,5,6 The pressure
is not specified, but 100 atm has been a nominal pressure for
research. As a reference, for a compact passenger vehicle pow-
ered by fuel cell, 4 kg H2 is needed for a driving range of 400 km.
To store hydrogen in gas tanks at the normal ambient temper-
ature, 700 atm is needed for a compressed tank (of a reasonable
size), which is unacceptably high. To store hydrogen in the liquid
form requires large energy consumption for liquefaction at 20 K
and it also suffers from the ‘‘boil-off’’ problem. Other examples
for mobile applications are storage for portable electronics such
as laptop computers and cell phones that are powered by fuel
Department of Chemical Engineering, University of Michigan, Ann Arbor,
Michigan 48109, USA. E-mail: yang@umich.edu; Fax: (+1 734) 764-7453
such as motorcycles. The research targets in hydrogen storage
capacities depend on the specific applications. The most chal-
lenging targets are for automobile application.
Metal hydrides have been studied intensively for over four
decades.7,8 Studies on adsorbents are more recent. Carbon
materials, metal organic frameworks (MOFs) and other nano-
structured and porous materials have received considerable
interest due to their high surface areas.9–15 These materials
have exhibited promising hydrogen storage capacities at 77 K.
However, among the currently available candidate storage
materials, none is capable of meeting the DOE criteria for
personal transportation vehicles at moderate temperatures and
pressures.16–18 The hydrogen adsorption capacities at the ambient
temperature on all known sorbents are below 0.6–0.8 wt% at
298 K and 100 atm. This is true for all sorbent materials
including the MOFs and templated carbons. In fact, the capac-
ities for MOF-177 and MIL-101 are well below 0.7 wt% at 298 K
and 100 atm, although these two materials are claimed to have
the highest BET surface areas and storage capacities at 77 K.19–24
Based on experimental results and molecular orbital calcula-
tions, Yang et al. proposed to use the hydrogen ‘‘spillover’’
approach for hydrogen storage at ambient temperature.25,26
Hydrogen spillover may be broadly defined as the transport (i.e.,

Lifeng Wang received his BS Ralph T. Yang is Dwight F.

degree in 2002 and PhD degree
in 2007 in Chemistry from Jilin
University, China. From 2007,
he has been a postdoctoral fellow
in the group of Professor Ralph
T. Yang at the University of
Michigan.
Lifeng Wang
Benton Professor of Chemical
Engineering at University of
Michigan. He received his PhD
from Yale University in 1971.
He has published two books:
‘‘Gas Separation by Adsorption
Processes’’ and ‘‘Adsorbents:
Fundamentals and Applica-
tions’’. He has received three
national awards from AIChE,
one ACS National Award,
and he is a member of the U.S.
Ralph T: Yang National Academy of Engi-
neering.

268 | Energy Environ. Sci., 2008, 1, 268–279 This journal is ª The Royal Society of Chemistry 2008

via surface diffusion) of dissociated hydrogen adsorbed or
formed on a first surface onto another surface. The first surface is
typically a metal (that dissociates H2) and the second surface is
typically the support on which the metal is doped. Hydrogen
spillover is a well documented phenomenon in the catalysis
literature, and has been known in the catalysis community for
over four decades, although it is still not well understood.27,28
Much evidence has been shown in the literature on its roles
played in catalytic reactions. Very little has been studied on
hydrogen storage by spillover at ambient temperature, although
it is also known to occur at such temperatures. To exploit spill-
over for storage, among the key questions are whether spillover is
reversible at ambient temperature and if the desorption rates at
ambient temperature are fast enough for automotive applica-
tions.
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By using the spillover approach, significant amounts of
hydrogen storage capacities at 298 K have been obtained on
a number of sorbents, including single-walled carbon nanotubes
(SWNTs) and multi-walled carbon nanotubes (MWNTs)25,29,30
and graphite nanofibers,30,31 activated carbons,32,33 MOFs,34,35
covalent organic frameworks (COFs),23 zeolites,36 and meso-
porous silica.37 It has been found in our studies that the hydrogen
isotherms are reversible at ambient temperature and that the
discharge rates are fast enough to meet the DOE targets on
discharge rates. This review is aimed at summarizing the recent
developments in hydrogen storage by spillover, as well as
a fundamental understanding of the hydrogen spillover
phenomena for hydrogen storage. The literatures on hydrogen
storage in carbon, MOFs, metal hydride and other sorbents
without using hydrogen spillover have been reviewed and
discussed by many authors,3,4,7–15 which will not be focused on
in this review.
2. Hydrogen storage by hydrogen spillover
2.1. Hydrogen storage on carbon by spillover
Since the first report on hydrogen storage in carbon nanotubes
by Dillon et al.,38 carbon materials have attracted considerable
attention for hydrogen storage. High hydrogen adsorption
capacities have been reported in various carbon nano-
structures.39–42 However, the large amounts of hydrogen stored
in carbon materials were disputed because of the difficulties in
obtaining reproducible adsorption capacities from different
laboratories.2 This discrepancy in the hydrogen storage abilities
of carbon nanostructures is considered to be due to difficulties
in accurate measurements, impurities in the carbon samples and
in the hydrogen gas, and poor understanding of the hydrogen
sorption mechanism.43–45 The controversy was partly or largely
caused by the large experimental errors involved in the high-
pressure measurements of hydrogen storage.4 This is true for
both volumetric and gravimetric measurements. The volumetric
technique is the most commonly used method for measuring
high pressure isotherms.46 The experimental pitfalls in volu-
metric measurements for hydrogen storage have been discussed
in detail by Tibbetts et al.47 and Darkrim et al.48 A more detailed
analysis and discussion on all issues on the accuracies of volu-
metric measurements at high pressures have been given by us
recently.49 A very small error in the experiment can cause large
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errors in the result. For example, in a typical setup, an artefact
of 2.6 wt% adsorption can be caused by a 1  C temperature rise.
Calibration was sometimes not done properly. LaNi5 (a known
metal hydride) was often used for calibration. The hydrogen
uptake in LaNi5 (to form LaNi5H 6, or 1.37 wt% gain) occurs at
2 bar at 298 K, in one step. Thus, the high pressure range (2–
100 atm), where the large errors occur, was not calibrated.
Helium is typically used for calibration of dead spaces; ignoring
adsorption by He also causes significant errors.49 We have
established a calibration procedure using the commercially
available superactivated carbon, AX-21 (with BET surface area
2600–2800 m2 g
1), as the calibration material,30,49 which yields
0.6 wt% storage at 100 atm and 298 K, with a slightly concave
isotherm from 0–100 atm. The same result has been reported by
several laboratories.50 When all errors were eliminated from the
experimental measurements, the hydrogen storage capacities
for all purified carbon nanotubes (both single-walled and multi-
walled) were below 0.3 wt% at 298 K and 100 atm. More
recently, it was claimed that an exceptionally high hydrogen
storage capacity of 6.9 wt% at 77 K and 20 bars over all known
sorbents was obtained on a microporous carbon (with a BET
surface area of 3200 m2 g
1) that was synthesized by templating
using zeolite beta.51 Our recent work showed that the hydrogen
storage capacity in a microporous carbon with an ultra-high
BET surface area of >3700 m2 g
1 was still less than 1 wt% at
298 K and 100 atm. On the basis of numerous theoretical studies
and careful experimental validation, several reports have
claimed that at ambient temperature the hydrogen storage
capacities in pure carbon materials are all well below 1 wt%.52–54
However, recent results have shown that hydrogen storage in
carbon materials can be significantly enhanced by spillover
techniques.
2.1.1. Spillover by physical mixing. Hydrogen storage in
carbon materials can be increased by secondary spillover27 from
a supported catalyst.
Mixing a catalytic material with an otherwise inert secondary
material has been used to demonstrate hydrogen spillover by
Srinivas and Rao.55 They studied the effect of H2 spillover on
benzene hydrogenation over a Pt/C catalyst and a Pt/C catalyst
diluted with carbon. From chemisorption results a direct obser-
vation of hydrogen spillover at room temperature was made.
Lueking and Yang investigated hydrogen storage on various
carbon materials (SWCNTs, MWCNTs, graphite nanofiber,
activated carbon and carbon fibers) by secondary spillover.30 It
was found that a supported catalyst as a hydrogen source
enhanced the overall hydrogen uptake of the carbon materials:
by simple mixing of carbon nanotubes with supported palladium,
the hydrogen uptake on carbon nanotubes was increased by
a factor of three. The adsorption of spiltover hydrogen on carbon
was the predominant factor in the magnitude of the overall
hydrogen uptake.30
Secondary spillover provides a method to clearly delineate the
role of carbon surface functionalities; maintaining the primary
metal–carbon material and varying the secondary carbon
establishes a constant hydrogen source to the secondary
material. This eliminates several variables inherent to primary
spillover, including doping efficiencies, carbon–metal interface,
and metal content.
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2.1.2. Spillover assisted by carbon bridge building. The

