international journal of hydrogen energy xxx (xxxx) xxx

Available online at www.sciencedirect.com

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Development of PteCo/Al2O3 bimetallic catalyst

and its evaluation in catalytic hydrogen
combustion reaction

A.E. Kozhukhova*, S.P. du Preez, D.G. Bessarabov**

Hydrogen South Africa (HySA) Infrastructure, Faculty of Engineering, North-West University (NWU), Potchefstroom
Campus, Private Bag X6001, Potchefstroom, 2520, South Africa

highlights graphical abstract

Reactive PteCo bimetallic catalyst

was prepared for catalytic
hydrogen combustion.

Pt colloidal dispersion resulted in
deposition of Pt particles of 1.2 nm
in size.

The maximum conversion of 86%
was obtained for PteCo catalyst.

No decrease in catalytic activity
after 500 h of hydrogen combus-
tion at >270  C.

Co metal demonstrated low per-
formance even at temperatures as
low as 80  C.

article info abstract

Article history: A PteCo/Al2O3 bimetallic catalyst for catalytic hydrogen combustion (CHC) is prepared and
Received 28 July 2023 its performance is evaluated. A colloidal dispersion of a Pt-sulphite complex is used as the
Received in revised form Pt precursor instead of the conventional H2PtCl6 solution. The prepared catalyst maintains
4 September 2023 its catalytic activity at a temperature of up to 337  C for 500 h of continuous CHC. To assess
Accepted 11 September 2023 the catalytic activity and thermal conductivity of the catalyst, a catalytic cartridge for a
Available online xxx recombiner section is designed. The thermal distribution over the catalytic surface during
CHC is measured, using an infrared camera, as a function of inlet hydrogen concentration
Keywords: (0e10 vol%) and gas flow velocity (4e12 m/s). Hydrogen conversion is also determined, to
Pt-sulphite complex evaluate the catalytic activity of the prepared catalysts. Results of this study indicate that
Al2O3 support

* Corresponding author.
** Corresponding author.
E-mail addresses: Alina.Kozhukhova@nwu.ac.za (A.E. Kozhukhova), Dmitri.Bessarabov@nwu.ac.za (D.G. Bessarabov).
https://doi.org/10.1016/j.ijhydene.2023.09.119
0360-3199/© 2023 The Authors. Published by Elsevier Ltd on behalf of Hydrogen Energy Publications LLC. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Please cite this article as: Kozhukhova AE et al., Development of PteCo/Al2O3 bimetallic catalyst and its evaluation in catalytic hydrogen
combustion reaction, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.09.119
2 international journal of hydrogen energy xxx (xxxx) xxx

PteCo bimetallic catalyst
Cobalt catalyst
Catalytic hydrogen combustion
the Pt reactive metal can be partially replaced with Codthus reducing the cost of the
catalyst, without diminishing the catalyst performance towards CHC.
© 2023 The Authors. Published by Elsevier Ltd on behalf of Hydrogen Energy Publications
LLC. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).

benefit of using a PAR is that it does not require any external

1. Introduction
The excessive use of fossil fuels over past decades has resul-
ted not only in the depletion of the reserves but also defor-
estation, air pollution and global warming [1,2]. In response,
there has been intense interest in the development of an
alternative, clean and sustainable energy infrastructure.
Hydrogen is widely regarded as a sustainable, environmen-
tally friendly and economically viable energy solution [3e5].
Despite its advantage of net zero greenhouse gas and low NOx
emissions, hydrogen can be produced by splitting water using
renewable energy sources [6].
Here, the reduction of NOx emissions, especially its most
prevalent form of NO2, is of great importance. NO2 is not only
an important air pollutant by itself but it also reacts in the
presence of air to form ozone (O3) and eventually acid rain [7].
Tropospheric O3 (the lowest part of the earth's atmosphere)
has been and continues to be a significant air pollution prob-
lem. Elevated levels of NOx can cause damage to the human
respiratory system: long-term exposure to high levels can
cause chronic lung disease. In addition, NOx and SOx in the
atmosphere are captured in terrestrial moisture to form acid
rain. Acid rain, along with cloud and dry deposition, severely
affects certain ecosystems and directly affects some segments
of our economy. Many facts indicate that NOx emissions have
to be reduced. If hydrogen combustion is to be implemented
on a large scale, then catalytic hydrogen combustion (CHC)
with air is one of the pathways to significantly reduce NOx in
domestic applications.
However, the use of hydrogen poses a critical safety risk. It
is widely known that hydrogen forms explosive mixtures with
air over a wide range of hydrogen concentrations (4e75 vol%)
[8,9]. Therefore, the utilization of hydrogen in confined spaces
is accompanied by the risk of accidental hydrogen release, its
accumulation and then inadvertent ignition. When explosive
hydrogen concentrations are reached, damage to construction
as well as loss of life may occur during accidental ignition. To
mitigate the latter risk, a passive autocatalytic recombiner
(PAR) can be installed. A PAR is a device used to mitigate
accidently released hydrogen to non-flammable concentra-
tions (<4 vol% in air) through the CHC reaction. The CHC re-
action is a reaction of hydrogen oxidation generating heat and
gaseous water as a by-product that occurs according to Re-
action 1 [10]:
H2(g) þ 0.5 O2(g) ¼ H2O(g), DH ¼ 241 kJ/mol [1].
The recombiners usually comprise a rectangular box with a
catalytic section inside. The CHC reaction must initiate
spontaneously on the catalytic surface when hydrogen enters
the PAR. Preferably, the PAR should recombine hydrogen even
at extremely low concentrations (ppm levels). An added
power source/s (hence the use of “passive” in PAR). Mitigation
of the risk associated with hydrogen explosion by utilizing a
PAR can be applied to any confined spaces where the risk of
accidental hydrogen release exists (e.g., garages for hydrogen-
fuelled cars or underground mines) [11]. In addition, a PAR can
be installed with industrial water electrolysers to mitigate the
risks associated with hydrogen leaks [12,13].
A key element of a PAR is the incorporated catalyst. Metals
such as Pt and Pd are the most useful for the CHC reaction,
among which Pt shows an overall higher catalytic activity at
higher inlet hydrogen concentrations (>2 vol% hydrogen in
air) when compared to Pd counterparts. Currently, Pt-based
catalysts are predominant in commercial PARs although
they are susceptible to aggregation/sintering in the presence
of moisture at elevated temperatures. Generally, the perfor-
mance of PAR catalysts is significantly affected by the support
material. The latter improves the dispersion of the reactive
metal as well as the thermal conductivity of the catalyst,
hence, reducing the possibility of reactive metal aggregation.
This, in turn, results in high catalytic activity and stability of
the catalyst [8].
In addition, the CHC reaction has been successfully applied
as a mitigation strategy to address gas cross-over issues in
water electrolysis [14e16]. The cross-over of evolved hydrogen
from the cathode side of the electrolysis cell to the anode side
has an adverse effect on the electrolysis cell efficiency [17,18].
Moreover, if sufficient hydrogen is present at the oxygen-rich
anode side, an explosive mixture may form [12]. To mitigate
the effect of hydrogen cross-over, a recombination catalyst
(i.e., Pt black) can be incorporated into the anodic catalyst
layer [15,16,19]. By doing so, hydrogen that has crossed over to
the anode side is recombined with oxygen to form water ac-
cording to Reaction 1.
Various catalyst supports have been explored for the CHC:
e.g., Ni foams, g-Al2O3, ZrO2, TiO2, SiC foam, stainless steel
(SS) mesh, Ti mesh, Al/anodized aluminium oxide (Al/AAO)
and CeeZreY mixed oxide (CZY) [20e32]. Based on the find-
ings of previous studies, the following can be deducted: (i) the
catalyst support plays a key role in catalysts’ performance, (ii)
the support should be able to stabilize reactive metals at
elevated temperatures associated with reaction 1, (iii) the
support material should be resistant to chemical attack (e.g.,
sulphur, CO, water vapour) and (iv) the support should be
economically viable (low cost) [8,30]. Among the mentioned
supports and preferred properties, the SiC foam, Al/AAO and
CZY supports are considered to be the most suitable.
A Pt-based SiC foam catalyst was explored for CHC appli-
cations by Fernandez et al. [33]. The catalyst initiated the CHC
reaction at room temperature, suggesting high catalytic ac-
tivity of the Pt/SiC foam catalyst. A hydrogen conversion of
100% was achieved during CHC.

