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Applied Catalysis A: General 518 (2016) 102114

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Applied Catalysis A: General


journal homepage: www.elsevier.com/locate/apcata

Sonochemical synthesis of Pt, Ru doped TiO2 for methane reforming


Satyapaul A. Singh, Giridhar Madras
Department of Chemical Engineering, Indian Institute of Science, Bangalore 560012, India

a r t i c l e

i n f o

Article history:
Received 18 July 2015
Received in revised form 29 October 2015
Accepted 30 October 2015
Available online 4 November 2015
Keywords:
Eley-Rideal mechanism
DRIFTS
Sonochemical synthesis
Bimetallic catalysts

a b s t r a c t
Platinum group materials (Pt, Ru, Rh) are highly active materials for reforming. In the present study,
bimetallic Pt and Ru substituted TiO2 catalysts were synthesized by sonochemical method. The bimetallic 2% Pt 2% Ru/TiO2 showed high surface area of 66 m2 /g compared with the other catalysts. The prepared
catalysts were characterized by XRD, XPS, TEM, TPR and BET. Dry reforming, partial oxidation and combined reforming (CR) with CO2 were studied on these materials. Synthesized catalysts were found to be
highly active for dry reforming reaction. 26% and 95% of methane conversions were obtained with Ru
substituted TiO2 (4% Ru/TiO2 ) at 400 C and at 700 C. The H2 /CO ratio was close to unity with both Pt
and Ru substituted catalysts after 650 C. The apparent activation energies found to be 51 and 56 kJ mol1
with respect to methane for 4% Ru/TiO2 and 4% Pt/TiO2 , respectively. High oxygen storage capacity of 4%
Pt/TiO2 further showed the good activity for dry reforming. The bimetallic catalyst 2% Pt 2% Ru/TiO2 sintered under time on stream condition and also resulted in the formation of amorphous carbon on to the
surface of catalysts, which made them an inactive catalyst for reforming process. The surface intermediates during these reactions were found by in situ FTIR at different temperatures for reforming processes.
The peaks corresponding to CO2 adsorption were not observed in case of 4% Ru/TiO2 and 2% Pt 2% Ru/TiO2
for dry reforming and this indicates the Eley-Rideal mechanism on both catalysts. A kinetic model was
developed by considering CH4 dissociation as rate determining step (RDS) and the model was validated
to the obtained experimental data.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Abundant resources of methane from natural wet lands, fermentation, biomass, fossil fuels and agriculture would be useful
for exploiting the syngas production [1]. FischerTropsch synthesis (FTS) for the production of liquid fuels production, ammonia
and methanol industries utilizes syngas as a feed stock [2,3]. Syngas can be produced by processes like steam reforming (SR), dry
reforming (DR), autothermal reforming (ATR), combined reforming
(CR) and partial oxidation (PO). The product H2 /CO ratio depends
on the reaction process and conditions used. For the production of
oxygenated compounds and for liquid hydrocarbons by FT process,
the H2 /CO ratio of syngas must be close to unity [4], which can be
achieved by dry reforming.
Both steam and dry reforming reactions are highly endothermic, whereas partial oxidation is exothermic. High temperatures
are required for both steam and dry reforming to achieve maximum
CH4 and CO2 conversions. The economics of the overall process can
be minimized by combining one of the reforming reactions with
partial oxidation of methane [5]. This process is called autother-

Corresponding author. Fax: +91 80 23600683.


E-mail address: giridhar@chemeng.iisc.ernet.in (G. Madras).
http://dx.doi.org/10.1016/j.apcata.2015.10.047
0926-860X/ 2015 Elsevier B.V. All rights reserved.

mal reforming where SR + PO are combined or combined reforming


where DR + PO are combined [69]. Other than these, energy efcient trithermal reforming processes for syngas production without
CO2 separation have been studied by various groups [10,11a,b].
Autothermal reactions have garnered scientic interest in
recent years on Ni and platinum group metals (PGM) [11a,b14].
Though various catalysts have been studied extensively, many of
these catalysts deactivate over a period of time under reaction conditions. The major reasons for catalyst deactivation are (a) due to
sintering of the catalyst at higher temperatures (b) oxidation of
the metallic sites and (c) coke deposition on the catalyst surfaces.
In reforming processes, carbon deposition on the catalyst surface
occurs majorly due to Boudouard reaction/methane cracking [3]. Ni
based catalysts have been reported as promising catalysts for their
stability and less carbon deposition [1518]. A detailed study of dry
reforming and partial oxidation was studied on various other noble
metals, and the activity order is observed as, Rh Ru > Ir > Pt > Pd
[19,20]. Bimetallic catalysts have been employed for reforming of
methane, which include the combination of Ni-Co, Ni-Pt, Co-Ce, PtRh and even trimetallic catalysts on single or composite of supports
like CeO2, ZrO2 , Al2 O3 [3,4,14,2126].
The mechanisms of reforming reactions are well studied on various supports and the mechanistic pathway includes either CH4 or
CO2 activation. The mechanisms have been proposed based on the

S.A. Singh, G. Madras / Applied Catalysis A: General 518 (2016) 102114

103

4% Ru/TiO2 After reaction

4% Ru/TiO2 Before reaction

Int ensit y, a.u.

2% Ru 2% Pt/TiO2 After reaction

2% Ru 2% Pt/TiO2 Before reaction

*
4% Pt/TiO2 After reaction

4% Pt/TiO2 Before reaction

20

30

40

50

60

Diffraction angle, 2

70

80

Fig. 1. X-ray diffraction pattern of Pt, Ru catalysts on TiO2 supports (*anatase phase
TiO2 ).

