Ionics (2006) 12: 103–115

DOI 10.1007/s11581-006-0016-4

REVIEW

J. W. Phair . S. P. S. Badwal

Review of proton conductors for hydrogen separation

Received: 22 February 2006 / Revised: 9 March 2006 / Accepted: 13 March 2006 / Published online: 15 June 2006
# Springer-Verlag 2006

Abstract There is a global push to develop a range of Introduction

hydrogen technologies for timely adoption of the hydrogen
economy. This is critical in view of the depleting oil reserves Many studies predict that global oil production is likely to
and looming transport fuel shortage, global warming, and peak within the next 5 to 15 years [1–3]. With declining
increasing pollution. Molecular hydrogen (H2) can be gen- global oil reserves and consequent concern over the supply
erated by a number of renewable and fossil-fuel-based of liquid fuels for transport application for future genera-
resources. However, given the high cost of H2 generation by tions, increasing pollution and global warming prospects,
renewable energy at this stage, fossil or carbon fuels are there is an increasing worldwide interest in the hydrogen
likely to meet the short- to medium-term demand for hy- economy and hydrogen (H2) technologies. In this scenario,
drogen. In view of this, effective technologies are required hydrogen will be the main energy carrier, currency, and
for the separation of H2 from a gas feed (by-products of coal storage media.
or bio-mass gasification plants, or gases from fossil fuel Currently, world H2 production is about 500 billion m3/Y
partial oxidation or reforming) consisting mainly of H2 and or 42 million tons per annum [4] and would barely meet
CO2 with small quantities of other gases such as CH4, CO, ∼1.5% of total global energy demand or US transportation
H2O, and traces of sulphur compounds. Several technologies needs. Most of the H2 presently generated is via the steam
are under development for hydrogen separation. One such reforming of natural gas. About half of this is used for
technology is based on ion transport membranes, which ammonia, fertilizer, and explosive production and just over
conduct protons or both protons and electrons. Although 1/3 for the impurity removal and upgrade of heavy oil
these materials have been considered for other applications, fractions into lighter and more valuable products. The re-
such as gas sensors, fuel cells and water electrolysis, the mainder, in small quantities, is used in methanol produc-
interest in their use as gas separation membranes has tion, chemical and metallurgical industries, and space
developed only recently. In this paper, various classes of missions as rocket fuel. However, to use hydrogen as the
proton-conducting materials have been reviewed with spe- main energy carrier and storage media, H2 has to be gen-
cific emphasis on their potential use as H2 separation erated in significantly larger quantities. A range of new
membranes in the industrial processes of coal gasification, technologies based on renewable energy (photoelectrolysis,
natural gas reforming, methanol reforming and the water– photo-biological processes, water electrolysis, thermolysis,
gas shift (WGS) reaction. Key material requirements for their etc.) or fossil fuels (reforming, partial oxidation, coal or bio-
use in these applications have been discussed. mass gasification, etc.) or their combination (e.g., solar
thermal reforming of natural gas) are under development or
Keywords Proton conductors . Hydrogen separation . consideration [5–7]. Although generation of H2 from
Hydrogen economy . Coal gasification . Methane renewable energy sources has the potential to provide a
reforming sustainable energy cycle, there is consensus that fossil fuels
would provide a short- to medium-term solution, provided
H2 can be generated without additional adverse environ-
mental impacts [8, 9].
J. W. Phair . S. P. S. Badwal (*) In principle, apart from steam reforming of natural gas,
CSIRO Manufacturing and Infrastructure Technology, H2 can also be produced from steam reforming or partial
Private Bag 33, oxidation of a range of other carbon fuels and by the
Clayton, Victoria, 3169, Australia
e-mail: [email protected] gasification of coal or bio-mass. These processes may be
Tel.: +61-3-95452719 followed by the water–gas shift reaction to convert CO in
Fax: +61-3-95452720 the reformate into more H2 and CO2. However, to avoid
104

gases, the technologies available specifically for H2 sepa-

ration include:
1. Polymer membranes
2. Dense metal membranes
3. Nano-porous ceramic or glass ceramic membranes
4. Dense ion transport membranes
5. Dense cermet membranes consisting of an ion trans-
port material and a metal.
Polymer membranes operate with selective permeation of
one or more gases from the feed side to the permeate side
under a concentration gradient. The gas separation factor
Fig. 1 A schematic of a coal gasification/natural gas reforming depends on the size of the gases to be separated and the
plant for H2 production (NG Natural gas, ICE internal combustion molecular sieving capability of the membrane, which in turn
engine) depends on the diffusivity and solubility selectivity factors.
Typically, small molecules, such as H2, move rapidly,
compared with bulky CO2 molecules. These membranes are
greenhouse gas emission penalties, the H2 subsequently used in various industrial processes. The major drawbacks
needs to be separated from CO2 and other gases to attain are that they cannot be used in aggressive chemical envi-
the desired level of purity, followed by CO2 sequestration ronments or at high temperatures, and gases must be cooled
(Fig. 1). sufficiently for hydrogen separation and reheated—a costly
Coal gasification for power generation is being actively and energy-intensive process. Moreover, the separation
pursued to improve the competitiveness and environmental factor is low, and it is often difficult to get high purity
performance of coal-based power generation. Instead of hydrogen and flux rates are significantly lower [9].
burning coal directly, coal gasification produces syn-gas, In nano-porous membranes, H2 is separated from gases
which can be used to run a gas turbine, a solid oxide, or a such as CO2, CO, CH4, etc., by molecular diffusion if the
molten carbonate fuel cell to generate power. Syn-gas may pore size of the membrane material is such that smaller H2
also act as a feedstock for the production of liquid fuels and molecules (diameter=2.83 Å) can move freely while large
other chemicals. However, coal-based power plants would molecules of other gases are restricted. Therefore, the mate-
still be quite greenhouse-gas-intensive and produce CO2 in rial acts as a molecular sieve, allowing only H2 to pass
a dilute form, which needs to be separated and sequestrated through. Typical membrane materials used are metal oxides
to reduce greenhouse gas emissions. Technologies available and often silica, aluminosilicates, silicalite, and zeolites.
for post-combustion CO2 separation are expensive and The hydrogen flux is directly proportional to the pressure
bulky although they have the advantage of being integrated differential across the membrane. The major disadvantages
into existing power plants with minimum penalty on power are the difficulty of fabricating thin membranes free of flaws
generation infrastructure. Alternatively, the pre-combustion and with a discrete pore structure to achieve a large sepa-
separation of CO2 in new coal-based power plants is ex- ration factor. Thus, the H2 produced is not of high purity.
pected to be more economical, as the gas is in concentrated Metal membranes, such as Pd, Zr, Ta, and Nb or their
form and at a high pressure. alloys and many amorphous alloys are known to be effective
For pre-combustion separation of CO2 for its sequestra- in separating hydrogen from other gases at high temperatures
tion, the syn-gas is shift-converted into CO2 and more H2. (300–600 °C) (Phair and Donelson 2006, submitted for
Following separation of H2 from CO2, the H2 then can be publication). The process for H2 separation relies on their
combusted in a gas turbine or an internal combustion en- ability to allow only H2 gas to diffuse through and restrict the
gine, or used in low temperature fuel cells (e.g., polymer flow of all other gases. Hydrogen permeation proceeds in
electrolyte membrane or phosphoric acid) at higher electric several steps via adsorption and dissociation of H2 to the
and system efficiencies. The CO2 can be transported in a atomic form, solution in the metal, diffusion, and re-asso-
concentrated form for sequestration. The use of hydrogen as ciation and desorption. The hydrogen flux through the mem-
a transport fuel, for example, in polymer electrolyte brane is generally proportional to the square root of the
membrane fuel cell engines, would significantly reduce pressure differential (assuming fast hydrogen exchange at the
the dependence on oil and reduce the burden on depleting gas/metal interface), with hydrogen migrating from the high
oil reserves. pressure side to the low-pressure side. The hydrogen
A range of technologies are available for the separation of permeation flux rates are a function of hydrogen solubility,
H2 from CO2 and other gases [10, 11]. The technologies, hydrogen diffusion characteristics, operating temperature,
which can be directly integrated into the reforming or gasi- and the membrane thickness. In addition, the metal mem-
fication plants (temperature, pressure), are more attractive brane must have the ability to dissociate and reassociate H2 at
from operational and economic points of view [10]. the surface. Alternatively, effective dissociation/association
Apart from chemical scrubbing, cryogenic, and pressure catalytic layers may be required to perform this function. The
swing adsorption techniques for CO2 removal from product H2 produced is of very high purity and can be directly
 105

