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Palladium Based Nanomaterials For Enhanced Hydrogen Spillover and Storage
Palladium Based Nanomaterials For Enhanced Hydrogen Spillover and Storage
Palladium Based Nanomaterials For Enhanced Hydrogen Spillover and Storage
RESEARCH: Review
Hydrogen storage remains one of the most challenging prerequisites to overcome toward the realization
of a hydrogen based economy. The use of hydrogen as an energy carrier for fuel cell applications has been
limited by the lack of safe and effective hydrogen storage materials. Palladium has high affinity for
hydrogen sorption and has been extensively studied, both in the gas phase and under electrochemical
conditions. In this review, recent advancements are highlighted and discussed in regard to palladium
based nanomaterials for hydrogen storage, as well as the effects of hydrogen spillover on various
adsorbents including carbons, metal organic frameworks, covalent organic frameworks, and other
nanomaterials.
1369-7021/ß 2015 Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/). http://dx.doi.org/10.1016/j.mattod.2015.08.002
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RESEARCH: Review
FIGURE 1
Overview of various solid-state hydrides, plot of decomposition
temperatures (under 1 bar H2 pressure) as function of heavy-metric
hydrogen content. The ultimate DOE target is shown in the shadowed bar.
(Reprinted with permission from [9]. ß 2015 Elsevier).
Hydrogen spillover
It was observed by Khoobiar in 1964 that WO3 was reduced by H2
to blue WO3 x when it came into contact with a platinum (Pt)
catalyst. The presence of blue color was due to the chemisorptive
dissociation of H2 molecules on the surface of Pt particles that
migrated to the yellow WO3 particles, reducing them to blue
FIGURE 2 WO3 x particles [31]. Subsequently, Boudart et al. coined the term
(Left) Pressure-composition isotherm plot of metal to metal hydride phase ‘spillover’ to describe the migration of H atoms from the metal
transition. (right) Van’t Hoff plot related to the phase transition from metal
to metal hydride. Schematic representation of alpha-phase (left) and beta-
particles to the substrate, explaining that H atoms spill over from
phase (right) of metal hydride are also shown. (Reprinted with permission hydrogen-rich to hydrogen-poor surfaces [32]. Extensive investi-
from [19]. ß 2011 Royal Society of Chemistry). gations as to the nature of hydrogen spillover were undertaken,
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RESEARCH Materials Today Volume 19, Number 2 March 2016
particularly as relates to the partial electron transfer from the source and a secondary receptor. As shown in Fig. 4, a Pd–C catalyst
hydrogen species to the solid material [33]. Hydrogen spillover served as the hydrogen atom source via dissociation and primary
has since emerged as one of the most promising techniques for the spillover, whereas AX-21, or single-walled carbon nanotubes
achievement of high-density hydrogen storage at close to ambient (SWNTs) functioned as secondary spillover receptors. By carbon-
conditions within lightweight, solid-state materials. Spillover is izing a bridge forming precursor in the presence of these compo-
defined as ‘the transport of active species that have sorbed or nents, the hydrogen adsorption volume was increased by a factor
formed on a first surface, migrated onto another surface that does of 2.9 for the AX-21 receptor, and 1.6 for the SWNT receptor, at
not sorb or form active species under the same conditions’. Thus, 298 K at 100 kPa and 10 MPa, indicating that the enhancement
the adsorbed species gain access to a different surface phase factor was a weak function of pressure. Reversibility was demon-
(accepting surface) that is in contact with the original adsorbing strated through desorption and re-adsorption at 298 K. The bridge-
RESEARCH: Review
and activating surface. Spillover is critical in adsorption, and as a building process appeared to be receptor specific, where optimi-
mechanistic step in heterogeneous catalysis [34–37]. The process zation might yield an even greater enhancement [38]. Further, the
of hydrogen spillover involves three primary steps: (i) chemisorp- effect of surface contacts between Pd and the carbon support and
tive dissociation of gaseous hydrogen molecules on a transition the thermodynamics involved were demonstrated by Bhat et al. As
metal catalyst; (ii) migration of hydrogen atoms from the catalyst shown in Fig. 5, a greater proportion of Pd/carbon contacts for Pd
to the substrate; and (iii) diffusion of hydrogen atoms onto sub- nanoparticles embedded within a microporous carbon matrix
strate surfaces. The migration of H atoms from catalysts to sub- induced the efficient ‘pumping’ of hydrogen from the b-PdHx.
