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 Journal of Physics D: Applied Physics

J. Phys. D: Appl. Phys. 54 (2021) 334003 (15pp) https://doi.org/10.1088/1361-6463/abfddd

Influence of ionic conductivity and

dielectric constant of the catalyst on
DBD plasma-assisted CO2
hydrogenation into methanol
Maxwell Quezada Feliz1,2, Isabelle Polaert2,∗, Alain Ledoux2, Christian Fernandez1
and Federico Azzolina-Jury1,∗
1
Normandie Univ, ENSICAEN, UNICAEN, CNRS, LCS, Laboratoire Catalyse et Spectrochimie, 14000
Caen, France
2
Normandie Univ, UNIROUEN, INSA Rouen, LSPC, Laboratoire de Sécurité des Procédés Chimiques,
76000 Rouen, France

E-mail: isabelle.polaert@insa-rouen.fr and federico.azzolina-jury@ensicaen.fr

Received 8 December 2020, revised 17 April 2021

Accepted for publication 4 May 2021
Published 4 June 2021

Abstract
Dielectric barrier discharge (DBD) plasma technology is a promising method for producing
methanol from CO2 hydrogenation as the reaction can be run at atmospheric pressure and
temperatures below 100 ◦ C. The choice of the catalyst is crucial and has to be made not only
according to its activity and selectivity towards the desired product, but its effect on plasma
properties. In this work, the influence of several important catalytic properties of DBD plasma
such as the dielectric constant of the catalyst and ionic conductivity is studied. The effects of the
catalyst support and the addition of promoters on CO2 hydrogenation under DBD plasma are
also studied. To this end, Cu and Cu–ZnO catalysts supported on γ-Al2 O3 and a template-free
seedless ZSM-5 (Si/Al molar ratio of 23) were prepared to study their catalytic performance on
CO2 hydrogenation into methanol under DBD plasma. These catalysts were fully characterized
by XRD, SEM, N2 physisorption, temperature programmed reduction and in situ FTIR CO
adsorption. The relative complex permittivity of the catalysts was measured and the ionic
conductivity was estimated using a modified Debye model. In this paper, the role of the ionic
conductivity of the catalyst was identified as a crucial parameter in plasma-assisted CO2
hydrogenation. It was found that the lower the value of the ionic conductivity, the better the CO2
conversion. Indeed, high ionic conductivity reduces the density of the plasma and decreases the
dissociation of CO2 . The highest CO2 conversion value (34.0%) was observed for the
nonconductive alumina support, whereas the highest methanol yield (0.5%) was observed for
the zeolite-supported Cu–ZnO catalyst.

Supplementary material for this article is available online

Keywords: DBD plasma, methanol synthesis, CO2 hydrogenation, dielectric constant,
ionic conductivity, ZSM-5

(Some figures may appear in colour only in the online journal)

∗
Authors to whom any correspondence should be addressed.

