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Role of Hydrogen and Oxygen Activation over Pt and Pd-Doped

Composites for Catalytic Hydrogen Combustion
Satyapaul A. Singh, Karan Vishwanath, and Giridhar Madras*
Department of Chemical Engineering, Indian Institute of Science, Bangalore 560012, India
ABSTRACT: Removal of excess amount of hydrogen in a catalytic route
is a safety measure to be implemented in fuel cell technologies and in
nuclear power plants. Hydrogen and oxygen activation are crucial steps for
hydrogen combustion that can be achieved by modifying supports with
suitable noble metals. In the present study, Pt- and Pd-substituted Co3O4
ZrO2 (CZ) were synthesized using PEG-assisted sonochemical synthesis.
Ionic states of Pt and Pd in CZ supports were analyzed by X-ray photoelectron spectroscopy. Pd and Pt improved H2 and O2 activation
extensively, which reduced the temperature of 50% conversion (T50%) to
33 C compared with the support (CZ). The activation energy of PdCZ
catalyst was decreased by more than 2 folds (13.4 1.2 kJ mol1)
compared with CZ (34.3 2.3 kJ mol1). The eect of oxygen vacancies
in the reaction mechanism is found to be insignicant with Pt- and
Pd-substituted CZ supports. However, oxygen vacancies play an important
role when CZ alone was used as catalyst. The importance of hydrogen and oxygen activation as well as the oxygen vacancies in
mechanism was studied by H2TPD, H2TPR, and in situ FTIR spectroscopy.
KEYWORDS: H2 combustion, temperature-programmed desorption, in situ FTIR, ionic substitution, Co3O4, ZrO2,
oxygen storage capacity, temperature programming reduction

INTRODUCTION

Thus, the design of catalysts for hydrogen combustion becomes

important.
For hydrogen combustion reaction, the catalysts should
possess properties such as oxygen storage capacity and thermal
stability and should be able to oer hydrogen and oxygen
activation (which can be attained with noble metals in support).
Noble metals have high adsorption capability of hydrogen and
oxygen at low temperatures.12,13 Recently Borguet et al. have
reported high adsorption capacity of hydrogen on palladium and
low H2 dissociation temperature.12 Moreover, understanding
H2 and O2 behavior on the catalyst surface is crucial to focus on
the mechanisms of various commercialized processes such as
preferential oxidation and H2 combustion. The activity of noblemetal-substituted reducible supports is predominant because of
its high oxygen storage capacity (OSC) and the role of such
supports (CeO2) was studied elsewhere.14,15
Supports like CeO2, TiO2, and SnO2 are reducible and possess high OSC, but these materials are not thermally stable at
high temperature.4,16 Supports like ZrO2 are nonreducible and
thermally stable materials but these materials do not have
reasonable OSC.17 Particularly in nuclear industries, temperatures usually reaches more than 1200 C. In this particular
application, hydrogen is released at high temperature and can be

In nuclear power plant history, the major failures registered were

Three Mile Island (1979), Chernobyl (1986) and Fukushima
(2011). The prime reason for these disasters is because of the
coremeltdown in boiling water reactor (BWR).13 At elevated
temperatures (>1200 C), reactor fuel cladding material Zircaloy
(alloy of >97% Zirconium) generates hydrogen gas upon
oxidation reaction with steam.4,5 The extensive quantities of
H2 and steam generated in the BWR system create high pressure
and temperatures as the oxidation is highly exothermic. This
may lead to the reactor failure and blasts. Thus, the removal of
excess amount of hydrogen is necessary and extensive research is
required to overcome the current challenge in nuclear industries.
Designing passive catalytic hydrogen recombiners for the
removal of hydrogen could avoid such disasters.6,7
Further, large-scale fuel cell plants are being established for
power generation for stationary, transportation and portable
applications.8,9 Often, fuel cells require excess amount of hydrogen to achieve stable voltage. The removal of excess hydrogen
from the exhaust stream is required for safe operation.10 Apart
from these applications, residential central heating can be
accomplished by hydrogen or natural gas combustion boilers
(HCB or NGCB). However, direct hydrogen combustion in
NGCB results in NOx emissions because of high operating
temperatures. Catalytic hydrogen combustion boilers operate
at relatively low temperatures and are able to generate heat
for household applications without CO2 and NOx emissions.11
XXXX American Chemical Society

Special Issue: Focus on India

Received: July 1, 2016
Accepted: October 7, 2016

DOI: 10.1021/acsami.6b08019
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reduced to 900 C before reaching the hydrogen combustion
reactor inlet.4 High concentrations of H2 might also release in the
reactor, which further leads to an increase in the temperature due
to its highly exothermic nature. For such an application it is
critical to have stable OSC against thermal aging. Earlier reports
have shown that CeO2ZrO2 composites preserved oxygen
vacancies for long time with ramping temperature.18 Considering
this practical application in nuclear industries, thermally stable
ZrO2 and high OSC materials Co3O4 were chosen over other
materials such CeO2 and TiO2.
In this study, we have synthesized 50 wt % Co3O4-ZrO2 (CZ)
as support and with substitution of Pt and Pd by using PEG
assisted sonochemical synthesis. Pd/Co3O4-ZrO2 (PdCZ) and
Pt/Co3O4-ZrO2 (PtCZ) have showed high catalytic activity for
H2 combustion compared with the support CZ. The reaction
mechanism was studied with the assistance of in situ FTIR,
temperature programming reduction with H2 (H2TPR),and
temperature programming desorption with H2 (H2TPD). The
role of lattice oxygen as well as chemisorbed hydrogen in the
mechanism has been elucidated.

