International Journal of Hydrogen Energy

Volume 45, Issue 23, 28 April 2020, Pages 12641-12652

Hydrogen generation by electrolysis under subcritical

water condition and the effect of aluminium anode
Rasiha Nefise Mutlu a , Ibrahim Kucukkara b, Ahmet Murat Gizir a

Show more

Share Cite

https://doi.org/10.1016/j.ijhydene.2020.02.223
Get rights and content

Highlights

• The subcritical water for a new generation of alkaline electrolysis systems.

• The designed reactor reduced energy consumption from 1400 kJmol- to 300
kJmol-.

• The amount of hydrogen gas production increased from 18 mlcm−2h- to 300

mlcm−2h-.

• Aluminium electrode was used as anode to prevent mixing oxygen and

hydrogen.

• Economically and pure hydrogen gas produced with high efficiency.

Abstract

The productions of catalytic active materials and the reactor designs increasing the kinetics of the system are very
important because of efficient energy production for electrolysis systems. In this study, the effects of subcritical water's
conditions on electrolysis were investigated. All experiments were carried out under the subcritical water conditions,
high temperature and pressure resistant reactor was used and the three electrodes were integrated in to the reactor.
The aluminium anode was used to prevent the formation of oxygen in the reactor during obtaining pure hydrogen gas.
The effect of pure (Al), Al-6013 and Al-7075 aluminium anodes on the electrolysis of water were investigated and
compared with Pt anode. For all electrodes, Pt was used as cathode and Ag/AgCl electrode was used as reference
electrode. Electrochemical Impedance Spectroscopy (EIS) measurements, current potential measurements were
managed at −2 V, electrolysis current at 2 V constant potential during 1800 s was being followed and gas volume
produced was measured to determine the most efficient aluminium anode. Energy consumption and hydrogen gases
efficiency were also calculated for 25 °C room temperature. After determining the most efficient aluminium anode, the
experiments were repeated in the subcritical water environment. Nitrogen gas was used to purge the system. The
temperature was 130 °C and the pressure was 20 Bar. As a result, the use of aluminium alloys as an anode under the
subcritical water conditions reduced energy consumption from 1400 kJ mol−1 to 300 kJ mol−1. The current density was
increased to 370 mA cm−2 at 2 V. The efficiency increase from %15 to %70, and the amount of hydrogen gas produced
was increase from 18 mL cm−2 h− to 300 mL cm−2 h−. In addition, using the aluminium anode eliminated the gas
separation processes by providing purer hydrogen gas production.

Graphical abstract

Download : Download high-res image (167KB)

Download : Download full-size image

Introduction

With the growth of the population and the development of the economy, global energy demand and environmental
problems will continuously increase in the future. Most of the energy are obtained from mainly fossil fuel resources
including coal, oil and natural gas. However, the depletion of non-renewable fossil fuels and the harmful effects of
fossil fuel use on the environment have encouraged intensive research in innovative technologies for the
transformation and storage of sustainable and clean energy sources such as the sun and wind [[1], [2], [3], [4], [5]].
Although the use of solar and wind energy systems (or similar systems) are attractive; their efficiency mainly
dependent on seasonal conditions, and day-night differences that both system is not suitable for use alone. In the case
of renewable energy, H2O electro-catalytic electrolysis of water has been considered an attractive approach [6]. One of
these reactions is cathodic electro-reduction, i.e. Hydrogen Evaluation Reaction (HER), another is the anodic electro-
oxidation reaction, i.e. Oxygen Evaluation Reaction (OER). These reactions, which are expected to occur theoretically
fast, are very slow in practice regarding to mass-charge transfer and electrode dynamics. In order to make the system
economically feasible, the production of catalytic active materials and reactor designs to increase the kinetics of the
system are considerable [[7], [8], [9], [10], [11]]. Recent studies have shown that heating under sufficient pressure to
maintain water at the boiling point (called subcritical water) is beneficial in reducing the problems discussed above
and causing physicochemical changes in water [[12], [13], [14], [15]]. These important properties that vary when water
is heated from normal conditions of the subcritical state are the dielectric constant (polarity) in water decreases from
80 to about 20 [[16], [17], [18]]. Note that subcritical water typically is 100 °C–250 °C, but always less than 374 °C critical
temperature under pressure. Viscosity in water and surface tension both reduce the degree of magnitude [1]. The
concentration of H+ and OH− ions increases by 20 times [17]. There are also studies using non-electrochemical systems
using subcritical medium for hydrogen generation [19]. The minimum necessary cell voltage for the start-up of
electrolysis, E° cell, is given under standard conditions (P, T constant), and it depends the change in the Gibbs free
energy under standard conditions and n is the number of electrons transferred [18,20,21]. The necessary voltage for an
electron to overcome the Helmholtz energy barrier reduces when temperature and pressure are increased and this will
reduce the potential required for hydrogen gas production. Systems that require high temperature and pressure for the
subcritical environment bring two problems along with their benefits [22]. One of them is the reference electrode to be
used during electrochemical tests is not resistant to high temperature-pressure. The other is the membrane
requirement due to the formation of hydrogen and oxygen gas in the same reactor [21,23,24]. On the other hand,
electrochemical hydrogen formed by electrolysis can be used as fuel in the fuel cells, but chemical conversion of
methanol on board, cars and busses to produce hydrogen with sufficient purity is not attainable in practice. Besides,
hydrogen storage problem for cars and buses has not been solved in a proper sense; the weight and the volume are
much too high [25,26]. In the literature, high temperature and pressure hydrogen gas production has been studied
[13,27,28]. It is observed up to 900–1000 °C using solid oxide membranes as well as moderate temperatures [29,30].
However, sufficient progress has not been observed due to gases separation problem and high temperature resistant
reference electrode problem. Additionally, economic and durable reactor designs are of great importance in such
systems. Mei et al, using other molecules that are more susceptible to oxidation to replace the OER in the anode and
combine with the cathode to obtain a high-performance auxiliary H2 production system [31].