1361-6463/21/334003+15$33.00 1 © 2021 IOP Publishing Ltd Printed in the UK

J. Phys. D: Appl. Phys. 54 (2021) 334003
1. Introduction
Carbon dioxide is a major greenhouse gas, but it can also be
seen as an abundant source of C1 . For decades, several propos-
als to reduce anthropogenic CO2 emissions have been made
for recycling carbon dioxide into fuels. CO2 is a non toxic,
non corrosive, non flammable [1] and very thermodynamic-
ally stable molecule (∆f G0 298K = −394 kJ mol−1 ), requiring a
large amount of energy for its dissociation (+283 kJ mol−1 or
2.9 eV molecule−1 ) [2]. CO2 is produced from almost all com-
bustion processes and is the main greenhouse gas (after water
vapour). The concentration of CO2 in the atmosphere reached
417 ppm in March 2020, according to NOAA [3]. Currently,
to prevent its release into the atmosphere, one of the existing
technologies is its capture and storage in underground reser-
voirs [4], but this technique does not benefit from CO2 as a car-
bon source. Another approach, as proposed in this article, is the
chemical utilization of this captured CO2 for its valorization
into hydrocarbons, in this particular case into methanol. The
source of pure CO2 would be the exhaust gases from chem-
ical industry that are not pure and which are purified via cap-
ture technology already proposed in literature [5, 6]. The main
interest in making methanol is to create a source of chemical
energy, which would be used to store energy from renewable
sources [7]. Methanol is preferred to gaseous fuels (methane,
hydrogen, etc) because, at ambient conditions, it is liquid and
therefore easily transportable, without the safety risks associ-
ated with the transportation of pressurized gases. Methanol is
also one of the most important products of the petrochemical
and chemical industries, serving as raw material for the pro-
duction of formaldehyde, dimethyl ether [8], etc.
Methanol can be synthesized from carbon oxide hydrogen-
ation reactions. Possible reactions involving methanol produc-
tion from carbon oxides are presented in table 1. Methanol can
be produced via CO2 hydrogenation (table 1, line 1). However,
this reaction is accompanied by an undesired secondary endo-
thermic reaction (RWGS), which is favoured at high temperat-
ures and consumes the same reactants (table 1, line 2). In both
reactions, low CO2 conversion is usually achieved without
the use of a catalyst as a consequence of the high molecu-
lar stability of CO2 . Thus, both reactions are usually stud-
ied at high temperatures (>200 ◦ C) and pressures (>20 atm)
over alumina-supported copper-based catalysts in convention-
ally heated fixed-bed reactors [1, 9–13]. Methanol can also be
obtained from CO hydrogenation (table 1, line 3), which is
the current reaction used in the industry. In this case, CO is
obtained either by methane reforming or through coal gasific-
ation [9]. Carbon oxide hydrogenation can also produce meth-
ane as a secondary product (refer to table 1 of Gao et al [14]).
A nonconventional approach to methanol synthesis from
CO2 hydrogenation is the use of plasma technology (this
work). Plasma is the fourth state of matter, consisting of a mix-
ture of highly energetic species, such as electrons, ions, rad-
icals and excited molecules. Among the numerous available
technologies for the generation of plasma, nonthermal plasmas
(NTPs) are among the most used in plasma-assisted catalysis.
NTPs are nonequilibrium plasmas since the electron energy
(characterized by the electron temperature T e ) is much higher
2
M Q Feliz et al
Table 1. Possible reactions involved in methanol production from
carbon oxides.
∆r H 0 298K ∆r G0 298K
Reaction (kJ mol−1 ) (kJ mol−1 )
CO2 + 3H2 ↔ CH3 OH + H2 O −49.51 3.30
CO2 + H2 ↔ CO + H2 O 41.17 28.64
CO + 2H2 ↔ CH3 OH −90.68 −25.34
than the energy (or temperature) of the other species present
in the gas mixture. Electrons travelling to the positive elec-
trode can interact with other plasma species or collide with
gas molecules leading to ionization, vibrational excitation or
even dissociation of these molecules. The high density of these
highly energetic species allows plasma-assisted reactions to
take place at relatively low temperatures. Dielectric barrier dis-
charge (DBD) NTP reactors have been used to produce meth-
anol from CO2 hydrogenation at atmospheric pressure and
temperatures below 100 ◦ C, which is fairly low when com-
pared to conventional heating methods [15–19]. However, sev-
eral key parameters related to plasma-assisted catalysis need
to be fully understood when aiming to optimize CO2 hydro-
genation reactions.
In plasma-assisted catalysis, the plasma can modify the
properties of the catalyst but the catalyst itself can also affect
the properties of the plasma. In a review by Neyts and Bogaerts
[20], several of these effects, which lead to a plasma-catalyst
synergy, were addressed. Among the effects of a catalyst on
the properties of the plasma, the following can be mentioned:
the enhancement of the electric field, the modification of the
discharge type and the formation of micro discharges within
the catalyst pores. Concerning the effects of the plasma on the
properties of the catalyst, we can cite the modification of the
adsorption capacity of the catalyst, the surface area, oxidation
state of the metallic active phase, formation of hot spots and
modification of the surface reaction pathway.
The synergetic effects observed in plasma catalysis can be
tailored and plasma-assisted catalytic processes can be optim-
ized through a better understanding of the parameters govern-
ing the mutual interaction between the catalyst and the plasma
[21]. In this regard, the effect of four magnitudes has mainly
been studied: the dielectric constant of the catalyst, its ionic
conductivity, its particle size and the porosity of the bed. Con-
cerning the first one, Butterworth et al [22, 23] reported that an
increase in the dielectric constant of the catalyst decreases the
breakdown voltage. In their work, the authors described two
types of discharge modes: the polar mode and surface streamer
mode. For a given dielectric, the plasma discharge first occurs
in polar mode and then switches to surface streamer mode
upon voltage increase. If the dielectric constant is increased,
the necessary voltage for the transition between these two
modes is also increased. However, the authors also reported
that this transition can be related to the ionic conductivity and
the porosity of the bed. The influence of the dielectric constant
has also been addressed by van Laer and Bogaerts [24]. Upon
simulation studies, the authors quoted that plasma relocates
into the catalyst bed voids when the dielectric constant of the
J. Phys. D: Appl. Phys. 54 (2021) 334003
material is increased. The authors claim that higher voltages
are needed for plasma ignition when the material possesses a
low dielectric constant. They also addressed the influence of
the particle size of the catalyst; the smaller the particle size,
the higher the voltage required to ignite the plasma. Song et al
[25] found that the dielectric constant of the material influ-
enced the plasma-catalyst synergetic effect on chlorobenzene
decomposition. The decomposition rate is higher in the case of
catalysts with high dielectric constant because the ionization
of the gas and the electron energy are enhanced by increas-
ing the dielectric constant of the packed materials [26, 27].
Michielsen et al [28] studied CO2 dissociation in a packed-
bed DBD reactor using different dielectric materials and bead
sizes. The authors identified three important effects: (a) the
positive effect of the packing due to electric field enhancement,
(b) the negative effect of the packing due to the reduction of
the reactant residence time and (c) the influence of the packed-
bed porosity with a positive or negative effect depending on
the dielectric constant of the material inside the DBD reactor.
Finally, Jo et al [29] studied the effect of the catalyst conduct-
ivity on methane production using an alumina-supported plat-
inum catalyst. They found that the presence of Pt decreases
the magnitude of the electric field and thus, the methane yield.
Based on these results, they inferred that the conductivity of
the catalyst was responsible for the decrease in magnitude of
the electric field. They also suggested that further studies using
conductive and nonconductive solids were needed to better
identify the aforementioned effects.
From the previous paragraph, it is clear that even though
several parameters have been observed to be influential
(dielectric constant, ionic conductivity, pellet size and bed
porosity), their effects are yet to be fully understood. In this
regard, we have chosen to study the effects of the ionic
conductivity and dielectric constant on CO2 hydrogenation
into methanol in DBD plasma using two types of supports:
γ-alumina and a ZSM-5 with Si/Al molar ratio of 23. The γ-
alumina support is the traditional support for this reaction due
to its amphoteric properties [30] while zeolites are good poten-
tial candidates because of their high surface area and catalytic
activity [31–33]. These two supports were also chosen because
they differ in their ionic conductivity and dielectric properties
[34, 35]. These supports were impregnated with copper (Cu)
and copper-zinc oxide (Cu–ZnO) to produce four catalysts and
were fully characterized and tested in DBD plasma to ascertain
the influence of the two aforementioned parameters. Finally,
the role of copper and zinc oxide active sites in CO2 hydro-
genation reactions is also addressed.
2. Experimental
2.1. Catalyst preparation
The MFI zeolite support used in this work was prepared in
its sodium form (Na-ZSM-5) following a template-free seed-
less method [8]. The following reactants were used: LUDOX
HS-30 Colloidal Silica from Sigma Aldrich (30% wt. SiO2
suspension in water), CAS No. 7631-86-9, as the silica source;
NaOH pellets from VWR Chemicals (⩾98% assay), CAS No.
3
M Q Feliz et al
Table 2. List of the catalysts used in this work.
Metal content
Si/Al molar
Support ratio Cu Zn Code
γ-Al2 O3 — — — A
γ-Al2 O3 — 10% wt. — Cu/A
γ-Al2 O3 — 10% wt. 10% wt. Cu–Zn/A
ZSM-5 23 — — Z23
ZSM-5 23 10% wt. — Cu/Z23
ZSM-5 23 10% wt. 10% wt. Cu–Zn/Z23
1310-73-2; NaAlO2 from Sigma Aldrich (Al2 O3 : 50%–56%
wt., Na2 O: 37%–45% wt.) CAS No. 11138-49-1 as the alu-
minium source and distilled water. The Si/Al molar ratio of
the prepared ZSM-5 was 23.
The γ-alumina supports were obtained from commer-
cially available boehmite DISPAL 23N4-80 (Sasol) with large
particles (50 mm). Boehmite was dehydrated through calcina-
tion at 550 ◦ C for 3 h, as reported elsewhere [36].
The prepared supports were then shaped into cylindrical
extrudates (5 mm in length and 2 mm in width) using boehmite
as a binder [36]. The binder used in the manufacture of the
extrudates (boehmite) was transformed into γ-alumina during
