i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 1 6 9 9 e1 7 1 0

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High temperature hydrogenation of TieV alloys:

The effect of cycling and carbon monoxide on the
bulk and surface properties

S. Suwarno a,*, J.K. Solberg a, B. Krogh c, S. Raaen d, V.A. Yartys a,b

a
Department of Materials Science and Engineering, NTNU, NO-7491, Trondheim, Norway
b
Institute for Energy Technology, P.O. Box 40, NO-2027, Kjeller, Norway
c
Statoil ASA Research Centre, Rotvoll, NO-7005, Trondheim, Norway
d
Department of Physics, NTNU, NO-7491, Trondheim, Norway

article info abstract

Article history: In the present work, the high temperature (425e575
C) hydrogen storage properties of
Received 4 September 2015 TieV alloys have been studied, both at static conditions and in a flow of hydrogen gas.
Received in revised form The selected isothermal temperature range is considered as an optimal condition for
10 November 2015 hydrogen sorption enhanced steam reforming. When hydrogenation and dehydrogena-
Accepted 10 November 2015 tion were performed in pure hydrogen gas and in vacuum, a large reversible hydrogen
Available online 24 December 2015 capacity of 3.95 wt. % H was obtained, demonstrating completeness of the formation and
decomposition of (Ti,V)-dihydrides. However, when cycling was performed in a flow of
Keywords: hydrogen gas, the reversible hydrogen capacity decreased to ~2 wt. % H caused by the
Titaniumevanadium alloys formation of stable lower (Ti,V)-hydrides. A further decrease in the reversible hydrogen
Metal hydrides storage capacity took place when pure hydrogen gas was replaced by a mixture of
High-temperature hydrogen storage hydrogen and carbon monoxide CO. This decrease was caused by the formation of an
Hydrogen production oxygen rich layer on the surface of the alloy, which was partially blocking the hydrogen
Carbon monoxide exchange between the surface and the bulk of the sample.
Copyright © 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

utilisation [1]. Today hydrogen is mostly produced by

Introduction
Hydrogen is an important industrial gas that is used mostly
for ammonia synthesis and refining oil products. Other in-
dustrial processes such as production of metals and food
preparation also use large amounts of hydrogen. An emerging
application is hydrogen as a fuel for the FC hydrogen vehicles,
because of its high energy density and zero emission
reforming of hydrocarbon feedstocks via a steam reforming
process. The steam reforming is an established process for
hydrogen production at large industrial scale. Nevertheless,
further improvements are needed, particularly in the effi-
ciency of the reforming and in decreasing the emissions.
Several new technologies are now widely studied as having
a potential of improvement of the conventional steam
reforming process [2,3]. The working temperature of steam

