Fundamental Properties and Applications of Dielect

These are not the final page numbers!
((
Chemie
Ingenieur Review Article 1
Technik
Fundamental Properties and Applications of

Dielectric Barrier Discharges in Plasma-Catalytic
Processes at Atmospheric Pressure
Kevin Ollegott1, Philipp Wirth2, Christian Oberste-Beulmann1, Peter Awakowicz2, and
Martin Muhler1,*
DOI: 10.1002/cite.202000075
This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any
medium, provided the original work is properly cited.
The combination of a nonthermal plasma and a heterogeneous catalyst provides unique opportunities for chemical trans-
formations. High densities of reactive species, such as ions, radicals or vibrationally excited molecules, are generated by
electron collisions and initiate a multitude of chemical reactions in the gas phase. By shifting the reaction site from the gas
phase to the surface of the catalyst, the selectivity of these reactions can be significantly enhanced. Dielectric barrier dis-
charges (DBDs) are a promising plasma source for these kinds of applications due to their non-equilibrium conditions
and their simple construction. This review provides a brief introduction to the breakdown mechanism and the various
geometries of DBDs and presents several plasma-catalytic DBD applications.
Keywords: Atmospheric pressure plasma, Dielectric barrier discharge, Hydrogen plasma, Plasma catalysis, VOC abatement
Received: April 07, 2020; revised: July 10, 2020; accepted: July 14, 2020
1 Introduction plasma-chemical process. As O3 is decomposed at elevated

temperatures, thermal processes cannot be utilized. There-
Industrial applications of man-made plasmas include the fore, the non-equilibrium conditions of the plasma are ex-
production of modern microelectronics [1], surface coatings ploited to achieve high ozone concentrations [13]. Other
by plasma-enhanced chemical vapor deposition (PECVD) applications of DBDs are in the biological and medical sec-
[2], surface modifications of polymer films [3, 4], waste- tors including the disinfection of surfaces [19] and wound
water treatment [5], gas purification [6, 7] and many others healing [20]. Advantages of DBDs are low costs for the con-
[8, 9]. Several concepts of plasma discharges and geometries struction of reactors and a low-frequency power supply in
are known such as corona discharges, gliding arc discharges, comparison to other discharge types. Another favorable
atmospheric pressure plasma jets, pulsed microwave dis- property is the scalability by numbering-up [9].
charges, or dielectric barrier discharges (DBDs) [8–10]. A large variety of comprehensive reviews dealing with the
They cover wide pressure ranges from high vacuum to wide field of plasma catalysis has been published during the
atmospheric pressure and above and provide very different last decades [6, 7, 21–31]. Some of them focus on particular
properties [8]. Therefore, each plasma source has its indi- applications such as the oxidation of VOCs [7], while others
vidual advantages depending on the kind of application. emphasize the importance of modeling and simulation to
Especially the combination of a nonthermal atmospheric understand plasma catalysis [24].
pressure plasma source with a heterogeneous catalyst is of
great interest for chemical transformations in gas or air
treatment. Plasma catalysis can achieve improved perfor-
mance in comparison to both methods applied separately –
1
[11, 12]. For example, the reactivity of the plasma may pre- Kevin Ollegott, Christian Oberste-Beulmann, Prof. Dr. Martin
vent catalyst deactivation or reduce catalyst poisoning. Muhler
muhler@techem.rub.de
DBDs are widely used for ozone production [13, 14], ex-
Ruhr University Bochum, Laboratory of Industrial Chemistry,
haust gas purification removing CO [15], NOx [16], SO2 Universitätsstraße 150, 44780 Bochum, Germany.
[17] or volatile organic compounds (VOCs) [18]. Depend- ORCID Martin Muhler: http://orcid.org/0000-0001-5343-6922
ing on the given plasma-catalyst configuration, the long- 2
Philipp Wirth, Prof. Dr.-Ing. Peter Awakowicz
lived or/and the short-lived species generated in the plasma Ruhr University Bochum, Institute for Electrical Engineering and
can contribute to chemical conversion. The formation of O3 Plasma Technology (AEPT), Universitätsstraße 150, 44780 Bochum,
is a well-known example for the unique capabilities of a Germany.
Chem. Ing. Tech. 2020, 92, No. 10, 1–18 ª 2020 The Authors. Published by Wiley-VCH GmbH www.cit-journal.com
’’ These are not the final page numbers!
Chemie
2 Review Article Ingenieur
Technik
This review provides a brief introduction to the applica- sure, breakdown mechanism or the geometry of the setup.
tion of DBDs for chemical conversion and plasma catalysis. In general, two major categories are defined: thermal plas-
The fundamental properties of nonthermal plasmas and the mas and nonthermal plasmas (NTP) [5]. Thermal plasmas,
typical breakdown mechanism of DBDs are discussed to e.g., arc discharges, are in thermodynamic equilibrium and
provide an understanding of the complex chemical reac- all particles have the same temperature. They can be gener-
tions and interactions. The main configurations of DBDs ated by increasing the temperature of the gas. In contrast,
and their unique properties are presented followed by a NTPs like dielectric barrier discharges or corona discharges
short description of the principles of plasma catalysis and are not in thermodynamic equilibrium, and different tem-
the interactions between plasma and catalyst. Based on the peratures are associated with different particles or degrees
oxidation of VOCs the basic mechanisms are discussed. As of freedom [38]. They require a smaller energy input and
part of the Carbon2Chem project the plasma-catalytic are generated by applying electric fields. The electron tem-
removal of oxygen traces from coke oven gas (COG) is perature Te can be several orders of magnitude higher than
investigated, as conventional techniques for the removal of the temperature of the ions Ti or the temperature of the
oxygen traces may be overstrained by the complex gas mix- neutral gas Tg. An equilibration of these temperatures by
tures and numerous impurities. The similar plasma-catalyt- Joule heating is prevented by limiting discharge time or
ic synthesis of H2O2 and its mechanisms are discussed energy input. Typical electron temperatures can be in the
[32, 33]. One main goal of Carbon2Chem is the conver- range of 1–10 eV (1 eV approx. equals 11 600 K), while the
sion of steel mill gases to basic chemicals such as methanol heavy particles stay close to ambient temperature. The elec-
or ammonia to reduce the net CO2 emission of steelmaking trons are accelerated in the electric field and can induce
[34–36]. The future possibilities of plasma catalysis for these vibrational or rotational excitation and chemical reactions
reactions are summarized as well. like ionization, bond dissociation, radical formation and
many others. These chemical reactions do usually not occur
under equilibrium conditions at comparable gas tempera-
2 Nonthermal Atmospheric Pressure Plasma: tures and are directly controlled by the electron temperature
Properties and Breakdown Mechanism and density, or more accurately by the electron energy dis-
tribution function. [8]
In order to gain a deeper understanding of the plasma-
chemical processes, detailed information about plasma for-
mation, the variety of particles and their interactions with 2.2 Electric Breakdown: Townsend Mechanism and
each other are crucial. Therefore, a brief introduction to the Paschen Curves
fundamental properties of nonthermal atmospheric pres-
sure plasmas and to the most significant breakdown mecha- Chemical reactions applied in industry are usually operated
nisms is given in this section. A more detailed description at atmospheric or elevated pressure. The applied pressure
of the physical processes during gas breakdown and plasma influences the mean free path of the gas particles and can,
formation can be found in textbooks [8, 37]. therefore, significantly change the properties of the plasma.
In high vacuum at 10–3 mbar to 10–7 mbar, the mean free
path is in the order of centimeters to kilometers, whereas at
2.1 Definition atmospheric pressure at approx. 1000 mbar, the mean free
path is in the order of tens of nanometers [39, 40]. The short
Matter is commonly thought of to exist in one of three mean free path is associated with a higher collision fre-
states: solid, liquid or/and gas. By increasing the kinetic quency, which is relevant for processes that rely on collisions
energy of the particles, matter can change its state in the such as chemical reactions. However, the pressure is not
given sequence. However, when enough energy is added to only relevant for the mean free path, but also for the voltage
a gas, it starts to get (partially) ionized and transforms into needed to ignite and sustain the plasma. For a simple geom-
a plasma, which is often referred to as the fourth state of etry of two planar metal electrodes separated by a gas, the
matter. A plasma is quasi-neutral as the number of positive- breakdown voltage required to start the discharge in a con-
ly and negatively charged particles is equal, distinguishing it stant electric field is given by Paschen’s law (Eq. (1)). It is an
from similar phenomena such as ion beams. Due to these empirical formula discovered by Paschen in 1889 [41] that
free charges a plasma is electronically conductive and chem- describes the influence of pressure, gap distance and the gas
ically active. It contains a variety of highly reactive species, composition on the breakdown voltage [42, 43].
such as electrons, ions, atoms, radical or metastable species.
Accordingly, it emits electromagnetic radiation. Each of Bpd
UB ¼ (1)
these components may participate in chemical reactions or lnðApd Þ lnð lnð1 þ g1 ÞÞ
interact with the surface of the catalyst [8].
Several types of plasmas and discharges can be distin- with the breakdown voltage UB, the pressure p, the gap dis-
guished according to a variety of parameters such as pres- tance d and g the ion-induced secondary electron emission
www.cit-journal.com ª 2020 The Authors. Published by Wiley-VCH GmbH Chem. Ing. Tech. 2020, 92, No. 10, 1–18
These are not the final page numbers! ((
Chemie
Technik
coefficient of the electrode material. A and B are empirically cules. By repetition of these processes the number of elec-
determined values for each gas. The resulting Paschen trons increases exponentially, and avalanches are generated
curves for several gases are shown in Fig. 1. The required as illustrated in Fig. 2. These ionization avalanches may lead
breakdown voltage at a given pd strongly depends on the to electron densities in the range of 1013 cm–3 and are often
type of gas, because the ionization potential as well as the described by the Townsend ionization coefficient a. On the
mean free path differ for each gas. At larger gap distances other hand, the positively charged ions are accelerated
and higher pressures, the breakdown voltage is approxi- towards the cathode and lead to the emission of secondary
mately proportional to the product of gap distance and electrons from the cathode material according to g. The sec-
pressure. For very small pd the curves tend towards infinity, ondary electrons can then initiate additional avalanches. All
suggesting that it is impossible to create a discharge. How- these processes lead to a rather homogeneous breakdown
ever, this is not necessarily the case and discharges can still and are called Townsend breakdown mechanism provided
occur due to effects that were neglected by Paschen [44, 45]. that a self-sustaining current between both electrodes is
In general, all curves reveal a minimum corresponding to established [8, 47].
the lowest breakdown voltage. Differentiating Eq. (1) leads
to Eq. (2), allowing to identify the gap distance and pressure
of this minimum. At atmospheric pressure p is fixed and
the breakdown voltage primarily depends on the dimen-
sions of the discharge gap.
lnð1 þ g1 Þ
pd ¼ e (2)
A
Actually, Paschen’s law is only applicable to the described

geometry. Nevertheless, it allows gaining qualitative insight Figure 2. Townsend breakdown and electron avalanche forma-
into the plasma behavior when comparing different gases, tion between two electrodes. Adapted from [8].
e.g., to assess which gas requires a lower breakdown voltage.
2.3 Streamer Mechanism