Please cite this article as: Kozhukhova AE et al., Development of PteCo/Al2O3 bimetallic catalyst and its evaluation in catalytic hydrogen
combustion reaction, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.09.119
 international journal of hydrogen energy xxx (xxxx) xxx
A comparative study on the sintering of Pt-based catalysts
supported on Al2O3 and CZY was performed by Nagai et al.
[34]. The Pt/CZY catalyst did not sinter when calcined at
800  C, whereas Pt/Al2O3 catalyst showed significant sintering
(under similar conditions). The absence of sintering of Pt on
CZY support was ascribed to a strongly reactive metal (Pt
oxide)esupport interaction; the PteOeCe bond acted as an
anchor and inhibited Pt migration under oxidizing conditions
at elevated temperatures. The authors also determined the
correlation between the electron density of oxygen in the
support and the strength of the Pt oxideesupport interaction
for different supports. The Pt oxideesupport interaction
strengthened as the electron density increased in the
following order: SiO2, Al2O3, ZrO2, TiO2, CeO2 and CZY.
In an earlier study by Kozhukhova et al., Pt/CZY/AAO
catalyst was prepared and evaluated for CHC applications
[31,32]. The Pt/CZY/AAO catalyst demonstrated high catalytic
activity towards CHC: hydrogen conversion up to 92% was
reached. The authors emphasized the significance of the Al/
AAO support present in the catalyst. Due to the high thermal
conductivity of the Al/AAO support, the possibility of hot spot
(areas with a temperature higher than the average surface
temperature) formation was significantly reduced. This, in
turn, resulted in a uniform temperature distribution over the
catalytic surface, with a maximum temperature gradient of
22.7  C over a catalytic surface of 18 cm2 in a 10 vol% hydrogen
flow at 12 m/s gas flow velocity [32].
In recent years, bimetallic catalysts have attracted
attention for catalytic combustion reactions due to their
improved catalytic activities when compared to mono-
metallic catalysts [10,35e38]. The effect of additives on the
catalytic activity of a Pt/Al2O3 catalyst for propane combus-
tion was investigated by Yazawa et al. [36]. They demon-
strated that the catalytic activity of the catalyst increased
with an increase in the electronegativity of the additives.
This was ascribed to the fact that the additives control the
oxidation state of Pt (a higher oxidation resistance of Pt is
observed with an increase in the electronegativity of addi-
tives), therefore, affecting the catalytic activity. For example,
in a study by Lalik et al., Li and Cs additives to Pd/Al2O3
catalysts were studied for hydrogen combustion [35]. It was
found that both the PdeLi and PdeCs catalysts showed high
activity towards CHC. However, in the presence of water
vapour, these catalysts became deactivated, and their cata-
lytic activity could not be restored by heating to 50  C.
The use of PteSn bimetallic catalysts supported on Al2O3
and ZneAleO was explored for the dehydrogenation of pro-
pane, combined with selective hydrogen combustion, by
Kaneko et al. [37]. They found that PteSn bimetallic catalysts
had higher catalytic activity towards selective hydrogen com-
bustion when compared to Pt-only catalysts. The authors also
demonstrated that the addition of Zn to the PteSn/Al2O3 cata-
lyst further enhanced its catalytic activity. However, the
bimetallic catalyst showed severe degradation after 1 h of CHC,
ascribed to the formation of carbon on the catalytic surface.
Additives such as Co have been extensively tested for their
ability to increase the catalytic activity of PGM-based catalysts
for preferential CO oxidation [39e43]. For example, Jain et al.
tested Pt/Al2O3 with Cr, Mn, Fe, Co, Ni, Cu and Sn additives
(M:Pt atomic ratio 1:2, where M is Cr, Mn, Fe, Co, Ni, Cu or Sn)
Please cite this article as: Kozhukhova AE et al., Development of PteCo/Al2O3 bimetallic catalyst and its evaluation in catalytic hydrogen
combustion reaction, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.09.119
3
for preferential oxidation of CO in hydrogen. They found a
significant enhancement in catalytic activity for the Fe- and
CoePt bimetallic catalysts and insignificant changes in cata-
lytic activity for the Mn-, Sn-, Cu- and NiePt catalysts [41]. This
increase in catalytic activity was likely due to the changes in
the adsorption characteristics, either through electron trans-
fer or resulting bimetallic characteristics/effects (e.g., syner-
getic effect) [39,44,45].
In a study by Suh et al., Co, Ni and Mn were evaluated as
additives to improve the catalytic activity of a Pt catalyst for
CO oxidation [43]. Here, the catalytic activities of bi-metallic
catalysts increased as follows: PteMn, PteNi, PteCo. In
addition, the temperature-programmed reduction (TPR) of
the PteCo catalyst was performed to investigate the reason
for the increased catalytic activity of the catalyst. The
following was deduced from the results: (i) the major
reduction peak of PteCo catalyst was shifted to <500  C
when Co was added to Pt; (ii) peaks corresponding to the
reduction of Co only were not observed distinctly within the
PteCo TPR pattern, suggesting that Co atoms were located
around the Pt. It has been reported that Pt and Co form a
new phase with a lower reduction temperature, resulting in
the increased catalytic synergetic effect [43]. Moreover,
PteCo catalysts have been successfully applied in
commercially available proton exchange membrane fuel cell
vehicles (FCV) such as Toyota Mirai. The oxygen reduction
reaction activity was enhanced by a factor of 1.8 over the
2008 FCV model via optimization of the composition of the
PteCo catalyst [46].
In addition, Co-containing catalysts were found to be
promising water-oxidation catalysts with low overpotential
and long-term oxidative stability [47,48].
In the present study, the preparation of a PteCo bimetallic
catalyst supported on Al2O3 is proposed for its application in
CHC technologies such as in a PAR. The bimetallic catalyst
was prepared using the wet impregnation method and then
characterized using energy-dispersive X-ray spectroscopy
(EDS) and transmission electron microscopy (TEM). The cata-
lytic activity and thermal conductivity of the PteCo bimetallic
catalyst were evaluated in 0e10 vol% hydrogen/air mixture in
an in-house developed recombiner section. Furthermore, the
stability and durability were evaluated during prolonged
hydrogen exposure (500 h).
2. Experimental
2.1. Preparation of PteCo/Al2O3 catalyst and its
characterization
An extruded g-Al2O3 catalyst support was purchased from
Clariant (Clariant International Ltd, USA). The PteCo bime-
tallic catalyst supported on Al2O3 was prepared by the wet
impregnation method. The Pt precursor was synthesized
using hexachloroplatinic acid (H2PtCl6.6H2O, ~38% Pt basis;
Sigma-Aldrich, Italy) according to the sulphite complex route
[49]. In short, Pt-sulphite complex was prepared by the re-
action of hexachloroplatinic acid solution with sodium
dithionite (Na2S2O4; Sigma-Aldrich, Germany). Before adding
the solution of sodium dithionite, the pH of the Pt-containing
4 international journal of hydrogen energy xxx (xxxx) xxx

