international journal of hydrogen energy xxx (xxxx) xxx

Available online at www.sciencedirect.com

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Integrated approach for textile industry

wastewater for efficient hydrogen production and
treatment through solar PV electrolysis

Atin K. Pathak a, Richa Kothari b,c,*, V.V. Tyagi a,**, Sanjeev Anand a
a
School of Energy Management, Shri Mata Vaishno Devi University, Kakryal, Katra, J&K 182320, India
b
Department of Environmental Sciences, Central University of Jammu, Samba, J&K 181143, India
c
Department of Environmental Sciences, Babasaheb Bhimrao Ambedkar University, Lucknow (U.P.), 226025, India

highlights graphical abstract

Utilization of textile dyeing in-

dustry wastewater with solar PV
based electrolysis.

Inverse relationship in between
hydrogen production rate and ef-
ficiency observed.

Inorganic/Steel electrode found
best in terms of hydrogen produc-
tion rate (12 V).

Maximum efficiency was achieved
with steel electrode at 3 V.

Dual benefits noticed for waste-
water selected.

article info abstract

Article history: Combining solar PV based electrolysis process and textile dyeing industry wastewater for
Received 22 September 2019 hydrogen production is considered feasible route for resource utilization. An updated
Received in revised form experimental method, which integrates resource availability to assess the wastewater
22 February 2020 based hydrogen production with highlights of wastewater treatment, use of solar energy to
Accepted 4 March 2020 reduce the high-grade electricity for electrolysis (voltage, electrode materials) efficiency of
Available online xxx the process was employed. Results showed that maximum pollutant removal efficiency in
terms of conductivity, total dissolved solids, total suspended solids, biological oxygen de-
Keywords: mand, chemical oxygen demand, hardness, total nitrogen and total phosphorus were ob-
Solar electrolysis tained from y73% to y96% at 12 V with steel electrode for pollutant load. The maximum
Hydrogen input voltage was found at 3 V for the best efficiency i.e. 49.6%, 67.8% and 57.1% with
Electrodes carbon, steel and platinum electrodes respectively. It was observed that with high voltage
Textile dyeing industry wastewater (12 V) of the electrolyte the rate of production of hydrogen was higher with carbon, steel
Pollution reduction and platinum electrodes. However, the increase in the efficiency of the production of
hydrogen was not significant with high voltage, may be due to energy loss through heat

* Corresponding author. Department of Environmental Sciences, Central University of Jammu, Samba, J&K-181143, India.
** Corresponding author.
E-mail addresses: kothariricha21@gmail.com (R. Kothari), vtyagi16@gmail.com (V.V. Tyagi).
https://doi.org/10.1016/j.ijhydene.2020.03.079
0360-3199/© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article as: Pathak AK et al., Integrated approach for textile industry wastewater for efficient hydrogen production and
treatment through solar PV electrolysis, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.03.079
2 international journal of hydrogen energy xxx (xxxx) xxx

during extra-over potential voltage to the electrodes. Hence, this integrated way provides a
new insight for wastewater treatment and hydrogen energy production simultaneously.
© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

[15,16] discussed in literature but not practically viable due to

Introduction
Water and energy are two important issues for the develop-
ment and growth of any country in today's era. Scarcity of
water is becoming a serious issue in many countries due to
high use of freshwater in the industrial sector, increasing
population supply and an increase in energy demand simul-
taneously [1]. In Asia, textile industries are sharing a good
number at industrial sector in China, Bangladesh and India [2].
They are the largest consumer of freshwater, requiring around
3e308 L/kg in different processing steps for different fabrics.
The effluent produced there contains a large amount of acid,
dyes, alkalis, hydrogen peroxide, surfactants and metals
soaps [3]. There are different processing steps involved in
textile industry which consumes a large amount of freshwater
(Table 1). Typical textile industry wastewater characterized by
high ranges of pH, colour, total dissolved solids (TDS), total
suspended solids (TSS), total solid (TS), chloride, biological
oxygen demand (BOD), chemical oxygen demand (BOD), heavy
metals, sodium etc. with colour (Table 2) in comparison to
tannery, dairy wastewater etc. [4e7].
Chemical compounds i.e. dyes are the main colour imparity
compounds on fabrics (cotton/woollen) by the process of ab-
sorption. They are mostly permanent in nature, can't be
removed via detergents etc. So, leave a mark on freshwater
resources in terms of high turbidity, which ultimately reduces
the sunlight penetration and reduces the biological and
photochemical reaction [8]. It is globally estimated that
around 1,00,000 commercial dyes are well known with an
annual production of 7  105 tons/year of dye stuff [5,8].
Different techniques like physicochemical, biochemical
and combined treatment processes have been developed with
different treatment efficiency by different researchers in
favour of textile industry wastewater treatment [3,7]. The
physicochemical and chemical treatment technologies are
usually highly efficient in terms of pollutant removal but not
much efficient in terms of energy and environmental security.
The biological treatment options among the all is being more
environment friendly and economically viable [9], but, due to
high retention time this process is not much efficient. Use of
conventional methods for textile industry wastewater (TIWW)
which consumes large energy and time is not significant.
Therefore, in search of a clean alternative way with dual
benefits is proposed here in this study with experimental
analysis. As per some researchers, electrolysis process can be
a novel approach for wastewater treatment and simulta-
neously renewable energy production in the form of hydrogen
gas with negligible greenhouse gas emissions [10,11].
Although different ways for hydrogen production including
biological process of waste conversion through dark fermen-
tation [11,12], photo-fermentation [13,14], microbial fuel cells
less conversion efficiency, applicability and process insta-
bility. Among different methods, biological hydrogen pro-
duction is less costly but it requires specific type of
environment (bioreactor, pH, temperature etc.) for the growth
of biological communities, which process the whole mecha-
nism and this process, is more restrict with organic type waste
materials only. So, at national/international level, this method
needed more research for associated challenges [11,12,16,17].
Hence, here in this article, to make hydrogen production more
cost-effective and efficient, use of solar energy is proposed in
coupling with wastewater treatment. Recent researches sup-
port the solar energy treatment options for water treatment to
convert into portable water using solar desalination, solar
photo-catalysis and solar electrolysis [18e20].
Solar electrolysis produces hydrogen which has high en-
ergy content in comparison to natural gas, or combination of
both. Ursua [21] explained that hydrogen produced from
electrolysis is 99.99 vol% pure. The production of hydrogen
with wastewater generating industries can be achieved from
solar by two different ways: (i) direct water electrolysis; (ii)
utilization of solar based electricity for electrolytic conversion
of water into hydrogen. Although, researches on direct water
electrolysis are more in comparison to second way of
hydrogen production coupled with solar energy, as per liter-
ature availability [22,23].
Whereas, Kovac et al. [24] utilizes solar energy for hydrogen
production through water electrolysis using solar power
plant. The study was conducted against single and double axis
tracking solar power plant. A novel alkaline is used as an
electrolyzer of bipolar design. The system performance was
examined for one year and results shows that design param-
eters and UI characteristics are tuned to electrolyzer for
maximum production. The hydrogen production rate was
calculated as 1.138 g/h which is capable in producing
1.234 MWh of energy.
De Fa
tima et al. [25] designed cylindrical electrolytic cell
made of acrylic with stainless steel electrode for hydrogen
production. The system is equipped with 20 W photovoltaic
panel which is exposed to direct solar radiation till mid noon.
The direct current voltage of 2.0 V, 2.7 V and 3.4 V is applied to
NaOH as an electrolyte with varying concentration. They
observed that maximum hydrogen production was achieved
with 5.0 mol/L electrolytic concentrations and 3.4 V current
voltages, the system was found stable during the various
testing process. Similarly, Paola et al. [26] worked on techno-
economic optimization of hydrogen production based on PV-
electrolysis using simulation process “RenHydrogen”.
Different tilt angles with direct/indirect connections and
electrolyzer are the optimizing process parameters of study.
Further, Boudries et al. [27] optimized the PV system design for

