i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 1 4 8 8 e1 1 4 9 4

Available online at www.sciencedirect.com

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

Ni catalysts derived from MgeAl layered double hydroxides

for hydrogen production from landfill gas conversion
Qingsong Wang a,*, Wei Ren a, Xueliang Yuan a, Ruimin Mu b, Zhanlong Song a,
Xiaolin Wang a
a
b

School of Energy and Power Engineering, Shandong University, Jinan 250061, Shandong, China
School of Municipal and Environmental Engineering, Shandong Jianzhu University, Jinan 250100, Shandong, China

article info

abstract

Article history:

A layered double hydroxide (LDH) precursor with a hydrotalcite-like structure containing

Received 17 October 2011

Ni/Mg/Al cations was prepared. A series of Ni catalysts containing mixed-oxides and spinel

Received in revised form

phases were then obtained through thermal treatment of the LDH precursor. X-ray

2 May 2012

diffraction (XRD), transmission electron microscopy (TEM), and temperature-programmed

Accepted 3 May 2012

reduction (TPR) revealed that the LDH derived Ni catalysts have well-dispersed nickel

Available online 5 June 2012

phases upon reduction. The thermal treatment temperatures have noticeable effects on
the specific surface area, pore volume, phase transformation, particle size, and reducibility

Keywords:

of the catalysts. Thermal treatment temperatures up to 700
C promote the generation of

LDH material

mesopores which facilitate an increase in specific area and pore volume. Beyond 700
C

Ni catalyst

sintering occurs, mesopores collapse, and specific area and pore volume decrease. High

Landfill gas

thermal treatment temperatures favor the phase transformation to spinel solid solutions

Methane reforming

and the particle size growth. Metal-support interaction is enhanced but reducibility is

Carbon dioxide

hindered due to the formation of spinel solid solution phases. The LDH derived Ni catalysts
were tested for landfill gas conversion at 750
C and have shown excellent activity and
stability in terms of methane conversion. At gas hourly space velocity (GHSV) of 240,000 h1
and pressure of 1 atm, 81% methane conversion was achieved during a 48 h test period
without apparent catalyst deactivation.
Copyright 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1.

Introduction

In the transition to sustainable alternative energy, hydrogen

will play a pivotal role as an energy carrier. Currently, hydrogen
is most economically produced from fossil fuels. Drying
reforming is one of the most studied technologies, in which
methane reacts with carbon dioxide, producing a mixture of
hydrogen and carbon monoxide. The carbon monoxide can be
then converted to hydrogen through wateregas shift reaction
to maximize hydrogen production. Mainly composed of

methane and carbon dioxide, landfills account for a significant

portion of greenhouse gas emissions. With the increasing
awareness for the greenhouse effect, utilization of landfill gas
is becoming of great interest. Conversion of landfill gas
provides an ideal alternative energy resource which mitigates
greenhouse emissions from municipal landfills. To achieve an
acceptable reaction rate, a catalyst is required to accelerate the
process of dry reforming. The catalyst should be stable under
extreme reaction temperatures, which reach over 700
C to
achieve a high methane conversion.

* Corresponding author. Tel.: 86 531 88399372; fax: 86 531 88395877.

E-mail address: energy_sdu@163.com (Q. Wang).
0360-3199/$ e see front matter Copyright 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2012.05.010

