i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2

Available online at www.sciencedirect.com

ScienceDirect

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

Review Article

Plasma reforming for hydrogen production:

Pathways, reactors and storage

Neeraj Budhraja*, Amit Pal, R.S. Mishra

Department of Mechanical Engineering, Delhi Technological University, Delhi, 110042, India

highlights

Hydrogen production via the methane reforming pathway is discussed.

Ethanol decomposes into intermediate species that further splits into
H radical

Various plasma reforming reactors for H2 production are discussed.

Influencing parameters in plasma reforming are identified.

Various process parameters affecting H2 production are reviewed.

article info abstract

Article history: Hydrogen is an energy carrier with a very high energy density (>119 MJ/kg). Pure hydrogen
Received 5 August 2022 is barely available; thus, it requires extraction from its compounds. Steam reforming and
Received in revised form water electrolysis are commercially viable technologies for hydrogen production from
10 October 2022 water, alcohols, methane, and other hydrocarbons; however, both processes are energy-
Accepted 16 October 2022 intensive. Current study aims at understanding the methane and ethanol-water mixture
Available online 5 November 2022 pathway to generate hydrogen molecules. The various intermediate species (like CHX,
CH2O, CH3CHO) are generated before decomposing methane/ethanol into hydrogen radi-
Keywords: cals, which later combine to form hydrogen molecules. The study further discusses the
Hydrogen production various operating parameters involved in plasma reforming reactors. All the reactors work
Dielectric barrier discharge on the same principle, generating plasma to excite electrons for collision. The dielectric
Pulsed plasma barrier discharge reactor can be operated with or without a catalyst; however, feed flow
Gliding arc plasma rate and discharge power are the most influencing parameters. In a pulsed plasma reactor,
Microwave plasma feed flow rate, electrode velocity, and gap are the main factors that can raise methane
conversion (40e60%). While the gliding arc plasma reactor can generate up to 50%
hydrogen yield at optimized values of oxygen/carbon ratio and residence time, the
hydrogen yield in the microwave plasma reactor is affected by flow rate and feed con-
centration. Therefore, all the reactors have the potential to generate hydrogen at lower
energy demand.
© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

* Corresponding author.
E-mail address: neeraj_budhraja@yahoo.com (N. Budhraja).
https://doi.org/10.1016/j.ijhydene.2022.10.143
0360-3199/© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
2468 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2

Contents

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2468
Hydrogen production pathways . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2469
Methane pathway . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2469
Alcohol-water mixture pathway . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2470
Plasma reforming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2471
Dielectric barrier discharge (DBD) plasma reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2473
Pulsed plasma reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2474
Gliding arc plasma reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2475
Microwave (MW) plasma reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2476
Advantages and disadvantages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2478
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2479
Funding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2479
Availability of data and material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2479
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2479
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2479

energy source are the availability of feedstocks, extraction,

Introduction
Hydrogen is currently the best energy source available due to
its exceptional properties and can fulfill the energy re-
quirements of various sectors, thus, making it a good alter-
native to conventional fuels. It has a very high energy density
(>119 MJ/kg) and a longer flammability limit (4e75%) which no
other fuel matches [1]. In addition, hydrogen-burning results
in water vapour (H2O), a harmless and clean product. Thus,
hydrogen use can lower greenhouse gas (GHG) emissions, help
reduce everyday carbon emissions, facilitate a cleaner envi-
ronment, and reduce climate change threats [2,3]. Hydrogen
can potentially eradicate the mismatch created in the
renewable sources' demand for seasonal and daily supply; its
usage may extend energy service to rural areas inaccessible to
the grid. Therefore, hydrogen can be envisioned as the future
fuel, energy storehouse, and long-distance energy carrier
[4e6]. However, the main hurdles to accepting hydrogen as an
storage systems, and safety concerns.
Hydrogen is plentiful in the environment, but free
hydrogen gas is rarely available. Thus, hydrogen extraction is
required from various compounds to get the benefits of
hydrogen as a fuel. At present, fossil fuels, i.e., natural gas
(75%) and coal (20%), along with 2% from water electrolysis,
meet the utmost global hydrogen demand [7], which con-
sumes about 6% natural gas and 2% coal globally, generating
approx. 830 Mt-CO2 Equiv. Greenhouse gases (GHG) annually,
and only 130 Mt-CO2 is captured annually by the fertilizer
industries [8]. The hydrogen demand in refining oil (33%),
ammonia production (27%), alcohol production (11%), steel
manufacturing (3%), and others have increased drastically,
making significantly less space for power generation appli-
cations [9]. Fig. 1 gives the estimated global hydrogen demand
for the next 30 years [8].
Hydrogen is a cleaner fuel because its combustion has
zero-carbon products; thus, it is currently the most

Fig. 1 e Estimated global hydrogen demand in different sectors.

 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2
acceptable fuel for replacing conventional fuels that badly
pollute the environment with harmful and carcinogenic
emissions [10]. However, conventional hydrogen production
processes like steam methane reforming generate GHG gases
that harm the environment [11e14]. Many researchers and
scientists have developed renewable energy integrated de-
vices that can efficiently achieve hydrogen production goals
with low emissions generation [15,16], though the availability
of renewable energy sources is dynamic. Therefore, tradi-
tional methods like natural gas reforming [17,18] and elec-
trolysis are the most common techniques being preferred. In
contrast, many researchers and scientists also worked on the
biological hydrogen production processes that reduce elec-
tricity dependence, but maintaining the physical environ-
ment in the reactor is challenging [3]. Plasmolysis is another
technique that may solve on-demand hydrogen production at
no or significantly less GHG emissions when integrated with
other renewable energy sources. Plasmolysis is a process of
breaking down hydrogen compounds into hydrogen mole-
cules under the action of a plasma arc. The electrons in the
arc zone exist at a very high temperature of about
15,000e20,000  C; however, the system temperature remains
near room temperature. Plasmolysis requires comparatively
less infrastructural capital cost and the compatibility of
various feedstocks is an additional advantage in hydrogen
production. Kheirollahivash et al. [19] examined the methane
decomposition into hydrogen via plasmolysis and studied the
effects of multiple parameters. A 6 L/h hydrogen production
rate was achieved at a 9 L/h methane flow rate with 26.8 g/
kWh energy yield and 0.2e3.9s residence time, respectively.
A hydrogen storage system is essential in energy trans-
portation and on-board applications [20]; however, it con-
sumes about 1/3rd of the system's total energy. Every fuel
requires a safe and easy storage system that helps in the
efficient availability of power for various applications [21,22].
Hydrogen has a very low gas density, making it challenging for
larger quantity storage. An estimate showed that the hydrogen
storage system is more than 3000-fold gasoline, making the
whole storage system bulky for on-board hydrogen storage
[20]. Thus, several kinds of research have been accomplished
to develop a safe and lightweight hydrogen storage system in
the last few years. Metal hydride (MH) has proved to be a
promising candidate in this regard [23,24]. MH's hydrogen
storage and release are simpler and less costly [21]. The
exothermic reaction forms MH at a somewhat higher pressure
during hydrogenation, whereas at elevated temperatures, the
endothermic reaction releases hydrogen at comparatively
lower pressures [25].
Hydrogen has extensive usage in chemical industries for
fertilizer production, pharmaceuticals, glass purification,
semiconductor manufacturing, and many others like power
generation using fuel cells, engine fuel for automobiles, and
rocket propulsion in aerospace industries; thus, its safe and
easy storage is required. However, the on-board hydrogen
production system can overcome the costly and bulky
hydrogen storage system. The hydrogen production from
plasma reactors can achieve the goal of the on-board
hydrogen production system. The plasma reactors are
compact, easy to install, and have a quick operation. These
advantages will solve the problem of bulky and energy-
2469
consuming hydrogen storage systems, and the reactors can
be installed at the demand site. This will further reduce
transportation issues.
In the current study, detailed hydrogen production path-
ways via methane decomposition and ethanol-water decom-
position are discussed. The study aims to understand the
working principles of different plasma reactors and discusses
the various operating parameters in the hydrogen production
processes that influence the hydrogen production rate. A
comparative study of the different plasma reactors' advan-
tages and disadvantages is determined to understand plasma
reactors’ suitability for a particular application. Therefore, a
good understanding of different plasma techniques will aid in
determining the most effective plasmolysis process for
hydrogen production in a specific application based on the
production rate and purity.
The paper initially discusses the pathway of methane and
water-alcohol mixture conversion to hydrogen in section 2.
The paths of methane and water-alcohol mixture conversion
are simplest to understand, and the higher hydrocarbons and
alcohols follow a similar pathway. Section 3 discusses four
different plasma reforming rectors with diagrams of the
respective rector. Here, a brief study is performed to under-
stand the working and influencing parameters from the works
of other authors. From all the discussions, various advantages
and disadvantages of different plasma reforming reactor is
determined in section 4 to understand better how to use
plasma reactor for a suitable application. Lastly, section 5 is
the conclusion of all the discussions.
Hydrogen production pathways
Methane pathway
The proposed reaction pathway of methane (CH4) decompo-
sition into CHX (CH3, CH2, CH) molecules [26,27] and then into
hydrogen and carbon inside a plasma reactor is depicted in
Fig. 2. In a plasma reactor, the electrons get excited when they
come into contact with the plasma zone. The high-energy
electrons collide with methane molecules, breaking the
methane bonds and creating active species for the standard
thermodynamic reactions. The CH4 decomposition results in
CH3, CH2, and CH molecules at the various threshold energies
[28,29] (as described in Table 1) and generates
H radicals. The
minimum amount of energy that transforms the reactant by
activating the hydrogen atoms is called activation energy. It
enables the reactants to overcome repulsive forces and start
breaking the bonds to generate
H radicals. These
H radicals
combine to form hydrogen (H2) molecules, while the standard
thermodynamic reactions produce hydrocarbons (C2). The
methane dissociation results in carbon particle deposition
inside the reactor, which requires regular removal. Few kinds
of research have used rotating electrodes to remove carbon
particle deposits, thus, restricting any decline in the reactor's
efficiency [26,29]. The process does not require a very high
temperature (except in the plasma-arc zone) as in methane
steam reforming [30]. Thus, the CHX molecules resulting in
dehydrogenation inside the plasma reactor are possible under
near-ambient conditions.
2470 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2