Please cite this article as: Pathak AK et al., Integrated approach for textile industry wastewater for efficient hydrogen production and
treatment through solar PV electrolysis, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.03.079
 international journal of hydrogen energy xxx (xxxx) xxx 3

High colour, heavy metal content, BOD, TDS and low SS

Table 2 e Characteristics of dyeing industry wastewater
[5].

High coloured, BOD, Oil and grease, SS, low pH, SS

Parameters Composition
pH 6.0e10.0
Colour (PteCo) 50e2500
TDS 1800e6000

High BOD, COD, SS, Dissolved solids

TSS 100e5000
Composition

TDS, TSS, TS, High pH, High COD

Chloride 1000e6000

High pH, SS, alkalinity, and TS

Total Alkalinity 500e800

High pH, TDS and low BOD

Sodium 610e2175
TKN 70e80
BOD 100e4000
COD 150e10,000
a
Except pH & color, all values are in mg/L.

SS, low BOD

industrial hydrogen production. The study is conducted

through simulating (HOMER) software and considered all
Sodium Hydroxides, Oils, Waxes, Fats, Disinfectants and Insecticides residues, Surfactants, Anti-

techno-economic parameters that comprise the system with

Colour, Metals, Salts, Surfactants, Organic Processing assistants, Sulphide, Acidity/Alkalinity,

the use of sun tracking system (N/S and two axis). The
maximum hydrogen requirement (3.95 ± 0,05 kWh/Nm3 H2)
for the energy generation in industry is required during the
Resins, waxes, Chlorinated compounds, Acetate, Stearate, Spent solvents, Softeners

peak solar hours, which make this study more viable and
suitable. Dahbi et al. [28] also provides their findings in favour
Table 1 e Different textile processing steps with their water consumption and specific pollutants [4,5].

of hydrogen production by simulation software (MATLAB).

During the study two different control systems (MPPT and
water flow) are simulated with PV hydrogen production and
result revealed that use of MPPT control allows enhanced
adaptation between the PV generator and electrolysis
Static agents, Soaps, Pectin, Sizes, Spent, Solvents, enzymes

whereas, the use of water flow gave the optimal hydrogen

Compounds

production rate. They suggested the use of MPPT and water

High pH, Hydrogen Peroxide, AOX, organic stabiliser

flow control for PV based electrolysis for maximum hydrogen

production on theoretical studies only. Tran et al. [29], inves-
tigated the removal of chromium from tannery industry
Sizes, Enzymes, Starch, Ammonia, Waxes

wastewater using agriculture substrates as adsorbents in

electrochemical systems and simultaneously producing the
hydrogen gas as a clean energy. The experiment was done at
low input voltage of 10 V using platinum as anode and carbon
Urea, Solvents, Colour, metals

fiber as cathode. The results revealed that after 48 h of

experimental performance, 80% of chromium removal was
observed, the various factors influencing the system efficiency
was pH value, voltage applied, dose of adsorbent and tem-
High pH, NaOH

perature. During the experiment 45e65 cc/min hydrogen

Formaldehyde

production is observed and the bagasse and straw is reported

as best adsorbent membrane during the study. Nawarkar and
Salkar [30] studied the solar powered electrocoagulation sys-
tem for municipal wastewater treatment and found as a sole
unit. The effect of different operating parameters was studied
Amount of water
Discharge (L/kg)

on the COD and TDS removal rate. The optimum condition

was found at 40 A/m2 current density and 20 min with 92.01%
232e308
26e43

3e124

8e300

8e300
5e250

COD and 93.97% TDS removal efficiency. Ahad and Klerk [31]
3e9

worked on the production of water and oil by utilizing Kolbe

electrolysis process for Fischer-Tropsch synthesis. The Kolbe
electrolysis process is one of the potential technology for acid
water treatment as suggested. The final product of the elec-
trolysis process includes methane, ethane, CO2 besides
Processing