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 1 4 8 8 e1 1 4 9 4

Catalyst deactivation has been a long-standing problem for

dry reforming. New catalyst development has dominated the
research activities involving dry reforming. It is known that
the reaction can be catalyzed by almost all of the VIII transition metals. Among them, nickel (Ni) has been studied
extensively [1e4]. In comparison with precious metals such as
Rh, Ru, Pd, and Pt, Ni catalysts suffer severe catalyst deactivation due to carbon formation [2]. As a result, a lot of efforts
have been devoted to develop Ni catalysts with special properties to combat the carbon formation problem. Ruchenstein
and Hu [3,4] reported that NiO/MgO has excellent stability and
good resistance to carbon formation. This is attributed to the
formation of a solid solution between NiO and MgO.
Tomisshge et al. [5] reported the additive effects of Sn, Ge, and
Ga to a NiOeMgO solid solution and found that the addition of
Sn can effectively decrease the carbon formation. Choudhary
and Mamman [6] reported that catalyst performance can be
improved when partial NiO is replaced with CoO in the
NiOeMgO solid solution. Recently, Zhang et al. [7e9] reported
a NieCo bimetallic catalyst was tested for 2000 h without
apparent deactivation. They attributed the stable performance to the formation of NieCo containing spinel-like solid
solution phase, which has a strong metal-support interaction
and can be reduced at high temperatures to form small
metallic particle sizes. Other authors reported a negative
effect on the catalytic performance over nickel catalysts
modified by Co [8,9].
Layered double hydroxides (LDH) are a class of anionic
clays or hydrotalcite compounds in which divalent cations
within the brucite-like layers are replaced by trivalent cations.
The LDH materials have a general formula:
x h n i

II
Ax=n $mH2 O
M1x MIII
x OH2
The layers are built up by condensation of octahedrons
with M2 and M3 cations in the center and hydroxides ions
in the vertices. The anion An is exchangeable and can
1
1
. The cationic charges of the layers are
beCO2
3 , NO3 , or Cl
compensated by hydrated anions in the interlayer space.
These LDH materials are promising precursors of multicomponent catalysts [10,11]. Mixed oxide catalysts of high
specific surface area can be obtained through thermal treatment inducing dehydroxylation of the layers and decomposition of the vaporizable anions [12,13]. The LDH derived
catalysts have been reported to exhibit good catalytic activity
and structural stability for a number of reactions, including
FischereTropsch synthesis [14], wateregas shift reactions
[15], base-catalyzed aldol condensations and double-bond
isomerization [16], alkylations [17], and Knoevenagel
condensations [18].
In this work, we investigate nickel catalysts derived
from a MgeAl LDH precursor for hydrogen production using
landfill gas. We present the synthesis of the Ni/Mg/Al
containing LDH precursor, the preparation and characterization of LDH derived Ni catalyst through thermal
treatment, and the activity and stability of the prepared
Ni catalyst for landfill gas conversion. It has been shown
that LDH derived Ni catalysts show promise as active and
stable catalysts for landfill gas conversion to produce
hydrogen.

2.

Experimental

2.1.

Preparation of the LDH precursor

11489

The LDH precursor was synthesized through co-precipitation

under low supersaturating conditions. A solution containing
the metallic nitrate salts Ni(NO3)2$6H2O, Mg(NO3)2$6H2O,
Al(NO3)3$9H2O and a solution of 0.5 M NH4OH were fed to
a glass beaker simultaneously. pH was maintained at
a constant value of 8.5  0.5 during precipitation. The
precipitates were aged while stirring at 25
C for 4 h after the
precipitation was complete. The solid product was separated
using filtration and washed thoroughly using distilled water. It
was then dried 20 h in air at 100
C in an electric oven. The Ni
wt% is 6.0% in the LDH precursor.

2.2.

Preparation of LDH derived Ni catalyst

Considering the high reaction temperatures for the landfill gas

conversion, the prepared LDH precursors were divided into 4
samples and placed in a furnace for thermal treatment
between 600 and 900
C. The final thermal treatment
temperatures were set at 600, 700, 800, and 900
C, respectively. Samples were calcinated for 8 h in air and named LDH600, LDH-700, LDH-800, and LDH-900, respectively.

2.3.