utilized in a fuel cell. However, the major drawback is that Pd key criteria they must meet, and application regimes of
is too expensive and has to be used as a very thin film (few proton and mixed proton/electron conductors.
microns) on a porous support structure to reduce cost and
increase flux rates. Other metals or alloys are sensitive to
hydrogen embrittlement, exhibit low hydrogen flux density Key criteria of proton conductors to separate H2
or lack stability under operating environments.
In ion transport membranes, H2 is separated and trans- A H2 separation membrane based on dense ceramic proton
ported through the material electrochemically by a surface conductors has similar performance targets to any other
exchange reaction at the feed surface of the membrane to hydrogen separation membrane. That is, the membrane
dissociate and ionize H2 into protons. These protons then must have: (1) high H2 permeation flux rates; (2) low cost;
migrate through the membrane material and are reduced to (3) sufficient lifetime durability in real operating environ-
form H2 molecules on the permeate side of the membrane. ments; (4) low parasitic power requirements; and (5) low
The driving force for hydrogen migration is the H2 partial membrane fabrication costs. Specific target values for dense
pressure differential across the membrane, with hydrogen ceramic H2 separation membranes outlined by the U.S.
migrating from the high-pressure side to the low-pressure Department of Energy are described in Table 1.
side. One of the major advantages of this technology is that To operate a H2 separation membrane, a hydrogen chem-
the dense membranes are 100% selective with an infinite ical potential gradient must be applied to drive the flow of
separation factor. Thus, no secondary purification of the gas hydrogen through the membrane. The chemical potential
is required. gradient across the membrane may be controlled by the
Ideally, the ion transport membrane material must have pressure gradient, concentration gradient, temperature gra-
both proton and electronic conductivity to avoid external dient, or electric field gradient. Typically, a hydrostatic
electrochemical loading of the cell and to save energy. To gradient is used to promote the transport of H2 through the
optimize proton and electronic conductivity, these materials membrane, so it must be able to withstand extreme pressure
may be mixed with a metal to enhance electronic conduc- (up to 7 MPa ΔP hydrogen partial pressure) and operating
tion. If the metal is also a proton transporting metal, such as temperature between 300 and 900 °C, depending on the
Pd, Pd-alloys, or cheaper alternatives, then the hydrogen specific industrial process (e.g., steam reforming of natural
flux can be substantially enhanced. Major technical issues gas, methanol partial oxidation, or coal gasification) in
relate to the availability of suitable proton conductors with which it is applied.
high proton flux rates and which are stable at the operating Overall, the process of hydrogen permeation through a
temperatures (300–600 °C), pressures (to 20–30 bar A), dense ion transport membrane involves several steps
and in the presence of other gases and contaminants (CO2, (Fig. 2):
CO, CH4, H2O, H2S, and metal vapors). Other major chal-
1. H2 diffusion in the gas phase to reaction sites on the
lenges relate to ensuring the materials used have adequate
surface of the feed side
mechanical strength and toughness, that chemical and
2. H2 adsorption, dissociation, and charge transfer at the
thermal compatibility exists between metal and ceramic
membrane surface
phases, and that the fabrication and optimization of the
3. H+ diffusion in the bulk of the membrane
microstructure can provide dense, defect-free thin mem-
4. H+ diffusion along and through grain boundaries
branes. To become attractive for use at an industrial scale,
5. Proton reduction and hydrogen re-association at the
H2 separation rates in excess of 50 ml(stp)/min cm2 should
membrane surface
be achieved.
6. H2 desorption and movement away from the surface on
Several materials exhibit reasonable proton conductivity
the permeate side.
in the temperature range of 100 to 900 °C. These materials
may have the potential to be used for the construction of
electrochemical cells for the separation of H2 from CO2. The hydrogen permeation rate increases with increasing
This paper provides an overview of various classes of temperature, decreasing membrane thickness—as it is in-
proton-conducting materials available for H2 separation, versely proportional to the thickness of the membrane, and

Table 1 Hydrogen dense ceramic membrane separation targets [120, 121]