Mercerizing
Bleaching

hydrogen. The parameters influencing the electrolysis process

Finishing
Scouring
Desizing

Printing
Textile

Dyeing

are temperature (10e30  C), the current density required

Steps

is  3% for acetic acid conversion. The water electrolysis is

observed and become dominant after 2.5 h of operation with

Please cite this article as: Pathak AK et al., Integrated approach for textile industry wastewater for efficient hydrogen production and
treatment through solar PV electrolysis, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.03.079
4 international journal of hydrogen energy xxx (xxxx) xxx
time on stream. The system consumes high voltage of 29 V
which increases the overall energy consumption 2 GJ/kg
acid. The result is concluded with Kolbe electrolysis process is
not technically viable in compare to other alternative elec-
trolysis like electrohydrolysis etc.
Therefore, solar electrolysis concept is feasible on practical
level for hydrogen production but optimization of influencing
parameters like electrolytic concentration, voltage applied,
temperature and electrode materials are required. Among
various parameters, electrode materials also cited as an
important one for efficient hydrogen production rate.
Different researchers have utilized different electrodic mate-
rials (steel, aluminium, iron, platinum, nickel etc.) during their
experimental analysis. The search of best quality electrode
material is still under process [25e27,32,33] in results and
development sector.
According to above cited researches and others also, very
less number of works with dual objectives of hydrogen pro-
duction with wastewater treatment in coupling with PV
panels are reported. Researchers have utilized different elec-
trolytic units and commercial available electrolyzer during
their study for hydrogen production. The major limitations
are the use of commercial electrolyzer which make it costly
and requires large quantity of artificial electrolytes (use of
fresh water). Therefore, the novelty of this work is related to
the use of solar PV for electrolysis of industrial wastewater as
an electrolyte which will be a sustainable option. The goal of
this study is to determine the efficiency of the system in terms
of hydrogen production process and pollutant removal with
three electrodes i.e. organic (carbon) and inorganic (steel and
platinum) at selected voltages. These electrodes have been
chosen on the basis of their reactive performance to analyse
the hydrogen production rate (HPR) and pollutant removal
efficiency from textile dyeing industry wastewater (TDIWW).
Although, electrolysis with any type of electrolyte is an energy
demanding process therefore the replacement of chemical
electrolyte from wastewater is an innovative approach in an
era of freshwater crisis and utilization of solar PV for elec-
tricity provides a sustainable solution for high grade elec-
tricity option in this proposed study.
Materials and methods
This section describing the four objectives delineated for
present study: description of experimental setup; Wastewater
(electrolyte) collection for analysis, efficiency of the process
(voltage and electrode based HPR) and pollutant removal ef-
ficiency. Electrochemical device is utilized to carry electrolysis
process which disassociates water into oxygen (O2) and
hydrogen (H2) gas. The minimum voltage required for disso-
ciation of water is 1.229 V [24]. The overall electrolytic reaction
is given by:
1
H2 O / H2 þ O2 (1)
2
The best result was found with the alkaline electrolytes.
The reaction inside the electrolytic unit can be expressed as:
Please cite this article as: Pathak AK et al., Integrated approach for textile industry wastewater for efficient hydrogen production and
treatment through solar PV electrolysis, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.03.079
1
H2 O þ e / H2 þ OH ðCathodeÞ (2)
2
1
H2 O / 2Hþ þ O2 þ 2e ðAnodeÞ (3)
2
These methods employ metal electrodes for anode and
cathode. When voltage is applied to both the electrode coag-
ulation process occur due to development of coagulant at
anode of metals ions used as anodic material. At cathode
hydrogen and hydroxyl ions generated which causes the
floatation of coagulated compounds.
Experimental setup
Hoffmann voltammeter was used as an electrolysis instru-
ment (Fig. 1.) for experimental procedure. The capacity of the
Hoffmann voltammeter was 150 mL capacity with two col-
lecting tubes graduated downwards from 0 to 50 mL in an
increment of 0.2 mL. Electrodes are used from the lower end of
tubes and sealed by using rubber stoppers to avoid the leakage
of wastewater as well as produced gas. The gases produced at
cathode and anode was collected through water displacement
method [33]. The average temperature of room during the
experiment is measured between 25 and 30  C. The system
was connected to DC voltage supply assisted through solar PV
based inverter system. To gain maximum output from the
solar panel (750 kW capacity) are installed at rooftop of School
of Energy Management, Shri Mata Vaishno Devi University,
Katra, J&K (India) facing south which provides maximum ef-
ficiency. The output is stored in two batteries rating through
solar Su-Kam inverter (1000 W), which convert DC to AC. The
DC current provided for the experiment is converted through
Crown DC voltage converter for constant supply of current.
Specifications for experimental setup are discussed in
Table 3. The electrolytic solution used for the study is TDIWW.
Different electrode materials, organic (carbon) and inorganic
(steel and platinum) are utilized in the experimental
procedure.
Sample collection and analysis
Wastewater is collected from dyeing industry through com-
posite sampling method from the industry situated at Panipat
district in Haryana, India. The analytical characteristics of
wastewater collected were shown in Table 4. Collected sam-
ples stored at 4  C in sterile bottles to prevent its degradation
and contamination and filtered through 1 mm sieve to remove
larger particles. The parameters selected are: temperature,
pH, TDS as procedures of American Physical Health Associa-
tion, 2012 (APHA) [34]. pH was measured with Hanna handy
pH meter, TDS, conductivity was measured with Hanna (HI
98194) multi-parameter kit. Hardness was analysed by titri-
metric method and chemical oxygen demand (COD) by reflux
method. Total suspended solid and total solid was analysed by
standard procedure from APHA, total nitrogen was analysed
by Kjeldahl digestion method and total phosphorus was
measured by spectrophotometric method [34]. All parameters
were analysed in triplicate. A lab grades chemical (Hi-Media,
 international journal of hydrogen energy xxx (xxxx) xxx 5

Fig. 1 e Arrangement of different components of experimental setup (a) Photographic view (b) Schematic view.

Mumbai) was used to perform the experiment. Colour in-
tensity of the wastewater was analysed after filtering the su-
pernatant by Whatmann filter paper 100 through
spectrophotometer (Shimadzu Model: UV-1800 240 V, Serial
no. A116353) by absorption at different wavelength ranging
from 190 to 700 nm. After parametric analysis, wastewater
collected found to be suitable to use as an electrolyte due to
presence of good ionic concentration.
Electrode materials
In this section, different electrodes utilized during the exper-
imental process are explained and discussed. The merits and
demerits of electrode material are tabulated in Table 5. In the
present study, three different electrodes carbon (organic) and
steel and platinum (inorganic) are selected for study. Elec-
trodes are selected on the basis of three criteria i.e. (i)

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treatment through solar PV electrolysis, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.03.079
6 international journal of hydrogen energy xxx (xxxx) xxx

Table 4 e Characterization of textile dyeing industry

Pmax 250 W; Voltage (Vmax) 36 V; Current (Imax) 7.00 A; Open Circuit Voltage (Isc) 7.60 A; By Pass
wastewater.
Parameters Initial Permissible limit [31]
a
pH 8.62 ± 0.1 5.5e9

Diode Rating 20 A, Series Fuse Rating 15 A; System Voltage 1000 V DC; Safety Class II
Conductivity 5455.4 ± 54 e
TDS 3884.7 ± 16 e
TSS 215 ± 81 200
TS 4099 ± 94 e
BOD 402 ± 17 100
COD 11363.4 ± 61 250
Hardness 1118.4 ± 55 e
Total Nitrogen 78.2 ± 14 100
Total Phosphorus 6.7 ± 36 5.0
a
Except pH and Conductivity (mS/cm) all values are in mg/L.
Error

Table 5 e Merits and demerits of organic and inorganic

electrode material.
Properties Organic Inorganic
Electrode Electrode
Availability High Moderate
Bio-degradability High Low
0.1 V and 1 mA resolution

Conductivity Low High

Density Low High
Economic viability High Moderate
Effect on human health Low High
Environmental stability High Low
Error 0.1 mL

Nature of electrode Non-metallic Metallic

Reaction time Moderate High
0.1 V

Reactivity with Low-reactivity High-reactivity

substrates
e
e

Resistivity High Very low

Retention time Moderate Low
150 mL capacity, 50 mL for both collecting tubes, graduated in

Sustainability More Less

Thermal conductivity High Low
3  250 W solar panel connected to inverter system

conductivity; (ii) density; and (iii) cost to assess the rate of

hydrogen production through lab-scale electrolysis unit.
Textile Dyeing Industry Wastewater (TDIWW)

1000 W DC to DC and DC to AC; Two battery

Platinum- Area (0.1 ± 0.2 cm2), Purity (99.02)

Conductivity, is the fundamental property, which quantifies

Steel- Area (1.07 ± 0.23 cm2), Purity (99.57%)
Carbon- Area (23 ± 1.5 cm2), Purity (99.05%)

the material's resistance/conductance towards electric cur-

Specifications

rent. Materials are classified as metals, semiconductors and

0e50 mL with Increment of 0.2 mL

insulators. Metals are considered to be as the most conductive

due to their inversely proportional nature towards resistivity.
In simple words, high resistivity means lowest conductivity to
Table 3 e Specifications for experimental setup.