Characterization of the LDH derived Ni catalyst

Thermogravimetry (TG) was performed in a PerkineElmer,

Pyris Diamond TG/DTA instrument for the LDH precursor
and spent Ni catalyst after 48 h of reaction time to test for
landfill gas conversion. As well, the LDH derived Ni catalyst
was measured using N2-physical adsorption. Specific
surface area was calculated using the BET method. Pore
volume and diameter were obtained from the adsorption
branch of the N2 isotherm by the BarretteJoynereHalenda
(BJH) method. X-ray powder diffraction (XRD) analysis was
conducted for the fresh LDH derived Ni catalyst using
a Shimadzu XRD-6000 diffractometer. The reducibility of
LDH derived Ni catalysts were investigated through
temperature-programmed reduction (TPR) in a quartz
reactor using 3% H2 at a flow rate of 10 ml/min and a ramp
rate of 5
C/min. A Hitachi H-7600 transmission electron
microscope (TEM) was employed to examine the
morphology of the LDH derived Ni catalyst.

2.4.
Landfill gas conversion over the LDH derived Ni
catalyst
Landfill gas used to test the LDH derived Ni catalyst was
simulated using 50% methane (99% purity) and 50% carbon
dioxide (99% purity). The tests were carried out in a benchtop, fixed-bed quartz micro reactor with an inner diameter
of 4 mm, at 750
C and 1 atm. In each test, 10 mg of catalyst
were charged in the reactor and was tested for 48 h. The
catalysts were reduced using hydrogen at 800
C for 4 h
prior to reaction. Reaction products were analyzed using an
on-line GC.

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3.

Results

Table 1 e Physicochemical characteristics of the LDH

derived Ni catalysts.

3.1.

Thermal stability of the LDH material

Sample

SBET (m2 g1)

Vt (cm3 g1)

Dp (nm)

LDH-600
LDH-700
LDH-800
LDH-900

23
220
132
31

0.193
0.351
0.247
0.120

25.5
6.4
7.5
15.4

Thermogravimetry was performed in a temperature range

from 30 to 1000
C. The TG and DTG curves of the LDH sample
are shown in Fig. 1. The total weight loss was 46%, presumably
due to three stages. H2O and NO were identified as gases
released during the thermal treatment. The first stage weight
loss between 73 and 175
C can be attributed to H2O in terms of
moisture. The second stage weight loss between 181 and
300
C was primarily due to H2O bonding to the exchangeable
anions in the interlayer space [19]. The weight loss between
300 and 600
C corresponded to the H2O release from the
dehydroxylation of the layers, accompanied by the evolution
of NO from the residue of NO
3 in the sample. It is clear that the
LDH material tends to be stabilized in terms of weight loss
after 600
C.

3.2.
Textural characteristics of the LDH derived Ni
catalyst
The LDH material was activated to get Ni catalysts through
thermal treatments at 600, 700, 800, and 900
C, respectively.
The obtained catalysts were labeled as LDH-600, LDH-700,
LDH-800, and LDH-900. Table 1 summarizes the physicochemical properties of the LDH materials after thermal
treatment. It is clear that the increase in calcination temperature from 600 to 700
C produced a remarkable increase of
specific surface area, SBET, and pore volume, Vt. Specific
surface area increased from 23 to 220 m2 g1 and pore volume
increased from 0.193 to 0.351 cm3 g1. However, average pore
diameter, Dp, dropped dramatically from 25.5 nm to 6.4 nm.
The change in specific surface area, pore volume, and average
pore diameter indicate that the textural characteristics of the
samples are drastically affected when calcination temperature increases from 600 to 700
C. This is confirmed by the
adsorption isotherms and pore distributions of the LDH
materials shown in Fig. 2.
100

3.3.
Crystalline phase and morphology of the LDH
derived Ni catalysts
The XRD patterns of calcinated LDH samples at various
temperatures are shown in Fig. 3. In comparing the XRD
spectra of the samples, only weak diffraction peaks

280
LDH-600
LDH-700

240

10

LDH-800

80

60

TG

-20

50
-30

40
30

-40

20

160

120

80

-50

40

-60
100 200 300 400 500 600 700 800 900 1000

10
0

DTG ( g/min )

-10

70

Temperature ( o C )

Fig. 1 e TG-DTG profiles of the Ni/Mg/Al containing LDH

precursor.