the calcination step. Therefore, zeolite extrudates also con-
tained alumina. In the case of the alumina support, the extrud-
ates were made of pure γ-alumina only. The reason for the
preparation of these extrudates is that they were also used in a
conventionally heated fixed-bed setup to study the kinetics of
CO2 hydrogenation to methanol under pressure in a pilot plant
[37, 38]. For the catalytic tests presented in this work, a final
catalyst particle size between 400–800 µm was used and was
obtained by grinding the aforementioned extrudates.
Copper (10% wt.) and zinc (10% wt.) were added to the
alumina and zeolite extrudates by wet impregnation. Cop-
per nitrate trihydrate, Cu(NO3 )2 ·3H2 O from Sigma-Aldrich
(⩾99%), CAS No. 10031-43-3 and zinc nitrate hexahydrate,
Zn(NO3 )2 ·6H2 O were used as metal precursors. In the case
of the bimetallic catalysts, both metal precursors were added
simultaneously. Liquid removal was performed under vacuum
at 80 ◦ C overnight and the dried catalysts were calcined under
air at 600 ◦ C for 3 h. The list of catalysts prepared for this work
is summarized in table 2.
2.2. Catalyst characterization
The alumina and ZSM-5 structures (powder and extrudates)
were verified using a PANalytical X’Pert PRO diffractometer
with CuKα radiation (λ = 0.154 18 nm, 40 mA, 45 kV).
The XRD patterns were recorded between 2θ = 5◦ − 75◦
for the alumina catalysts and 2θ = 5◦ − 60◦ for the MFI
catalysts, with a step size of 0.016 73◦ and a time per step
of 40 s.
The size and morphology of the catalysts were examined
using a Philips XL-30 SEM with an acceleration voltage
of 30 kV. The results of these first two characterization
J. Phys. D: Appl. Phys. 54 (2021) 334003
Figure 1. Plasma DBD reactor (left) and conventional packed-bed reactor (right) for CO2 hydrogenation to methanol.
tests (XRD and SEM) allowed us to identify and valid-
ate the adequate crystallinity and morphology of the pre-
pared catalysts, as well as the presence of the desired metals.
Their corresponding figures are available in the supplementary
information provided (available online at stacks.iop.org/JPD/
54/334003/mmedia) (figures 1 and 2).
The metal content of the synthesized catalysts was determ-
ined by inductively coupled plasma (ICP).
Nitrogen adsorption-desorption isotherms were measured
at 77 K with a Micrometrics Model ASAP 2020 volumetric
adsorption analyzer. The corresponding figures are available
in the supplementary information. Before each analysis, the
catalysts were outgassed at 220 ◦ C overnight. The specific sur-
face area of the catalysts was determined from the Brunauer–
Emmett–Teller (BET) equation. Their total pore volume was
estimated from the N2 adsorbed volume at P/P0 = 0.99.
The reducibility of the catalysts was determined through
temperature-programmed reduction (TPR) analysis in a
Micromeritics AutoChem II analyzer. Samples of 50 mg of
catalysts were loaded into a quartz U-tube. TPR was per-
formed using 5% v/v H2 in Ar with a total flow rate of
40 ml min−1 at standard temperature and pressure (STP) from
room temperature up to 1000 ◦ C with a heating ramp of
10 ◦ C min-1 .
In situ FTIR measurements were carried out using carbon
monoxide as a probe molecule with a NicoletMagna 550 FTIR
spectrometer equipped with an MCT detector. The FTIR spec-
tra were recorded from 4000 to 600 cm−1 with an optical resol-
ution of 4 cm−1 and 32 scans. Then, the catalysts were pressed
(2 × 108 Pa) into self-supported wafers (2 cm2 , ∼20 mg). Prior
to all infrared (IR) measurements, the catalysts were first activ-
ated under secondary vacuum (6.10−4 Pa) at 350 ◦ C for 4 h
with a heating rate of 5 ◦ C min−1 . After activation, the tem-
perature was raised to 400 ◦ C using the same heating rate.
Then, the catalysts were consecutively reduced twice (with
an in between evacuation of the formed water) for 30 min
under 100 Torr of H2 . After the reduction step, the temper-
ature was reduced to room temperature using a cooling rate of
4
M Q Feliz et al
5 ◦ C min−1 . Once the desired temperature was reached, small
volume doses (1.57 cm3 ) of CO were sent to the catalyst wafers
until complete surface saturation. The CO was used to study
the dispersion of the metallic active phase and to identify the
different copper species (Cu0 , Cu+ , Cu2+ ). The CO adsorp-
tion was performed at room temperature.
The complex permittivity of catalysts can be measured by
two techniques: the method of small perturbations in the res-
onant cavity or the reflection method. The former is gener-
ally used to measure permittivities at a given frequency as
a function of temperature and has been developed specific-
ally for microwave frequencies [39]. The latter is frequency-
dependent and allows the precise characterization of solids
in a wider frequency domain. From these measurements, the
static and infinite dielectric constants, as well as the ionic con-
ductivity, can be calculated using an appropriate mathematical
model. This allows us to evidence physical phenomena occur-
ring at the microscopic scale, such as dielectric relaxation.
In this work, the complex permittivities of the prepared cata-
lysts were measured by a reflection technique described else-
where [40, 41]. Complex permittivity data were acquired in the
microwave range between 0.5–20 GHz using a vector network
analyzer from Agilent 2-PortPNA-L of the 5230 A series con-
nected to a high-temperature open-ended coaxial probe. The
measurements were carried out at room temperature (20 ◦ C).
Prior to the measurements, the catalysts were sieved in order to
have a particle size of less than 100 µm. For the measurement
of their dielectric properties, the catalysts were manually com-
pacted in a cylindrical polytetrafluoroethylene block of 20 mm
(height) × 20 mm (width). The complex permittivity measure-
ments were repeated three times for each catalyst.
2.3. Catalytic tests
The experimental set-up used in this work to evaluate the per-
formance of the prepared catalysts on CO2 hydrogenation to
methanol under both DBD plasma and conventional heating is
presented in figure 1.
J. Phys. D: Appl. Phys. 54 (2021) 334003
Both conventional and DBD plasma reactors were fed with
40 ml min−1 (STP) of CO2 (3.75% v/v), H2 (11.25% v/v)
and Ar (85% v/v) using Brooks mass flow controllers at atmo-
spheric pressure. A CO2 :H2 stoichiometric molar ratio of three
was adopted for this study. Both reactors were made of quartz
and had the same dimensions: an inner diameter, outer dia-
meter and length of 1.0, 1.3 and 13 cm, respectively. Reaction
products were identified and quantified using a Bruker vertex
80v FTIR spectrometer with an optical resolution of 0.2 cm−1
and 16 scans, between 4000–600 cm−1 and a quadrupole mass
spectrometer (Pfeiffer Omnistar GSD 301). The gases at the
reactor outlet were heated at 120 ◦ C to avoid methanol con-
densation before analysis.
All the catalyst extrudates prepared in this work were
ground to a size between 400–800 µm for all catalytic tests.
A mass of 2 g of catalyst was used for both plasma-assisted
and conventional heating tests. The height of the catalytic bed
was approximately 3 cm for all cases. Prior to each catalytic
test, the catalysts were reduced at 400 ◦ C with an H2 /N2 mix-
ture (5% v/v) for 3 h.
In the case of plasma-assisted reactions, a 0.5 cm dia-
meter high-voltage electrode made of iron (Fe) was used.
A 9 cm long hollow cylinder (copper), wrapping the quartz
reactor, , was used as a ground electrode. Catalyst particles
were held in place by a porous glass frit and placed within
the plasma discharge zone. The gap between the electrodes
was equal to 2.5 mm. The plasma discharge was generated
at atmospheric pressure, using a plasma function generator
(FI5350GA) coupled to a high-voltage amplifier (Trek model
20/20 C). A sine voltage wave of 20 kV (peak-to-peak) at a fre-
quency of 9 kHz was adopted for all plasma-assisted catalytic
tests. These operating conditions were found to be optimal dur-
ing a preliminary testing phase performed with the same DBD
reactor. Finally, the temperature inside the reaction zone was
measured by manually inserting a thermocouple right after
plasma extinction.
In the case of the tests under conventional heating, the
reactor was placed inside a furnace to regulate the reaction
temperature. A thermocouple was placed inside the catalytic
bed to measure the temperature at its centre during the reac-
tion. Conventional heating catalytic tests were performed at
seven different temperatures: 25 ◦ C, 75 ◦ C, 150 ◦ C, 200 ◦ C,
250 ◦ C, 300 ◦ C and 350 ◦ C. A heating ramp of 3 ◦ C min−1
was adopted to adjust the reaction temperature to the desired
value.
The CO2 conversion and the corresponding product
selectivity and yields were calculated as follows:
ṅ0CO2 − ṅCO2
XCO2 (%) = × 100, (1)
ṅ0CO2
ṅproduct
Sproduct (%) = × 100, (2)
ṅ0CO2 − ṅCO2
ṅproduct
Yproduct [%] = ∗ 100, (3)
ṅ0CO2
5
M Q Feliz et al
Figure 2. CO2 conversion versus temperature under conventional
heating.
where ṅ0 represents the inlet flow rate of a given spe-
cies and ṅ the flow rate of that species measured at the
reactor outlet. The molar flow of the different species is
calculated according to the gas chromatography results. For
each compound, a specific calibration is done just before
the tests using gas calibration standards. The experimental
error was estimated at 5% by repeating the experiments three
times.
3. Results
3.1. Catalytic tests
3.1.1. Conventional heating catalytic tests. Prior to the tests
under DBD plasma, a few experiments were performed at the
same pressure and gas flow but under conventional heating to
verify whether methanol was produced. These tests were car-
ried out without a catalyst (empty reactor), with the alumina
support and with the Cu/A. They were performed at atmo-
spheric pressure between 20 ◦ C–350 ◦ C. The CO2 conversion
as a function of the reaction temperature is shown in figure 2
for the three studied cases. The relative experimental error of
these measures (and of all future measures presented in this
work) was 5%.
In all three cases, CO2 conversion increased with tem-
perature. The reaction products were CO and H2 O only and
they were produced through the endothermic reverse water
gas shift (RWGS) reaction (table 1, line 2). Compared to the
empty reactor, CO2 was converted into CO at lower tem-
peratures when the alumina catalysts (A and Cu/A) were
used. The alumina support was able to catalyze the RWGS
reaction via its basic sites (oxygen of alumina structure).
Both CO2 conversion and CO yield were enhanced after
Cu addition into the alumina support, evidencing the role
of copper as an active metal for this reaction. In all cases,
no methanol was produced under conventional heating at
atmospheric pressure. Based on these results, no other cata-
lytic tests under conventional heating were pursued in this
work.
J. Phys. D: Appl. Phys. 54 (2021) 334003 M Q Feliz et al