hydrogen storage capacity in nanostructured and porous carbon
materials can be increased by physically mixing the carbon
materials with a supported catalyst. It was suggested that the
improved hydrogen storage capacity was due to the atomic
hydrogen spillover from the supported catalyst and hence
improved contacts between the spillover source and the
secondary receptor would facilitate the hydrogen spillover,
resulting in the enhanced hydrogen capacity.55–57
Conner and Falconer proposed that secondary spillover
requires intimate contact between the two unlike materials and
there may be an energy barrier to transfer hydrogen from one
material to another.28
Lueking and Yang studied the hydrogen storage on MWNTs
with various degree of catalyst removal (Ni, Mg).25 In that study,
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they observed that removal of the catalyst decreased the uptake

from 0.6 wt% to below detection limits. Normalization by
metal content and temperature-programmed desorption studies
suggested hydrogen dissociation and subsequent spillover to the
MWNT. It was found that metal–support interactions were key
to the spillover.
To improve the contact between the spillover source and the
secondary receptor, a bridge-building technique was proposed by
Yang et al.58 The bridge building technique involves mixing
the catalyst (a small amount) and the sorbent with a small
amount of carbon precursor such as glucose, followed by
a temperature programmed heating protocol to carbonize the
precursor. By using this simple technique, carbon ‘‘nanobridges’’
can be built between a spillover source particle and a secondary
receptor particle.
The bridge-building techniques were first applied to two
typical carbon materials of SWNTs and superactivated carbon
(AX-21) due to their relative chemical stabilities and high surface
areas. In this case, a supported catalyst (Pd/C) served as the
source of hydrogen atoms via dissociation and primary spillover
and AX-21 or SWNTs was the secondary spillover receptor.
Fig. 1 depicts the spillover process in a supported catalyst system.
The spillover source is shown in Fig. 1a, along with an adsorbed
hydrogen molecule. Fig. 1b is a schematic of the low-capacity
receptor, which could be bundles of SWNTs or AX-21. The size
of the hydrogen molecule precludes it from accessing the inter-
stices in the SWNT bundle or additional micropores of AX-21.
The molecular size may also prevent transport of hydrogen
through any defects in an individual SWNT surface; thus, the
adsorption at endohedral sites is dependent upon diffusion to
uncapped ends and further transport inside the tube to these
sites. Examples of primary and secondary spillover are shown
schematically in parts c and d, respectively, of Fig. 1. Dissocia-
tion is assumed to take place on the metal particle, and atomic
hydrogen spills over to the support. The atoms are transported
to the receptor via diffusion across the bridge and can access
additional sites on the receptor. It is noted that the creation of
more intimate contacts between the metal particle and the
support may also contribute to primary spillover enhancement,
as depicted in Fig. 1e.
By using our bridge building technique, the hydrogen
adsorption amounts were increased by a factor of 2.9 on the
AX-21 receptor and 1.6 on the SWNT receptor at 298 K and
100 kPa. Similar results were also obtained at 10 MPa, indicating
Fig. 1 Hydrogen spillover in a supported catalyst system: (a) adsorption
of hydrogen on a supported metal particle; (b) the low-capacity receptor;
(c) primary spillover of atomic hydrogen to the support; (d) secondary
spillover to the receptor enhanced by a physical bridge; (e) primary and
secondary spillover enhancement by improved contacts and bridges.
(Reprinted with permission from ref. 32. Copyright 2005 American
Chemical Society).
that the enhancement factor was a weak function of pressure.
Moreover, reversibility was demonstrated through desorption
and readsorption at 298 K.32
2.1.3. Spillover by chemical doping. Hydrogen spillover
through mixing a hydrogen dissociation source and a receptor is
an effective method for enhancing the hydrogen storage capacity
on carbon sorbents. However, the mixing process involves many
factors, such as particle sizes, sample amounts, grinding time
and intensity. These factors will affect the particle sizes and the
contacts between particles. This would result in different
connectivities between the particles, hence leading to poor
reproducibility in sample and the storage capacity.
Another way to introduce metal onto the receptor material is
by chemical-doping. Chemical doping has been developed
extensively, particularly in catalysis. Compared with physical
mixing, chemical doping produces identical samples and is more
reproducible. Several studies showed that hydrogen uptake on
nanostructured carbons (CNTs, active carbon, carbon nano-
fibers, etc.) was enhanced by doping with transition metals (Ni,
Pd, Pt, etc.), and the maximum uptake could be achieved by
optimizing adsorbents and treatment conditions.59–64
Back et al. investigated the hydrogen storage capacities
of Pd-doped sepiolite-derived carbon nanofibers (SDCNs) at
different Pd particle sizes and different Pd doping levels.59 It was
found that the hydrogen storage capacity was dependent on the
Pd particle size and doping amount as the Pd particle surface
area and the carbon BET surface area changed with them. The