surface area analyzer. The elemental compositions were analyzed by

quadrupole inductively coupled plasma mass spectrometer (ICPMS,
Thermo X Series II).
H2TPD was performed to understand the hydrogen interactions
with PtCZ and PdCZ composites. Ten mg of the catalyst was packed in a
quartz reactor (4 mm ID) at center by plugging with ceramic wool and
analysis was conducted with series of steps. First, the material was
reduced under H2 atmosphere in a tubular furnace at 400 C for 1 h and
allowed to cool to room temperature. Helium gas was purged for 1 h
through the tubular reactor to remove weakly adsorbed H2 species. The
temperature of the furnace was increased to 1000 C with a ramping rate
of 10 C min1 using a programmable PID controller and the TCD
signal was recorded in this temperature range.
H2TPR was performed on the catalysts to determine OSC and to
understand the role of lattice oxygen in H2 combustion mechanism.
5% H2 (rest He) gas was purged through the tubular reactor from room
temperature to 1000 C using a programmable PID controller with a
ramping rate of 10 C min1. The OSC calculations were performed by
calibrating with CuO (99.7% purity, Alfa Aesar).
In situ FTIR spectra was collected under feed conditions at
various temperatures using PerkinElmer equipment with the Praying
Mantis accessory and DTGS detector. Catalysts were loaded in the
high temperature reaction chamber and closed with a dome. The
temperature of the reaction chamber was controlled by PID controller
and a cooling jacket connected to the chamber. N2 gas was purged for
30 min after setting the reaction chamber temperature, and the
background was collected right after temperature stabilization.
The reactants were fed according to the experimental conditions and
an IR spectrum was collected after reaching equilibrium (30 min).
32 scans were performed in the range of 6504000 cm1 with 4 cm1
resolution.

EXPERIMENTAL SECTION

Catalyst Synthesis. The catalysts were prepared by sonochemical

synthesis with cobaltous nitrate hexahydrate (Co(NO3)26H2O,
Sigma-Aldrich), zirconium(IV) oxynitrate hydrate (ZrO(NO3)2.
xH2O, Sigma-Aldrich), palladium chloride (PdCl2, Sigma-Aldrich),
and hexachloroplatinic acid (H2PtCl6, Sigma-Aldrich) as starting
materials. In a typical synthesis, 3.498 g of Co(NO3)26H2O in
100 mL was added dropwise to 65 mL of 1.812 g of ZrO(NO3)2xH2O
with continuous stirring. To control the orientation of nanoparticles
aggregation and nucleation, we added 2 g of PEG600. To synthesize noble-metal-doped catalysts, we took Pt and Pd precursors
(corresponding to 2 at %) in stoichiometric quantities (43 mg of
H2PtCl6 in 10 mL and 19 mg of PdCl2 in 10 mL) and added dropwise
after mixing with PEG600. To ensure eective doping, 5 mL of
diethylene triamine (DETA) was added to the solution, which led to
the formation of gelation. After rigorous stirring, 0.1 M NH4OH was
added to increase the solution pH. In the presence of the ultrasonic
radiation (25 kHz, 125 W, Electrosonic Industries, India), 0.1 M
NH4OH was added dropwise until the solution pH reaches 8. Under
basic pH conditions, the precipitated catalyst was collected after 3 h of
eective sonication. The precipitate was separated by centrifugation
and the collected precipitate was washed thrice with ethanol. Finally,
the catalyst was dried at 120 C for 6 h and kept for calcination at
500 C for 2 h.
H2 Combustion Experimental Conditions. The catalysts were
made into pellets by using hydraulic press sieves of 60/80 mesh size.
In a typical experiment, 25 mg of catalyst was packed with ceramic
glass wool plugs, at the center of 4 mm ID quartz reactor. The bed
length of 1 cm was maintained by diluting the catalysts with silica.
The catalyst loading was varied from 15 to 50 mg in case of PtCZ and
PdCZ for studying the kinetics, whereas the loading was increased to
100 mg for CZ as the activity of this material was lower than the other
materials.
Characterization Techniques. The phases were determined with
Rigaku X-ray diractometer using CuK as radiation source at 40 kV
and 30 mA. The presence of atoms like Co, Fe absorbs incident X-rays
and uoresce at dierent wavelength, which further decreases the
intensity of diracted signal and increases the background noise. The
background noise was removed by using a diracted-beam
monochromator. A scanning rate of 0.5 min1 was used in a range
of 2080. XPS spectra of Pt and Pd substituted CZ composites
were recorded with AXIS ULTRA equipment with AlK source.
All samples were calibrated by using graphite at a binding energy of
284.5 eV. TEM images of all composites were recorded by FEI Tecnai
F30 instrument operated at 200 kV. The specic surface areas of
synthesized catalysts were analyzed with liquid N2 at 77 K with Belsorb

RESULTS AND DISCUSSION

XRD patterns of the synthesized catalysts are shown in Figure 1,
which conrmed the presence of both Co3O4 and ZrO2 phases by

Figure 1. XRD pattern of Co3O4ZrO2 (CZ), Pt/Co3O4ZrO2

(PtCZ) and Pd/Co3O4ZrO2 (PdCZ). JCPDS patterns of Co3O4
and ZrO2 are also shown.