* Corresponding author. Present address. Department of Mechanical Engineering, ITS, Kampus ITS, Keputih Sukolilo Surabaya, 60111,
Indonesia. Tel./fax: þ62 315946230.
E-mail addresses: warno@me.its.ac.id, warnoise@yahoo.com (S. Suwarno).
http://dx.doi.org/10.1016/j.ijhydene.2015.11.077
0360-3199/Copyright © 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
1700 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 1 6 9 9 e1 7 1 0
reforming can be reduced while maintaining or increasing the
hydrogen yield by removing one or more of the reaction
products. Such a strategy is employed for example by allowing
hydrogen to pass a membrane [4]; another approach is an in
situ absorption of the reaction products by absorbent mate-
rials. In such a way, by absorbing CO2 as one of the products by
absorbent materials, e.g. CaO [5] or LieZr mixed oxides [6,7],
achievement of a higher degree of hydrocarbon conversion is
anticipated.
One recent approach is hydrogen sorption enhanced steam
reforming (HSER) [8]. Thermodynamic modeling confirmed
that HSER allows increasing energy efficiency and reducing
the operation temperatures. HSER utilizes metal hydride
forming alloys that absorb hydrogen and form hydrides. In the
HSER process, the properties of the hydrogen sorbent are
crucial for its realization. Ideal metal hydrides reversibly store
large amounts of hydrogen and maintain unchanged the
reversible hydrogen capacity during long term cycling. An
important issue is that, in the HSER reactors, the metal hy-
dride should be able to form even at very harsh operating
conditions. Hydrogen should be absorbed from a mixture of
the reactants/products containing significant amounts of the
chemically reactive gases, CO, CO2 and H2O. Properly
addressing the effect of these impurity gases is very chal-
lenging as it is well-known that they suppress hydrogen ex-
change in hydrogen storage alloys [9e11].
Another requirement is that the hydride must be formed/
decomposed at rather high operating temperatures,
450e800
C. One of a potentially promising from this view-
point systems is TieH system. The exceptionally high volu-
metric density of hydrogen in TiH2, being 150 kg/m3, is more
than two times higher than in liquid hydrogen. The high for-
mation enthalpy of TiH2 of 123.4 kJ/mol H2 at 298 K [12]
causes a significant heat release during the hydrogenation
process. This makes titanium and its alloys promising candi-
dates for applications in hydrogen enhanced steam reform-
ing. However the hydride formation enthalpy and the kinetics
of hydrogen exchange of the TiH2 must be tuned to obtain
favorable properties suitable at HSER working temperature.
One of the alloying elements to combine with titanium is
vanadium. Interaction of hydrogen with elemental vanadium
is rather complex and leads to the formation of several hy-
drides with different H/V ratios reaching 2.0 at maximum.
Stable vanadium hydrides are formed at temperatures below
appr. 200
C. The formation enthalpy of FCC vanadium dihy-
dride VH2 is much lower than that of TiH2, only 40 kJ/mol H2
[13,14]. As the equilibrium pressure of 1 bar H2 is reached at a
rather modest temperature, ~20
C, vanadium dihydride is
classified as a low temperature hydride [15]. Alloying titanium
with vanadium results in the formation of solid solutions at all
Ti/V ratios, which in turn form dihydrides (Ti,V)H2. An in-
crease in the vanadium content decreases the enthalpy of
formation and thus allows adjustment of the stability of the
hydrides and, consequently, optimization of the working
temperature required for a particular application.
In a previous publication [16], hydrogen sorption properties
and in situ synchrotron X-ray diffraction study of TieV alloys
interacting with hydrogen gas mixed with CO were reported.
The study [16] showed that hydrogenation-dehydrogenation
occurred even when the gas mixture contained a substantial
amount of CO. However, significant degradation was observed
leading to a decreased reversible hydrogen capacity during the
cycling. The purpose of the present study was to investigate in
detail microstructural changes in the bulk and surface prop-
erties of the Ti0.8-0.9V0.2-0.1 H storage alloys during hydrogen
absorption-desorption cycling at high temperatures. The goal
was to understand the controlling factor for degradation. The
effects of pressure, temperature and gas composition on the
performance of the alloys as well as the kinetics of the
chemical transformations were studied.
Materials and experimental methods
Synthesis of alloys and hydrides
Alloy buttons with compositions Ti0.8V0.2 and Ti0.9V0.1 were
prepared from titanium sponge (99.7%) and vanadium turn-
ings (99.7%) using an Edmund Bühler arc melter. During the
melting, zirconium was used as a getter material to reduce
oxygen contamination of the prepared alloy buttons. The al-
loys were remelted three times to ensure their homogeneity.
Activation of the alloys and synthesis of their hydrides
were performed following the procedures described in our
earlier publication [17]. After the hydrogenation, the initial as
cast millimeter-size particles were pulverized to the powders
of the dihydrides (Ti,V)H2 with average particles size of
200 mm.
Hydrogenation and dehydrogenation experiments
Hydrogen absorption-desorption experiments were per-
formed in a Sievert's volumetric set-up. Hydrogen absorption
was done at quasi-isothermal conditions while dehydroge-
nation was performed non-isothermally by heating the sam-
ple from the hydrogenation temperatures to 800e850
C with a
rate of 5 deg/min, with a starting pressure of appr.
~1  105 mbar. Hydrogenation-dehydrogenation experi-
ments were also performed in a flow of gas using the
temperature-programmed desorption (TPD) equipment by
Altamira Instrument Inc. The TPD equipment consisted of two
parts that could be used for the experiments performed both
at atmospheric conditions and at high pressures. A Thermo-
star Mass Spectrometer (MS) from Pfeiffer Vacuum GmBH was
connected to the TPR outgoing gas flow for measuring the
composition of the outgoing gases. The MS was calibrated to
determine the contents of H2, Ar, CH4, CO, CO2, O2 and H2O.
The experiment control and data acquisition were conducted
using the LabView based software program developed by the
provider of the equipment. Two kinds of the experiments
were conducted in the gaseous flow; the first was hydroge-
nation and dehydrogenation cycling at 1 bar. The hydroge-
nation experiments were performed at various temperatures
(425, 475, 525 and 575
C) in a mixture Ar þ 10% H2 using a rate
of gas flow of 50 ml/min while the dehydrogenation were done
in pure Ar at 1 bar. The cycling experiments of second type
were done in flows of pressurized gaseous mixtures Ar þ 25%
H2 and Ar þ 25%H2 þ 1%CO. The hydrogenation was per-
formed at 425
C at a total pressure of 20 bar while the
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 1 6 9 9 e1 7 1 0 1701

dehydrogenation was done by heating the sample in pure Ar

to 760
C at the same pressure.

Materials characterizations

A Zeiss Ultra 55LE field emission scanning electron micro-

scope (FE-SEM) equipped with a Bruker energy dispersive
spectrometry (EDS) was used for the studies of the micro-
structure, morphology and chemical analyses. In addition,
some chemical micro analyses were performed using a JEOL
JXA-8500F electron probe micro-analyzer (EPMA). Samples for
the SEM investigations were prepared by dispersing small
amounts of the powders on a carbon tape attached to the
sample holder. To examine the powder particle cross-sections
in the EPMA, powder particles were embedded into a carbon
filled resin, grinded and mechanically polished down to 1 mm.
During the SEM investigations, the surface morphology of the
powders was investigated using secondary electrons at a
typical accelerating voltage of 5 kV. EDS area analyses were
performed at 15e20 kV accelerating voltage and at 200 s
acquisition time. EPMA point analyses were done at 15 kV
accelerating voltage and 10 s acquisition time.
Laboratory XRD was performed using a Bruker D8 Focus
diffractometer with a Cu Ka X-ray source. A crushed powder
sample was dispersed on a single crystal silicon sample holder
using ethanol as dispersing agent. Powder diffraction patterns
were collected using a square slit of 0.6e1 mm side length. The
data was collected in a 2q angle range from 10 to 90 deg. using
a step size of 0.01 deg., while the sample holder was contin-
uously rotated. Some diffraction patterns were obtained using
synchrotron X-ray diffraction (SR-XRD) at the Swiss Norwe-
gian Beam Lines (BM01A, SNBL), Grenoble, France.