Air
Nitrogen The Townsend breakdown mechanism is limited to relative-
Hydrogen ly low pressures and small gap distances [8]. It is only valid
Breakdown voltage UB / V
Argon
Carbon dioxide
for a parallel plate configuration and heavily relies on the
10000
emission of secondary electrons from the cathode to sustain
the discharge. In case of atmospheric pressure, a more accu-
rate description of the breakdown mechanism is provided
by the so-called streamer or spark mechanism. It is also pri-
1000
marily based on ionization avalanches, additionally taking
the interactions between individual avalanches into account.
The electrons in the head of the avalanche drift away from
the heavier ions in the trail because of their higher mobility,
100
0.1 1 10 100 1000 thereby creating a strong local space charge at the front of
pd / Pa m the avalanche and consequently an additional electric field
ESc. This additional electric field ESc superimposes with the
Figure 1. Breakdown Paschen curves for different gases. The external electric field E0 in such a way that the resulting
data is plotted with Paschen coefficients A and B from [46] and field in front of the avalanche is enhanced. Due to the
[43]. enhanced electric field in front of the primary avalanche,
ionization processes are accelerated, and secondary ava-
The predominant breakdown mechanism for this paral- lanches predominantly grow in this region. If ESc is in the
lel-plate configuration was described by Townsend [47]. same order of magnitude as the external electric field, then
The applied DC (direct current) voltage U generates a cor- the avalanche transforms into a streamer, which can be best
responding constant electric field E = U/d. Primary elec- described as a thin ionized channel growing between the
trons generated naturally near the cathode, e.g., by cosmic electrodes [8, 37]. At short gap distances and relatively low
radiation, are accelerated in the electric field and collide voltages the avalanche-to-streamer transition is only possi-
with gas molecules. Bound electrons are removed from the ble when the avalanche reaches the surface of the anode.
gas molecules by impact ionization and positively charged There are two types of streamers that can evolve: positive
ions are formed. The ejected electrons are again accelerated streamers and negative streamers (Fig. 3). Positive streamers
by the external electric field and ionize further gas mole- propagate towards the cathode. Photons are emitted in the
Chemie
Technik
and thickness of the dielectric material. When the electric

field outside the dielectric is sufficiently high, discharges
occur. At atmospheric pressure these microdischarges typi-
cally have a filamentary structure that originates from the
streamer mechanism discussed in the previous section [50].
In DBDs the build-up of charge on the dielectric causes
an opposed electric field that equalizes the electric field
induced by the applied AC voltage during the initial half
period and prevents the formation of new streamers at the
same position in the same half period. Therefore, streamers
are distributed statistically over the entire discharge gap. A
single streamer is typically choked on a timescale of nano-
seconds and a burst of short-living streamers emerges for
Figure 3. Illustration of the propagation of a positive streamer every half-wave of the applied alternating voltage. Each time
(a) and a negative streamer (b). Adapted from [8]. the polarity is reversed the surface charge accumulated dur-
ing the first half period and the pre-ionized gas facilitates
head of the streamer by electron-ion recombination pro- the formation of a streamer at the same position in the next
cesses and initiate secondary avalanches in front of the half-wave leading to a spatially localized microdischarge.
streamer head by photoionization. The free electrons are This behavior is called memory effect. The short lifetime of
pulled into the ionic trail leaving behind a positive charge in the microdischarges leads to a low heating of the back-
the head of the streamer. Negative streamers propagate into ground gas typically only in the order of several tens of Kel-
the opposite direction towards the anode. The secondary vin. The electrons gain a large fraction of the power
avalanches for negative streamers are primarily initiated by absorbed by the plasma leading to ionization, dissociation
electrons moving in front of the primary avalanche leading and excitation processes that can induce chemical reactions.
to electron impact ionization. In addition, photoionization The typical lifetime of the electrons is in the order of nano-
may also occur for negative streamers. The propagation of seconds, while the ions have lifetimes of several microsec-
both types of streamers is based on the high electric fields at onds [8].
their tips. The corresponding streamer growth velocities are DBDs are attractive for industrial applications and can be
much faster than the electron drift velocity. Depending on divided into two main categories depending on the configu-
the type of streamer the space charge layer at the tip of the ration of the setup. When the space between the electrodes
streamer is either positive or negative, whereas the trail of includes a dielectric and a discharge gap the plasma is
the streamer consists of a quasi-neutral plasma channel [8]. ignited in the volume between the electrodes and, therefore,
referred to as volume dielectric barrier discharge (VDBD).
When the space between the electrodes is completely filled
3 Dielectric Barrier Discharges by a dielectric, the plasma ignites on the surface of the
dielectric that is exposed to the gas volume. Streamers
Dielectric barrier discharges, otherwise known as silent dis- evolve close to the electrodes where the electric field is max-
charges, are transient self-sustained discharges and have imal due to its strong nonuniformity. Such a setup is
been investigated for more than a century. One of the first referred to as surface dielectric barrier discharge (SDBD).
DBDs was already described in 1857 by W. Siemens for the Several DBDs are schematically shown in Fig. 4 and will be
generation of ozone [48]. A variety of different DBD designs briefly discussed in the following sections [9, 51].
and geometries have been proposed in literature, but all
have the following characteristics in common: two elec-
trodes are connected to a high voltage AC (alternating cur- 3.1 Volume Dielectric Barrier Discharges
rent) generator and are separated by at least one layer of
dielectric material. Different dielectric materials such as Typical setups for volume dielectric barrier discharges are
glass, quartz, polymers and ceramics are used to limit the shown in Fig. 4. In the planar configuration (Fig. 4 a–c) the
flow of current from one electrode to the other [8, 9, 49]. dielectric is placed at different positions between the elec-
Due to this current limitation by the dielectric the forma- trodes. In Fig. 4c the dielectric covers the powered electrode.
tion of arcs and the associated heating of the gas are pre- The discharge occurs between the dielectric and the
vented. The presence of a dielectric barrier between the two grounded electrode. Such a setup is often used in medical
electrodes requires an AC voltage supply. Typical driving applications to prevent inadvertent contact of the powered
frequencies range from 50 Hz to 500 kHz, and driving volt- electrode. In Fig. 4b the dielectric is centered between the
ages are in the range of 10 kV depending on the exact reac- electrode, and the discharge occurs in between the elec-
tor configuration [8]. The applied AC voltage induces a dis- trodes and the dielectrics. In Fig. 4a both electrodes are cov-
placement current that is limited by the dielectric constant ered by a dielectric, and the discharge occurs in between the
Chemie
Technik
trode. Offerhaus et al. [53] presented a twin-surface DBD

designed for the application in gas streams based on two
conducting metal grids on both sides of an Al2O3 plate. The
ignition of the plasma was shown to be homogeneous along
the electrode for all tested conditions on both sides of the
electrode configuration.
Due to the low flow resistance and the operation at atmo-
spheric pressure, SDBDs are a research topic for industrial
application in gas and air treatment. Abdelaziz et al. [54]
presented a single-sided setup allowing to ignite a plasma
on the powered side of the electrode. They included spikes
to intensify the electric field in order to intensify the plasma
discharge. The setup was operated at frequencies between
1 kHz and 10 kHz to produce ozone without significantly
heating the gas stream. The production of ozone was found
to strongly depend on the applied frequency and on the
input voltage, which was varied between 3 kV and 6 kV. The
Figure 4. Different configurations of VDBD and SDBD geome- input power was in the range of 0.21 W to 2.02 W depend-
tries: (a) symmetric VDBD with two dielectric barriers, (b) VDBD
with a floating dielectric barrier, (c) asymmetric VDBD, (d) sym- ing on the input frequency [54]. The same setup was used
metric single-sided SDBD, (e) asymmetric SDBD, (f) coplanar for the gas-phase decomposition of naphthalene in dry and
SDBD, (i) symmetric double-sided SDBD, (g) cylindrical VDBD, humid air. The decomposition efficiency again strongly
(h) packed-bed DBD. Adapted from [9]. depended on the applied voltage and was derived to be
around 90 % for 6 kV and a relative humidity between 0 %
dielectrics. Fig. 4h shows a cylindrical setup typically used and 60 % [55].
for industrial-scale ozone production. In Fig. 4i a setup of a
packed-bed DBD is shown. Different packing materials can
be used in direct contact with the plasma. Furthermore, an 4 Plasma-Assisted Catalysis: Principles and
enhancement of the local electric field can facilitate the igni- Interactions
tion of the plasma. Typically, materials with a high dielectric
constant such as BaTiO3 are used to maximize this effect Nonthermal plasmas exhibit unique properties and high
[8, 11]. The plasma parameters of packed-bed reactors can- chemical reactivity [8]. Induced reactions are typically not
not be accessed as easily, which is a drawback concerning limited thermodynamically, because the electrons reach
basic research. Furthermore, the high flow resistance is high temperatures, while the heavy particles almost remain
often disadvantageous for gas treatment. The discharge gap at ambient temperature. However, plasma chemical pro-
of VDBDs is typically in the range of 0.1 mm to several cen- cesses can suffer from low energy efficiencies and a poor
timeters and an AC power supply with a driving voltage of selectivity, which lead to the formation of undesired
around 10 kV is used. VDBDs have been used for various by-products [24, 56, 57]. One of the most promising
applications ranging from disinfection of bacteria [19] to approaches to overcome these drawbacks is the combina-
surface modification [52] to chemical reactions in the gas tion of the nonthermal plasma discharge with a heteroge-
phase. neous catalyst, which is called plasma catalysis, plasma-as-
sisted catalysis or plasma-enhanced catalysis. It can lead to
synergistic effects and conversion efficiencies and yields
3.2 Surface Dielectric Barrier Discharges superior to the theoretical sum of plasma and catalysis
applied separately [11, 12, 22].
When the gap between the electrodes is entirely filled with a In general, two concepts for plasma-assisted catalysis can
dielectric as it is the case for SDBDs, a discharge can only be distinguished depending on the position of the catalyst
occur on the surface. The dielectric changes the shape of the relative to the plasma. In a one-stage configuration, com-
electric field lines leading to a locally enhanced electric field, monly known as in-plasma catalysis (IPC), the catalyst is
which reduces the breakdown voltage and promotes dis- directly placed in the discharge zone, which leads to the
charges close to the surface [8]. Figs. 4d and 4e show sym- strongest interactions between the plasma and the surface
metric and asymmetric single-sided SDBDs, respectively. of the catalyst. The second concept, referred to as post-plas-
The plasma ignites around the powered electrodes. In Fig. 4f ma catalysis (PPC), consists of a two-stage configuration, in
a coplanar setup is depicted. Both electrodes are embedded which the catalyst is placed downstream of the discharge
in the dielectric and the plasma ignites on the surface of the region [21]. The two different concepts are illustrated in
dielectric. In Fig. 4g a symmetric double-sided setup is illus- Fig. 5.
trated allowing to treat the gas on both sides of the elec-
Chemie
Technik
behavior of the discharge, e.g., the formation of microdi-