Fig. 2 e Methane decomposition pathway for H2 production.

Alcohol-water mixture pathway

Alcohol-water mixture also has the potential for hydrogen

Table 1 e Dissociation reactions involved in methane
decomposition. production via plasma reforming. The proposed pathway for
ethanol-water decomposition depicting the alcohol-water
Reactions Threshold Activation
energy (eV) energy (eV) dissociation into hydrogen molecules via different interme-
diate species is described in Fig. 3. Initially, the plasma region
e þ CH4 / CH3 þ H þ e 8.8 4.4
excites electrons to higher energy levels of 3e20 eV [17],
e þ CH4 / CH2 þ H2 þ e 9.4 4.7
e þ CH4 / CH þ H2 þ H þ e 12.5 4.5 allowing these excited electrons to collide with the ethanol-
e þ CH4 / C þ 2H2 þ e 14.0 6.0 water mixture. When the high-energy electrons strike
e þ CH3 / CH2 þ H þ e 9.5 4.7 ethanol-water molecules, the water molecules break down
e þ CH3 / CH þ H2 þ e 10.0 5.5 into
H,
O, and
OH radicals [31], while the ethanol molecules
e þ CH3 / C þ H2 þ H þ e 15.0 7.0 decompose into H2, CO, CO2, and C, following the intermediate
e þ CH2 / CH þ H þ e 8.5 4.25
species CH4, CH2O, CH3CHO [32]. The electron collision results
e þ CH2 / C þ H2 þ e 8.2 4.9
in the dehydrogenation of ethanol molecules, generating
H
e þ CH2 / C þ 2H þ e 14.0 6.2
e þ CH/ C þ H þ e 7.0 3.5 radicals that later combine to form H2 molecules [33,34]. The
various dissociation reactions involved in the electron-
ethanol collusion are presented in Table 2 [32,35]. The elec-
trode's carbon deposition significantly reduces reactor

Fig. 3 e Ethanol-Water decomposition pathway for H2 production.

 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2 2471

Table 2 e Dissociation reactions involved in ethanol Plasma reforming

decomposition.
Reactions

e þ CH3 CH2 OH/ CH4 þ CH2 O þ e 
e þ CH3 CH2 OH/ CH3 CHO þ H2 þ e
e þ CH3 CH2 OH/ CH3 þ CH2 OH þ e
e þ CH3 CH2 OH/ CH3 CHOH þ H þ e
e þ CH3 CH2 OH/ CH3 CH2 þ OH þ e
e þ CH3 CH2 OH/ CH3 CH2 O þ H þ e
e þ CH3 CHOH/ CH3 CHO þ H þ e
e þ CH3 CHO/ CH3 CO þ H þ e
e þ CH3 CO/ CH2 CO þ H þ e
e þ CH2 CO/ CH2 þ CO þ e
e þ CH2 / CH þ H þ e
e þ CH/ C þ H þ e
efficiency [31,32]. Researchers have used rotating electrodes to
minimize carbon particle deposition to avoid reactor effi-
ciency decline [26].
Activation energy (eV) In the plasma zone, the electrons exist at very high temper-
0.75 atures up to 15,000e20,000  C, and these electrons support
1.03 decomposing of the organic matter in the feed while inorganic
4.2 matters deteriorate partially [36,37]. High temperatures
4.3 completely decompose waste plastics and other hydrocarbons
4.4
into syngas containing H2, CO, and a few higher hydrocarbons;
4.7
however, the system temperature remains near room tem-
2.11
3.97 perature, and in some reactors, it may reach 300e400  C [38].
3.14 Putra et al. [39] studied a banana's pseudo-stems hydrogen
3.35 production potential using an in-liquid plasma reactor. The
4.25 pseudo-stem with long fibers showed 70.7% maximum
3.5 hydrogen yield and 98.8% hydrogen selectivity, making it an
excellent raw material for hydrogen production [39]. Various
plasma reactors used for generating hydrogen are thoroughly
discussed. Dielectric barrier discharge and gliding arc plasma
reactor can be pulsed; however, the study pulsed plasma
reactor is considered separately.

Fig. 4 e Dielectric barrier discharge plasma reactor.

2472 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2
Table 3 e Plasma reforming studies for H2 production in the Dielectric Barrier Discharge (DBD) Reactor.
Feed Technical Modifications
Methanol Cu/ZnO supported Al2O3
catalyst used
Ethanol Water-ethanol mixture is
preheated to 120  C
Ammonia 10% Ni/Al2O3 catalytic reactor
Ammonia Non-catalytic plasma
membrane reactor for H2
separation
Methane NiO/g-Al2O3 catalyst with
cordierite honeycomb
monoliths as substrate
Water Plate micro-channel reactor
(PMCR) with ice trap for H2eO2
separation
Process parameters
Temperature: 180e250  C
Feed rate: 0.5e2.0 mL/h
Discharge voltage: 0e4.0 kV
Discharge frequency: 10e50 kHz.
Discharge power: 10e30 W
Water/Ethanol ratio: 1e5
Feed rate: 0.4e1.4 mol/h
Gas flow rate: 60e300 L/h
Power-supply voltage: 90e110 V
Temperature: 400e800  C
Power: 100e400 W
NH3 flow rate: 30e120 L/h
Gap length: 1.5 or 4.5 mm
Frequency: 6e14 kHz
Feed rate: 1.8e5.4 L/h
CH4/O2 molar ratio: 1e3
Discharge power: 40e100 W
Voltage: 14e16 kV
Steam flow rate: 0.1e0.2 L/h
PMCR temperature: 293e403 K
Fig. 5 e Pulsed plasma reactor.
H2 rate/yield Highlights Ref.
e Highest methanol conversion of [31]
39.1% is achieved by 4.0 kV
discharge voltage and 50 kHz
discharge frequency at 180  C.
137.76 L/h At 20 W, highest H2 energy yield of [40]
137.76 L/h is obtained with 3 water/
ethanol ratio and 1.4 mol/h feed
rate.
Maximum ethanol conversion
(71%) is achieved with 5 water/
ethanol ratio at a 0.6 mol/h feed
rate.
120 L/h Maximum H2 production rate is [42]
achieved at 150 L/h of NH3 flow rate
at 110 V, and the overall system
obtains 28.5%
120 L/h Maximum H2 production rate is [43]
obtained by 4.5 gap length and
400 W power with the H2 purity of
100%, and the conversion rate is
24.4%
28.4% (H2 yield) H2 yield is enhanced from 23.1% to [44]
28.4% at a 30 mL/min feed rate,
CH4/O2 ratio of 1, and discharge
power of 100 W.
Methane conversion increases
from 60.1% to 83.6%.
105.5 L/h Maximum H2 flow rate is achieved [47]
with a 0.2 L/h steam flow rate at
18 kV and 403 K PMCR heating
temperature, while the highest
conversion rate obtained is 42.51%.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2 2473