1.23 V, 3 V, 6 V, 9 V, 12 V

applied electrical current due to presence of an electron con-

duction band. The conductivity of the material also increases
downward direction

with increase in cross sectional area of electrode whereas,

length shows an inverse impact with increase in length (L) and
0.01 Ve30.0 V

decrease in conductivity (sÞ of the material. Mathematically,

expressed as:

A
r¼ (4)
sL
Solar Inverter with battery

Furthermore, density and conductivity also shows direct

Process parameters

relationship to each other but inverse with resistivity. Hence,

DC voltage regulator
Electrolytic solution

Solar power supply

the relationship between electrical conductivity and density

Electrode material

for the selected materials is in an agreement with percolation

theory [35]. Economic viability of electrodic material is also
Voltameter

considered as one criteria with others. Because, overall pro-

Voltage

duction process with efficiency always includes the cost of

raw materials used for cost-effectiveness.

Please cite this article as: Pathak AK et al., Integrated approach for textile industry wastewater for efficient hydrogen production and
treatment through solar PV electrolysis, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.03.079
 international journal of hydrogen energy xxx (xxxx) xxx
Organic material
Carbon is used as a non-metallic element with low reactivity
and high biodegradability. The conductivity of carbon
(1.25  103 S/m) is very less in comparison to steel and plat-
inum but the cost of the material is very less. The carbon is
used as an electrode material with a specific area of
23 ± 1.5 cm2 with 99.05% purity. The material is organic in
nature and economically viable to be used as a sustainable
point of view.
Inorganic material
Steel and platinum are used as an inorganic electrode material
during the study. The steel is an electrode material with
moderate conductivity (1.45  106 S/m) and cost. The surface
area of steel electrode is 1.07 ± 0.23 cm2 with 99.57% purity
index. Platinum electrode is used to examine the rate of
hydrogen production rate due to its high conductivity
(9.43  106 S/m) and purity 99.02% with surface area of
0.1 ± 0.02 cm2. Platinum is one the noble metals found on
earth with very less reactivity and high conductivity.
Efficiency of the process
The electrolysis efficiency of the system is defined as ratio of
electrical energy input to the chemical energy of hydrogen
produced in the electrolysis process. The electrolytic effi-
ciency of the system is calculated as [20]:
mhRP
h¼
VI
where, h is efficiency (%), m stands for mass flow rate of
hydrogen (kg/sec), hRP is the enthalpy of combustion of
hydrogen (J/kg), V is the applied voltage to the electrolyte
(Volt), and I is the current (A).
Whereas, efficiency of hydrogen produced during the
wastewater electrolysis process can be calculated as:
VH2 real
Eff ð%Þ ¼  100
VH2 ideal
Ideal volume of hydrogen can be calculated by using Far-
aday's Law of electrolysis equation:
I  Vmass  ti
VH2 ideal ¼
2F
where, I stand for the current (in Amps) which passes through
the electrolytic cell during the time period (ti), F is Faraday's
number (96485 C/mol) and Vmass is the ideal gas molar volume
under standard conditions (298.15 K and 1 atm).
Pollutant load remediation
The pollutant load removal efficiency is calculated in terms of
initial and final parameter [7]:
IO  IF
Pollutant removal efficiency ¼  100
IO
Please cite this article as: Pathak AK et al., Integrated approach for textile industry wastewater for efficient hydrogen production and
treatment through solar PV electrolysis, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.03.079
7
where, Io denotes initial parameter and IF stands for final
parameter after treatment for electrolysis process.
Results and discussion
In present study, the experimental investigation of solar PV
based electrolysis process has been carried out for wastewater
treatment and hydrogen production with two types of elec-
trodes (organic (carbon)) and inorganic (steel and platinum) at
different operating voltages i.e. 1.23 V, 3 V, 6 V, 9 V and 12 V.
Based on the investigation, process efficiency of the system
has done with the help of Eq. (5)e(7) and pollutant load
remediation on the basis of Eq. (8). In this section, the pa-
rameters affecting the experimental process including
voltage, electrode material and HPR have investigated with
experiments.
Characterization of wastewater used as an electrolyte
The wastewater collected and analysed from Textile Dyeing
Industry Wastewater (TDIWW) has a high values of parame-
ters and compared in terms of permissible limits of discharge
by Central Pollution Control Board, Government of India
(CPCB) [36]. The pH, conductivity and TDS were found as 8.6,
5455 mS/cm and 3885 mg/L respectively. It's well known
concept that electrolysis efficiency totally depends on the
presence of ionic strength in electrolyte and by passing direct
current (DC) through it. Ionic concentration in the TDIWW,
(5)
favour of its use as electrolyte i.e. high conductance and high
value of total dissolved solids. Hence, electrolyte is a waste-
water solution is more conductive due to high TDS and other
conductive ions. pH is alkaline in nature of selected waste-
water (8.6), so the half-reaction mechanism maybe as in vol-
tammeter cell, dominated by OH ion:
Cathodic half-reaction:
4Hþ þ 4e /2H2 (9)
(6)
Anodic half-reaction:
4OH / O2 þ 2H2 O þ 4e (10)
Overall reaction:
(7)
2H2 O / 2H2 þ O2 (11)
It can be observed from reaction that, the ions present in
wastewater, dissociated and performed with the conditions
selected for optimization and responsible for high conduc-
tance, without interfering the overall electrolysis process, as
observed here in this study. Prades et al. [37] also suggested
that parameters (TDS, Hardness, Phosphate, Potassium,
Chloride, Calcium, Sodium and Magnesium) with values
1000 mg/L, 358.7 mg/L, 210.0 mg/L, 3560 mg/L, 477.0 mg/L,
1310.0 mg/L, 480.0 mg/L and 150.0 mg/L, best use aqueous
solution as an electrolyte and results of present study sup-
(8)
ported by this.
8 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 3 e Efficiency variation at varying voltage through

Fig. 2 e Effect of voltage on HPR with carbon, steel and different electrode.
platinum electrode.