LDH-900

200

( cm 3/g STP )

Volume of N 2 Adsorbed

DTG

90

TG ( % )

All samples display the type IV adsorption isotherms based

on the IUPAC classification. The LDH-600 exhibited a hysteresis of type H3. Adsorption with respect to total adsorption
was greatest at high relative pressures. It reflected that macropores accounted for a majority of pore volume and the
mesopores contributed the rest [20]. The LDH-700, 800, and
900 adsorption isotherms had the type H2 hysteresis loops,
which are the typical shapes of network mesopores. It is clear
that the increase in calcination temperature changed the pore
structures of the LDH material. Moreover, the increase in
calcination temperature from 700 to 800 and 900
C resulted in
dramatic drops in specific surface area and pore volume as
well as an increase in average pore diameter. It was attributed
to sintering effects at higher calcination temperatures, where
mesopores are likely to collapse. From Fig. 1, it can be seen
that the decomposition reaction appeared to complete after
600
C in terms of weight loss. Phase transformation of nickel
oxide to spinel and formation of solid solution commenced
and continued at higher calcination temperatures [21].

0.2

0.4

0.6

0.8

Relative Pressure

Fig. 2 e Adsorption isotherms of the LDH derived Ni

catalysts.

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corresponding to NiO can be observed from the LDH-600 and

LDH-700 samples. Well dispersed Ni was observed using highresolution electron microscopy as shown in Fig. 4. Nickel was
evenly distributed in the LDH-600 and LDH-700 samples with
small particles. The increase in calcination temperature of 800
and 900
C intensifies the peaks of NiO phases at 2q 37.2
, 43.2
,
and 62.4
. The intensified XRD peaks indicate the formation of
well-crystallized phases. TEM images in Fig. 4 show that big
particle sizes were realized in the LDH-800 and LDH-900
samples. Furthermore, from Fig. 3 the XRD patterns of LDH800 and 900, spinel phases are shown at 2q 45.2
, 59.8
, and
65.2
. The spinel phases could be NiAl2O4 or MgeAl2O4 or their
composite NixMg1xAl2O4, which were deemed indistinguishable by XRD due to their similar patterns [22,23]. High
calcination temperatures favored the formation of Ni2eMg2
solid solution as well as stoichiometric NiAl2O4 and MgeAl2O4
spinel phases [21]. From the XRD patterns, it can be seen that
the phases of the LDH samples can change significantly when
the calcination temperature is increased from 600 to 900
C.
This confirms the occurrence of phase transformation reactions during high temperature thermal treatments of the LDH
material.

3.4.

Reducibility the LDH derived Ni catalysts

The temperature-programmed reduction (TPR) profiles of the

samples are shown in Fig. 5. During the reduction of the LDH600, there were two broad domains, both with shoulders
signifying H2 consumption. The low-temperature reduction
range was 250e450
C and the high-temperature reduction
range was 650e950
C. The low-temperature H2 consumption
can be ascribed to the reduction of NiO. The existence of NiO
phases were confirmed by the XRD analysis. The NiO phases
had low interaction with the MgeAl layers [22] and was easy to
be reduced under H2 atmosphere. With the increase in
thermal treatment temperature, the interaction between NiO
and MgeAl layers increased through solid-state reactions.
Spinel type solid solutions NiAl2O4 and/or NixMg1xAl2O4 can
be produced. This was clearly demonstrated by the

Fig. 4 e TEM of the LDH derived Ni catalysts.

disappearance of low-temperature reduction of NiO in the

samples LDH-700, LDH-800, and LDH-900. Consequently,
higher thermal treatment temperatures required higher
reduction temperatures. As shown in Fig. 5, the reduction
peaks shifted to higher temperatures in the LDH samples with
increased thermal treatment temperatures. The high-

Intensities ( a.u. )

LDH-900

LDH-800

LDH-700

LDH-600
5

10

15

20

25

30

35

40

45

50

55

60

65

2 x Theta ( degree )
Fig. 3 e The XRD patterns of the LDH derived Ni catalysts.