solution was raised to 7.0. After adding the sodium dithion-
ite, the pH of the obtained solution was 3.0 and the colour
was a clear dark orange. Next, the pH of the solution was
raised to 6.0 using a 10% NaOH solution (NaOH; CC Imelmann
(Pty) Ltd, South Africa). A precipitate Na6Pt(SO3)4 was then
obtained; it was filtered, washed with distilled water and
then dried at 80  C for 2 h. The prepared Pt salt was dissolved
in 0.5 M H2SO4 (H2SO4, 98%; Rochelle Chemicals, South Af-
rica), diluted with distilled water to 500 ml and then the pH
was adjusted to 5.0 using a 10% NaOH solution. The resulting
colloidal dispersion contained 600 ppm Pt, as determined by
inductively coupled plasma-optical emission spectroscopy
(ICP-OES). ICP-OES was performed using an ICP-OES instru-
ment (5110; Agilent, USA) coupled with a CCD detector
(VistaChip II; Agilent, USA).
The Pt/Al2O3 catalyst was then prepared by wet impreg-
nation to obtain a 0.2 wt% Pt loading. To prepare a PteCo
bimetallic catalyst, Co was deposited on the Pt/Al2O3 catalyst
by wet impregnation using a 0.1 g/L Co(NO3)2 solution
(Co(NO3)2.6H2O, 98%; Sigma-Aldrich, UK). The prepared
PteCo bimetallic catalyst had a Pt:Co atomic ratio of 3:1.
Scanning electron spectroscopy (SEM) was used to
characterize the PteCo catalyst surface. SEM analysis was
performed using a FEI Quanta FEG 250 field emission gun
scanning electron microscope (Thermo Fisher Scientific, USA)
equipped with an Oxford EDS detector for elemental
quantification. EDS was used to evaluate the Pt:Co ratio in the
prepared PteCo/Al2O3 catalyst. The PteCo/Al2O3 catalyst was
characterized by TEM before and after the stability test to
evaluate catalyst degradation. TEM analyses were carried out
using a Tecnai F20 FEI instrument (Thermo Fisher Scientific,
USA).
2.2. Catalyst stability test
The Pt/Al2O3 and PteCo/Al2O3 catalysts were subjected to a
stability procedure to evaluate the stability of the catalyst
during prolonged CHC at elevated temperatures. In this case,
an elevated temperature refers to the maximum observed
temperature a specific catalyst can reach under a certain set of
experimental parameters. The experimental setup used for
the catalyst stability test was reported in an earlier paper of
ours [50]. A summary only of the experimental setup is given
here. Hydrogen was generated from an in-house developed
and produced hydrogen generator (HySA Infrastructure,
South Africa) and was fed from the bottom of the experi-
mental setup. The flow rate was kept at 100 NL/min for all
tests. The hydrogen nozzle was placed 5 mm below a SS mesh,
which was used to keep the catalyst in place. The generated
hydrogen was mixed with ambient air before reaching the
catalyst. A K-type thermocouple was placed inside the top
tube (length 15 cm) to make contact with the catalysts. Tem-
perature measurements were recorded every 1 s throughout
the test. The hydrogen concentration after CHC was measured
using a 0e100 vol% hydrogen sensor (NEO986A; NEO Hydrogen
Sensors GmbH, Germany).
2.3. Catalytic test and thermal imaging
The prepared catalysts were tested in an in-house-developed
recombiner section testing station (HySA Infrastructure,
South Africa) [30]. The experimental setup is schematically
presented in Fig. 1.
The general operating principle of the experimental setup
has been discussed in our earlier papers [31,32,50]. The testing

Fig. 1 e Schematic of the experimental setup (front and side views) used to determine the catalytic activity and thermal
conductivity of the catalysts.