CH4 dissociation or CO2 dissociation on support as a rate determining step (RDS) [27,28]. The reaction pathway of reforming on the
catalyst surface depends on the surface acidity and/or basicity. If
the support possesses Lewis acidity, CO2 can adsorb on the surface
of the support and dissociate. In case of basic support, carbonates
and bicarbonates play a role in the CO and H2 formation [29]. PGM
catalysts enhance the transport of hydrogen and oxygen between
the precious metal and support by spillover mechanism. This metal
support interaction is important to achieve higher rates and low
coke formation on the catalyst. Despite this, strong metal support
interactions at higher temperatures can reduce the catalytic activity
due to loss of active sites [30].
In the present study, monometallic and bimetallic Pt, Ru catalysts with TiO2 supports were synthesized by sonochemical
synthesis. These catalysts were employed for dry reforming, partial oxidation and dry autothermal reforming reactions for the rst
time with these catalysts based on this particular synthesis route.
The mechanisms of all these reactions were proposed according to
the information obtained from in situ FTIR or DRIFTS. The kinetics
of dry reforming was studied further due to the catalytic activity
towards this reaction. Eley-Rideal mechanism was proposed for
dry reforming reaction on these materials as per the information
collected from DRIFTS study. All catalysts were characterized with
XRD, XPS, TEM before and after the reaction and the chemical stability was studied. The amount of coke deposition was determined
by using high pressure thermogravimetric analysis after stability
studies.
2. Experimental
2.1. Catalyst synthesis
Sonochemical synthesis is one of the well employed techniques to synthesize metal oxides of homogeneous size distribution

Fig. 2. TEM images of fresh catalysts (a), (b) 4%Pt/TiO2 , (c), (d) 2%Pt 2%Ru/TiO2 and
(e), (f) 4%Ru/TiO2 .

[31,32]. In a typical synthesis of bimetallic Ru, Pt doped TiO2 , titanyl


nitrate (TiO(NO3 )2 ), chloroplatinic acid (H2 PtCl6 xH2 O) and ruthenium chloride (RuCl3 xH2 O) are used as starting materials. Titanyl
hydroxide (TiO(OH)2 ) was precipitated by controlled hydrolysis of
5 ml titanium iso-propoxide under ice bath temperature at 4 C.
20 ml of 1:1HNO3 was added drop wise to TiO(OH)2 , which results
in a clear solution of TiO(NO3 )2 . To synthesize 2%Pt 2%Ru/TiO2 ,
20 ml of 0.017 M H2 PtCl6 xH2 O and RuCl3 xH2 O solutions were
added drop wise to TiO(NO3 )2 solution. To ensure effective doping,
5 ml of diethyltetramine (DETA) was added that results in the gelation of the solution. The solution was irradiated with high intensity
ultrasonic horn (25 kHz, 125 W) with 20 min ON and 15 min OFF
cycle for 5 h (i.e., 3 h effective sonication). The precipitate was collected by centrifuging the colloidal mixture and washed several
times with ethanol. The obtained material was dried at 120 C for
12 h on a hot plate. The resultant material was calcined at 500 C
for 2 h. The bimetallic composites were also prepared by the same
protocol. The amounts taken for synthesis are listed in Table 1.

Table 1
Amounts of precursors required for the bimetallic Pt, Ru TiO2 catalysts synthesis for 5 ml of titanium iso-propoxide.
Catalyst

Amount of RuCl3 xH2 O, g

Amount of H2 PtCl6 xH2 O, g

Specic surface area, m2 /g

4% Pt/TiO2
3% Pt 1% Ru/TiO2
2% Pt 2% Ru/TiO2
1% Pt 3% Ru/TiO2
4% Ru/TiO2

0
0.0356
0.0712
0.1069
0.1425

0.2815
0.2111
0.1407
0.0704
0

10
43
66
13
22

104

S.A. Singh, G. Madras / Applied Catalysis A: General 518 (2016) 102114

Fig. 3. TEM images of spent catalysts (a), (b) 4%Pt/TiO2 , (c), (d) 2%Pt 2%Ru/TiO2 and (e), (f) 4%Ru/TiO2 after reaction 20 h time on stream condition.

2.2. Catalyst characterization


X-ray diffraction patterns were collected by using Rigaku X-ray
diffraction equipment with 0.35 /min in the scan range of 2080
with a Cu K source. XPS data was collected using AXIS ULTRA
instrument with Al-K as radiation source. The specic surface area
was measured by using Belsorb surface area analyzer (Smart instruments) by adsorption at 77 K with liquid N2 . TEM micrographs for
the prepared catalysts (before and after reaction) were recorded by
using FEI F 30 instrument operating at 200 kV.

2.3. Catalytic activity studies


100 mg of catalyst of 60/80 mesh size was packed with ceramic
wool at the center of the quartz tube (ID of 4 mm) quartz reactor.
A bed length of 1 cm was maintained in a quartz reactor with gas
hourly space velocity of 38,200 h1 (48,000 ml/(g catal h1 )). Concentrations of CH4 , CO2 and N2 maintained as 2:2:96 (in vol%), The
concentrations of CH4 or CO2 were varied to different concentrations at 2 vol% of the other reactant concentration and accordingly
N2 ow rate was adjusted to maintain the specied space velocity.
Reactor temperatures were maintained by using a PID controller
(Care instruments, India) and the product gas mixture was analyzed
under steady state conditions. After conversion was obtained at a
particular temperature, the controller was set to a different temperature, and the conversions were measured at each temperature
under steady state conditions. Gas chromatograph equipped with