Characteristic Units 2003 status 2007 target 2010 target 2015 target

Flux rate m3/h/m2 18.3 30.5 61 91.5

Cost US*$/m2 1,940 1,620 1,080 <1,080
Durability Years <1 1 3 >5
Operating temp °C 300–600 400–700 300–600 250–500
Parasitic power kWh/1,000 m3 H2 generated 113 113 105 <100
ΔP operating capability MPa 0.69 1.38 <2.76 2.76–6.89
Hydrogen recovery % of total gas 60 70 80 90
Hydrogen purity % of total (dry) gas >99.9 >99.9 >99.95 99.99
106

substrate, but this may be controlled by altering the pro-

perties of the membrane material and micropores of the
porous support structure. A relatively simple and cheap
method of thin-film preparation that may avoid these dif-
ficulties is dry pressing to prepare dense ceramic mem-
branes on porous substrates [22]. The effect of preparative
techniques for proton conductors (liquid-phase or solid
state) on the microstructure and the H2 permeation proper-
ties remains to be fully investigated.
Critical to the design of dense H2 separation membrane is
Fig. 2 Process steps for H2 separation with a mixed proton/ the surface of the membrane, which must catalyze the H2
electron-conducting membrane dissociation/reassociation reactions necessary for the per-
meation of hydrogen through the membrane. Generally, the
surface properties of proton conductive materials are insuf-
ficient to allow for the spontaneous dissociation or re-
maximum H2 dissociation and re-association reaction rates association of H2 on the surface. As a consequence, surface
at the surface. However, finding a single phase material with modification of the proton-conductive thin film or electrodes
both high hydrogen diffusivity in the bulk and which also may be required to promote hydrogen exchange reactions at
allows fast surface exchange of hydrogen is not easy. the gas/membrane interface. Often, the requirements of
Achieving high H2 flux remains the greatest obstacle for having secondary catalytic layers or electrodes are reduced or
developing proton conductors into commercially useful eliminated if a metal phase (e.g., Ni) is added in sufficient
hydrogen separation membranes. Both proton and electron quantities to improve the electron-conducting properties of
conductivities in excess of 0.1 S cm−1 are required in order the material and promote the hydrogen exchange reaction
for a proton conductor to be useful for hydrogen separation. [23]. In addition, the surface must be free of impurities and
In materials, which have sufficient proton conductivity, it is undesired phases that may form as a result of the membrane
the rate of electron transport that is the limiting step in the preparation methods used, handling, or operation. For exam-
permeation of hydrogen through a proton conductor [12]. ple, BaCe0:90 Yb0:10 O3
δ (BCYb10) thin films synthesized
Thus, if the proton conductor cannot conduct sufficient through a combined EDTA-citrate complexing method,
quantity of electrons by itself, it must be capable of forming underwent phase segregation in an asymmetric atmosphere
a composite material with a second phase that can conduct and failed to maintain a perovskite structure at the surface
sufficient quantity of electrons. [24].
While hydrogen ion transport membranes may be used as Another critical property for a proton conductor to serve
self-supported structures of variable shapes (e.g., flat plates as a useful hydrogen separation membrane is high
or tubes) and sizes, the manufacture of a very thin mem- mechanical strength. However, if a proton conductor with
brane (of the order of few microns) on a support structure is high flux capabilities has poor mechanical strength, then it
attracting significant interest for achieving high hydrogen must be incorporated into a composite structure to improve
flux rates and for imparting mechanical integrity to thin- the device’s mechanical properties. It may be necessary, for
film structures. The porous support may be constructed instance, to impregnate the proton-conductive material into
from a ceramic or metallic alloy and may consist of multiple a porous ceramic or metal, such that it can withstand the
layers of variable pore structure for ease of gas diffusion physical demands (e.g., high pressures and temperatures)
(more open microstructure) and deposition of impervious of its application as a H2 separation membrane [25]. Alter-
coatings (nano-porous microstructure) of ion transport ma- natively, proton conductors may be combined with a re-
terial at the surface. Several variations to this design are fractory oxide to form a composite material with stronger
possible, such as a tri-layer structure reported in the lit- physical properties upon sintering, which widens its appli-
erature that consists of a thin-film mixed conducting mem- cation domain [26].
brane surrounded by a porous support/catalyst layer on Chemical stability under conditions in which proton
either side [13]. In any case, due consideration needs to be conductors may be used for H2 separation is another key
given to match the thermal expansion coefficient of the criterion. Under all situations of practical use, the H2
membrane material with the support structure; otherwise, separation membrane will be exposed to reducing condi-
delamination and cracking of the membrane can occur tions on both sides of the membrane. Not only must the
during fabrication and subsequent use. ceramic be stable under these conditions, but also exhibit
Dense thin-film membranes of the proton conductive stability in the presence of CO, CO2, H2O, H2S, NOx, and
layer can be deposited on to the porous support by a variety chlorides, as these are typically present in the gases from
of methods, including spin coating [14, 15], sputtering [16], which the H2 must be separated. Many oxides with high
slip-casting [17], sol–gel methods [18], particulate or vapor conductivity (e.g., BaCeO3−derived compounds) are often
phase deposition methods (e.g., chemical or electrochem- unstable and susceptible to reaction with CO2 and H2O,
ical vapor phase deposition) [19–21]. Complications with forming insulating carbonates and hydroxides [27]. This
wet dense-film preparative methods can arise due to the may be overcome by doping highly conducting oxides to
impregnation of the membrane materials into the porous improve stability (e.g., Zr-doped cerates) [28], improving
 107