Figure 3. Results of the catalytic tests in DBD plasma for the alumina and Z23 supports (ER: empty reactor).

Table 3. Textural properties of alumina and zeolite supports and catalysts.

Microporous Mesoporous
surface area surface area Total surface Total pore volume Average pore Al2 O3 content (%
Catalyst (m2 g−1 ) (m2 g−1 ) area (m2 g−1 ) (cm3 g−1 ) size (nm) wt.) in extrudates

A 0 190 190 0.43 12.3

Cu/A 0 164 164 0.38 10.4 100
Cu–Zn/A 0 143 143 0.32 9.7
Z23 146 99 245 0.27 7.3
Cu/Z23 128 64 192 0.22 6.9 17
Cu–Zn/Z23 125 60 185 0.20 6.1

3.1.2. Plasma DBD catalytic tests. Figure 3 shows the
CO2 conversion and the selectivity towards methanol and
methane obtained during the plasma-assisted catalytic tests.
As a reference, the results obtained under the same exper-
imental conditions but without any solid (with an empty
reactor) are shown. CO, methanol and methane were the
only carbon-based products detected and were quantified
at the outlet of the plasma reactor. The CO selectivity is
not displayed, but it can be deducted from the other two
as no other carbon products were detected. Thus, the CO
selectivities were: A (95.2%) > Z23 (94.9%) > Cu/Z23
(94.6%) > Cu/A (93.9%) > CuZn/A (93.6%) > empty reactor
(92.9%) > CuZn/Z23 (92.6%). The temperature of the sys-
tem was measured right after plasma extinction by inserting
a thermocouple into the centre of the catalyst bed. Its value
fluctuated between 83 ◦ C and 87 ◦ C, serving as an indic-
ator of the average temperature of the catalyst bed during the
reaction.
First of all, it can be observed that CO2 is converted into
methanol, methane and carbon monoxide in the absence of
a support/catalyst (empty reactor). After the introduction of
alumina, CO2 conversion increased at the cost of a decrease
in both methanol and methane production. Copper addition to
the alumina support decreased CO2 conversion while increas-
ing both methanol and methane selectivity. Similar behaviour
is observed after ZnO addition (CuZn/A), but only with respect
to methane selectivity. On the other hand, CO2 conversion
remained the same after the introduction of the Z23 support
(when compared to the empty reactor), whilethe selectivity
of both products decreased. A slight increase in methanol
selectivity is observed after copper addition, accompanied by
a decrease in CO2 conversion. Finally, CO2 conversion and
the selectivity of both products increased after ZnO addition
for the CuZn/Z23.
In order to better understand and explain the observed beha-
viour, the following (sections 3.2–3.4) will provide the results
of the performed characterization tests. Finally, section 4 of
this work is devoted to the discussion of these characteriza-
tion results and their relationship to figure 3.
3.2. Physicochemical characterization of the catalysts
3.2.1. BET surface area. The textural properties of alumina
and zeolite supports and catalysts are presented in table 3. The
alumina content of alumina and zeolite catalyst extrudates was
estimated by ICP and is also available. For all supports, the
introduction of either copper or copper and zinc reduced the
total surface area. In addition, the total pore volume and aver-
age pore size of all supports were found to be diminished after
the introduction of the metal(s), indicating a partial blocking of
the pores of the support. The Z23 presented the highest surface
area whether as a standalone support or as a catalyst. Better

