Catalysis Letters (2019) 149:1216–1223

https://doi.org/10.1007/s10562-019-02715-9

Efficient Electrochemical Reduction of High Concentration Nitrate

by a Stepwise Method
Lian‑Kui Wu1 · Yi‑Jie Shi1 · Cheng Su2 · Hua‑Zhen Cao1 · Guo‑Qu Zheng1

Received: 2 October 2018 / Accepted: 13 February 2019 / Published online: 22 February 2019
© Springer Science+Business Media, LLC, part of Springer Nature 2019

Abstract
A combined anode, Ti/IrO2 (0–3.5 h)–Ti/RuO2 (3.5–7 h) is designed to promote the removal of high concentration of nitrate
by a stepwise method. During the electrolysis process, Ti/IrO2 is used as anode at the first stage to promote the generation
of ammonia-N and then Ti/RuO2 is switched as anode at the next stage to enhance the chlorine evolution. The generated ­Cl2
will further react with ­H2O to produce ­ClO−, which will oxidize ammonia-N to N ­ 2, therefore improve the nitrate removal
efficiency. Results shown that both of the reduction of nitrate and oxidation of the by-product of ammonia-N are enhanced
and the total nitrogen removal efficiency is 85% when the initial nitrate concentration is 500 mg L−1. The avoid using cation
exchange membrane not only efficiently reduces the operation cost but also simplifies the operation and maintain procedure.
Graphical Abstract

Cl-
Change anode Cl-
-e- -e-
Ti/RuO2 anode
Ti/IrO2 anode

NO3- Cl2 NO3- Cl2

Fe cathode

Fe cathode

+e- -e- +e- -e-

NO2- N2 NO2-
HClO N2
+e- NH4+ •OH +e- HClO
+e- H2 O +e- •OH
NH4+
N2 -e- N2 H2O
NH4+ NH4+ -e-
O2 O2

At the first stage At the second stage

Keywords  Nitrate · Electrochemical reduction · Ti/IrO2 · Ti/RuO2 · Fe cathode

* Lian‑Kui Wu 1 Introduction
lkwu@zjut.edu.cn
* Guo‑Qu Zheng In recent years, nitrate contaminated water have caused great
zhenggq@zjut.edu.cn attention due to their threat to humans health, including the
“blue baby syndrome” in infants, liver damage and even
1
College of Materials Science and Engineering, Zhejiang cancer [1–3]. Till now, several strategies have been pro-
University of Technology, Hangzhou 310014, China
posed to remove nitrate from the contaminated water, such
2
Zhejiang Jiuli Hi-Tech Metals Co. Ltd, Huzhou 313028, as, biological denitrification [4, 5], reverse osmosis [6, 7],
China