the conductivity of more chemically stable oxides by Water-containing systems

reducing grain boundary resistance [29], by composite
design, or by developing new alternatives (e.g., pyrochlores Hydrated compounds or water-containing systems that may
without any Ba or Sr) [13]. be of potential use as H2 separation membranes, include a
The proton conductor must also be thermally stable under diverse array of inorganic and organic compounds. While
the operating conditions expected for H2 separation, and relatively few novel compounds have been discovered over
any spontaneously combustible or decomposing phases the past 20 years with high conductivity, significant ad-
should be eliminated or modified to remove the potential for vances have been made in the characterization of these
thermal degradation. materials and the formation and properties of composite-
Compared to dense metal membrane structures on a derived materials.
porous metal support, which may undergo interdiffusion Water-containing proton conductors with high proton
of metals resulting in a reduction of the H2 transporting conductivity are the hydrated hetero-polyoxo-metallate
ability, proton-conducting ceramics, which can also be acids (heteropolyacids), such as hydrated phosphomolybdic
manufactured as dense membranes on porous support acid (H3PMo12O40·nH2O, denoted as PMA) and phospho-
structures, are expected to be more stable [30]. As a result, tungstic acid (H3PW12O40·nH2O, denoted as PTA), due to
there will be less complications in designing thermally three-dimensional conductivity network. Proton conductiv-
compatible support structures for ceramic proton con- ities of the order of 10−2 S cm−1 are routinely achieved at
ductors allowing an easy integration into industrial room temperature for pure compounds. However, under
processes. Furthermore, dense ceramic membranes have conditions of low humidity, the hydrates lose their water of
the potential to exist as self-supported structures at high crystallization, leading to a decrease in the proton conduc-
temperatures (>600 °C). tivity. Furthermore, pelletization of the compounds can also
One other important stage in the integration of a proton- force the water of crystallization out of the compound
conducting membrane into the overall H2 separation pro- affecting the ionic conductivity. Therefore, novel ap-
cess is ensuring that the membrane is hermetically sealed proaches have been investigated to improve the stability
to the support structure of the separation chamber by a seal and robustness of such heteropolyacids as protonic con-
that is both mechanically robust and resistant to high ductors, which include the insertion of the heteropolyacids
temperatures [31]. Recent attention has focused on brazing within the pores of SiO2 gel [34], or the mixing and grinding
as a method to seal ceramic membranes used in the with a refractory oxide (e.g., Al2O3) to form a composite
purification of gases derived from gasification processes membrane [35, 36].
with certain braze alloys that are stable at high temperature Of probably greater technological interest, however,
(800 °C) [32]. Inconel 600 has been reported as a useful have been proton conductors based on sulfonated polymer
brazing alloy for joining ceramic membranes to their metal membranes with hydrated layers, such as sulfonated fluo-
holders [13], while Gold ABA (3% Ni, 0.6% Ti, balance rocarbon NAFION [37], sulfonated polybenzimidazole (S-
Au by weight) and Nioro ABA (16% Ni, 0.75% Mo, PBI) [38], and sulfonated polyether ether ketone (S-PEEK)
1.25% V, balance Au by weight) have also been tried and, [39], which all exhibit high proton conductivity and
while they undergo oxidative damage in an oxygenated reasonable chemical stability. While NAFION is generally
atmosphere [32], their properties in a reducing atmosphere considered a stable and robust material, limitations to its use
at high temperature are expected to be better. Thus, some exist due to the fact that its glass transition temperature is at
proton conductors also have the advantage of being ∼105 °C and the membrane loses water and, thus, ionic
hermetically sealable for practical use in separating conductivity at temperatures >80 °C. As a result, recent
hydrogen. research has sought to expand the conditions under which
they may be used by developing composite materials or
polymer-based alternatives to NAFION, which maintain
high conductivity at higher temperatures (300–600 °C).
Classes of proton conductors Composite membranes in which NAFION is sorbed onto
high-surface-area structures, such as polystyrene micro-
Solid-state proton conductors may be classified in a variety beads, have been reported to exhibit higher proton flux than
of ways based, for example, on their chemical structure, ordinary NAFION films [40]. Alternative polymeric mem-
composition, preparative method, or cost, to name a few. As branes also receiving interest include other poly(perfluoro-
high-bulk H2 flux is a fundamental requirement for any sulfonic acid) membranes, styrene-based polymers, poly
proton conductor to be applied as a hydrogen separation (arylene ether)s, poly(imide)s, polyphosphazene, and poly-
membrane, it is useful to review proton conductors which, mers containing alternative hydrating moieties, such as the
as a minimum, are already known to exhibit high proton phosphonic group [41]. Success at increasing the maximum
conductivity. Kreuer has already identified four main operating temperature up to 145 °C has already been
groups of compounds as “fast” proton conductors of achieved by combining perfluorinated ionomers (NAFION)
technological and engineering significance [33]. The chal- and non-perfluroinated ionomers (silica) to form a hybrid
lenge now is to review the various “fast” proton conductors composite membrane [42]. However, significant modifica-
based on the Kreuer classification system, with reference to tions of present polymeric membranes are still required to
the application as H2 separation membranes. demonstrate that their chemical, thermal, and physical sta-
108

bility can satisfy the demands of an industrial H2 separation OUO2AsO4·3H2O undergo a phase transition above
process. ∼50 °C resulting in at least an order of magnitude increase
Inorganic acid hydrates with a layered structure, on the in conductivity or “superconductivity”. Above 350 °C,
other hand, have the advantage of being prepared using however, prevention of complete acid condensation, while
more thermally stable acid groups. Thus, it is possible to maintaining high proton conductivity, becomes extremely
synthesize a variety of acid hydrates with high proton difficult, so their use is limited to below this temperature
conductivity that are stable up to around 350 °C. These in pure form. Of notable interest are layered acidic
include H3OUO2XO4·3H2O [X=P, As], H3Sb3P2O14·10 zirconium silicates (e.g., K2ZrSi3O9 or wadeite, K2ZrSi3O9
H2O, H2Ti4O9·1.2H2O and HSbP2O8·10H2O, using or khibinskite), phosphates (α-Zr(HPO4)2 · nH2O and
phosphonic groups. Typically, compounds such as H3 γ-Zr(PO4)-(H2PO4)·2H2O) and phosphonates (α- and

Table 2 Conductivity of potential proton-conducting materials for hydrogen separation membranes

Material Optimal conducting Proton conductivity (S cm−1) Reference
temperature (°C)

Hydrated sulfonated polymers

NAFION <100 5×10−2 at 25 °C, 4×10−2 at 160 °C [37, 39]
S-PBI <100 1×10−2 at 25 °C [38]
S-PEEK <100 3×10−2 at 25 °C, 4×10−2 at 160 °C [39]
Heteropolyacid hydrates
H4SiW12O40·28H2O <100 2×10−2 at 25 °C [122, 123]
H3PW12O40·29H2O <100 8×10−2 at 25 °C [122, 123]
H3PMo12O40·29H2O <100 1.7×10−1 at 25 °C [122, 123]
Layered hydrates
HUO2PO4·4H2O <100 5×10−3 at 25 °C [124, 125]
α-Zr(HPO4)2·nH2O <100 1×10−4 at 25 °C [126]
γ-Zr(PO4)(H2PO4)·2H2O <100 3×10−4 at 25 °C [127]
γ-Zr sulfo phosophonates <180 1×10−2 at 25, 100 °C [128]
Oxide hydrates
Sb2O5·4H2O <300 3×10−4 at 25 °C [47, 49]
V2O5·nH2O, ZrO2·nH2O, <150 1×10−2 at 100 °C [48]
SnO2·nH2O <300 4×10−4 at 25 °C [129]
Ce(HPO4)2·nH2O <150 1×10−3 at 100 °C [48]
Polyphosphate composite
NH4PO3/(NH4)2SiP4O13 200–300 8.7×10−3 (dry atm), 3.3×10−1 [53, 54]
(wet atm) at 300 °C.
NH4PO3/TiP2O7 150–250 2.4×10−2 at 250 °C [54]
Layered polyvalent (Zr or Ta) hydrogen phosphate 25 (Ta>Zr) 2×10−4 at 25 °C [130]
Sr-doped La3P3O9 700 7×10−7 to 3×10−4 at 300–700 °C [131, 132]
Sr-doped LaPO4 500–925 6×10−6 to 3×10−4 at 500–925 °C [133, 134]
in wet atm
Perovskites
BaCe0:9 Y0:1 O3