both ame ionized detector (FID) and thermal conductivity detector (TCD) was used to analyze CO, CO2 , CH4 and H2 concentrations
at the reactor outlet.
2.4. H2 TPR study
Temperature programmed reduction (TPR) with H2 was performed with 10 mg of catalyst, loaded in a quartz reactor. The
experiments were done under the ow rate of 30 ml/min of 5% H2
gas mixture diluted with Ar (Chemix gases, India) in temperature
range of 50600 C with a rate of 10 C/min. Hydrogen consumption during the reduction was analyzed with thermal conductivity
detector connected to outlet stream. The temperatures were controlled by using a PID controller (Culture instruments, India) during
the experiments.
2.5. In situ FTIR (DRIFTS) analysis
Fourier transform infrared spectroscopy (FTIR, Perkin Elmer)
machine was connected to Praying mantis system which contains
a high temperature reaction chamber. The reaction chamber was
lled with a catalyst and FTIR spectra were collected at different temperatures (30 C, 300 C, 450 C and 600 C, respectively).
At each temperature the background was collected with 32 scans
and 4 cm1 resolution with nitrogen purging. For each reaction, IR
spectra were collected after 30 min of the respective composition
of gas ow depending upon the process (CR/PO/DRM). After nishing the study at a particular temperature, the reaction chamber

S.A. Singh, G. Madras / Applied Catalysis A: General 518 (2016) 102114

(b)

(a)
2

2% Pt 2% Ru/TiO

4% Pt/TiO

Ru-3d after reaction

Intensi ty, cps

Intensi ty, cps

4% Ru/TiO

Ru-3d before reaction

279

200

400

600

800

282

1000

Pt

Ti

Ti -2p Before reaction

4+

Pt-4f after reaction


for 4% Pt/TiO 2

Pt

70

455

291

4+

Intensi ty, cps

Intensi ty, cps

Ti

288

(d)

Ti -2p After reaction

(c)

285

Binding energy, eV

Binding energy, eV

450

105

460

72

Pt-4f after reaction


for 2% Pt 2% Ru/TiO

74

465

76

78

80

82

84

Binding energy, eV

Binding energy, eV

Pt - 4f Before reaction for 4% Pt/TiO

(e)

Intensi ty, cps

Pt

Pt - 4f Before reaction for 2% Pt 2% Ru/TiO


Pt

66

68

70

72

74

4+

4+

76

78

80

82

84

Binding energy, eV

Fig. 4. (a) Wide spectra of 4%Pt/TiO2 , 2%Pt 2%Ru/TiO2 and 4%Ru/TiO2 , (b) Core level Ru3d spectra for 4%Ru/TiO2 , (c) Core level Ti2p spectra for 4%Ru/TiO2 , (d) Core level
Pt4f spectra (after reaction) in 4%Pt/TiO2 , 2%Pt 2%Ru/TiO2 , (e) Core level Pt4f spectra (before reaction) in 4%Pt/TiO2 , 2%Pt 2%Ru/TiO2 .

temperature was set to 500 C and purged with the mixture of N2


and O2 for 30 min. The temperature of reaction chamber was set to
another value and the same procedure was repeated for collecting
the spectra.

2.6. Thermogravimetric analysis


In typical analysis, 100 mg of the spent catalyst was taken in a
crucible, placed in a heating chamber of Mettler Toledo thermal
analyzer (Germany). The amount of coke deposition was found at

S.A. Singh, G. Madras / Applied Catalysis A: General 518 (2016) 102114

3.0x10

2.5x10

2.0x10

1.5x10

(a)

C o ncentrati o n, ppm

C o ncentratio n, ppm

106

CH 4
1.0x10

CO 2

H2
5.0x10

CO

3.0x10

2.5x10

2.0x10

(b)

CH 4
CO 2

1.5x10

1.0x10

5.0x10

0.0

H2
CO

0.0
300

400

500

600

700

800

900

300

C o ncentrati o n, ppm

Temperature, C

2.5x10

2.0x10

1.5x10

1.0x10

400

500

600

700

800

900

Temperature, C

(c)

CH 4
CO 2
H2

5.0x10

CO

0.0
300

400

500

600

700

800

900

Temperature, C
Fig. 5. CR reaction with (a) 4%Pt/TiO2 , (b) 2%Pt 2%Ru/TiO2 and (c) 4%Ru/TiO2 .

operating conditions of 50 ml/min of moisture free air ow rate,


with a ramping rate of 10 C/min from 25 C to 800 C.
3. Results and discussion
3.1. Material characterization
All catalysts were characterized with XRD and that conrms the
presence of TiO2 in all composites of bimetallic catalysts (as shown
in Fig. 1). No metallic form of Pt and Ru was found in the synthesized catalysts. Fig. 2 shows the TEM micrographs of 4%Pt/TiO2 ,
2%Pt 2%Ru/TiO2 and 4%Ru/TiO2 . The particle sizes of synthesized
catalysts are found to be in the order of 20 nm. The diffraction patterns conrms the (1 0 0) planes of TiO2 . The catalysts are formed in
both anatase and rutile phases. Under the same preparation conditions, 2%Pt 2%Ru/TiO2 showed anatase phase as the dominant
phase. With the same synthesis method, TiO2 alone was also prepared that showed specic surface area of 122 m2 /g with combined
anatase and rutile phases (46% anatase, not shown here). The speTable 2
Activation energies of bimetallic Pt, RuTiO2 catalysts.
Catalyst

