A review on direct methane conversion to methanol by plasma

Antonius Indarto
Korea Institute of Science and Technology, PO BOX 131 Cheongryang, Seoul, South Korea
Università degli studi di Torino, Corso Massimo D’Azeglio 48, Turin, Italy

Abstract: The topic on conversion and utilization of methane were important issues in
tackling the global warming effect. Several technologies including catalytic and plasma were
proposed to improve the process involving the conversion and utilization of methane. The
direct conversion of methane to methanol in the assistance of plasma has attracted a great deal
of attention in recent years. In this reviewed paper, the usage of methanol and concept of
plasma were brief summarized. The recent advancements in direct conversion of methane to
methanol by plasma were summarized. The synthesis methanol from methane and oxygen,
methane and carbon dioxide, methane and water, methane and nitrogen oxide by plasma were
discussed in this article. Various effects of feed gas ratio, gas flow rate, applied voltage and
inert gas on the conversion and reaction selectivity were clarified mainly on methane and
oxygen system. Plasma technology served as an unconventional catalysis will be widely used
in methane conversion to methanol.

Key words: methane; non-equilibrium plasma; methanol; plasma reactor

1. Introduction

Oil and natural gas, the main fossil fuels, not only remain our major energy sources but they
are also the feedstocks for a great variety of manmade materials and products that range from
gasoline and diesel oil to varied petrochemical and chemical products, including synthetic
materials, plastics, and pharmaceuticals. As the fossil fuels continue to be significantly depleted
and will become increasingly costly, we need to search for new sources and solutions.
The natural gas, with more than 90% consists of methane, is becoming a new promising
resource to replace the petroleum oil. Recently, the studies related to the utilization of methane are
increasing. One of them, and could be the most challenging is the conversion of methane methane
to liquid chemical. There are, however, two major reasons: 1. Most of natural gas is found in
remote areas far from the consumer markets, it is difficult to transport and needs special pipelines.
In situ process to convert methane to liquid chemical will reduce the cost of the transportation; 2.
As the fuel cell is more preferable as the clean electrical resources together with the safety
consideration, the liquid fuel from methane could be more promising. Many attempts have been
made to synthesize methanol from methane [1]. Recently, studies were also carried out in
producing methanol from methane by plasma [2].
Methanol is a clean renewable fuel with a large part of useful energy and is in great demand as
an intermediate source of energy, particularly in space heating, automobiles, fuel cell, electric
power generation, and so on. In order to decrease the effect of automobiles’ off-gas on air,
methanol is being recognized as a replacement for methyl tertiary butyl ether, used as an additive
in petroleum to increase the oxygen content. Therefore, methanol could prove to be a principal
fuel for the 21st century.

1.1. In dus tria l methanol synthesis

Nowadays, methanol is manufactured by a two-step method, which means that, to begin with,
syngas is produced from methane,
CH4 + H2O  CO + 3H2 ΔHo = 206 kJ/mol (1)
o
CH4 + ½O2  CO + 2H2 ΔH = -36 kJ/mol (2)
then, methanol synthesis from syngas. This process is called indirect routes.
CO + 2H2  CH3OH ΔHo = -90.6 kJ/mol (3)
o
CO2 + 3H2  CH3OH + H2O ΔH = -49.5 kJ/mol (4)
o
CO + H2O  CO2 + H2 ΔH = -41.2 kJ/mol (5)
As the first reaction is highly endothermic, the process suffers from high cost and thermal
insufficiencies. The second process is an exothermic reaction and needs copper as catalyst. The
synthesis reactor is typically operated at the condition of high temperature and high pressure to
achieve high yields of methanol. On the other hand, this environment tends to shorter the lifetime
of the catalyst due to sintering of the active metal on the surface of the catalyst.
Due to the fact that the commercial methanol synthesis process is energy intensive, it may not
be economical when the natural gas is in remote places or expensive. However, a desirable
alternative maybe the direct partial oxidation of methane to methanol since a one-step process
could potentially reduce both capital and operating costs. Meanwhile, an increasing number of
applications and manufacturing processes that require methanol in much smaller quantities than
refineries or methanol plants emerge, e.g. in fuel cell applications [3]. Developing new techniques
and processes of direct conversion of methane to methanol is becoming a challenging research
subject. Among other methods and techniques, non-thermal plasma chemical process is one of the
most promising technologies in synthesizing methanol.