70

75

80

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100

LDH-600

LDH-900

LDH-700
LDH-800

LDH-800

LDH-700

LDH-600

200

400

600

800

1000

Temperature ( o C )

Fig. 5 e Temperature-programmed reduction profiles of the

LDH materials.

Methane Conversion ( % )

Intensities ( a.u. )

90

LDH-900

80

70

60

50
0

10

20

30

40

50

Time ( h )

temperature H2 consumption domain existed in all the LDH

samples. The trend had broader shoulders in comparison with
the low-temperature reduction in the LDH-600 sample. The
broader reduction temperature range indicates that several
different nickel species were formed through solid-state
reactions during the thermal treatment process [24]. As indicated by the XRD analysis, they could be NiAl2O4 and/or
NixMg1xAl2O4, both of which are reported to have difficulty in
reduction [23e25].

3.5.
Landfill gas conversion using the LDH derived Ni
catalysts
Landfill gas is the product of microbiological decomposition of
land-filled garbage. Typical landfill gas is composed of 45e50%
methane and 45e50% carbon dioxide, including hundreds of
other impurity gases such as nitrogen, moisture, and oxygen.
As expressed in Eq. (1), to convert landfill gas into valuable
synthesis gas or hydrogen has significant environment and
green-energy implications.
CH4 CO2 /2H2 2CO DH 247 kJ

(1)

The LDH derived catalysts were tested using the simulated

landfill gas at 750
C, 1 atm, and 240,000 h1 of GHSV. Other
conditions including higher temperatures were not considered due to the fact that at higher temperatures the methane
conversion is close to equilibrium where it is hard to evaluate
the catalyst deactivation. The activity of the catalysts in terms
of methane conversion was shown in Fig. 6 and also
summarized in Table 2. Here the methane conversion rate is
defined as the percentage of reacted methane out of the total
feeding methane. The major products of the reaction are
hydrogen and carbon monoxide with minor byproduct of
water. As shown in Fig. 7, the H2/CO ratio was between 0.60
and 0.85 and relatively stable in comparison to the methane
conversion. The H2/CO ratio was lower than 1.0 due to the
formation of water which was the product of side reactions
between hydrogen and carbon dioxide.
The catalytic activity of LDH-600 in terms of methane
conversion slowly increased in the first 20 h of reaction time.
Methane conversion rose from 66.5% at the beginning, to

Fig. 6 e Catalytic activity of the LDH derived Ni catalysts in

terms of methane conversion during a 48 h testing period.

80.5% at the 20th hour. From the 20th to 30th hour of reaction
time, the methane conversion of LDH-600 stabilized at
approximately 80%. The LDH-600 activity started to drop after
the 30th hour of reaction. At the end of testing, methane
conversion of LDH-600 was 76.3%. Ruchkenstein et al. [24] and
Zhang et al. [25,26] reported that the increased activity of
catalysts during the initial stage of methane dry reforming is
due to the formation of new active sites. These are created
when the catalyst is exposed to the reaction mixture. The
reaction took place at 750
C, which is higher than the thermal
treatment temperature of LDH-600. The higher reaction
temperature induced phase transformations and a change in
the nature of active sites. The products of landfill gas
conversion were hydrogen and carbon monoxide, which can
continue to reduce the nickel to Ni0 in the catalysts.
Similar activity evolution behavior was also observed over
LDH-700, where activity increased in the first 2 h and dropped
afterward. The activity evolution behavior of LDH-700
occurred faster in comparison to LDH-600. This indicates
that phase transformation plays a more important role in the
formation of new active sites than continuous reduction by
hydrogen and carbon monoxide. The activity of LHD-800 was
very stable in terms of methane conversion. Conversion was
in the range of 80.0e81.0% during the entire testing period.
The stable performance of LDH-800 further confirms the

Table 2 e Catalytic activity and carbon formation of the

LDH derived Ni catalysts.
Sample

Initial
Conv.
(%)

Max
Conv.
(%)