strates, as well as H atom diffusion within the substrates, may be It was also discovered that the thermal cleaning of carbon surface
mapped out by calculating minimum energy pathways. A simple groups prior to exposure to hydrogen further enhanced the
and effective technique was developed for the creation of carbon hydrogen pumping power of the microporous carbon substrate.
bridges that served to improve the contact between a spillover In brief, this study highlighted that the stability of the b-PdHx
FIGURE 4
Hydrogen spillover in a supported catalyst system: (a) adsorption of hydrogen onto a supported metal nanoparticle; (b) 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 [38]. ß 2005 American Chemical Society).
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Materials Today Volume 19, Number 2 March 2016 RESEARCH
RESEARCH: Review
Effects of surface area on hydrogen storage
High surface area carbon materials are promising for the low-
temperature storage of hydrogen via physisorption, where surface
area is a critical structural parameter of porous adsorbent materi-
als. Linear relationships between hydrogen storage capacity and
surface area have been observed for the family of carbon based
FIGURE 5
adsorbents. This is because an adsorbent that possesses a higher
Schematic energy diagram for hydrogen absorption and desorption into a
surface area provides additional available/accessible surface sites
Pd lattice, which illustrates the basis for the difference between DHb/a and
DHa/b. In the figure, energy of hydrogen dissociation (EDIS), physisorption per sample mass, for hydrogen. Among activated carbons, com-
(EPH), chemisorption (ECH), subsurface states (ESS) and diffusion (EDIF) are mercially available super-activated carbons (e.g., AX-21 and Max-
shown along with DHb/a and DHa/b. (Reprinted with permission from [39]. sorb possessing surface areas of 2800 m2 g 1 and 3300 m2 g 1,
ß 2009 IOP publishing Ltd.). respectively) at room temperature have exhibited high hydrogen
storage capacities of 0.6 and 0.67 wt% at 100 bar [50]. Chemical-
ly activated carbon with a hydrogen adsorption capacities of 1.2
phase supported on carbon is contingent on the degree of contact and 2.7 wt% have been obtained at 20 and 50 MPa at 298 K,
between the Pd catalysts and carbon supports, as well as the nature whereas at 77 K, the level of hydrogen adsorption was dependant
of the carbon surface [39]. on the surface area and the total micropore volume of the activated
carbon. Hydrogen adsorption capacities of 5.6 wt% at 4 MPa and
Experimental and theoretical studies of hydrogen 77 K have been attained by chemically activated carbons [51],
spillover whereas the surface area of mesoporous carbon was increased from
Hydrogen spillover has been studied extensively, particularly in 833 to 2700 m2 g 1, subsequent to KOH activation [52]. The trend
the field of catalysis. Direct evidence for the spillover of atomic of H2 uptake vs. surface area revealed that hydrogen storage via
hydrogen at room temperature may be studied using different graphene materials did not exceed 1 wt% at 120 bar H2 at ambient
techniques. The inelastic neutron scattering (INS) method is temperature. As shown in Fig. 6, a linear increase in hydrogen
uniquely capable of revealing the state of hydrogen, in either adsorption vs. surface area was observed at 77 K with a maximal
atomic or molecular form. The INS results indicate a direct quan- observed value of 5 wt% for a 2300 m2/g sample. It may be
titative evaluation of the volume of hydrogen adsorbed on acti- concluded that bulk graphene samples obtained through the
vated carbon in atomic form via spillover. Atomic hydrogen use of graphite oxide exfoliation and activation, follows the stan-
spillover was observed from a Pd catalyst, to activated carbon dard of other nanostructured carbon hydrogen uptake trends, and
fibers loaded at 77 K with 2.5 wt% H2. It was found that new C– do not demonstrate superior hydrogen storage parameters as have
H bonds were formed at the expense of physisorbed H2, during been reported in several previous studies. Nevertheless, graphene
prolonged in situ exposure to 1.6 MPa hydrogen at 20 8C. This remains as one of the optimal materials for the physisorption of
verified the atomic nature of H species that were formed in the hydrogen, particularly at low temperatures [53]. Most studies on
presence of a Pd catalyst and of their subsequent spillover and MOF storage capacity have been focused at 77 K, and significant
binding to a carbon support [40]. A similar observation by Tsao storage capacities were achieved on MOFs with high surface areas.