Surface characterization: AES and XPS Fig. 1 e Quasi-isothermal hydrogenation of Ti0.9V0.1 at

Auger electron spectroscopy (AES) analyses were performed
in a JAMP 9500F field emission Auger electron microscope.
Some amounts of the powders were dispersed on the
aluminum foils attached to the AES microscope sample
holder. The specimens were analyzed applying 10 kV accel-
erating voltage. Ion sputtering was employed to analyze sub-
surface compositions. X-ray photoelectron spectroscopy
(XPS) measurements were done using a monochromatized Al
Ka (hn ¼ 1487 eV) X-ray source (Gammadata-Scienta) and a
SES2002 electron energy analyzer. Ti2p, V2p, and O1s spectra
were recorded.
Results and discussion
Hydrogen absorption properties
Hydrogenation at static conditions
When the driving force for the hydride formation was high, at
30
C and at hydrogen pressure 4 bar H2, both Ti0.9V0.1 and
Ti0.8V0.2 alloys instantly, in less than 1 min, formed dihydrides
containing up to 3.95 wt. % H (see Figs. 1, a and b).
At higher interaction temperatures of 450
C and 550
C, the
process of hydrogen absorption slows down; however, for
both alloys it still completes rather fast, in less than 5 min. The
dynamic pressure conditions using volumetric methods:
(a) Ti0.9V0.1; (b) Ti0.8V0.2. Hydrogen absorption experiments
in pure H2 were performed at 450
C and 550
C and at 2
and 4 bar initial hydrogen pressures. Dehydrogenation
was done in vacuum by heating the sample from the
hydrogenation temperature to 800e850
C.
relative rates of hydrogen uptake and reaching the saturation
hydrogen content in the formed hydrides appear to be
affected by a) Ti/V ratio; b) temperature of interaction; c) hy-
drogenation pressure. The hydrogenation rates increase with
the Ti content of the alloys (being the highest for Ti0.9V0.1) and
with decreasing interaction temperature (being the highest at
450
C). In contrast, increasing the hydrogenation pressure
from 2 bar to 4 bar caused only a marginal increase in the
amount of absorbed hydrogen and in the rates of
hydrogenation.
Hydrogenation properties in a flow of hydrogen gas
In order to simulate the conditions applied during the steam
reforming process, the hydrogenation properties of the sam-
ples were studied in a gas flow. This allowed performing ki-
netics studies of hydrogen absorption at close to isothermal
conditions. Small amounts of the completely hydrogenated
samples, around 20 mg each, were used in the measurements
1702 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 1 6 9 9 e1 7 1 0
runs to achieve stable, close to isothermal, conditions. The
experiments were performed using the TPD equipment. The
hydrogenation experiments were performed at various tem-
peratures (425, 475, 525 and 575
C) in a mixture Ar þ 10% H2
(1 bar) using a rate of gas flow of 50 ml/min.
As expected, the hydrogen saturation content of the
Ti0.9V0.1 alloy depends on the processing temperature (see
Fig. 2a). The highest hydrogen content was reached when the
hydrogenation was performed at the lowest temperature of
425
C. A progressive decrease of H content took place
following a temperature increase up to 575
C.
After the hydrogenation process was completed, the
formed hydrides were cooled to room temperature and
dehydrogenated by heating the samples from RT to 800
C at a
rate of 5 deg/min. The hydrogen desorption spectra acquired
during the heating are shown in Fig. 2b. During the 1st
desorption, the fully hydrogenated sample desorbed 3.7 wt.%
H, which indicates a complete decomposition of the starting
g-dihydride.
Non-isothermal cycling of hydrogen absorption-desorption
in a gas flow mixture of H2 þ CO has been reported by the
present authors earlier [16]. The experiments showed that
Fig. 2 e Ti0.9V0.1 hydrogenation and dehydrogenation in a
gas flow of 1 bar at 50 ml/min: a) isothermal hydrogen
absorption in a flow of 10%H2 þ Ar, b) non-isothermal
dehydrogenation during heating from RT to 800
C at 5 K/
min in a pure Ar flow after hydrogenation at temperatures
given in the parentheses.
reversible hydrogenation took place at the end of the 4th cycle
and led to formation of g-(TiV)H1.45 with a body centered
tetragonal unit cell (distorted face centered cubic lattice).
During the consecutive four hydrogen desorption experi-
ments, hydrogen release took place from the partially hydro-
genated samples obtained during hydrogenation at 425
C
(des. 2), 475
C (des. 3), 525
C (des. 4), and 575
C (des. 5) (see
Fig. 2b). Regular changes in the desorption traces are observed
and show a shift of the desorption peaks to higher tempera-
tures when the temperature of the synthesis increases.
Furthermore, a gradual transformation of the double-peak
desorption traces into a single-event decomposition during
des.5 is observed. This indicates that the initial hydride syn-
thesized at room temperature was g-dihydride Ti0.9V0.1H2,
while the hydride synthesized at the highest synthesis tem-
perature of 575
C was b-hydride Ti0.9V0.1H1-1.5, and the in-
termediate samples (des.2-des.4) were the samples with
gradually decreasing content of g-dihydride and, corre-
spondingly, increasing content of b-hydride.
Similarly, also for the Ti0.8V0.2 alloy, the reversible
hydrogen absorption behavior was found to be temperature-
depended. Dehydrogenation spectra of the Ti0.8V0.2 hydrides
showed that only high temperature peaks associated with
decomposition of b-hydrides were observed. In all, the
hydrogen capacity of Ti0.8V0.2 was found to be lower than that
of Ti0.9V0.1 since only b-hydrides were formed in the former
alloy at the applied experimental conditions (see supple-
mentary information, Fig. S1, for further details).
Hydrogenation kinetics
Since the hydrogenation experiments were performed at a
constant hydrogen partial pressure of 0.1 bar H2, the ther-
modynamic driving force remained constant, and the kinetics
of the hydrogen absorption can be expressed as
gðxÞ ¼ KT $dt (1)
where gðxÞ is a dimensionless quantity being characteristic of