scharges or enhancement of the electric field at the surface
or in the pores of the catalyst [62]. Therefore, these direct
effects of the catalyst on the discharge are primarily
observed in IPC configurations, where the catalyst is placed
in the discharge volume. Introducing solid materials in the
discharge gap of a cylindrical DBD (with two coaxial quartz
tubes covered by mesh electrodes) drastically alters the
behavior of the discharge [63, 64]. Tu et al. [63] investigated
the influence of TiO2 pellets (500 mm–800 mm) on the dis-
charge in N2. Due to the decreased discharge volume the
number and amplitude of current pulses is reduced. The
presence of the TiO2 pellets hinders the formation of fila-
mentary microdischarges, because they can only ignite in
Figure 5. Schematic illustration of plasma-catalysis configura-
tions. (a) Plasma-only: one-stage configuration without catalyst. the voids between the pellets. Furthermore, surface dis-
(b) In-plasma catalysis (IPC): single-stage configuration with cat- charges are generated across the surface of the pellets.
alyst in the discharge region. (c) Post-plasma catalysis (PPC): Thereby, the discharge changes from a filamentary dis-
two-stage configuration with the catalyst bed positioned down-
stream of the discharge. Adapted from [21].
charge occupying the complete cross section of the void to a
combination of spatially confined microdischarges and sur-
face discharges. As a consequence, a higher applied voltage
Direct and indirect exposure of catalytically active sur- is required to sustain the discharge at a given dissipated
faces to atmospheric pressure plasmas allows for manifold power. Moreover, the vibrational temperature of N2 is in-
physical and chemical interactions [6, 7, 58]. The general creased indicating a shift of the electron energy distribution
principles of plasma catalysis are the same as in convention- function to higher energies [63].
al heterogeneous catalysis. The molecules adsorb on the sur- However, the properties of the solid material such as parti-
face of the catalyst and are then transformed by post-ad- cle size, particle shape, packing structure or the relative per-
sorption chemical reactions. Depending on the nature of mittivity determine its influence on the discharge [63–65].
the adsorbate-surface interaction, a distinction is made Gallon et al. [64] investigated the influence of different
between physisorption and chemisorption. In a Langmuir- materials such as porous quartz wool, Al2O3 and zeolite 3A
Hinshelwood mechanism both reactants are chemisorbed on the performance of the reactor in the H2 production by
on the surface, while in an Eley-Rideal mechanism only one dry reforming of CH4. Due to electron-impact dissociation
reactant is chemisorbed and reacts directly with a gas-phase of CH4 to CH3, CH2 and CH, higher hydrocarbons are
species. The most noticeable change in the reaction pathway formed in addition to H2 and CO. The impact of Al2O3 and
is caused by the presence of the various reactive species. In zeolite 3A on the nature of the discharge is comparable to
an IPC configuration both the long-lived and the short- the one caused by TiO2. Due to the suppression of strong fil-
lived species can reach the surface of the catalyst. Therefore, amentary discharges the conversion of CH4 and CO2 is
not only neutral molecules adsorb at the surface as in ther- decreased in comparison to the empty reactor, while the
mal catalysis, but also ions, radicals, atoms, and electrons selectivity towards both CO and H2 is altered. Governed by
impinge on the surface. Furthermore, vibrationally excited its pore size zeolite 3A enhances the selectivities to H2 and
molecules may adsorb, resulting in a lower effective activa- acetylene/ethylene. To compensate the negative change of
tion barrier for consecutive reactions due to either a higher the discharge properties (decreased discharge current and
energy level of the reactant or a lower energy level of the microdischarges) on the degree of conversion, the catalyst
transition state on a multidimensional potential energy sur- has to be activated under the utilized reaction conditions.
face [59]. Based on ground-state oxygen atoms and .OH On the other hand, quartz wool enhances the conversion of
radicals Kim et al. [27] calculated that species generated at a CH4 due to stronger current pulses. As the material is
distance of 50 mm away from the surface can reach the cata- porous, the void fraction of the discharge gap is rather large,
lyst. The interaction of these species with the catalyst may which does not hinder the strong filamentary discharge.
lead to improved conversion or to completely different reac- Furthermore, surface discharges can form and propagate
tion pathways resulting in products not obtained by apply- along the surface. Holzer et al. [65] focused on the effect of
ing conventional thermal catalysis. The adsorption of these ferroelectric materials and catalyst on the oxidation of vola-
species may also increase the lifetime of the reactants at the tile organic compounds using a coaxial DBD. Filling the
surface [60, 61]. reactor with BaTiO3 pellets, which is a material with a high
Beyond these interactions, it is necessary to distinguish relative permittivity, enhances the energy input by a factor
between effects that the catalyst has on the plasma and of 6–10 in comparison to an empty reactor or a filling with
those that the plasma has on the catalyst. The presence of glass beads. It is proposed that more microdischarges per
the catalyst can have manifold influences on the type and reactor volume or microdischarges with a higher energy
Chemie
Technik
density are generated due to the high relative permittivity. catalytically active nanoparticles on the oxidation of ben-
The effect of the increased surface area can be neglected, zene, it is assumed that the expansion of the plasma area is
because the presence of glass beads does not change the also beneficial [69].
energy input. Furthermore, the composition of the gas On the other hand, various properties of the catalyst can
phase is greatly affected by BaTiO3. Without BaTiO3 the O3 be changed by the atmospheric-pressure plasma. Some of
mole fraction in the exhaust gas linearly increases as a func- these are the morphology of the surface or the electronic
tion of the energy input, whereas for BaTiO3 a maximum properties, like the work function or oxidation state
O3 mole fraction is achieved for medium power densities, [70, 71]. In general, these changes may be caused by (ir)re-
because the generated O3 is thermally decomposed due to versible adsorption of species blocking active sites, implan-
the elevated temperatures of BaTiO3. It was shown that the tation of energetic ions in the bulk of the catalyst, sputtering
energy efficiency for the oxidation of both toluene and or etching [61]. One of the most impressive examples for
methyl-tert-butyl ether is substantially improved by BaTiO3, the extent of structural changes of the catalyst can be found
while the selectivity to CO2 is unchanged. In order to also when a plasma is utilized to prepare catalysts prior to the
improve selectivity, BaTiO3 was combined with the catalyti- reaction. In these cases, the improved activity cannot be
cally active material LaCoO3, which increases the formation related to the reactive species generated by the plasma, but
of CO2 [65]. solely to the structural and electronic modifications of the
Another drastic change of the discharge properties caused catalyst. Gao et al. [70] reported that a pretreatment of Cu
by a porous catalyst is the formation of microdischarges in nanotubes with an O2 plasma can significantly improve
the pores of the catalyst, which was shown experimentally their catalytic activity in the carbon dioxide electroreduc-
[66] and by modeling [67]. Ion and electron densities can tion. They propose that the plasma treatment creates defect
significantly exceed the values outside of the pores, as the sites and stabilizes surface and subsurface oxygen species,
local electric field inside the pores is enhanced. Pore sizes in which modify the adsorption of molecules on the surface
the range of tens to hundreds of micrometers seemed to be [70]. Transferring these observations to an in situ modifica-
the most beneficial [67]. Due to the enhanced electric field tion of the catalyst during the reaction may prevent catalyst
the mean electron energy is increased resulting in a modi- deactivation. Most of the studies on plasma catalysis use the
fied energy pattern of the reactive species as well as a higher same catalysts applied in conventional catalysis. However,
number of reactive species, which may strongly influence plasma-induced modification of the electronic properties
the plasma-chemical kinetics. The enhancements of the may lead to new catalyst systems. Bal et al. [71] investigated
electric field, which may also form at nonporous materials, supported single-atom catalysts containing Ti, Ni or Cu and
are usually caused by two different effects. The local electric reported based on a quantum-chemical model that negative
field is always enhanced at tip-like structures, depending on surface charges not only improve the reductive potential of
the aspect ratio according to Eq. (3) [61]. the catalysts, but also change their relative activity. Further-
more, the trapped surface charges initiate the formation of
E ¼ bE0 (3) streamers as the trapped surface charges are released by
photons emitted from a single filament [72].
Here, E0 is the initial electric field and b is the field
enhancement factor, which is typically in the range of tens
or hundreds. For materials such as carbon nanotubes it can
5 Plasma-Assisted Oxidation of Volatile
even be in the range of thousands. The second effect is
Organic Compounds
caused by the relative permittivity of the packing material
and the gas, which leads to further enhancements of the
Some of the most prominent applications of atmospheric
electric field. This is shown in Eq. (4) [68].
pressure DBDs include the plasma-catalytic purification of
3ep exhaust gas streams by removing CO [15], NOx [16], SO2
E ¼ Eex (4) [17] and VOCs [18]. Especially the total oxidation of VOCs
2ep þ eg
to CO2 and H2O is one of the major challenges in environ-
Here, Eex is the external electric field, ep is the relative per- mental protection and can be used to obtain fundamental
mittivity of the pellet and eg is the relative permittivity of insight into the plasma-chemical mechanisms. During the
the void between the pellets. last decades, numerous studies have been performed on the
Furthermore, supported metal catalysts are widely used oxidation of different types of VOCs, such as cyclohexane
for plasma-catalytic processes. In addition to the influence [73], benzene [12] dichloromethane [74], toluene [75] or
of the support material, Kim et al. [69] reported that dis- formaldehyde [76]. An overview about the performance
persed metal nanoparticles influence the propagation of and conditions of the plasma-assisted oxidation of different
surface streamers. Due to the supported metal nanoparticles VOCs over heterogeneous catalysts is provided in Tab. 1.
the discharge expanded over a wider surface area, while it More extended lists can be found in reviews primarily
was limited to the edges of the bare support material with- focusing on the application of plasma-catalytic processes in
out nanoparticles. In addition to the chemical aspects of the the abatement of VOCs [77, 78].
Chemie
Technik
Table 1. Examples for the abatement of different VOCs found in literature.
VOC Catalyst Flow rate VOC mole fraction Conversion CO2 selectivity Energy Ref.
[mL min–1] [ppm] [%] [%]
Butane TiO2/g-Al2O3 1000 927 91 99 100 W [79]
Isopropanol MnOx 500 100 100 100 295 J L–1 [80]
Diethylether Mn-Fe/cordierite 1000 150 96 600 J L–1 [81]
Acetone CuOx/g-Al2O3 1000 1184 94.2 80.1 1012 J L–1 [82]
Formaldehyde Ag-MnOx-CeO2 100 80 100 >95 [83]
Hexanal MnOx/g-Al2O3 100 1.2 96.5 2.8 W [84]
Benzene AgMn/HZSM-5 200 100 70 100 6W [85]

–1
Toluene FeOx/SBA-15 300 100 95 60 284 J L [86]
–1
Chlorobenzene AgOx/MnOx/SMF 100 100 100 300 J L [87]
–1
Nitrobenzene CoOx/SMF 250 100 100 300 J L [88]
Commonly, packed-bed reactors are utilized to establish

an IPC configuration, as exemplarily shown in Fig. 6.
Figure 7. Proposed mechanism of the plasma-catalytic oxida-