comparing with JCPDS database les 000421467 and

000030640 respectively. The CZ composite consists of
cubic Co3O4 (a = b = c = 8.084 , space group: Fd3m) and cubic
ZrO2 (a = b = c = 5.103 , space group: Fm3m) phases.
Monoclinic ZrO2 and cubic CoO phases are possible in the
synthesis of composites but these phases were not detected by
XRD. Peaks corresponding to Pt and Pd (at 39.7 and 40.4) or its
oxides (at 34.8 and 33.8) are not observed. XRD has detection
limits for small percentages of dopants. The change in lattice
parameters has to be analyzed by Rietveld renement and this
could give an insight of substitution. The renement was
performed with JANA 2006 with pseudo-Voigt as peak function
and the background was corrected with Legendre polynomial
B

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presence of low concentrated CoO phase. The ratio of Co3+:

Co2+ was found to be 2:1. The binding energies of core level Co
2p3/2, 2p1/2 peaks were observed at 779.6 and 794.6 eV for Co3+
and 781.0 and 796.0 eV for Co2+; the dierence in Co 2p3/2 and
Co 2p1/2 of Co3+ and Co2+ was 15.0 eV.2325 Co 2p3/2 and Co
2p1/2 shakeup satellite peaks are observed at 783 and 798 eV,
a peak corresponds to 789 eV in Figure 3a is because of CoO
satellite.25,26 Figure 3b shows the Zr 3d spectra and the data
was deconvoluted according to 3d5/2 and 3d3/2 coreshells.
The peaks at 181.9 and 184.3 eV are assigned to 3d5/2 and 3d3/2
coreshells.27 Apart from these two peaks, an extra shoulder at
186.1 eV was observed and it could be due to inelastic scattering
of X rays.28 Figure 3c shows the deconvoluted Pd 3d spectra
and binding energy of Pd 3d5/2 at 337.4 eV, which indicates the
shift in the binding energy of metallic Pd and thus it can be
assigned to ionic Pd.29 The concentration of Pd2+ compared with
metallic Pd is signicant and the metallic Pd is found to be less
than 7% of total Pd content in the composite. A satellite peak
was observed at 339.3 eV and this peak is due to the presence of
PdO phase.30 In PtCZ catalyst, Pt was in dierent ionic states
+4, +2, and 0 (metallic) respectively. From Figure 3d, the
concentration of metallic Pt is found to be equivalent
contribution of combined Pt4+ and Pt2+ at 73 and 72.3 eV for
4f7/2 coreshell and at 76.6 and 75.6 eV for 4f5/2 coreshell.31,32
A peak at 74.5 eV was detected which could be because of
PtO2 satellite33 and inelastic scattering of X-rays resulted a peak
at 77.5 eV.28 39.9% of total Pt (as shown in Table 2) is
substituted in its ionic state and rest might be doped in interstitial
sites of the metal oxides. Although the ionic radii of both Pt and
Pd are equivalent, Pt was not substituted in its ionic state as
eectively as Pd in CZ composite and that could be due to highly
reducible nature of Pt. Compositions of all Pt4+, Pt2+, Pd2+, and
both metallic Pt and Pd before and after the stability study are
listed in Table 2.
Figure 4a shows the variation of H2 conversion with temperature at dierent concentrations such as 2, 5, and 10 vol % H2
and with 10 vol % O2 and the rest N2. At low concentrations of H2
(at 2 vol %), the conversions are higher and the temperature of
50% conversion (T50%) is 33 C with PdCZ catalyst. At higher
concentrations such as 10 vol % H2, the temperatures cannot be
controlled because of the exothermicity of the reaction.
Therefore, to have more control over the reaction and to study
the reaction at isothermal conditions, we optimized the feed
conditions at 5 vol % H2, 10 vol % O2, and the rest N2, gas hourly
space velocity (GHSV) of 47750 h1, and catalyst loading of
25 mg for all studies. Figure 4b shows the variation of conversion
of H2 with temperature for PdCZ and PtCZ. The T50% of PdCZ
and PtCZ are 75 C, which is considerably lower than that
obtained with CZ, which is 241 C.
The catalytic hydrogen combustion on Cu doped SnO2
catalysts was studied and the T50% was found to be 250 C at a
GHSV of 42310 h1.34 Hydrogen combustion with both
reducible (TiO2) and nonreducible (ZrO2) supports has been
studied with Pt and Pd substituted supports at a GHSV of
20000 h1 and 2:1 ratio of H2:O2. T50% were obtained at 70 and
95 C with Pd- and Pt-substituted ZrO2 catalysts, whereas Pt and
Pd substituted reducible support TiO2 showed much higher
activity by reducing temperatures to 37 and 35 C.15 Other than
metal oxide supports, the eect of Pt containing washcoat on SiC
foam for H2 combustion was studied and T50% was found to be
34 C in excess amount of air with 1 vol % H2.13 However, either
high catalyst loading or low GHSV were employed in earlier
studies compared with present study, which indicates that our

with 30 terms. The lattice parameters for the unsubstituted

Co3O4 and ZrO2 are 8.084 and 5.103 , respectively. The rened
lattice parameters of Co3O4 and ZrO2 decreased to 8.0812 and
5.0814 for PdCZ catalyst, whereas for PtCZ the parameters
decreased to 8.0806 and 5.1021 . The distortion in lattice
parameters is because of Pt and Pd substitution in the CZ
composites.
The wt % of Pt and Pd in composites were found to be 1.01%
and 0.53% using inductively coupled plasma mass spectrometer.
The specic surface areas of PdCZ, PtCZ and CZ were
determined by BET analysis and were 60 2, 47 1, and
48 2 m2 g1, respectively.
From Figure 2, ZrO2 and Co3O4 phases are conrmed with
HRTEM results by analyzing fringes of the dspacing of the