the particular selected kinetics model, x is a normalized extent
of conversion, and KT is a temperature-dependent kinetics
constant. Consequently, a linear time-dependent gðxÞ is
anticipated.
The experimental data were fitted using the common ap-
proaches described in the reference data (Supplementary in-
formation, Table S1). Following the described procedure, the
kinetic hydrogenation data at 425
C can be fitted using two
related nuclei-growth models, a three-dimensional Avrami-
Erofeev model for Ti0.9V0.1 and a two-dimensional Avrami-
Erofeev model for Ti0.8V0.2 (Supplementary Information Fig. S2).
By using above presented linear relationship for gðxÞ, the KT
value for each hydrogenation temperature was obtained. The
activation energies of hydrogenation were then calculated
from plots of KT vs. 1/T (Supplementary Information Fig. S3).
In the case of Ti0.8V0.2, the activation energy was rather low,
17 kJ/mol, being comparable with the activation energy of
hydrogenation for LaNi5, 16e37 kJ/mol [18,19]. For Ti0.9V0.1, the
activation energy was found to be slightly higher, 35 kJ/mol.
This value is similar to the activation energy for hydrogena-
tion of beta titanium, 38e45 kJ/mol [20]. One reason why the
activation energy was changed from Ti0.9V0.1 to Ti0.8V0.2 may
be in the difference of growth dimensionality.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 1 6 9 9 e1 7 1 0
Cycle life and stability of the hydrogen absorption-
desorption performance
For both Ti0.9V0.1 and Ti0.8V0.2, cycling experiments performed
at conditions giving complete hydrogenation and dehydroge-
nation, resulted in high values of the reversible hydrogen
storage capacity, which remained constant for nine cycles
without any degradation (see supplementary information,
Fig. S4).
The second cycling test was done in flows of pressurized
gaseous mixtures Ar þ 25%H2 and Ar þ 25%H2 þ 1%CO. The
hydrogenation was performed at 425
C at a total pressure of
20 bar, while dehydrogenation was done by heating the
sample in pure Ar to 760
C. Fig. 3 presents changes in the
amounts of hydrogen desorbed during the cycling of Ti0.8V0.2
and Ti0.9V0.1.
For both alloys, the reversible hydrogen storage capacity
decreased during the cycling in Ar þ 25%H2. While the initial
Ti0.9V0.l based hydride released about 3.7 wt.% H, this value
was reduced to 2.9 wt.% H during the second cycle, and it
decreased further to 2 wt.% H during the 11th cycle. The
reversible H capacity of the initial sample of Ti0.8V0.2H2.0,
3.8 wt.% H, was even stronger affected by cycling. During the
second cycle this sample desorbed only 1.7 wt.% H, and after
the 5th cycle the amount of desorbed hydrogen continuously
decreased during the cycling.
As can be seen from Fig. 3, the reversible H storage capacity
of Ti0.9V0.1 decreases faster than that of Ti0.8V0.2. This is
probably a consequence of a higher stability of the Ti0.9V0.1
hydride so that the amount of “trapped” hydrogen in Ti0.9V0.1
becomes higher than in Ti0.8V0.2. It appears that the amount of
un-desorbed hydrogen accumulatively increased during each
consecutive cycle so that a continuous decrease in reversibly
released hydrogen took place during the experiments.
The detrimental effect of CO on the reversibility of the H
storage capacity is evident from the data presented in Fig. 3.
The alloy only absorbed about 0.5 wt. % H in presence of CO.
Fig. 3 e Amount of hydrogen desorbed in each cycle for
TieV alloys hydrogenated at 15e20 bar Ar þ 25%H2 or
Ar þ 25%H2 þ 1%CO, flow rate 300 ml/min. Absorption was
done isothermally at 425
C and desorption was performed
non-isothermally from 425 to 760
C, heating rate 5 K/min.
1703
Fig. 4 e Reversible hydrogen storage capacity of Ti0.9V0.1
during hydrogenation and dehydrogenation cycling in the
temperature range 150e780
C, 5 deg/min cooling and
heating rate. Hydrogenation was done at different
hydrogen pressures, and dehydrogenation was done in
pure Ar, 100 ml/min gas flow. CO was introduced into the
gas flow before cycle 16 and removed after cycle 18.
The third series of the cycling tests was performed at var-
iable hydrogen pressures and at a higher content of CO in the
gas stream. Fig. 4 shows the cycle dependence of the hydrogen
desorption capacity during the experiments performed in a
mixture of Ar þ H2. As can be seen from the figure, the effect of
pressure was marginal. The reversible hydrogen storage ca-
pacity was around 3 wt.% H, and was only slightly dependent
on the pressure changes. When 2% CO was introduced into the
gas mixture at the 16th cycle, the hydrogen absorption and
desorption significantly decreased to just ~1 wt% H. However,
when CO was removed from the gas flow, 80% (2.3 wt.% H) of
the initial H storage capacity was recovered.
Phase-structural studies
The data of the phase-structural analyses of the samples was
related to the testing conditions in order to get insight into the
reasons of the variations of their cycling performance. The
data for the dehydrogenated samples after the 1st and the 8th
cycle performed in pure H2 are compared in Table 1. The
samples contained a mixture of the BCC solid solutions (Ti,V)
and HCP type alloys based on b-Ti. The ratio between the BCC
and HCP compounds appeared to be related to the test history
of the samples.
After the 1st cycle, the two-phase Ti0.9V0.1 was found to
contain HCP a-phase as the main phase and the BCC phase as
the secondary phase. Interestingly, the fraction of the BCC
phase had increased to 48 wt.% after the 8th cycle.
The situation was quite different for the Ti0.8V0.2 alloy. In
this alloy, the BCC phase constituent was initially the vast
majority, and it remained so upon cycling (94e99%), while the
amount of the HCP a-phase slightly increased from 1 wt.%
after the 1st cycle to 3 wt.% after the 8th cycle. A small amount
of rutile related oxygen-hydrogen containing compound
1704 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 1 6 9 9 e1 7 1 0