13
Vol:.(1234567890)
Efficient Electrochemical Reduction of High Concentration Nitrate by a Stepwise Method 1217

and ion exchange resins [8, 9] ion-exchange membrane [10].
Recently, electrochemical reduction of nitrate has attracted
great attention owing to its convenience, low cost and envi-
ronmental friendliness [11–14].
Generally, researches are mainly focused on developing
cathodes with high nitrate reduction activity, including graph-
ite [15–17], diamond [18], Pt [19], Pd [20–22], Au [23], Al
[24], Zn [24], Cu [25–30], Ti [25, 31, 32], and Fe [25, 33]. It
has been reported that the low cost Fe cathode exhibits much
higher nitrate removal efficiency than Cu, Ti, Ni or graphite
[25, 31]. Meanwhile, it should be noted that the promotion of
­N2 yield and suppression the generation of by-products are
critical important during the electrochemical reduction pro-
cess. Nitrite and ammonia are the main by-products in neutral
or basic electrolyte. Therefore, the removal or suppressing the
generation of ammonia-N and nitrite-N is critical important
to improve the total nitrogen removal efficiency.
On the other hand, the reduction of nitrate-N and oxi-
dation of the by-products, nitrite-N/ammonia-N are closely
related to the solution composition and anode material. For
the solution without C ­ l− ions, the oxidation of ammonia-N
to ­N2 mainly originates from the direct oxidation by stepwise
dehydrogenation and/or from indirect oxidation by hydroxyl
radicals. While if C­ l− ions were present in the solution, they
can be oxidized on the anode to form ­Cl2, which can react
with ­H2O to produce C ­ lO−. The generated C ­ lO− will fur-
ther oxidize ammonia-N to ­N2 [17, 34–37]. Compared to Ti/
IrO2, Ti/RuO2 performs higher chlorine evolution activity
and therefore benefits the removal of nitrate.
In this work, we designed a novel electrode system to
promote the removal of high concentration nitrate ions from
water solution by a stepwise method. In this process, the
low-cost Fe is used as the cathode, while different anodes
are chosen at different stages. As shown in Fig. 1, during the
first stage, Ti/IrO2 is used as the anode to produce abundant
ammonia-N. Then Ti/RuO2 is switched as the anode, which
has higher chlorine evolution activity and benefits the gener-
ation of ­ClO−, therefore promotes the oxidation of ammonia-
N to ­N2. The collaboration of this two anodes by a stepwise
method is beneficial to improving the total nitrogen removal
efficiency. The avoid using cation exchange membrane not
only efficiently reduces the operation cost but also simplifies
the operation and maintain procedure.
2 Experimental
2.1 Materials
NaNO3 (99.0%), NaCl (99.5%), N ­ a2SO4 (99%), H­ 2IrCl6 (Ir
35% in HCl) and R ­ uCl3 (99.9%) were all purchased from
Aladdin Reagent (Shanghai, China). All chemicals were ana-
lytical grade and used as received without further purifica-
tion. Deionized (DI) water was used in all experiments. The
preparation of Ti/IrO2 and Ti/RuO2 was accomplished by
thermal decomposition of ­H2IrCl6 and ­RuCl3 on Ti substrate
[38], respectively. The total loading of the noble metal oxide
was ~ 2.0 mg cm−2.
2.2 Electrochemical Reduction of Nitrate
A single cuboid electrochemical cell with a net working vol-
ume of 200 mL was manufactured by acryl material. Fe plate
(6.0 cm × 10.0 cm) was used as cathode, while Ti/IrO2 and
Ti/RuO2 were chosen as anodes. The distance between the
cathode and anode was set to be 1.0 cm and the immersed
areas of the anode and cathode in the treated solution were
the same (6.0 cm × 4.0 cm). The electrochemical reduction
of nitrate was conducted on a DC power (SMA 30V10A) at
current density of 20 mA cm−2. Synthetic nitrate solutions

Fig. 1  Schematic diagram of the

electrochemical apparatus for
cathodic reduction of high con-
centration nitrate by a stepwise
method with the combination
of Ti/IrO2 anode and Ti/RuO2
anode

Cl-
Change anode Cl-
-e- -e-
Ti/RuO2 anode
Ti/IrO2 anode

NO3- Cl2 NO3- Cl2

Fe cathode

Fe cathode

+e- -e- +e- -e-

NO2- N2 NO2-
HClO N2
+e- NH4+ •OH +e- HClO
+e- H2 O +e- •OH
NH4+
N2 -e- N2 H2O
NH4+ NH4+ -e-
O2 O2