Figure 2. (ac) TEM micrographs, (df) HRTEM micrographs, and

(gi) diraction patterns of PdCZ, PtCZ, and CZ catalysts (from left to
right).

particles. The large particles indicate the ZrO2 phase whereas

smaller particles were conrmed as Co3O4. The presence of Pt
(111) and Pd (111) was found in the lattice fringes of the
particles. (111), (222), (220) planes of ZrO2 and (311), (422)
planes of Co3O4 were conrmed by analyzing diraction rings
(Figure 2gi). Figure 2d, e showed very small clusters of Pt and
Pd dispersed in a solid solution. The ionic substitution of Pt and
Pd is due to the atomically dispersed Pt and Pd in the support,
which can oxidize by utilizing bulk oxygen or oxygen vacancies in
the support.19,20 Figure 2d, e shows the HRTEM images of PdCZ
and PtCZ and the d-spacing of lattice fringes was observed as
2.21 and 1.86 , respectively. These d-spacing values are
lower compared with the reference Pd (111) and Pt (200) planes
(2.27 and 1.95 , respectively). Distortion in d-spacing of these
planes occurred probably because of substitution of noble metals
in composites.
The ionic substitution of the catalysts provide more support
metal interaction (SMSI) compared with the impregnated
catalysts.15,21,22 The presence of their ionic states was conrmed
with XPS analysis. Figure 3a shows Co 2p spectra of the catalyst,
which indicates the presence of Co3O4 phase as well as the
C

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Figure 3. XPS of (a) Co 2p core level spectra of CZ composite, (b) Zr 3d core level spectra of CZ composite, (c) Pd 3d core level spectra of PdCZ, and
(d) Pt 4f core level spectra of PtCZ, (e) Pd 3d core level spectra of PdCZ after 50 h, (f) Pt 4f core level spectra of PtCZ after 50 h.

Figure 4. Variation in H2 conversion with temperature (a) at various initial H2 concentrations in the presence of PdCZ catalyst (with 10 vol % O2,
GHSV = 47750 h1, catalyst loading = 25 mg), (b) for CZ, PtCZ, and PtCZ catalysts (with H2:O2:N2 = 5:10:85 vol %, GHSV = 47750 h1, catalyst
loading = 25 mg).

studies were conducted at much more stringent conditions

compared with the literature. The noble metal loading, catalyst

loading, and activation energies are compared with previous

reports and showed in Table 1.
D

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Table 1. Activation Energies, Catalyst Loading, and Dopant Loading of Various Catalysts for Catalytic Hydrogen Combustion
activation energy,(kJ mol1)

catalyst

temperature range

amount of catalyst (mg)

dopant loading

Pd/Al2O3
Pt/Al2O3
(Pd65Pt35)2.79%/Al2O3

70140 C
4090 C
4090 C

36
41
40

2000
2000
2000

(Pd20Pt80)2.79%/Al2O3

70110 C

44

2000

Cu/SnO2
Cu/CeO2
Cu/Al2O3
Cu/ZrO2
Pd/Monolith supports
0.5 (wt %) Pd/Al2O3
Pt/SiC washcoat
Co3O4 ZrO2
Pt/Co3O4 ZrO2
Pd/Co3O4 ZrO2

220300 C
220300 C
220300 C
240340 C

27.6
31.5
38.8
56
26
73.8
34
34.3 2.3
39.3 2.0
13.4 1.2

0.92 wt %
1.78 wt %
Pt = 1.38 wt %
Pd = 1.41 wt %
Pt = 0.20 wt %
Pd = 1.41 wt %
5 at %
5 at %
5 at %
5 at %

3585 C
2550 C
180210 C
3060 C
3060 C

200
200
200
200
30000
400
50
25
25

0.5 wt %
0.27 wt %
0
2 at %
2 at %

ref
4
4
4
4
34
34
34
34
44
45
13
present study
present study
present study

Figure 5. Conversion of H2 with catalyst loading (W) for (a) CZ, (b) PdCZ, and (c) PtCZ catalysts (with 5 vol % of H2); (d) Arrhenius plot for PdCZ,
PtCZ, and CZ catalysts.

The reaction rates were calculated by assuming dierential ow

reactor and the activation energies were calculated within the range
of linear relationship of conversion of H2 with W . W represents the

from the slope of Figure 5ac) with reciprocal of temperature,

which follows Arrhenius relationship and the activation energies
were calculated from the slope. Among all catalysts, PdCZ has the
least activation energy (13.4 1.2 kJ mol1) compared with PtCZ
(29.3 2.0 kJ mol1) and CZ (34.3 2.3 kJ mol1). The preexponential factors for PdCZ, PtCZ, and CZ are 1.4 106,
5.0 107, and 2.7 107 mol0.5 m1.5 min1, respectively.
Understanding the mechanism of hydrogen combustion is
crucial because of its fast kinetics. Numerous studies have

FH2

catalyst loading and FH2 represents the molar ow rate of the H2.
Figure 5 shows the linear variation of H2 conversion with