In this study, the effect of subcritical water environment on electrolysis was investigated. To do this a high temperature
and high pressure (20 bar or more) resistant reactor was designed. The three-electrode system mainly used in
electrochemical experiments was adapted to reactor. The effects of the aluminium electrodes as anode on hydrogen
efficiency in the reactor system were investigated. Using aluminium electrodes introduces number of positive effects
on the system during the hydrogen production process. The one of the effect is that the aluminium anode prevents the
formation of oxygen gas in the reactor. Another effect is that it contributes to hydrogen production. The subcritical
water and aluminium anode was preferred for the reasons described above. The cost analysis of such high pressure and
temperature requirements was made by Allebrod et al. [27,32]. Contrary to the popular belief, it is mentioned that it
was more economical in many respects. Firstly, the energy required to reach the subcritical condition (130 °C) is only
7.9 kJ mol−1 [33]. No membrane is required to separate hydrogen from oxygen and the costs of pressurized hydrogen
will be reduced. Aluminium is abundant in the nature and it is recyclable and economical material. Alkaline water
electrolysis has been used in large-scale industrial applications since 1920 [[34], [35], [36]]. The electrolyte (KOH) used
in the system is also economical [37,38]. The gases such as carbon dioxide will cause the loss of activity of electrode
(especially used with Platinum (Pt) electrode) [28,39]. In our system, nitrogen gas was purged. When the nitrogen
passed through the system, electrodes does not interfere with the air and impurities are removed from the system. As a
result, hydrogen production was achieved efficiently and economically with free of air pollutants (eg. carbon dioxide)
and oxygen-free.

Section snippets

Determination of aluminium anode for hydrogen generation

The cylindrical pure aluminium (Al) 99.5% and Al-7075 and Al-6013 aluminium alloy with 0.785 cm2 surface area are
used and compositions are given in Table 1.

First, the electrodes were coated with polyester and a copper wire provided electrical conductivity. Second, the surface
was mechanically abraded with a series of emery papers (100–1200 grit). Then, it was cleaned with distilled water and
dried with filter paper. The effect of pure (Al), Al-6013 and Al-7075 aluminium on water electrolysis…

Results and discussion

Electrochemical impedance measurements (101-105 Hz) of Pt, Pure Al, Al-6013 and Al-7075 electrodes in room
conditions are given in Fig. 2. At the point at which the curve starts, the resistance is the solution resistance (Rs). The
resistance value obtained from the intersection of the horizontal axis of the curve; load transfer resistance (Rct),
diffuses layer resistance (Rdl) and resistance of all other accumulated species (corrosion products, present molecules or
ions, etc.) (Ra) are…

Conclusions

High temperature electrolysis is more efficient economically than traditional room-temperature electrolysis because
some of the energy is supplied as heat, which is cheaper than electricity, and the electrolysis reaction is more efficient
at higher temperatures. The subcritical water condition with reasonable temperature provides a basis for the
development of a new generation of alkaline electrolysis systems [53]. The subcritical water condition reduced energy
consumption and increased…

Acknowledgement
The authors are thankful to the Mersin University research fund (2019-1-AP4-3460) and TUBITAK (2218 Post-doc
program) for their financial support.…

Recommended articles

References (52)

D. Prabakar et al.
Advanced biohydrogen production using pretreated industrial waste: outlook and prospects
Renew Sustain Energy Rev (2018)

G. Kumar et al.
Insights into evolutionary trends in molecular biology tools in microbial screening for biohydrogen
production through dark fermentation
Int J Hydrogen Energy (2018)

S.S. Kumar et al.