At the first stage At the second stage

13

1218
with initial nitrate-N ­(NO3−–N) concentrations of 100 or
500 mg L−1 were newly prepared. 500 mg L−1 ­Na2SO4 was
used as supporting electrolyte in all experiments. In order
to investigate the effect of NaCl on the nitrate removal effi-
ciency, various of NaCl concentrations from 0 to 1.00 g L−1
(w/v) were added into the synthetic nitrate solutions.
2.3 Analysis
All analyses were done according to standard methods [39].
Nitrate was estimated by UV method using spectrophotome-
ter (HACH DR6000 USA). Nitrite was colorimetrically ana-
lyzed by N-(1-naphthyl)-ethylenediamine spectrophotometry
[GB 7493-87, Water quality-Determination of Nitrite-Spec-
trophotometric Method (1987)]. And the determination of
ammonia was performed by sodium hypochlorite spectro-
photometric method [HJ 536-2009, Water Quality-Derter-
mination of Ammonia Nitrogen-Salicylic Acid Spectropho-
tometry (2009)] [33]. Hydrazine and hydroxylamine will not
be produced in the electrolyte because the solution would
change into basic after electrolysis [25].
2.4 Nitrate Removal Efficiency and Current
Efficiency
The ­NO3−–N removal efficiency [R(NO3−–N)], ­NO2−–N
generation efficiency [G(NO2−–N)], ­NH4+–N generation effi-
ciency [G(NH4+–N)] and total nitrogen removal efficiency
[R(TN)] were calculated according to the following equations:
c(NO3 − − N)0 − c(NO3 − − N)t
R(NO3 − − N) = × 100%
c(NO3 − − N)0
(1)
c(NO2 − − N)t
G(NO2 − − N) = × 100% (2)
c(NO3 − − N)0
c(NH4 + − N)t
G(NH4 + − N) = × 100% (3)
c(NO3 − − N)0
R(TN) = R(NO3 − − N) − G(NO2 − − N) − G(NH4 + − N)
(4)
where c(NO3−–N)0 is the initial concentration of ­NO3−–N,
and c(NO3−–N)t, c(NO2−–N)t, and c(NH4+–N)t are the con-
centrations of ­NO3−–N, ­NO2−–N and ­NH4+–N at time t.
The current efficiency was calculated to evaluate the influ-
ence of anode type on the electrochemical nitrate reduction:
2NH4 +
− − − +
[
c(NO3 − N)0 − c(NO3 − N)t − c(NO2 − N)t − c(NH4 − N)t × V × z × F
𝜂=
t×M×I
13
L.-K. Wu et al.
where η is the average current efficiency, z is the number
of transferred electrons from nitrate to nitrogen (5), V rep-
resents the volume of reactor (L), F is the Faraday constant
(F = 96,485 C mol−1), t is the electrolytic reaction time (s),
M is the molar mass of the nitrogen (14 g mol−1) and I is the
actual current applied to the system (A).
3 Results and Discussion
It has been reported that ­C lO −, the reaction product of
chlorine with water, can oxide ammonia-N to nitrogen,
therefore increase the total nitrogen removal efficiency
[37]. And the electrocatalytic activity for chlorine evolu-
tion is greatly dependent on anode material. Therefore,
two typical anodes, Ti/IrO 2 and Ti/RuO 2 are chosen to
investigate the influence of anode materials on the nitrate
removal efficiency.
Figure 2 reveals the influence of NaCl concentration on
the evolution of nitrate-N removal, nitrite-N generation,
ammonia-N generation, and total nitrogen removal with Fe
cathode and Ti/IrO2 anode. It is shown that the nitrate-N
removal efficiency is 85.1% in absence of NaCl after elec-
trolysis for 3.5 h. Whereas the introduction of 300, 500
and 1000  mg  L−1 NaCl slightly decreases the nitrate-N
removal efficiency to 82.3%, 81.9%, and 80.5%, respectively
(Fig. 2a). Similar phenomenon has been also reported by
other researchers [40–42]. This is because that high NaCl
concentration may accelerate the specifically adsorption of
­Cl− onto the electrode surface, and therefore resulting in
the poisoning of nitrate reduction [43, 44]. Interestingly,
the introduction of NaCl is beneficial to suppressing the
generation of nitrite-N (Fig. 2b). Specifically, the generated
nitrite-N decreases from 0.27 to 0.1% after the addition of
300 mg L−1 NaCl, and nearly no nitrite-N can be detected
if 500 mg L−1 or more NaCl was contained in the solution.
Figure 2c exhibits the influence of NaCl on the generation
of ammonia-N. It is shown that the ammonia-N generation
efficiency dramatically decreases from 52.1 to 1.2% with the
NaCl concentration increasing from 0 to 500 mg L−1. And
no ammonia-N can be detected when 1000 mg L−1 NaCl is
added. It has been reported that appropriate amount of chlo-
ride is beneficial to the removal of ammonia-N [39]. This is
because that the evolution of chlorine at anode leads to the
generation of C­ lO− which can further oxidize the by-product
of ammonia-N into ­N2 (Eq. 6) [45, 46].
(6)
− − +
] 3ClO → N2 + 3H2 O + 3Cl + 2H
(5)
Efficient Electrochemical Reduction of High Concentration Nitrate by a Stepwise Method 1219

(a) -1
(b) 2.0 -1
(c)
NaCl:0 mg L NaCl:0 mg L
80 -1 50
NaCl:300 mg L NaCl:300 mg L
-1

Ammonia-N Generation / %
Nitrate-N Removal / %

Nitrite-N Generation / %
-1
NaCl:500 mg L NaCl:500 mg L
-1
-1
NaCl:0 mg L
NaCl:1000 mg L
-1
1.5 NaCl:1000 mg L
-1
40

Nitrite-N Generation/%
0.30 -1
3.5 h NaCl:300 mg L
60 0.25 -1
NaCl:500 mg L
0.20
30
-1
0.15 NaCl:1000 mg L
88 1.0 0.10
40
Nitrate-N Removal/% 86
3.5 h 0.05

84
0.00 20
0 200 400 600 800 1000
NaCl Concentration/mg L-1
20 82
0.5
80 10
78
0 200 400 600 800 1000