270 | Energy Environ. Sci., 2008, 1, 268–279 This journal is ª The Royal Society of Chemistry 2008

maximum hydrogen uptake of about 0.59 wt% was obtained at
298 K and 90 bar for the 3 wt% Pd-doped SDCN due to the
smaller Pd particle size and relatively high surface area of carbon.
Anson et al. prepared palladium-loaded single-walled carbon
nanotubes and palladium-loaded MAXSORB activated carbon
by reaction of the raw carbon support with Pd2(dba)3$CHCl3.60
A maximum hydrogen capacity of 0.7 wt% was obtained at 90
bar in a palladium-loaded MAXSORB sample, while the
capacity for the raw MAXSORB at the same pressure was
0.42 wt%. They observed that the H/Pd atomic ratios in the
palladium-loaded samples were always higher than in the bulk
Pd. The spillover effect was considered as the cause for the high
H/Pd atomic ratios.
Bettahar et al. investigated hydrogen storage on nickel cata-
lysts supported on amorphous activated carbon.61 They found
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that the hydrogen storage capacity depended on the metal
content and the temperature of pre-treatments.
Among the aforementioned catalysts, the reversible hydrogen
capacities were all below 1.0 wt% at high pressure and room
temperature. More recently, Kim et al. reported a higher
hydrogen capacity of 2.8 wt% on Ni doped on multi-walled
carbon nanotubes at a moderate temperature.64 But the
hydrogen adsorbed on the material could only be released at
temperatures higher than 340 K (340–520 K).
2.1.4. Spillover by ultrasonication assisted doping. Doping of
metal nanoparticles is one of the key factors for storage capacity
as well as for catalyst preparation. It still remains, for the most
part, as an art. The importance of doping at the point of zero
charge (PZC, i.e., the pH at which the surface is neutral) has been
illustrated by Regalbuto and coworkers.65 Recently, Yang et al.
showed that doping under ultrasonication was efficient.66 Yang
and Li doped Pt nanoparticles on a superactivated carbon
(AX-21) by using ultrasound-assisted impregnation of H2PtCl6
in a solution of acetone.33 The TEM results revealed that the
uniform Pt particles of approximately 2 nm were highly dispersed
on the carbon support. As shown in Fig. 2, the hydrogen storage
Fig. 2 High-pressure hydrogen isotherms at 298 K for pure AX-21 (-),
and the Pt/AX-21 sample: adsorption (B), and desorption (:).
(Reprinted with permission from ref. 33. Copyright 2007 American
Chemical Society).
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capacity of 0.6 wt% was obtained on the undoped AX-21 sample
at 298 K and 10 MPa. By ultrasound assisted doping of Pt, the
Pt/AX-21 sample had a hydrogen storage capacity of 1.2 wt%
under the same conditions, which was enhanced by a factor of 2.
It is worth noting that the hydrogen storage capacity was lower
on doped samples without using ultrasound. In this work, the
doping of AX-21 in an acetone solution of H2PtCl6 was per-
formed under ultrasonication (at 100 W, 42 kHz) at room
temperature for 1 h. The main phenomena responsible for
ultrasound actions are cavitation and acoustic streaming, the
effects of which on adsorption and desorption from solution
have been studied.67 The conditions of ultrasonication should be
optimized further for enhanced storage capacity.
Our recent studies indicated that uniform nanoparticles of Ru,
Pt and Ni could be also effectively doped on porous carbon
supports by using the ultrasonication assisted doping method.
2.1.5. Spillover by plasma assisted doping. From the view-
point of spillover, high dispersion of metals would enhance
the utilization efficiency of metals for dissociation of hydrogen
for hydrogen spillover. Back et al.59 and Yang et al.33 have
observed that smaller particle size and high dispersion of parti-
cles enhanced the storage capacity. Recently, a new reduction
method assisted by plasma has received much attention for
preparing nanosized metal-doped materials.68–72 Plasma appli-
cation in catalyst preparation has been previously reviewed.68
Catalysts produced by this method had uniform metal particle
sizes and the particles were highly dispersed on the surface of the
supports. Li et al. doped Pt nanoparticles on Norit activated
carbon with post-doping plasma treatment, and investigated its
hydrogen storage properties.66,73 It was discovered that plasma
treatment significantly enhanced the hydrogen storage capacity
of the doped sample.
As shown in Fig. 3, the equilibrium hydrogen adsorption
isotherms on Norit activated carbon (NAC), 3 wt% Pt doped
on Norit carbon prepared by hydrogen reduction, and 3 wt%
Pt doped on Norit carbon prepared by plasma reduction are
Fig. 3 High-pressure hydrogen isotherms at 298 K for NAC (,),
H2-reduced Pt/NAC-H (A), and plasma-treated Pt/NAC-P sample:
adsorption (B), and desorption (:). (Reprinted with permission from
ref. 73. Copyright 2007 American Chemical Society).
Energy Environ. Sci., 2008, 1, 268–279 | 271