1.2. Plasma and plasma chemistry

Plasma can be defined as gas consisting of electrons, highly excited atoms, ions, radicals and
molecules photons and neutral particles. One important type of plasma is the non-thermal plasma
in which the electrons have a much higher energy than the other particles. Non-thermal plasma is
also called non-equilibrium plasma due to the difference of temperature or kinetic energy between
the electrons and the neutral particles [4].
The non-thermal plasma can be generated and maintained by electrical discharge such as
corona discharges, pulse discharge, microwave discharge and dielectric-barrier discharge (DBD).
DBDs have been known for more than a century. The bulk gas temperature remains as low as
room temperature, while the electrons can reach as high as 10 5K in a dielectric-barrier discharge.
The gas discharge can produce non-thermal plasma by applying a high voltage to a gas space and
inducing gas breakdowns. The gas breakdowns generate electrons that are accelerated by an
electric filed forming non-thermal plasma. In the plasma reactor, the energetic electrons collide
with reactant molecules in the gas, resulting in excitation, ionization, electron multiplication and
the formation of atoms and metastable compounds [5]. The active atoms and metastable
compounds then collide with molecules, and reactions then happen. When the electric filed in the
discharge gap is high enough to cause breakdowns in most gases, a large numbers of micro-
discharges can be observed.
Recently, the use of non-thermal plasmas has been proposed as a new technology for
methanol synthesis at ambient pressure and room temperature. The basic principle of this
technique is the same as the above described. A lot of investigations have been made to apply
plasma chemical reaction for direct methanol synthesis from methane in combination with other
gases such as O2 [6-16], CO2 [22-25], H2O [26-28], etc.

2. Plasma-chemistry of methane to methanol in the presence of oxygen

2.1. Various designs of plasma reactor for CH4 and O2 conversion to methanol

(a) Double-cylindrical tube reactor by Larkin et al. [7]

(b) Single-Cylindrical tube reactor by Okumoto et al. [10]

 (c) Micro-scale DBD by Nozaki et al. [16]

Figure 1. Various designs of plasma reactor

Various designs of plasma reactor for methane and oxygen conversion to methanol have been
proposed shown in Figure 1. A dielectric-barrier discharge (DBD) is one of the most extensively
investigated devices producing non-thermal plasma at ambient pressure and room temperature.
The typical tubular discharge reactor is consisted of two concentric cylinders. The outer cylinder
serves as ground electrode. The inner cylinder is usually made of glass or quartz tube and acts as
the dielectric. A metal rod, made of steel or copper, is located the inner wall of the inner cylinder
and acts as another electrode. The feed gases flow along axially in a gas gap between the two
concentric cylinders. This type of reactor has a captive nature with a glass dielectric that evenly
distributes the “micro-discharges” and limits their duration [6].
The DBD reactor was considered as the catalytic reactor an analog to a catalytic reactor by
Larkin et al. [7] because the DBD reactor reduced the required temperature and pressure needed
for reactions to occur within it as well as control product selectivity just as with the catalytic
reactor which was shown in Figure 1(a). In their studies, the DBD reactor was used to synthesis
methanol from methane and oxygen. However, methanol partially oxidized from methane could
further react to form other oxygenates such as formic acid, formaldehyde and methyl formate. The
partial oxidation of methane to methanol with oxygen or air was investigated experimentally and
theoretically in a DBD by Zhou et al. [8]. The highest methanol yield of 3% and 2% were
obtained respectively in CH4/O2 mixtures and CH4/air mixtures.
Another type of DBD reactor was proposed by Aghamir et al. [9] and Okumoto et al. [10]. It
was shown in Figure 1(b). Their discharge reactor consisted of a 10mm inner diameter quartz tube,
which was also served as dielectric barrier. Two electrodes, one made of a stainless steel rod and
the other made of a 15cm long aluminum foil, formed the anode and the cathode of the discharge.
The aluminum foil was tightly wrapped around the quartz tube, which had a 12mm outer diameter.
The stainless steel electrode had 2mm diameter and was placed on the symmetric axis of the tube.
Two gas inlets located at the top and the bottom of the reactor provided a means for the gas to
flow steadily. Non-thermal plasma was generated in this DBD reactor. C2 hydrocarbons and
methanol were produced in their research and the selectivity of methanol was as high as 75%
when the ac applied voltage is 16 kV. Similar principles were shown by Okumoto et al. [10] using
pulsed corona discharge with co-axial cylindrical reactor. The inner metal electrode was a stainless
steel wire and an outer electrode of aluminum sheet wraps around a quartz tube. The quartz tube
prevented sparking between the electrodes. The pulsed corona discharge reactor has been used by
other researchers for synthesizing methanol from methanol and oxygen [11-15].
An interesting reactor design was also proposed by Nozaki et al. [16] using a micro-plasma
reactor shown in Figure 1(c). It consisted of a Pyrex thin glass tube and a twisted metallic wire
inside the tube. The reactor was secured in a heat reservoir to maintain a constant reaction
temperature. A high-voltage sine wave was applied between the twisted metallic wire and the
grounded heat reservoir. The principal of generating plasma was similar to DBD which was
characterized by a large number of filamentary micro discharges of 1-10 ns duration. In this
reactor, methanol was the major product, whose selectivity reached 34% at 30% of methane
conversion.
Although the designs of the above four reactors were different, they all belonged to DBD
reactor. They all had large volume excitation and the entire electrode area was effective for
discharge reactions. Moreover, the electron density in DBD was higher than other kinds of plasma
reactor. All of these advantages were benefit for the conversion of methane.