Final
Conv.
(%)

Final /Max
(%)

Carbon
formation
( gc/gcat)

LDH-600
LDH-700
LDH-800
LDH-900

66.5
75.5
80.5
83.0

80.5
77.5
80.6
83.0

76.3
67.2
80.0
72.0

94.8
86.7
99.3
86.7

0.0112
0.0381
0.0001
0.0853

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 1 4 8 8 e1 1 4 9 4

Fig. 7 e H2/CO ratio as a function of reaction time.

assumption of phase transformation of the LDH-600 and LDH700 in a higher reaction temperature of 750
C. Since this
temperature is higher than their thermal treatment temperatures, it is possible that the catalyst undergoes further phase
transformation. It is interesting to see that the LDH-900 had
the highest initial activity of 83.0%; however, it dropped to
72.0% at the end of testing and showed faster deactivation in
comparison with other samples performance. TG analysis for
the spent LDH derived catalysts showed that LDH-900 had the
most severe carbon formation in comparison with other
samples, as shown in Table 2. Using maximum methane
conversion to indicate stable activity, one finds that stability
followed the order of LDH-800 > LDH-600 > LDH-700 LDH900. TG analysis for the spent catalysts showed that carbon
formation followed the opposite order of LDH-900 > LDH700 > LDH-600 > LDH-800. The correlation of stability and
carbon formation indicates that carbon formation is the major
cause of deactivation in LDH derived catalysts used in landfill
gas conversion.

4.

Discussion

4.1.
Catalyst properties and catalytic activity of the LDH
derived Ni catalysts
For solid heterogeneous catalysts, surface area is critical as it
is related to the availability of catalytic active sites, but is not
proportional to the activity of LDH derived Ni catalysts. LDH700, with the highest specific surface area, had the lowest
activity and the lowest stability among the samples. LDH-800,
with the highest activity and stability, had less surface area in
comparison with LDH-700. It suggested that higher surface
area of the LDH did not provide higher amount of active sites.
Zhang et al. [10] reported it is necessary to calcine catalysts at
a temperature higher than reaction temperature. Catalysts
made in this way possess strong interactions between metals

11493

and support, resulting in the formation of stable active sites.

The higher reduction temperature of LDH-800 indicates that it
had stronger metal-support interaction. It was reported that
sintering occurs when the metal-support interaction is weak
[27]. Due to its weaker metal-support interaction, sintering
likely caused the fast deactivation of LDH-700. LDH-600
possessed better activity and stability, but also a weaker
metal-support interaction than LDH-700, as indicated by their
TPR profiles. This further suggests that metal-support interactions are not the sole factor in determining active sites of
the LDH derived Ni catalyst.
From the TPR profile, it is clear that LDH-600 had two
reduction peaks. The low-temperature H2 consumption was
confirmed due to the existence of NiO species. The NiO species
also serves as active sites upon reduction for landfill gas
conversion. The different active sites from the NiO species
may be attributed to the higher maximum activity of LDH-600.
LDH-900 possessed the highest maximum activity and also
had the strongest metal-support interaction among the
samples. It did, however, have the most severe carbon
formation and fastest deactivation. From the TEM images, it is
clear that LDH-900 had the largest metal particle sizes among
the samples. It has been reported by many research groups
that large metal particle sizes accelerate carbon formation
and deactivation [22,28,29]. The complexity of the relationship
between catalyst properties and activity indicated that the
landfill gas conversion reaction takes place on many active
sites with different nature. It also suggests that the thermal
treatment process is complex and critical during the preparation of catalysts. 800
C appeared to be an optimal temperature for the thermal treatment of LDH derived Ni catalysts for
landfill gas conversion.