compared. The Norit carbon with a BET surface area of about
1000 m2 g
1 had a hydrogen storage capacity of 0.3 wt% at 298 K
and 10 MPa. After doping the Norit carbon with 3 wt% Pt by
hydrogen reduction, the hydrogen storage capacity was increased
by about 50%, due to spillover. For the Pt-doped carbon treated
with plasma, the hydrogen storage capacity was increased by
approximately 270% from the value of the plain carbon. From
TEM results and thermal stability tests, it was concluded that
the Pt particles were highly dispersed and strongly anchored on
the carbon supports. This large enhancement by plasma treat-
ment was attributed to high dispersion of Pt particles and
chemical bridges that were built between the Pt particles and the
carbon surface, which enhanced the spillover.
In the preliminary study, glow discharge Ar plasma was used.
The glow discharge was generated by applying 900 V to the
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planar electrodes. The temperature of the plasma was near the
ambient temperature. Previous studies suggested that the ambient
temperature during plasma treatment was the main reason for the
high dispersion of metal particles. It is known that plasmas
consist of ionized atoms and molecules as well as energized elec-
trons. Other plasmas (microwave plasma, plasma spraying, radio
frequency, etc.) and other gases (H2, O2, Air and CO2 etc.) will
give similar or even better results than the glow discharge Ar
plasma. This would further reduce the costs of plasma treatment,
and consequently the costs of sorbents for hydrogen storage.
2.2. Hydrogen storage on MOFs by spillover
Metal–organic frameworks (MOFs) are porous materials con-
structed by coordinate bonds between multidentate ligands and
metal atoms or small metal-containing clusters. MOFs can be
generally synthesized via self-assembly from different organic
linkers and metal nodules. Due to the variable building blocks,
MOFs have very large surface areas, high porosities, uniform
and adjustable pore sizes and well-defined hydrogen occupation
sites. These features make MOFs promising candidates for
hydrogen storage.13,14
Yaghi et al. first reported a high hydrogen adsorption of 4.5
wt% on Zn4O(bdc)3 (bdc ¼ 1,4-benzenedicarboxylate) at 77 K
and less than 1 atm, which is known as MOF-5 or IRMOF-1.74
The reported hydrogen capacities were lower in their subsequent
studies.75 The novelty of this work provided a promising
candidate for hydrogen storage. A number of unique MOFs
have been synthesized and evaluated for their hydrogen storage
capacity.76–88 It has become clear that high surface area and pore
volume are important factors for high hydrogen uptakes on
MOFs at 77 K.77–80 The effects of surface area, pore volume and
heat of adsorption on hydrogen uptake in MOFs were recently
discussed by Snurr et al.81 Extensive work was directed toward
the synthesis of MOFs with high surface areas and pore
volumes. A series of isoreticular (meaning having the same
underlying topology) metal organic frameworks, Zn4O(L)3,
were constructed by changing the different linking zinc
oxide clusters with linear carboxylates L, so as to get a high
porosity.75–77 Recently, MOF-177 (Zn4O(BTB)2) was formed by
linking the same clusters with a trigonal carboxylate. MOF-177
was claimed to have a high Langmuir surface area of 5640 m2
g
1, and the highest hydrogen storage of 7.5 wt% H2 at 77 K and
70 bar.21,22 The more meaningful surface area, BET surface area,
272 | Energy Environ. Sci., 2008, 1, 268–279
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for MOF-177 is around 3000 m2 g
1. More recently, Férey et al.
reported a nanoporous chromium terephthalate-based material
(MIL-101) with the highest Langmuir surface area (4500–5900
m2 g
1) among all MOFs. It was reported that the hydrogen
storage capacities in this material at 8 MPa were 6.1 wt% at 77
K, and 0.43 wt% at 298 K.19,20 Although these MOFs have
remarkable hydrogen capacities at 77 K, no significant hydrogen
storage capacities were obtained with the MOFs at room
temperature.23,24
2.2.1. Spillover on IRMOFs
2.2.1.1. Spillover by physical mixing. Significant hydrogen
storage capacities at ambient temperature on nanostructured
carbon materials have been achieved by using secondary spill-
over. It is expected that the hydrogen storage on MOFs at room
temperature can also be much improved by hydrogen spillover
techniques. The hydrogen spillover was first applied to MOF-5
(also known as IRMOF-1) and IRMOF-8, which were con-
structed by linking tetrahedral [Zn4O]6+ clusters with linear
carboxylates.34
For spillover experiments, a commercial catalyst containing
5 wt% Pt supported on active carbon was used for dissociation of
H2. Active carbon was the primary receptor for hydrogen spill-
over. The catalyst and the secondary spillover receptor (MOF-5
or IRMOF-8) (at a weight ratio of 1 : 9) were ground together to
produce the physical mixture.
As shown in Fig. 4, pure MOF-5 had a hydrogen storage
capacity of 0.4 wt% at 298 K and 10 MPa. Similar results were
also observed by Panella and Hirscher82 and Rowsell et al.75 By
thoroughly mixing MOF-5 with Pt/AC catalyst, the H2 storage
capacity of MOF-5 was enhanced to 1.5 wt% at 10 MPa.
Considering the relatively low H2 uptake of Pt/AC (1.0 wt% at
10 MPa) and the small amount of Pt/AC in the mixture (10 wt%),
the hydrogen uptake on MOF-5 was increased by a factor of 3.3.
The enhanced storage capacity was clear evidence for secondary
spillover of H atoms to MOF-5, as a secondary receptor. It is
noted that there was no apparent saturation value for the
physical mixture at 10 MPa. Reversibility was assessed by
measuring the desorption branch down to 1 atm. The second
adsorption branch was in complete agreement with the first
adsorption branch.
Fig. 4 High-pressure hydrogen isotherms at 298 K for MOF-5. Dotted
line is prediction based on the weighted average of the mixture.
(Reprinted with permission from ref. 34. Copyright 2006 American
Chemical Society).
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 View Article Online

Similarly remarkable enhancement of H2 storage capacity by

spillover was also observed on IRMOF-8. The H2 uptake on
pure IRMOF-8 was 0.5 wt% at 298 K and 10 MPa. By physically
mixing IRMOF-8 with Pt/AC, the hydrogen uptake on IRMOF-
8 was increased to 1.8 wt% under the same conditions. This
uptake is equivalent to 8.3 H2 (or 16.6 H atoms) per formula unit,
which is well below the saturation of IRMOF-8.74 Furthermore,
the adsorption was also totally reversible and did not show any
saturation up to 10 MPa, similar to results on MOF-5.