Table 1 e Phase-structural data for dehydrogenated samples after 1st and 8th cycle.
Sample Dehydro- Phase Phase content (wt.%) Lattice parameter (
A) Unit cell volume (
A3)
genation cycle#
Ti0.9V0.1 1st b  ðTiVÞðIm3mÞ 33 (5) a ¼ 3.20770(2) 33.005(5)
a  TiðVÞðP63 =mmcÞ 67 (3) a ¼ 2.94277(21) 35.097(8)
c ¼ 4.6798(4)
8th b  ðTiVÞ ðIm3mÞ 48 (4) a ¼ 3.2460(6) 34.200(1)
a  TiðVÞ ðP63 =mmcÞ 51 (3) a ¼ 2.9444(6) 34.999(7)
c ¼ 4.6615(9)
Ti0.8V0.2 1st b  Ti0:8 V0:2 ðIm3mÞ 98.55(3) a ¼ 3.2322 (4) 33.76(1)
a  TiðH=OÞ ðP63 =mmcÞ 1.4 (1) a ¼ 2.956(2) 35.55(8)
c ¼ 4.69(1)
8th b  Ti0:8x V0:2þx ðIm3mÞ 94.1(3) a ¼ 3.239(1) 33.98(4)
a  TiðH=OÞ ðP63 =mmcÞ 3.0(5) a ¼ 2.947(2) 34.99(7)
TiðO; HÞ2 ðP42=mnmÞ 2.8(3) c ¼ 4.652(8) 68.0(1)
a ¼ 4.740(4)
c ¼ 3.027(6)

TiOHx [21] appeared after the cycling (XRD pattern can be seen
in Supplementary Information Fig. S5).
The results of the SEM investigations are in agreement with
the XRD study. Small oxygen-rich areas within the microstruc-
ture of alloy Ti0.8V0.2 were observed for the cycled sample after
the 8th cycle. As can be seen from the EPMA results in Fig. 5, a
local segregation of oxygen is observed in the area crossed by the
line AB, with the highest concentration of oxygen in the center.
In addition, since the vanadium content is decreasing when the
oxygen content increases, the oxygen-rich area is most likely an
island of an HCP Ti-based a-phase that dissolves large amounts
of oxygen. Oxygen segregation was observed also for
TieVeCreFe alloys, where high oxygen concentration in the
alloy leads to the formation of aTi phase [22].
A similar segregation did not occur in the Ti0.9V0.1 alloy since
it contains high amounts of the HCP a-phase. However, it ap-
pears that the oxide/oxygen rich phase formation did not give
significant impact on the hydrogenation behavior, probably
because the amount of these phases in Ti0.8V0.2 was rather
small.
The X-ray diffraction patterns collected for Ti0.9V0.1 and
Ti0.8V0.2 after cycling in Ar þ 25%H2 and Ar þ 25%H2 þ 1%CO
are shown in Fig. 6. As can be seen in Fig. 6a, the Ti0.9V0.1 alloy
that was cycled in Ar þ H2, is composed of aHCP and BCC
phases. In addition to that, a small amount of monohydride
(TiV)H~1 was observed. This indicates that some hydrogen was
not completely released during the dehydrogenation when
the sample was heated to 760
C in Ar flow.
After the cycling of Ti0.9V0.1 in CO-containing mixtures,
XRD pattern revealed the presence of the HCP aTi and FCC d-
TiHx phases (see Fig. 6c). During the cycling, interaction with
CO resulted in enrichment by oxygen and/or carbon of the
surface layers, preventing hydrogen desorption at lower
temperatures. Consequently, decomposition of d-TiHx (FCC)
hydride was eliminated, in contrast with the behavior of the
samples cycled in the mixtures of hydrogen that did not
contain CO.
After dehydrogenation, the Ti0.8V0.2 alloy cycled in Ar þ H2
was composed of mainly BCC and only small amounts of HCP
a-phase. As can be seen from Fig. 6b, the composition of the
dehydrogenated alloy was similar to that of the alloy having
been cycled in pure H2 and vacuum, except for the presence of
a small amount of (TiV)Hx. This confirms that hydrides of the
Ti0.9V0.1 and Ti0.8V0.2 alloys were not completely decomposed

Fig. 5 e a) Metallographic cross section of a Ti0.8V0.2 powder particle after 8 cycles; b) Oxygen and vanadium point analyses
along the line AB in (a). Formation of an oxygen rich phase was observed.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 1 6 9 9 e1 7 1 0 1705

Fig. 6 e XRD diffraction patterns (Cu Ka) of dehydrogenated alloys after 11 cycles: a) Ti0.9V0.1 hydrogenated in Ar þ 25% H2; b)
Ti0.8V0.2 hydrogenated in Ar þ 25% H2; c) Ti0.9V0.1 hydrogenated in Ar þ 25% H2 þ 1%CO; d) Ti0.8V0.2 hydrogenated in
Ar þ 25% H2 þ 1%CO.