(BCY) 500–900 1.8×10−2 to 7×10−2 at 600–1,000 °C [135]
BaZr0:9 Y0:1 O3

(BZY) 500–900 1.6×10−3 to 6×10−3 at 600–1,000 °C [135]
Ba3Ca1.18Nb1.82O8.73 (BCN18) 500–900 5.5×10−4 at 600 °C [136]
Oxo acid salts
K3H(SO4)2 100–200 9.5×10−6 to 2.2×10−2 at 80–250 °C [137]
CsHSO4 2×10−7 to 3×10−2 at 110–190 °C [138]
H3OClO4 3.5×10−4 at 25 °C [139]
Oxo acid composites
MeNO4–SiO2 (Me=Rb, Cs) 100–200 1×10−6 to 1×10−2 at 60–280 °C [140]
Cs3(HSO4)2(H2PO4) 1×10−6 to 1×10−2 at 40–180 °C [141]
Pyrochlore
(La1.95Ca0.05)Zr2 O7
 500–900 6.8×10−2 at 600 °C [142]
La2Ce2O7, Eu2Zr2O7 7×10−7 to 1×10−2 at 300–800 °C [78]
Chalcogenides
H2S/(B2S3 or Ga2S3)/(GeS2, SiS2, As2S3 or CsI) 200–500 5×10−11 to 4×10−7 at 60–300 °C [94, 143]
 109

γ-Zr sulfophenylphosphonate or sulfoarylphosphonates), for applications in numerous technologies where ionic

which can exhibit good conductivity even in dry form conductors are required (e.g., fuel cell electrolytes) [50].
[25]. Moreover, research has shown that novel forms of Proton conductors based on the hydrosulphate of larger
acidic phosphate and phosphonates intercalated with large alkali metals tend to exhibit a superprotonic transition
molecules, such as imidazoles, pyrazoles, heterocyclic with anomalously high conductivities at higher tempera-
bases and alkyls, have significant proton conductivity tures (usually >140 °C). Typically, the conductivity
[43–45]. These may provide a useful direction for future increases and the activation energy decreases with
research along with dispersed systems of hydrated acidic increasing cation radius, whereby Cs+ provides the highest
particles and xerogels [46]. conductivity, followed by Rb+, K+, Na+ and Li+. It has
A variety of other non-layered hydrated oxides, such as been suggested that this increase is not due to the metal
antimonic acid (Sb2O5·2H2O) [47], V2O5·nH2O, ZrO2· cations themselves but due to the softer M–O bonds, the
nH2O, SnO2·nH2O and Ce(HPO4)2·nH2O demonstrate high resultant crystal structure and proximity of heteroatoms,
proton conductivity in the order of 10−2 S cm−1 at 150 °C which promote the rapid reorientations observed in
[48]. Although maintaining conditions of saturated water superprotonic phases [51].
vapor pressure is a requirement for the operation of a A significant advantage of oxo-salts is that they do not
number of hydrated compounds as proton conductors, some necessarily have to exist as a Bronsted acid or with a struc-
compounds, such as antimonic acid, are insensitive to tural proton to exhibit high conductivity. Proton conduc-
humidity [49]. tivity will occur in H2- or water- rich atmospheres for
Unfortunately, the use of water-containing systems or neutral sulphates [52], phosphates [53, 54], and nitrates
acid hydrate compounds as H2 separation membranes is [51]. Major limitations of oxo-salts for H2 separation in-
often restricted, as conductivity is highly related to the water clude the fact that they may decompose at higher tem-
content. To operate most effectively, the membranes must peratures if not properly stabilized. For instance, nitrates
retain H2O as a hydrate or surface liquid to allow the ion may decompose at temperatures above 350 °C (e.g., RbNO3
jump mechanism to occur, which restricts their application to NO
2 ) [55], while sulphates may undergo reduction to
to temperatures <100 °C in their pure form. Even in fully form H2S and H2O [50].
dense materials, it is difficult to maintain a hydrated state at As a consequence of these chemical susceptibilities, oxo-
temperatures above 100 °C, unless a water-impermeable anion systems based on phosphates or complex hetero-
barrier covers the membrane keeping the water within the polyacids are more likely to be of practical use. In particular,
material or there is a way of preserving an even and close polyphosphate glasses, aluminium polyphosphate, ammo-
distribution of water molecules across the surface of the nium polyphosphate, and polyphosphate composites (e.g.,
membrane to sustain the necessary surface interactions for NH4PO3/(NH4)2SiP4O13 or NH4PO3/TiP2O7) [53, 54] have
proton conduction. recently attracted interest for applications as proton
To date, there have been scant reports of water-containing conductors due to their high conductivities at intermediate
systems or hydrated compounds as proton conductors used temperature ranges. (e.g., 0.1 S cm−1 at 300 °C) [56].
as membranes for H2 separation. While separation mem- Recent work has examined the dynamics and nature of the
branes constructed from these materials will probably not species responsible for charge transport, although the full
undergo any structural damage due to the presence of steam mechanism has not yet been elucidated. On the downside,
in the feed gas, the extent to which the steam may affect the synthesis of polyphosphates is slightly more complicated
operation and efficiency of such membranes remains un- than for other oxo-acid salt composites, based on sulphate
explored at this stage. Moreover, the effect of other and nitrate.
contaminants such as CO, H2S, particulate, and metal Oxo-acid salts also have the distinct advantage that
vapor on their chemical stability is largely unknown. while the physical properties of the salts alone are
Table 2 gives conductivity data for various water-contain- probably inadequate to form a mechanically useful
ing materials. separation membrane, they may be combined with inter-
granular oxides (e.g., SiO2 [57, 58], Al2O3 [55, 59],
Fe2O3, TiO2 [60], ZrO2, MgO, etc.) to form proton-
Oxo-acid salt conductors conducting composite materials, which are stable over a
wider temperature range and show an increase in total
This group includes the range of salts and acids pertaining conductivity due to modifications to the phase boundaries
to the heteroatom oxo-anions of sulphate, selenate, phos- of the pure salt. Oxo-acid salts have also been combined
phate, arsenate, nitrate, etc. In the anhydrous state, these with polymers, such as polyacrylamide [61], poly(ethylene
compounds are able to conduct protons due to self- oxide), and poly(benzimidazole) to produce highly
dissociation and the hopping or jumping mechanism of conducting hybrid materials [62]. Their applicability to
protons among hetero-oxo ions (e.g., NO
2
2

3 ; SeO4 ; SO4 ; H2 separation has received limited attention to date, but
3
3

PO4 ; AsO4 ; etc.) by aid of rotating hetero-oxo ions, given their relative cost effectiveness and ease of prep-
from one group to the next. So-called oxo-acid salt aration, compared to a host of other proton conductors,
“superionic” conductors (e.g., CsHSO4, RbHSO4) are they remain an attractive choice for H2 separation
receiving considerable research interest at the moment membranes.
110

