Available online at www.sciencedirect.

com
JOURNAL OF
SCIENCE
@ DIRECT'
Mlm EI4R9lE

JOURNAL OF RARE EARTHS 24 (2006) 5 13 - 5 18 www ,elsevier.Comnocateljre

Partial Oxidation of Methane with Sol-Gel Fe/Hf/YSZ Catalyst in

Dielectric Barrier Discharge : Catalyst Activation by Plasma
Antonius Indarto'**, Jae-Wook Choi' , Hwaung Lee', Hyung Keun Song' * , Jelliarko Palgunadi3
(1. Clean Technology Research Center, Korea Institute of Science and Technology, Korea; 2 . Department of
Chemical and Biological Engineering , Korea University , Korea ; 3 . Hydrogen Energy Research Center, Korea
Institute of Science and Technology, Korea )

Received 11 May 2006; revised 30 June 2006

Abstract: A 1% Fe-30% Hf over yttria-stabilized zirconia catalyst in cornbination with novel plasma-assisted activation
techniques for a direct partial oxidation of methane to methanol was tested using dielectric barrier discharge plasma at am-
bient temperature and atmospheric pressure. However, instead of methanol, the reaction products were dominated by H2,
CO, COZ , C2, and H20. A catalytically activated plasma process increased the production of methanol compared with a
noncatalytic plasma process. The maximum selectivity of methanol production was achieved using a catalyst that was treat-
ed at higher applied power.

Key words : methane oxidation ; dielectric barrier discharge ; catalyst ; plasma activation ; rare earths
CLC number: Document code: A Article ID: 1002 - 0721(2006)05 - 0513 - 05

The catalytic conversion of methane to methanol
is one of the major challenges faced by chemists.
Methane, as the major constituent of natural gas, is
the cheapest source of hydrocarbons, and the demand
for methanol is expected to increase in the near future.
Currently, methanol is produced using synthesis gas
(CO, C 0 2 , and H2) . However, this process can be
drastically changed if an effective method to oxidize
methane to methanol is found. Catalytic homogeneous
oxidation of methane at low temperatures is economi-
cally interesting but very difficult to achieve because of
the high stability of C - H bonds. Much work was re-
ported in the past decade on catalytically oxidative
coupling of methane (OCM) , a promising process for
the direct conversion of natural gas into
Due to the high degree of oxidation reactions in the
gaseous phase as well as on the surface of the catalyst,
the maximum yield of methanol obtained thus far p i n g
OCR! on any catalyst is less than 25%, whereas meth-
anol selectivity is higher than 5 0 % , which is far below
the requirement for making OCM economically attrac-
-
tive ( > 30% 40%)[41.
The oxidation of methane to methanol in nonther-
mal plasmas has been investigated worldwide using co-
rona discharges, spark discharges, gliding arc, and
dielectric barrier discharge (DBD) at atmospheric pre-
ssure and ambient temperature. As a part of the inves-
tigation process, some researchers tried to add auxilia-
ry gases, such as hydrogenr5], airr5-'] , oxygen'6-91,
noble gas'7' l o ] . Others used different types of plasma
discharges that possibly led to the distribution of dif-
ferent products"' - 12' .
This research is a comprehensive study of the
performance of the plasma process and 1%Fe-30% Hf

* Corresponding author ( E-mail : indarto - antonius @yahoo. corn )

Foundation item: Project supported by the National Research Laboratory Program of the Korea Ministry of Science and Technology
Biography: Antonius lndarto (1980 - ), Male, Researcher; Interested field: Plasma and simulation process