Dielectric barrier discharge (DBD) plasma reactor
In a DBD reactor, an alternating current (AC) potential differ-
ence is applied between the electrodes. Here, the dielectric
barrier that limits charge transport between electrodes covers
at least one of the two electrodes; this counteracts the con-
version of discharge into a thermal regime transition. The gas
transition requires electrodes in concentric cylindrical config-
urations. Fig. 4 shows an electric discharge and a reforming
membrane used for hydrogen generation in a DBD plasma
reactor [31]. The electric discharge initiates alcohol-water
dissociation at a comparatively lower temperature [31], and
optimization of other operating parameters enhances the
hydrogen production rate. In the optimization process, Lee and
Kim [31] examined the effects of various parameters in
methanol-water decomposition using a hybrid plasma-
catalytic (Cu/ZnO supported Al2O3 catalyst) reactor, where
Copper (Cu) provides active sites and Zinc oxide (ZnO) is a
surface stabilizer. It enhances methanol conversion from 5.7%
to 39.1% when raising the electric discharge to 4.0 kV and
50 kHz. The result shows the significance of electric discharge
in alcohol decomposition. Likewise, Ulbejczyk et al. [40] per-
formed ethanol conversion in a DBD reactor and studied the
effects of operating parameters on hydrogen production. Re-
sults showed that the discharge power, water/ethanol ratio,
and feed flow rate influenced the ethanol conversion. At 20 W
discharge power, 5 water/ethanol ratio, and 0.6 mol/h feed
flow rate, the maximum ethanol conversion (71%) is obtained
[40]. Zhang et al. [41] used simulated gasoline (n-C5H12) to
produce hydrogen-enriched syngas. The background temper-
ature played a significant role in n-C5H12 conversion, where the
conversion increases upto 498K, and then declines at 523K.
Hayakawa et al. [42,43] designed a low-temperature
plasma membrane reactor (PMR) that continuously de-
composes ammonia (NH3) into high-purity hydrogen gas. The
PMR works stage-wise; firstly, plasma decomposes NH3 into

Table 4 e Plasma reforming studies for H2 production in the Pulsed Discharge Reactor.
Feed Reactor Process parameters H2 CH4 Highlights Ref.
selectivity/rate conversion
Methane Continuous rotating Power: 7, 14, 21 W 95% 60% Highest H2 selectivity is [26]
electrodes plasma Flow rate: 3, 6, 9 L/h achieved by 9 L/h CH4 flow rate
reactor Electrode velocity: 0e6000 rpm at 21 W and 2000 rpm electrode
speed.
Energy efficiency of 1.46 mol/kJ
was obtained without a
catalyst.
Methane Reactor with parallel Power: 20 W 97% 47% Highest H2 rate (7.96 L/h) is [27]
screw-type helix and Flow rate: 9 L/h achieved with a 9 L/h CH4 flow
rod-like electrodes Electrode velocity: 200e800 rpm rate at 20 W and 200 rpm, while
a 36.8 g/kWh of energy yield is
obtained.
Methane Non-equilibrium warm Applied Voltage: 15.5e18.5 kV 44.6% 40% At 17.2 kV and 100 SCCM CH4 [29]
plasma reactor Flow rate: 100 & 200 SCCM flow rates, 85.6% and 40% CH4
conversion and H2 selectivity
are obtained.
Higher CH4 conversion (92%)
reduces H2 selectivity to 30.6%
and H2 concentration
percentage to 56%.
Ethanol Pulsed discharge reactor Voltage: 22e30 kV 66 L/h (rate) e Highest H2 flow rate and energy [49]
with needle-ball Discharge frequency: 30 kHz yield are achieved at 30 kV and
configuration Ethanol concentration: 50% 50% ethanol concentration in
Electrode distance: 15 mm water.
Higher voltage helps jumping
electrode balls enhance the
randomness and strength of
discharge.
Bio-oil Solution plasma process Reaction time: 5, 10, 20 min 114.6 L/h (rate) e 1.41 L H2 yield obtained by 1:4 [50]
in quartz reactor Ethanol/bio-oil ratio: 1:0, 1:1, 1:4 ethanol/bio-oil ratio in 20 min.
While at 1:1 ethanol/bio-oil and
5 min, the H2 production
reaches to maximum
containing 65.51% H2 content.
Ethanol Pinhole and plate Voltage: 28 kVe31 kV 7.2 L/h (rate) e H2 and CO consist of about 99% [51]
electrodes Power: 0.25e2.9 MW of syngas.
Electrode distance: 2e10 mm Both high peak voltage and
appropriate electrode distance
increase the H2 yield to the
maximum value.
2474 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2
Fig. 6 e Gliding arc plasma reactor.

H radicals, then
H radical adsorption and penetration into
the membrane surface takes place, and finally, the
H radicals
recombine to form hydrogen molecules. The process gener-
ates hydrogen gas (99.99% pure, which feeds directly to the
fuel cell) at a 1.2 L/h rate at 400 W input power. PMR gap length
and gas differential pressure showed a 120 L/h hydrogen flow
rate against a 150 L/h ammonia flow rate at 110 V, giving 28%
energy efficiency. Similarly, Song et al. [44] investigated the
hydrogen production potential of a DBD plasma reactor with &
without a NiO/g-Al2O3 catalyst. The DBD plasma and NiO/g-
Al2O3 catalyst synergized, resulting in better CH4 conversion
and H2 yield. The results showed improved CH4 conversion
from 60.1% to 83.6% and H2 yield from 21.3% to 28.4% using a
honeycomb catalyst. The observation also showed that the
high temperature reduces Nickel oxide (NiO) to Nickel (Ni),
affecting the catalyst life; thus, a low temperature is favorable
for longer catalyst life. King et al. [45] determined the
hydrogen production rate from landfill gas/coal mine gas in a
DBD reactor. The catalytic DBD reactor generates about
1456 kL/h H2 at 500  C and near atmospheric pressure. Like-
wise, Shareei et al. [46] studied the influence of applied voltage
and Argon flow rate on methane conversion. About 99.9%
methane conversion was observed at 1.84 synthesis gas
module, and 10 kV applied voltage. Table 3 discusses other
modified DBD reactors, operating parameters, and H2 yield
and production rate. The observation shows that the
hydrogen yield is mainly affected by discharge voltage (or
power) and feed flow rate, while temperature, electrode gap
length, and O/C ratio have a significantly less or negligible
impact on hydrogen yield.
Pulsed plasma reactor
Pulsed discharge is chemically active and produces high cur-
rent density, generating reactive ions, electrons, and radicals,
which break the hydrogen bonds [29,35]. Corona discharge
and spark discharge are two pulsed electrode plasma forms
that depend on the variation in peak voltage. The low voltage
generates corona discharge which appears as many
streamers, while high voltage results in spark discharge,
which appears as a flash between electrodes. The components
and working of a fabricated pulsed DC plasma reactor are
given by Morgon and ElSabbagh [29] in Fig. 5. It was observed
that the methane flow rate of 100 standard cubic centimetres
per minute (SCCM) is more effective in CH4 conversion than a
200 SCCM flow rate, while the CH4 conversion raises with
applied voltage in both cases. However, the H2 selectivity at
low voltage has similar results (as CH4 conversion), and the
opposite results were obtained at a voltage higher than 17 V.
The reactor showed 92% CH4 conversion and 44.6% H2 selec-
tivity at specific input conditions. Thus, the methane flow rate
and applied voltage directly influence the reactor's CH4 con-
version and H2 selectivity. Meanwhile, a valuable by-product
(graphite oxide) is also produced within the reactor by
methane decomposition, which can be collected and purified,
for different applications in electronic, optics, chemistry, en-
ergy storage, and biology [48]. In contrast, Xin et al. [35]
operated a pulsed discharge reactor with a needle-balls-like
electrode configuration, generating hydrogen at a 66 L/h flow
rate and a 141.3 g-(H2)/kWh hydrogen energy yield at 30 kV.
During the discharge shock waves, the jumping of electrode
balls increases the discharge randomness and strength, giving
a higher energy yield. The study also includes pulsed
discharge through constant rate comparison and found that
formaldehyde (CH2O) addition may significantly raise
hydrogen flow rate.
Moshrefi and Rashidi [26] investigated the methane con-
version into hydrogen in a rotating plasma electrode reactor at
almost ambient temperature and found no COX radicals gen-
eration in the reactor. The method showed about 60% methane
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2 2475