et al. illustrated that the modification of molecular hydrogen MOF-177 with a surface area of 4500 m2 g 1 has the capacity to
in Pt-doped activated carbon samples provided evidence that store 7.5 wt% H2 at 70 bar. MOF-210 with the highest surface area
significant populations of hydrogen atoms may diffuse to a of 6240 m2 g 1 can store 7.9 wt% at 50 bar. At room temperature,
carbon surface at room temperature during the spillover process however, the storage capacities of MOFs were substantially lower.
[41]. For comparison, a material known to exhibit hydrogen MOF-177 and UMCM-2 were reported to store 0.6 wt% and
spillover at room temperature (Pt/C) was also studied with the 0.8 wt% hydrogen, respectively, at 100 bar. A common feature
hydrogen–deuterium scrambling reaction, where the isotherms for the storage performance of MOFs at both cryogenic and
were reversible. For desorption, sequential doses of H2 and D2 at ambient temperatures was that higher surface areas led to higher
room temperature, and subsequent temperature programmed storage capacities. Hydrogen storage capacities are also influenced
desorption (TPD), yielded product distributions that were by more complex factors, such as doping methods, metal particle
strong indicators of a surface diffusion controlled reverse spill- size and distribution, as well as interfacial contacts between the
over process [42]. Spectroscopic study has provided evidence of metals and supports [54].
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RESEARCH Materials Today Volume 19, Number 2 March 2016
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Materials Today Volume 19, Number 2 March 2016 RESEARCH
capacities for raw carbon nanotubes and MAXSORB under the the dimensions of Pd nanoparticles have an impact on hydrogen
same pressure were 0.21 and 0.42 wt%., respectively [68]. A Pd uptake [86]. The insertion of Pd nanoparticles into the MOF 101
doped graphene carbon composite demonstrated a storage capaci- (Cr) pores, while simultaneously ensuring good contact, resulted
ty of 0.82 wt% of hydrogen at 8 MPa under 298 K [73]. Several in the ambient temperature hydrogen uptake of the framework
studies have been conducted using different types of porous due to the formation of palladium hydride [87]. By solution
carbon materials at close to room temperature, under different infiltration of Pd into MOF-5, the surface area was decreased from
pressures; however, to date none of these materials have attained 2885 m2 g 1 to 958 m2 g 1; however, the hydrogen absorption
the high capacities that have been set for vehicular hydrogen capacity was increased from 1.15 to 1.85 wt% [88]. When MIL-
storage [74–82]. Recent work in our group has shown that PdCd 100(Al) was employed as a host for the synthesis of Pd nanopar-
and PdCdAg catalysts on PAC200 substrates exhibited enhanced ticles (2.0 nm) that were embedded within its pores, as described
RESEARCH: Review
hydrogen storage capacities, which were achieved at room tem- by Zlotea et al., it exhibited one of the highest metal contents
perature under ambient pressure (Fig. 7) [29,74]. (10 wt%) without the degradation of the porous host. The textural
MOFs have become of great interest due to their broad range of properties of MIL-100(Al) were strongly modified by Pd insertion,
potential applications, particularly in the field of heterogeneous leading to significant changes in its gas sorption properties. A
catalysis, and for gas storage [83,84]. These nanomaterials have schematic model of how the Pd nanoparticles were embedded in
provided enticing solutions to the hydrogen storage problem due MOFs is depicted in Fig. 8 [89].