Copyright @ZOOS, by Editorial Committee of Journal of the Chinese Rare Earths Society, Published by Elsevier B. V . All rights reserved.
514
over yttria-stabilized zirconia (YSZ) catalyst for partial
oxidation of methane. DBD was chosen as the plasma
medium due to the mild temperature condition that
probably improves methanol synthesis. Among all the
metal catalysts, well-dispersed Fe was believed to be
the most active species that has the ability to activate
methane molecules on the catalyst ~ u r f a c e " ~ - ' The
~~.
reaction that occurs on the catalyst surface is the key
for the conversion of methane to methanol. YSZ was
used as the catalyst support. In methanol synthesis,
YSZ is claimed to be an active component. YSZ
showed better performance as the catalyst support for
methane reforming compared with A1203and Si0,'151.
The existence of Hf in the catalyst structure was used
to maintain the conductivity of catalyst due to molecule
structure. Conductivity is one of the main factors that
can affect the oxidation rate of a reaction.
1 Experimental
Fig. 1 shows the experimental setup. Methane and
oxygen were introduced into the reactor at room temper-
ature and atmospheric pressure. The products were an-
alyzed by gas Chromatography. Details of each part of
the system are described in the following sections.
1.1 Reactor
The reactor is a cylindrical Pyrex tube (ID of 7.5
mm) with two parallel straight wires ( 0 . 2 mm diame-
ter, stainless steel) as the inner metal electrode and
silver film coated on the outer side of the tube as the
outer electrode. A high-frequency alternating current
(AC) power supply was connected to the electrodes.
The effective volume and length of the reactor were
8.8 ml and 200 mm, respectively. To maintain the
similarity of the reactor configuration, e. g. , electro-
des gap distance, the reactor capacitance was checked
by an RCL meter (Fluke PM6304) before and after
the experiments. The reactor capacitance was kept
JOURNAL OF RARE EARTHS, Vol. 24, No.5 , Oct 2006 .
constant in the range of 8 . 5 - 9.5 pF in an air-filled
gap condition.
1.2 Power supply
Plasma was generated by AC power supply (Auto
electric, model A1831), which has a maximum volt-
age and frequency of 10 kV and 20 kHz , respectively.
A digital power meter (Metex, model M-3860M) was
inserted into the electric line of power supply to mea-
sure the total power supplied to the reactor. The typi-
cal waveform of the voltage and the current used dur-
ing the experiments is shown in Fig. 2.
1.3 Materials
All experiments were carried out by introducing
methane (CH4, purity > 99.99% ) and oxygen ( 02,
purity > 99.9% ) with fixed methaneoxygen ratio of
4: 1 (volume basis). The input gases were controlled
by calibrated mass flow conbllers (Milipore, model
FC-280SAV). Analysis of the products was carried out
using gas chromatography ( YoungLin , model M600D )
with a thermal conductivity detector (TCD , Column:
Hayesep D 80/100) for measuring Hz and CH4, and a
flameionized detector (FID) for measuring CH4 and
higher hydrocarbons.
The evaluation of system performance was done
on the basis of product selectivity and methane conver-
sion that are formulated as:
moles of Hz produced
x 100%
Of H2 = 2 x moles of CH4 converted
x x moles of C,H, produced X
Selectivity of C,H, =
moles of CH4 converted
100% (2)
moles of CH30H produced
Selectivity of CH@H = moles of cH, converted X
100% (3)

I
AC power supply
I

Blow heater
Catalyst

Plasma Heating tape

Reactor

Fig. 1 Schematic diagram of experimental set up

 Antonius Indarto et a1 . Partial Onidation Dielectric Bam'er Discharge : Catalyst Activation by Plasma 515

moles of CO, produced
Selectivity of CO, = x 100%
moles of CH, converted
moles of CH, conversion
Conversion of CH4 =
moles of initial CH4
x 100%
The catalyst was prepared by sol-gel technique
using nitrate solution of metal precursors dissolved in
ethanol and oxalic acid, which act as the precipitating
agents. The nitrate solution consisted of 8% mol frac-
tion of Yz03and 1% mol fraction of Fe in the solid so-
lution of 30% rnol fraction of Hf02 and 61% mol frac-
tion of ZrO,. The gel was formed by quick mixing of
nitrate and oxalic acid solution. To ensure equal spe-
cies distribution on the gel, the stirring was vigorous
during the phase transformation from liquid to gel. The
gel thus produced was heated to evaporate the solvent
and dried at atmospheric air. Calcination was done by
increasing the oven temperature at the rate of 2 . 5
T a m i n - ' from room temperature to 650 C
' and kept
constant for 8 h . Fig. 3 shows the XRD spectrum of
the catalyst, which confirms the stable cubic structure
of YSZ. It also shows that the addition of 30% Hf
(Fig.3(b)) does not change the crystal structure of
"t
the YSZ catalyst. Using XRD analysis, the content of
Fe , which was only 1% by mass weight, was relative-
ly difficult to detect.
1.4 Catalyst treatment
(5) Novel catalyst activation approaches by plasma
were used as the variables for the investigation. It be-
gan with the inert gas-plasma treatment. In our experi-
ment, first, helium was used at applied power of 75 W
for 2 h . The flow of helium was controlled at
10 ml*min-'. The next step was plasma-assisted oxi-
dation (PAO) , which was carried out by flowing a gas
mixture of oxygen-helium at the ratio of 6 : 4 for 2 h .
The total gas flow rate and supplied power were 10
ml-min-' and 50 W, respectively. The third step was
plasma-assisted reduction (PAR) , which was done by
flowing a gas mixture of hydrogen-helium in the ratio
of 6 : 4. Plasma reduction was done at the supplied
power of 50 W and total gas flow rate of 10 ml-min-'
for 2 h . Fig. 4 shows the waveform of applied plasma
during the activation process. To check the effects of
each step, the treatments using the catalyst was divid-
ed into four cases as follows: ( 1) no-treatment, ( 2 )
helium plasma treatment, ( 3 ) helium + PA0 treat-
f LUU
ment, and ( 4 ) helium + PA0 + PAR treatment. To
check the stability and durability of the catalyst, con-
tinuous reaction was canied out for 80 min and the
first data point was obtained at the 20th minute.