W
FH2

for

CZ, PtCZ and PdCZ catalysts. The reaction rates were calculated
by, rH2 =

X H2

FH2

. Figure 5 (d) shows the logarithm of rate (obtained

E

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and 610 C represents the irreversible desorption of hydrogen.35

The noble metal catalysts can dissociate hydrogen even at room
temperature. From H2TPD results, it is conrmed that this is the
atomic hydrogen release. Several studies have shown that Pd
requires lower temperatures (200 K) to dissociate O2 compared
with the Pt (400 K).3638 The activation energy of PdCZ is
2 times lower compared with PtCZ because of having both hydrogen and oxygen activation on the surface (as shown in Scheme 1).
The role of lattice oxygen vacancies can be explained with
H2TPR analysis. The TPR proles start at 202 C in the case
of CZ, but the starting temperatures are 102 and 107 C with
PtCZ and PdCZ. The lattice strains created due to ionic or
interstitial substitution further causes the breakdown of MO
(M = Co, Zr, Pt, and Pd) bond of the composite. Moreover, Zr4+
creates the structural defects that further increase the OSC of the
catalysts.17 Thus, the observed oxygen storage capacities of PtCZ
and PdCZ are lower compared with CZ, as shown in Figure 6a.
As noble metals reduce at low temperatures, the reduction peaks
can be observed at temperatures below 100 C.39 However,
PtCZ and PdCZ catalysts oered reduction at low temperatures
but not below 100 C and this could be due to overlap with
Co3O4 reduction peaks. Pd or Pt incorporation in metal oxide
cause structural changes and enhances the oxygen mobility for
the reduction of supports.4042 The reduction peaks of Co3O4
also shifted to low temperature compared with the reduction
peaks in CZ composite. Earlier reports showed that CeO2ZrO2
composites preserved oxygen vacancies for long time with
temperature aging.18 All these supports have wide reduction
distribution over a temperature range up to 850 C.
OSC is a crucial parameter for catalytic oxidation reactions;14,15 however, the lowest activation energy was observed
with PdCZ compared to PtCZ and CZ because of the reaction
pathway over the catalyst surface. From Figure 4a, it is clear that
the temperatures of complete conversion (T100%) of the reaction
for both PtCZ and PdCZ are 100 C. The oxygen uptake is
controlled by the mobility of oxygen molecules at a given temperature irrespective of its overall OSC of the support.43 In case
of PtCZ and PdCZ, the H2TPR proles started at temperatures higher than 100 C, which indicate that there is negligible

reported hydrogen and oxygen adsorption over Pt, Pd based

catalysts and their single crystals. As per literature, Pt (111) and
Pd (111) are highly active for hydrogen dissociation and this step
occurs even at temperatures <300 K. These planes are highly
active for hydrogen adsorption at temperatures <100 K.35,36
From Figure 6a, H2TPD results indicate desorption of

Figure 6. (a) H2TPR proles for CZ, PdCZ, and PtCZ catalysts;
(b) H2TPD proles for PdCZ and PtCZ catalysts.

chemisorbed hydrogen species even below 50 C. These data

can split into four stages. The region below 150 C indicates the
reversible desorption and regions with temperatures <275, 400,

Scheme 1. H2 Combustion Mechanism over CZ, PtCZ, and PdCZ Composites

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Figure 7. In situ FTIR spectra for (a) CZ; (b) PtCZ; (c) PdCZ catalysts; (d) CZ, PdCZ, and PtCZ catalysts at 50 C.

mechanism. The intermediate steps and possible reaction

mechanism on various CZ, PdCZ, and PtCZ catalysts are shown
in Scheme 1. Because of eective substitution of Pd in CZ supports,
both H2 and O2 activation over Pd makes PdCZ as the eective
catalyst for hydrogen combustion. The activation energies of PtCZ,
PdCZ and CZ catalysts are compared with the literature in Table 1.
Among all those catalysts, PdCZ has the lowest activation energy
along with low temperature range.
The long-term application of the catalysts can be studied by
performing stability experiments at critical conditions. PtCZ and
PdCZ catalysts were operated under stringent conditions such as
10 vol % H2, 10 vol % O2, the rest N2, with 25 mg of catalysts
at a GHSV of 47750 h1. Full conversions were obtained for
50 h of study at 105 C indicating the stability of the catalysts.
The hydrogen combustion rate at these conditions is as high as
0.4 LH2 min1 g1. The catalysts after 50 h stability experiments
were characterized using XPS analysis (shown in Figure 3e, f).
Interestingly, the ionic states of Pt and Pd increased after the
stability study (PdCZ S and PtCZ S). Pt was oxidized to
+4 state from 12.6% to 58.8% and the metallic Pt quantity was
reduced to 17.7% from 52.3% (shown in Table 2). Metallic Pd