to the physisorptive nature of their interactions. The rapid release The synthesis of Pd nanoparticles within a porous MOF, incor-
kinetics of MOFs has served to sustain their stature as a frontrunner porating redox active organic linkers, was undertaken by Cheon
for hydrogen storage. Advances in bridging the gaps between et al., by simple immersion of the MOF solid. Here, the hydrogen
physi- and chemisorptive materials, such as metal hydrides, have storage capacity was dependant on the volume of Pd nanoparticles
also provided dramatic boosts in hydrogen uptake capacities, thus that were loaded within the MOF for the duration of immersion.
providing researchers with even more exciting work for the future. The hydrogen capacities are reported were far lower than reported
Enhanced storage capacities coupled with rapid hydrogen uptake by other methods [90]. Recent work by Kalidindi et al., has shown
have been demonstrated with Pd nanocrystals, encapsulated with- that COFs are new class of templates for metal nanoparticles, as
in a HKUST-1 (copper (II) 1,3,5-benzenetricarboxylate) MOF, they have synthesized a three-dimensional covalent Pd@COF-102
which was double the storage capacity of bare Pd nanocrystals. hybrid material. The Pd@COF-102 hybrid material is a rare exam-
The kinetics of hydrogen absorption within the Pd nanocrystals ple of a metallic nanoparticle-loaded porous crystalline material
was also enhanced by the MOF coating [85]. In the case of MOFs, that has a narrow size distribution without the presence of larger
FIGURE 7
(a) Hydrogen adsorption isotherms at room temperature for PAC200, Pd/PAC200, PdCd/PAC200, and PdAg/PAC200 samples. Calculated isotherms are shown
with crosses and experimental isotherms are shown with dots. (b) Optimized molecular geometries and adsorption energies for Pd–H, Ag–H, and Cd–H were
calculated using DFT. (c) Anodic sweeps of PdAg10Cd10 nanoparticles with and without PAC200. (d) Overall hydrogen oxidation charges (QH) for each Pd-
based catalyst with various compositions. (Reprinted with permission from [29,74]. ß 2010, 2013 American Chemical Society).
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RESEARCH Materials Today Volume 19, Number 2 March 2016
RESEARCH: Review
FIGURE 8
(a) The MTN topology of MIL-100(Al): large cages in yellow and small cages
in turquoise. (b) Space-filling perspective view of the large cage of MIL-
100(Al): carbon in gray, oxygen in red, terminal groups (water or OH) in
pale blue. (c) Space-filling representation of the hexagonal window of the
large cage. (d) Steric hindrance of the [PdCl4] anion at the same scale.
(Reprinted with permission from [89]. ß 2010 American Chemical Society).
FIGURE 9
Excess hydrogen sorption isotherms of pristine COF-102, Pd3.5 wt%@COF-
agglomerates. At room temperature, the uptake of these samples 102, and Pd9.5 wt%@COF-102 at (a) 77 and (b) 298 K. The volume of
was superior to that of similar systems, such as Pd@MOFs. Studies hydrogen adsorbed by the physisorption process (i), hydrogenation of
indicated that the H2 capacities were enhanced by a factor of 2–3 residual organic compounds (ii), and by Pd hydride (iii); iii-a is due to the
through impregnation with Pd on COF-102 at room temperature 6 wt% difference in Pd loading, 0.036 wt% of H2; iii-b is due to the 3.5 wt%
under a pressure of 20 bar. The significantly higher reversible of Pd impregnated in COF-102, 0.02 wt% of H2. Filled symbols: adsorption,
open symbols: desorption. (Reprinted from [91]. ß 2012 Wiley-VCH Verlag
hydrogen storage capacity that comes from decomposed products GmbH & Co. KGaA. Reprinted with permission).
