Hydrogen Production From Water Under UV

Radiation with Carbon Dioxide Mediation

Antoni Morawski
West Pomeranian University of Technology
Ewelina Kusiak-Nejman
West Pomeranian University of Technology
Iwona Pelech
West Pomeranian University of Technology
Katarzyna Ćmielewska
West Pomeranian University of Technology
Daniel Sibera
West Pomeranian University of Technology
Piotr Staciwa
West Pomeranian University of Technology
Agnieszka Wanag
West Pomeranian University of Technology
Marcin Gano
West Pomeranian University of Technology
Ewa Ekiert
West Pomeranian University of Technology
Joanna Kapica-Kozar
West Pomeranian University of Technology
Urszula Narkiewicz (  [email protected] )
West Pomeranian University of Technology

Research Article

Keywords: Hydrogen production, carbon dioxide utilization

DOI: https://doi.org/10.21203/rs.3.rs-646517/v1

License:   This work is licensed under a Creative Commons Attribution 4.0 International License.
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Hydrogen production from water under UV radiation with carbon dioxide mediation

A.W. Morawski, E. Kusiak-Nejman, I. Pelech, K. Cmielewska, D. Sibera, P. Staciwa, A. Wanag, M.

Gano, E. Ekiert, J. Kapica-Kozar, U. Narkiewicz*

West Pomeranian University of Technology in Szczecin, Faculty of Chemical Technology and

Engineering, Department of Chemical Inorganic Technology and Environment Engineering,
Pułaskiego 10, 70-322 Szczecin, Poland

Abstract
A simple method of hydrogen production through the decomposition of water subjected to UV
radiation is presented. Water contained dissolved sodium hydroxide and the solution was
saturated with carbon dioxide gas. During saturation, the pH value dropped from about 11.5 to
7-8. The produced bicarbonate and carbonate ions acted as scavengers for hydroxyl radicals,
preventing recombination of hydroxyl and hydrogen radicals, and giving priority to the
formation of hydrogen gas.
In the presented method, the production of hydrogen is combined with the utilization of carbon
dioxide.

Keywords: Hydrogen production; carbon dioxide utilization

Introduction
The rapid development of the world economy and the growth of the number of people
are related to the high demand for energy. According to the IEA, it is estimated that by 2040
energy needs will increase by 30% [1,2]. At the same time, the scenario is proposing to reduce
more than 40% of CO2 emission during 2015-2040 period. At present EU Commission reported
that global fossil CO2 emissions in 2019 still increased by 0.9 % to a total of 38 Gt CO 2. Also,
CO2 per capita emissions have increased by ca. 15% from 4.26 t CO2/cap/year to 4.93 t
CO2/cap/year between 1990 and 2019 [3]. Therefore in order to reduce CO2 emission, the search
for new technologies with zero CO2 emissions is still attractive. One of the directions is the
splitting of water to obtain hydrogen as a fuel.

*
corresponding author: [email protected]
 The milestone was the experiment carried out by A. Fujishima and K. Honda, in which
water was more effectively broken down into hydrogen and oxygen when a semiconductor p-
type electrode with TiO2 was irradiated with visible light radiation [4].
Since then, the photocatalytic direction of research related to the decomposition of
water (water splitting) into oxygen and hydrogen has developed intensively. Then, the
decomposition of water was combined with the reduction of CO 2 to obtain hydrogen, carbon
monoxide, and useful hydrocarbons, as shown in the publication of T. Soltani et al. [5], where
selective photocatalysts for hydrogen production with reduction of CO2 were developed.
This work uses the fact that the energy of radiation with a wavelength in the UV range
is sufficient to excite the H-OH bond in water, which is 498 KJ/mol. For example, a radiation
quantum with a wavelength of 200 nm has an energy of about 590 kJ/mol [6,7].
Another fact of significant importance for these studies was the use of the inactivation
capacity of OH. hydroxyl radicals. by HCO3- and CO32- ions, formed during the saturation of
water with carbon dioxide [8], which act as radical scavengers.