Please cite this article as: Kozhukhova AE et al., Development of PteCo/Al2O3 bimetallic catalyst and its evaluation in catalytic hydrogen
combustion reaction, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.09.119
 international journal of hydrogen energy xxx (xxxx) xxx
station represents a rectangular box (28.0  42.0  4.5 cm) with
a cartridge-type catalytic section inside. The hydrogen/air
mixture is supplied from the inlet pipe (1) placed at the bottom
of the experimental setup. High-purity hydrogen (>99.9%
hydrogen; HySA Infrastructure, South Africa) and compressed
air were utilized as the inlet gas mixture. The inlet conditions,
such as flow rate and hydrogen/air volume ratio, were
controlled by digital mass flow controllers (EL-FLOW F-201AV,
Hi-Tec Bronkhorst, The Netherlands). To ensure relatively
uniform gas flow distribution, the mixing plate (2) was placed
above the inlet pipe (1). Thereafter, the gas mixture reaches
the catalyst cartridge (3). The catalyst cartridge (3) consists of
three rectangular sections (also referred to as rows)
(1.0  16.0  2.5 cm) made of SS mesh, filled with the catalyst.
The catalyst cartridge (3) was fixed 8 cm above the mixing
plate (2) using the catalyst holder (4). Hydrogen concentration
before and after CHC was evaluated with six hydrogen sensors
(5) (XEN-5320; Xensor Integration, The Netherlands) posi-
tioned below and above the catalyst cartridge, as schemati-
cally shown in Fig. 1. Hydrogen measurements were logged
every 1 s, using LabVIEW software. The hydrogen conversion
was calculated using the following equation:
CH2 ;0  CH2 ;t
Hydrogen conversion; % ¼ *100% (1)
CH2 ;0
where CH2 ;0 and CH2 ;t are the molar amounts of hydrogen at
time 0 and t (steady-state conditions).
The thermal distribution of the catalyst was determined
using a high-resolution IR camera (M100hd; Telops, Canada).
The camera was fitted with a lens to capture data within a
temperature range 0e325  C and an optional lens to capture
data within the range 173e600  C. Thermal data were recorded
every 1 s, using Reveal IR software.
3. Results and discussion
3.1. Characterization of Pt/Al2O3 and PteCo/Al2O3
catalysts
In previous works by the authors, hexachloroplatinic acid
solution was used as a Pt precursor solution in the wet
impregnation method. Combination of the use of the con-
ventional precursor and the wet impregnation method, fol-
lowed by the reduction in a hydrogen atmosphere, resulted in
the formation of Pt particles sized 3e5 nm on the Al2O3 surface
[29,30]. In the present study, Pt particles were obtained by
deposition of a Pt-containing colloidal dispersion followed by
the reduction procedure. To investigate the effect of the pre-
cursor nature (solution vs colloid), the prepared catalysts were
analyzed by TEM. Fig. 2 shows a representative TEM image of
the Pt/Al2O3 catalyst (a), Pt particle size distribution (b), TEM
image of the PteCo/Al2O3 bimetallic catalyst (c) and the cor-
responding PteCo particle size distribution (d) before expo-
sure to CHC.
Fig. 2a shows a TEM image of the Pt/Al2O3 catalyst prepared
using a colloidal Pt precursor. In this figure, Pt particles are
represented as prominent circular black particles. The average
particle size of Pt, determined from TEM images taken at
different spots of three samples, was 1.29 ± 0.24 nm. The
Please cite this article as: Kozhukhova AE et al., Development of PteCo/Al2O3 bimetallic catalyst and its evaluation in catalytic hydrogen
combustion reaction, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.09.119
5
corresponding Pt particle size distribution is shown in Fig. 2b.
The distribution is narrow and it peaks at a particle size value
of 1.5 nm, for 72% of all the Pt particles measured. In addition,
the distribution obtained in the present study was narrower,
compared to that obtained for the Pt catalyst prepared using Pt
precursor solution [29], suggesting that the colloidal Pt pre-
cursor resulted in more uniform Pt particle deposition and
smaller standard deviation. Furthermore, the average Pt par-
ticle size prepared using the colloidal precursor was deter-
mined to be smaller than that of the Pt catalyst prepared using
the conventional hexachloroplatinic acid solution (1.29 vs
3 nm). The reason for this may be that Pt forms finely
dispersed particles, 1.5e2.5 nm in size, in the colloidal
dispersion, according to Petrow and Allen [51]. Therefore,
finely dispersed Pt particles could readily be deposited onto
the Al2O3 surface. As the conditions of the reduction proced-
ure in the present work were similar to those used in our
previous works (350  C, 150 NmL/min hydrogen flow), it is
likely that the difference in the Pt particle size and distribution
was caused by the colloidal nature of the Pt precursor [30e32].
It can be noted here, that the colloidal Pt precursor may be
used in different applications where highly dispersed Pt-based
catalysts are required to achieve high performance, for
example for liquid organic hydrogen carrier (LOHC) dehydro-
genation reaction [52].
Lastly, Fig. 2c represents the TEM image of the PteCo/Al2O3
bimetallic catalyst. The average PteCo bimetallic particle size
was determined to be 1.25 ± 0.25 nm. The PteCo particle dis-
tribution (Fig. 2d) is similar to that of Pt alone, and peaks at a
particle size value of 1.5 nm, for 75% of all the PteCo particles
measured. Here, the Pt and Co particles were not differenti-
ated due to the limitations of the TEM technique, although
EDS was applied to confirm Co deposition onto the Pt/Al2O3
catalyst surface as well as to verify the Pt:Co ratio.
Fig. 3 shows a SEM image of the PteCo catalyst surface, and
EDS mapping where red and green colours represent the
detected Pt and Co, respectively. The Pt and Co were uniformly
distributed on the Al2O3 surface. Then, EDS elemental analysis
was performed to confirm that the atomic Pt:Co ratio in the
prepared catalyst met the desired value of 3:1. Results gave the
atomic Pt:Co ratio in the prepared catalyst as 2.8:1, thus sug-
gesting that the desired PteCo bimetallic catalyst had indeed
been prepared. EDS results for three samples of PteCo catalyst
are presented in Table 1.
3.2. Catalyst stability test
Stability (i.e., resistance to chemical attacks and thermal
degradation) and durability (i.e., ability to maintain the cata-
lytic performance) are the key characteristics of a catalyst if it
is intended for use in catalytic combustion applications,
particularly if the intended applications are safety-related
(e.g., PAR) and for domestic uses (e.g., cooker, heater). Good
stability and durability characteristics determine the lifetime
of the catalystdthe longer the catalyst maintains its catalytic
activity, the less frequently it has to be replaced. A suitable
path to follow to check catalyst stability and durability is to
subject the catalyst to prolonged CHC (previously defined as a
stability test) at elevated temperatures [29e31]. In this
research work, a 500 h stability test was performed for Pt/
6 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 2 e (a) TEM image of Pt/Al2O3 catalyst and (b) corresponding Pt particle size distribution, (c) TEM image of PteCo/Al2O3
bimetallic catalyst and (d) corresponding PteCo particle size distribution before exposure to CHC.

Al2O3 and PteCo/Al2O3 catalysts (5 g each) using an in-house
developed experimental setup [50].
Fig. 4 shows the combustion temperature profile during
500 h of CHC for the catalysts Pt/Al2O3 and PteCo/Al2O3. In the
case of the Pt/Al2O3 catalyst (Fig. 4a) it is clear that the catalyst
maintained its catalytic activity during the entire test. As the
stability test was performed in an open atmosphere, the
temperature fluctuations in the combustion profile were
attributed to change in environmental temperature, natural
airflow, and day/night cycles [29e31]. The average combustion
temperature was determined to be 337.4 ± 7.0  C. A similar
combustion temperature profile was observed for the PteCo/
Al2O3 catalyst (Fig. 4b). The average combustion temperature
was determined to be 272.9 ± 6.6  C.
The difference in the combustion temperatures and, there-
fore, in the catalytic activities can be ascribed to the formation
of the PteCo (Pt3Co) metal alloy on the surface of the PteCo/
Al2O3 catalyst. The formation of the PteCo alloy had been re-
ported in other studies [40,42,53,54]. It is expected that,
compared to the pristine Pt catalyst, this alloy retains Pt reac-
tive sites in a reduced oxidation state, where Pt oxidation takes
place. Therefore, catalyst deactivation is prevented/limited. In
a study by Dosso et al., the catalytic activity of Pt, PteCo and
PteNi catalysts was compared for the reforming of oxygenated
hydrocarbons, specifically for the cyclohexane dehydrogena-
tion reaction [55]. The catalysts were then analyzed using the
CO chemisorption technique. The active surface areas of the
PteNi and PteCo bimetallic catalysts were lower than that of
the pristine Pt catalyst. Ko et al. reported a similar observation
for the PteNi catalyst [56]. They determined that the addition of
Ni to Pt catalyst decreased the number of active surface sites for
CO chemisorption. However, the active surface area of the
PteNi catalyst increased with an increase in the reduction
temperature from 150 to 300  C. In addition, in a study by