0 NaCl Concentration/mg L-1

0.0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
Time / h Time / h Time / h
(d) (e) 100 (f) 500 Nitrate-N
80 NaCl:0 mg L
-1
Nitrate-N
NaCl:300 mg L
-1
Ammonia-N Ammonia-N
-1

-1
-1
Nitrite-N Nitrite-N
Concentration / mg L
NaCl:500 mg L 80 400

Concentration / mg L
TN
TN Removal / %

-1
60 NaCl:1000 mg L TN

60 300
40
40 200

20
20 100

0 0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 0 1 2 3 4 5 6 7
Time / h Time / h Time / h

Fig. 2  Effect of NaCl concentration on nitrate-N removal (a), tained in the solution. The insets in a–b are corresponding data after
nitrite-N generation (b), ammonia-N generation (c), and total nitro- electrolysis for 3.5 h. Fe and Ti/IrO2 are acted as cathode and anode,
gen removal (d). The evolution of total nitrogen, nitrate, nitrite, and respectively
ammonia when 100 mg L−1 (e) and 500 mg L−1 (f) nitrate-N are con-

Besides, it is known that highly oxidative hydroxyl after electrolysis for 3.5 h. If further increasing the initial
radicals (·OH) will generate at the anode surface during nitrate-N concentration to 500 mg L−1 (Fig. 2f), although the
electrolysis. Therefore, the by-products, ammonia-N can nitrate-N concentration decreases from 500 to 24.7 mg L−1
also be removed by dehydrogenation at electrode-liquid after 7 h electrolysis, a great deal of by-product generates.
interface of the anode, revealing as follows: Specifically, the ammonia-N concentration is as high as
227.6 mg L−1. At this time, the total nitrogen removal effi-
OH + NH4 + → NH2 + H2 O + H+ +e− (7)
⋅
ciency is only 50%, suggesting that the Ti/IrO2 anode is not
⋅
OH + NH2 → NH + H2 O + e− (8) suitable to remove high concentration of nitrate-N.
As mentioned above, the introduction of NaCl benefits to
1 reduce the nitrite-N and ammonia-N concentrations, there-
⋅
OH + NH → N + H2 O + e− (9) fore improves the total nitrogen removal efficiency. In fact,
2 2
all these processes are related to the oxidation of ­Cl− at the
As shown in Fig. 2d, the introduction of NaCl also ben-
anode. It is known that the chlorine evolution performance
efits to enhance the total nitrogen removal efficiency. After
of Ti/RuO2 outperforms that of Ti/IrO2. So the total nitrogen
the addition of 500 mg L−1 NaCl, the total nitrogen removal
removal efficiency will be enhanced if Ti/RuO2 was used
efficiency dramatically increases from 32.7 to 80.6%. While
as anode.
the removal efficiency almost un-changes when further
As revealed in Fig. 3a, although the nitrate-N removal
increasing the NaCl concentration to 1000 mg L−1. Fig-
efficiency slightly reduces when Ti/RuO2 is used as anode, it
ure 2e summaries the evolution of total nitrogen, nitrate-N,
increases with the NaCl concentration. In detail, the nitrate-
nitrite-N, and ammonia-N with Ti/IrO2 anode in presence
N removal efficiency increases from 71.6 to 74.8% when
of 100 mg L−1 nitrate-N and 1000 mg L−1 NaCl. It mani-
1000 mg L−1 NaCl is added. While the nitrite-N (Fig. 3b)
fests that over 80% nitrate can be removed from the solution
and ammonia-N (Fig. 3c) concentrations dramatically reduce

13

1220 L.-K. Wu et al.

(a) 75 (b) 1.6 (c)

Nitrite-N Generation/%
0.4
25
-1
NaCl:0 mg L
-1 3.5 h
NaCl:300 mg L

Ammonia-N Generation / %
0.3
Nitrate-N Removal / %

Nitrite-N Generation / %
-1
-1 NaCl:0 mg L
60 NaCl:500 mg L -1
NaCl:300 mg L
NaCl:1000 mg L
-1 1.2 0.2
20 -1
0.1
NaCl:500 mg L
-1
NaCl:1000 mg L
45 0.0
15

Ammonia Generation/%
-1 0 200 400 600 800 1000
NaCl:0 mg L 25
0.8 3.5 h
-1
76 NaCl Concentration/mg L

Nitrate-N Removal/%
-1
NaCl:300 mg L 20
3.5 h
30 74 NaCl:500 mg L
-1
10 15
-1
72
NaCl:1000 mg L 10
0.4
15 70 5
5