of the employed organometallic Pd precursor suggests that this
discovery may be relevant to the spillover phenomenon in metal/
MOFs and related systems [91]. At higher pressures (>10 bar), the pore volume controls the capac-
Pd doped double-walled silica nanotubes show promise as a ity for hydrogen uptake [99]. In the case of zeolites, due to the
hydrogen storage material at room temperature [92]. Similar work existence of a high energy barrier for crossing the framework
by Chen et al. has shown that when titanium dioxide nanotubes hexagonal apertures, H2 was not able to enter the sodalite-cages.
were used as support materials, improved hydrogen sorption was In experiments by Scarano et al., Pd(0) containing zeolites were
observed [93]. Studies on new boron and nitrogen based hydrides prepared and the dispersion of the metal was characterized, where
illustrate how hydrogen release and uptake properties may be hydrogen was adsorbed in atomic form to give a metal-hydride
improved [94]. Several works have been carried out with graphene phase. Subsequent spill-over effects allowed the confinement of
as a support materials using Pd as a catalyst for hydrogen storage hydrogen into the diminutive sodalite-cages, demonstrated by H/
[78,95–98]. Among these, nitrogen doped Pd decorated graphene D isotopic substitution experiments [100].
exhibited very high hydrogen capacities of up to 4.4 wt% at 298 K
and 4 MPa [95]. Very recent work by Zhong et al., have proposed Summary and outlook
three dimensional carbon aerogel (CA) as a promising support Significant improvements in hydrogen storage capacities have
material for hydrogen uptake. The effects of different Pd loads on been achieved at ambient temperatures and pressure via the
the hydrogen uptake capacities of CAs were investigated, where hydrogen spillover effect by the design and utilization of nano-
the results showed (Fig. 9) that Pd doping imparted a negative structured materials. A summary of the hydrogen storage capaci-
effect on hydrogen uptake capacity at 77 K. At 298 K, the hydrogen ties of Pd based nanomaterials is shown in Table 1. It is
uptake capacity was contingent on the Pd content and nanoparti- recommended that several aspects including catalysts and sup-
cle size in the low pressure region (<10 bar). The hydrogen uptake ports with high surface areas should be further developed to
capacity of the 4.8 wt% Pd/CA was 0.11 wt% at 10 bar and 298 K. improve hydrogen storage capacity by spillover.
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Materials Today Volume 19, Number 2 March 2016 RESEARCH
TABLE 1
Metal hydrides and their hydrogen storage properties
Metal catalyst Catalyst in (wt%) Support Surface area (m2/g) T (K) P (MPa) wt% of H Ref.
Pd 3 CNF 150 298 9 0.59 64
Pd 2 CNF – 298 7.7 1.38 65
Pd – CNT – 298 0.1 7 66
Pd – CNT 89 298 5 0.87 67
Pd 31.5 SWNT 232 298 9 0.51 68
Pd 2 DWNT 209 298 3 2.0 69
Pd 20 CNT – 298 10.7 3.5–4.5 70
RESEARCH: Review
PdNi18 5.5 MWNT – 298 1.5 2.3 71
PdPt – MWNT 212 298 2 2.0 72
Pd 49 Maxsorb AC 199 298 9 0.7 68
Pd/GS – AC 3328 298 8 0.82 73
Pd – AC-ox1 824 298 8 0.37 75
Pd 2 ACF 1878 298 2 0.23 76
Pd 10 AC – 303 5 0.53 77
Pd 10 AX-21 2466 298 10 1.38 78
Pd 10 AX-21-O 2362 298 10 0.98 78
Pd 18.4–24.5 C-nanosheet 80–230 298 0.11 0.1–0.26 79
Pd 10 OMC 342 298 30 0.80 80
Pd/Ni 10.2/6.5 TC 874 298 0.5 0.027 81
Pd 10 TC 712 298 0.5 0.05–0.08 82
Pd – MIL 101 (Cr) – 298 4.5 0.23 87
Pd 1 MOF-5 958 77 0.1 1.86 88
Pd 10 MIL-100 (Al) 380 77 4 1.3 89
Pd 3 MOF 242 298 9.5 0.3 90
Pd 9.5 COF-102 1419 298 2 0.42 91
Pd 5, 10, 15 SN 160–264 298 3.5 0.15–1.9 92
Pd 10 GO 687 298 10 0.95 78