6
J. Phys. D: Appl. Phys. 54 (2021) 334003
Table 4. Catalyst metal content and hydrogen uptake.
H2 /Cu CuO/Cu2 O
Catalyst % wt. Cu % wt. Zn mole ratio mole ratio
Cu/A 8.5 — 0.71 0.5
Cu–Zn/A 7.8 7.1 0.76 6.7
Cu/Z23 9.8 — 0.98 0.3
Cu–Zn/Z23 10.0 10.0 0.80 4.9
dispersion of the active phase may have been achieved in the
case of the Z23 catalysts.
3.2.2. Temperature programmed reduction (TPR). The TPR
profiles of all catalysts are shown in figure 3. The H2 /Cu mole
ratio (H2 uptake) and catalyst metal content, determined by
ICP, are presented in table 4.
First, the effect of the support can be analyzed through
comparison of the monometallic copper catalysts (Cu/A and
Cu/Z23) in figure 4(a). For both supports, two reduction peaks
were identified by deconvolution. In the case of alumina sup-
ports, CuO reduction presented two peaks located at 230.0 ◦ C
and 270.1 ◦ C. These reduction peaks can be ascribed to the
stepwise reduction of CuO to Cu2 O (Cu2+ to Cu+ ) followed
by the reduction of Cu2 O to metallic copper (Cu+ to Cu0 ),
respectively [42, 43]. In the case of the zeolite support, a con-
voluted CuO reduction peak at 307 ◦ C was observed. This
peak is the contribution of the two CuO reduction peaks loc-
ated at 268.7 ◦ C and 307.3 ◦ C, respectively. It can be observed
that, overall, lower temperatures are needed for CuO reduction
into metallic copper (Cu2+ to Cu0 ) in the case of the alumina
support. This can be explained by the interaction between the
CuO and the support. This interaction can be observed by ana-
lyzing the pre-reduction CuO/Cu2 O mole ratio of the catalysts
(table 4), which was estimated by dividing the area of the cor-
responding CuO and Cu2 O peaks during reduction in figure 4.
This ratio was of 0.5 and 0.3 for alumina and zeolite supports,
respectively. More easily reducible CuO species (Cu2+ ) can
be obtained with the alumina support, which can be an indic-
ator of lower interaction between the introduced CuO and the
alumina support. It is worth mentioning that for the mono-
metallic copper catalysts (figure 4(a)), H2 consumption was
stopped after 380 ◦ C. This indicates the absence of copper
spinels (CuAl2 O4 ), which are reduced in the temperature range
of 550 ◦ C–800 ◦ C [42, 44].
Finally, the effect of adding ZnO to the Cu catalysts is
addressed. Copper reducibility was increased for the alumina
catalyst, where H2 uptake was increased by 0.05, in accord-
ance with the available literature [45]. Nevertheless, H2 uptake
decreased by 0.18 in the case of the Z23 catalyst. This could be
explained by the higher metal (Cu and Zn) content of this cata-
lyst when compared to the alumina one (table 4). This means
that ZnO can enhance Cu reducibility only if the total metal
content remains lower than approximately 15% wt. When ZnO
was added, the temperature and area of the two CuO reduc-
tion peaks were modified. For both supports, the two CuO
reduction peaks were shifted towards higher temperatures.
Moreover, the presence of a new reduction peak is observed
7
M Q Feliz et al
in figures 4(b) and (c). The high-temperature reduction peaks,
located at 513.5 ◦ C and 629.2 ◦ C for the alumina and Z23
catalysts, respectively, are ascribed to the reduction of mixed
CuAl2 O4 and ZnAl2 O4 spinels [42]. This can be explained by
the introduction of a higher total amount of metal into the sup-
ports, which allowed the formation of spinels. On the other
hand, the pre-reduction CuO/Cu2 O mole ratio was consider-
ably modified after the addition of ZnO, indicating the pres-
ence of the more easily reducible Cu2+ species. This last fact
suggests that ZnO addition lowered the interaction between
the CuO particles and the supports.
3.2.3. CO adsorption. Carbon monoxide was used as a
probe molecule to study the copper species in the alumina
and zeolite catalysts. The CO IR bands were normalized with
respect to the total amount of CO adsorbed at full surface
coverage. The complete surface coverage for the Cu/A and
Cu/Z23 was reached at 170 and 210 µmol CO/g, respectively.
The unprocessed CO adsorption IR spectra are shown in the
left side of figure 5, while the corresponding smoothed and
deconvoluted spectra are shown to the right. In the case of the
Z23, deconvolution was stopped at 2090 cm−1 because the IR
bands after this value corresponded to the Z23 support itself
and thus did not vary with CO dosing.
Several IR bands were observed in the case of the alumina
catalyst. The bands at 2071 and 2097 cm−1 are assigned to car-
bonyls on metallic copper (CO-Cu0 species) [46–48]. The IR
bands at 2140 and 2120 cm−1 are ascribed to CO adsorbed on
Cu+ species [46–48]. The difference between these two bands
is based on the oxygen coordination of Cu+ species: tetragonal
at 2120 cm−1 associated with ordinary Cu2 O phase and tetra-
gonal pyramid at 2140 cm−1 as a consequence of the interac-
tion of CuO and Cu2 O phases with support oxygen ions [46].
The IR bands above 2140 cm−1 are usually assigned to linear
carbonyls over Cu2+ species [48]. It is worth mentioning that
no IR bands in the range of 2200–2245 cm−1 were observed,
indicating the absence of CO adsorption over alumina support
through dative ligation to uncoordinated Al3 + cations [47].
In the case of zeolite catalysts, only the CO adsorption IR
bands associated with Cu+ and Cu0 species were observed.
The IR bands at 2104–2019 cm−1 and 2121–2126 cm−1 can
be ascribed to CO adsorption on reduced copper (CO-Cu0 )
[49, 50]. The well-known IR band at 2158 cm−1 is assigned
to Cu+ -CO species (mono or bicarbonyls). The initial CuO
(Cu2+ ) species observed at the beginning of the TPR profiles
did not appear after in situ catalyst reduction in the case of Z23,
indicating that all Cu+2 species were either partially (Cu+ ) or
totally (Cu0 ) reduced. This can be explained by the higher H2
uptake (and thus copper reducibility) of the Cu/Z23 catalyst.
However, in the case of alumina catalyst, all three Cu2+ , Cu+
and Cu0 species were observed.
The influence of ZnO addition on Cu catalysts could not
be studied because of the low IR absorbance intensity of the
Cu–ZnO samples caused by the relatively high metal loading.
Copper dispersion and crystallite size for the two cata-
lysts could be estimated through the integration of the IR
bands associated with the CO-Cu0 complexes. Quantification
J. Phys. D: Appl. Phys. 54 (2021) 334003 M Q Feliz et al

Figure 4. TPR profiles of the catalysts.

Figure 5. CO adsorption over the Cu/A and Cu/Z23.