Table 5 e Plasma reforming studies for H2 production in the Gliding Arc Plasma Reactor.
Feed Process parameters
CH4eCO2 CH4/CO2 ratio: 0 to 2.4
Injection gas velocity: 45
e120 m/s
CO2 flow rate: 300e900 L/h
Orifice baffle: Type 1, 2 and 3
Methanol O2/C ratio: 0.15e3.0
S/C ratio: 0.15e2.0
Specific energy input: 24e36 kJ/
mol
n-heptane Power: 26e34 W
O/C ratio: 0.48 to 1.1
Residence time: 14.8e46.5 s
Discharge gap: 3.8e6.5 mm
Toluene Power: 26e36 W
O/C ratio: 0.55 to 1.3
Residence time: 11.5e35 s
Ar addition: 0e30 vol%
Methanol Frequency: 84 kHz
Gas flow rate: 2.5 SLM
Water concentration: 0e95 mol
% maximum value, and H2O conc.
CH4eCO2 Input voltage: 20e100 V
Frequency: 10e30 kHz
Discharge gap: 1e4 mm
CH4/CO2 ratio: 0.25 to 2.0
n-heptane Input power: 28e38 W
O/C ratio: 0.55 to 1.2
Residence time: 20.4e66.7 s
H2 selectivity/yield Conversion Highlights Ref.
percentage
16% 48% Highest conversion rate is [54]
obtained by 69.5 m/s injection
gas velocity, 300 L/h CO2 flow
rate, and Type 1 orifice baffle at
1 CH4/CO2 ratio.
CO2 destruction rates ranged
between 35.7 and 42.6%,
depending upon the various
process parameters.
70% 88% Highest CH4 conversion is [53]
obtained at 0.3 O2/C ratio, 0.5 S/
C ratio, and 24 kJ/mol SEI.
A 74% and 0.45 kWh/Nm3 are
the energy efficiency and cost
50.1% (H2 yield) e Highest H2 yield is achieved at [52]
30 W input power, 0.71 O/C
ratios, 6.5 mm discharge gap,
and 24.7 s residence time.
The best H2 energy yield of
94.5 L/kWh is achieved.
48.6% (H2 yield) e The ideal H2 yield is achieved [57]
with a 0.68 O/C ratio, 18.4 s of
residence time with Ar addition
of 10 vol% at 32 W.
97.2% 80.3% Methanol conversion and H2 [59]
selectivity increased from
24.0% to 87.7% to their
from 0 to 95 mol%
⁓72% 32.6% (CH4) and 22.5% (CO2) Optimal conversion is obtained [60]
by 3 mm discharge gap and
20 kHz discharge frequency at
60 V.
Higher CH4/CO2 ratio results in
H2 production, but CH4 will
remain unreacted; thus, the
ideal CH4/CO2 ratio is 1e2.
73.9% 42.6% (CO2) 34.1% peak selectivity and [61]
53.9 L/kWh are achieved at
36 W.

conversion and 1.46 mol/kJ energy efficiency without any
expensive catalyst, thus, making the process more energy-
efficient than a fixed electrode reactor. Similarly, Kheir-
ollahivash et al. [27] developed a screw-type electrode and
recorded the reactor performance parameters to determine the
impacts of arc extension and electrode traveling at different
angular velocities. The maximum CH4 conversion, hydrogen
production rate, and H2 energy yield obtained with the double-
helix electrode are 47%, 7.96 L/h, and 36.8 g/kWh, respectively.
At the same time, it showed a 2.1 g/h carbon decomposition
rate, where carbon has a graphite-like structure. Table 4 gives
details of other pulsed discharge reactors operating at different
parameters for hydrogen production. It was observed from the
study of different pulsed discharge plasma reactors that feed
flow rate, electrode distance, and electrode velocity (rotating
electrode) play a significant role in hydrogen production. While
the parameters like power, reaction time, and concentration
have less significance, their optimization will benefit the sig-
nificant parameters in the process.
Gliding arc plasma reactor
The gliding arc discharge is another plasma technique that
produces warm plasma at about 1000e3000 K gas temperature
and, thus, possesses properties between thermal and non-
thermal plasmas [52]. It is a transient arc discharge formed
between two flat diverging electrodes. The shortest inter-
electrode space initiates the arc that glides along the elec-
trodes due to the gas blast and reaches the larger
interelectrode space before it vanishes; then, a new arc gen-
erates, and the process continues. Fig. 6 shows various gliding
arc plasma reactor components and different attachments
[53]. Kim and Chun [54] designed a similar gliding arc plasma
for CO2 decomposition and CH4 steam inflow and measured
the effects of varying orifice baffles in hydrogen-rich syngas
production. The orifice baffle with the smallest inner diameter
showed the highest CO2 destruction rate (42.5%) due to higher
retention time while achieving 48% methane conversion at a
300 L/h CO2 flow rate. In contrast, Lian et al. [53] investigated
2476 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2
Fig. 7 e Microwave plasma reactor.
the methanol-reforming in a gliding arc plasma reactor and
observed an 88% methanol conversion by 0.3 oxygen/meth-
anol ratio, 0.5 steam/methanol ration, and 24 kJ/mol specific
energy input, respectively. It gives high energy efficiency with
low energy costs. Liu et al. [55] investigated ethanol reforming
for hydrogen production in a gliding arc plasma reactor and
achieved 38.6% of the highest H2 yield during the experi-
mentation. In continuation, Wang et al. [52] examined the
influence of various other operating parameters in continuous
n-heptane decomposition at room temperature and achieved
50.1% H2 yield and 94.5 L/kWh H2 energy yield at 30 W input
power, 0.71 O/C ratios, 6.5 mm discharge gap, and 24.7 s
residence time, respectively. Any fluctuation in the above
parameters decreases H2 yield, while CO and CH4 yield in-
creases drastically.
Piavis and Turn [56] also fabricated a reverse vortex flow
plasma reactor and tested the reactor performance for
methane reforming. The reactor achieved 66.5% H2 yield and
79.8% methane conversion at 43.5% efficiency and 144 kJ/mol
specific energy requirement. In contrast, Song et al. examined
the CH4eCO2 decomposition in a rotating gliding arc reactor
and observed a 1e2 CH4/CO2 ratio ideal for hydrogen pro-
duction, while a higher ratio resulted in incomplete CH4
reforming. At the same time, the higher voltage and fre-
quency enhance gas energy yield, whereas overall energy
consumption is improved. Baowei et al. [57] performed the
toluene reforming in a gliding arc plasma reactor while add-
ing a smaller amount of Argon (Ar) gas. With 10 vol% Ar
addition, the reactor achieved a 48.6% H2 yield and 60.2 L/
kWh H2 energy yield, respectively. Ma et al. [58] studied the
potential of n-dodecane for hydrogen production in a gliding
arc plasma reactor. The highest n-dodecane conversion of
68.1% gives 76.7% H2 selectivity, while the other products
generated are acetylene and ethylene. Both acetylene and
ethylene help in the selectivity enhancement of light olefins.
Meanwhile, Lian et al. [59] examined the behavior of water (at
several concentrations) in a gliding arc plasma reactor for
methane reforming. During the process, water plays a ho-
mogeneous catalyst and CO oxidant between 33 and 95 mol%
content and a side-product below 33 mol% concentration.
Both a catalyst and an oxidant behavior of water enhanced
hydrogen production, while the side-product behavior resul-
ted in hydrocarbon formation, drastically reducing hydrogen
production. Table 5 discusses other gliding arc plasma re-
actors and operating parameters for higher hydrogen yield.
The hydrogen yield in the gliding arc plasma reactor depends
on the O/C ratio, power, and feed flow rate. The O/C ratio
between 0.4 and 0.7 at a power input of 30e32W is considered
favorable for maximum hydrogen production, while in case of
methanol, the power input can reach as high as 120 W for
effective results.
Microwave (MW) plasma reactor
A microwave (MW) plasma reactor is another plasma tech-
nique for hydrogen production that works between 300 MHz
and 10 GHz frequency range. It utilizes electromagnetic radi-
ation to excite electrons to higher energy levels, and these
excited electrons break the hydrogen bonds to form
H radi-
cals, which later combine to form H2 molecules [62,63]. The
discharge initiation happens when gas flows through a quartz
tube and intersects with a rectangular waveguide. The plasma
absorbs wave energy, and MWs spread through quartz tubes.
Czylkowski et al. [62] used a microwave plasma reactor
(shown in Fig. 7) and determined the effects of spraying
ethanol microdroplets into Nitrogen (N2) MW plasma flame at
atmospheric pressure. Direct spraying saved energy re-
quirements for vaporizing ethanol. The results show
hydrogen concentration and production rate of 28% and
1043 L/h at 3.7 L/h ethanol flow rate and 5 kW microwave
power. Wang et al. [64] investigated the liquid-phase methane
reforming for hydrogen production in an MW plasma reactor.
The highest H2 yield of 74% was achieved by 94.3% methane
conversion and 900W power. In another study, Czylkowski
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2 2477