tion of benzene over MnO2. Reprinted with permission from
[12]. Copyright 2004, with permission from Elsevier.
Figure 6. Photograph of a discharge inside a packed-bed DBD. catalyst is supported by other studies [89, 90]. In addition to
Reprinted with permission from [74]. Copyright 2014, American ozone, also pre-oxidized VOC molecules and dissociation
Chemical Society.
products can interact with the surface of the catalyst in a
PPC configuration [91].
From the chemical point of view, Futamura et al. [12] A study on the role of ozone was performed by Harling
proposed a mechanism for the oxidation of benzene using et al. [73], in which toluene and cyclohexane were added to
manganese oxide catalysts. They assume that atomic oxygen the gas flow between the plasma stage and the catalyst stage
is formed as a product of ozone decomposition on the sur- in a PPC reactor, eliminating any effect of direct exposure
face of the catalyst. Atomic oxygen can be present as O(3P) to the plasma on the oxidation process. A commercial
in the gas phase, or it can adsorb on the surface of the cata- MnO2-CuO catalyst, which was specifically designed for the
lyst denoted as O*. In the latter case, it can interact with thermal oxidation of contaminants and the decomposition
VOC molecules via Eley-Rideal-type reactions as shown in of ozone, was used to facilitate the assumed oxidation reac-
Fig. 7, leading to a plausible explanation for the higher deg- tions. The system showed a significant degree of toluene
radation rates observed in IPC configurations. Atomic oxy- and cyclohexane conversion even when every other possible
gen formed in the active plasma volume is directly gener- interaction apart from the reactions of the long-lived plas-
ated near the surface of the catalyst, where it can adsorb ma-generated species with the toluene and cyclohexane
and react with the VOC molecules. In PPC only the atomic molecules on the surface of the catalyst was excluded. Fur-
oxygen originating from the dissociation of ozone is avail- thermore, almost no oxidation of toluene and cyclohexane
able for VOC oxidation. Hence, in IPC larger quantities of was observed in the absence of the catalyst, confirming that
atomic oxygen are present on the surface of the catalyst the high degree of degradation observed in the former case
resulting in a much higher oxidation capacity [12]. The did not primarily originate from gas-phase reactions with
importance of atomic oxygen formed at the surface of the ozone. Comparing the rate constants for the gas-phase
Chemie
Technik
reaction of ozone with toluene (1.2 10–20 cm3molecule–1s–1) The properties of the surface of the catalyst play a crucial
and for the reaction of atomic oxygen with toluene role in the plasma-catalytic oxidation of VOCs, because the
(5.7 10–14 cm3molecule–1s–1) [NIST, Chem. Kin. Datab.] applied plasma may change the surface, and the presence of
further helped to deduce that the mechanism of the the surface changes the discharge properties. Lu et al. [86]
observed process is based on the adsorption and dissocia- reported the transition of Mn2O3 to Mn3O4 during the plas-
tion of ozone. However, ozone is only one species out of a ma-catalytic oxidation of toluene at ambient temperature,
large variety of reactive oxygen species generated in a di- which not only improved the oxidation potential, but also
electric barrier discharge. the CO2 selectivity. Each of the manganese oxidation states
A preliminary study performed by the same group was crucial for the oxidation. It was assumed that the active
addressed the effect of plasma treatment on the operating oxygen of Mn2O3 was transferred to Mn3O4, where it oxi-
temperature of the catalyst [92]. In this case, benzene in dized toluene adsorbed on the catalyst surface. The result-
synthetic air was passed through a PPC reactor. The down- ing oxygen vacancies in Mn2O3 were immediately refilled
stream catalyst stage was filled with Ag/g-Al2O3 and heated by gas-phase oxygen species. Moreover, the presence of the
from 50 C to 600 C in order to determine the onset tem- plasma can increase the degree of crystallinity and the active
perature of the catalyst from simultaneously recorded FTIR site dispersion by decreasing the particle size, which
spectra. For mere thermal catalysis, first signs of benzene increased the removal of toluene over manganese oxide/alu-
destruction occurred at 200 C, but prominent changes to mina/nickel foam catalysts [97]. In addition, a ‘‘cleaning
the spectrum were only monitored from 300 C onwards effect’’ of the surface has been reported, which may prevent
and an almost complete disappearance of the benzene IR catalyst deactivation [98]. Ni-based catalysts showed an
bands was only observed in the range from 500 C to enhanced coke resistance after treatment with a DBD plas-
600 C. On the other hand, for plasma-assisted catalysis, the ma.
onset temperature shifted to 100 C, and full conversion of Apart from the goal of high degrees of conversion, a high
benzene was observed for 150 C to 200 C and higher tem- selectivity to the total oxidation products CO2 and H2O is
peratures. There is no detailed information available so far required. In addition to CO2, CO is often formed as well as
about the mechanisms inducing the shift in the catalytic on- a result of incomplete oxidation. Thevenet et al. [99] report-
set temperature, but it was stated that plasma-catalytic sys- ed that the addition of water vapor can improve the CO2
tems for both IPC and PPC configurations are always found selectivity in the plasma-catalytic oxidation of C2H2, while
and reported to be more efficient than thermal catalysis at the same time the degree of conversion is decreased. The
[92]. Similar results were reported by Blackbeard et al. [11] decrease in conversion is attributed to the dissociation of
for the plasma-catalytic oxidation of propane and propene H2O to OH and H by electron impact. Due to this process
over supported MnO2 and Pt catalysts. By using a heatable the electron density and consequently the density of atomic
packed-bed reactor in an IPC configuration, up to 40 % O and O3, which are assumed to be crucial for the oxida-
higher degrees of conversion were obtained at lower tem- tion, are decreased. The improved CO2 selectivity may be
peratures than in thermal catalysis. attributed to different effects such as an improved CO oxi-
Another concept under discussion for the interaction dation or a shift of the CO/CO2 equilibrium by OH [99]. A
between the plasma and the catalysts is whether UV emis- similar improvement of the CO2 selectivity can be achieved
sion in atmospheric pressure plasma can induce photocatal- by the utilization of a catalytic material capable of oxidizing
ysis when paired with a semiconducting catalyst such as CO such as MnOx [86] or LaCoO3 [65]. In addition to CO,
TiO2. It has already been established that the photocatalytic a multitude of organic reaction intermediates and by-prod-
activity of TiO2 in oxidation reactions can be improved by ucts can be found for several reactions. The oxidation of tol-
the addition of precious metals such as Au and Pd [93]. uene was reported to produce formic acid, acetic acid as
Nitrogen molecular photoemission stemming from the so- well as other acids, ketones and aromatics [75, 100].
called second positive system (SPS) in the wavelength range Since products of the incomplete oxidation are undesir-
from 300 nm to 400 nm covers the band gap of TiO2. How- able, their production needs to be suppressed. This role can
ever, the UV doses occurring in a DBD reactor are usually be fulfilled by the catalyst choice [86]. Since the abatement
in the range of mW, which has been reported by some of VOCs is usually performed in (synthetic) air, undesired
researchers to be too low for photoactivation, requiring UV nitric oxides may be formed as O2 and N2 can react with
doses in the range of mW [27]. Nevertheless, there are sev- each other after plasma activation. Guo et al. [101] found
eral publications that report indications of photocatalytic that the NOx formation during toluene oxidation can be
effects induced by DBD plasmas [94, 95]. Furthermore, oxy- limited by the choice of the catalyst. While all investigated
gen vacancies and Ti3+ defects on the surface of TiO2 catalysts decreased the NOx amount, CuO showed the most
induced by an Ar DBD plasma decreased the band gap significant effect. However, CuO exhibited a lower degree of
and enhanced the photocatalytic degradation ability of toluene conversion and a lower CO2 selectivity than FeOx
organic dyes [96]. Therefore, more research on this topic is and MnOx catalysts. Several effects may contribute to the
needed. decrease of NOx formation such as microdischarges in
pores, a shift of the electron energy distribution function by
Chemie
Technik
the catalyst or adsorption of NOx. The presence of the cata- over Pt-based catalysts. Photographs of the reactor and the
lyst may furthermore suppress the formation of O3 [97]. ignited plasma are shown in Fig. 9.
To sum up, a variety of different effects and interactions The electrode configuration consists of an Al2O3 plate
are reported for plasma-catalytic VOC oxidation (Fig. 8). In with conducting metal paths on both sides, and the plasma
general, short-lived reactive oxygen species (IPC) and long- is ignited along these conducting paths. In comparison to
lived reactive oxygen species (PPC) are generated in the typical packed-bed reactors, this setup has distinct advan-
plasma and may interact with the surface of the catalyst. tages for both basic research and industrial application. Due
These species may change the reaction pathway, suppress to the optical access to the reactor provided by windows,
coke formation, or lower the activation barrier. Further- the plasma parameters and reactive species can be moni-
more, photoemission from the plasma is discussed to acti- tored in the discharge zone. Therefore, the performance of
vate photocatalysts. The presence of the catalyst can lead to the process can be directly correlated to the plasma proper-
the formation of surface discharges or significant field ties providing detailed insights on the ongoing reaction.
enhancements inside of pores. On the other hand, the The Pt-based catalyst is introduced into the discharge zone
applied plasma can also change the surface morphology of by spray coating maintaining the low flow resistance of the
the catalyst and change its electronic structure such as the reactor even in an IPC configuration.
oxidation state. Up to now plasma catalysis has not been applied to deox-
ygenation, but plasma-assisted catalysis was studied for
similar systems. As part of the hydrogen peroxide synthesis
plasma-induced reactions between oxygen and hydrogen
were investigated at atmospheric pressure. Information that
was already gained can be valuable for further research in
the Carbon2Chem framework. The synthesis of ammonia
and methanol are also interesting research topics for the
project, as they are not only widely used base chemicals, but
also target products for the conversion of steel mill gases to
valuable products.
Figure 8. Interactions between the catalyst and the plasma. 6.2 Hydrogen Peroxide Synthesis
Hydrogen peroxide (H2O2) is a broadly used oxidizing

6 Plasmas at Atmospheric Pressure agent in chemical industry. It finds applications in bleaching
Involving H2 processes, as an epoxidation agent, in the semiconductor
industry and even as a propellant for space travel
6.1 Plasma-Catalytic Removal of Oxygen Traces [103, 104]. It is a sustainable oxidizing agent and therefore
from Coke Oven Gas in high demand, now and in the near future. The current
state of the art anthraquinone process is operated at large
As part of the Carbon2Chem project, the plasma-assisted scales and struggles to meet the purity required for the
removal of oxygen traces (DeOxo process) from coke oven semiconductor industry (SEMI) [105]. Additionally, it is
gas (COG) is investigated. Coke oven gas is rich in hydro- less atom-efficient than the direct synthesis from H2 and
gen (60 %) and has a rather high CO content (10 %), which O2. The latter has long been a research target approached
makes it a promising future feedstock for the synthesis of by various methods. The catalytic approach employs noble
basic chemicals such as methanol or
higher alcohols [102]. O2 traces must be
reduced to a minimum to guarantee
the safe operation of downstream pro-
cesses. Conventional purification meth-
ods based on noble metal catalyst may
reach their limits due to the complex gas
mixtures and the variety of impurities,
like sulfur compounds.
The authors of this review utilize the
twin-surface DBD presented by Offer-
haus et al. [53] for the plasma-catalytic
removal of oxygen traces from coke oven Figure 9. Photographs of the twin-surface dielectric barrier discharge and the ignited
gases and hydrogen-rich gas mixtures plasma.
Chemie
Technik
metal catalysts in three-phase reactors [106–108]. A disad-

vantage of this method is the decomposition of H2O2,
which is also catalyzed by the used metals. To avoid this
decomposition, inhibiting agents can be added [109], which
may be possible sources of contamination and further com-
plicate the application in the semiconductor industry. A dif-
ferent approach is the fuel cell technology producing H2O2
by a two-electron reduction step [110].
The synthesis of H2O2 from H2 and O2 by a non-equilib-
rium plasma was first reported in the 1940s by the company
IG Farben and further investigated in the 1960s by Kobozev
et al. [104]. Both reported yields that made the process
uninteresting for industrial applications. In recent years the
Guo group [104] revisited the concept and managed to
drastically improve the efficiency of the plasma process.
Their initial double dielectric barrier discharge (DDBD)
design consisted of two glass tubes and featured a liquid
grounding electrode [111]. The high voltage electrode con-
sisted of copper wire in their initial configuration and was
later replaced by another liquid electrode [105] or a metal
powder electrode [112]. The whole reactor design allows
continuous cooling of the gas mixture by an external water
circuit. The group also highlights the possibilities of Figure 10. Schematic illustration of the scaled-up design con-
sisting of five integrated reactors. Reprinted with permission
improving the setup from an engineering point of view.
from [112].
Direct integration of the H2O2 production into a propylene
oxidation process allows on-site production of the oxidizing
agent [113]. Tuning of the input power and gas feed enables O þ H2 fi HO þ H (11)
the precise controlling of the production rate of H2O2. To
improve the efficiency of H2O2 production, the system can OH þ H2 fi H2 O þ H (12)
be scaled-up by increasing the number of reactors, while
the individual reactor dimensions are kept unchanged. A The mechanism can be initiated either by the dissociation
scaled-up version with five integrated reactors is shown in of H2 or O2. While the former reaction leads to the forma-
Fig. 10 [112]. The improvements of the reactor also led to a tion of the product, the latter favors the formation of unde-
higher possible oxygen content in the hydrogen gas flow. It sired H2O. The key reaction is Eq. (7), where HO2. reacts
is claimed that the diffusive discharge can be operated with with another HO2. to form H2O2. To improve the selectiv-
up to 30 % O2 in H2, which is far above the explosion limit. ity of the process, reactions (5)–(7) have to be facilitated,
It is supposed that this reaction proceeds by a radical while reactions (8)–(12) need to be inhibited. The Gao
chain reaction. Herein, the formation of hydrogen and oxy- group [104, 114] showed that the addition of Ar and H2O
gen radicals plays a key role to initiate the reaction. Optical improved the efficiency by two different routes. The addi-
emission spectroscopy (OES) allows to observe atomic tion of Ar increases the electron density by lowering the
hydrogen (Ha 656.3 nm) and atomic oxygen (OI 777.4 nm required breakdown voltage. Moreover, metastable Ar*
and OI 844.7 nm). For the mechanism taking place a multi- (Ar 1s3 or Ar 1s5) can accelerate H2 dissociation selectively
tude of reactions has to be considered [114]: through both the Penning effect and as a molecular catalyst,
as shown in reaction (13).
H2 fi 2H (5)
H2 þ Ar* fi Ar þ 2H (13)