Pd 20 N-HEG – 298 4 4.4 95
Pd – HCS 150 298 2.4 0.36 96
Pd – N-Graphene 146 298 2 1.9 97
Pd 1 g-C3N4 26 298 4 2.6 98
Pd 4.8 CA 499 298 1 0.11 99
Note: CNT: carbon nanotube; CNF: carbon nanofiber; SWNT: single walled carbon nanotube; DWNT: double-walled carbon nanotube; MWNT: multi-walled carbon nanotube; AC: activated
carbon; AX-21-O: oxidized AX-21; ACF: activated carbon fiber; OMC: ordered mesoporous carbon; TC: templated carbon; MOF: metal organic framework; COF: covalent organic framework;
SN: silica nanotubes; GO: graphite oxide; N-HEG: nitrogen doped hydrogen exfoliated graphene; HCS: hollow carbon sphere; g-C3N4; carbon nitride; CA: carbon aerogels.
Hydrogen storage by spillover is an atomic hydrogen adsorption gravimetric capacity, hydrogen embrittlement, and excessive hy-
process, where the surface adsorption sites of the adsorbent deter- drogen adsorption strength. Great progress has been made toward
mine the storage capacity. It is understood that an adsorbent addressing these challenges by alloying Pd with cost-effective
which possesses a higher number of surface adsorption sites for metals, synthesizing Pd-based nanomaterials, increasing the lat-
hydrogen atoms should have a higher hydrogen spillover capacity. tice, and using appropriate support materials. Once these chal-
In this regard, carbon based materials (e.g., CNTs, activated car- lenges have been met, the use of Pd-based nanomaterials for
bon, mesoporous carbon, and carbon fibers) have been extensively effective hydrogen spillover will be much closer to practical appli-
explored; however, the hydrogen storage capacity of pure carbo- cation in contributing to onboard hydrogen storage in vehicular
naceous materials at ambient temperature and pressure is still well fuel cells. On the other hand, the development of advanced
below the DOE onboard vehicular targets. Even though the opti- physical storage devices and chemical constituents with low sys-
mization of surface area and pore size may improve hydrogen tem weight, volume and costs, high efficiency, long durability, and
storage, the modification of structural properties alone would limit rapid charging/discharging kinetics would provide alternative
this augmentation. An auspicious strategy for simultaneously approaches to address the technical barriers toward hydrogen
enhancing the interaction of hydrogen with sorbents and promot- storage. Further basic research will be required to fully elucidate
ing spillover may be achieved by the doping of carbon based the interactions between hydrogen with various other materials,
materials, MOFs, COFs and other nanostructured materials with and how it reacts under variable conditions, as prerequisites for the
catalysts such as metallic nanoparticles. However, more funda- successful transition to a hydrogen economy.
mental research and the development of advanced techniques are
required to completely understand the kinetics of hydrogen spill- Acknowledgements
over as it relates to hydrogen storage methods. This work was supported by a Discovery Grant from the Natural
Although Pd has strong potential to serve as a catalyst for Sciences and Engineering Research Council of Canada (NSERC
hydrogen spillover and storage, several issues pertaining to RGPIN-2015-06248). S.K. Konda acknowledges the Ontario
pure Pd include its limited supply, considerable expense, poor Trillium Scholarship. A. Chen acknowledges NSERC and the
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RESEARCH Materials Today Volume 19, Number 2 March 2016
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