Eapp,CH4 , kJ mol1

Eapp,CO2 , kJ mol1

4% Pt/TiO2
2% Pt 2% Ru /TiO2
4% Ru/TiO2

56.5 4.2
17.4 0.6
50.8 3.8

49.8 2.0
36.8 2.0
48.3 4.4

cic surface areas of the bimetallic catalysts are in the range of


1066 m2 /g. 4% Pt/TiO2 was having low surface area of 10 m2 /g,
3%Pt 1%Ru/TiO2 , 2%Pt 2%Ru/TiO2 and 1%Pt 3%Ru/TiO2 have shown
43, 66 and 13 m2 /g. 4%Ru/TiO2 has shown surface area of 22 m2 /g.
In general rutile phase is more thermally stable than the anatase
phase. Anatase TiO2 is having relatively lower surface energy compared with rutile, which causes more stable crystallite sizes of
smaller sizes that further results higher surface area [33]. The %
of anatase phase in 2%Ru 2%Pt/TiO2 was found to be 79%, which is
higher than all other catalysts. The general temperatures of reforming reactions are above 500 C, which leads to formation of most
stable rutile phase. Without the presence of any metal, pure TiO2
was found to be inactive at the temperature above 700 C, irrespective of the initial phase composition. Thus the phase of titania has
no signicant effect on conversion. The surface areas of the catalysts are decreased after reaction at 650 C under time on stream
condition for 20 h. The nal surface areas were found to be 4, 24
and 7 m2 /g for 4%Pt /TiO2 , 2%Pt 2%Ru/TiO2 , 4%Ru/TiO2 . After reaction, the catalysts were characterized with XRD, which indicates
that the materials phase ratios were changed and the rutile phase
TiO2 was found at the end of the reaction. The% anatase phase of
2%Pt 2%Ru/TiO2 after reaction was found to be 25%.
Fig. 3 shows the TEM micrographs taken after reaction for 20 h.
From Fig. 2 and Fig. 3, the catalyst particle sizes are found to be
increased by 45 times. This is due to the sintering of the catalyst
particles under the reaction conditions. Fig. 3(b), (d) and (f) shows

S.A. Singh, G. Madras / Applied Catalysis A: General 518 (2016) 102114

the HRTEM images of 4%Ru/TiO2 , 2%Pt 2%Ru/TiO2 and 4%Pt/TiO2 .


The graphitic carbon traces were observed on the catalysts surfaces
as shown in HRTEM images, where 0.34 nm dspacing indicates the
presence of graphitic carbon.
X-ray photoelectron spectroscopy (Fig. 4) reveals the existence
of the oxidation states of synthesized catalysts. Fig. 4(a), shows the
wide, Fig. 4(b) and (c) shows the core level spectra of Ru3d and
Ti2p for 4%Ru/TiO2 . From Fig. 4(c), the core level Ti2p shows the
oxidation state of Ti in 4+. The 2p3/2 and 2p1/2 core level binding
energy difference was 5.7 eV. A small shift in peaks was observed
due to reduction in Ti4+ to Ti3+ . The peak at 460.6 eV is assigned as
satellite peak [34]. Fig. 4(b) shows the core level 3d spectra of Ru
and the as synthesized catalyst existed in 3+ oxidation state. The
binding energies of 3d3/2 and 3d5/2 are 286.2 and 280.7 eV, respectively [35]. After treating in chemical reaction for 20 h at 650 C,
the material was found to be reduced. XPS spectra revealed that Ru
existed in metallic form after the chemical reaction. Before reaction,
Pt in the catalysts have shown +4 oxidation state (at 74.1 eV) and
metallic Pt was not observed (shown in Fig. 4(e)) in 4%Pt/TiO2 and
2%Pt 2%Ru/TiO2 . In case of spent catalysts of 2%Pt 2%Ru/TiO2 and
4%Pt/TiO2 , platinum was found to be in +4 oxidation state (Fig. 4(d)).
But, after reaction, Pt was found to be in Pt0 , Pt2+ and Pt4+ oxidation
states [36].

2.5x10

3.2. Catalytic activity studies


3.2.1. Dry autothermal reforming and partial oxidation with
4%Pt/TiO2 , 2%Pt 2%Ru/TiO2 and 4%Ru/TiO2
The synthesized catalysts were employed for dry autothermal
reforming reaction. From Figs. 5 and 6, it is very clear that the catalysts 4%Pt/TiO2 and 4%Ru/TiO2 have shown very high activity for
the production of hydrogen for CR and PO reactions. From Fig. 5,
the concentration of CO at outlet was found to be small due to
signicant effect of RWGS and methane combustion reactions. In
case of 2%Pt 2%Ru/TiO2 , CO2 concentration was increased further,
which indicates the possibility of RWGS and methane combustion reactions. Similar results were observed with partial oxidation
reaction also. With PO reaction, 4%Pt/TiO2 and 4%Ru/TiO2 were able
to produce more amount of hydrogen. CH4 concentrations were
decreased up to a temperature (500 C in case of 4%Pt/TiO2 and
600 C in case of 4%Ru/TiO2 ) and then further increased with temperature. This is because of the equilibrium shift that occurs due to
the endothermic nature of partial oxidation.
3.3. Dry reforming of methane (DRM) studies over bimetallic TiO2
Synthesized catalysts for DRM reaction have shown trends as
depicted in Fig. 7(a) and Fig. 7(b). Here CH4 to CO2 ratio is 2:2
(vol%) balanced with nitrogen. Fig. 7 shows that the species con-

(a)
2.0x10

(b)

CH 4

1.5x10

CH 4

H2

1.0x10

5.0x10

C o ncentrati o n, ppm

CO 2
H2
CO

1.0x10

5.0x10

0.0

0.0
400

500

600

700
o

800

900

300

Temperature, C

400

500

600

Temperature, C

C o ncentratio n, ppm

C o ncentrati o n, ppm

2.0x10

CO 2

CO
1.5x10

107

3.0x10

2.5x10

2.0x10

1.5x10

1.0x10

5.0x10

(c)

CH 4
CO 2
H2
CO

0.0

300

400

500

600

700

800

900

Temperature, C
Fig. 6. POM reaction with (a) 4%Pt/TiO2 , (b) 2%Pt 2%Ru/TiO2 and (c) 4%Ru/TiO2 .