Densely packed oxides which, despite exhibiting high chemical stability, have
low conductivity and require high sintering temperatures
This group of proton conductors is extremely large and to achieve dense structures free of pores [28]. Often,
encompasses a series of different classes of materials. however, it is possible to achieve a compromise between
Their main advantages are that they are generally quite the proton conductivity and chemical stability (for use as
stable and durable materials particularly up to high tem- H2 separation membranes), by preparing mixed solid
peratures (1,000 °C), and may also be able to conduct solutions of BaCeO3 and BaZrO3.
electrons. Achieving high conductivities and chemical Furthermore, increased stability of perovskite materials
stability at low temperatures remains a challenge for these may best be achieved by synthesizing mixed perovskites, such
systems. For most of these materials, ionic defects form the that A2 B01þx B00 1
x Mx O6
α (where A=Ba or Sr, B′= trivalent
basis for proton transport. The systems, which have po- ion and B00=pentavalent ion) or A3 B01þx B002
x Mx O9
α (where
tential application to H2 separation membranes, are out- A=Ba or Sr, B′=divalent ion and B00 =pentavalent ion) [65–
lined below. 68]. In addition to increased thermodynamic stability, off-
stoichiometric perovskites, also exhibit higher proton con-
ductivity, for example, Ba3CaNb2O9 exhibits higher proton
Perovskites conductivity than Nd-doped BaCeO3 [65, 66]. Mixed
perovskites have been demonstrated to maintain their struc-
Numerous cerate and zirconate perovskite oxides (e.g., ture sitting in boiling water for 5 days, while their simple
SrCeO3, BaCeO3, CaZrO3, or SrZrO3) have been reported perovskite counterparts decomposed after a few hours [69,
to have reasonable proton conductivity in hydrogen-rich 70]. This has been attributed to lower Madelung (electrostatic)
and humid atmospheres, particularly at high temperature energies [71].
when they are doped with a rare earth ion [63, 64]. Their While researchers have examined the effects of A-site
basic formula is AB1
x Mx O3
α ; where M is some tri- doping and stoichiometry on increasing the stability of
valent dopant like rare earth element (e.g., Nd3+, Gd3+, barium cerates while preserving high conductivity [72],
Y3+, Yb3+, La3+) and α is the oxygen deficiency in the there are very few reports on the possibilities of using
perovskite-type oxide lattice. mixed perovskites as proton conductors for H2 separation.
Materials based on BaCeO3 and SrCeO3 with the Furthermore, recent work comparing polycrystalline con-
perovskite structure are p-type or hole conductors in ductors to single crystal conductors has demonstrated that
atmospheres free of H2 or water vapor. However, in the the grain boundary interface plays a significant role in
presence of hydrogen or water vapor, they develop proton controlling the total conductivity [73]. Attaining a high
conductivity with a decrease of electronic conductivity. level of understanding of grain-boundary microstructure as
BaCeO3 and SrCeO3 are typically doped with an aliovalent a function of composition and sintering conditions is
cation (Y, Yb, Gd) at the B site to replace some Ce in the critical to the design of new materials, whereby, the grain
lattice and, as a consequence, oxygen vacancies are created boundaries may be manipulated to optimize conductivity
to maintain electroneutrality. These vacancies play an [74, 75]. However, there are very few reports in the
important role for proton conduction. Due to the presence of literature on the relationship between grain boundaries, the
water vapor, mobile protons are created when the water is ceramic microstructure, and proton conductivity of poly-
absorbed into the oxygen vacancies, formed by the presence crystalline perovskites.
of the trivalent ion in the lattice structure. A distinct Efforts are also continually being made to develop
advantage of perovskites is their ability to also conduct perovskites that conduct protons at intermediate tempera-
electrons in the single phase. While electronic conductiv-
ture ranges (300–700 °C). Recently, significant focus has
ities may typically be relatively low, they can be increased
been given to a class of perovskites with the formula A3
significantly by doping aliovalent ions in the B site.
SrCe0.95Yb0.05O3−x has been reported to have proton B01þx B002
x Mx O9
δ ; where A and B′ are divalent ions and
conductivity of 0.005 S cm−1 at 800 °C and 0.018 S cm−1 B″ are pentavalent ions [65]. Initial results indicate that
at 1,000 °C [64]. This conductivity, however, is not non-stoichiometric compounds of this group (e.g.,
sufficient to achieve the target H2 flux. non-stoichiometric Ba3CaNb2O9) yield promising proton
It should be noted that very few perovskites exhibit both conductivity exceeding that of Nd-doped BaCeO3 [66].
high proton conductivity and thermodynamic stability, However, the stability of barium oxides in CO2 and H2
which are vital pre-requisites for use as a H2 separation is a drawback for practical operations. Other materials
membrane. For example, while cerate oxides (e.g., considered include strontium zirconates (Sr3Ca1þxþy
BaCeO3) may display reasonable proton conductivity char- Zr1
x Ta1
y O9
δ (SCZT), where δ ¼ ð2x þ 3yÞ 2; ), al-
acteristics, their chemical stability is very low under real though the proton conductivities are slightly lower [76].
operating environments (e.g., reaction with CO2, the major The ionic conductivity data are given in Table 2.
constituent of the gas mixture from which H2 is to be Some of the other major issues in relation to the use of
separated). Research is underway to overcome some of these materials as H2 separation membranes are their poor
these problems. However, any degradation in the membrane mechanical strength and toughness, and their preparation
would lead to a decrease in the H2 flux rate. The reverse as thin and impervious coatings on controlled porosity
may be said to be true of zirconate oxides (e.g., BaZrO3), support structures.
 111