<
._2
2
*
z
3
1-200 -2
-25 -15 -5 5 15 25 2) lie : 02=4 : 6, so w
'Time cycld !-Is (3) H e : H,-4 : 6, SOW
-6
Fig.2 Voltage and current profile -2 -1 0 I 2
Timc/lOTmin

(3) Hc : H2=4 : 6, 5 0 W
I -0.08
10 20 30 40 50 60 70 80 00
-2 -1 0 1 2
2 "/(") Timeil0-' inin
Fig.3 XRD spectra of catalyst after calcination Fig.4 Profile of voltage ( a ) and current waveform ( b ) of plas-
( 1 ) Pure YSZ; (2) 30% Hf/YSZ ma-assisted catalyst activation
516
2 Results and Discussion
2.1 Non-catalytic process
The direct methane oxidation process using DBD
was conducted at ambient temperature and atmospheric
pressure. The total gas flow rate and the ratio of meth-
ane to oxygen were kept constant at 30 ml*min-’ and
4 : 1 (vol/vol) respectively, and the power supplied to
the plasma reactor was varied by 50, 60,and 80 W.
Our previous research shows that different power sup-
plies produce different pathways of reactions for meth-
ane ~ o n v e r s i o n [ ~.” ~ ” ~ ~
Table 1 shows the effect of power variations on
the methane conversion. The conversion gradually in-
creased and reached a maximum of 25.7 % at the sup-
plied power of 80 W. It can be easily concluded that
increasing the power will increase the energy that is
required to break the chemical bond of methane. In
contrast to the thermal process, in the direct methane
oxidation process using DBD, the energy supplied in
the plasma reactor is used to activate the molecules to
a higher energy level or to produce nonoeutral species,
such as electrons and ions. These species, especially
electrons, have enough capacity to break the chemical
bond of methane.
As shown in Table 1 , the products were dominat-
.
ed by H , CO , and CO, The selectivity of hydrogen is
-
in the range of 10% 15%. However, the selectivi-
ties of CO and COz, which were classified as undesir-
able products, were around 48% and 22% , respec-
tively. Higher hydrocarbons (C,) were also detected,
and ethane was the most predominant undesirable
product.
The highest selectivity of H, was produced at the
highest supplied power. It is believed that the fiag-
mentation of methane into smaller molecules, for ex-
ample, H, and C , is more favorable than recombinant
reactions to produce higher hydrocarbons, and this
will lead to the redecomposition reactions of higher
hydrocarbons produced during plasma reactions by
Table 1 Methane conversion and products distribution (data were obtained at the ratio of CH,:O2= 4: 1 and flow
rate of 30 ml*mh-’)
Supplied CHq Sd&ivity/%
power/W conversion/% H~ co c02
50 20.17 f 3.07 11.28 f 0 . 9 49.73 f 4.12 22.09 f 3.04
60 23.43 f 2.95 11.05 f 4.18 *
48.42 4.18
22.39 2.29
80 25.76 f 3.56 14.19 i 2.38 48.44 f 3.07 21.47 f 2.63
JOURNALOFRAREEARTHS, Vo1.24, No.5, Oct. 2006
electron and other energetic species.
Electron, which plays an important role in cold
plasma process, for example, DBD[~], will initiate
radical reactions :
CH4+ e+CH4 (6)
CH4*+CH3* + H - + e ( 7)
A recombinant reaction of higher hydrocarbons is
brought about by the coupling reactions of methyl radi-
cal (CH3 ) . However, the presence of hydrogen in the
reactor will result in an opposite effect as the hydrogen
radical (Ha) has a tendency to become a reducing or a
decomposing agent for higher hydrocarbons.
CH3 + CH3 *-CzH6 (8)
CH3 + CH3 *+CzH4 + H2 (9)
CH3. + CzH3*+C3Hsa ( 10)
C,H, +H*+C,H,-,* +H2 (11)
Instate of H , redecomposition of higher hydrocarbon
can be caused by electrons. Electron collision with
molecules is faster than molecule collision with ion or
radical“81.
2.2 Catalyst-assisted plasma process
To increase the selectivity of methanol as the de-
sired product, 1% Fe-30% Hf over YSZ catalyst was
added to the process and located at the end of the
plasma zone. This location was chosen to prevent the
decomposition of catalytic products by plasma. The
catalyst loaded in the reactor was only 0.5 g . A novel
catalyst activation approaches by plasma were used as
the variable of investigation. Table 2 shows the effects
of the catalyst-assisted plasma treatment on methane
oxidation. The power supply was kept constant at 80
W and methane to oxygen ratio was 4:1. It shows that
the plasma treatment activates the catalyst. Using
DBD, the gas bulk temperature is equal to the room
temperature, which is much lower than the tempera-
ture required to activate the catalyst. However, the
abundance of energetic-unstable species, such as elec-
tron, ion, and radical species, can be the source for
catalyst activation in the catalyst-assisted plasma treat-
ment process.
Yields/%
CP c3 CH30H
19.67 f 2.29 7.33 f 0.76 5 . 4 4 f 0.35
*
19.13 f 2.29 7.60 f 2.29 5.17 f 0.1
15.33 i2.04 5.14 i1.22 4.49 f 0.57
 Anfonius Inahrto et a1 . Partial Oxidation Dielectric Barrier Discharge : Catalyst Activation by P l a s m 517