700

800

900

S.A. Singh, G. Madras / Applied Catalysis A: General 518 (2016) 102114


4.0x10

3.5x10

3.0x10

2.5x10

2.0x10

1.5x10

1.0x10

(a)

CH 4

2.5x10

2.0x10

1.5x10

1.0x10

H2
CO

CH 4
CO 2
H2
CO
5.0x10

5.0x10

(b)

CO 2

C o ncentrati o n, ppm

C o ncentrati o n, ppm

108

0.0

0.0
300

400

500

600

700

800

300

400

500

C o ncentrati o n, ppm

Temperature, C

600

700

800

900

Temperature, C

3.5x10

3.0x10

2.5x10

2.0x10

1.5x10

1.0x10

CO 2

5.0x10

CO

(c)

CH 4
H2

0.0
300

400

500

60o0

700

800

Temperature, C
Fig. 7. DRM reaction with (a) 4%Pt/TiO2 , (b) 2%Pt 2%Ru/TiO2 and (c) 4%Ru/TiO2 .

centration at outlet of the reactor. Fig. 8(a) and (b) shows the
methane and CO2 conversion variation with temperature. Clearly
from these gures, 4% Ru/TiO2 and 4% Pt/TiO2 have shown better
performance compared with the bimetallic catalysts. 4%Ru/TiO2
has shown methane conversion as high as 98% and CO2 conversion of 95% at 800 C, whereas 4%Pt/TiO2 has shown 92% and 93%
CH4 and CO2 conversions. All these conversions are found to be
lower than equilibrium values at various temperatures denoted
by a dotted line in Fig. 8. Among all the catalysts, 2%Pt 2%Ru/TiO2
has shown very poor activity for the reforming reaction. All the
materials started showing activity from 400 C (other than 3%Pt
1%Ru/TiO2 ). With 2%Pt 2%Ru/TiO2 , the CO2 and CH4 conversions
reduced to 4% and again increased to higher conversion. This is
due to the coke formation during reaction and sintering of active
metal on the support as shown in Fig. 3. 2%Pt 2%Ru/TiO2 showed
37%CH4 conversion even at 900 C, so this bimetallic catalyst can
be considered to be ineffective for dry reforming reaction. With
3%Pt 1%Ru/TiO2 the DRM reaction started at 600 C, which is higher
compared with the other materials. At 900 C, CH4 and CO2 conversions reached 72% and 83%. Among all bimetallic catalysts, 1%Pt
3%Ru/TiO2 showed higher CH4 and CO2 conversions due to high Ru
content. With this material CH4 and CO2 conversions reached 83%
and 91% at 800 C. In all cases, at temperatures >700 C, CH4 and CO2
conversions are comparable, which indicates that the contribution
of reverse water gas shift (RWGS) reaction is negligible.

In DRM process, H2 /CO ratio is one of the important parameters


for downstream processes. With all materials, H2 /CO ratio gradually increased with temperature in a range of 400650 C and after
that the ratio was almost same. From Fig. 8(c), the value reached
0.97 for 4%Ru/TiO2 at 900 C and this material showed higher than
H2 /CO ratio of 0.9 above 700 C. 4%Pt/TiO2 showed more than 0.80
of H2 /CO ratio from 600 C and reached a maximum of 0.92 by
900 C. Bimetallic catalysts also showed reasonably good H2 /CO
ratios, but not as high as 4%Pt/TiO2 and 4%Ru/TiO2 . The H2 /CO ratio
in case of 3%Pt 1%Ru/TiO2 , 2%Pt 2%Ru/TiO2 and 1%Pt 3%Ru/TiO2
reached 0.89, 0.85 and 0.86 at 900 C. Considering the CH4 and CO2
conversions, it was found that 4%Pt/TiO2 and 4%Ru/TiO2 were the
best catalysts. Fig. 9 shows the methane conversion with varying
W/FCH4 and W/FCO2 . The reaction rates were calculated by assuming the packed bed as differential ow reactor. The Arrhenius plot
was developed with the obtained rates. From this plot, the activation energy of 4%Ru/TiO2 , 2%Pt 2%Ru/TiO2 and 4%Pt/TiO2 are listed
in Table 2.
Among these materials, 4%Pt/TiO2 has shown higher oxygen
storage capacity compared to 4%Ru/TiO2 and 2%Pt 2%Ru/TiO2 . The
reduction peaks are well spread all over the regions of 50600 C for
4%Ru/TiO2 . From Fig. 10, the rst reduction peak can be observed at
113 C, which indicates reduction of ruthenium oxide [37]. In case of
4%Pt/TiO2 , the reduction peaks are observed at temperatures below
500 C. This indicates the reduction of PtOx to metallic Pt [38]. The

S.A. Singh, G. Madras / Applied Catalysis A: General 518 (2016) 102114

109

Fig. 8. (a) Variation of methane conversion (XCH4 ) with temperature, (b) Variation of carbon dioxide conversion (XCO2 ) with temperature, (c) H2 /CO molar ratio variation for
dry reforming reaction with temperature with bimetallic catalysts.