H þ O2 fi HO2 (6)
In contrast, the addition of H2O leads to the stabilization
of HO2.. The higher amount of this radical leads to a high
HO2 þ HO2 fi H2 O2 þ O2 (7) rate of H2O2 formation, as described by reactions (14)–(18).
O2 fi 2O (8) HO2 þ HO2 fi H2 O4 * (14)
O2 fi O2 * (9) H2 O4 * fi H2 O2 þ O2 (15)
H þ O2 * fi HO þ O (10) HO2 þ H2 O fi HO2 þ H2 O (16)
Chemie
Technik
HO2 þ HO2 H2 O fi H2 O2 þ O2 Table 2. Comparison of NH3 yield and energy yield/cost for various DBD processes with
different catalysts published in the last 5 years.
þ H2 O (17)
Catalyst NH3 yield Energy yield Energy cost Ref.
HO2 H2 O þ HO2 H2 O fi H2 O2 [%] [gNH3kWh–1] [MJ mol–1]
þ O2 þ 2H2 O (18) BaTiO3/Pb[ZrxTi1–x]O3 2.75 0.72 136 [124]
The plasma process produces concen- Cu (wool-like) 3.5 3.3 93 [125]

trated H2O2 with high purity and only Pb[ZrxTi1–x]O3 powder 7 408 [126]
H2O as a by-product. Additionally, it al-
Au (wool-like) 4.72 4.45 93 [127]
lows easy switching on and off and scaling
its production capacity. These features Ru-MCM-41 0.1 1.7 27 [121]
make it attractive for the use in semicon- Ni(porous)/BaTiO3 9 81 [128]
ductor industry. A disadvantage is the not
yet achieved economic feasibility. The pro- Diamond-like carbon/Al2O3 2 0.18 [118]
duction cost of H2O2 currently exceeds Ru/Al2O3 13.5 32.39 [129]
the price of the anthraquinone process,
g-Al2O3 0.9 1.9 27.9 [130]
depending on the electricity price.
Zeolite 5A 0.24 15.5 [119]
g-Al2O3 0.64 6.58 [131]

6.3 Ammonia Synthesis
Ammonia (NH3) is a base chemical with

a high demand in industry. It is one of the most produced It was reported for supported catalysts that the shape and
inorganic chemicals (>150 Mt a–1) and mostly used for fer- the structure of the support mainly influence the properties
tilizer production. Industrial production of NH3 started of the discharge as elaborated in Sect. 4, while the chemical
around 1909 when Fritz Haber and Carl Bosch developed nature of the metal influences the ongoing reactions
the Haber-Bosch process. The exothermic reversible con- [127, 130, 132]. The general mechanism of plasma-assisted
version of N2 and H2 to NH3 is typically performed at tem- ammonia synthesis can be roughly divided into three parts,
peratures between 400 C and 500 C requiring pressures namely N2 activation, hydrogenation and NH3 desorption.
between 150 bar and 250 bar due to thermodynamic limita- Due to the high bond-dissociation energy of N2, the first
tions [115]. With the help of a multiply promoted iron cata- step is generally considered rate-limiting suggesting high N2
lyst and the recycling of unreacted gas a total conversion up mole fractions [120, 123, 130]. The applied plasma can
to 97 % can be achieved. Disadvantages of the Haber-Bosch accelerate the activation of N2. In thermal catalysis N2 acti-
process are the low NH3 yield per pass and the unfavorable vation includes the dissociative adsorption of N2 on the sur-
reaction conditions requiring costly high-pressure equip- face of the catalyst forming adsorbed atomic nitrogen,
ment. To develop a sustainable process a major challenge is where * denotes an active surface site (Eq. (19)). This is fol-
the reduction of the large amounts of CO2 currently emitted lowed by sequential hydrogenation by adsorbed hydrogen
by the conventional H2 production based on steam reform- to NH3 (Eq. (20)), which involves several elementary steps
ing of CH4. Nonthermal plasmas offer the opportunity to not shown here [116].
split N2 at much lower temperatures and pressures. In this
way, decentralized NH3 production based on H2 generation N2 þ 2* fi 2N* (19)
by water electrolysis may become feasible in small-scale
plants operated at near ambient pressure, rendering the N* þ 1:5H2 fi NH3 þ * (20)
plasma-assisted production an attractive alternative. Prom-
ising results were reported using packed-bed DBD reactors, In the plasma-assisted ammonia synthesis N2 can be acti-
operating at ambient conditions. Moreover, the plasma pro- vated by electron impact. This may include vibrational or
cess allows to surpass the equilibrium limitation of thermal electronic excitation or even the direct dissociation to N
catalysis at elevated temperatures by kinetically trapping radicals [116]. Therefore, the greatest improvements by the
ammonia [116]. A wide variety of different catalysts has combination of the catalyst with plasma are expected for
been applied in plasma-assisted ammonia synthesis, ranging materials, where N2 activation is rate-limiting. Shah et al.
from the semimetal gallium [117] over diamond-like carbon [117] proposed a mechanism for a RF-plasma-assisted am-
structures [118] and zeolites [119] to traditional ammonia monia synthesis at low pressures over Fe catalysts including
synthesis catalysts such as Ru, Fe and other metals support- direct dissociation of N2 and H2 by electron impact
ed on Al2O3 or MgO [117, 120–123]. In Tab. 2 a compari- (Eqs. (21)–(27)).
son of the ammonia yield and energy utilization for differ-
ent DBD processes over various catalysts is shown. N2 þ e fi 2N þ e (21)
Chemie
Technik
H2 þ e fi 2H þ e (22) the optimization of the methanol yield, an improvement of

the product distribution is also desirable. Common by-
N þ * fi N* (23) products in the selective oxidation of methane process are
HCHO, CO, CO2 and C2H6 [135, 136].
The production of methanol can also be performed by
H þ * fi H* (24) the hydrogenation of CO2. This approach is closely related
to the plasma-assisted splitting of CO2 to CO, which has
N* þ H fi NH* (25) attracted a lot of interest from the scientific community
[137–140]. The generated CO can then be used to produce
NH* þ H* fi NH2 * þ * (26) methanol by established industrial processes [35]. A new
route to produce methanol by hydrogenating CO2 is also
investigated in the context of plasma catalysis. In this way,
NH2 * þ H* fi NH3 þ 2* (27)
the greenhouse gas CO2 is converted into value-added
A variety of different species may be generated by the chemicals and fuels. High degrees of conversion for the exo-
plasma including electronically excited states or charged thermic reversible reaction are favored by low reaction tem-
species as shown in [117]. Furthermore, DFT calculations peratures, which lead to low rates. The plasma-catalytic
suggest that the formation of metal nitrides M3N over var- approach tries to overcome this barrier by performing the
ious metals plays a key role and that their stability can be reaction at 100 C and atmospheric pressure. Catalysts used
linked to the rate of ammonia production [127]. The results are, e.g., CuO or Pt nanoparticles, and investigations of new
indicate that a less stable M3N surface intermediate results catalysts are ongoing [141, 142]. Methanol yields of up to
in higher catalytic activity. The rate of ammonia desorption 23 % have already been reported [141]. The hydrogenation
is strongly influenced by the acidity of the support material. of CO2 may become economically feasible depending both
A more basic support is associated with a higher rate of on increased governmental incentives for CO2 utilization
ammonia production as ammonia can desorb more easily and significant progress in lowering the cost of sustainable
[131]. Besides the use of catalysts, addition of other gaseous H2 production by water electrolysis. In addition, the plas-
compounds also showed improvements. Adding Ar is gen- ma-catalytic synthesis of methanol could be more tolerant
erally associated with a higher electron density and, there- towards demanding gas streams and catalyst poisons. Sulfur
fore, increased conversion [129], while the addition of water compounds are known to be poisons for the conventional
to a pure H2/N2 mixture over a Ru catalyst led to the forma- Cu/ZnO/Al2O3 methanol synthesis catalyst [17]. Therefore,
tion of RuO2, promoting the reaction [120]. it might be possible to operate a plasma-catalytic methanol
synthesis even in sulfur-containing feed gases.
6.4 Methanol Synthesis

7 Summary and Conclusion
Methanol is a widely used platform chemical in industry.
The current route of production often involves the genera- The combination of nonthermal plasmas and heteroge-
tion of synthesis gas from methane by steam reforming, fol- neous catalysts provides unique possibilities for industrially
lowed by the production of methanol from synthesis gas. relevant processes. By shifting the reaction site from the gas
This two-step process may be substituted by the one-step phase to the surface of the catalyst impressive results can be
partial oxidation of methane to methanol [133], which is obtained for plasma catalysis. In order to further improve
one of the so-called dream reactions. Methane is available the performance of these systems a detailed understanding
in large quantities from natural gas, and the partial oxida- of the various interactions between the catalyst and the
tion is, therefore, in direct competition to other processes, plasma are essential, as both strongly influence each other.
such as dry reforming, methane pyrolysis and the conven- Nonthermal plasma generates highly reactive species such
tional steam reforming. Partial oxidation of methane suffers as ions, radicals or excited molecules under non-equilibri-
either from low selectivity or low conversion, and a route um conditions avoiding high gas temperatures. Further-
with high degrees of conversion and high selectivity is more, the induced surface charges and structural changes
desired [134]. A potential approach to improve the process can enhance the catalytic performance and may prevent
beyond thermal catalysis is plasma-assisted catalysis. The catalyst deactivation. On the other hand, the presence of the
investigated setups featured DBD reactors with transition catalyst facilitates the plasma discharge due to local field
metal oxides as catalysts. A variety of materials was used enhancements at the surface or inside the pores. For future
and yields of up to 12 % were reported for Mn2O3 [133] research, it is essential to adjust the properties of both the
and CuO [135, 136], but further optimization of the cata- plasma and the catalyst to optimize these interactions.
lysts is expected. Processes without catalyst integration also Dielectric barrier discharges are widely used for industrial
manage to produce methanol, but in lower quantities, indi- applications as they can easily generate the desired non-
cating a synergistic effect of plasma catalysis. In addition to equilibrium conditions. The filamentary nature of the
Chemie
Technik
discharge caused by the streamer breakdown mechanism PPC post-plasma catalysis