Table 6 e Plasma reforming studies for H2 production in the Microwave Plasma Reactor.
Feed Process Parameters H2 production Energy Highlights Ref.
rate (g/h) Yield (g/kWh)
Ethanol Frequency: 2.45 GHz 86.7 17.4 Highest H2 production rate with [62]
Power: 2e5 kW 28% H2 content is achieved by
N2 gas flow rate: 2000e4000 L/h ethanol and N2 gas flow rate of
3.7 L/h and 2700 L/h at 5 kW
power.
Ethanol Frequency: 2.45 GHz 71.9 15.0 Highest H2 production rate with [65]
Power: 2e5 kW 27.6% H2 content is achieved by
Flow rate: 0.14e2.7 kg/h raising microwave power to
5 kW, while the increased
ethanol mass flow rate resulted
in higher hydrogen production
efficiency.
Ethanol Frequency: 2.45 GHz 72.48 48.32 Highest H2 flow rate with 58.1% [67]
Power: 900e1500 W H2 content is achieved at
Ethanol conc.: 10e100 vol% 1500 W and 70 vol% ethanol
concentrations.
Water Frequency: 2.45 GHz 7.6e23.1 13.3 Ceriated tungsten showed [68]
Power: 900 W higher H2 production than pure
Flow rate: 2 bbl/s tungsten. However, the overall
Temperature: 107  C system attained 53% energy
efficiency and 44% exergy
efficiency.
Synthetic Biogas Frequency: 915 MHz 156 21 Highest H2 production rate is [69]
Power: 4.5e7.5 kW achieved with 6000 L/h flow
CH4/CO2 ratio: 0.1e1.0 rate at 7.5 kW; however, the
Flow rate: 3000e9000 L/h peak energy yield of 21 g/kWh is
obtained at 4.5 kW, and
maximum CH4 conversion
(86.5%) is achieved by 3000 L/h
flow rate at 6.5 kW power.
Ethanol Frequency: 2.45 GHz 66.6 41 Ethanol decomposes into [70]
Power: 700e1500 W CH3CHO and H2 by high-energy
Ethanol conc.: 20e100 vol% electrons and produces CH4
Discharge time: 3e15 min. and CH2O.
While H2O decomposes into

OH and
H radicals.
Ethanol Frequency: 2.45 GHz 85.8 57.4 80 PPI Cu foamed metal [71]
Power: 900e1500 W suspended electrode shows a
Flow rate: 660e1800 L/h 31.5% increase in total gas flow
Bubble retention time: 60 rate than no suspended
e90 ms electrode.
Methane Frequency: 915 MHz 2247 70 A 74.6%e97.7% rise in methane [72]
Power: 15e50 kW conversion was observed with
Flow rate: 240e420 L/h an increase in the S/C ratio.
H2O/CH4 molar ratio: 3-6 Hydrogen production rate rises
from 1532 to 2247 g (H2)/h when
the absorbed microwave power
is raised from 27 to 32 kW.