reduction peak shifted to 120 C corresponding to oxides of Ru and


at 262 C, 328 C, 483 C corresponds to oxides of Pt are observed
with 2%Pt 2%Ru/TiO2 .
3.4. Reaction mechanism and kinetic model
The intermediate species of the catalysts 4%Ru/TiO2 , 2%Pt
2%Ru/TiO2 and 4%Pt/TiO2 were analyzed with FTIR under in situ
conditions of partial oxidation (CH4 :O2 = 2:1 vol%), dry autothermal reforming (CH4 :CO2 :O2 = 2:2:1 vol%) and dry reforming
(CH4 :CO2 = 2:2 vol%) conditions.
In combined reforming and dry reforming, methane was
observed in both adsorbed (at 3013, 3090 cm1 ) and gaseous form
(12501350 cm1 ), gaseous form of CO2 (2358, 2311 cm1 ) as represented in Figs. 1113 [39,40]. In the case of all catalysts, the
adsorbed methane species intensities decreased with increasing
temperature. Particularly at 600 C, the adsorbed methane species
intensities decreased for all the catalysts, whereas the intensities completely vanished in case of 4%Ru/TiO2 . These observations
indicate that CH4 activation plays a major role in all reforming processes. In Figs. 11(a) and 12(a), at higher temperatures i.e., at 450 C
and 600 C physically adsorbed CO to Pt metal ions was observed
assigned at 2186 cm1 [41]. In addition, small peaks were observed
at 2065 cm1 and 2058 cm1 in the case of 4% Pt/TiO2 at 300 C (Figs.
11(a) and 13(a)). These peaks can be assigned to linear carbonyl
bond attached to Pt [41]. As temperature increases, these peaks
assigned to linearly bonded carbonyl species with Pt disappeared.

This interesting step occurred in CR and DRM process, where there


is CO2 in the feed mixture. This step was not observed in the case
of POM process, which indicates this peak is due to the conversion
of CO2 to linearly bonded CO to Pt ion. In Fig. 11(b), other than
linear carbonyl group to Pt ion, all other groups mentioned earlier
were observed for 2%Pt 2%Ru/TiO2 . The peaks at 2175 cm1 can be
assigned to either carbonyl group attached to Pt ion or CO coordinated to reduced TiO2 , but they are not distinguishable clearly. In
Figs. 11(c) and 13(c), a shoulder was observed at 2175 cm1 in case
of 4%Ru/TiO2 at 600 C and it can be assigned to CO coordinated to
reduced TiO2 [41,42]. This is possible due to reduction of TiO2 at
temperatures higher than 500 C. In partial oxidation of methane,
at 30 C no peaks were observed at 2358, 2311 cm1 which correspond to gaseous CO2 . But after 300 C onwards, gaseous and
adsorbed CO2 peaks were observed. This clearly denotes the formation of CO2 species due to chemical reaction between CH4 and
oxygen. From Fig. 12(b), carbonyl group attached to Pt ion and/or
CO coordinated to reduced TiO2 are negligible. This indicates the
possibility of Eley-Rideal mechanism on the catalyst surface.
In Figs. 1113, no peaks were observed at 1580, 1400, 1640,
1485 and 37003745 cm1 which indicates the adsorbed formate,
bicarbonate and hydroxyl species [43] were absent. This indicates
these catalysts do not follow formate mechanism. The mechanism
for dry reforming is discussed based on the information obtained
from DRIFTS analysis.
On Pt/TiO2 catalyst, CH4 adsorbed species were observed on Pt
ions but no CO2 was adsorbed. Only gaseous CO2 information is

S.A. Singh, G. Madras / Applied Catalysis A: General 518 (2016) 102114

-7

(b)
-8.0

0.35

-8.5

-8

C O 2 co nv ersi o n, X CO

0.3

0.40

(a)
ln(rate), (rate in mol/(g-s))

Methane conversion, XCH

0.4

ln(rate), (rate in mol/(g-s))

110

-9

-10
1.2

0.2

1.3
1.4
-1
1000/T (K )

1.5

400 C
o
450 C
o
500 C
o
550 C

0.1

0.30

-9.0

0.25

-9.5
1.2

0.20

1.3
1.4
-1
1000/T (K )

1.5

400 C
o
450 C
o
500 C
o
550 C

0.15
0.10
0.05
0.00

0.0

200

400

600

800

-0.05
-200

1000

200

400

0.25

0.35
2

-8

-9

C O 2 co nv ersi o n, X CO

0.30

ln(rate), (rate in mol/(g-s))

Methane conversion, XCH

0.35

0.40

-10

0.20

1.2

1.3
1.4
-1
1000/T (K )
o

1.5

400 C
o
450 C
o
500 C
o
550 C

0.15
0.10

0.30
0.25

200

400

600

800

W/FCH (g-s/mol)

1000

1200

1.2

1.3
1.4
-1
1000/T (K )

1.5

400 C
o
450 C
o
500 C
o
550 C

-200

1400

200

400

W/F

0.25

0.16
2

-8.8

C O 2 co nv ersi o n, X CO

0.20

ln(rate), (rate in mol/(g-s))

Methane conversion, XCH

-8.6

-9.0

0.15

-9.2

0.10

1.3

1.4
-1
1000/T (K )
o

1.5

400 C
o
450 C
o
500 C

0.05

CO 2

800

1000

1200

1400

1600

1200

1400

1600

(g-s/mol)