generates electrons with high kinetic energies, while the SDBD surface dielectric barrier discharge
heavier particles remain close to ambient temperature. The SEMI semiconductor equipment and materials
composition and properties of the plasma depend on the VDBD volume dielectric barrier discharge
feed gas mixture and the applied pressure. Further advan- VOC volatile organic compound
tages of DBDs are their low cost and efficient scalability by
numbering-up. Many plasma-catalytic reactions are in the
focus of current research. The oxidation of volatile organic References
compounds by using atmospheric pressure air plasmas pro-
vides important insights into the mechanisms of plasma [1] D. B. Graves, AIChE J. 1989, 35 (1), 1–29. DOI: https://doi.org/
10.1002/aic.690350102
catalysis. The research on the synthesis of hydrogen perox-
[2] L. Remache, E. Fourmond, A. Mahdjoub, J. Dupuis, M. Lemiti,
ide, ammonia or methanol demonstrates that plasma cataly- Mater. Sci. Eng., B 2011, 176 (1), 45–48. DOI: https://doi.org/
sis may also be attractive for small-scale decentralized 10.1016/j.mseb.2010.08.010
industrial processes. Therefore, we expect the number of [3] N.-Y. Cui, N. M. D. Brown, Appl. Surf. Sci. 2002, 189 (1–2),
investigated reactions to grow in the future. 31–38. DOI: https://doi.org/10.1016/S0169-4332(01)01035-2
[4] G. Borcia, C. A. Anderson, N. M. D. Brown, Plasma Sources Sci.
Technol. 2003, 12 (3), 335. DOI: https://doi.org/10.1088/
We gratefully acknowledge the financial support received 0963-0252/12/3/306
[5] B. Jiang, J. Zheng, S. Qiu, M. Wu, Q. Zhang, Z. Yan, Q. Xue,
from the German Federal Ministry of Education and
Chem. Eng. J. 2014, 236, 348–368. DOI: https://doi.org/10.1016/
Research (Bundesministerium für Bildung und j.cej.2013.09.090
Forschung, BMBF, Verbundvorhaben Carbon2Chem [6] J. van Durme, J. Dewulf, C. Leys, H. van Langenhove, Appl. Cat-
L3 03EK3040B ,,Gasreinigung’’ Teilvorhaben RUB: ‘‘Ein- al., B 2008, 78 (3–4), 324–333. DOI: https://doi.org/10.1016/
satz von nicht-thermischem Plasma zur Gasreinigung’’). j.apcatb.2007.09.035
Open access funding enabled and organized by Projekt [7] A. M. Vandenbroucke, R. Morent, N. de Geyter, C. Leys, J. Haz-
DEAL. ard. Mater. 2011, 195, 30–54. DOI: https://doi.org/10.1016/
j.jhazmat.2011.08.060
[8] A. A. Fridman, Plasma Chemistry, Cambridge University Press,
Cambridge 2012.
[9] R. Brandenburg, Plasma Sources Sci. Technol. 2017, 26 (5),
Symbols used 53001. DOI: https://doi.org/10.1088/1361-6595/aa6426
[10] C. Tendero, C. Tixier, P. Tristant, J. Desmaison, P. Leprince, Spec-
A [Pa–1m–1] Paschen parameter trochim. Acta, Part B 2006, 61 (1), 2–30. DOI: https://doi.org/
B [Pa m] Paschen parameter 10.1016/j.sab.2005.10.003
d [m] gap distance [11] T. Blackbeard, V. Demidyuk, S. L. Hill, J. C. Whitehead, Plasma
E [V m–1] electric field Chem. Plasma Process. 2009, 29 (6), 411–419. DOI: https://
E0 [V m–1] initial electric field doi.org/10.1007/s11090-009-9189-8
[12] S. Futamura, H. Einaga, H. Kabashima, L. Y. Hwan, Catal. Today
ESc [V m–1] additional electric field
2004, 89 (1–2), 89–95. DOI: https://doi.org/10.1016/
Te [K] electron temperature j.cattod.2003.11.014
Tg [K] neutral gas temperature [13] S. Jodpimai, S. Boonduang, P. Limsuwan, J. Electrost. 2015, 74,
Ti [K] ion temperature 108–114. DOI: https://doi.org/10.1016/j.elstat.2014.12.003
U [V] voltage [14] S. Yao, Z. Wu, J. Han, X. Tang, B. Jiang, H. Lu, S. Yamamoto,
UB [V] breakdown voltage S. Kodama, J. Electrost. 2015, 75, 35–42. DOI: https://doi.org/
b [–] enhancement factor 10.1016/j.elstat.2015.03.001
[15] R. Yarahmadi, S. Soleimani-Alyar, Emiss. Control Sci. Technol.
g [–] secondary-electron-emission coef-
2020, 6 (1), 17–27. DOI: https://doi.org/10.1007/
ficient s40825-020-00154-2
[16] P. A. Gorry, J. C. Whitehead, J. Wu, Plasma Processes Polym.
2007, 4 (5), 556–562. DOI: https://doi.org/10.1002/
Abbreviations ppap.200700010
[17] M. Rong, D. Liu, X. Wang, Wang Junhua, Plasma Sci. Technol.
AC alternating current 2007, 9 (6), 717–720. DOI: https://doi.org/10.1088/1009-0630/9/
COG coke oven gas 6/18
DBD dielectric barrier discharge [18] X. Zhu, X. Gao, X. Yu, C. Zheng, X. Tu, Catal. Today 2015, 256,
108–114. DOI: https://doi.org/10.1016/j.cattod.2015.01.028
DC direct current
[19] H. Miao, G. Yun, Appl. Surf. Sci. 2011, 257 (16), 7065–7070.
DDBD double dielectric barrier discharge DOI: https://doi.org/10.1016/j.apsusc.2011.03.014
FTIR Fourier-transform infrared spectroscopy [20] J. Balzer, K. Heuer, E. Demir, M. A. Hoffmanns, S. Baldus, P. C.
IPC in-plasma catalysis Fuchs, P. Awakowicz, C. V. Suschek, C. Opländer, PloS one 2015,
NTP nonthermal plasma 10 (12), e0144968. DOI: https://doi.org/10.1371/journal.pone.
OES optical emission spectroscopy 0144968
Chemie
Technik
[21] J. C. Whitehead, Pure Appl. Chem. 2010, 82 (6), 1329–1336. [48] W. Siemens, Ann. Phys. Chem. 1857, 178 (9), 66–122. DOI:
DOI: https://doi.org/10.1351/PAC-CON-10-02-39 https://doi.org/10.1002/andp.18571780905
[22] J. C. Whitehead, J. Phys. D: Appl. Phys. 2016, 49 (24), 243001. [49] U. Kogelschatz, B. Eliasson, W. Egli, J. Phys. IV France 1997,
DOI: https://doi.org/10.1088/0022-3727/49/24/243001 07 (C4), C4-47–C4-66. DOI: https://doi.org/10.1051/jp4:1997405
[23] J. C. Whitehead, Front. Chem. Sci. Eng. 2019, 13 (2), 264–273. [50] A. Klemenc, H. Hintenberger, H. Höfer, Z. Elektrochem. Angew.
DOI: https://doi.org/10.1007/s11705-019-1794-3 Phys. Chem. 1937, (43), 708–712.
[24] E. C. Neyts, A. Bogaerts, J. Phys. D: Appl. Phys. 2014, 47 (22), [51] U. Kogelschatz, J. Phys. D: Appl. Phys. 2010, 257, 12015. DOI:
224010. DOI: https://doi.org/10.1088/0022-3727/47/22/224010 https://doi.org/10.1088/1742-6596/257/1/012015
[25] E. C. Neyts, Plasma Chem. Plasma Process. 2016, 36 (1), [52] J. Yang, F. Cui, I. S. Lee, Ann. Biomed. Eng. 2011, 39 (7),
185–212. DOI: https://doi.org/10.1007/s11090-015-9662-5 1857–1871. DOI: https://doi.org/10.1007/s10439-011-0300-y
[26] E. C. Neyts, K. K. Ostrikov, M. K. Sunkara, A. Bogaerts, Chem. [53] B. Offerhaus, J.-W. Lackmann, F. Kogelheide, V. Bracht, R. Smith,
Rev. 2015, 115 (24), 13408–13446. DOI: https://doi.org/10.1021/ N. Bibinov, K. Stapelmann, P. Awakowicz, Plasma Processes Pol-
acs.chemrev.5b00362 ym. 2017, 14 (10), 1600255. DOI: https://doi.org/10.1002/
[27] H.-H. Kim, Y. Teramoto, N. Negishi, A. Ogata, Catal. Today ppap.201600255
2015, 256, 13–22. DOI: https://doi.org/10.1016/j.cattod.2015. [54] A. A. Abdelaziz, T. Ishijima, T. Seto, N. Osawa, H. Wedaa,
04.009 Y. Otani, Plasma Sources Sci. Technol. 2016, 25 (3), 35012. DOI:
[28] H.-H. Kim, Y. Teramoto, A. Ogata, H. Takagi, T. Nanba, Plasma https://doi.org/10.1088/0963-0252/25/3/035012
Chem. Plasma Process. 2016, 36 (1), 45–72. DOI: https://doi.org/ [55] A. A. Abdelaziz, T. Ishijima, T. Seto, Phys. Plasmas 2018, 25 (4),
10.1007/s11090-015-9652-7 43512. DOI: https://doi.org/10.1063/1.5020271
[29] H.-H. Kim, Plasma Processes Polym. 2004, 1 (2), 91–110. DOI: [56] A. J. M. Pemen, V. R. Chirumamilla, F. J. C. M. Beckers, W. F. L.
https://doi.org/10.1002/ppap.200400028 M. Hoeben, T. Huiskamp, IEEE Trans. Plasma Sci. 2018, 46 (12),
[30] M. Bahri, F. Haghighat, Clean Soil Air Water 2014, 42 (12), 4078–4090. DOI: https://doi.org/10.1109/TPS.2018.2855402
1667–1680. DOI: https://doi.org/10.1002/clen.201300296 [57] U. Roland, F. Holzer, F.-D. Kopinke, Catal. Today 2002, 73 (3–4),
[31] H. L. Chen, H. M. Lee, S. H. Chen, M. B. Chang, S. J. Yu, S. N. Li, 315–323. DOI: https://doi.org/10.1016/S0920-5861(02)00015-9
Environ. Sci. Technol. 2009, 43 (7), 2216–2227. DOI: https:// [58] H. Chen, H. Lee, S. Chen, Y. Chao, M. Chang, Appl. Catal., B
doi.org/10.1021/es802679b 2008, 85 (1–2), 1–9. DOI: https://doi.org/10.1016/j.ap-
[32] J. Zhou, H. Guo, X. Wang, M. Guo, J. Zhao, L. Chen, W. Gong, catb.2008.06.021
Chem. Commun. (Cambridge, U. K.) 2005, (12), 1631–1633. [59] R. R. Smith, D. R. Killelea, D. F. DelSesto, A. L. Utz, Science
DOI: https://doi.org/10.1039/b416835f 2004, 304 (5673), 992–995. DOI: https://doi.org/10.1126/
[33] J. Zhao, J. Zhou, J. Su, H. Guo, X. Wang, Gong, Weimin, Plasma science.1096309
Sci. Technol. 2009, 11 (2), 181–186. DOI: https://doi.org/10.1088/ [60] S. T. Oyama, Catal. Rev. 2000, 42 (3), 279–322. DOI: https://
1009-0630/11/2/10 doi.org/10.1081/CR-100100263
[34] G. Deerberg, M. Oles, R. Schlögl, Chem. Ing. Tech. 2018, 90 (10), [61] E. C. Neyts, Plasma Chem. Plasma Process. 2016, 36 (1),
1365–1368. DOI: https://doi.org/10.1002/cite.201800060 185–212. DOI: https://doi.org/10.1007/s11090-015-9662-5
[35] J. Schittkowski, H. Ruland, D. Laudenschleger, K. Girod, K. Käh- [62] Y.-R. Zhang, K. van Laer, E. C. Neyts, A. Bogaerts, Appl. Catal., B
ler, S. Kaluza, M. Muhler, R. Schlögl, Chem. Ing. Tech. 2018, 2016, 185, 56–67. DOI: https://doi.org/10.1016/
90 (10), 1419–1429. DOI: https://doi.org/10.1002/cite.201800017 j.apcatb.2015.12.009
[36] Ö. Yildirim, K. Nölker, K. Büker, R. Kleinschmidt, Chem. Ing. [63] X. Tu, H. J. Gallon, J. C. Whitehead, J. Phys. D: Appl. Phys. 2011,
Tech. 2018, 90 (10), 1529–1535. DOI: https://doi.org/10.1002/ 44 (48), 482003. DOI: https://doi.org/10.1088/0022-3727/44/48/
cite.201800019 482003
[37] Y. P. Raizer, Gas discharge physics, Springer, New York 1997. [64] H. J. Gallon, X. Tu, J. C. Whitehead, Plasma Processes Polym.
[38] A. von Keudell, V. Schulz-von der Gathen, Plasma Sci. Technol. 2012, 9 (1), 90–97. DOI: https://doi.org/10.1002/ppap.201100130
2017, 26 (11), 113001. DOI: https://doi.org/10.1088/1361-6595/ [65] F. Holzer, F. D. Kopinke, U. Roland, Plasma Chem. Plasma Pro-
aa8d4c cess. 2005, 25 (6), 595–611. DOI: https://doi.org/10.1007/
[39] W. C. Hinds, Aerosol Technology: Properties, Behavior, and Mea- s11090-005-6804-1
surement of Airborne Particles, 2nd ed., Wiley-Interscience, New [66] K. Hensel, S. Katsura, A. Mizuno, IEEE Trans. Plasma Sci. 2005,
York 2012. 33 (2), 574–575. DOI: https://doi.org/10.1109/TPS.2005.845389
[40] P. Reuss, Neutron physics, Nuclear engineering, EDP Sciences, [67] Y.-R. Zhang, K. van Laer, E. C. Neyts, A. Bogaerts, Appl. Catal., B
Les Ulis France 2008. 2016, 185, 56–67. DOI: https://doi.org/10.1016/j.apcatb.2015.
[41] F. Paschen, Ann. Phys. Chem. 1889, 273 (5), 69–96. DOI: https:// 12.009
doi.org/10.1002/andp.18892730505 [68] K. Takaki, J.-S. Chang, K. G. Kostov, IEEE Trans. Dielect. Electr.
[42] K. T. A. L. Burm, Contrib. Plasma Phys. 2007, 47 (3), 177–182. Insul. 2004, 11 (3), 281–290. DOI: https://doi.org/10.1109/
DOI: https://doi.org/10.1002/ctpp.200710025 TDEI.2004.1306726
[43] J. D. Cobine, Gaseous conductors: Theory and engineering appli- [69] H.-H. Kim, J.-H. Kim, A. Ogata, J. Phys. D: Appl. Phys. 2009,
cations, Dover, New York 1958. 42 (13), 135210. DOI: https://doi.org/10.1088/0022-3727/42/13/
[44] D. B. Go, D. A. Pohlman, J. Appl. Phys. 2010, 107 (10), 103303. 135210
DOI: https://doi.org/10.1063/1.3380855 [70] D. Gao, I. Zegkinoglou, N. J. Divins, F. Scholten, I. Sinev,
[45] E. Hourdakis, B. J. Simonds, N. M. Zimmerman, Rev. Sci. Ins- P. Grosse, B. Roldan Cuenya, ACS nano 2017, 11 (5), 4825–4831.