et al. [65] examined the ethanol conversion in a similar MW
plasma reactor at atmospheric pressure by directly supplying
ethanol from the induction vaporizer to the plasma flame. The
experiments showed that microwave power enhanced
hydrogen production rate and volume concentration, while
the increased ethanol mass flow rate gave higher hydrogen
production efficiency. In comparison, Ogungbesan et al. [66]
investigated the methane dissociation at atmospheric pres-
sure with a quartz tube to generate an MW plasma torch at
2 kW and 2.45 GHz. The temperature caused by the microwave
plasma torch is as high as 5000 ± 500 K, which is suitable for
methane decomposition into hydrogen.
Sun et al. [67] described a significant hydrogen production
process from ethanol using a microwave discharge plasma
reactor. H2 and CO are produced in the reactor, while other
gases like CH4, C2H2, and CO2 are also in smaller quantities.
The highest hydrogen concentration and energy yields ob-
tained are 58.1% and 48.32 g/kWh at 1500 W with 70% ethanol
concentration in the solution. Thus, a feasible on-board
hydrogen production showed good potential with less en-
ergy demand. Similarly, Chehade et al. [68] designed an MW
plasma reactor using a commercially available 2.45 GHz mi-
crowave oven for water plasmolysis. The steam at 107  C en-
ters the reactor, having a tungsten electrode with a flow rate of
2478 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2
Table 7 e Advantages and Disadvantages of various plasma reforming reactors.
Gliding Arc Discharge Plasma Reactor
Microwave Plasma Reactor
Dielectric Barrier Discharge Plasma Reactor
Pulsed Plasma Reactor
2 bbl/s, and the effects of pure and ceriated tungsten elec-
trodes are examined. The ceriated tungsten sustained a
higher H2 rate, and the H2 production rate ranges between 1.65
and 4.7 L/h, respectively, while the highest hydrogen energy
yield achieved is 13.3 g/kWh. Therefore, the fabricated mi-
crowave reactor generates hydrogen through water plasmol-
ysis making hydrogen production more affordable. More MW
plasma reactors with process parameters to achieve high H2
yield are depicted in Table 6. The MW plasma reactors are
based on electromagnetic waves; thus, the frequency of the
electromagnetic waves, input power, and feed flow rate play a
significant role in hydrogen production rate.
Advantages and disadvantages
The study enlightens the development of various plasma
reforming techniques for hydrogen production. The
Advantages:
1. High-energy efficiency
2. Low operating cost
3. Uses extensive concentration range of volatile organic compound
4. Flexibility of treating various pollutants
Disadvantages:
1. Overall Higher power consumption
2. Unstable plasma discharge
3. Moderate equipment cost
Advantages:
1. Highest hydrogen yield
2. Most efficient and productive
3. Catalyst (both homogeneous and heterogeneous) addition improves hydrogen
selectivity
4. Feedstock flexibility
Disadvantages:
1. Hot spot formation causes uneven temperature distribution within the system
2. Variable penetration depth due to low stability of microwave frequency
3. Microwave generation requires high power consumption
4. Batch-type reactor, not suitable for continuous hydrogen production
Advantages:
1. Require comparatively low-frequency power supply
2. Reactor scalability by integration
3. Quiet and silent discharge process
4. Higher-purity hydrogen gas production
Disadvantages:
1. Not yet achieved economic feasibility
2. Catalyst Sensitivity and cost raise the overall production cost
3. Catalyst deactivation due to by-product contamination may lead to system shutdown
4. Catalyst performance plays a vital role due to plasma-catalyst synergetic effect
Advantages:
1. Efficiently use of feedstocks like bio-oil and alcohols
2. Produces valuable by-product ‘graphite oxide.’
3. Energy-efficient for radical species and energetic photons production
4. Generate reactive products for the consistent reaction
Disadvantages:
1. Comparatively lower hydrogen yield
2. Carbon deposition on electrodes reduces the system's efficiency
3. Unable to dissipate all energy immediately will result in distortion of pulse and cause
altered polarity
4. Voltage may locally double in amplitude and can damage equipment
5. Propagation of discharge depends on the properties of the source
discussion also shows that the plasma reforming technique is
promising and efficient for hydrogen production from multi-
ple feedstocks, whether alcohol or other hydrocarbons. From
the above discussion, a summary of the advantages and dis-
advantages of different plasma reforming techniques is pre-
pared and is described in Table 7 for better understanding.
Each technique has its advantages and disadvantages
depending on influencing parameters and feedstocks. A
gliding arc plasma reactor is energy-efficient and flexible in
treating various feedstocks, but it generates unstable plasma
discharge and has a moderate component cost. Similarly,
microwave plasma rector gives the highest hydrogen yield at
atmospheric pressure, but the hot spot formation within the
reactor results in uneven temperature distribution causing
stability reduction. DBD plasma reactor requires a low-
frequency power supply and has scalability by numbering
up, but the use of a catalyst raises the overall cost of the
system, and catalyst sensitivity is also a topic of concern. A
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2
Fig. 8 e Comparison of hydrogen yield by different plasma
reactors.
pulsed plasma reactor is a continuous hydrogen-producing
technique, generating a valuable by-product (graphite oxide);
however, the electrode's carbon deposition requires constant
cleaning to maintain the high system efficiency.
The study also revealed that the microwave plasma re-
actors give the highest hydrogen yield, as depicted in Fig. 8,
while the other techniques have other advantages. Plasma
reforming has an additional advantage over conventional
methods because it has a quick ON/OFF mechanism.
Hydrogen fuel is needed for every nation (whether devel-
oped or developing) to cut emissions and meet daily energy
requirements. Hydrogen production from plasma reforming is
a new process that needs to be set to get maximum benefits.
Future research may focus on optimizing various influencing
parameters for enhanced hydrogen yield. Adding highly effi-
cient electronic components is another prospect to resource-
fully utilize the electrical energy for plasma generation and
reduce its demand for plasmolysis.
Conclusions
Hydrogen is an energy carrier that can fulfil energy-sector
requirements, but pure H2 is rarely available in the atmo-
sphere. Various techniques have been developed so far for
hydrogen extraction from its compounds. The present study
briefly discusses the different plasma reforming processes for
hydrogen production: dielectric barrier discharge (DBD)
reactor, pulsed plasma reactor, gliding arc plasma reactor, and
microwave (MW) plasma reactor. All reactors work on the
same principle, the generation of high-temperature electrons
at the plasma zone while maintaining the system temperature
near or slightly above room temperature. The following are
the findings:
2479

The influencing parameters in DBD reactors are feed flow
rate and reactor temperature; the hydrogen production
rate is slightly above 100 L/h.

Pulsed plasma reactors show variations in hydrogen yield
by feed flow rate, electrode gap and velocity, and applied
voltage. However, the hydrogen production rate is similar
to DBD reactors.

The H2 selectivity in gliding arc plasma reactors is mainly
influenced by the oxygen-to-carbon (O/C) ratio, power, and
residence time. The hydrogen selectivity in gliding arc
plasma reactor is above 70% and may reach up to 97% in
some cases.