8
J. Phys. D: Appl. Phys. 54 (2021) 334003
Table 5. Characterization of metallic copper over alumina and
zeolite supports.
Catalyst Cu/A Cu/Z23
Cu dispersion (%) 9.4 13.7 (min.)
Cu crystallite average size (nm) 10.5 7.2
of Cu2+ , Cu+ and Cu0 species was performed using the molar
extinction coefficients proposed by Kohler et al for these three
species: εCu2+ = 1.16 cm mol−1 , εCu+ = 0.72 cm mol−1 and
εCu0 = 0.39 cm mol−1 [51]. The details of the calculations are
provided in the supplementary information. For the Cu crys-
tallite size estimation, a crystallite cubic shape was adopted
and a Cu density of 8.96 g cm−3 was used. The copper disper-
sion and crystallite size of the two catalysts are presented in
table 5.
The highest copper dispersion as well as the smallest Cu
particle size were both obtained with the Cu/Z23. These prop-
erties are closely related to the support itself. The alumina
support favoured the creation of more easily reducible copper
species (Cu2+ ), but it also presented low copper reducibility
and poor dispersion due to the relatively large metallic copper
particles present after catalyst reduction.
The results from this section can be summarized as follows.
The specific surface area (with and without metal) was higher
for Z23, while the alumina catalysts presented higher pore
volumes. The TPR analysis showed that the addition of ZnO to
the copper catalysts produced two effects: (a) enhancement of
Cu reducibility as long as the metal (Cu and ZnO) loading was
lower than 15% wt. and (b) modification of the pre-reduction
CuO/Cu2 O molar ratio. The CO adsorption over the copper
catalysts allowed the estimation of Cu dispersion and particle
size. Cu dispersion was found to be higher for Cu/Z23 than
Cu/A, and Cu/Z23 presented a smaller crystallite size.
3.3. Measurement of the relative complex permittivity of the
catalysts
The relative complex permittivity, εbr (T, ω) = εr ′ (T, ω) +
iεr ′ ′ (T, ω), of a material is composed of two parts. Its real part
(εr ′ ) is related to the capacity of the material to store energy
when submitted to an external electric field. On the other hand,
its imaginary part (εr ′ ′ ) is related to the capacity of the mater-
ial to either convert into heat or dissipate the received energy
when submitted to an external electric field. Figure 6 shows the
measurements of both parts of the relative complex permittiv-
ity of the prepared alumina and Z23 catalysts as a function
of frequency between 0.5–20 GHz at 20 ◦ C. By computing
repeatability experiments, the maximum relative errors on the
reported dielectric properties were ∆εr ′ = 5% and ∆εr ′ ′ = 8%.
Figure 6(a) shows that the dielectric constant of Z23
increased slightly after the addition of both Cu and ZnO, while
the dielectric loss factor remained practically unchanged. In
figure 6(b), different behaviour was observed for the alumina
catalysts. After copper addition, both the dielectric constant
and the dielectric loss factor decreased (11% and36%, respect-
ively). After ZnO addition, the dielectric constant of Cu/A
9
M Q Feliz et al
increased slightly (+6%), while the dielectric loss factor did
not experience any significant variation. These two different
kinds of behaviour may highlight important differences in the
dielectric properties of these two materials. Next, several con-
clusions can be drawn from the Argand diagram of the Z23
catalysts (figure 6(c)). First, the initial shape of the curve of
all three solids can be approximated to a semicircular arc,
indicating the presence of relaxation processes. Second, after
this semicircular portion, the dielectric loss factor increases
as the value of the dielectric constant increases, which is a
clear indicator of ionic conductivity [40]. In zeolites, such
as the one synthesized in this work, this conductivity can be
attributed to the Na+ ions present in the zeolite framework.
Finally, the different overall values obtained for the curves
shown indicate different dielectric behaviour for Z23, Cu/Z23
and CuZn/Z23. Concerning the alumina (figure 6(d)), it shares
the first and third conclusion with the Z23 catalysts, but not the
second. After the corresponding semicircular portion, it can be
observed that, as the value of the dielectric constant increases,
the dielectric loss factor only decreases. This is a clear indic-
ator of the absence of ionic conductivity and is present for all
the alumina catalysts, representing a key distinction between
them and the Z23 catalysts.
To better understand the implications of the aforementioned
differences between the catalysts and how they would affect
CO2 hydrogenation, their quantification is necessary. In this
regard, a Debye model has been used and is presented in the
following section.
3.4. Estimation of the dielectric constant and ionic
conductivity of the catalysts
For the quantification of the desired parameters, the real and
imaginary parts of the relative complex permittivity were fit-
ted using a modified Debye model. This model includes two
relaxation times as well as a term for the ionic conductivity,
as is often recommended when working with zeolitic supports
[40, 52]. The equations were as follows:
εS1 − ε∞ εS2 − ε∞
εr ′ = ε∞ + + , (5)
1 + ω 2 τ12 1 + ω 2 τ22
σ (εS1 − ε∞ ) ωτ1 (εS2 − ε∞ ) ωτ2
εr ′ ′ = + + , (6)
ωε0 1 + ω 2 τ12 1 + ω 2 τ22
where ω (rad s−1 ) is the wave pulsation, ε∞ is the permittivity
at an infinite frequency, εS is the static permittivity, τ (1/2πf )
is the relaxation time (s) and σ is the conductivity (s m−1 ).
The imaginary part of the complex permittivity of all prepared
supports and catalysts is shown in figure 6. The real part of
their respective complex permittivities is presented in supple-
mentary figure 4.
In figure 7, several contribution terms were observed upon
deconvolution of the curves of the imaginary part of the com-
plex permittivity: (a) two main relaxation phenomena for both
Z23 and alumina catalysts and (b) a conductivity term, but
only for the Z23 catalysts. In the microwave frequency range,
both catalysts presented a high relaxation frequency f 1 loc-
ated at approximately 12 GHz, which can be ascribed to the
J. Phys. D: Appl. Phys. 54 (2021) 334003
Figure 6. (a) Dielectric constant and dielectric loss factor of the Z23 catalysts as a function of frequency, (b) dielectric constant and
dielectric loss factor of the alumina catalysts as a function of frequency, (c) Argand diagram of the Z23 catalysts and (d) Argand diagram of
the alumina catalysts.
rotational polarization of adsorbed water molecules. A second-
ary low relaxation frequency f 2 was also observed at approx-
imately 1.5 GHz probably due to an interfacial polarization
mechanism.
The obtained fitted values for all supports and catalysts
are presented in table 6. The static dielectric constants calcu-
lated in this study are particularly relevant because they are
the dielectric constant values of the catalysts when used at low
frequencies (such as 9 kHz), which are those of DBD plasma.
The conductivity thus determined can be assimilated to dir-
ect current conductivity and does not depend on the frequency
for many materials and in particular ionic materials [53]. The
values of the direct current conductivity, obtained by meas-
uring dielectric losses over a frequency interval around GHz,
are therefore applicable to the characteristic frequencies of
the plasma used here. Thus, the identification of phenomena
occurring at low frequency is key as they will be predominant
under the conditions used in this work.
In table 6, both the static and infinite dielectric constants εS
and ε∞ of the alumina catalysts first decreased after the addi-
tion of Cu and then increased after ZnO addition. However,
the same trend could not be confirmed in the case of the Z23
catalysts, most likely due to the different metal/support inter-
action discussed in section 3.2.2. Overall, the zeolite catalysts
presented higher values of εS and thus a slightly higher capa-
city to store energy than their alumina counterparts.
Following the experimental trend (figures 6(c) and (d)), the
term corresponding to the ionic conductivity was not evalu-
ated for the alumina catalysts. In contrast, ionic conductivity
10
M Q Feliz et al
is significant for Z23. It was improved after Cu addition and
then decreased upon ZnO introduction, the latter probably due
to the steric effect caused by the increased metal loading.
Overall, the measurements of the complex permittivity
provided very important information about the dielectric prop-
erties of the prepared catalysts. In this regard, the two static
dielectric constants (εS1 and εS2 ) associated with the two main
relaxation phenomena of the Z23 catalysts were found to be
slightly higher than those of the alumina catalysts. This indic-
ates that the Z23 catalysts have a slightly higher capacity to
store energy than their alumina counterparts. On the other
hand, ionic conductivity (at low frequency) was observed in
the case of the zeolite catalysts only. Consequently, the alu-
mina catalysts should present a better dielectric character than
zeolites in the DBD plasma frequency range.
4. Discussion
The effect of the properties analyzed of sections 3.2–3.4
over CO2 conversion and product selectivity is discussed and
presented below. Table 7 summarizes the CO2 conversion
andproduct yields of the catalysts discussed in this work.
4.1. CO2 conversion
Figure 3 evidences that carbon monoxide was the major spe-
cies issued from CO2 conversion. It was shown in section 3.1.1
that CO was produced through the RWGS reaction over a
J. Phys. D: Appl. Phys. 54 (2021) 334003 M Q Feliz et al

Figure 7. Imaginary part of the relative complex permittivity of the alumina and Z23 catalysts versus frequency.

Table 6. Complex permittivity terms obtained from the modified Debye model for alumina and Z23 catalysts.