Please cite this article as: Kozhukhova AE et al., Development of PteCo/Al2O3 bimetallic catalyst and its evaluation in catalytic hydrogen
combustion reaction, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.09.119
 international journal of hydrogen energy xxx (xxxx) xxx 7

Fig. 3 e (a) SEM image of PteCo/Al2O3 catalyst, and corresponding EDS mapping of (b) Pt and (c) Co.

Alconada and Barrio, it has been demonstrated that the PteCo temperature might be the fact that the Pt3Co metal alloy
bimetallic catalyst had higher performance and selectivity to- formed on the surface of the PteCo bimetallic catalyst and
wards the dehydrogenation reaction of LOHC when compared could potentially affect the hydrogen adsorption and activa-
to the Pt catalyst due to the PteCo synergetic effect [53]. tion energies. This, in turn, results in different reaction rates,
In the present research work, however, the addition of Co which has a significant effect on the combustion temperature.
to Pt catalyst resulted in a lower combustion temperature Therefore, additional assessment is required to compare the
when compared to the pristine Pt catalyst determined at the catalytic activity of the PteCo bimetallic catalyst and the
same hydrogen flow. This does not necessarily serve as an pristine Pt catalyst. Specifically, hydrogen conversion may
indication of the lower catalytic activity of the PteCo bime- serve as an indication of the catalytic activity if measured
tallic catalyst, however. The reason for the lower combustion under similar/equal experimental conditions (hydrogen flow,
gas flow velocity, etc.).
The hydrogen conversion values during CHC for both the Pt
Table 1 e Elemental analysis of the PteCo/Al2O3 catalyst: and PteCo catalysts were therefore measured: values were
EDS results (atomic %).
99.9% and 98.5% for the Pt and PteCo catalysts, respectively.
Spectrum O Na Al S Co Pt Pt:Co ratio This suggests that the catalysts have relatively similar cata-
Sample 1 62.57 2.57 22.95 1.05 0.14 0.38 2.71 lytic activity. It is likely that the formation of the PteCo metal
Sample 2 55.63 1.71 17.32 0.65 0.09 0.27 3.00 alloy on the surface of the PteCo/Al2O3 catalyst will result in
Sample 3 62.18 2.36 22.58 0.89 0.13 0.37 2.85 lower combustion temperature. The formation of the Pt3Co
Average 60.12 2.21 20.95 0.86 0.12 0.34 2.83
metal alloy on the catalyst surface was not confirmed in the
Std. deviation 3.9 0.45 3.15 0.2 0.03 0.06
present studydfurther investigation into this should be
Max. 62.57 2.57 22.95 1.05 0.14 0.38
Min. 55.63 1.71 17.32 0.65 0.09 0.27 considered as future research.
To further assess the catalytic activity and stability of the
*All results are presented in at%.
catalysts, the start-up characteristics such as initiation time

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8 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 4 e Combustion temperature profiles of catalysts during 500 h of CHC at a hydrogen flow rate of 100 NmL/min: a) Pt/
Al2O3 and (b) PteCo/Al2O3.

(time required to initiate CHC) and temperature (temperature
at which CHC initiates), as well as stabilization time (time at
which combustion temperature stabilizes), were determined
before and after exposure to stability tests. Should the catalyst
show any time delay associated with achieving the initiation
time and temperature, then the accumulation of explosive
mixtures with air is likely. Determination of start-up charac-
teristics is therefore highly important.
Fig. 5 shows the combustion temperature profiles of Pt/
Al2O3 and PteCo/Al2O3 catalysts during the first 600 s of CHC
before and after CHC exposure. Fig. 5a shows that the CHC
reaction initiated spontaneously during the first 35e40 s
(initiation time) after hydrogen exposure, before and after the
stability test. The initiation temperature in this set of tests
was in the range 23e25  C. The figure further shows that the
stabilization time for the fresh and the stability-tested