sectional area but due to low ions transfer as compared to

Impact of electrode materials for hydrogen production rate
inorganic electrodes produces low hydrogen.
with voltages and textile dyeing industry wastewater
Impact of electrode material and cross sectional area on the
Hydrogen production rate with different electrode materials
hydrogen production rate and efficiency of the process
(Organic and Inorganic) at 1.23 Ve12 V using TDIWW were
selected to assess the potential. The HPR with different
The efficiency of the system in respect of hydrogen production
selected voltages using organic (carbon), inorganic (steel and
rate was different for various voltages with all three elec-
platinum) were presented in Fig. 2. It has been found that with
trodes, as depicted in Fig. 3. The efficiency of the system was
increase in voltage, rate of hydrogen production increases.
calculated using Eq. (4)- (6). The efficiency of the system de-
The highest HPR of 16.4 mL/h was found to be significant with
creases with increase in HPR at voltages 1.23 Ve12 V. The
steel electrode at 12 V. This may be due to increase in size of
hydrogen production varies with increasing voltage but due to
bubble formation, which leads to formation of flocs and in-
high voltage and current intensity the rate of HPR increases
creases the rate of hydrogen production [38]. High voltage acts
but efficiency of the system decreases. The efficiency of the
like an electrical pressure that pinches the coulombs through
system is maximum with low voltage as less energy is utilized
the circuit [39]. Furthermore, carbon and platinum also
during the process. But, in the present study the higher
showed highest HPR at 12 V only i.e. 11.5 mL/h and 14.9 mL/h.
voltage can be considered with high hydrogen production as
Kargi [40], in his research investigate the effect of three elec-
solar PV based system is utilized for energy supply as it is
trodes (stainless steel, aluminium and graphite) for hydrogen
green energy with less carbon emission. The efficiency of the
production. Results with steel electrode found to be 4.32 L/day
system was found maximum (67.8%) with steel electrode at
but researcher used the process of electrohydrolysis for
3 V as efficiency of the system compared to platinum (57.1%)
organic wastewater at 13.5 V. The effect of voltage for
at 3 V and carbon electrode (49.6%). The different variation in
hydrogen production with different electrodes depict that
efficiency of the system is presented through Table 6. Elec-
high voltage shows high HPR. The rate of HPR increases with
trode produces current due to which hydrogen production
cumulative voltage increment. The various researchers have
rate enhanced at higher voltage and utilized high power to
worked on different voltage variation to examine the most
produce hydrogen.
effective one for hydrogen production [41]. Oz Ayman with his
It can be clearly observed from Fig. 3, the HPR of platinum
co-workers [38] examined best voltage for hydrogen produc-
electrode is high at 1.23 V in compared to steel and carbon and
tion from olive mill wastewater and found that 8 V is best
the efficiency of the system is 54.2% whereas, with carbon
suited for hydrogen production; whereas other researchers
efficiency is only 21.2% and steel has 34.2%. But, the rate of
have worked with low voltage and high voltage from different
increment was observed with steel and carbon from 3 V to
industrial wastewater [42,43]. In another study, pulp and
12 V. Increasing the voltage decreases the efficiency of the
paper mill industry was pre-treated at high voltage 15 V and
system from 49.6% to 24.8% in case of carbon electrode and
found effective with findings. Hence, it can be observed from
67.8%e19.7% with steel electrode. The rate of efficiency with
the figure that hydrogen gas formation escalates with applied
platinum also decreases with increasing voltage. So, general
voltage from 1.23 V to 12 V. The loss in the weight on electrode
trend of increase in relationship between voltage and effi-
decreases the HPR [9]. As, per our findings, area increases the
ciency was observed, it may be due to high electron transfer
rate of formation of hydrogen, reason for high HPR with steel
rate. Furthermore, rate of increment was observed up to 3 V
electrodes because it has large cross-sectional area in com-
but then after there was fall in efficiency observed after that,
parison with platinum. In comparison carbon has large cross-
although rate of decrease at 6 V is minimum from 3 V but the

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 international journal of hydrogen energy xxx (xxxx) xxx 9

Table 6 e Comparison of hydrogen production rates and efficiency of the system from different electrode with other
properties.
Electrode Density Thermal Electrical Diameter Length Cross- Voltage Current HPR Efficiency
material (gm/ conductivity conductivity s (S/m) (cm) (cm) section area (V) (mA) (mL/ (h)
cm3) (W/mK) at 20e25  C (cm2) h)
Carbon 1.24e2.26 2000 1.25  103 0.44 7.86 0.131 1.23 0.0058 0.52 21.2
3 0.00431 2.2 49.6
6 0.00524 4.4 40.8
9 0.01 8.7 28.2
12 0.0112 11.45 24.8
Steel 8.94 45 1.45  106 0.03 7.82 0.041 1.23 0.006 0.9 34.2
3 0.002 1.4 67.8
6 0.006 8.1 63.5
9 0.012 9.4 25.0
12 0.020 16.3 19.7
Platinum 24.3 77.8 9.43  106 0.1 0.1 0.001 1.23 0.0042 0.96 54.2
3 0.0032 1.8 57.1
6 0.0093 7.3 38.2
9 0.0255 9.1 15.3
12 0.041 14.9 8.8

difference was more from 9 V to 12 V with all type of elec-
trodes used. Hence, efficiency found at 3 V was an optimized
range of voltage process of hydrogen production with TDIWW.
Comparison of different electrodes for electro-hydrolysis
process is found with aluminium (74%) as a most efficient
electrode material followed by stainless steel (42%) studied by
Kargi [40]. When compared from the present study found that
the present system is more efficient with different voltage and
electrode for wastewater removal. Kothari et al. [33] worked
on the different electrolyte concentration of different
composition (10%, 25% and 50%) with varying voltages from
1.8 V to 12Vwith two different electrode materials (steel and
platinum). The result of the study revealed that increasing the
voltage from 3 V to 12 V, decreases the efficiency of the pro-
cess from 37.1% to 11.9% with platinum electrode and 10%
electrolyte concentration and 40.5%e9.3% in case of steel
electrode with same electrolyte. Whereas, positive increase is
observed from 3 V to 1.24 V but below this again the efficiency
of the system start decreasing. The result shows that positive
relation with the present experimental data of increasing the
voltage decreases the efficiency of the system. In another
study, Buddhi et al. [32] study the effect of electrolyte con-
centration on HPR and found that increasing the dissolved
solid concentration with 6.0 V showed maximum efficiency
(12.7%) whereas, increase in voltage from 6 V to 12 V the ef-
ficiency has decreased from 12.7% to 9.8% with high TDS
(42.4 gm/L). In another study, hydrogen production from olive
mill wastewater with simultaneous COD removal was
observed by Kargi and Catalkaya [43] and found maximum
efficiency at 2 V. The all result from previous studies has a
supportive relation with the present study of increasing the
voltage decrease the efficiency of the system in vertical
observations.
But, on comparative basis, platinum as electrode material
found to be more effective in terms of efficiency (54.1%), than
steel and carbon at 1.23 V. It may be due to non-reactive na-
ture of electrode material. Further, a variation in nature of
results for efficiency was observed at 3 V i.e. 67.8% with steel
electrode in comparison to others, due to large area and
conduciveness of electrode. Hence, efficiency of any process
very much depends on the type of electrode used in integra-
tion with voltage provided.
Furthermore, materials and area of electrodes play an
important role in hydrogen production rate with efficiency.
Present study involves the use of organic and inorganic ma-
terials like carbon, steel and platinum. The selection of elec-
trode material is based on the variation in their conductivity,
cost and density as discussed in Electrode materials. The se-
lection is further categorised on the material properties as
detailed in Table 5. The conductivity of the material as one of
the critical parameter affecting hydrogen production rate de-
pends largely on the resistivity of the material. Another aspect
in the appropriate choice of other physical parameter as
length and the cross-sectional area which largely influence