2.2. Effect of operating conditions

In synthesizing methanol from methane and oxygen, methane conversion and methanol
formation were affected by many parameters. The main parameters were the feed gas mixing ratio,
residence time, applied voltage and inert gas.

2.2.1. CH4 to O2 ratio

The ratio of methane to oxygen in the feed gas plays an important role to produce a good
selectivity of methanol. Similar to the thermal-based process, O2-rich condition will drive the
reaction to the perfectly oxidation reaction where the products will be dominated by CO 2 [17,18]
and less production of methanol. This situation is similar when the concentration of O 2 in the feed
is low, the lack of oxygen will inhibit the synthesis of methanol and methyl coupling will be the
major pathway. Aghamir et al. [9] reported that the existence of oxygen in gas mixture leaded to
the production of methanol and with the increasing of the ratio O2/CH4, the selectivity of methanol
first increased rapidly, then decreased. The optimum ratio of methane to oxygen was reported to
be 4:1 which result methanol selectivity of 12% in catalyst-free process [19]. Oppositely, it was
concluded by Yao et al. [13], and supported by Larkin et al. [7], that oxygen concentration could
not influence the methane conversion rate and methanol selectivity, but high oxygen concentration
resulted in the increase of CO and CO2 formation. Moreover, the reported methanol production by
plasma method was higher than that resulted by thermal process in all ranges of methane to
oxygen ratios [19].
 Following the different above ideas, it was strongly concluded that the methanol production is
also affected by other variables. Larkin et al pointed that at longer residence time, the produced
methanol will be consumed to the formation of organic acids and formaldehyde [7]. The
difference of reactor used in the experiment and supplied powers could also be the reason of
different results. For example, the applied voltage of former reactor was 23kV, while the later was
only 15kV. The amount of methane activated was mainly influenced by the discharge
characteristics, but the rates of oxidation of ·CH3, ·CH2, and ·CH to CO and CO2 were depended on
oxygen concentrations.

2.2.2. Residence time

Under the conditions of fixed temperature, pressure, and methane/oxygen feed ratio,
increasing the total gas flow rate could increase the methanol concentration in the products
reported by Okumoto et al. [12]. The similar result was reported by Okazaki et al. [11]. A clear
profile of methanol production under different residence times were presented in Larkin et al.
paper [7]. They reported that when the residence time <2.5 s, the methanol selectivity was initially
the dominant products among other organics liquids then decreased gradually on longer residence
time. It means that methanol scavenging reaction was occurred just after methanol formed by
plasma reaction. The methanol will be decomposed to form other oxygenates such as formic acid,
methyl formate.
By different way of the presentation, Indarto’s work shows that the CO 2 concentration was
higher at longer residence times [18]. In the conclusion, they mentioned that longer residence time
will drive the plasma reactions into perfect oxidation reaction by giving more chance to oxygen to
react with molecules. As CO2 is thermodynamically stable molecule, the pathways of CO2
synthesis are preferable. However, the shorter residence time or faster feed to the reactor will
definitely reduce the conversion of methane and affect to the lowering the yields of methanol.