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 international journal of hydrogen energy xxx (xxxx) xxx
Fig. 5 e Combustion temperature profiles of catalysts during the first 600 s of CHC before and after the stability tests: (a) Pt/
Al2O3 and (b) PteCo/Al2O3.
catalysts was approximately 500 s. The stabilization temper-
atures were 313  C and 304  C for the fresh and stability-tested
catalysts, respectively. The maximum standard deviation
between the fresh and stability test values was 13.1  C.
Fig. 5b presents combustion temperature profiles before
and after the stability test for the PteCo/Al2O3 catalyst. Fig. 5b
shows that the CHC reaction initiated during the first 40 s
before and after the stability tests. The initiation temperature
was in the range 24e26  C. The stabilization time for the
PteCo/Al2O3 catalyst was approximately 400 s, before and
after the stability test. The stabilization temperatures deter-
mined for the fresh and stability-tested catalysts were 288  C
and 273  C, respectively. The maximum standard deviation
between values for fresh and stability-tested catalysts was
13.5  C.
It was therefore deduced that the Pt/Al2O3 and PteCo/Al2O3
catalysts retained their catalytic activities. The small deviations
in temperature profiles of fresh and stability-tested catalysts
could be ascribed to the onset of catalyst deactivation (Pt ag-
gregation). To investigate this further, the Pt/Al2O3 and PteCo/
Al2O3 stability-tested catalysts were analyzed by TEM.
Fig. 6 shows TEM images of the stability-tested catalysts (Pt
and PteCo) and the corresponding particle size distributions.
Fig. 6a and c presents TEM images of the Pt/Al2O3 and PteCo/
Al2O3 catalysts. When comparing the surface morphology of
the fresh catalysts (Fig. 2a and c) and stability-tested catalysts
(Fig. 6), no obvious changes are evident. The average Pt par-
ticle size for the stability-tested Pt/Al2O3 catalyst determined
from TEM images was 1.29 ± 0.37 nm, while the average PteCo
bimetallic particle size for the stability-tested PteCo/Al2O3
catalyst was 1.30 ± 0.28 nm. Although the particle size distri-
bution presented in Fig. 6b and d shows that the peaks
decreased from 72 to 65% and from 75 to 58% for the Pt and
PteCo particles, respectively.
Therefore, it can be concluded, based on the observed
minimal difference between the properties of the pre- and
post-stability-tested catalysts and that reactive metal sinter-
ing did not occur, that no evident catalyst degradation
occurred during 500 h of high-temperature CHC tests. More-
over, considering the effects of water vapour on Pt metal at
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combustion reaction, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.09.119
9
elevated temperatures, it is clear that the bond energy be-
tween the reactive metal particles and the support material
was sufficient to anchor the reactive metal particles. In a study
by Peng et al., it was found that water vapour had no detri-
mental effect on the performance of PteCo/Al2O3 catalyst
during CO and toluene oxidations at 150e190  C [57]. There-
fore, the occurrence of reactive metal aggregation is unlikely
to occur if the catalysts were to be employed for applications
under similar conditions (i.e., CHC temperature of 270e340  C,
levels of exposure to water vapour) for periods » 500 h.
3.3. Catalytic activity of pristine Co catalyst towards
CHC
In a study by Dosso et al., the formation of the CoOx (e.g., CoO,
Co3O4) active phase was observed during the calcination at
450  C and the reduction in a hydrogen atmosphere at 500  C
treatments, in addition to the formation of the PteCo metal
alloy phase [55]. According to Guczi et al., Co/Al2O3 can be
reduced in two steps from Co3þ to Co2þ at approximately
400  C and from Co2þ to Co0 at approximately 600  C [54].
Therefore, it was considered of interest to determine the
contribution of the CoOx active phase to the catalytic activity
of the PteCo bimetallic catalyst. In the present work, a Co/
Al2O3 catalyst was prepared similarly to the Pt and PteCo/
Al2O3 catalysts; the Co loading in the resulting catalysts was
0.2 and 2 wt%. The catalysts were tested at the hydrogen flow
of 100 NmL/min. The corresponding combustion temperature
profiles during 1 h of CHC are presented in Fig. 7.
The 2 wt% Co catalyst demonstrated higher catalytic ac-
tivity towards CHC than the 0.2 wt% Co catalyst. The
maximum temperature obtained during 1 h of CHC for the
2 wt% Co catalyst peaked at 73.9  C after 13 min and 25 s, while
the maximum temperature of 30.1  C was obtained for the
0.2 wt% Co catalyst when the time was 9 min and 27 s.
Thereafter, both the 0.2 and 2 wt% catalysts cooled to room
temperature. The observed discrepancies in the combustion
temperature profiles during CHC were due to fluctuations in
the ambient air environment (similar to what was observed in
Fig. 4). The initial temperature in this set of experiments was
10 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 6 e (a) TEM image of the stability-tested Pt/Al2O3 catalyst and (b) Pt particle size distribution, (c) TEM image of the
stability-tested PteCo/Al2O3 catalyst and (d) PteCo particle size distribution.

Fig. 7 e Combustion temperature profiles of Co/Al2O3
catalysts (a) 0.2 wt% and (b) 2 wt%, during 1 h of CHC,
including the first 200 s (inset).
in the range 24e26  C. In the cases of the Co 0.2 and 2 wt%, the
CHC reaction initiated spontaneously during the first 30e40 s,
suggesting relatively high catalytic activity of Co metal to-
wards CHC. However, after approximately 13 min of the CHC
test, the combustion temperature began to decrease, indi-
cating a loss in the catalytic activity for both catalysts. They
may be ascribed to the Co sintering. To confirm this, the 2 wt%
Co catalyst was analyzed by TEM (see Fig. 8).
The d-spacing of the particles determined on the surface of
the Co catalyst before and after the stability test were 2.04 and
2.17 nm, which is in agreement with d-spacing values for
Co3O4 (004) and CoO (002) [58]. The particle size before expo-
sure of the Co catalyst to CHC was found to be 2.12 ± 0.27 nm,
while the particle size after 1 h of CHC was 8.61 ± 0.82 nm. The
increase in Co particle size suggested that the Co particles
aggregate during CHC, even at temperatures <80  C.

Please cite this article as: Kozhukhova AE et al., Development of PteCo/Al2O3 bimetallic catalyst and its evaluation in catalytic hydrogen
combustion reaction, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.09.119
 international journal of hydrogen energy xxx (xxxx) xxx 11

Fig. 8 e TEM images of 2 wt% Co/Al2O3 catalyst (a) before CHC, (b) the IFFT of the area of interest (Co particle) showing FFT
pattern, and (c, d) TEM images of the 2 wt% Co/Al2O3 catalyst after 1 h of CHC showing Co aggregates. (FFT: Fast Fourier
Transform; IFFT: Inverse FFT).

Based on the results presented in this section, we conclude
that the pristine Co catalyst is unsuitable for high-
temperature combustion applications. There is limited liter-
ature on the subject of pristine Co catalysts, and their prepa-
ration, for CHC applications. Nevertheless, the preparation
method used for the PteCo bimetallic catalyst presented in
this study (high dispersion of the reactive metal and Pt:Co
ratio of 3:1) limited excess formation of the CoOx phase, and
hence the detrimental effect thereof on the catalytic activity
(as is shown in Fig.. 4b, 5b and 6b).
3.4. Catalytic test and thermal imaging
To further assess the catalytic activity and thermal conduc-
tivity, the prepared catalyst was placed in an in-house-
developed cartridge-type recombiner section (see Fig. 1). A
similar cartridge was used in our previous work [50]. In the
present study, however, this cartridge was modified: instead
of using one 7-cm-thick section, three thinner 1-cm rows were
used, and evaluated. The reason was to reduce the tempera-
ture gradient by disseminating the reactive sites (i.e., intro-
ducing open spaces between the rows).
A catalytic test was carried out at 0e10 vol% hydrogen/air
mixture and gas flow velocities 4, 6, 8, 10 and 12 m/s. The
temperature distribution over the catalytic cartridge was
determined using an IR camera. An example of the IR camera
temperature mapping during CHC on the PteCo/Al2O3 catalyst
surface at the inlet hydrogen flow of 5 vol% in the air is pre-
sented in Fig. 9. It shows stabilized temperatures over Rows
1e3 of the catalytic cartridge at different inlet gas flow