Table 2 CH,:O, = 4:1, Effects of catalysts on methane conversion and products distribution (Data were obtained at
ratio of flow rate of 30 ml-min-' and suDDlied Dower of 80 W)
Selectivity/% Yields/%
Supplied CHq
treatment conversion1% Hz co co2 ~
cz _
c3
_
CH30H
Blank 25.76k3.56 14.19k2.38 48.44k3.07 21.4722.63 15.33k2.04 5.14t1.22 4.49k0.57
YSZ 30.80k4.17 28.46k2.18 39.01 k3.079 30.48*2.74 14.90k1.54 0.00 * 0 6.64 f 0.31
No-treatment 24.25+4.34 17.03k2.13 45.54k4.57 20.78k2.67 15.32 k 2.14 3.26k1.23 4.89k0.44
He 34.91k3.33 20.09k2.29 45.02k1.73 11.84k1.37 14.47*1.58 0.00*0 10.14k0.8
He + PA0 30.84 k 2.36 23.72k2.29 54.41 f 2.25 32.05 k 1.78 9.45 f 2.29 o.oo*o 7.42 f 0.22
He + PA0 + FAR 35.34 f 2.56 20.13k1.98 46.77k1.13 11.98k1.29 15.57k1.96 0.00 k 0 9.63 k0.25