dependency of OSC parameter on these two catalysts when

operating below 100 C. The dopants Pd and Pt are substituted
in both supports ZrO2 and Co3O4 in a composite. However, it is
dicult to quantify how much dopant is available in each
support. From a mechanistic point of view, the crucial steps of
hydrogen and oxygen activation occurs on Pd and Pt irrespective
of the support. The support plays a major role at elevated
temperatures. The role of Co3O4 phase is negligible when
reaction occurs at temperatures <100 C. At such low temperatures, the oxygen release to the reaction is negligible. However,
at temperatures close to 100 C, the OSC contribution in hydrogen combustion mechanism cannot be omitted as the H2 consumption has been observed at temperatures below 110 C. The
role of Co3O4 is an important parameter in the mechanism, as
oxygen vacancies too play a signicant role in the mechanism even at
a low temperatures where oxygen vacancies are not high enough.26
Instead of reaction with lattice oxygen vacancies, most crucial
steps like H2 and O2 dissociations occur on the PdCZ surface,
whereas with PtCZ the extent of H2 dissociation step is higher
compared with O2 activation. These predictions were cross
checked by performing experiments under oxygen decient
conditions. Twenty-ve mg of PtCZ and PdCZ materials were
subjected to 2% H2 (rest N2) feed without oxygen at a ow rate of
100 mL min1. Both noble metal substituted CZ supports were
inactive in a range of 30110 C.
To obtain more insights about the mechanism, we performed an
in situ FTIR study on these catalysts by maintaining the same
reaction feed condition. Stretching and bending modes of OH
group were observed with all catalysts (Figure 7). However, these
modes are strong with PtCZ and PdCZ catalysts. Interestingly, the
intensity of these bands decreased after 50 C but broadened,
which indicates the hydrogen bonding becomes stronger with
increasing temperature due to spillover on catalysts surface. Thus,
we can conrm the role of hydroxyl intermediates during the

Table 2. Composition of Ionic States in PtCZ and PdCZ

Catalysts before and after Stability Study
%

catalyst

Pd2+

Pd0

PdO

PdCZ
PdCZ-S

88.3
89.8

6.4
0
%

5.3
10.2

catalyst

Pt4+

Pt2+

Pt0

PtO2

PtCZ
PtCZ-S

12.6
58.8

27.3
23.5

52.3
17.7

7.8
0

DOI: 10.1021/acsami.6b08019
ACS Appl. Mater. Interfaces XXXX, XXX, XXXXXX

Forum Article

ACS Applied Materials & Interfaces

Passive Auto-Catalytic Recombiners under Operational Containment

Atmosphere Conditionsan Interdisciplinary Investigation. Nucl. Eng.
Des. 2009, 239, 274280.
(8) Wilberforce, T.; Alaswad, A.; Palumbo, A.; Dassisti, M.; Olabi, A. G.
Advances in Stationary and Portable Fuel Cell Applications. Int. J.
Hydrogen Energy 2016, 41, 16509; Int. J. Hydrogen Energy 2016, 41,
1650916522.
(9) Chu, S.; Majumdar, A. Opportunities and Challenges for a
Sustainable Energy Future. Nature 2012, 488, 294303.
(10) Woo, C. H.; Benziger, J. B. PEM Fuel Cell Current Regulation by
Fuel Feed Control. Chem. Eng. Sci. 2007, 62, 957968.
(11) Dodds, P. E.; Staffell, I.; Hawkes, A. D.; Li, F.; Grunewald, P.;
McDowall, W.; Ekins, P. Hydrogen and Fuel Cell Technologies for
Heating: A Review. Int. J. Hydrogen Energy 2015, 40, 20652083.
(12) Sil, D.; Hines, J.; Udeoyo, U.; Borguet, E. Palladium NanoparticleBased Surface Acoustic Wave Hydrogen Sensor. ACS Appl. Mater.
Interfaces 2015, 7, 57095714.
(13) Fernandez, A.; Arzac, G. M.; Vogt, U. F.; Hosoglu, F.;
Borgschulte, A.; Jimenez de Haro, M. C.; Montes, O.; Zuttel, A.
Investigation of a Pt Containing Washcoat on Sic Foam for Hydrogen
Combustion Applications. Appl. Catal., B 2016, 180, 336343.
(14) Deshpande, P. A.; Madras, G. Catalytic Hydrogen Combustion
for Treatment of Combustible Gases from Fuel Cell Processors. Appl.
Catal., B 2010, 100, 481490.
(15) Deshpande, P. A.; Madras, G. Noble Metal Ionic Sites for
Catalytic Hydrogen Combustion: Spectroscopic Insights. Phys. Chem.
Chem. Phys. 2011, 13, 708718.
(16) Sasikala, R.; Gupta, N. M.; Kulshreshtha, S. K. TemperatureProgrammed Reduction and CO Oxidation Studies over CeSn Mixed
Oxides. Catal. Lett. 2001, 71, 6973.
(17) Fornasiero, P.; Dimonte, R.; Rao, G. R.; Kaspar, J.; Meriani, S.;
Trovarelli, A.; Graziani, M. Rh-Loaded CeO2-ZrO2 Solid-Solutions as
Highly Efficient Oxygen Exchangers: Dependence of the Reduction
Behavior and the Oxygen Storage Capacity on the Structural-Properties.
J. Catal. 1995, 151, 168177.
(18) Mamontov, E.; Egami, T.; Brezny, R.; Koranne, M.; Tyagi, S.
Lattice Defects and Oxygen Storage Capacity of Nanocrystalline Ceria
and Ceria-Zirconia. J. Phys. Chem. B 2000, 104, 1111011116.
(19) Hegde, M. S.; Madras, G.; Patil, K. C. Noble Metal Ionic Catalysts.
Acc. Chem. Res. 2009, 42, 704712.
(20) Dvorak, F.; Farnesi Camellone, M.; Tovt, A.; Tran, N.-D.;
Negreiros, F. R.; Vorokhta, M.; Skala, T.; Matolinova, I.; Myslivecek, J.;
Matolin, V.; Fabris, S. Creating Single-Atom Pt-Ceria Catalysts by
Surface Step Decoration. Nat. Commun. 2016, 7, 10801.
(21) Matte, L. P.; Kilian, A. S.; Luza, L.; Alves, M. C. M.; Morais, J.;
Baptista, D. L.; Dupont, J.; Bernardi, F. Influence of the CeO2 Support
on the Reduction Properties of Cu/CeO2 and Ni/CeO2 Nanoparticles.
J. Phys. Chem. C 2015, 119, 2645926470.
(22) McFarland, E. W.; Metiu, H. Catalysis by Doped Oxides. Chem.
Rev. 2013, 113, 43914427.
(23) Wang, Y.; Yang, X.; Hu, L.; Li, Y.; Li, J. Theoretical Study of the
Crystal Plane Effect and Ion-Pair Active Center for CH Bond
Activation by Co3O4 Nanocrystals. Chin. J. Catal. 2014, 35, 462467.
(24) Xie, S.; Dai, H.; Deng, J.; Liu, Y.; Yang, H.; Jiang, Y.; Tan, W.; Ao,
A.; Guo, G. Au/3DOM Co3O4: Highly Active Nanocatalysts for the
Oxidation of Carbon Monoxide and Toluene. Nanoscale 2013, 5,
1120711219.
(25) Gwag, J. S.; Sohn, Y. Interfacial Natures and Controlling
Morphology of Co Oxide Nanocrystal Structures by Adding Spectator
Ni Ions. Bull. Korean Chem. Soc. 2012, 33, 505510.
(26) Singh, S. A.; Madras, G. Detailed Mechanism and Kinetic Study of
CO Oxidation on Cobalt Oxide Surfaces. Appl. Catal., A 2015, 504,
463475.
(27) Xin, G.; Yao-Qing, S.; Kun, C. Darkening of Zirconia: A Problem
Arising from Oxygen Sensors in Practice. Sens. Actuators, B 1996, 31,
139145.
(28) Van der Heide, P. X-Ray Photoelectron Spectroscopy: An
Introduction to Principles and Practices; John Wiley & Sons: Hoboken,
NJ, 2012.