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12 international journal of hydrogen energy xxx (xxxx) xxx

velocities. The IR region is presented on a colour scale, with
blue and yellow representing low and high temperatures,
respectively. In this case, the yellow colour corresponds to
high temperatures and can be observed only on the catalyst-
filled cartridge rows.
Fig. 9a shows a temperature increase only over Rows 1 and
2, suggesting that the CHC reaction mainly occurs over Rows 1
and 2 (due to low inlet gas flow velocity of 4 m/s). Fig. 9bee
shows the onset of CHC over Row 3 of the catalytic cartridge
with the brightest spot (i.e., the highest temperature) captured
at the inlet gas flow velocity of 8 m/s (Fig. 9c).
These results are in good agreement with our previous
findings [50]; the maximum combustion temperatures are
typically observed at the inlet gas flow velocities of 8e10 m/s,
thereafter (at >10 m/s), the so-called cooling effect occurs,
which results due to a reduced residence time of the fuel on
the catalytic surface. The occurrence of the cooling effect
results in lower combustion temperatures and conversions
[50].
Fig. 10 presents the quantified temperature distribution of
the thermal mapping obtained over Rows 1e3 of the catalytic
cartridge filled with PteCo/Al2O3 bimetallic catalyst, using the
IR camera (0e10 vol% hydrogen/air mixture and 4, 6, 8, 10 and
12 m/s gas flow velocities). The maximum combustion tem-
peratures obtained at different inlet gas flow velocities were
476, 506, 525, 483 and 439  C at 4, 6, 8, 10 and 12 m/s, indicated
as red dashed lines in Fig. 10. It is evident that the combustion
temperature increased as the inlet gas flow velocity increased
from 4 to 8 m/s. The temperature peaked at 525  C at a flow
velocity of 8 m/s. By further increasing the flow velocity from 8
to 12 m/s, the temperature decreased from its maximum to
439  C. This observation was ascribed to the cooling effect, as
mentioned earlier.
Fig. 10a shows the combustion temperatures over Rows
1e3 at the inlet gas flow velocity of 4 m/s. The combustion
temperature increased over Rows 1 and 2 with increasing
hydrogen concentration. The combustion temperature over
Row 3 increased when the hydrogen concentration increased
from 1 to 5 vol%, whereafter it remained practically un-
changed. The figure further shows that the highest combus-
tion temperature was obtained over Row 1 and the lowest over
Row 3. This was expected, as Row 1 is positioned close to the
hydrogen inlet and exposed to the major hydrogen fraction.
Thereafter, the unreacted hydrogen passes through the first
row, reaching Row 2. Lower combustion temperatures were
recorded due to the smaller hydrogen fraction reaching Row 2.
The lowest combustion temperature was therefore expected
over Row 3. The maximum combustion temperature of 476  C
was obtained at the inlet hydrogen concentration of 10 vol%
and gas flow velocity of 4 m/s. A similar observation was made
for the test carried out at 0e10 vol% and gas flow velocities of 6
and 8 m/s (Fig. 10b and c).

Fig. 9 e IR camera temperature mapping of the cartridge filled with PteCo/Al2O3 catalyst at 5 vol% hydrogen flow and (a) 4, (b)
6, (c) 8, (d) 10 and (e) 12 m/s gas flow velocity. As shown in (a), Row 1 is closest to the hydrogen inlet and Row 3 is at the top of
the cartridge. (Blue colour: low temperatures; yellow colour: high temperatures). (For interpretation of the references to
colour in this figure legend, the reader is referred to the Web version of this article.)

Please cite this article as: Kozhukhova AE et al., Development of PteCo/Al2O3 bimetallic catalyst and its evaluation in catalytic hydrogen
combustion reaction, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.09.119
 international journal of hydrogen energy xxx (xxxx) xxx 13

Fig. 10 e Combustion temperatures of PteCo/Al2O3 catalyst determined at hydrogen concentrations 0e10 vol% and gas flow
velocity (a) 4 m/s, (b) 6 m/s, (c) 8 m/s, (d) 10 m/s, and (e) 12 m/s. Each horizontal dashed line corresponds to the maximum
measured temperature for each experimental set.

However, as observed in Fig. 10cee, the combustion tem-
perature for Rows 1 and 2 decreased at a gas flow velocity of
8e12 m/s, while an increase was observed for Row 3. The
maximum combustion temperatures were 260, 194 and 250  C
at the inlet gas flow velocities of 8, 10 and 12 m/s, respectively.
Therefore, due to the high gas flow velocity, the hydrogen
fraction that passed through Rows 1 and 2 could still be
combusted (at least partially) over Row 3.
To further assess the catalytic activity of the prepared
catalyst, the hydrogen conversion over the entire cartridge
was measured during CHC. Results are shown in Fig. 11. The
hydrogen conversion increased with an increase in the inlet
hydrogen concentration at all inlet gas flow velocities
considered here. The hydrogen conversion values were
similar for the inlet gas flow velocities of 4, 6, 8, and 10 m/s,
whereas the hydrogen conversion determined at 12 m/s gas

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14 international journal of hydrogen energy xxx (xxxx) xxx

A similar catalytic test was performed for the Pt/Al2O3

Fig. 11 e Hydrogen conversion of PteCo/Al2O3 catalyst
determined during CHC at hydrogen concentrations of
0e10 vol% and gas flow velocities of 4, 6, 8, 10, and 12 m/s.
flow velocity was slightly lower. The maximum hydrogen
conversion degrees were 85, 86, 82, 82 and 74% for the gas flow
velocities 4, 6, 8, 10, and 12 m/s, respectively.
catalyst at inlet hydrogen concentrations of 0e10 vol% and gas
flow velocities of 6 and 8 m/s. Here, the inlet hydrogen flow
velocities of 6 and 8 m/s were selected because the maximum
combustion temperature and hydrogen conversion were ob-
tained at these velocities for the PteCo bimetallic catalyst.
Fig. 12 shows combustion temperatures measured as well
as hydrogen conversions obtained during CHC at 6 and 8 m/s
over the hydrogen concentration range (0e10 vol%). The
maximum combustion temperatures determined at the inlet
gas flow velocities 6 and 8 m/s (Fig. 12 a and b) were lower than
those obtained for the PteCo bimetallic catalyst (420 and
354  C vs 506 and 525  C at 6 and 8 m/s, respectively). However,
the temperature over Row 3 was higher at the inlet hydrogen
concentrations of 5e10 vol% than that of the PteCo bimetallic
catalyst (194.9e334.7 and 231.9e309.6  C vs 153.1e161.4 and
226.6e259.5  C at 6 and 8 m/s, respectively). This may be
because a smaller portion of hydrogen is recombined in the
catalytic Row 1 when it is filled with Pt/Al2O3 catalyst than
when filled with PteCo/Al2O3 catalyst. Therefore, the greater

Fig. 12 e Combustion temperatures of Pt/Al2O3 catalyst determined at inlet hydrogen concentrations of 0e10 vol% and gas
flow velocity of (a) 6 m/s and (b) 8 m/s, and (c) hydrogen conversion of Pt/Al2O3 catalyst determined during CHC at hydrogen
concentrations of 0e10 vol% and gas flow velocities of 6 and 8 m/s.