2.2.1.2. Spillover by bridge-building techniques. Secondary

spillover requires intimate contacts between the two unlike
materials because there exist tremendous physical/energy
barriers for surface diffusion of hydrogen atoms from one
material to another. It has been demonstrated that bridge-
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building technique could facilitate secondary spillover and hence

increase the storage capacities in nanostructured carbon mate-
rials. Yang and Li further extended the bridge-building technique
to MOFs.35
This work was first focused on IRMOF-1 and IRMOF-8,
whose hydrogen uptakes had been proved to be enhanced via
secondary spillover induced by physical mixing. In previous
work, it was found that carbon bridges could be built between an Fig. 5 (a) Primary spillover of atomic hydrogen from Pt metal to the
activated carbon and a Pd/AC catalyst by carbonizing an added activated carbon support and secondary spillover to the MOF receptor
glucose precursor at 673 K.32,58 It is expected that carbon bridges that has limited contacts with the support. (b) Facilitated primary and
can also be formed by carbonization of a hydrocarbon precursor secondary spillover by using carbon bridges (dark black zone).
that was previously introduced into a physical mixture of the (Reprinted with permission from ref. 35. Copyright 2006 American
Chemical Society).
MOF and catalyst. However, it is difficult to build carbon
bridges in MOFs by using glucose precursor because MOFs are
thermally unstable at temperatures >573 K.74 Yang et al. used
sucrose instead of glucose as the carbon precursor. The ternary
physical mixture of sucrose, Pt/AC catalyst, and MOF was first
heated in He to 473 K (melting point of sucrose ¼ 463 K) for 3 h
to allow the sucrose to melt thoroughly and to fill the interstices
(by capillarity) between the particles of the catalyst and the MOF
(Fig. 5). Then the temperature was finally increased to 523 K to
carbonize the sucrose. This temperature program was effective
for building carbon bridges and avoiding the collapse of the
MOF structure. Thermogravimetric analysis (TGA) confirmed
the complete carbonization of sucrose by this heating protocol.
X-Ray diffraction (XRD) and N2 adsorption results indicated
that the structures of MOF materials were well retained during
the bridge-building treatment.
By building carbon bridges, the bridged sample exhibited
a hydrogen uptake of 3 wt% at 10 MPa. It represented an
enhancement factor of 2 compared with the physical mixture
without bridges. This enhancement indicated the built bridges Fig. 6 High-pressure hydrogen isotherms at 298 K for pure IRMOF-8
further facilitated secondary spillover of hydrogen atoms from (,), Pt/AC and IRMOF-8 physical mixture (1 : 9 weight ratio; A) and
the catalyst to the surface of the MOF material. Compared with for a bridged sample of Pt/AC-bridges-IRMOF-8: first adsorption (B),
desorption (:), and second adsorption (>). (Reprinted with permission
pure IRMOF-1, the hydrogen adsorption amount of bridged
from ref. 35. Copyright 2006 American Chemical Society).
IRMOF-1 has been enhanced by a factor of 7.5. These results
indicated that the creation of carbon bridges was crucially
important for achieving a high hydrogen adsorption capacity (Zn4O(C12H6O4)3), which is much lower than the total number of
by spillover. atoms in IRMOF-8, assuming 1 H per surface atom. Further-
Similar enhancement of hydrogen storage by spillover was also more, the ab initio molecular orbital calculation results indicated
observed on IRMOF-8. As shown in Fig. 6, by using the bridge- that it was favorable for one surface atom (such as oxygen) to
building technique, the H2 uptake was increased from 0.5 wt% adsorb two H atoms at the same time. Thus, the theoretical
on pure IRMOF-8 to 4 wt% at 10 MPa on bridged IRMOF-8. maximum storage would be at least 6.5 wt%. No apparent
This uptake amount is equivalent to 34 H per formula unit saturation value was approached for the bridged sample; as the

This journal is ª The Royal Society of Chemistry 2008 Energy Environ. Sci., 2008, 1, 268–279 | 273