-9.0

-9.5

-10.0

0.12

-10.5

1.2

1.3
1.4
-1
1000/T (K )
o

1.5

200

400

400 C
o
450 C
o
500 C
o
550 C

0.08

0.04

0.00

0.00
-200

600

(f)
ln(rate), (rate in mol/(g-s))

0.20

(e)

1600

-9.5

0.10

0.00

1400

-9.0

0.15

0.00

1200

-8.5

0.20

0.05

1000

(g-s/mol)

-8.0

-10.0

0.05

800

CO 2

(d)
ln(rate), (rate in mol/(g-s))

(c)

0.40

600

W/F

W/FCH (g-s/mol)

200

400

600

800

1000

1200

1400

1600

-200

W/F

W/FCH (g-s/mol)
4

600
CO 2

800

1000

(g-s/mol)

Fig. 9. Arrhenius plot for (a), (b) 4%Ru/TiO2 , (c), (d) 4%Pt/TiO2 , (e), (f) 2%Pt 2%Ru/TiO2 .

obtained from DRIFTS study. This clearly indicates no adsorption


of CO2 was observed either on the surface of metal or support. The
carbonates and molecular adsorption on Pt metal and TiO2 support
were observed in the DRIFTS study for Pt/TiO2 synthesized with an
incipient wetness technique [43]. However, in this catalytic system where the catalyst has been synthesized by a sonochemical
technique, the contributions of carbonates, bidentate carbonates
and adsorbed CO2 is minimal. This is conrmed with the DRIFTS
study at different feed and temperature conditions. Moreover with

these catalytic systems, CO adsorption on Pt ions was observed at


higher temperatures (450 C and 600 C). With this information the
reaction pathway is as follows,
k1,f

M + CH4  M CH4
k1,b

k2

M CH4 M C + 2H2

(1)

(2)

S.A. Singh, G. Madras / Applied Catalysis A: General 518 (2016) 102114


k3,f

M C + CO2 + M  2M CO

(3)

k3,b

k4,f

2M CO  2M + 2CO

k2 K1 K3 K4 PCH4 PCO2

1 + K1 PCH4 K3 K4 PCO2 + K3

(5)

2
K4 PCO + PCO

TCD Signal, mV

By considering methane dissociation (Reaction (2)) as rate


determining step, the rate expression for this mechanism is,

4% Ru/TiO2

(4)

k4,b

rate =

111

2% Pt 2% Ru/TiO2

Ru/TiO2 does not result in any CO adsorption peak at any temperature. For dry reforming, Eley-Rideal mechanism without CO
adsorption on support is as follows,
k5,f

M C + CO2  M + 2CO

4% Pt/TiO2

100

(6)

k5,b

where, k2 = A2 exp

 E 
2

RT

and Ki =

(7)
ki,f
ki,b

= Ai exp

Hi
RT

500

600


.

The kinetic parameters were found by using nonlinear regression and listed in Table 3. The initial guesses were taken from the
literature [44]. Fig. 14 shows the kinetic model that ts the variation
of rate with partial pressure of CH4 .

(b)

(a)

3095

2953
3017

2186

2186

1341

3095

1267

2311
2358

1267

2311
2358

1341

600 C

Transmi ttance

600 C

1299

2109

1299

2109
2953
3017

Transmi ttance

400

Fig. 10. H2 TPR for 4% Ru/TiO2 , 2% Pt 2% Ru/TiO2 and 4% Pt/TiO2 .

k2 K1 K5 PCH4 PCO2
2
1 + K1 PCH4 K5 PCO2 + PCO

300

Temperature, C

The rate expression for second reaction pathway is,


rate =

200

450 C

300 C

450 C

300 C

2065
o

30 C

3500

3000

2500

2000

Wavenumber, cm

1500

-1

1000

4000

3500

3000

2500

1299
2953
3017

2175
1267

2311
3095

2358

1341

600 C

450 C
o

300 C

30 C

4000

3500

3000

2000

Wavenumber, cm

(c)

Transmi ttance

4000

30 C

2500

2000

Wavenumber, cm

-1

1500

Fig. 11. DRIFTS for CR with (a) 4%Pt/TiO2 , (b) 2%Pt 2%Ru/TiO2 , (c) 4%Ru/TiO2 .

1000

-1

1500

1000

112

S.A. Singh, G. Madras / Applied Catalysis A: General 518 (2016) 102114

(a)

1267

2311
2358

1299

2953
3017

2186

3095

3095

600 C
o

450 C
o

300 C

1267

2311
2358

600 C

1341

Transmi ttance

Transmi ttance

(b)

1299

2109

2953
3017

1341

450 C

300 C

30 C

4000

3500

30 C

3000

2500

2000

Wavenumber, cm

1500

1000

4000

-1

3500

3000

2500

2000

Wavenumber, cm

-1

1500

1000

(c)
1267
1341

600 C

Transmi ttance

1299

2311
2358

2953
3017
3095

450 C

300 C

30 C

4000

3500

3000

2500

2000

Wavenumber, cm

-1

1500

1000

Fig. 12. DRIFTS for POM with (a) 4%Pt/TiO2 , (b) 2%Pt 2%Ru/TiO2 , (c) 4%Ru/TiO2 .