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 international journal of hydrogen energy xxx (xxxx) xxx
hydrogen portion reaches Row 2 and Row 3, resulting in higher
combustion temperatures there.
In a study by Botha et al., the catalytic activities of the
bimetallic PteNi and PteCo surfaces were compared to the
pristine Pt surface for the CHC reaction using density func-
tional theory (DFT) calculations [59]. It has been demon-
strated by Botha et al., that the Pt3Co (111) surface has the
weakest adsorption energy for the reaction intermediates
among considered metals (Pt, PtNi3), which makes it more
favourable to remove the reaction intermediates from the
surface of Pt3Co compared to the surface of the pristine Pt
(111) and PtNi3 (111) surfaces. In addition, it has been
demonstrated that the Pt3Co (111) surface is more energeti-
cally favourable in the CHC reaction compared to the pristine
Pt and PtNi3 surfaces [59]. In the present study, therefore, a
smaller hydrogen portion being recombined over Row 1 for
the pristine Pt/Al2O3 catalyst can be ascribed to the stronger
adsorption energy of the intermediates on the Pt surface
than on the Pt3Co surface.
It was observed that the Pt catalysts reached lower
maximum combustion temperate than the PteCo catalysts
(420 and 354  C vs 506 and 525  C at 6 and 8 m/s, respectively),
which was in agreement with the results predicted by DFT
calculations.
Fig. 12c shows the hydrogen conversions determined during
CHC on the surface of Pt/Al2O3 catalyst (inlet hydrogen con-
centrations 0e10 vol%, gas flow velocities 6 and 8 m/s).
Maximum hydrogen conversion degrees of 77 and 75% at gas
flow velocities 6 and 8 m/s, respectively, were observed. The
hydrogen conversion determined for the pristine Pt catalyst
was lower than that determined for the PteCo bimetallic
catalyst (77% vs 86%). However, the hydrogen conversion value
for the Pt catalyst was similar to that obtained in our previous
studies [32,50]. For example, Kozhukhova et al. earlier reported
hydrogen conversions of 76 and 65% for a similar Pt/Al2O3
catalyst at gas flow velocities 8 and 10 m/s, respectively [50]. In
another study by Kozhukhova et al., a hydrogen conversion of
80% was reported for a Pt/CZY/AAO catalyst at gas flow velocity
8 m/s [32]. In both cases, similar experimental setups/condi-
tions were used. Lower hydrogen conversion determined dur-
ing CHC for the pristine Pt catalyst, can be ascribed to the same
strong adsorption energy of the intermediates on the Pt surface
compared to on the Pt3Co surface.
The key findings of the research work can be summarized
as follows.

A colloidal dispersion containing Pt was used to achieve
the uniform deposition of finely dispersed Pt particles
(average size 1.29 ± 0.24 nm) and PteCo bimetallic particles
(average size 1.25 ± 0.25 nm).

Both Pt/Al2O3 and PteCo/Al2O3 catalysts demonstrated
high catalytic activity, stability and durability in CHC.

The maximum combustion temperatures for the PteCo/
Al2O3 catalyst were 476, 506, 525, 483 and 439  C at gas flow
velocities 4, 6, 8, 10 and 12 m/s, respectively. The maximum
hydrogen conversion degrees were 85, 86, 82, 82 and 74%
for gas flow velocities 4, 6, 8, 10 and 12 m/s, respectively.

The maximum combustion temperatures for the Pt/Al2O3
catalyst were 420 and 354  C at 6 and 8 m/s gas flow
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combustion reaction, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.09.119
15
velocities, respectively. The maximum hydrogen conver-
sion degrees were 77 and 75% at gas flow velocities 6 and
8 m/s, respectively.

Stability tests for 500 h were performed with the prepared
catalyst to evaluate the catalyst stability and durability.
The average combustion temperature for the Pt/Al2O3
catalyst was determined to be 337.4 ± 7.0  C. The average
combustion temperature for the PteCo/Al2O3 catalyst was
determined to be 272.9 ± 6.6  C. The average Pt particle size
after the stability test was 1.29 ± 0.37 nm, while the average
PteCo bimetallic particle size after the stability test was
1.30 ± 0.28 nm, suggesting that sintering/aggregation was
avoided.

A pristine Co catalyst was prepared to investigate the effect
of the CoOx formation on the catalytic activity towards
CHC. It was found that the pristine Co catalyst is unsuitable
for CHC, even at temperatures as low as 80  C. Significant
sintering of the Co particles was observed. For the 2 wt% Co
catalyst, the particle size increased from 2.12 ± 0.27 to
8.61 ± 0.82 nm during 1 h of CHC. However, due to the
preparation method used in the present study, Co particles
were finely dispersed on the entire catalytic surface and,
most likely, contributed to the formation of the PteCo
metal alloy phase and influenced the reaction rate.
Therefore, the PteCo (atomic ratio 3:1) bimetallic catalyst
may be considered for high-temperature combustion
applications.
4. Conclusions
Pt/Al2O3 and PteCo/Al2O3 catalysts were prepared and evalu-
ated for their performance in the CHC reaction. In addition, we
have demonstrated that although the pristine Co catalyst is
unsuitable for combustion applications, even at low temper-
atures, it can be considered a partial replacement for the high-
cost Pt catalyst. From the preparation method and reactive
metal precursor used in the present study, high dispersion of
the PteCo bimetallic particles was obtained, resulting in the
stabilization of the Co particles. Besides improved stability,
due to the weaker adsorption energy of the intermediates on
the PteCo metal alloy surface, compared to the pristine Pt
catalyst, higher recombination reaction rates were obtained,
resulting in higher hydrogen conversions and combustion
temperatures. The PteCo bimetallic catalyst can therefore be
considered a suitable catalyst for CHC applications. Further
improvements in reactive metal loading, such as a reduction
in the precious Pt loading with an increase in the Co loading,
as well as improvement in the catalyst performance, may be
attractive.
Due to the above-mentioned characteristics of the pre-
pared PteCo bimetallic catalyst, further scalability opportu-
nity may be an implementation of the catalyst to the real-
world PAR device. Also, additional evaluation of the catalyst
in real-world conditions (i.e., humid conditions, dust) should
be taken into account. In addition, the catalyst proposed in
this research can be utilized in CHC-related technologies, for
example in domestic heating and cooking applications.
16 international journal of hydrogen energy xxx (xxxx) xxx
Author contributions
A.E. Kozhukhova: Conceptualization, Validation, Methodology,
Investigation, Formal analysis, Writing - original draft, Writing -
review & editing, Visualization. S.P. du Preez: Conceptualiza-
tion, Validation, Writing - review & editing, Supervision, Project
administration. D.G. Bessarabov: Conceptualization, Resources,
Writing - review & editing, Supervision, Project administration,
Funding acquisition. The manuscript was written through the
contributions of all authors.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgments
This work is based on the research supported in part by the
Department of Science and Innovation (DSI) and HySA Infra-
structure in Potchefstroom, South Africa, through their
financial support KP5 program and by the National Research
Foundation of South Africa and Sasol Ltd (SASPD22080347739).
The authors would like to acknowledge the help and support
from Dr Innocent Shuro for TEM-EDS analysis at North-West
University.
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Please cite this article as: Kozhukhova AE et al., Development of PteCo/Al2O3 bimetallic catalyst and its evaluation in catalytic hydrogen
combustion reaction, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.09.119