0
0 200 400 600 800 1000
68 -1
0 200 400 600 800 1000 NaCl Concentration/mg L
0 NaCl Concentration/mg L -1
0.0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
Time / h Time / h Time / h

(d) (e) 100 (f) 500

75 NaCl:0 mg L
-1
Nitrate-N
NaCl:300 mg L
-1
Ammonia-N Nitrate-N

-1
-1
Nitrite-N Ammonia-N
-1

NaCl:500 mg L 80 400

Concentration / mg L
60
Concentration / mg L
-1
TN Nitrite-N
TN Removal / %

NaCl:1000 mg L
TN
45 60 300

30 40 200

15 20 100

0 0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 0 1 2 3 4 5 6 7
Time / h Time / h Time / h

Fig. 3  Effect of NaCl concentration on nitrate-N removal (a), tained in the solution. The insets in a–c are corresponding data after
nitrite-N generation (b), ammonia-N generation (c), and total nitro- electrolysis for 3.5 h. Fe and Ti/RuO2 are acted as cathode and anode,
gen removal (d). The evolution of total nitrogen, nitrate, nitrite, and respectively
ammonia when 100 mg L−1 (e) and 500 mg L−1 (f) nitrate-N are con-

after the introduction of NaCl, and none of them can be is over 80% with Ti/RuO2 anode, which is 60% higher than
detected after the addition of 1000 mg L−1 NaCl. This is that with Ti/IrO2 anode.
because that besides the direct oxidation occurred on anode, In order to remove high concentration of nitrate ions, a
ammonia-N can also be oxidized by ­ClO− to form ­N2. Fur- stepwise method with combined anodes is designed. In this
thermore, the total nitrogen removal efficiency increases device, Ti/IrO2 is used as anode at the first stage to generate
from 46.7 to 74.8% after the addition of 1000 mg L−1 NaCl large amount of ammonia-N (Fig. 2f), which could be effi-
(Fig. 3d). ciently oxidized to ­N2 when Ti/RuO2 is switched as anode
The evolution of total nitrogen, nitrate-N, nitrite-N, and at the next stage. As shown in Fig. 4, the nitrate-N and total
ammonia-N with Ti/RuO2 anode in presence of 1000 mg L−1 nitrogen removal efficiencies are greatly dependent on the
NaCl and 100 mg L−1 nitrate-N are displayed in Fig. 3e. switching time for changing the anode. Specifically, they are
It is shown that although the total nitrogen removal effi- enhanced firstly and then deteriorated when the switching
ciency is slightly reduced, the selective reduction of nitrate time is delayed from 2 to 5 h, and the optimal switching time
is improved when Ti/RuO2 is used as anode and nearly is 3.5 h. As shown in Fig. 4b, the nitrate-N concentration
no nitrite-N and ammonia-N are detected. Different phe- decreases from 500 to 44.9 mg L−1 after 7 h electrolysis,
nomenon are observed under high nitrate-N concentration while the ammonia-N concentration increases from 0 to
(Fig. 3f). In detail, the nitrate-N concentration decreases 212.9 mg L−1 over the first 4 h and then decreases to only
from 500 to 82.5 mg L−1 with Ti/RuO2 anode. Interestingly, 23.5 mg L−1. After 7 h electrolysis, only 1.8 mg L−1 nitrite-
the ammonia-N concentration is only 15.8 mg L−1, which is N is detected and the total nitrogen removal efficiency is
less than 10% compared to that generated with Ti/IrO2 anode about 85%. Therefore, the combination of Ti/IrO2 (0–3.5 h)
(Fig. 2f). The low ammonia-N concentration with Ti/RuO2 and Ti/RuO2 (3.5–7 h) with a stepwise method performs
anode is ascribed to its good electrochemical activity toward better total nitrogen removal efficiency when high concen-
chlorine evolution. And the total nitrogen removal efficiency tration nitrate is contained in the solution. In fact, only few

13
Efficient Electrochemical Reduction of High Concentration Nitrate by a Stepwise Method 1221

Fig. 4  Nitrate converted to (a) 500 (b) 500

nitrite and ammonia by Ti/ Nitrate-N
Nitrate-N
IrO2 (0–2 h)–Ti/RuO2 (2–7 h) Ammonia-N
Ammonia-N