2.2.3. Applied voltage

Voltage and power are the intrinsic property of electrical generator used to generate plasma.
Many studies have examined the effects of different wave power, e.g. alternating current (AC),
direct current (DC), mono-pulse, bi-pulse, etc., or different power strengths on methane
conversion to methanol by plasma. Song et al. showed that different wave forms will result
different products distribution quantitatively [20]. The effect of supplied power will similar to the
temperature effect that higher amounts will produce higher reactants conversion. Aghamir et al.
[9] reported that the conversion of methane increased with an increase in applied voltage and
increasing the applied voltage had almost no effect on the product selectivity in without oxygen
and helium.
In general, many papers mentioned that there is an optimum point of supplied power to the
reactor for methanol production [7,19,21]. This idea is still arguable since Okazak et al. found that
all data coincided closely for various combinations of applied voltage and electrode gap [11].
Below an electric field of 21.3kV/cm, almost no methanol yield was observed.

2.2.4. Nobel gas

 In most synthesizing methanol from methane and oxygen by plasma, the inert gas was added
to feed gas. The inert gas acted as dilution and played an important role on reaction. Firstly, inert
gas could not only decrease the partial pressure of source gases (methane and oxygen), but also it
changed discharge process. Secondly, the breakdown potential of inert gas, such as He, was lower
than that of methane or oxygen on the same condition, discharge could occur in low applied
voltage by adding inert gas to source gases. Thirdly, population of energetic free electrons might
increase as the discharge of inert gas; this would enhance the conversion of methane. The detailed
effect of inert gas on the experiment was much less pronounced. It was reported by Okumoto et al.
[14] that with the increase of dilution ratio which resulted in decreased of the O2 partial pressure,
the methanol synthesis had a peak and then decreased, while ethane production was increased.
They also found that when the O2 partial pressure was kept constant, the methanol synthesis was
increased with increase of the dilution, ethane production stayed still. The number of electron
produced in one pulse was increased at higher dilution ration. The gas dilution analysis among
different inert gases of Ar, He, Ne and nitrogen was investigated by Okumoto et al. [15]. Their
research revealed that for the dilution with these inert gases, the production of liquid products
showed almost the same. Only in the case of using nitrogen as the dilution gas, the maximum
value of the production ability was low compared to other rare gases, but the same tendencies of
enhancement of production with the dilution rate were obtained.

2.2.5. Carbon dioxide (CO2)

Experimental investigations on plasma methane conversion in the presence of carbon dioxide

using dielectric barrier discharges have been conducted. Similar to oxygen, carbon dioxide also
acted as oxidant. Because the oxidizing ability of carbon dioxide was lower than that of oxygen,
the content of methanol in product was very small, even in some experiments no methanol was
detected. For instance, Jiang et al. [22] reported that syngas, light hydrocarbons and liquid fuels
could be produced in plasma methane conversion with carbon dioxide, there was no methanol in
products. It was reported by Zou et al. [22] oxygenates could be produced from methane and
carbon dioxide using DBDs in the presence of starch, a selectivity of oxygenates as high as 41 ％
were obtained. The total oxygenates yield was 5-26wt.%, formaldehyde, alcohols, and acids were
the main compounds. The highest content of methanol in the product distribution of oxygenates
was only 7.1%. Zhang et al. [24] reported that acetic acid was the primary product in the
condensate with the highest selectivity of 5.2 ％ at 66.8 ％ vol. ％ of methane in the feed.
However, the highest selectivity of methanol was only 1.1 ％ . The effect of concentration of
reactants (CH4+O2 and CH4+CO2 mixtures) was studied by Rajanikanth et al. [25]. In their studies,
the maximum methanol concentration reached 5×10-3(mol) in case of CH4+O2, but only 4×10-
3
(mol) of methanol production was observed in the case of CH4+CO2. The fewer yields might
attribute to energy required to decompose carbon dioxide.
Since methane and carbon dioxide are the top two greenhouse gases which can lead to global
warming, the combination of utilization of carbon dioxide and methane will be promising in
future. More and more researchers have focused on the methanol synthesis directly from methane
and carbon dioxide using plasmas. However, the co-feed of carbon dioxide induces a more
complex product during plasma methane conversion. Except for methanol, other oxygenates such
as formic acid can also be generated. How to increase selectivity of methanol is the ticklish
problem now.