Table 7 e Comparison of hydrogen production rate with different electrode material and area.
Electrode Resistivity r (U
m) Electrical Thermal Dimension of Hydrogen production Reference
material at 20  C conductivity conductivity electrodes rate (L/d)
s (S/m) at 20  C W/(m$K)
Diameter Length
(cm) (cm)
Platinum 1.06  107 9.43  106 77.8 5 5 64.8 [41]
Aluminium 2.82  108 3.5  107 205.0 0.9 49.5 16.33 [35]
Nickel 6.99  108 1.43  107 91 0.2 7.0 11.04 [23]
Steel 4.60  107 2.17  106 50.2 0.11 4.01 0.194 Present study
Platinum 1.06  107 9.43  106 77.8 0.1 0.1 0.175 Present study
Carbon 5  104 to 8  104 1.25 to 2  103 1000 0.44 7.86 0.105 Present study

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10 international journal of hydrogen energy xxx (xxxx) xxx
the conductivity and hence the hydrogen production rate. The
influence has been shown in the respective Figs. 2 and 3 and
Table 6. The conductivity of the electrode material can be
calculated by using Eq. (4), which clearly explains the property
of materials conductive nature.
The present study involves the choice of electrode based on
the conductive nature and accordingly to balance the con-
ductivity of all electrodes, the variation in area of the mate-
rials is done. Platinum electrode with highest conductivity
and cross sectional area of 0.001 cm2 is taken in to consider-
ation with 0.1 cm (length) and 0.1 cm (diameter). Whereas,
steel electrode with cross sectional area 0.041 cm2 is utilized
with 4.0 cm (length) and 0.108 cm (diameter) and carbon
electrode of 0.131 cm2 cross sectional area with low conduc-
tivity is utilized with 7.8 cm (length) and 0.44 (diameter). The
results of the present study clearly supported by the previous
researches i.e. platinum with high conductivity shows high
hydrogen production rate followed by steel and carbon. The
hydrogen production rate from different electrodes are tabu-
lated in Table 7. Kargi [40] in his research work also reports
that high hydrogen production rate depends on electron
releasing/transfer rate due to electrical conductance. Simi-
larly, Givirovskiy et al. [44] also disclose their research studies
with different electrode materials for electrolysis and clearly
justified that hydrogen production rate is directly proportional
to the conductance of material. Experimental results of the
study are fundamentally supported by this. The material of
the electrode has a major impact on hydrogen production rate
due to difference in their electrical, thermal conductivity and
density. It can be observed from Table 7 that high conductive
material (platinum) produces high hydrogen per day in
compare to the less conductive material (steel and carbon).
Deviation in area and length of the electrode also influence the
hydrogen production, as discussed by Nagai et al. [45]. The
higher rate of hydrogen production is reported with small
length of electrode and this is due to the fact that average void
fraction between electrode is larger in high length electrode in
comparison to the small length when mass flux of gas is
uniform on both electrodes with hydrogen and oxygen bub-
bles being densely pack at the upper end between both the
electrodes. The length of electrodes plays a major role in
deciding the optimum space between electrodes. The increase
in space between electrodes decrease the rate of hydrogen
production. The formation of hydrogen and oxygen gas is
related proportionally to current density, the volume flux of
oxygen (O2) and hydrogen (H2) gas generated from the region,
can be calculated from Eq. (12).
3 RT FW
dx (12)
4 P F
where, R stands for universal gas constant; T is temperature
(K); P is pressure (Pa); F is the Faraday constant (9.65  104, C/
mol), W stands for diameter of the electrodes (m); ɸ stands for
current density (A/m2).
This relation shows positive interaction between electrode
material as high conductivity material transfer high current
density. Whereas, increase in area directly increases the dis-
tance between electrode which effect the rate of formation of
hydrogen. The platinum with lowest area shows low
hydrogen production rate due to increase in the distance
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treatment through solar PV electrolysis, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.03.079
between the electrode material/void fraction. The average
void fraction between electrodes can be calculated from Eq.
(13). The diameter of the electrode also plays a significant role
in hydrogen production rate, higher the diameter, lesser the
distance between electrode. In present study, the diameter of
the steel electrode is larger than platinum electrode, which
shows a significant increase in the rate of formation of
hydrogen whereas, carbon with larger area and larger diam-
eter shows lesser hydrogen production rate due to the low
current density transfer rate as it can also be clearly observed
from Eq. (13), that current density is directly proportional to
the void fraction which leads to the hydrogen formation rate:
ZL
1 3 RT FL
aav ¼ adx ¼ (13)
L 8 P Fud
0
whereas, aav stands for average void fraction; L is the length of
the electrode (m); u stands for the velocity of rising bubbles.
In the present study, economic viability of the system was
also studied with selection of electrode and maximum effi-
ciency with lower cost. It can be clearly observed that plat-
inum shows high efficiency besides lowest area in
comparative to organic (carbon) electrode whereas steel
shows high efficiency due to more surface area. The results
obtained clearly supports that cost of material and conductive
nature make system more economically sustainable. So, most
conductive and costly platinum procured with lowest area
followed by steel (moderate cost with conductive nature) and
carbon (low-cost with conductive nature). Therefore, steel and
carbon are found to be significant with experimental findings
on part of cost also for hydrogen production and efficiency
both. Although, results with platinum are good enough but
cost involvement approximate in respect of carbon is 93.2%
higher whereas with steel it is 95.7% higher. Whereas, when
same amount or area of platinum is taken as of carbon the
cost gets increased by y 237% and if same area as of steel is
taken the cost of the platinum increased up to y100%.