was not detected after stability study and PdO content increased
to 10.2% from 5.3%. This indicates PtCZ and PdCZ catalysts
are highly stable and more oxidation of noble metal ions was
observed because of maintaining oxygen rich conditions than the
actual requirement according to its stoichiometry.

CONCLUSIONS
Pt- and Pd-substituted CZ catalysts are highly active for
hydrogen combustion. Because of its special features of hydrogen
and oxygen activation (analyzed from H2TPD and H2TPR
studies), 100% conversions were obtained at 100 C and sudden
light-os were observed. In this study, we found that the lattice
oxygen release is insignicant for Pt/Pd substituted CZ but is
crucial with CZ composites. The activation energies of PdCZ is
lowest compared with the other catalysts because eof the
predominant steps of O2 and H2 activation on the catalyst
surface. The noble metal ions were oxidized after 50 h stability
study. From XPS characterization the compositions of Pt4+
increased to 52.3% from 17.7% and no metallic Pd was observed
after the stability study that indicates the enhancement of
availability of oxygen vacancies. This further suggests that both
PtCZ and PdCZ catalysts are stable and durable catalysts for
hydrogen combustion. These studies gave an outlook of such
catalysts for safety applications in nuclear power plants as well as
to remove an excess amount of hydrogen at the outlet of fuel
cells.

AUTHOR INFORMATION

Corresponding Author

*E-mail: giridhar@chemeng.iisc.ernet.in. Tel: +91 80 22932321.

Fax: +91 80 23600683.
Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
The authors are grateful to the Centre for Nanoscience and
Engineering (CeNSE), IISc, for the XRD and XPD facilities and
Department of Advanced Facilities for Microscopic and
Macroscopic analysis (AFMM), IISc, for providing the TEM
facility. G.M. thanks the Department of Science and Technology
(DST), India, for the J.C. Bose fellowship.

REFERENCES

(1) Burns, P. C.; Ewing, R. C.; Navrotsky, A. Nuclear Fuel in a Reactor

Accident. Science 2012, 335, 11841188.
(2) Nakamura, A.; Kikuchi, M. What We Know, and What We Have
Not yet Learned: Triple Disasters and the Fukushima Nuclear Fiasco in
Japan. Publ. Admin. Rev. 2011, 71, 893899.
(3) Ten Hoeve, J. E.; Jacobson, M. Z. Worldwide Health Effects of the
Fukushima Daiichi Nuclear Accident. Energy Environ. Sci. 2012, 5,
87438757.
(4) Morfin, F.; Sabroux, J.-C.; Renouprez, A. Catalytic Combustion of
Hydrogen for Mitigating Hydrogen Risk in Case of a Severe Accident in
a Nuclear Power Plant: Study of Catalysts Poisoning in a Representative
Atmosphere. Appl. Catal., B 2004, 47, 4758.
(5) Sawarn, T. K.; Banerjee, S.; Kumar, S. Study of the Response of
Zircaloy- 4 Cladding to Thermal Shock During Water Quenching after
Double Sided Steam Oxidation at Elevated Temperatures. J. Nucl. Mater.
2016, 473, 237248.
(6) Reinecke, E.-A.; Tragsdorf, I. M.; Gierling, K. Studies on Innovative
Hydrogen Recombiners as Safety Devices in the Containments of Light
Water Reactors. Nucl. Eng. Des. 2004, 230, 4959.
(7) Kelm, S.; Schoppe, L.; Dornseiffer, J.; Hofmann, D.; Reinecke, E.A.; Leistner, F.; Juhe, S. Ensuring the Long-Term Functionality of
H