Pyrochlores stability of these systems over a wide temperature range

makes these materials potentially useful candidates for
Pyrochlores have been attracting growing interest for H2 investigation as H2 separation membranes. At this stage,
separation due to their relatively high resistance to chemical however, it appears their conductivities are not high
attack by CO2 and H2O, compared to strontium and barium enough, and significant microstructual improvements are
cerates [13]. Pyrochlores exist in the stable fluorite-type required before they can become a feasible alternative [85].
structure with multiple oxygen vacancies available for pro- In addition to bronzes, a range of other oxides have been
ton conduction and do not require strontium or barium, so suggested as potential useful proton conductors for H2 sep-
they are, therefore, more chemically durable. For example, aration membranes, including compounds, such as brown
lanthanum zirconate (La2Zr2O7) has been reported to pos- millerites [86], fluorites [13, 87–89], and phosphates [90] in
sess reasonable proton conductivity in the 600–1,000 °C the structure of apatite, although data on their proton and
temperature range [77, 78], and substitutional doping of Sr electron conductivities, as well as thermal and chemical
for La and Y for Zr in La2Zr2O7 can further increase the stability in a reducing environment, are limited. Again, high
conductivity, with the highest gains obtained for a 4 and proton conductivity is normally only attained at high tem-
8 mol% substitution of Y for Zr [79]. Other pyrochlores, peratures, which is a significant drawback to the application
such as (Gd0.98Ca0.02)2Ti2O7, have demonstrated high ionic of such materials [90]. Recently, efforts have been made to
conductivity at high temperature (0.01 S cm−1 at 1,000 °C), prepare so-called intermediate temperature (400–700 °C)
as well as good electron conductivity [80], while mixed electron and proton-conducting composite materials
Gd2Mo2O7 is reported to possess metallic-like electron of a fluorite structure, but only limited reports on the proton
conductivities at room temperature [81]. conductivity of such materials that would be relevant to H2
The patent literature refers to a series of pyrochlores that separation have surfaced [91, 92].
may be useful for proton conduction, including Structurally modified glasses remain another option for
A2 Zr2
x Yx O7
δ (A=La, Nd, Gd, Sm),  Y2 Ti2
x Mx O7
δ further research with sulfur glasses in particular, offering
(M=In, Mg) [82], and A2 B1þβ B1
β O6
λ or A3 B01þβ
0 00 promise for high conductivity, compared to oxide glasses
given the lower bond energies sulfur has with protons, com-
B002
ϕ ÞO9
λ ; where A are divalent ions (e.g., Ba2+, Sr2+, pared to oxygen in anhydrous form. Chalcogenide glasses
Ca2+, La2+), B′ ions are trivalent (e.g., Y3+, Ga3+, Sc3+, In3+, offer a new method for proton conduction at 100–300 °C,
Yb3+, Nd3+), or tetravalent (e.g., Zr4+, Ti4+, Ce4+), and B′′ while maintaining good mechanical stability in a reducing
ions are pentavalent (e.g., Bi5+, Nb5+) [83]. However, there atmosphere [93] with PbO-SiO2, BaO-SiO2 and CaO–SiO2
are no detailed reports on the proton conductivity of these cited for practical potential [94]. The ionic conductivity data
compounds and pyrochlores in general, as a function of for various materials are given in Table 2.
composition in a reducing environment. While there is
substantial opportunity for characterizing new proton con-
ductors and mixed conductors based on pyrochlores, initial Application of proton conductors as mixed ionic and
data seem to indicate that they may not be able to provide electronic conductors
high enough proton conductivity to be useful as H2
separation membranes (certainly not higher than perovs- Often, materials with high proton conductivity do not have
kites); thus, interest in these materials is somewhat limited sufficient electron conductivity to be useful as mixed ionic
[13]. The ionic conductivity data for various materials are and electronic conductors, unless they are modified in
given in Table 2. some way. Ideally, the H2 separation membrane material
must have both proton and electronic conductivity to avoid
the need to apply external electrical power to the cell. There
Other potential useful proton conductor oxides, are two options to enhance the electronic transport. One
sulfides involves intrinsic doping of the materials with aliovalent
cations, and the second involves mixing the materials with
On hydrogen insertion into WO3 or MoO3 or other tran- a metal or another electronic conducting material to
sition metal oxides, they can act as useful proton con- enhance electronic conduction. Achievement of optimum
ductors. Recently, a series of tetragonal tungsten bronzes, proton/electronic conductivity by the former route may be
Na1−xHxNbWO6 have exhibited conductivities of the order somewhat more difficult.
of 10−2 S cm−1 at 90 °C [84]. Typically, the addition of Nb to Initial attempts to improve the electron conductivity of
the system is done so as to suppress electronic conduction. proton conducting perovskites (e.g., BaCe1−xMxO3 and
So, if the goal is to produce a mixed proton and electron SrCe1−xMxO3, where M is a rare earth metal), by replacing
conductor, it may not be necessary to substitute W; rather, the usual univalent dopant with a multivalent dopant
try to maximize the mixed oxidation states of W. There has cation, such as Eu2þ=3þ and Sm2þ=3þ ; have been only
been little focus on bronzes to date as mixed proton and partially successful [95]. Further work is required to
electron conductors and whether increased electrical con- maximize electron conductivity by optimizing the dopant
ductivity increases proton conductivity and vice versa. level. A more recent approach to improving the electron
While no startling conductivities have yet been reported, the conductivity of perovskites has been to introduce a
112

transition metal (e.g., Ru) as a partial substitute for Ce in Y- and fabrication process so that reducing membrane thick-
doped BaCeO3. A significant increase in the hydrogen ness of the composite cermet-mixed conductor may not lead
permeation was observed due to an increase in ambipolar to an increase in the bulk resistivity. It may also be nec-
diffusion associated with hole conduction [96]. Another essary to accompany the reduction in membrane thickness
challenge is to optimize surface exchange reaction at the with a reduction in the interfacial resistance at the gas/
membrane/gas interface either by modifying the surface membrane interface to maximize high levels of H2 trans-
structure of the materials or by using coatings of catalytic portation [101]. For example, applying a catalytic layer to
materials, which facilitate H2 dissociation/reassociation the surface can be an important way to maintain the high H2
reactions. flux through a dense cermet membrane [102].
For a proton conductor, which does not exhibit sufficient Other significant criteria in designing composite mem-
electron conduction with or without doping, a second con- branes include the chemical and thermal compatibility
ducting phase must be added forming a composite mixed between metal (or oxide) and ceramic phases, as well as
conductor to function as a useful H2 separation membrane. possible thermal expansion mismatch between various
Typically, this involves the addition of a metal (e.g., Pd or phases during fabrication of the membrane and its sub-
Ni) in powdered or oxide form. For instance, a mixed sequent use. Also, fabrication process and optimization of
conductor based on perovskite as the proton-conducting the microstructure to obtain dense, defect-free thin mem-
phase and Pd as the electron-conducting phase, preferably branes are critical issues.
has the Pd added as a coating on the individual particles
(size <45 μm) of the proton conducting oxide by wet
impregnation of the powder, electroless plating, or chemical Application regimes of proton conductors for H2
vapor deposition [97]. Addition of a metal, such as Ni, to separation
form a dual-phase cermet not only increases the electron
flow in cerate or zirconate-based perovskite oxides but im- The application in which the separation membrane is to be
proves their mechanical stability. Moreover, as the presence used will largely dictate the performance requirements of
of Ni leads to an increase in the endothermic hydrogen the proton conductor. The main applications, to date, for H2
solubility of the membrane, the hydrogen permeability separation membranes are in the industrial processes of coal
increases due to enhanced H2 ionization and adsorption at gasification, natural gas reforming, methanol reforming,
the membrane surface [98]. and the water–gas shift reaction. While the potential exists
One further possibility for improving the electron con- for utilizing other fossil fuels (e.g., naphtha and other
ductivity is by adding a secondary ceramic phase (e.g., an n- heavier alkanes), biofuels, or biomass for H2 generation
type semiconductor) to the proton conducting perovskite [103, 104], there is limited immediate demand for devel-
oxide. For instance, the addition of doped ceria to perov- oping technology to separate H2 from these fuels. Con-
skite materials above the percolation limit results in a ditions of the different industrial processes do vary most
substantial improvement to the electronic conductivity of notably in the temperature, pressure, likely operating vol-
the composite in a reducing atmosphere as well as im- umes, and composition (including contaminants) of the gas
proving the thermodynamic stability of the composite in mixture from which H2 is to be separated.
both a CO2− and H2O-rich environment [83]. Other For example, with regard to operating temperatures,
ceramic phases which may be added include semi-con- large-scale coal gasification requires temperatures in the
ductors, such as SnO2, WO3, or SiC. While dual-phase range of 1,040–1,540 °C for entrained flow systems (e.g.,
ceramics have not been extensively studied for mixed Texaco, Shell, and E-Gas) or 760–1,040 °C for fluidized
proton and electron conductors for H2 separation, some bed systems (e.g., U-Gas) [105]. Coal gasification, there-
reports do exist of dual ceramic-phase mixed oxygen-ion fore, requires ceramic membranes with high chemical and
and electron conductors for separating H2 [99]. These mechanical and thermal stability to yield high proton con-
perovskite composites utilize Y- and Al-doped SrTiO3
(YSTA) as the electron-conducting phase, while Gd-doped
CeO2 (GDC) is the oxygen-conducting phase, and exhibit
good stability under reducing conditions associated with H2
separation.
Critical to the development and improvement of com-
posite mixed electron and proton conductors as a membrane
for H2 separation is a proper understanding of the nature and
relative contributions of electron transport and proton
transport to the bulk H2 flux. Recent attempts at modeling
the process of hydrogen permeation through mixed ionic-
electronic conductor membranes have been based on con-
sidering the bulk solid-sate diffusion of hydrogen as the rate
Fig. 3 Incorporation of water–gas shift catalyst in the H2 separation
limiting step [23], and by the resistor network approach membrane reactor to reduce overall system cost and to drive the
[100]. Another important consideration when optimizing water–gas shift reaction equilibrium forward ðCO þ H2 O ¼ CO2 þ
membrane design, is to carefully control the microstructure H2 Þ with continual removal of H2
 113