trum. 2006, 77 (3), 34702. DOI: https://doi.org/10.1063/ DOI: https://doi.org/10.1021/acsnano.7b01257
1.2185149 [71] K. M. Bal, S. Huygh, A. Bogaerts, E. C. Neyts, Plasma Sources Sci.
[46] A. Engel, M. Steenbeck, Elektrische Gasentladungen: Ihre Physik Technol. 2018, 27 (2), 24001. DOI: https://doi.org/10.1088/
und Technik, Springer, Berlin 1932. 1361-6595/aaa868
[47] J. S. Townsend, Nature 1900, 62 (1606), 340–341. DOI: https://
doi.org/10.1038/062340b0
Chemie
Technik
[72] O. Guaitella, F. Thevenet, C. Guillard, A. Rousseau, J. Phys. D: [95] T. Sano, N. Negishi, E. Sakai, S. Matsuzawa, J. Mol. Catal. A:
Appl. Phys. 2006, 39 (14), 2964–2972. DOI: https://doi.org/ Chem. 2006, 245 (1–2), 235–241. DOI: https://doi.org/10.1016/
10.1088/0022-3727/39/14/015 j.molcata.2005.10.002
[73] A. M. Harling, D. J. Glover, J. C. Whitehead, K. Zhang, Appl. [96] Y. Li, W. Wang, F. Wang, L. Di, S. Yang, S. Zhu, Y. Yao, C. Ma,
Catal., B 2009, 90 (1–2), 157–161. DOI: https://doi.org/10.1016/ B. Dai, F. Yu, Nanomaterials 2019, 9 (5). DOI: https://doi.org/
j.apcatb.2009.03.005 10.3390/nano9050720
[74] Z. Abd Allah, J. C. Whitehead, P. Martin, Environ. Sci. Technol. [97] Y.-F. Guo, D.-Q. Ye, K.-F. Chen, J.-C. He, W.-L. Chen, J. Mol.
2014, 48 (1), 558–565. DOI: https://doi.org/10.1021/es402953z Catal. A: Chem. 2006, 245 (1–2), 93–100. DOI: https://doi.org/
[75] W. Liang, H. Sun, X. Shi, Y. Zhu, Catalysts 2020, 10 (5), 511. 10.1016/j.molcata.2005.09.013
DOI: https://doi.org/10.3390/catal10050511 [98] X. Yan, B. Zhao, Y. Liu, Y. Li, Catal. Today 2015, 256, 29–40.
[76] S. Zhang, W. Wang, L. Zhang, Z. Zhao, D. Yang, Eur. Phys. J. DOI: https://doi.org/10.1016/j.cattod.2015.04.045
Appl. Phys. 2017, 78 (2), 20803. DOI: https://doi.org/10.1051/ [99] F. Thevenet, O. Guaitella, E. Puzenat, C. Guillard, A. Rousseau,
epjap/2017160361 Appl. Catal., B 2008, 84 (3–4), 813–820. DOI: https://doi.org/
[77] B. Wang, X. Xu, W. Xu, N. Wang, H. Xiao, Y. Sun, H. Huang, 10.1016/j.apcatb.2008.06.029
L. Yu, M. Fu, J. Wu, L. Chen, D. Ye, Catal. Surv. Asia 2018, [100] T. Pham Huu, L. Sivachandiran, P. Da Costa, A. Khacef, Top.
22 (2), 73–94. DOI: https://doi.org/10.1007/s10563-018-9241-x Catal. 2017, 60 (3–5), 326–332. DOI: https://doi.org/10.1007/
[78] X. Feng, H. Liu, C. He, Z. Shen, T. Wang, Catal. Sci. Technol. s11244-016-0619-6
2018, 8 (4), 936–954. DOI: https://doi.org/10.1039/C7CY01934C [101] Y. Guo, X. Liao, M. Fu, H. Huang, D. Ye, J. Environ. Sci. (Beijing,
[79] M. S. Gandhi, Y. S. Mok, Surf. Coat. Technol. 2014, 259, 12–19. China) 2015, 28, 187–194. DOI: https://doi.org/10.1016/
DOI: https://doi.org/10.1016/j.surfcoat.2014.07.085 j.jes.2014.06.048
[80] J. Karuppiah, L. Sivachandiran, R. Karvembu, C. Subrahma- [102] A. Frey, V. Goeke, C. Voss, Chem. Ing. Tech 2018, 90 (10), 1384–
nyam, Chem. Eng. J. 2010, 165 (1), 194–199. DOI: https:// 1391. DOI: https://doi.org/10.1002/cite.201800046
doi.org/10.1016/j.cej.2010.09.017 [103] J. M. Campos-Martin, G. Blanco-Brieva, J. L. G. Fierro, Angew.
[81] Q. Trinh, Y. Mok, Catalysts 2015, 5 (2), 800–814. DOI: https:// Chem., Int. Ed. 2006, 45 (42), 6962–6984. DOI: https://doi.org/
doi.org/10.3390/catal5020800 10.1002/anie.200503779
[82] X. Zhu, X. Gao, X. Yu, C. Zheng, X. Tu, Catal. Today 2015, 256, [104] Y. Yi, L. Wang, G. Li, H. Guo, Catal. Sci. Technol. 2016, 6 (6),
108–114. DOI: https://doi.org/10.1016/j.cattod.2015.01.028 1593–1610. DOI: https://doi.org/10.1039/C5CY01567G
[83] C. Shi, B.-b. Chen, X.-S. Li, M. Crocker, Y. Wang, A.-M. Zhu, [105] Y. Yi, J. Zhou, H. Guo, J. Zhao, J. Su, L. Wang, X. Wang,
Chem. Eng. J. 2012, 200–202, 729–737. DOI: https://doi.org/ W. Gong, Angew. Chem., Int Ed. 2013, 52 (32), 8446–8449. DOI:
10.1016/j.cej.2012.06.103 https://doi.org/10.1002/anie.201304134
[84] C. Chen, T. Liu, H. Wang, Q. Yu, J. Fan, L. Xiao, X. Zheng, Chin. [106] A. Pashkova, L. Greiner, U. Krtschil, C. Hofmann, R. Zapf,
J. Catal. 2012, 33 (4–6), 941–951. DOI: https://doi.org/10.1016/ Appl.Catal., A 2013, 464–465, 281–287. DOI: https://doi.org/
S1872-2067(11)60391-4 10.1016/j.apcata.2013.06.007
[85] Y. Liu, X.-S. Li, J.-L. Liu, J. Wu, D. Ye, A.-M. Zhu, Catal. Sci. [107] T. Ishihara, K. Shigeta, Y. Ooishi, M. Matsuka, H. Hagiwara,
Technol. 2016, 6 (11), 3788–3796. DOI: https://doi.org/10.1039/ S. Ida, Catal. Sci. Technol. 2013, 3 (11), 2971. DOI: https://
C5CY02022K doi.org/10.1039/C3CY00273J
[86] M. Lu, R. Huang, P. Wang, L. Chen, J. Wu, M. Fu, W. Wen, [108] L. Torrente-Murciano, Q. He, G. J. Hutchings, C. J. Kiely,
B. Huang, D. Ye, Plasma Chem, Plasma Process, 2014, 34 (5), D. Chadwick, ChemCatChem 2014, 6 (9), 2531–2534. DOI:
1141–1156. DOI: https://doi.org/10.1007/s11090-014-9556-y https://doi.org/10.1002/cctc.201402361
[87] J. Karuppiah, E. L. Reddy, P. M. K. Reddy, B. Ramaraju, R. Kar- [109] Y. Han, J. Lunsford, J. Catal. 2005, 230 (2), 313–316. DOI:
vembu, C. Subrahmanyam, J. Hazard. Mater. 2012, 237–238, https://doi.org/10.1016/j.jcat.2004.12.001
283–289. DOI: https://doi.org/10.1016/j.jhazmat.2012.08.040 [110] K. Otsuka, I. Yamanaka, Electrochim. Acta 1990, 35 (2), 319–322.
[88] J. Karuppiah, L. Sivachrandiran, R. Karvembu, C. Subrahma- DOI: https://doi.org/10.1016/0013-4686(90)87004-L
nyam, Chin. J. Catal. 2011, 32 (5), 795–799. DOI: https://doi.org/ [111] J. Zhou, H. Guo, X. Wang, M. Guo, J. Zhao, L. Chen, W. Gong,
10.1016/S1872-2067(10)60190-8 Chem. Commun. (Cambridge, U. K.) 2005, 12, 1631–1633. DOI:
[89] X. Zhang, J. Zhu, X. Li, Z. Liu, X. Ren, K. Yan, IEEE Trans. Plas- https://doi.org/10.1039/b416835f
ma Sci. 2011, 39 (6), 1482–1488. DOI: https://doi.org/10.1109/ [112] Y. Yi, J. Zhou, T. Gao, H. Guo, J. Zhang, AIChE J. 2014, 60 (2),
TPS.2011.2128351 415–419. DOI: https://doi.org/10.1002/aic.14327
[90] X. Tang, F. Feng, L. Ye, X. Zhang, Y. Huang, Z. Liu, K. Yan, Catal. [113] J. Zhao, J. Zhou, J. Su, H. Guo, X. Wang, W. Gong, AIChE J.
Today 2013, 211, 39–43. DOI: https://doi.org/10.1016/ 2007, 53 (12), 3204–3209. DOI: https://doi.org/10.1002/aic.11317
j.cattod.2013.04.026 [114] Y. Yi, L. Wang, J. Yu, H. Guo, J. Zhang, C. Meng, AIChE J. 2018,
[91] Y. Ren, X. Li, S. Ji, S. Lu, A. Buekens, J. Yan, Chemosphere 2014, 64 (3), 981–992. DOI: https://doi.org/10.1002/aic.15999
117, 730–736. DOI: https://doi.org/10.1016/j.chemosphere.2014. [115] H.-H. Kim, Y. Teramoto, A. Ogata, H. Takagi, T. Nanba, Plasma
09.091 Processes Polym. 2017, 14 (6), 1600157. DOI: https://doi.org/
[92] A. M. Harling, V. Demidyuk, S. J. Fischer, J. C. Whitehead, Appl. 10.1002/ppap.201600157
Catal., B 2008, 82 (3), 180–189. DOI: https://doi.org/10.1016/ [116] P. Mehta, P. M. Barboun, Y. Engelmann, D. B. Go, A. Bogaerts,
j.apcatb.2008.01.017 W. F. Schneider, J. C. Hicks, ACS Catal. 2020, 10 (12), 6726–
[93] A. Lüken, M. Muhler, J. Strunk, Phys. Chem. Chem. Phys. 2015, 6734. DOI: https://doi.org/10.1021/acscatal.0c00684
17 (16), 10391–10397. DOI: https://doi.org/10.1039/c4cp05423g [117] J. Shah, W. Wang, A. Bogaerts, M. L. Carreon, ACS Appl. Energy
[94] S. Yu, Y. Liang, S. Sun, K. Zhang, J. Zhang, J. Fang, PloS one Mater. 2018, 1 (9), 4824–4839. DOI: https://doi.org/10.1021/
2013, 8 (4), e59974. DOI: https://doi.org/10.1371/journal.pone. acsaem.8b00898
0059974 [118] J. Hong, M. Aramesh, O. Shimoni, D. H. Seo, S. Yick, A. Greig,
C. Charles, S. Prawer, A. B. Murphy, Plasma Chem. Plasma Pro-
Chemie
Technik
cess. 2016, 36 (4), 917–940. DOI: https://doi.org/10.1007/ [130] B. S. Patil, A. S. R. van Kaathoven, F. J. J. Peeters, N. Cherkasov,
s11090-016-9711-8 J. Lang, Q. Wang, V. Hessel, J. Phys. D: Appl. Phys. 2020, 53 (14),
[119] J. R. Shah, F. Gorky, J. Lucero, M. A. Carreon, M. L. Carreon, 144003. DOI: https://doi.org/10.1088/1361-6463/ab6a36
Ind. Eng. Chem. Res. 2020, 59 (11), 5167–5176. DOI: https:// [131] X. Zhu, X. Hu, X. Wu, Y. Cai, H. Zhang, X. Tu, J. Phys. D: Appl.
doi.org/10.1021/acs.iecr.9b05220 Phys. 2020, 53 (16), 164002. DOI: https://doi.org/10.1088/
[120] H.-H. Kim, Y. Teramoto, A. Ogata, H. Takagi, T. Nanba, Plasma 1361-6463/ab6cd1
Processes Polym. 2017, 14 (6), 1600157. DOI: https://doi.org/ [132] F. A. Herrera, G. H. Brown, P. Barboun, N. Turan, P. Mehta,
10.1002/ppap.201600157 W. F. Schneider, J. C. Hicks, D. B. Go, J. Phys. D: Appl. Phys.
[121] P. Peng, Y. Cheng, R. Hatzenbeller, M. Addy, N. Zhou, C. Schiap- 2019, 52 (22), 224002. DOI: https://doi.org/10.1088/1361-6463/
pacasse, D. Chen, Y. Zhang, E. Anderson, Y. Liu, P. Chen, ab0c58
R. Ruan, Int. J. Hydrogen Energy 2017, 42 (30), 19056–19066. [133] H. Lee, D. H. Kim, Sci. Rep. 2018, 8 (1), 9956. DOI: https://
DOI: https://doi.org/10.1016/j.ijhydene.2017.06.118 doi.org/10.1038/s41598-018-28170-x
[122] K. H. R. Rouwenhorst, H.-H. Kim, L. Lefferts, ACS Sustainable [134] A. Indarto, J.-W. Choi, H. Lee, H. K. Song, Sci. Bull. 2008,
Chem. Eng. 2019, 7 (20), 17515–17522. DOI: https://doi.org/ 53 (18), 2783–2792. DOI: https://doi.org/10.1007/
10.1021/acssuschemeng.9b04997 s11434-008-0384-4
[123] Q. Xie, S. Zhuge, X. Song, M. Lu, F. Yu, R. Ruan, Y. Nie, J. Phys. [135] P. Chawdhury, D. Ray, D. Nepak, C. Subrahmanyam, J. Phys. D:
D: Appl. Phys. 2020, 53 (6), 64002. DOI: https://doi.org/10.1088/ Appl. Phys. 2019, 52 (1), 15204. DOI: https://doi.org/10.1088/
1361-6463/ab57e5 1361-6463/aae635
[124] A. Gómez-Ramı́rez, J. Cotrino, R. M. Lambert, A. R. González- [136] P. Chawdhury, D. Ray, T. Vinodkumar, C. Subrahmanyam, Catal.
Elipe, Plasma Sci. Technol. 2015, 24 (6), 65011. DOI: https:// Today 2019, 337, 117–125. DOI: https://doi.org/10.1016/
doi.org/10.1088/0963-0252/24/6/065011 j.cattod.2019.03.032
[125] K. Aihara, M. Akiyama, T. Deguchi, M. Tanaka, R. Hagiwara, [137] R. Aerts, W. Somers, A. Bogaerts, ChemSusChem 2015, 8 (4),
M. Iwamoto, Chem. Commun. 2016, 52 (93), 13560–13563. DOI: 702–716. DOI: https://doi.org/10.1002/cssc.201402818
https://doi.org/10.1039/C6CC06752B [138] A. Ozkan, A. Bogaerts, F. Reniers, J. Phys. D: Appl. Phys. 2017,
[126] A. Gómez-Ramı́rez, A. M. Montoro-Damas, J. Cotrino, R. M. 50 (8), 84004. DOI: https://doi.org/10.1088/1361-6463/aa562c
Lambert, A. R. González-Elipe, Plasma Processes Polym. 2017, [139] T. Kozák, A. Bogaerts, Plasma Sources Sci. Technol. 2014, 23 (4),
14 (6), 1600081. DOI: https://doi.org/10.1002/ppap.201600081 45004. DOI: https://doi.org/10.1088/0963-0252/23/4/045004
[127] M. Iwamoto, M. Akiyama, K. Aihara, T. Deguchi, ACS Catal. [140] R. Snoeckx, A. Bogaerts, Chem. Soc. Rev. 2017, 46 (19), 5805–
2017, 7 (10), 6924–6929. DOI: https://doi.org/10.1021/ 5863. DOI: https://doi.org/10.1039/c6cs00066e
acscatal.7b01624 [141] Y.-L. Men, Y. Liu, Q. Wang, Z.-H. Luo, S. Shao, Y.-B. Li, Y.-X.
[128] G. Akay, K. Zhang, Ind. Eng. Chem. Res. 2017, 56 (2), 457–468. Pan, Chem. Eng. Sci. 2019, 200, 167–175. DOI: https://doi.org/
DOI: https://doi.org/10.1021/acs.iecr.6b02053 10.1016/j.ces.2019.02.004
[129] S. Li, T. van Raak, F. Gallucci, J. Phys. D: Appl. Phys. 2020, 53 (1), [142] L. Wang, Y. Yi, H. Guo, X. Tu, ACS Catal. 2018, 8 (1), 90–100.
14008. DOI: https://doi.org/10.1088/1361-6463/ab4b37 DOI: https://doi.org/10.1021/acscatal.7b02733
Chemie
Technik
DOI: 10.1002/cite.202000075
Fundamental Properties and Applications of Dielectric Barrier