during the desorption step. These effects were gradually
accumulated and led to the decreasing H capacity during the
cycling.
For the Ti0.8V0.2 alloy, only BCC phase was observed after
the sample had been cycled in Ar þ 25% H2 þ 1% CO. A
competitive adsorption of H2 and CO [23] explains the small
amount of hydrogen absorbed by this alloy at the applied
conditions. The adsorption of CO at the surface is known to
block the active sites for hydrogen adsorption from mixtures
of hydrogen with CO [24]. As a result, only limited amounts of
hydrogen can be absorbed by the Ti0.8V0.2 alloy during the
absorption cycles. Bulk hydrogen storage properties can only
be altered at conditions when the alloy experiences
hydrogenation-dehydrogenating cycling. Since no significant
hydride formation occurred during the cycling in Ar þ 25%
H2 þ 1% CO, there was no change in the bulk behavior and,
therefore, no other phases than BCC were observed after the
cycling.
Fig. 7 shows results of an EPMA analysis that was per-
formed within the microstructure of the Ti0.8V0.2 alloy after 8
cycles in the gas mixture containing CO. A line analysis was
performed along the line AB across the interface between two
grains. The interface is seen as the weak curved line through
the center of Fig. 7a. As shown in Fig.7b, the oxygen content
was highest at the boundary, which is seen to be the interface
between two Ti0.8V0.2 particles. This result is different from
the sample that was cycled in pure H2 (Fig. 5), in which aTieO
phase was concentrated in small areas within the bulk. Thus,
it can be concluded that CO-containing gas increased the ox-
ygen content at the surface of the TieV particles.

Fig. 7 e a) Metallographic cross section of a Ti0.8V0.2 powder particle after 8 cycles. Hydrogenation was done in Ar þ 25%
H2 þ 1%CO. b) Oxygen and vanadium point analyses performed along the AB line.
1706 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 1 6 9 9 e1 7 1 0

Fig. 8 e Ti0.9V0.1Hx after hydrogenation and dehydrogenation at the conditions given in Fig. 4: a) Particle morphology; b) EDS
spectrum; c) high magnification view of a hydride particle surface; d) synchrotron XRD pattern (l ¼ 0.72085 A)  measured ex
situ.