Microbial fuel cells (MFCs) for bioelectrochemical treatment of different wastewater streams
Fuel (2019)

S.S. Kumar et al.

Microbial fuel cells as a sustainable platform technology for bioenergy, biosensing, environmental
monitoring, and other low power device applications
Fuel (2019)

S. Nanda et al.
Subcritical and supercritical water gasification of lignocellulosic biomass impregnated with nickel
nanocatalyst for hydrogen production
Int J Hydrogen Energy (2016)

M. Balat
Potential importance of hydrogen as a future solution to environmental and transportation problems
Int J Hydrogen Energy (2008)

J. Chi et al.
Water electrolysis based on renewable energy for hydrogen production
Chin J Catal (2018)

A.D. Maksic et al.

Energy consumption of the electrolytic hydrogen production using Ni–W based activators—Part I
Appl Catal Gen (2011)

D.L. Stojić et al.

Hydrogen generation from water electrolysis—possibilities of energy saving
J Power Sources (2003)

E.A. Franceschini et al.

Kinetics of the hydrogen evolution on nickel in alkaline solution: new insight from rotating disk electrode
and impedance spectroscopy analysis
Electrochim Acta (2015)
 View more references

Cited by (10)

Recent advancement and assessment of green hydrogen production technologies

2024, Renewable and Sustainable Energy Reviews

Show abstract

Bibliometric and content analysis on emerging technologies of hydrogen production using microbial
electrolysis cells
2020, International Journal of Hydrogen Energy

Citation Excerpt :
…Besides, it is cost-effective, sustainable, and storable [5]. Therefore, renewable methods for hydrogen production are established
and developed, such as water electrolysis [6–8], photo-fermentation [9–11] and dark fermentation [12–14]. The rising of microbial
electrolysis cells (MECs) should be ascribed to the continuing pursuit of energy/resource recovery from wastewaters, especially
considering the research of (1) biohydrogen production by dark-fermentation and (2) bioelectricity by microbial fuel cell (MFC) from
wastewater.…

Show abstract

Enhanced hydrogen generation from graphite-mixed aluminum hydroxides catalyzed Al/water reaction
2020, International Journal of Hydrogen Energy

Citation Excerpt :
…Chen et al. [33] found that the hydrogen generation performance of Al–CaO–NaCl composite is improved when the CaO content
and NaCl addition are increased. Active agents have been reported to improve the activity of aluminum such as using alkali and acidic
conditions [34]. Metals, oxides, salts and graphene oxide materials have been considered in the enhancement of hydrogen generation
of Al/water system [35].…

Show abstract

Analysis of the yield and production cost of large-scale electrolytic hydrogen from different solar
technologies and under several Moroccan climate zones
2020, International Journal of Hydrogen Energy

Citation Excerpt :
…As a result, the northeast and southwest part of the country were found to be the most suitable with a hydrogen production cost of
4.7 $/kg and 8.7 $/kg respectively. Many other authors have treated this topic with different approaches for instance we cite [31–46].
For a successful transition to a hydrogen economy, several aspects should be considered which mainly consists of a good use of
renewable energy resource in order to produce hydrogen in an economically advantageous way [47], especially that the hydrogen
production cost is dominated by the cost of the electricity needed to drive the water electrolysis process.…

Show abstract

Solar water splitting for hydrogen production using Zn electrodes: A green & sustainable approach
2023, Research Square

Review on Catalytic Biomass Gasification for Hydrogen Production as a Sustainable Energy Form and
Social, Technological, Economic, Environmental, and Political Analysis of Catalysts
2022, ACS Omega
 View all citing articles on Scopus

View full text

© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

All content on this site: Copyright © 2024 Elsevier B.V., its licensors, and contributors. All rights are reserved, including those for text and data mining, AI training, and similar technologies. For all open
access content, the Creative Commons licensing terms apply.