Therefore, when all electrodes compared on the basis of effi-
ciency and economic viability the steel electrode proves to be
the best solution with high efficiency and economically fitted
for solar electrolysis process with wastewater treatment fol-
lowed by carbon and platinum as per this study finding.
Further, keeping in view the above, variation in area of the
electrode is done to maintain the conductivity of all electrode
materials equal to observe the impact of material on hydrogen
production rate. The above study is an attempt to evaluate the
influence of electrode material on rate of hydrogen production
rate. The experiments involved various interactive ap-
proaches for the optimum choice of material, area, weight etc.
So, as to ascertain the authenticity of the experiment. The
confirmation for the same is being endorsed with the results
as obtained and validated with previous studies as discussed
in this and previous sections.
Integrated approach for pollutant removal with hydrogen
production rate
The TDIWW is rich with pollutant load as detailed in Table 1.
Solar PV based electrolysis process is one of the new in its type
due to direct utilization of energy/power produced during the
 international journal of hydrogen energy xxx (xxxx) xxx
sunshine hour and use of stored energy during no sun/night
through storage method. This hybrid system provides no
greenhouse gas emission and carbon foot print for wastewater
treatment. The reaction which takes place during the removal
of pollutant from wastewater with various electrodes at anode
and cathode, may be as:
DYE þ monomeric metal ions/½DYE  monomeric metal ionðsÞ
DYE þ polymeric metal ions/½DYE  polymeric metal ionðsÞ
Organic=inorganic compounds / nHþ þ decomposed organics
(14)
n Adsorption:
nHþ þ ne / ðgÞ (15)
2H2
The wastewater produces more hydrogen as compared to
simple water due to high organic and salt content which en-
hances the rate of formation of ions and eventually resulted in
high hydrogen production with pollutant removal efficiency.
The solar electrolysis study resulted in various pollutant's
removal in integration with HPR simultaneously which were
studied in terms of pollutant removal efficiency with different
electrodes at various voltages.
TDIWW was initially characterized on the basis of colour
which is basically due to high dye (azo-dye, organic dye etc.)
content. As, it harms the aquatic life of water by inhibiting
light to penetrate deep in the water [46]. These dyes are
complex in nature and causes cancer as a prolonged intake.
Hence, it is the primary objective of any removal method to
reduce the colour intensity of the wastewater. The present
study is utilized to decrease the colour intensity of wastewater
by PV solar based electrolysis process with varying voltage
and different electrodes material. The wastewater utilized is
dark blueish in colour which turned to nearly light blue colour
after electrolyte treatment. The maximum absorbance peak
was obtained at 609 nm which shows the presence of eCH and
benzene rings [47]. The result was revealed against 609 nm for
removal efficiency. The maximum removal efficiency of 72.7%
was found at 12 V with steel electrodes. The minimum
removal efficiency of 63.3% was reported with carbon elec-
trode at 1.23 V. The removal efficiency increased with
increasing voltage from 1.23 V to 12 V for all selected electrode.
The significant decrease in absorbance was observed in all
cases with increasing voltage and time. The electrolysis pro-
cess is effective in removal of colour up to 91% [48]. Different
other processes like biological and chemicals cited with high
removal in long course of time but they are not environmental
friendly due to high use of chemicals. But, during electrolysis
process dye forms precipitate with metal ions produced at
electrodes which is interdependent on pH of the process
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treatment through solar PV electrolysis, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.03.079
11
explained through Eqs. 13e16. Although many intermediate
compounds forms and break during this process which helps
in decolourization of wastewater, reason for removal effi-
ciencies achieved in current study above than 50% for all
experimental setups.
Precipitation
ðpH ¼ 4:0  5:0Þ (16)
ðpH ¼ 4:  5:0Þ (17)
DYE þ metal hydroxidesðsÞ /½Particle (18)
DYE þ polymeric metal ionsðsÞ þ metal hydroxidesðsÞ /½Particle
(19)
pH of the wastewater was increased from 8.62 to 8.85, 8.82,
8.76, 8.71 and 8.67 with carbon electrode, 8.92, 8.85, 8.77, 8.71,
8.69 with steel electrode and 8.81, 8.76, 8.72, 8.67, 8.64 with
platinum electrode at 12 V, 9 V, 6 V, 3 V and 1.23 V respectively.
The increase in pH was observed with all electrode and
increasing trend were observed from low to high voltage this is
due to the formation of Hþ during hydrogen production from
wastewater hence leading towards the pH of the experimental
setup with increasing time. The pH increment leads towards
more pollutant removal due to formation of metal hydroxide
explained above with Eq. (13)- (14). In different experiments the
similar result was also observed at the end of process [49].
Turbidity were observed through turbidity meter and
found that 85 NTU is present in initial wastewater which is
reduced up to 80.0%, 75.3% and 69.4%, at maximum scale with
steel, platinum and carbon electrode respectively at 12 V. The
maximum of 51 NTU removals were observed with steel
electrode due to high rate of ions development. The removal
was found maximum at 12 V due to high rate of transfer of
electron and bubbles formation which resulted in breakdown
of different solid particles which leads in decrement of
turbidity. The highest removal above 90% turbidity was
observed with olive oil mill wastewater through hydro-
electrolysis process in one of the recent experiment per-
formed by Oz Ayman [38].
The removal efficiency of conductivity from TDIWW de-
creases from y5455 to y210 with steel electrode at 12 V which
leads to 96.1% removal. The conductivity removal is achieved
due to removal of ions present in the wastewater which
combines to form precipitate or flocs which leads in pollutant
removal. It is also stated that conductivity is an important
12 international journal of hydrogen energy xxx (xxxx) xxx