Without any treatment, the catalyst does not show
any significant activity in terms of the products distri-
bution differences compared with the blank or pure
plasma process. The production of methanol was
around 4 . 5 % . To study the effect of pure YSZ on the
plasma process, commercialized YSZ made by
TOSOH , was placed in the reactor. It showed that the
yield of methanol increased by factor of 1.4. Another
interesting finding in the experiments was the oxidation
of CO into CO,. The concentration of COz drastically
increased from 21% to 30% and was simultaneously
followed by a decrease in the concentration of CO in
the products. YSZ has oxygen vacancy sites that ad-
sorb 0 - onto the surface of the catalyst, based on this
kinetic scheme"91 :
O2 + e-0, - (12)
0,- + 2e-O;- (13)
0 2 2 - + 2 0 - (dissociation) (14)
0- + Vo,s+ e + O,,,,(incorporation) (15)
The Kroger-Vink notation is used for lattice de-
fects : denotes an oxygen vacancy on the surface of
the catalyst; O,,,, , an oxygen ion in the lattice form;
and e , an electron. Using this proposed formulation,
YSZ is classified as a material for selective oxidation
in the thermal process. This role was not changed in
the plasma reaction caused by the dense population of
0 ions and electrons. However, only the surface-lat-
tice oxygen will be accessible for the catalytic reac-
tion. The reaction between methanelC0 and surface-
lattice oxygen can be the reason for the increasing
methanol and C 0 2 concentrations.
By treating the catalyst using helium, the metha-
nol yield increased from 5% to 10%. It can be prop-
osed that the Fe sites that activate methane on the cat-
alyst surface can be also activated by helium plasma
exposure. Panov et al . described methane activation
on so-called a-oxygen sites that are formed on Fe
sites"31. Knops-Gerrits and Goddard showed the evi-
dent activation of Fe when the Fe metal concentration
was > 0. 5%[201. Based on the methane and oxygen
activation the production of H, will
decrease as some methane molecules will be adsorbed
and reacted with attached 0, to form methanol. This
also occurred in case of CO and CO, . However, a dif-
ferent result was found when the catalyst was oxidized
by 0,.The conversion of CO and especially that of
CO, became higher, which reduced the formation of
methanol. Oxidation of the catalyst transforms the met-
al into metal-oxide catalyst, or weak bonding of metal
and oxygen occurs on the surface of the catalyst. Met-
al-phase transformation decreases the activity to adsorb
methane ; the most possible mechanism that results in
this reduced activity is attributed to the formation of
CO and CO,. This condition can be overcome by con-
ducting the reduction process on the catalyst. Table 2
shows that the production of methanol of the PAR case
was 2 % higher than that without-PAR treatment case.
Based on the amount of methanol produced, the PAR
and PA0 are not urgently required to boost the pro-
duction of methanol. Helium plasma (or probably oth-
er inert gases) treatment was particularly adequate to
activate the catalyst.
3 Conclusion
The partial oxidation of methane using a DBD in
the presence of 1 % Fe-30% Hf over YSZ was dis-
cussed. The maximum methane conversion of the non-
catalytic process is 2 5 . 7 % at a flow rate of
30 ml-min-' and a supplied power of 80 W. The
products are dominated by Hz, CO, CO,, and C,.
The plasma activation techniques show that the catalyst
can be activated, and the yield is different using dif-
ferent plasma treatment methods. Activated by inert
gas (helium), the catalyst shows the highest produc-
tion of methanol. However, PA0 transforms the reac-
tants to complete oxidation products by producing more
CO and CO,.
Acknowledgments: The authors are thankful to the Korea In-
stitute of Science and Technology for its support.
 518
References :
Lee J S , Oyama S T. Oxidative coupling of methane to
. . . .
higher hydrocarbons [J] Catal Rev. Sci Eng , 1988,
30: 249.
Hutchings G J , Scurrell M S, Woodhouse J R . Oxida-
tive coupling of methane using oxide catalysts [ J ] .
Chem. SOC.Rev., 1989, 18: 251.
Amenomiya Y , Bins V I, Goledzinowski M , et. al.
Conversion of methane by oxidative coupling [J] . Catal.