Methods
The experiments were carried out in a cylindrical quartz reactor with a working capacity
of 766 cm3. A medium pressure mercury lamp TQ 150 (Heraeus, Germany) with a power of
150 W and UV-C radiation (or mercury lamp UV-A TQ 150 Z3 with lower UV-C component)
was placed in a cooler located inside the reaction vessel. The spectra of lamps are given in
Figures 1a) and 1b).
a)
 b)

Figure 1. Spectra of used lamps: a) UV-C TQ 150; b) UV-A TQ 150 Z3

The cooler was supplied with water during the experiments.

The reactor was closed in a thermostatic chamber in order to maintain stable temperature
conditions and cut off any other light source. The scheme of the reactor is shown in Figure 2.
500 cm3 of distilled water or 500 cm3 of 0,2M sodium hydroxide solution (made from
reagent grade NaOH; POCH, Poland) were poured into the reactor, and then the system was
saturated with CO2 by bubbling for 16 h. After this time, the reactor was tightly closed and the
lamp, as well as the magnetic stirrer, were turned on. The content of the reactor was irradiated
for 24 h. The gas phase from above the liquid surface was analyzed with gas chromatography
after 0 h, 2 h, 4 h, 6 h, and 24 h.
All analyzes of the gas phase composition were performed by
the chromatographic method using the SRI 310C gas chromatograph (SRI Instruments, USA),
equipped with a Porapak Q 100/120 packed column and the HID detector (Helium Ionization
Detector). The analyzes were carried out under isothermal conditions at 60°C. Helium was used
as the carrier gas. The gas flow through the column was 60 cm3/min, while the volume of the
tested gas sample was 1 cm3. The hydrogen content in the volume of the gas phase of the reactor
in subsequent measurements was calculated based on the calibration curve.

Figure 2. The scheme of the reactor for liquid phase processes

Results
We performed some preliminary and comparative experiments. In the first
experiment, 500 cm3 of water, which was not saturated with gaseous CO2, was placed in the
reactor. Water was irradiated with a UV-C TQ 150 lamp. After 6 hours of irradiation, no
hydrogen was found in the reactor.
In the second experiment, 500 cm3 of water was saturated with CO2 gas for 16 hours,
and then the UV-C lamp was turned on. In the gas phase above the water surface, the content
of hydrogen gas was analysed. The obtained results are shown below in Figure 3.
Figure 3. Hydrogen production from water saturated with CO2 under UV-C TQ lamp radiation

The measured hydrogen content increased gradually and reached 6.4 micromoles after
24 h of irradiation. These changes are not rectilinear in the experiment period. At 2-6 hours of
irradiation the rate of hydrogen formation increased to the level of 0.75 micromol/h and then
dropped to ca. 0.2 micromol/h. The overall average reaction rate hydrogen production over 0-
24 h may be estimated as 0.266 micromol/h.
The next step of the experiment was as follows: 500 cm3 of alkaline water containing 0.2 m
NaOH was saturated with CO2 for 16 h. During the UV-C irradiation with the TQ lamp, the
hydrogen content in the gas phase above the solution was measured. The obtained results are
shown in Figure 4. For comparison, an analogous experiment was performed with the use of
UV-A TQ 150 Z3 mercury lamp with lower UV-C component (Figure 5).
Figure 4. Hydrogen production by alkaline water (0.2 m NaOH) saturated with CO2 under UV-
C TQ lamp radiation.

The results presented in Figure 4 show almost a rectilinear dependence of hydrogen

concentration on time, and the reaction rate can be estimated with a constant of about 0.6
micromol/h. In the first 6 hours of the process the rate was ca. 0.83 micromol/h.