isotherm was linear even at 10 MPa. The absence of a saturation
value suggests that a further increase in capacity can be expected
at pressures >10 MPa; for example, 6 wt% storage is expected at
15 MPa, a viable pressure for practical automotive applications.
2.2.2. Spillover on MOF-177. Another interesting example is
the storage capacity of MOF-177 by spillover at ambient
temperature, which was expected to be promising, because
MOF-177 was reported to have the highest hydrogen storage
(among all MOFs) of 7.5 wt% H2 at 77 K and 70 bar.21,22 Pure
MOF-177 showed a hydrogen storage capacity of only 0.62 wt%
at 298 K and 10 MPa. This value is among the highest hydrogen
storage capacities reported in MOFs at room temperature. By
physical mixing of MOF-177 with Pt/AC catalyst, the hydrogen
uptake on MOF-177 at 10 MPa was enhanced to 0.8 wt%. After
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building bridges, the hydrogen uptake at 10 MPa on MOF-177
was increased to 1.5 wt%, representing an enhancement factor of
2.5 as compared with pure MOF-177. The enhancement was
lower than that on IRMOF-1 and IRMOF-8 samples under the
same conditions.35 This was due to the larger crystals of MOF-
177 (hundreds of microns) than those of IRMOF-1 and IRMOF-
8 (500 nm). The mismatch in the sizes resulted in poor
connectivity between the hydrogen atom source (Pt/AC) and the
MOF-177 receptor and consequently low hydrogen uptakes.24
Intimate contacts between the hydrogen dissociation source and
the receptor are required for facilitating the spillover of H atoms.
Our recent studies also indicated that reducing crystal size of
MOF-177 helped to improve its hydrogen storage capacity.
The lower heat of adsorption on MOF-177 (Table 1) is another
reason for the lower enhancement. Although MOF-177,
IRMOF-1 and IRMOF-8 have the same metal clusters (Zn4O),
the metal content in MOF-177 is lower than those of IRMOF-1
and IRMOF-8, which leads to the lower heat of adsorption on
MOF-177. The effects of heats of adsorption on hydrogen
storage will be discussed in detail in section 2.3.2.
2.2.3. Spillover on moisture-stable MOFs. Most MOFs such
as aforementioned IRMOFs and MOF-177 are unstable in air
because the moisture would cause decomposition of frameworks.
This always leads to the poor reproducibility and storage
capacity in the MOFs samples. Much care must be taken to avoid
the collapse of MOFs. The stability of MOFs is a key factor in
their practical application, because moisture exposure is inevi-
table in practical applications. Stable MOFs with high hydrogen
capacities at room temperature are desirable.
Recently, two kinds of new MOFs, MIL-10119 and HKUST-
1,89 have received more attention due to their relative stabilities in
air when compared with other MOFs. HKUST-1 and MIL-101
Table 1 Comparison of MOFs, pure and bridged to Pt/AC catalyst, on their H2 storage properties. Bridged sample: 10 wt% Pt/AC (containing 5 % Pt),
10 wt% carbon bridges, and 80 wt% MOF
BET surface H2 at 77 K, H2 at 298 K,
area/m2 g
1 1 atm (wt%) 100 atm (wt%)
IRMOF-8 548 1.4 0.4
COF-1 628 1.1 0.3
HKUST-1 1296 2.2 0.3
MIL-101 2930 1.8 0.5
MOF-177 3100 1.5 0.6
274 | Energy Environ. Sci., 2008, 1, 268–279
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were synthesized in the presence of H2O, so their structures are
stable upon water adsorption. HKUST-1 is a copper benzene-
tricarboxylate porous material reported by Williams et al.89
Recent research showed that it was a good adsorbent for H2 and
NO storage.90 The high gas capacities in HKUST-1 were due to
the presence of a metal site in the walls of the material that could
interact strongly with gas molecules.91 MIL-101 was synthesized
from benzene-1,4-dicarboxylate and trimetric chromium(III)
octahedral clusters by Férey’s group. It was reported to have the
largest surface area (Langmuir surface area, 4500–5900 m2 g
1)
among all MOFs.19 A high hydrogen storage capacity of 3.75
wt% was obtained on MIL-101 at 77 K and 2 MPa first, then it
was reported that the hydrogen storage capacity in this material
at 8 MPa was 6.1 wt% at 77 K, and 0.43 wt% at 298 K.20
Yang and Li investigated the hydrogen capacities of MIL-101
and HKUST (Fig. 7 and 8).23 The hydrogen uptakes on the pure
MIL-101 and HKUST are 0.51 wt% and 0.35 wt%, respectively.
By simply mixing with a small amount of Pt/AC catalyst (at 9 : 1
mass ratio), their hydrogen uptakes were enhanced to 0.9 wt%
and 0.7 wt% up to 10 MPa. By building carbon bridges between
the MOFs and the Pt/AC catalyst, the hydrogen capacities were
further enhanced to 1.5 wt% on bridged-MIL-101 and 1.1 wt%
on bridged-HKUST. There was no apparent saturation for the
bridged samples and the adsorption in the bridged samples was
fully reversible at 298 K, as found previously on the bridged
IRMOFs.
Fig. 7 High-pressure hydrogen adsorption at 298 K for the MIL-101
samples. A: pure MIL-101; B: Pt/AC and MIL-101 physical mixture;
:: MIL-101–bridges–Pt/AC. (Reprinted with permission from ref. 23.
Copyright 2008 Wiley).
Bridged sample, H2 at
298 K, 100 atm (wt%) DH (bridged)/kJ mol
1
2.2–4.0
21
0.7
7
1.1
9
1.5
13
1.5
10
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Fig. 8 High-pressure hydrogen adsorption at 298 K for the HKUST-1
samples. A: pure HKUST-1; B: Pt/AC and HKUST-1 physical mixture;
:: HKUST-1–bridges–Pt/AC. (Reprinted with permission from ref. 23.
Copyright 2008 Wiley).
Recently, Liu et al. studied the hydrogen storage properties
of doped (physical mixing with Pt/C) and bridged MIL-101 and
MIL-53 samples under mild conditions.92 Both doped and
bridged MIL-101 and MIL-53 samples showed enhanced
hydrogen storage capacities compared with pristine samples. The
gravimetric storage capacities of bridged MIL-101 and MIL-53
samples were 1.14 and 0.63 wt% at 293 K and 5 MPa.
2.3. Hydrogen storage on other adsorbents by spillover
2.3.1. Spillover on covalent organic frameworks (COFs).
Covalent organic frameworks (COFs) are constructed from light
elements (H, B, C, N, and O) that form strong covalent
bonds.93,94 Compared with MOFs, they have light weights and
good thermal stabilities (up to 600  C). These features could be
suitable for gas storage. Recently, COF-1 and COF-5 were
synthesized by condensation reactions of phenyl diboronic acid
{C6H4[B(OH)2]2} and hexahydroxytriphenylene [C18H6(OH)6].
Yang et al. investigated the hydrogen capacity of COF-1.23
The hydrogen uptake on pure COF-1 was 1.28 wt% at 77 K and 1
atm and 0.26 wt% at 298 K and 10 MPa. By using the bridge-
building technique, the bridged COF-1 sample had a hydrogen
storage capacity of 0.7 wt%, which was enhanced by a factor of
2.6. The relatively low hydrogen capacity was due to the lower
surface area of COF-1.
2.3.2. Comparison of MOFs and COFs. The main hydrogen
storage characteristics of the MOFs and COFs that were studied
in our laboratory can now be compared. Pure MOFs, COFs
and their counterparts bridged with 10 wt% Pt/AC catalyst (i.e., 5
wt% Pt/activated carbon) are compared.23,24,35 The results are
summarized in Table 1.
The overall heats of adsorption (DH) shown in the table were
obtained from the temperature dependence of the isotherms, i.e.,
by using the Clausius–Clapeyron equation. The isosteric heats of
adsorption declined with loading; the values shown in the table
were those after leveling off. The detailed relationship between
This journal is ª The Royal Society of Chemistry 2008
View Article Online
the overall heat of adsorption thus obtained and the binding
energy between the spiltover H and the MOF sites is not known,
but they are obviously related; i.e., a larger heat of adsorption
indicates a stronger binding energy. The DH values (for conve-
nience, referring to the absolute values) are somewhat related to
the contents of the metal clusters in the MOF. For example, COF
contains no metal, and shows the lowest DH. IRMOF-8 and
MOF-177 have the same metal clusters (Zn4O), and are directly
comparable. The metal content in IRMOF-8 is higher than that
in MOF-177, and the DH value is higher for IRMOF-8.
For pure MOFs, not only are surface area and pore volume
important factors for hydrogen storage capacity, framework
composition is another important factor. This is because inter-
actions other than the van der Waals interactions exist between
H2 and MOF. Electric charges (on metal oxide sites) play
a significant role in these systems.88 The effects of different
factors on hydrogen uptake in pure MOFs have been discussed
by many authors.77–81
For the bridged samples, IRMOF-8 has the highest storage
capacity because of the large DH value; whereas MIL-101 and
MOF-177 also show high storage capacities, due to their large
BET surface area. Thus, it is clear that both surface area and the
DH values are important for storage by spillover.
2.3.3. Spillover on zeolites. Zeolite is a type of microporous
solid used commercially in catalysis and gas separation.4,95
Recently, various types of zeolites have been investigated for
hydrogen storage due to their high thermal stability, low cost and
adjustable composition.96–104 Zecchina et al. obtained a hydrogen
capacity of 1.28 wt% on H-SSZ-13 zeolite at 77 K and 0.92 bar.103
Langmi et al. reported a high gravimetric storage capacity of
2.19 wt% on Ca exchanged X zeolite at cryogenic temperatures
and 15 bar.99 However, hydrogen adsorption on zeolites at room
temperature is low. Kayiran and Darkrim105 and Weitkamp et al.
reported that hydrogen capacities on zeolites were less than
0.5 wt% at room temperature and 60 bar.106
Recent studies have shown that the amount of hydrogen
adsorbed on zeolites depended on the framework structure,
composition, and acid–base nature of the zeolites.96–107 The
cations in the zeolite create strong electric fields (and field
gradients) that will favor gas adsorption.108 It is expected that
high H2 storage capacities could be obtained on zeolites with
high cation densities.
Yang et al. reported that low-silica (thus, high charge density)
type X (LSX) zeolite (Si/Al ¼ 1) had a hydrogen storage capacity
of 0.6 wt% at 298 K and 10 MPa.36 By hydrogen spillover,
bridged Li–LSX had a hydrogen storage capacity of 1.6 wt% at
298 K and 10 MPa, which was enhanced by a factor of 2.6
compared with that on pure Li–LSX. The storage capacity of
bridged Li–LSX is among the highest for zeolite materials at
ambient temperature. Li–LSX zeolite was selected as the
hydrogen adsorbent because it had the largest number of charge-
compensating cations per unit cell among all faujasites.
2.3.4. Spillover on mesoporous silica. Compared with micro-
porous zeolite materials, mesoporous silica has high surface area,
large pore sizes and amorphous pore walls. These features of
mesoporous silica facilitate the loading of nanoparticles in the
pore channels or tailoring of composition of pore walls.109,110
Energy Environ. Sci., 2008, 1, 268–279 | 275
 View Article Online