4.2.
Carbon formation and stability of the LDH derived
Ni catalysts for landfill gas conversion
It has been well known that carbon formation is the major
cause of catalyst deactivation for methane dry reforming
[17e19]. The correlation between stability and carbon formation shows that carbon formation is the major cause of
deactivation for LDH derived Ni catalysts. Zhang et al. [11]
reported if carbon generation and removal is maintained at
the same rate, no carbon formation will occur on the catalyst
surface, resulting in little catalytic deactivation. Carbon
accumulation rate on the catalyst surface is dependant upon
the carbon removal, as this is the rate limiting step [22,23].
Carbon removal efficiency is determined by the activation of
CO2, which will react with carbon species derived from CH4
decomposition [30,31]. Segner et al. [28] observed that small
particle size prompts CO2 activation. Rostrup-Nielsen [29]
reported that large Ni particles favor carbon formation. As
shown by the TEM image, LDH-900 had large metal particle
sizes, which could explain its severe carbon formation. LDH800, characterized by low carbon formation and excellent
stability, contained small metal particle sizes. LDH-600 and
LDH-700 had even smaller particle sizes when compared to
LDH-800, yet experienced more carbon formation and less
stability. It was reported that exceedingly small metal particle
sizes are susceptible to sintering [32]. This eventually results
in metal agglomeration and larger metal particle sizes. As

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previously discussed, sintering also occurs when weaker

metal-support interactions are present. LDH-600 and LDH-700
carbon formation can then be attributed to both their especially small metal particle sizes, as well as their weaker metalsupport interaction.

5.

Conclusion

LDH derived Ni catalysts show promise as a developing technology for landfill gas conversion. The thermal treatment
process is critical in producing a catalyst which demonstrates
long-lasting activity and reliability. A thermal treatment
process of 800
C is recommended for generating LDH derived
Ni catalysts.

Acknowledgment
The authors acknowledge the financial support from the
National Natural Science Foundation (51078224) and Special
Research Fund for the Doctoral Program of Higher Education
of China (200804221027).

references

[1] Richardson JT, Garrait M, Hung JK. Carbon dioxide reforming

with Rh and PteRe catalysts dispersed on ceramic foam
supports. Appl Catal A 2003;255:69e82.
[2] Ashcroft AT, Cheetham AK, Green MLH, Vernon PDF. Partial
oxidation of methane to synthesis gas using carbon dioxide.
Nature 1991;352:225e6.
[3] Ruchenstein E, Hu Y. Carbon dioxide reforming of methane
over nickel/alkaline earth metal oxide catalysts. Appl Catal A
1995;133:149e61.
[4] Hu Y, Ruchenstein E. An optimum NiO content in the CO2
reforming of CH4 with NiO/MgO solid solution catalysts.
Catal Lett 1996;36:145e58.
[5] Tomishige K, Himeno Y, Matsuo Y, Yoshinaga Y, Fujimoto K.
Catalytic performance and carbon deposition behavior of
a NiOeMgO solid solution in methane reforming with carbon
dioxide under pressurized conditions. Ind Eng Chem Res
2000;39:1891e7.
[6] Choudhary VR, Mamman AS. Simultaneous oxidative
conversion and CO2 or steam reforming of methane to
syngas over CoOeNiOeMgO catalyst. J Chem Technol
Biotechnol 1998;73:345e50.
[7] Zhang J, Wang H, Dalai AK. The development of NieCo
bimetallic catalyst for CO2 reforming of CH4. J Catal 2007;249:
300e10.
[8] Halliche D, Bouarab R, Cherifi O, Bettahar M. Carbon dioxide
reforming of methane on modified Ni/a-A12O3 catalysts.
Catal Today 1996;29:373e7.
[9] Xiao T, Suhartanto T, York A, Sloan J, Green M. Effect of
molybdenum additives on the performance of supported
nickel catalysts for methane dry reforming. Appl Catal A
2003;253:225e35.
[10] Cavani F, Trifiro F, Vaccari A. Hydrotalcite type anionic clays:
preparation, properties and applications. Catal Today 1991;
11:173e301.