Rev. Sci. Eng., 1990, 32: 163.
Fox J M . The different catalytic routes for methane val-
orization: an assessment of processes for liquid fuels
[J]. Catal. Rev. Sci. Eng., 1993, 35(2): 169.
Liu C J , Mallinson R, Lobban L. Nonoxidative meth-
ane conversion to acetylene over zeolite in a low tempera-
ture plasma [J]. J . Catal., 1998, 179: 326.
Zhou L M, Xue B , Kogelschatz U, et al . Partial oxida-
tion of methane to methanol with oxygen or air in a non-
equilibrium discharge plasma [ J] . Plasma Chem. Plas-
ma Process, 1998, 18(3): 375.
Indarto A , Choi J W , Lee H , Song H K. Effect of ad-
ditive gases on methane conversion using gliding arc dis-
.
charge [J] Energy, 2006, 31( 14) : 2986.
Cormier J M , Rusu I. Syngas Production via methane
steam reforming with oxygen: plasma reactors versus
chemical reactors [ J 1. J. Phys. D: Appl. Phys. ,
2001, 34: 2798.
Nozaki T, Hattori A , Okazaki K . Partial oxidation of
methane using a microscale non-equilibrium plasma reac-
.
tor [J] Catal. Today, 2004, 98 : 607.
Thanyachotpaiboon K , Chavadej S, Caldwell T A , et al.
Reactors, kinetics, and catalysis conversion of methane
to higher hydrocarbons in AC nonequilibrium plasmas
.
[J] AIChE J. , 2004, 44( 10) : 2252.
Song H K , Lee H, Choi J W, Na B K . Effect of elec-
trical pulse forms on the COz reforming of CH, using at-
.
mospheric barrier discharge [ J ] Plasma Chem Plasma
* * * a * * * * * *
Progress of Separation and Determination Methods for Rare Earth Elements
Hu Bin * , Yin Jun ( College of 'Chemistry and Molecular Sciences , Wuhan University, Wuhan
430072, China 1
Abstract: This review coverS the developments in rare
earth elements analysis over the period from 2003 to
2005. Some novel separation and determination meth-
ods and their applications in rare earth elements analy-
sis were presented and discussed in detail. Some new
materials, such as ionic liquids, nanometer materials
Key words : rare earth elements ; separation and determination; review
JOURNAL OF RARE EARTHS, Vol, 24, No.5 , a t . 2006
Process, 2004, % ( I ) : 57.
[121 L i a X S , Z h u a A M , WangaKJ, etal. Methaneconv-
ersion to C2 hydrocarbons and hydrogen in atmospheric
non-thermal p l a s m generated by different electric dis-
charge techniques [J] . Catal. Today, 2004, 98: 617.
[13] Panov G I , Sobolev V I, M k o v K A, et al. Iron com-
plexes in zeolites as a new model of methane monooxy-
genase [ J ] . React. Kinet. Catal. Lett., 1997, 61:
251.
[ 141 Ovanesyan N S M, Dubkov K A, balling A A M. The
Fe active sites in FeZSM-5 catalyst for selective oxidation
of CH, to CH3OH at room temperature [ J ] . J. Radio-
anal. NuclearChem., 2000, 246(1): 152.
[ 151 Chen Y Z , Liaw B J, Kao C F, et al . Yttria-stabilized
zirconia supported platinum catalysts (Pt/YSZs) for CH,/
COZ reforming [ J 1. Applied Catal. A : General, 2001,
217: 23.
[ 161 Indarto A , Choi J W, Lee H, et al. Kinetic modeling
of plasma methane conversion using gliding arc [ J ] . J .
Nat. Gas Chem., 2005, 14: 13.
[17] Indarto A, Choi J W, Lee H , et al. Methane conver-
sion using dielectric barrier discharge: comparison with
thermal process and catalyst effects [ J ] . J. Nat . Gas
Chem., ux)6, 15(2): 87.
[ 181 Liebennan M A , Lichtenberg A J. Principles of Plasma
Discharges and Material Processing [ M 1. New York:
John Wiley & Sons, 1994, 224.
[19] Zhu J, van Ommen J G, Bourneester H J M, et al.
Activation of 02 and CH, on yttrium-stabilized zirconia for
the partial oxidation of methane to synthesis gas [J ] . J .
Catal., 2005, 233: 434.
[ 201 Knops-Gemts P P, W .A. Goddard 111 W A. Methane
partial oxidation in iron zeolites: theov versus experi-
ment [J]. J. Mol. Catal. A: Chem., 2001, 166: 135.
[21] Tabata K, Teng Y , Takemoto T, et al. Activation of
methane by oxygen and nitmgen oxides [ J 1. Catal.
Rev., 2002, 44(1): 1.
* * * * * * * * *
and ion-imprinted polymers, and some new technolo-
gies, such as cloud point extraction, membrane ex-
traction and capillary electrophoresis were successful
used in rare ea& elements analysis. The determina-
tion methods of NAA , ICP-OES and ICP-MS were also
discussed in detail.
(See J. Chin. RE. Soc. (in Chin.), 2006, 2 4 ( 5 ) : 513 for f
d text)