100.0

Removal Efficiency (%)

80.0 12
9
60.0
6
40.0
3
20.0 1.23

0.0

Parameters

(a)

100.0
12
80.0
Removal Efficiency (%)

9
60.0
6
40.0 3
20.0 1.23

0.0

Parameters

(b)

100
Removal Efficiency (%)

80
12
9
60
6
40
3
20 1.23
0

Parameters

(c)

Fig. 4 e Removal efficiency of wastewater parameters with different electrodes (a) organic (carbon); (b) inorganic (steel); (c)
inorganic (platinum) at 1.23 V, 3 V, 6 V, 9 V, 12 V

factor affecting the rate of electrolysis and simultaneously shows effect of different electrode from 1.23 V to 12 V. It can be
hydrogen production. observed that solid content was removed with great extent.
Different solid content removal in terms of total solid, The treated wastewater was kept for 8 Hrs for total solid (TS)
dissolved solid and suspended solid is examined. Fig. 4 (a)e(c) and total suspended solid (TSS) to settle down. Although

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 international journal of hydrogen energy xxx (xxxx) xxx
dissolved solid remove during the experimental process as
different ionic floc forms during the process helps in extrac-
tion/removal of dissolved solid. The maximum of 89.2%
removal of TS solid were achieved with 84.7%, 89.5% TSS and
TDS removal at 12 V with steel electrode. Whereas, organic/
carbon electrode shows little less removal in case of TDS and
TS but slight less in case of TSS at 12 V due to less or no for-
mation of metal ions. The different researchers have achieved
with same removal efficiency in case of different wastewater.
The solid content mainly consists of different organic and
inorganic pollutant in form of nitrogen, chloride, phosphate
etc. The attraction of different ions towards their specific
alternative charged poles helps in solid removal and other
pollutant removal.
Biological oxygen demand (BOD) is considered one of the
major pollutants in TDIWW. The textile wastewater is mainly
characterized on the basis of BOD removal as it affects the
aquatic life this is mainly due to the presence of different
chemical, metals and other inorganic compounds in the
textile wastewater [50]. The wastewater used in this study is
high with BOD content of 402 mg/L which was removed up to
108 mg/L with steel electrode (73%) at 12 V. In case of carbon
and platinum electrode the decrement in COD was observed
up to 117 mg/L and 113 mg/L respectively. Fig. 4 (a)e(c) shows
removal efficiency observed during the experimental obser-
vation. The removal of organic content leads towards the
reduction in BOD and it is also suggested that this wastewater
after treatment can be utilized for biological treatment.
Recently, one researcher used electro-hydrolysis process for
pre-treatment of pulp and paper industry wastewater before
anaerobic treatment to enhance the biological treatment op-
tion [51]. Hence, it can be suggested that electrolysis process is
feasible for BOD removal and pre-treatment of wastewater
before biological treatment options as it is main parameter
which decreases the biological treatment efficiency [8,48].
Chemical oxygen demand is one of the major parameter in
any wastewater analysis. Reduction of chemical oxygen de-
mand is one of the major challenges for researchers as it is
mainly due to presence of complex organic and inorganic
molecules. COD removal efficiency ranged in between 79.4%
and 50.5% with steel and carbon electrode respectively. The
maximum COD removal efficiency of the system is achieved by
steel electrode i.e. 80.6%, 80.5%, 79.8%, 79.5% and 79.4% with
12 V, 9 V, 6 V, 3 V and 1.23 V respectively. Simultaneously, the
removal efficiency shows increasing to decreasing trend from
12 to 1.23 V for platinum and carbon electrode. COD removal is
achieved due to decomposition of organic compounds present
in wastewater. It has been found that pH level, metal hydroxide
formation and flocs/coagulation during electrolysis resulted in
COD removal and effected with increasing and decreasing
trends of following parameters [52]. Hence, it can be observed
during utilization of carbon/organic electrode in present study
removal of all the parameters as well COD is decreased due to
less formation of metal hydroxides and coagulation. Hydrogen
production yield is more with high COD/TOC [41]. Effect of
initial COD content on hydrogen production wastewater
removal with eletcro-hydrolysis from vinegar fermentation
wastewater and found that 48% efficiency of the system is
achieved with low COD. Hence, it can also be suggested that
this process is helpful for high and low COD [53].
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13
Hardness in the wastewater/water is due to presence of
calcium (Ca2þ) and magnesium (Mg2þ). The formations of
these ions contribute towards flocs formation with metal
ions or hydroxide formed during the experiment [25]. The
removal efficiency was found more due to more hydroxide
formation or metal ions. The maximum removal is achieved
at 12 V due to large amount of flocs formation as rate of
electron production is high with hydroxide. The maximum of
y103 mg/L (90.7%) reduction was observed from y1118 mg/
L. The steel electrode shows decreasing trend in removal of
hardness with decreasing voltage rate i.e. 90.7%, 87.2%,
83.5%, 82.5% and 76.9% for 12 V, 9 V, 6 V, 3 V and 1.23 V
respectively. Whereas, platinum shows 77.0%, 78.3%, 76.5%,
71.8% and 49.2% at 12 V, 9 V, 6 V, 3 V and 1.23 V respectively. It
has observed that with platinum electrode the maximum
removal is achieved with 9 V whereas, drastic change was
observed with 1.23 V with lowest removal efficiency as
decreasing trend was observed with all voltage from 9 to 3 V
but pollutant removal efficiency reduction from 71.8% to
49.2% is observed at 1.23 V. The different pollutant removal
efficiency with all electrode and varying voltage was pre-
sented through Fig. 4 (a)e(c).
It was observed from Fig. 4 (a)e(c) that total nitrogen
removal efficiency is found in between 93.6% and 84.3% with
all electrode material used with varying voltage. The
maximum removal efficiency is found with steel electrode
followed by platinum and carbon electrode. The efficiency of
the system is found minimum at 1.23 V with carbon electrode
which increase gradually with increasing the voltage from
1.23 V to 12 V for all different electrodes. The efficiency lies in
between 87.0% and 84.3% with carbon electrode, whereas
platinum electrode shows removal efficiency in between
88.4% and 85.5% and steel electrode shows maximum removal
efficiency in between 93.6% and 90.9%. The other complex
nitrogen can be recovered by plants or other organisms for
their metabolic activity which is present in treated water for
different applications.
A dramatic removal efficiency rate is observed with carbon
and platinum electrode which changes drastically from 81.3%
to 63.1% when moving from 12 V to 9 V for phosphorus in the
process. Whereas, a similar removal efficiency is achieved
with 9 V and 3 V with carbon electrode. The maximum
removal efficiency was found with steel electrode i.e. 80.6%,
77.6%, 73.1%, 65.7% and 62.7% with 12 V, 9 V, 6 V, 3 V and 1.23 V
respectively.
So, treatment of TDIWW with solar PV-based electrolysis
found to be significant in respect of pollutant load removal in
integration with hydrogen production.
Conclusions
Solar PV based electrolysis process and TDIWW treatment for
hydrogen production using two different types of electrodes:
organic (carbon), inorganic (steel and platinum) is examined
in this study with novel findings. This process is considered as
one of the feasible route for resource utilization and sustain-
able point of view. The use of a storage-based electricity
method also enhances the efficacy of the system during no
sunny days and at night also. A positive significant trend is
14 international journal of hydrogen energy xxx (xxxx) xxx
observed for hydrogen production rate at different voltages
(1.23 Ve12 V) in integration with pollutant load removal. The
maximum of hydrogen production (16.4 mL/h) was observed
with inorganic (steel electrode) at 12 V, whereas maximum
efficiency (67.8%) at 3 V with 1.95 mL/h. Hence, a reciprocal
relationship is noticed in HPR with efficiency at all voltages
and electrodes selected. As, HPR increases with increasing
voltage but efficacy of the system decreases from 3 V to 12 V,
when voltage is decreased to 1.23 V the dramatic change in
both efficiency and HPR of the system is observed with all
three electrodes. The pollutant removal efficiency was found
in the range of (y50% to y95%) with carbon electrode (y57%
to y96%), with steel electrode and (y60% to y96%) with
platinum electrode at varying voltage. The maximum
pollutant removal efficiency was achieved at 12 V with steel
electrode. Further, this method can be proposed as a pre-
treatment option for textile wastewater treatment before
biological treatment for further research on the part of the
low-cost and environment-friendly approach. Hence,
hydrogen gas production from the electrolysis of textile
dyeing industry wastewater using solar PV panels with stor-
age techniques for a constant supply of power proves to be an
efficient and energy-intensive process for wastewater treat-
ment and hydrogen production as compared to other alter-
native treatment methods.
Acknowledgment
Mr. Atin K. Pathak Junior Research Fellow (JRF) under Inspire
fellowship scheme by Department of Science and Technology,
Ministry of Science and Technology (Govt. of India), New
Delhi, India is gratefully acknowledged for financial
assistance.
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