[11] Jaimasith M, Phiyanalinmat S. Biodiesel synthesis from

Transesterification by clay-based catalyst, Chiang Mai. J Sci
2007;34:201e7.
[12] Reichle WT, Kang SY, Everhardt DS. The nature of the
thermal decomposition of a catalytically active anionic clay
mineral. J Catal 1986;101:352e9.
[13] McKenzie AL, Fishel CT, Davis RJ. Investigation of the surface
structure and basic properties of calcined hydrotalcites. J
Catal 1992;138:547e61.
[14] Sugier A, Freund E. Oxygenated azatetracyclic compounds,
U.S. Patent 4112110; 1978.
[15] Gines MJL, Amadeo N, Laborde M, Apestegua CR. Activity
and structure-sensitivity of the wateregas shift reaction over
CueZneAl mixed oxide catalysts. Appl Catal 1995;131:
283e96.
[16] Reichle WT. Aldol condensation of acetaldehyde using
calcined layered double hydroxides. J Catal 1985;94:547e57.
[17] Velu S, Swamy CS. Alkylation of phenol with methanol over
magnesiumealuminium calcined hydrotalcites. Appl Catal
1994;119:241e52.
[18] Corma A, Iborra S, Primo J, Rey F. One-step synthesis of
citronitril on hydrotalcite derived base catalysts. Appl Catal
1994;114:215e25.
[19] Ribet S, Tichit D, Coq B, Ducourant B, Morato F. Synthesis
and activation of CoeMgeAl layered double hydroxides. J Sol
Stat Chem 1999;142:382e8.
[20] Gregg SJ, Sing KSW. Adsorption, surface area and Porosity.
2nd ed. New York: Academic Press; 1982. p. 15e97.
[21] Chang FW, Kuo MS, Tsay MT, Hsieh MC. Effect of calcination
temperature on catalyst reducibility and hydrogenation
reactivity in rice husk ash-alumina supported nickel
systems. J Chem Tech Biotech 2004;79:691e9.
[22] Quincoces CE, Dicundo S, Alvarez AM, Gonzalez MG. Role of
Mo in CO2 reforming of CH4 over Mo promoted Ni/Al2O3
catalysts. Mater Lett 2001;50:21e7.
[23] Bradford MCJ, Vannice MA. The role of metal-support
interactions in CO2 reforming of CH4. Catal Today 1999;50:
87e96.
[24] TangS Ji L, Lin J, Zeng HC, Tan KL, Li K. CO2 reforming of
methane to synthesis gas over solegel-made Ni/g-Al2O3
catalysts from organometallic precursors. J Catal 2000;194:
424e30.
[25] Zhang Z, Verykios E. Carbon dioxide reforming of methane to
synthesis gas over Ni/La2O3 catalysts. Appl Catal A 1996;138:
109e33.
[26] Zhang Z, Verykios E, MacDonald S, Affrossman A.
Comparative study of carbon dioxide reforming of methane
to synthesis gas over Ni/La2O3 and conventional nickelbased catalysts. J Phys Chem 1996;100:744e54.
[27] Bond GC. Metal-Catalysed reactions of hydrocarbons.
Springer; 2004. 77e90.
[28] Segner J, Campbell CT, Doyen G, Ertl G. catalytic-oxidation of
Co on Pt (111) e the influence of surface-defects and
composition on the reaction dynamics. Surf Sci 1984;138:
505e12.
[29] Rostrup-Nielsen JR. Fuels and energy for the future: the role
of catalysis. Stud Surf Sci Catal 1991;68:85e94.
[30] Bitter JH, Seshan K, Lercher JA. The state of zirconia
supported platinum catalysts for CO2/CH4 reforming. J Catal
1999;183:336e43.
[31] Nagaoka K, Seshan K, Aika KI, Lercher JA. Carbon deposition
during carbon dioxide reforming of Methanedcomparison
between Pt/Al2O3 and Pt/ZrO2. J Catal 2001;197:34e42.
[32] Frusteri F, Arena F, Calogero G, Torre T, Parmaliana A.
Potassium-enhanced stability of Ni/MgO catalysts in the dryreforming of methane. Catal Comm 2001;2:49e56.