Ramachandran et al. evaluated the feasibility of Al–MCM-41

for hydrogen storage.37 The hydrogen storage properties of
Al–MCM-41 with varying contents of aluminium and different
metal oxide doped Al–MCM-41 were compared. Their gas chro-
matographic studies indicated that hydrogen uptake in Al–MCM-
41 samples was strongly dependent on the density of Brønsted acid
sites and the amount of metal oxide. Hydrogen spillover was
mainly responsible for the enhanced hydrogen adsorption for
the doped Al–MCM-41. The studies indicate the potential of
mesoporous materials as good candidates to form and stabilize
nanomaterials within their pores. Mesoporous materials could
also be exploited for better adsorption properties by producing
mono-, bi-, and tri-metallic alloys for hydrogen storage.

3. Mechanistic and kinetics studies of hydrogen

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storage by spillover
3.1. Evidence of hydrogen spillover

Although hydrogen storage by spillover is a rather new field, the

phenomenon of ‘‘hydrogen spillover’’ has been known for a long
time.111 Atomic hydrogen spillover was first observed during
studies of ethylene hydrogenation via heterogeneous catalysis
by Sinfelt and Lucchesi.112 Further evidence was observed by
Khoobiar.113 They found the formation of the hydrogen bronze
HxWO3 from WO3 at room temperature after WO3 was exposed
to hydrogen in the presence of a platinum-containing catalyst.
The experimental result could only be interpreted by the diffu-
sion of atomic hydrogen from the platinum catalyst to WO3.
During the last four decades, hydrogen spillover has been
extensively studied particularly in the field of catalysis. The
voluminous literature on atomic hydrogen spillover has been
reviewed.27,28,114 Recently, detailed structural characterization of
the hydrogen-adsorbed species has added insight into the
mechanism of hydrogen adsorption. Previously, Schwarz inves-
tigated the hydrogen adsorption on an activated carbon mixed
with transition metal from room temperature to 77 K, and Fig. 9 Rates of adsorption (a) and desorption (b) during stepped
observed that the spillover effects were strongest at 77 K and increases and decreases in pressure, at 298 K, for bridged MIL-101
nearly nil at room temperature.115 This observation was not sample.
correct.116–122 Direct evidence for spillover of atomic hydrogen at
room temperature has been reported. Inelastic neutron scattering
In the kinetics study, the pressure was increased or decreased
studies have shown the atomic hydrogen spillover from Pt to
in steps, all at 298 K. Thus, the pressure was increased from 0, to
carbon at room temperature.116,117 Infrared spectroscopic study
5, 20, 40, 60, 80 and 100 atm (approximate values) during
provided evidence of spillover of atomic hydrogen from Au
adsorption, and then the steps were reversed in desorption. At
nanoparticles to TiO2 also at room temperature.118 Evidence has
each end pressure, the percent completion with respect to the
also been shown by deuterium isotope tracer studies at room
final (equilibrium) value was recorded. These are shown in Fig. 9.
temperature on Pt/TiO2.119,120 The temperature programmed
It is clear that the rates depended on the loading; the rates were
desorption (TPD) technique was extended to study the spillover
slower at higher loading. This is another manifestation of spill-
on Pt/Al2O3 by Chen and White.121 A number of theoretical
over and that the surface diffusion step was the rate-limiting step,
studies have been done on the mechanism and energetics of
as the distance for surface diffusion increased with loading.
spillover. The more recent DFT study by Chen et al. illustrated
facile pathways for spillover from a Pt particle onto a graphene
basal plane via ‘‘physisorbed H atoms.’’122 3.3. Mechanistic isotherm model for spillover storage
The mechanism of hydrogen spillover has also been investi-
3.2. Kinetics of adsorption and desorption
gated.123–134 It was found that hydrogen molecules were dissoci-
The kinetics of adsorption and desorption via spillover storage ated rapidly on metal sites and then diffused slowly away from
have been studied for both metal-doped carbons and catalyst- them to the receptor. Surface diffusion of hydrogen atoms has
bridged MOFs in our laboratory. Our recent kinetics studies on been proposed to be the rate-determining step in hydrogen
bridged MIL-101 are shown in Fig. 9, as a representative result. spillover.