Hydrogen production in MW reactors is mainly influenced
by the frequency, power, and flow rate. These reactors
generate the highest hydrogen yield among all the reactors.
The plasma reactors are comparatively less costly, and
their construction requires less bulky equipment. Therefore, it
will likely replace cumbersome hydrogen storage systems
with compact on-board hydrogen production systems.
Therefore, the study helps understand the plasma reforming
techniques and their influencing operating parameters.
Funding
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
Availability of data and material
All data generated or analyzed during this study are included
in this published article.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
references
[1] Mazloomi K, Gomes C. Hydrogen as an energy carrier:
prospects and challenges. Renew Sustain Energy Rev
2012;16:3024e33. https://doi.org/10.1016/j.rser.2012.02.028.
[2] Dawood F, Anda M, Shafiullah GM. Hydrogen production for
energy: an overview. Int J Hydrogen Energy 2020;45:3847e69.
https://doi.org/10.1016/j.ijhydene.2019.12.059.
[3] Saleem F, Harris J, Zhang K, Harvey A. Non-thermal plasma
as a promising route for the removal of tar from the product
gas of biomass gasification - a critical review. Chem Eng J
2020;382:122761. https://doi.org/10.1016/j.cej.2019.122761.
[4] Damen K, Troost M Van, Faaij A, Turkenburg W. A
comparison of electricity and hydrogen production systems
with CO 2 capture and storage. Part A: review and selection
of promising conversion and capture technologies. Prog
Energy Combust Sci 2006;32:215e46. https://doi.org/10.1016/
j.pecs.2005.11.005.
2480 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2
[5] Nikolaidis P, Poullikkas A. A comparative overview of
hydrogen production processes. Renew Sustain Energy Rev
2017;67:597e611. https://doi.org/10.1016/j.rser.2016.09.044.
[6] Ni M, Leung DYC, Leung MKH. A review on reforming bio-
ethanol for hydrogen production. Int J Hydrogen Energy
2007;32:3238e47. https://doi.org/10.1016/
j.ijhydene.2007.04.038.
[7] The future of hydrogen. Futur Hydrog; 2019. https://doi.org/
10.1787/1e0514c4-en.
[8] Hydrogen Council. Hydrogen scaling up: a sustainable
pathway for the global energy transition. Hydrog Scaling up
A Sustain Pathw Glob Energy Transit; 2017. p. 80.
[9] Dickel R. Blue hydrogen as an enabler of green hydrogen.
2020.
[10] Alrazen HA, Abu Talib AR, Adnan R, Ahmad KA. A review of
the effect of hydrogen addition on the performance and
emissions of the compression - ignition engine. Renew
Sustain Energy Rev 2016;54:785e96. https://doi.org/10.1016/
j.rser.2015.10.088.
[11] Chen LG, Li PL, Xia SJ, Kong R, Ge YL. Multi-objective
optimization for membrane reactor for steam methane
reforming heated by molten salt. Sci China Technol Sci
2022;65:1396e414. https://doi.org/10.1007/s11431-021-2003-0.
[12] Li P, Chen L, Xia S, Kong R, Ge Y. Multi-objective optimal
configurations of a membrane reactor for steam methane
reforming. Energy Rep 2022;8:527e38. https://doi.org/
10.1016/j.egyr.2021.11.288.
[13] Li P, Chen L, Xia S, Zhang L. Maximum hydrogen production
rate optimization for tubular steam methane reforming
reactor. Int J Chem React Eng 2019;17:20180191. https://
doi.org/10.1515/ijcre-2018-0191.
[14] Li P, Chen L, Xia S, Zhang L, Kong R, Ge Y, et al. Entropy
generation rate minimization for steam methane reforming
reactor heated by molten salt. Energy Rep 2020;6:685e97.
https://doi.org/10.1016/j.egyr.2020.03.011.
[15] Maggio G, Nicita A, Squadrito G. How the hydrogen
production from RES could change energy and fuel markets:
a review of recent literature. Int J Hydrogen Energy
2019;44:11371e84. https://doi.org/10.1016/
j.ijhydene.2019.03.121.
[16] King B, Patel D, Zhu Chen J, Drapanauskaite D, Handler R,
Nozaki T, et al. Comprehensive process and environmental
impact analysis of integrated DBD plasma steam methane
reforming. Fuel 2021;304:121328. https://doi.org/10.1016/
j.fuel.2021.121328.
[17] Li P, Chen L, Xia S, Kong R, Ge Y. Total entropy generation
rate minimization configuration of a membrane reactor of
methanol synthesis via carbon dioxide hydrogenation. Sci
China Technol Sci 2022;65:657e78. https://doi.org/10.1007/
s11431-021-1935-4.
[18] Kong R, Chen L, Xia S, Li P, Ge Y. Minimization of entropy
generation rate in hydrogen iodide decomposition reactor
heated by high-temperature helium. Entropy 2021;23:82.
https://doi.org/10.3390/e23010082.
[19] Kheirollahivash M, Rashidi F, Moshrefi MM. Experimental
study and kinetic modeling of methane decomposition in a
rotating arc plasma reactor with different cross-sectional
areas. Int J Hydrogen Energy 2019;44:17460e9. https://doi.org/
10.1016/j.ijhydene.2019.05.011.
[20] Singh V. Fundamentals and use of hydrogen as a fuel. J Mech
Eng 2015;6:63e8.
[21] Ali NA, Ismail M. Advanced hydrogen storage of the Mg-Na-
Al system: a review. J Magnes Alloy 2021. https://doi.org/
10.1016/j.jma.2021.03.031.
[22] Ozaki M, Tomura S, Ohmura R, Mori YH. Comparative study
of large-scale hydrogen storage technologies: is hydrate-
based storage at advantage over existing technologies? Int J
Hydrogen Energy 2014;39:3327e41. https://doi.org/10.1016/
j.ijhydene.2013.12.080.
[23] Zhao W, Yang Y, Bao Z, Yan D, Zhu Z. Methods for measuring
the effective thermal conductivity of metal hydride beds: a
review. Int J Hydrogen Energy 2020;45:6680e700. https://
doi.org/10.1016/j.ijhydene.2019.12.185.
[24] Xueping Z, Jiaojiao Z, Shenglin L, Xuanhui Q, Ping L,
Yanbei G, et al. A new solid material for hydrogen storage. Int
J Hydrogen Energy 2015;40:10502e7. https://doi.org/10.1016/
j.ijhydene.2015.07.015.
[25] Andersson J, Gro € nkvist S. Large-scale storage of hydrogen.
Int J Hydrogen Energy 2019;44:11901e19. https://doi.org/
10.1016/j.ijhydene.2019.03.063.
[26] Moshrefi MM, Rashidi F. Hydrogen production from methane
decomposition in cold plasma reactor with rotating
electrodes. Plasma Chem Plasma Process 2018;38:503e15.
https://doi.org/10.1007/s11090-018-9875-5.
[27] Kheirollahivash M, Rashidi F, Moshrefi MM. Hydrogen
production from methane decomposition using a mobile and
elongating arc plasma reactor. Plasma Chem Plasma Process
2019;39:445e59. https://doi.org/10.1007/s11090-018-9950-y.
[28] Janev RK, Reiter D. Collision processes of CHy and CHyþ
hydrocarbons with plasma electrons and protons. Phys
Plasmas 2002;9:4071. https://doi.org/10.1063/1.1500735.
[29] Morgan NN, ElSabbagh M. Hydrogen production from
methane through pulsed DC plasma. Plasma Chem Plasma
Process 2017;37:1375e92. https://doi.org/10.1007/s11090-017-
9829-3.
[30] Hrabovsky M, Hlina M, Kopecky V, Maslani A, Krenek P,
Serov A, et al. Steam plasma methane reforming for
hydrogen production. Plasma Chem Plasma Process
2018;38:743e58. https://doi.org/10.1007/s11090-018-9891-5.
[31] Lee DH, Kim T. Plasma-catalyst hybrid methanol-steam
reforming for hydrogen production. Int J Hydrogen Energy
2013;38:6039e43. https://doi.org/10.1016/
j.ijhydene.2012.12.132.
[32] Wang W, Zhu C, Cao Y. DFT study on pathways of steam
reforming of ethanol under cold plasma conditions for
hydrogen generation. Int J Hydrogen Energy 2010;35:1951e6.
https://doi.org/10.1016/j.ijhydene.2009.12.170.
[33] O-Thong S, Prasertsan P, Birkeland NK. Evaluation of
methods for preparing hydrogen-producing seed inocula
under thermophilic condition by process performance and
microbial community analysis. Bioresour Technol
2009;100:909e18. https://doi.org/10.1016/
j.biortech.2008.07.036.
[34] Budhraja N, Pal A, Kumar A. In: Kumar A, Pal A,
Kachhwaha SS, Jain PK, editors. Investigations on ethanol as
the raw material for hydrogen production, storage, and
applications. Singapore: Springer Singapore; 2021. p. 317e26.
https://doi.org/10.1007/978-981-15-9678-0_28.
[35] Xin Y, Sun B, Zhu X, Yan Z, Zhao X, Sun X, et al.
Characteristics and pathways of hydrogen produced by
pulsed discharge in ethanol-water mixtures. Int J Hydrogen
Energy 2020;45:1588e96. https://doi.org/10.1016/
j.ijhydene.2019.11.101.
[36] Blom PWE, Basson GW. Non-catalytic plasma-arc reforming
of natural gas with carbon dioxide as the oxidizing agent for
the production of synthesis gas or hydrogen. Int J Hydrogen