Model parameter
Catalyst ε∞ εS1 εS2 f 1 (GHz) f 2 (GHz) σ (s m−1 )

A 2.37 3.09 2.83 11.1 1.6 0

Cu/A 2.26 2.77 2.57 12.3 1.5 0
Cu–Zn/A 2.40 2.98 2.70 12.2 1.0 0
Z23 2.46 3.13 2.79 12.3 1.4 7.1.10−3
Cu/Z23 2.65 3.25 3.03 12.6 1.2 9.9.10−3
Cu–Zn/Z23 2.69 3.39 3.05 12.2 1.2 7.8.10−3

catalyst, but only at temperatures higher than those reached
under plasma assistance. This means that most of the CO is
not formed over the catalyst but in the gas phase. According
to the work of Wang et al [18], this occurs mainly by CO2
electron impact dissociation, with a minor contribution from
electron impact vibrational excitation. With this in mind, it is
no surprise that the physico-chemical properties of the cata-
lysts themselves are not able to provide enough information
to explain the observed CO2 conversion trends. For instance,
the Z23 support presented a higher surface area than the alu-
mina one (table 3), yet a lower CO2 conversion (figure 3). After
copper addition, the surface area of both supports decreased,

11
J. Phys. D: Appl. Phys. 54 (2021) 334003 M Q Feliz et al

Table 7. CO2 conversions and product yields of the supports and and increased, respectively. It would then seem that CO2 con-
catalysts. version is somewhat favoured by the presence of non reduced
Catalyst X CO2 (%) Y MeOH (%) Y CH4 (%) Y CO (%) copper species. As both copper species are active sites for CO2
hydrogenation into methanol [12, 57–60], it is difficult to pre-
Empty reactor 25 ± 1.2 0.3 ± 0.01 1.5 ± 0.07 23.4 ± 1.2 cisely establish why unreduced copper species would better
A 34 ± 1.7 0.2 ± 0.01 1.4 ± 0.07 32.7 ± 1.6 catalyze CO2 under our experimental conditions. Both reduced
Cu/A 28 ± 1.4 0.4 ± 0.02 1.4 ± 0.07 26.6 ± 1.3
and unreduced species were evidenced by CO adsorption tests.
CuZn/A 27 ± 1.3 0.4 ± 0.02 1.4 ± 0.07 25.4 ± 1.3
Z23 25 ± 1.2 0.1 ± 0.00 1.1 ± 0.05 23.8 ± 1.2
These tests also allowed us to estimate the copper dispersion,
Cu/Z23 21 ± 1.0 0.2 ± 0.01 1.0 ± 0.05 19.7 ± 1.0 where the Z23 showed a higher value. However, this higher
CuZn/Z23 24 ± 1.2 0.5 ± 0.02 1.4 ± 0.07 22.5 ± 1.1 dispersion did not translate into better CO2 conversion.
The results observed in figure 3 can be better understood
and explained by the modification of the dielectric prop-
in coherence with the observed CO2 conversion. Nevertheless, erties of the medium between the two electrodes after the
after ZnO addition, both surface areas decreased, while CO2 introduction of a solid (either support or catalyst). After the
conversion decreased only for Cu/A. introduction of a solid into the DBD reactor, the breakdown
Along with the surface area, a question arises concerning voltage usually decreases as the discharge becomes easier to
the generation (and potential influence) of plasma in the cata- ignite [61]. Surface discharges around the solid pellets start to
lyst pores. It has been claimed that in order to generate plasma appear [62], increasing the plasma density and charge transfer
within the catalyst pores, the Debye length should be lower between electrodes along their gap.
than the pore size, as revealed by particle in cell + Monte The CO2 conversion was enhanced after the introduction of
Carlo collision model simulations [54]. The Debye length can the alumina support into the DBD reactor. This suggests that
be estimated through the following equation: the positive effect brought about by the increased dielectric
constant (because of the nonconductive character of the alu-
r
ε0 × kB × Te mina, table 6) is greater than the negative effect related to the
λD = , reduction of the residence time. After copper addition, CO2
n × e2
conversion decreased for the alumina support. This is related
where λD is the Debye length, ε0 is the permittivity of free to the two static dielectric constants (εS1 and εS2 ), which also
space (8.85 × 10−12 F m−1 ), kB is the Boltzmann con- decreased. Therefore, the addition of Cu decreased the energy
stant (1.38 × 10−23 J K−1 ), e is the charge of an electron storage capacity of the alumina leading to a decrease in the
(1.6 × 10−19 C), T e is the temperature of the electrons (K) plasma density and electron rates, which explains the lower
and n is the density of electrons (m−3 ). In our plasma DBD CO2 dissociation rates in the gas phase. Finally, the addition of
system, T e is around 3 eV (34 800 K) and the density of elec- ZnO slightly increased the static dielectric constants of Cu/A.
trons is approximately equal to 1018 m−3 [55, 56]. In this case, Nevertheless, this did not increase CO2 conversion as expec-
we would have a Debye length of 13 µm, which represents ted. The observed decrease in CO2 conversion might be related
three orders of magnitude larger than all catalysts’ pores in to a decrease in the catalytic contribution of CuZn/A towards
this study (table 3). From this point of view, plasma cannot be CO2 conversion due to its lowered surface area and increased
created inside the catalyst pores. However, we could consider copper reducibility (tables 3 and 4, respectively).
the diffusion of relatively long lifetime species inside them. In The modification of the dielectric properties also explains
the latter case, the internal surface area could be partially used the trends of the Z23 catalysts. The Z23 support presented
in plasma catalysis. a similar CO2 conversion to the empty reactor in figure 3.
For pores with smaller diameters than the Debye length, This implies that the increase in plasma density brought by
the plasma can only penetrate to some extent and at very the introduction of the Z23 was possibly countered by another
short times, i.e. at the beginning of a micro-discharge, before phenomenon. It was observed in section 3.2 that the Z23 sup-
the actual plasma streamer reaches the catalyst surface and port presented ionic conductivity at low frequency. A con-
a sheath is formed in front of the surface [54]. Zhang and ductive support would reduce the magnitude of the electric
Bogaerts studied the effect of surface charging on the forma- field (and ultimately the density of the plasma) as previ-
tion of plasmas inside catalyst pores for small and large pores. ously suggested by [29], thus explaining why CO2 conver-
They concluded that when the pore size is lower than 50 nm sion remained the same. The introduction of Cu into the
(which corresponds to this work), plasma cannot be formed Z23 support slightly increased both static dielectric constants,
inside the pores since plasma streamers at the dielectric surface but it also strongly enhanced its ionic conductivity (+39%).
will create sheath-rejecting plasma and only some short-lived This undesired increase in conductivity is responsible for the
reactive species can diffuse inside the pores. observed decrease in CO2 conversion. Finally, CO2 conver-
On the other hand, the TPR tests present an interesting trend sion was significantly increased for the Cu/Z23 after ZnO
between CO2 conversion and copper reducibility. Cu/Z23 addition. The addition of ZnO did not modify the two static
presented a higher H2 uptake (and thus copper reducibility) dielectric constants, but decreased the ionic conductivity of
than Cu/A, yet a lower CO2 conversion. After ZnO addition, Cu/Z23 (table 6), improving CO2 conversion.
the H2 uptake of the Cu/A increased, while that of the Cu/Z23 In summary, it can be concluded that the presence of a
decreased. Their corresponding CO2 conversions decreased solid in a DBD reactor can increase the density of the plasma