276 | Energy Environ. Sci., 2008, 1, 268–279 This journal is ª The Royal Society of Chemistry 2008

Hattori et al. investigated the kinetics of hydrogen adsorption on
SO42
–ZrO2, and WO3–ZrO2 supported platinum catalysts in the
temperature range 323–573 K.132,133 They observed very slow
uptake rates of hydrogen on these two supported platinum samples.
Yang et al. studied the mechanism of hydrogen adsorption on
bridged IRMOF-8 samples at room temperature. A two-
dimension sectional plot of the spherical model was proposed for
evaluating the diffusion time constants from the uptake rates, as
shown in Fig. 10.134 In this model, H2 is dissociated on the surface
of the Pt particle, where equilibrium is maintained. The atomic
hydrogen undergoes surface diffusion onto the surface of the
activated carbon particle, with radius R1, followed by diffusion
onto the surface of the IRMOF-8 receptor. The average sphere of
diffusion for the IRMOF-8 receptor is taken as R2, which
depends on the connectivity through bridging as well as the ratio
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of Pt/AC catalyst over receptor. Based on this model, it was
found that the diffusion time constant, D/R2, decreased sharply
with surface concentration. This result clearly indicates that the
diffusion distance, R2, was increasing with surface concentration.
The concentration dependence for surface diffusion has been
discussed in detail and explained satisfactorily by models by
Higashi et al.135 and Yang et al.46,136,137 Surface diffusion is the
result of a hopping process, for both physical adsorption and
chemisorption of small molecules or atoms. Within the mono-
layer coverage, the surface diffusivity usually increases with
surface concentration.
The mechanistic model was further extended to explain the
hydrogen adsorption on Pt/AX-21 systems.33 It was also
observed that the diffusion time constant (D/R2) decreased with
surface concentration. The proposed mechanistic model for
hydrogen spillover could interpret the experimental results.
Based on this mechanistic model, an equilibrium isotherm for
the spillover system was derived by Yang and co-workers, and
the isotherm was given as in eqn (1):134
pffiffiffiffiffiffiffiffi
K1 k1 PH2
q¼ pffiffiffiffiffiffiffiffi pffiffiffiffiffiffiffiffi (1)
1 þ k2 PH2
K 0 k1 PH2
Here, q is the equilibrium amount adsorbed at hydrogen
pressure PH2, and the constants were defined in ref. 134 and can,
Fig. 10 Two-dimension sectional plot of spherical model for hydrogen
spillover on bridged IRMOF-8 sample, including Pt/AC catalyst (AC:
activated carbon support) bridged with a receptor sorbent. (Reprinted
with permission from ref. 134. Copyright 2007 American Chemical
Society).
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View Article Online
in principle, be determined independently.134 This equation can
explain the nearly linear behavior of the isotherms that have been
observed for all spillover sorbent systems investigated so far.
More recently, Lachawiec and Yang used a deuterium isotope
sequential dosing and TPD technique to study the mechanism
and kinetics of spillover of atomic hydrogen on Pt/AX-21 and
IRMOF-8 at room temperature.138 The sorbent sample was
dosed sequentially with H2 and D2 and the sample was then
quickly ‘‘frozen.’’ Temperature programmed desorption fol-
lowed. TPD product distributions and HD formation showed
that desorption of the isotopes followed the reverse sequence of
that of dosing, indicating reverse spillover during desorption.
The HD was clearly formed by scrambling of the surface spilt-
over H and D atoms.
4. Summary and outlook
Significant hydrogen storage capacity has been obtained at
ambient temperature by spillover. Further enhanced hydrogen
capacity and understanding of hydrogen spillover are still needed
for meeting the DOE targets. Several aspects should be further
developed to improve the hydrogen capacity by spillover.
4.1. Heats of adsorption
Hydrogen storage by spillover is an atomic hydrogen adsorption
process. The surface adsorption sites of the adsorbent determine
the storage capacity by spillover. It is understood that an
adsorbent with more and stronger surface adsorption sites for
hydrogen atoms should have higher hydrogen capacity by
spillover. Our recent work on a series of MOFs showed that the
hydrogen uptakes were mainly related with the heats of
adsorption of hydrogen on these adsorbents. Higher hydrogen
uptakes were obtained on MOFs with higher heats of adsorption
(stronger surface adsorption sites) even some MOFs had rela-
tively lower surface areas. For example, IRMOF-8 has the
highest storage capacity among the MOFs studied in our work. It
has a high heat of adsorption (20 kJ mol
1) and a relative low
BET surface area (about 600 m2 g
1). The heat of adsorption for
hydrogen on the adsorbent is the key factor in the hydrogen
adsorption by spillover.
4.2. Pore volume and surface area
It was suggested that the hydrogen uptake on an adsorbent at
77 K and high pressures was related to its pore volume. This is
easily understood because at 77 K and high pressures, the
hydrogen storage in an adsorbent is mainly by condensation of
H2 molecules into its porosity, while adsorption by spillover is by
the interaction of hydrogen atoms with the surface sites of the
adsorbent. Therefore, the surface area and not the pore volume
of the adsorbent should be an important factor in hydrogen
adsorption by spillover. An adsorbent with high surface area
would provide more adsorption sites for hydrogen adsorption via
spillover. For example, Pt was doped on carbons with different
surface areas. The highest hydrogen uptake was obtained on Pt/
templated carbon with the highest surface area among the
carbons studied.
Energy Environ. Sci., 2008, 1, 268–279 | 277

4.3. Contacts between the source and the receptor
Contacts between the source and the receptor are very important
for hydrogen spillover. Enhanced storage capacity has been
achieved by several methods such as bridge building, plasma
assisted doping and ultrasound assisted building. However, the
contact effect is still least understood in spillover. It is suggested
that the enhanced contacts between the source and receptor
would facilitate the spillover and hence increase the storage
capacity. Significant hydrogen uptakes could be expected by
enhancing contact strength between the source and receptor,
creating more contact sites and option of the ratio of source and
receptor.
Acknowledgements
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The authors acknowledge the funding provided by the US
Department of Energy’s Office of Energy Efficiency and
Renewable Energy within the Hydrogen Sorption Center of
Excellence (HS CoE), and funding from NSF.
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