DOI: 10.1021/acsami.6b08019
ACS Appl. Mater. Interfaces XXXX, XXX, XXXXXX

Forum Article

ACS Applied Materials & Interfaces

(29) Shinde, V. M.; Madras, G. Nanostructured Pd Modified Ni/CeO2
Catalyst for Water Gas Shift and Catalytic Hydrogen Combustion
Reaction. Appl. Catal., B 2013, 132133, 2838.
(30) Tian, Q.; Zhang, Y.; Wu, Y. XPS Study on Mg0.9xTi0.1PdxNi (X =
0.04, 0.06, 0.08, 0.1) Hydrogen Storage Electrode Alloys after Charge
Discharge Cycles. J. Alloys Compd. 2009, 484, 763771.
(31) Bera, P.; Priolkar, K. R.; Gayen, A.; Sarode, P. R.; Hegde, M. S.;
Emura, S.; Kumashiro, R.; Jayaram, V.; Subbanna, G. N. Ionic
Dispersion of Pt over CeO2 by the Combustion Method: Structural
Investigation by XRD, TEM, XPS, and EXAFS. Chem. Mater. 2003, 15,
20492060.
(32) Fu, Q.; Saltsburg, H.; Flytzani-Stephanopoulos, M. Active
Nonmetallic Au and Pt Species on Ceria-Based Water-Gas Shift
Catalysts. Science 2003, 301, 935938.
(33) Arico, A.; Shukla, A.; Kim, H.; Park, S.; Min, M.; Antonucci, V. An
XPS Study on Oxidation States of Pt and Its Alloys with Co and Cr and
Its Relevance to Electroreduction of Oxygen. Appl. Surf. Sci. 2001, 172,
3340.
(34) Shinde, V. M.; Madras, G. Kinetic Studies of Ionic Substituted
Copper Catalysts for Catalytic Hydrogen Combustion. Catal. Today
2012, 198, 270279.
(35) Miller, J. T.; Meyers, B. L.; Modica, F. S.; Lane, G. S.; Vaarkamp,
M.; Koningsberger, D. C. Hydrogen Temperature-Programmed
Desorption (H2 TPD) of Supported Platinum Catalysts. J. Catal.
1993, 143, 395408.
(36) Leisenberger, F. P.; Koller, G.; Sock, M.; Surnev, S.; Ramsey, M.
G.; Netzer, F. P.; Klotzer, B.; Hayek, K. Surface and Subsurface Oxygen
on Pd(111). Surf. Sci. 2000, 445, 380393.
(37) Shojaee, K.; Montoya, A.; Haynes, B. S. Insight into Oxygen
Stability and Vacancy Formation on Co3O4 Model Slabs. Comput. Mater.
Sci. 2013, 72, 1525.
(38) Matsushima, T. Dissociation of Oxygen Admolecules on
Rh(111), Pt(111) and Pd(111) Surfaces at Low Temperatures. Surf.
Sci. 1985, 157, 297318.
(39) Colussi, S.; Gayen, A.; Boaro, M.; Llorca, J.; Trovarelli, A.
Influence of Different Palladium Precursors on the Properties of
Solution-Combustion-Synthesized Palladium/Ceria Catalysts for Methane Combustion. ChemCatChem 2015, 7, 22222229.
(40) Luo, J.-Y.; Meng, M.; Li, X.; Li, X.-G.; Zha, Y.-Q.; Hu, T.-D.; Xie,
Y.-N.; Zhang, J. Mesoporous Co3O4CeO2 and Pd/Co3O4CeO2
Catalysts: Synthesis, Characterization and Mechanistic Study of Their
Catalytic Properties for Low-Temperature CO Oxidation. J. Catal. 2008,
254, 310324.
(41) Duan, H.; Xu, D.; Li, W.; Xu, H. Study of the Redox Properties of
Noble Metal/Co3O4 by Electrical Conductivity Measurements. Catal.
Lett. 2008, 124, 318323.
(42) Guczi, L.; Bazin, D.; Kovacs, I.; Borko, L.; Schay, Z.; Lynch, J.;
Parent, P.; Lafon, C.; Stefler, G.; Koppany, Z.; Sajo, I. Structure of Pt
Co/Al2O3 and PtCo/Nay Bimetallic Catalysts: Characterization by in
situ EXAFS, TPR, XPS and by Activity in CO (Carbon Monoxide)
Hydrogenation. Top. Catal. 2002, 20, 129139.
(43) Cho, B. K. Chemical Modification of Catalyst Support for
Enhancement of Transient Catalytic Activity: Nitric Oxide Reduction by
Carbon Monoxide over Rhodium. J. Catal. 1991, 131, 7487.
(44) Guo, Q.; Luo, Y.; Jiao, K. Modeling of Assisted Cold Start
Processes with Anode Catalytic HydrogenOxygen Reaction in Proton
Exchange Membrane Fuel Cell. Int. J. Hydrogen Energy 2013, 38, 1004
1015.
(45) Sandeep, K. C.; Bhattacharyya, R.; Warghat, C.; Bhanja, K.;
Mohan, S. Experimental Investigation on the Kinetics of Catalytic
Recombination of Hydrogen with Oxygen in Air. Int. J. Hydrogen Energy
2014, 39, 1790617912.

DOI: 10.1021/acsami.6b08019
ACS Appl. Mater. Interfaces XXXX, XXX, XXXXXX