Discharges in Plasma-Catalytic Processes at Atmospheric Pressure
K. Ollegott, P. Wirth, C. Oberste-Beulmann, P. Awakowicz, M. Muhler*
Review Article: In plasma catalysis a plasma source is combined with a heterogeneous

catalyst. The application of dielectric barrier discharges at atmospheric pressure in the
oxidation of volatile organic compounds, oxygen trace removal from coke oven gas, and the
synthesis of hydrogen peroxide, ammonia and methanol are discussed in an industrial
context. .......................................................................................................... ¢

Fundamental Properties and Applications of Dielect

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Fundamental Properties and Applications of Dielect

Uploaded by

Copyright:

Available Formats

These are not the final page numbers!

Fundamental Properties and Applications of

1 Introduction plasma-chemical process. As O3 is decomposed at elevated

Actually, Paschen’s law is only applicable to the described

2.3 Streamer Mechanism

and thickness of the dielectric material. When the electric

trode. Offerhaus et al. [53] presented a twin-surface DBD

behavior of the discharge, e.g., the formation of microdi-

Table 1. Examples for the abatement of different VOCs found in literature.

Butane TiO2/g-Al2O3 1000 927 91 99 100 W [79]

Isopropanol MnOx 500 100 100 100 295 J L–1 [80]

Diethylether Mn-Fe/cordierite 1000 150 96 600 J L–1 [81]

Acetone CuOx/g-Al2O3 1000 1184 94.2 80.1 1012 J L–1 [82]

Formaldehyde Ag-MnOx-CeO2 100 80 100 >95 [83]

Hexanal MnOx/g-Al2O3 100 1.2 96.5 2.8 W [84]

Benzene AgMn/HZSM-5 200 100 70 100 6W [85]

Commonly, packed-bed reactors are utilized to establish

Figure 7. Proposed mechanism of the plasma-catalytic oxida-

Hydrogen peroxide (H2O2) is a broadly used oxidizing

metal catalysts in three-phase reactors [106–108]. A disad-

O2 ﬁ 2O (8) HO2 þ HO2 ﬁ H2 O4 * (14)

H þ O2 * ﬁ HO þ O (10) HO2 þ H2 O ﬁ HO2 þ H2 O (16)

The plasma process produces concen- Cu (wool-like) 3.5 3.3 93 [125]

g-Al2O3 0.64 6.58 [131]

Ammonia (NH3) is a base chemical with

H2 þ e ﬁ 2H þ e (22) the optimization of the methanol yield, an improvement of

6.4 Methanol Synthesis

discharge caused by the streamer breakdown mechanism PPC post-plasma catalysis

Fundamental Properties and Applications of Dielectric Barrier

Review Article: In plasma catalysis a plasma source is combined with a heterogeneous

You might also like