Fig. 8 shows SEM images, EDS spectrum and SR XRD
spectra from a Ti0.9V0.1H1.5 hydride surface after 21 hydroge-
nation/dehydrogenation cycles tested at varying conditions
given in Fig. 4. Fig. 8a shows typical particle morphologies at
low magnification, and Fig. 8c gives a high magnification view
of a hydride particle surface. As can be seen from the EDS
spectrum in Fig. 8b, the surface of the hydride contained sig-
nificant amounts of oxygen. In Fig. 8c it can be observed that in
addition to the oxygen, deposits of carbon materials were also
present at the hydride surface. The carbon deposits must
originate from the dissociation of CO, as frequently has been
observed in steam reforming processes performed at
300e1000
C [25]. Rietveld refinement of the X-ray powder
diffraction patterns presented in Fig. 8d showed that the
sample was composed of tetragonal BCT hydride (61 wt.%) and
HCP a-Ti (39 wt.%). The unit cell lattice parameters of the a-Ti
phase were larger than that of pure aTi, which indicates that
the HCP phase contained hydrogen and/or oxygen. This result
is in agreement with in situ SR-XRD data obtained in our pre-
vious work [16], in which we reported that high amounts of
the HCP a-phase were not converted to hydride during rehy-
drogenation in a gas mixture containing CO. Furthermore, the
original sample was only partially recovered after the expo-
sure to CO.
Surface studies
Surface studies were performed on the dehydrogenated alloys
which were cycled in pure hydrogen gas and in gaseous flows
using the mixtures Ar þ 25% H2 and Ar þ 25% H2 þ 1% CO.
XPS studies
An XPS study was performed on the Ti0.8V0.2 surface before
and after cycling under ideal conditions, i.e. hydrogenation in
pure H2 and dehydrogenation in vacuum. Ti2p, V2p, and O1s
spectra were recorded. As can be seen from Fig. 9, the Ti2p
spectrum can be deconvoluted into four individual spectra
with the main peaks located at 458.8 eV, 457.5 eV, 455.1 eV and
454.1 eV, which corresponds to titanium in the four oxidation
states Tiþ4, Tiþ3, Tiþ2 and Ti0, respectively [26]. As shown in
Fig. 9a, after the 1st dehydrogenation, the intensity of the Tiþ4
energy state (458.8 eV) was the highest one, showing that the
sample surface contained mainly TiO2. As can be seen in
Fig. 9b, after the 8th dehydrogenation, the surface contained
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 1 6 9 9 e1 7 1 0
Fig. 9 e Typical XPS Ti2p spectra of Ti0.8V0.2 vacuum-dehydrogenated powder after: a) 1st dehydrogenation; b) 8th
dehydrogenation; c) 1st dehydrogenation after 5 min sputtering; d) 8th dehydrogenation after 5 min sputtering.
less oxygen than after the 1st dehydrogenation. In other
words, a thinner oxide layer was observed after 8 de-
hydrogenations than after the first dehydrogenation. The V2p
and O1s intensities were very low, the highest intensity
observed in the V2p spectrum was only 1/3 of the maximum
intensity of the Ti2p spectrum, so deconvolution was not
performed (see supplementary data). Nevertheless, the V2p
spectrum consisted of 3 individual spectra related to Vþ5, Vþ3
and 2V0, which indicates the presence of the V2O5, VO2 and
metallic vanadium, respectively [27]. The highest contribution
was observed at 517.19 eV, which corresponds to V2O5.
After 5 min of ion sputtering inside the XPS chamber,
which resulted in removal of about ~5e~10 nm thickness of
the surface layer, it became possible to collect data on the
composition of the sub-surface layers. As can be seen in
Fig. 9c, after sputtering, the normalized intensity of metallic
titanium, Ti0, and the contribution from the lower oxidation
state of titanium increased, which indicates that only a thin
surface layer, not thicker than 10 nm, was enriched with C/O.
The Ti2p spectrum that was recorded from the sample after
completing the 8th dehydrogenation is shown in Fig. 9d, and it
can be observed that the amount of Ti0 has become higher
than the other oxidation states in this condition. From these
results, it can be inferred that cycling in pure hydrogen and
dehydrogenation in vacuum leads to removal of oxygen from
the alloy surface. Alternatively, EPMA data indicated that ox-
ygen concentrated in specific locations as an oxygen-rich
1707
phase within the bulk, resulting in a reduction in the oxygen
content at the surface.
AES studies
AES spectra of Ti0.8V0.2 after 8 vacuum dehydrogenations are
shown in Fig. 10a. As can be seen from the figure, oxygen and
carbon were observed in addition to titanium and vanadium.
The oxygen peak at ~513 eV appears to be rather dominant,
and oxygen is naturally bound to Ti since the prominent Ti
peaks at ~388 eV and ~419 eV are very strong. Previous ob-
servations have shown that possible compounds giving such
spectra are TiO and TiO2 [28,29]. A weak vanadium peak at
473 eV was observed in addition, most likely in the form of a
mixture of three various vanadium oxides. After sputtering for
210 s, which resulted in removal of about 7 nm of the surface
layer, the level of oxygen was reduced, as can be concluded
from the reduced intensities of its peaks in the spectrum. The
level of oxygen was decreased even further after a longer
sputtering time. Ion sputtering for 690 s, corresponding to
23 nm surface removal, resulted in an increase in the relative
intensity of the Ti peaks, which means that the oxygen con-
centration decreased even further when moving into the bulk.
After 690 s ion sputtering, the carbon peak at ~272 eV dis-
appeared, indicating that its presence at the sample surface
originated from handling of the sample. AES spectra of
Ti0.8V0.2 cycled in a mixture of Ar þ 25H2 þ 1% CO are pre-
sented in Fig. 10b. It can be seen that the surface composition
1708 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 1 6 9 9 e1 7 1 0
Fig. 10 e AES spectra of dehydrogenated Ti0.8V0.2 after 9
hydrogenation and dehydrogenation cycles: a)
hydrogenation in pure H2 and dehydrogenation in
vacuum; b) hydrogenation in Ar þ 25%H2 þ 1%CO and
dehydrogenation in pure Ar.
was similar to that of the sample cycled at ideal conditions,
which was dominated by titanium and oxygen. The difference
was that a carbon peak was observed after 690 s sputtering
after the cycling in the presence of CO. This means that CO
enriched the carbon content on the surface of the sample
cycled in the gas mixture.
Summary and final remarks
Ti0.9V0.1 and Ti0.8V0.2 were tested as candidate hydrogen
absorbent alloys to be employed in Hydrogen Sorption
Enhanced Reforming (HSER) e a novel process allowing an
improved efficiency of natural gas reforming [8].
Hydrogen absorption experiments were performed in two
different modes; (a) quasi-isothermally at static conditions
using pure hydrogen gas, and (b) isothermally at 425
C-575
C
using a flow of gaseous mixture containing argon, 1e2% CO
and 25% H2.
When the hydrogenation was performed at 450
C and
4 bar H2, both alloys instantly started to interact with
hydrogen and in less than 60 s formed saturated hydrides
containing FCC g(Ti,V)H2 as the majority constituent, with
an H storage capacity reaching 3.7 wt.% H for Ti0.9V0.1H~2. At
higher temperatures, 450e550
C, the hydrogenation process
led to increased formation of the lower hydride BCC b-(Ti,V)
H~0.7 [17] resulting in decreased reversible hydrogen storage
capacities.
Hydrogenation in an Ar þ 10% H2 gas flow reduced the
reversible H storage capacities (down to 1e3 wt. % H); the
extent of the decay was related to the alloy composition and
the hydrogenation temperature. In most cases the hydride
formed during the hydrogenation at 425e575
C was found to
be a lower bmonohydride with a BCC type structure. This
correlated well with the dehydrogenation properties of the