Energy 2013;38:5684e92. https://doi.org/10.1016/
j.ijhydene.2013.03.042.
[37] Favas J, Monteiro E, Rouboa A. Hydrogen production using
plasma gasification with steam injection. Int J Hydrogen
Energy 2017;42:10997e1005. https://doi.org/10.1016/
j.ijhydene.2017.03.109.
[38] Punc ocha
r M, Ruj B, Chatterjee PK. Development of process
for disposal of plastic waste using plasma pyrolysis
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2
technology and option for energy recovery. Procedia Eng
2012;42:420e30. https://doi.org/10.1016/j.proeng.2012.07.433.
[39] Putra AEE, Amaliyah N, Nomura S, Rahim I. Plasma
generation for hydrogen production from banana waste.
Biomass Convers Biorefinery 2020:3e8. https://doi.org/
10.1007/s13399-020-00765-3.
[40] Ulejczyk B, Nogal Ł, Młotek M, Krawczyk K. Hydrogen
production from ethanol using dielectric barrier discharge.
Energy 2019;174:261e8. https://doi.org/10.1016/
j.energy.2019.02.180.
[41] Zhang X, Wenren Y, Chen J, Zhang L, Jin Y, Liu Z, et al. Partial
oxidation of n-pentane to syngas and oxygenates in a
dielectric barrier discharge reactor. Fuel 2022;307. https://
doi.org/10.1016/j.fuel.2021.121814.
[42] Hayakawa Y, Miura T, Shizuya K, Wakazono S, Tokunaga K,
Kambara S. Hydrogen production system combined with a
catalytic reactor and a plasma membrane reactor from
ammonia. Int J Hydrogen Energy 2019;44:9987e93. https://
doi.org/10.1016/j.ijhydene.2018.12.141.
[43] Hayakawa Y, Kambara S, Miura T. Hydrogen production from
ammonia by the plasma membrane reactor. Int J Hydrogen
Energy 2020;45:32082e8. https://doi.org/10.1016/
j.ijhydene.2020.08.178.
[44] Song L, Kong Y, Li X. Hydrogen production from partial
oxidation of methane over dielectric barrier discharge
plasma and NiO/G-Al2O3 catalyst. Int J Hydrogen Energy
2017;42:19869e76. https://doi.org/10.1016/
j.ijhydene.2017.06.008.
[45] King B, Patel D, Zhu Chen J, Drapanauskaite D, Handler R,
Nozaki T, et al. Comprehensive process and environmental
impact analysis of integrated DBD plasma steam methane
reforming. Fuel 2021;304. https://doi.org/10.1016/
j.fuel.2021.121328.
[46] Shareei M, Taghvaei H, Azimi A, Shahbazi A, Mirzaei M.
Catalytic DBD plasma reactor for low temperature partial
oxidation of methane: maximization of synthesis gas and
minimization of CO2. Int J Hydrogen Energy
2019;44:31873e83. https://doi.org/10.1016/
j.ijhydene.2019.10.120.
[47] El-Shafie M, Kambara S, Hayakawa Y, Miura T. Preliminary
results of hydrogen production from water vapor
decomposition using DBD plasma in a PMCR reactor. Int J
Hydrogen Energy 2019;44:20239e48. https://doi.org/10.1016/
j.ijhydene.2019.05.199.
[48] Dideikin AT, Vul’ AY. Graphene oxide and derivatives: the
place in graphene family. Front Physiol 2019;6. https://
doi.org/10.3389/fphy.2018.00149.
[49] Xin Y, Sun B, Zhu X, Yan Z, Zhao X, Sun X, et al.
Characteristics and pathways of hydrogen produced by
pulsed discharge in ethanol-water mixtures. Int J Hydrogen
Energy 2020;45:1588e96. https://doi.org/10.1016/
j.ijhydene.2019.11.101.
[50] Lee H, Park YK. Hydrogen production from a solution plasma
process of bio-oil. Int J Hydrogen Energy 2020;45:20210e5.
https://doi.org/10.1016/j.ijhydene.2019.11.185.
[51] Xin Y, Sun B, Zhu X, Yan Z, Sun X. Hydrogen-rich syngas
production by liquid phase pulsed electrodeless discharge.
Energy 2021;214:118902. https://doi.org/10.1016/
j.energy.2020.118902.
[52] Wang B, Peng Y, Yao S. Oxidative reforming of n-heptane in
gliding arc plasma reformer for hydrogen production. Int J
Hydrogen Energy 2019;44:22831e40. https://doi.org/10.1016/
j.ijhydene.2019.07.042.
[53] Lian HY, Li XS, Liu JL, Zhu X, Zhu AM. Oxidative pyrolysis
reforming of methanol in warm plasma for an on-board
hydrogen production. Int J Hydrogen Energy 2017;42:13617e24.
https://doi.org/10.1016/j.ijhydene.2016.10.166.
2481
[54] Kim SC, Chun YN. Development of a gliding arc plasma
reactor for CO 2 destruction. Environ Technol
2014;35:2940e6. https://doi.org/10.1080/
09593330.2014.925979.
[55] Liu S, Wang B, Cheng Y, Wang C, Zou J. Ethanol partial
oxidative reforming in gliding arc discharge plasma: a better
understanding by a kinetic model study. Fuel 2022;328.
https://doi.org/10.1016/j.fuel.2022.125309.
[56] Piavis W, Turn S. An experimental investigation of reverse
vortex flow plasma reforming of methane. Int J Hydrogen
Energy 2012;37:17078e92. https://doi.org/10.1016/
j.ijhydene.2012.08.126.
[57] Baowei W, Shize L, Yeping P, Chengyu W. Gliding arc plasma
reforming of toluene for on-board hydrogen production. Int J
Hydrogen Energy 2020;45:6138e47. https://doi.org/10.1016/
j.ijhydene.2019.12.184.
[58] Ma Y, Harding JD, Tu X. Catalyst-free low temperature
conversion of n-dodecane for co-generation of COx-free
hydrogen and C2 hydrocarbons using a gliding arc plasma.
Int J Hydrogen Energy 2019;44:26158e68. https://doi.org/
10.1016/j.ijhydene.2019.08.067.
[59] Lian HY, Liu JL, Li XS, Zhu AM. Disclosure of water roles in
gliding arc plasma reforming of methanol for hydrogen
production. Plasma Process Polym 2020;17:1e9. https://
doi.org/10.1002/ppap.202000069.
[60] Song L, Liang T, Liu C, Li X. Experimental investigation of
hydrogen production by CH4-CO2 reforming using rotating
gliding arc discharge plasma. Int J Hydrogen Energy
2019;44:29450e9. https://doi.org/10.1016/
j.ijhydene.2019.05.245.
[61] Wang B, Liu S, Peng Y, Wang C, Zou J. Heptane dry reforming
and coupling with partial oxidation in gliding arc discharge
plasma for H2 production. Fuel Process Technol
2021;221:106943. https://doi.org/10.1016/
j.fuproc.2021.106943.
[62] Czylkowski D, Hrycak B, Jasin  ski M, Dors M, Mizeraczyk J.
Hydrogen production by direct injection of ethanol
microdroplets into nitrogen microwave plasma flame. Int J
Hydrogen Energy 2018;3:21196e208. https://doi.org/10.1016/
j.ijhydene.2018.09.143.
[63] Inayat A, Tariq R, Khan Z, Ghenai C, Kamil M, Jamil F, et al. A
comprehensive review on advanced thermochemical
processes for bio-hydrogen production via microwave and
plasma technologies. Biomass Convers Biorefinery 2020.
https://doi.org/10.1007/s13399-020-01175-1.
[64] Wang Q, Wang J, Zhu T, Zhu X, Sun B. Characteristics of
methane wet reforming driven by microwave plasma in
liquid phase for hydrogen production. Int J Hydrogen Energy
2021;46:34105e15. https://doi.org/10.1016/
j.ijhydene.2021.08.006.
[65] Czylkowski D, Hrycak B, Jasin  ski M, Dors M, Mizeraczyk J.
Hydrogen production by conversion of ethanol injected into
a microwave plasma. Eur Phys J D 2017;71. https://doi.org/
10.1140/epjd/e2017-80566-x.
[66] Ogungbesan B, Kumar R, Su L, Sassi M. Experimental
validation of local thermal equilibrium in a MW plasma torch
for hydrogen production. Int J Hydrogen Energy
2013;38:15210e8. https://doi.org/10.1016/
j.ijhydene.2013.09.099.
[67] Sun B, Zhao X, Xin Y, Zhu X. Large capacity hydrogen
production by microwave discharge plasma in liquid fuels
ethanol. Int J Hydrogen Energy 2017;42:24047e54. https://
doi.org/10.1016/j.ijhydene.2017.08.052.
[68] Chehade G, Lytle S, Ishaq H, Dincer I. Hydrogen
production by microwave based plasma dissociation of
water. Fuel 2020;264:116831. https://doi.org/10.1016/
j.fuel.2019.116831.
2482 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2
[69] Hrycak B, Czylkowski D, Jasin  ski M, Dors M, Mizeraczyk J.
Hydrogen production via synthetic biogas reforming in
atmospheric-pressure microwave (915 MHz) plasma at high
gas-flow output. Plasma Chem Plasma Process
2019;39:695e711. https://doi.org/10.1007/s11090-019-09962-z.
[70] Zhu T, Sun B, Zhu X, Wang L, Xin Y, Liu J. Mechanism
analysis of hydrogen production by microwave discharge in
ethanol liquid. J Anal Appl Pyrolysis 2021;156:105111. https://
doi.org/10.1016/j.jaap.2021.105111.
[71] Zhu T, Liu J, Xin Y, Zhu X, Sun B. Hydrogen production by
microwave discharge in liquid: study on the characteristics
effect of suspended electrode. J Anal Appl Pyrolysis
2022;164:105529. https://doi.org/10.1016/j.jaap.2022.105529.
[72] Akande O, Lee BJ. Plasma steam methane reforming (PSMR)
using a microwave torch for commercial-scale distributed
hydrogen production. Int J Hydrogen Energy
2022;47:2874e84. https://doi.org/10.1016/
j.ijhydene.2021.10.258.