ductivities in this temperature range. Significant work on Given that most proton conductors have optimal conduc-
perovskites has established that they may be well-suited to tivity over a limited temperature range (100–200 °C), the
application in this temperature regime (500–900 °C) [106, demand to develop proton conductors for a specific tem-
107]. Optimal temperatures for reforming of natural gas perature range and application will grow as the techno-
occur at 800 to 950 °C for good conversion at 2.6 MPa for logical means and sources of H2 production develop.
large-scale H2 production [108]. However, low-tempera- Significant effort continues to examine alternative reactor
ture reforming is gaining increasing interest [109], conditions [114, 115], catalysts [116, 117], and membrane
particularly in membrane reactor applications where the reactor designs [118], as well as H2 sources [103, 104], so
membrane allows sufficiently high H2 flux and has a high variations to H2−separating conditions and, therefore, to
separation factor [110]. Reforming temperatures for meth- membrane material performance requirements, are likely to
anol, on the other hand, are relatively low (250–350 °C), continue into the future [108].
and methanol has the advantage that it can generally be
obtained in consistently high purity (sulfur content
<5 ppm), compared to other fuels [111]. Other applications of proton conductors
Often, the gases from a coal gasifier or natural gas
reformer consist of, apart from H2, significant levels of CO, Once proton conductors are developed for use as H2
CO2, H2O, and CH4 as well as small quantities of separation membranes, there are a host of other applications
particulates, sulphur compounds, and metal vapors— where such membranes may be used. These include H2
especially in the case of coal gasifiers. Following removal sensors for process control and monitoring, H2 leak detec-
of particulates and sulphur compounds, gases are passed tors for safety monitoring, dehumidifiers (water removal
through a water–gas shift (WGS) reactor to convert CO to from wet gases), water electrolysis for H2, and oxygen
H2 and CO2 by reacting it with steam over a catalyst. The production (with or without coupling to renewable energy
WGS reaction is typically a two-stage shift process, with sources), electrochemical reactors for chemical production,
steam being added initially in the high-temperature WGS and fuel cells for power generation [119].
reactor (300–500 °C), followed by a low-temperature shift
reaction (around 200 °C), with each process employing
separate catalysts [112, 113]. The gases need to be cooled Conclusions
before entering the low-temperature shift reactor. Alter-
natively, in next generation membrane reactors under Proton-conducting materials have been reviewed for appli-
consideration, if the water–gas shift (WGS) catalyst and cations in industrial processes of coal gasification, natural
H2 separation membrane are incorporated into one unit, gas reforming, methanol reforming, and the water–gas shift
continuous removal of H2 will drive the equilibrium of the reaction. Key material requirements for their use in these
shift reaction forward (Fig. 3). Therefore, the requirement to applications have been discussed. Clearly, different tem-
use a two-stage shift reaction and a cooling step in-between perature regimes exist in which proton conductors may be
can be eliminated and the water–gas shift reaction may be required for the separation of H2. Given that most proton
carried out at higher temperatures in the vicinity of 500 °C. conductors have optimal conductivity over a limited tem-
Consequently, membranes that can be directly coupled with perature range, the demand to develop proton conductors
a shift reactor for pre-combustion H2 separation and operate for a specific temperature range and application will grow
in this temperature regime are considered more attractive. as the technological means and sources of H2 production
Based on temperature considerations, high-temperature develop. No single class of materials is able to cover all
proton conductors (e.g., perovskites) would be well-suited applications for H2 separation. More critically, no class of
to application in coal gasification and methane reforming. materials yet exists which meet the criteria of high H2 flux
While for methanol reforming and water–gas shift reac- rates, thermal and chemical stability, and mechanical
tions, low-temperature or intermediate-temperature proton properties. The field is at an early stage of development,
conductors, such as oxo-acid salt or heteropolyacid com- and considerable resources need to be devoted for the
posites, would be more attractive. Another factor for con- research and development of optimal materials and fabri-
sideration is that for large-scale applications, such as coal cation of membranes for H2 separation in the future. It is
gasification, the industrial throughput and, therefore, the unlikely that proton conductors will be used as a single-
membrane dimensions will differ substantially to that phase material for hydrogen separation. Most likely, they
required for a natural gas micro-reformer with potential will be used as cermets or mixed phase materials, where the
market in domestic or portable applications for distributed second phase acts as an electronic conductor. For cermets, if
H2 generation. Membrane technology with high H2 flux the metal phase also transports hydrogen, then higher
capabilities must, therefore, be able to be manufactured on hydrogen flux rates can be achieved.
different size scales, depending on the specific process
demands.
Clearly, different temperature regimes exist in which Acknowledgements The authors are thankful to Dr. Sarb Giddey
proton conductors may be required for the separation of H2. and Mr. Fabio Ciacchi for reviewing this manuscript.
114

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