2.2.6. Water (H2O)

Methanol conversion from a gas mixture of methanol and oxygen could be realized under
thermal equilibrium conditions using catalysts. However, this conversion process was not
optimized for the system because an input energy for methane conversion to methanol with
oxygen was used only as a trigger of this reaction and was not stored as chemical energy of
products because of the exothermic process. By contrast, methanol synthesis from a methane and
water-vapor mixture gas had an advantage of being able to store the injected energy as chemical
energy of products since this reaction takes place as an endothermic process. But this conversion
hardly finishes by thermal energy due to increasing of Gibbs free energy via this reaction. In order
to achieve this conversion, some researchers have undergone many investigations on plasma
methane conversion to methanol with water vapor or water.
Methanol was successfully produced from methane and water in a pulsed discharge plasma
reaction by Rajanikanth et al. [26]. They designed three types of reactor: straight wire reactor
(SWR), Helical wire reactor (HWR), and Barbed plate reactor (BPR) and found that Helical wire
and barbed plate reactors performed better than straight wire reactor in synthesizing methanol.
Methanol was synthesized at two different temperatures. The methanol output was highly
dependent on the state of the water in the reactor.
Direct methanol conversion from a methanol and water-vapor gas mixture by spark and a glow-
like discharge was investigated by Hijikata et al. [27]. The conversion and product yield were
depended on applied high voltage time, total pressure and ratio of gas mixture. The maximum
mole fraction of methanol produced from methane and water-vapor by spark and glow-like
discharge were 0.5% and 0.7%, respectively. A newly developed ultra-short pulsed barrier in an
extremely thin glass tube reactor was used by Okazaki et al. [28] to synthesize methanol from
methane and water-vapor mixture gases. In order to enhanced the value of methanol yield, adding
rare gas such as Kr or Ar to the source gas was chosen. Methanol yield reached the order of 1% at
the water-vapor concentration of about 50%. In our previous investigation [29], direct synthesis
methanol from methane and water vapor mixture was successfully realized in a novel plasma
reactor at room temperature and under atmospheric pressure. The plasma reactor was a concentric
cylinder with an inner steel electrode and an outer electrode of copper foil around a quartz glass
tube. The selectivity of methanol could reach as high as 50% and the yield was more than 10%
under optimal condition.
In the process of synthesizing methanol from methane and water vapor using plasma, no
oxidant, such as oxygen or carbon dioxide, is added which can avoid over-oxidation of methane.
Moreover, water, as co-feed reactant, is very cheap and abundant. This process is attractive in
synthesizing methanol through plasma.

2.2.7. Nitrous oxide (N2O)

The partial oxidation of CH4 with N2O to CH3OH was explored in a non-thermal dielectric-
barrier discharge system under mild condition by Matsumoto et al. [30]. The partial oxidation of
CH4 with N2O has been considered to be one of the most selective process in CH3OH synthesis. In
an Ar stream, about 10% of the combined yield of CH 3OH and HCHO, and 40% of the selectivity
to these products were achieved. This value is high compared with the above processes. However,
the experiments on the mixture of CH4+N2O are currently suspended due to the excess production
of lethal HCN gas.

3. Conclusion

The conversion of methane to methanol by plasma technology has just been studied for a few
years. This area is attracting more and more researchers’ attention and is flourishing. However,
there are still a lot of problems needed to be solved. The CH3OH yield in most experiments was
very low. Most experiments on plasma methane conversion to methanol are based on experiences
and the detailed mechanism on synthesizing methanol has not been formed. Only a few
mechanisms were assumed in the experiments [31, 32], but they are still needed to be improved.
In order to increase the methanol yield and methanol selectivity, the combination of plasma with
catalyst may be a good choice.

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