Figure 5. Hydrogen production from alkaline water (0.2 m NaOH) saturated with CO2 under
radiation of UV-A TQ 150 Z3 mercury lamp with lower UV-C component
 The measured hydrogen content increased gradually and reached 7.4 micromoles after
24 h of irradiation. These changes are not rectilinear in the experiment period. At 0-6 hours of
irradiation the rate of hydrogen formation increased to 0.83 micromol/h and then dropped to ca.
0.14 micromol/h. The overall average reaction rate hydrogen production over 0-24 h may be
estimated as 0.31 micromol/h.

Discussion
It is well known that water is sensitive to solar radiation [9]. Products of this process are
hydrogen and hydroxyl radicals:
H2O + hυ  H. + OH. (1)
Because of the short lifetime of radicals, the recombination of products occurs to produce water:
H. + OH.  H2O (2)
Another recombination ways that could be possible are as follows:
OH. + OH.  H2O2 (3)
or
H. + H.  H2 (4)
Reaction No. (2) is a support to explain why pure water without CO2 saturation in
the first experiment during UV-C irradiation did not generate hydrogen gas.
If we are interested in hydrogen production, the hydroxyl radicals OH. should be blocked
to prevent the recombination to water according to the reaction No. (2). For this purpose, we
used dissolved bicarbonate and carbonate ions formed following the mechanism presented
below. Dissolution of carbon dioxide in water results in the formation of carbonic acid which
is under equilibrium according to following reactions[8]:
CO2 + H2O  H2CO3 (5)
H2CO3  HCO3- + H+ (6)
HCO3-  CO32- + H+ (7)
Reaction No 5. is dominating at the value of pH below 8.3, reaction No. 6 is occurring at a value
of pH between 6-10, while reaction No. 7 from pH =8.3 to 11.
In our reactor the summarized saturation reactions are as follows:
2 NaOH + H2O +CO2  Na2CO3 + 2 H2O (8)
Na2CO3 + H2O + CO2  2 NaHCO3 (9)
Both bicarbonate and carbonate ions from reactions No. (6) and No. (7) respectively, are known
as quick acceptors (scavengers) of hydroxyl radicals in water [10] with constant rate:
k = 4.2x108 mol-1 xdm3s-1 for CO32- ions and k = 41.5x107 mol-1xdm3s-1 for HCO3- ions,
according to the following reactions:
OH. + CO32-  OH- + CO3-. (10)
OH. + HCO3-  OH- + HCO3-. (11)
In reactions No. (10) and (11) the reproduction of hydroxyl radicals is impossible. Hydroxyl
ions OH- could react with Na+ to NaOH and again with carbon dioxide as was pointed out in
reactions No. (8) and (9).
According to the above mechanism, the separated hydrogen radicals H. from reaction
No. (1) can freely participate in reaction No. (4) to form gaseous hydrogen H2.
The use of sodium hydroxide increases the concentration of bicarbonate and carbonate
ions during CO2 saturation. The proposed mechanism of hydrogen formation with the capture
of hydroxyl radicals acts like a pump extracting hydrogen from the water in a continuous
manner.

Conclusions
In order to obtain hydrogen gas from water, a way to prevent the recombination of the
hydrogen and hydroxyl radicals that arise in water during exposure to UV radiation is essential
and depending on the UV-C radiation component. For this purpose, the best way is to use
bicarbonate and carbonate ions, which are formed in an alkaline environment during the
saturation of water with carbon dioxide. When the pH is lowered, the hydroxyl radicals react
with bicarbonate and carbonate ions, with an irreversible inactivation of hydroxyl radicals.
In this way, the hydrogen radicals of H. combine to give hydrogen gas. The presented method
is a simple method of producing hydrogen with the utilization of CO 2 as an “extracting pump”
of hydrogen from water.

Acknowledgments

The research leading to these results has received funding from the Norway Grants 2014-2021
via the National Centre for Research and Development under the grant number
NOR/POLNORCCS/PhotoRed/0007/2019-00.
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