Table 3
Kinetic parameters of 4% Ru/TiO2 and 4% Pt/TiO2 .
Parameter
k2
K1
K3
K4 K5

4% Ru/TiO2



(1.216 0.11) 10 exp 1518112
RT


4
(2.279 0.210) 10 exp 75416
RT
 74318

5
10

(0.442 0.03) 10

exp

RT

3.5. Stability studies


The stabilities of 4%Pt/TiO2 and 4%Ru/TiO2 were studied under
time on stream conditions with 1:1CO2 :CH4 ratio. In each cycle,
the materials were treated with normal feed condition for 20 h at
650 C. The conversions decreased to 38% and 42% of CH4 and CO2
at the end of 20 h continuous operation. The coke deposition was
found to be 72, 247 and 113 mg of coke/g of catalyst for 4%Ru/TiO2 ,
2%Pt 2%Ru/TiO2 and 4%Pt/TiO2 respectively. From Fig. 15, the conversion at 650 C was found to be approximately 76% of CH4 and
78% of CO2 in the case of 4% Ru/TiO2 . The conversions decreased
to 38% and 42% of CH4 and CO2 after 20 h. 2%Pt 2%Ru/ TiO2 has
shown very poor conversions at 923 K. The methane and CO2 conversions are found to be 11% and 7%, but with time the gradual
increment in conversions were observed up to 2 h and decreased

4% Pt/TiO2
10
(6.724 0.21) 10 exp
4

(2.465 0.33) 10

exp

 1691105 
RT
 65613


(0.338 0.041) 10

exp

RT

 193237 
RT

at further time intervals. This could be due to formation of coke


on the catalyst surface at longer times of the study. From DRIFTS,
2%Pt 2%Ru/TiO2 follows the Eley-Rideal mechanism and where
methane combustion occurs on the 2%Pt 2%Ru/TiO2 surface.This
further generates carbon on to the catalyst surface. From Fig. 1, the
peaks corresponding to 26.4 are not observed, which indicates that
there is no traceable formation of pure graphitic carbon [3940].
From Fig. 3(b), (d) and (f) sintering of metal particles and traces of
graphitic carbon was observed. Thus the amount of the graphitic
carbon is very low and this is limited by the detection levels of
XRD. By comparing Figs. 2 and 3, the spent catalyst particle sizes
have increased by 45 times compared with fresh catalysts. The
active metals were not distinguished in fresh TiO2 solid solutions,
whereas in case of spent catalysts, active metal particles can be
distinguished clearly from the support.

S.A. Singh, G. Madras / Applied Catalysis A: General 518 (2016) 102114

113

(b)

(a)

2298

2298
3013

3013

2385

2385

600 C

Transmi ttance

Transmi ttance

600 C
o

450 C

300 C

450 C

300 C

2058
o

30 C

30 C
3095 2950

3095 2950

1349
1303

1349
1303

4000

3500

3000

2500

2000

Wavenumber, cm

1500

-1

4000

1000

3500

3000

2500

2000

Wavenumber, cm

1500

1000

-1

(c)
2298
3013

2385

2108
2179

Transmi ttance

600 C
3095 2950
o

450 C

300 C
o

1349
1303

30 C

4000

3500

3000

2500

2000

Wavenumber, cm

1500

1000

-1

Fig. 13. DRIFTS for DRM with (a) 4%Pt/TiO2 , (b) 2%Pt 2%Ru/TiO2 , (c) 4%Ru/TiO2 .

500

(a)

400

300

rCH , mo le/ (g-s)

300

200

673 K
723 K
773 K
823 K

200

rCH , mo le/ (g-s)

400

(b)

673 K
723 K
773 K
823 K

100

100

0
0

Partial pressure of methane, P CH in kPa


4

Partial pressure of methane, P CH in kPa

Fig. 14. Rate variation with partial pressure of methane (a) 4% Ru/TiO2 and (b) 4% Pt/TiO2 .

4. Conclusions
In the present study, Pt and Ru catalysts with TiO2 were prepared
by using sonochemical synthesis. The materials were characterized by XRD and combination of anatase and rutile phases was
observed. The bimetallic Pt and Ru doped TiO2 has higher surface

area among all composites. These materials are employed for all
dry reforming, partial oxidation and autothermal reforming and
combined dry autothermal reforming. 4%Ru/TiO2 and 4%Pt/TiO2
has shown favorable hydrogen conversions for all reactions. But
higher conversions and close to equal H2 /CO ratio were observed
in case of dry reforming for 4%Ru/TiO2 and 4%Pt/TiO2 . All bimetal-

114

S.A. Singh, G. Madras / Applied Catalysis A: General 518 (2016) 102114

80

CH4 for 4% Ru/TiO2


CO2 for 4% Ru/TiO2

70

CH4 for 4% Pt/TiO2


CO2 for 4% Pt/TiO2

% Conversion

60

CH4 for 2% Pt 2% Ru/TiO2

50

CO2 for 2% Pt 2% Ru/TiO2

40
30
20
10
0
0

10

12

14

16

18

20

Time on stream, h
Fig. 15. Stability of 4% Ru/TiO2 , 2%Pt 2% Ru/TiO2 and 4% Pt/TiO2 at 923 K.

lic and monometallic catalysts have shown activity at 400 C. The


greater than 90% conversions were observed with both 4%Ru/TiO2
and 4%Pt/TiO2 at 800 C. 4%Ru/TiO2 material was found to be stable among all materials studied. The Eley-Rideal mechanism was
observed with DRIFTS study with CH4 dissociation as the rate determining step and this model predicts the system behavior under
given operating conditions.
Acknowledgements
Authors thank Gas Authority India Ltd (GAIL) for nancial support. Authors are thankful for Advanced Facility for Microscopy
and Macroanalysis (AFMM), IISc for TEM analysis. S.A. Singh thanks
Dr. V.M. Shinde for his valuable suggestions in catalyst synthesis.
The corresponding author thanks the Department of Science and
Technology (DST), India for the J.C. Bose fellowship.
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