12
J. Phys. D: Appl. Phys. 54 (2021) 334003
and the electron rates, but only if the ionic conductivity of the
introduced dielectric material is null or low. A denser plasma
enhances CO2 dissociation into CO, mainly by CO2 electron
impact dissociation, but with a minor contribution from elec-
tron impact vibrational excitation.
4.2. Product selectivity
First, let us start by addressing the observed methane and
methanol selectivity within the empty reactor. This could be
related to the inner electrode of the reactor, which is mainly
made of iron. Iron is an active metal for CO2 methanation [2]
and, to a much lower extent, methanol formation [31]. The sur-
face sites present over the inner electrode could then catalyze
their formation, explaining their presence. With respect to the
supports, methane and methanol can only be produced over
the metallic surface of the inner electrode since neither the
alumina nor the Z23 support contains any metallic particles.
As a consequence, the production of both methane and meth-
anol could have only been decreased by two possible causes:
either a diminution of the reactants’ residence time (provoked
by the introduction of the respective supports), a difference in
the distribution of the produced species (due to the modified
dielectric properties) or both.
The increase in the methanol selectivity after copper addi-
tion to both supports implies that methanol formation is pos-
itively affected by the presence of copper sites (Cu0 and Cu+ ,
see section 3.2.3) of the catalyst [1, 9–12]. Nevertheless, we do
not have enough information to be able to discuss the corres-
ponding reaction mechanism. In the case of methane selectiv-
ity, its increase could be related to the improved availability
of dissociated hydrogen atoms over the copper surface, thus
favouring hydrogenation reactions.
It has been reported in the literature that zinc oxide addi-
tion into copper catalysts increases their selectivity towards
methanol [30, 63]. Even though most of these catalytic tests
were performed under conventional heating, the reported find-
ings are in accordance with the experimental trend observed in
this work; an increase in methanol selectivity after ZnO addi-
tion. However, additional studies are required to identify the
reaction mechanism under DBD plasma. Michiels et al [64]
recently published a micro-kinetic modelling study of plasma-
assisted methanol formation by CO2 hydrogenation on a Cu
catalyst surface, in which the mechanisms of plasma catalysis
were compared with those of thermal catalysis. Their model
revealed that the reverse water-gas shift reaction followed by
CO hydrogenation, together with the so-called formate path,
mainly contributed to methanol formation in thermal catalysis,
and that adding plasma generated radicals and intermediates
resulted in a higher methanol turnover frequency. In addition,
the conversion of plasma-generated CO to HCO∗ and sub-
sequent HCOO∗ or H2 CO∗ formation seemed to contribute to
methanol formation. Hence, the model suggested the import-
ant role of CO, but also O, OH and H radicals, as they influence
the reactions that consume CO2 and CO.
Two catalysts prove to be the most interesting when determ-
ining which one performs best in DBD plasma. On the one
hand, the alumina support makes it possible to obtain the
13
M Q Feliz et al
highest CO2 conversion (34%) mainly through its dissociation
into CO, justifying the highest carbon monoxide yield. On the
other hand, the CuZn/Z23 shows the highest methanol yield
(0.5%), which means that it is the most suitable for CO2 hydro-
genation into methanol. This is mainly attributed to its greater
energy storage capacity coupled with the catalytic effects of
the addition of copper and zinc oxide. Concerning the meth-
ane formation, it was thought to occur predominantly on the
surface of the high-voltage electrode and thus the addition
of any catalyst seems to decrease it slightly, probably due to
the reduced residence time of the gas. A comparison between
the results of the alumina support and those of the alumina-
supported catalysts shows that the methanol yield remained
constant while CO2 conversion decreased. This implies that
some of the methane produced by both Cu/A and CuZn/A were
catalyzed to a certain degree by the copper sites. This also jus-
tifies the fact that the methane yield remained similar between
Z23 and Cu/Z23 while CO2 conversion decreased.
Although these methanol and methane yields may appear
low, it is necessary to recall the operating conditions under
which they were obtained. Below 90 ◦ C and at atmospheric
pressure, neither of them was detected by conventional cata-
lysis, which opens up the prospect for CO2 hydrogenation
using DBD plasma under these operating conditions.
5. Conclusion
In this work, the hydrogenation of CO2 into methanol was
proved to occur under atmospheric pressure and temperature
below 90 ◦ C in a catalytic DBD plasma reactor, while the reac-
tion was found not to take place under these same conditions
via conventional heating. Four catalysts using two different
supports (alumina and ZSM-5), copper as the active metal and
ZnO as the promoter were prepared, fully characterized and
tested on CO2 hydrogenation under DBD plasma.
CO2 was mainly dissociated into CO in the gas phase by
both vibrational excitation and electron impact. CO2 dissoci-
ation was found to be closely related to the conductive and
dielectric properties of the medium. The introduction of a solid
(either support or catalyst) within the DBD reactor led to modi-
fication of the aforementioned properties. An increase in the
dielectric constant enhances the magnitude of the electric field,
thus enhancing the plasma density and favouring CO2 dissoci-
ation. This effect was observed while using the alumina sup-
port. However, when the introduced solid is conductive, the
magnitude of the associated electric field is decreased and CO2
conversion is not improved, as observed with the Z23 support.
The introduction of copper increased both methanol and
methane production by catalytic effect, but it also considerably
modified the dielectric behaviour of the catalyst and thus CO2
conversion. The Cu/A presented a decrease in CO2 conversion
due to a decrease in its dielectric constant, while the Cu/Z23
also presented a decrease in CO2 conversion but because of an
increase in its ionic conductivity.
The introduction of zinc oxide increased both methanol and
methane selectivity by improving the copper reducibility and
modifying the Cu2+ /Cu+ ratio of the catalysts. It also modified
J. Phys. D: Appl. Phys. 54 (2021) 334003
the dielectric properties of the solids. While methanol (and to
a lesser extent methane) formation was found to mostly take
place on the catalytic surface, the increased product selectivity
was attributed to a higher hydrogen availability at the Cu–ZnO
interface. The ionic conductivity ofCu/Z23 decreased signi-
ficantly after ZnO addition, thus improving CO2 conversion.
Overall, the alumina support showed the highest CO2 conver-
sion (34%) into CO since it did not present any ionic conduct-
ivity. On the other hand, the CuZn/Z23 showed the highest
methanol yield (0.5%) because of its greater energy storage
capacity coupled with the catalytic effects of the addition of
copper and zinc oxide.
Data availability statement
All data that support the findings of this study are included
within the article (and any supplementary files).
Acknowledgments
The authors gratefully acknowledge the project GENCOMM-
NWE334 for financial support. The project GENCOMM
has been funded by the European Union with the European
Regional Development Fund (ERDF) through the Interreg
North-West Europe Program. The authors also thank the LCS
laboratory technicians Benjamin Foucault, Marie Desmurs-
Lozier and Valérie Ruaux for their invaluable assistance.
ORCID iDs
Alain Ledoux  https://orcid.org/0000-0002-1117-1142
Federico Azzolina-Jury  https://orcid.org/0000-0003-
3807-8586
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