formed hydrides, as their desorption spectra contained only
one high temperature peak of hydrogen evolution.
Kinetic analysis of the process of hydrogen absorption
showed that hydrogenation of the two TieV alloys followed
the, respectively, two- and three-dimensional Avrami-Erofeev
nuclei growth model. Differences in the dimensionality of the
nuclei growth are likely to be caused by the microstructural
and phase-structural state of the alloys. Indeed, Ti0.9V0.1 alloy
is composed of a mixture of HCP and BCC phases (three-
dimensional model), while a BCC type Ti0.8V0.2 has close to a
single phase microstructure (two-dimensional model). How-
ever, in common to both studied alloys, the growth of the
nuclei of the hydride phases was found to be the rate-limiting
step of the hydrogenation process.
Even though cycling in pure hydrogen/vacuum resulted in
slight changes of the phase composition of the alloys, e.g.
increased content of HCP aphase and formation of oxygen-
rich TieO phase in the Ti0.8V0.2 alloy, these changes did not
affect the values of the reversible hydrogen capacity.
In contrast, hydrogen cycling in a flow of Ar þ H2 resulted
in reduced amount of hydrogen in the hydrides, down to
~2e2.5 wt.% H, already during the first testing cycles. The
hydrogen content was found to continuously decrease upon
cycling. This was caused by the presence of undesorbed
hydrogen that was trapped in the remnant (TiV)Hx observed in
the cycled alloys. The amount of remnant (TiV)Hx increased
upon cycling, which in part was caused by a tendency of for-
mation of Ti- and V-rich constituent phases during the cycling
as well as hydride separation during the hydrogenation. Thus,
at some stage, formation of Ti-rich high stability TieVeH
phase increases and negatively affects the cycling behavior.
In presence of carbon monoxide that was added to the gas
flow (Arþ25%H2 þ 1%CO), a limited amount of hydrogen, i.e.
~0.6 wt.% H, was absorbed during the hydrogen absorption-
desorption cycling at 425
C. This amount of hydrogen
remained relatively constant during the cycling.
Interestingly, when the hydrogenation was performed
non-isothermally in the experiments covering the tempera-
ture range RT-800
C, the amount of the absorbed hydrogen
slightly increased to ~1 wt.% H, despite of the higher CO
content in the mixture (see Fig. 7). In situ SR-XRD experiments
showed that d-(TiV)H~1.5 is formed during non-isothermal
hydrogenation in a gaseous flow of 90% H2 þ 10% CO [9]. In
that case, after the 3rd non-isothermal cycle in the tempera-
ture range RT-800
C the sample was composed of 70 wt.% the
dhydride. Differences in the hydrogenation mechanism have
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 1 6 9 9 e1 7 1 0
roots in variations of the employed experimental conditions,
including the time/temperature for introducing CO in the gas
mixture and, furthermore, conditions of the hydrogenation
processing - isothermal or non-isothermal.
As an illustration of the effect of the conditions of the al-
loys processing in hydrogen, HCP aphase was not observed
in the present work in the powder XRD pattern of the Ti0.8V0.2
sample cycled isothermally in Ar þ 25%H2 þ 1%CO, in contrast
with the significant amounts of HCP aphase that was re-
ported by Børresen at al. [8] to form during non-isothermal
cycling. AES analysis of the surface of a cycled specimen
(Fig. 10) showed that the surface layers contained significant
amounts of carbon and oxygen. This agrees well with the re-
sults of an investigation on LaNi5 [10], showing that, at high
interaction temperatures above 300
C, CO decomposes at the
metal surface, leading to deposition of carbon and formation
of methane and a surface oxide. Even at low interaction
temperatures, CO has been shown to dissociate on a LaNi5
surface, but at those conditions the reaction products were
methane and H2O [30]. The effect of carbon contamination
appears to be related to the gas composition and temperature,
and it has been shown in previous works that gas mixtures
containing carbon monoxide reduce the number of active
surface sites for metalehydrogen interaction [23,24,31].
The oxygen that was detected within the HCP a-phase after
non-isothermal hydrogenation, must originate from the
interaction of the alloy surface with CO. When the content of
CO in the gaseous mixture is high, non-isothermal cycling at
high temperatures will create conditions that allow oxygen
atoms to diffuse into the bulk material, leading to a shift in
equilibrium towards formation of HCP Ti a-phase which is
able to dissolve large amounts of interstitial oxygen [32].
Nevertheless, it was demonstrated that the reversible
hydrogen storage capacity was recovered up to 80% of its
initial value when CO was removed from the gas mixture
(Fig. 7). A similar recovery of the hydrogenation behavior has
also been observed to occur during low temperature cycling of
LaNi5 [30] and TieMn alloys [9] in hydrogen gas containing,
respectively, 0.1 and 0.5% CO. The reason for this recover-
ability is probably associated with removal of carbon/carbon
monoxide from the alloy surface and thus reactivation of the
active sites for hydrogen adsorption.
Conclusions
In the present work, hydrogen storage properties of Ti0.9V0.1
and Ti0.8V0.2 alloys were studied using various experimental
and characterization techniques. Ti-rich Ti0.9-0.8V0.1-0.2 solid
solution alloys demonstrated excellent hydrogenation ki-
netics, forming saturated g-dihydrides with high reversible
hydrogen storage capacity (up to 3.7 wt.% H) in less than 60 s.
A complete reversibility of the hydrogen absorption-
desorption capacity was achieved during the cycling experi-
ments (up to 9 cycles) when the hydrogenation was performed
in pure H2 gas and the hydride decomposition was accom-
plished by in a vacuum. However, when cycling was per-
formed in a flow of H2 mixed with Ar, decreased values of the
reversible hydrogen capacity were observed as a consequence
of the formation of stable b-(Ti,V)H1-1.2 lower hydrides. The
1709
ability of the (Ti,V) alloys to absorb hydrogen was significantly
suppressed in the presence of CO. Two complementary
mechanisms stand as the reasons for that. At lower temper-
atures, CO blocked the active sites of hydrogen adsorption at
the surface. It was possible to revert this condition since the
hydrogenation capabilities of the alloys were partially recov-
ered when CO was removed from the gas flow. At high pro-
cessing temperatures above 425
C, chemical decomposition
of CO took place at the sample surface. This resulted in (a)
carbon deposition on the surface, blocking the active surface
sites for hydrogen adsorption, and (b) oxygen diffusion into
the bulk alloys forming solid solutions of oxygen within the
alloy as well as oxide films at the grain boundaries, affecting
both kinetics and thermodynamics of the hydrogen exchange.
The most viable advantage obtained by using hydrogen
absorbent alloys in the HSER process lies in the possibility to
limit the process temperature below the value where unre-
coverable changes of the alloy (surface and bulk) take place
due to interaction with carbon monoxide, and at the same
time to adjust the reversible hydrogen storage capacity of the
formed hydrides to the operating temperatures, leading to an
overall improvement of the efficiency of the process.
Acknowledgments
Financial support from the Norwegian Research Council and
Statoil ASA are gratefully acknowledged. The thank staff of
SNBL/ESRF for the skillful assistance during SR XRD
experiments.
Appendix A. Supplementary data
Supplementary data related to this article can be found at
http://dx.doi.org/10.1016/j.ijhydene.2015.11.077.
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