-1
-1
(a), Ti/IrO2 (0–3.5 h)–Ti/ 400 Nitrite-N

Concentration / mg L
400

Concentration / mg L
Nitrite-N
RuO2 (3.5–7 h) (b), and Ti/ TN
TN
IrO2 (0–5 h)–Ti/RuO2 (5–7 h)
(c) anodes in the presence 300 300
of 1000 mg L−1 NaCl and
500 mg L−1 ­NO3−–N. Ti/ 200 200
IrO2 (0–Xh)Ti/RuO2 (X–7 h)
respects for the anode was
switched from Ti/IrO2 to Ti/ 100 100
RuO2 after electrolysis for X h
0 0
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7
Time / h Time / h
(c) 500 Nitrate-N
Ammonia-N

-1
Nitrite-N
400
Concentration / mg L
TN

300

200

100

0
0 1 2 3 4 5 6 7
Time / h

work has been done to remove high concentration nitrate by
electrochemical reduction process. Ghazouani et al. used two
pieces of boron-doped diamond with exposed area of 70 cm2
as cathodes to remove nitrate ions with initial concentra-
tion of 500 mg L−1 [47]. Results shown that the total nitro-
gen removal efficiency was 87% after electrolysis for 4 h at
40 mA cm−2. Table 1 collects the nitrate removal efficiency
of present work and other previous reports. It is shown that
even though with much higher initial nitrate concentration,
the ­NO3−–N and TN removal efficiencies are superior to
other systems when Ti/IrO2 (0–3.5 h)–Ti/RuO2 (3.5–7 h) are
used as anode. Although the combination of Fe cathode and
Ti/IrO2–Pt anode delivers a relatively high nitrate removal
efficiency in 3 h, the TN removal efficiency is very low [25].
Similar result is also observed when Ti/IrO2–TiO2–RuO2
was used as anode [48]. Whereas, it should be noted that
the combination of two BDD electrodes with large areas
can also be used for the removal of high concentration of
nitrate-N with a high removal efficiency [47].
After 7 h electrolysis, the current efficiencies for nitrate
removal with different anodes were also calculated. As
revealed in Fig. 5, the highest current efficiency of 24.5%
is observed with the combined anode, Ti/IrO2 (0–3.5 h)–Ti/
RuO2 (3.5–7 h). This is because that a great deal of by-product,
ammonia will generate when Ti/IrO2 is used as the anode
(Fig. 2f), therefore leading to a relative low current efficiency
for nitrate removal. While the high chlorine evolution activity
on Ti/RuO2 benefits the oxidation of ammonia to nitrogen,
leading to the current efficiency increased. The combination
of Ti/IrO2 and Ti/RuO2 will take the advantages of these two
anodes and therefore enhance the current efficiency. The cur-
rent efficiency with this combined anodes is comparable or
even superior to other reported electrochemical reduction sys-
tems. For instance, Cheng et al. reported a current efficiency
for nitrate removal of 24.5% by paired electrolysis in a solid
polymer electrolyte reactor [26]. Su et al. found that the cur-
rent efficiency for nitrate removal is 20% at 25 mA cm−2 by
­Co3O4/Ti cathode and Ir–Ru/Ti anode [42]. This work pro-
vides a membrane-free, easy to operation, and facile strategy
to remove high concentration of nitrate from water solution.
Based on this, the combination of several anodes and cathodes
at the same time to further enhance the nitrate removal effi-
ciency is being on investigation.

13

1222 L.-K. Wu et al.

­ O3−–N reduction with other cathodes

Table 1  Comparison of N

Cathode Anode Electrode area Initial Solution Current Nitrate-N removal TN removal References
solution volume density
(mg L−1) (mL) (mA cm−2)

Fe Ti/IrO2–Ti/RuO2 24 cm2 500 200 20  7 h, 91% 7 h, 85% This work
Fe Ti/IrO2–Pt 36.5 cm2 50 250 20 2 h, 67% 2 h, 67% [41]
Fe Ti/IrO2–Pt 40 cm2 100 200 20 3 h, 95% 3 h, 40% [25]
Fe Fe 16 cm2 100 300 140 5 h, 80% 5 h, 0% [49]
Al Ti/TiO2 24 cm2 50 200 15 4 h, 78% 4 h, 38% [33]
Al Al 16 cm2 100 300 140 5 h, 70% 5 h, 20% [49]
Cu Ti/TiO2 24 cm2 50 200 15 4 h, 60% 4 h, 24% [33]
Cu Ti/IrO2–Pt 36.5 cm2 50 250 20 2 h, 62% 2 h, 62% [41]
Cu Ti/IrO2–Pt 40 cm2 100 200 20 3 h, 60% 3 h, 30% [25]
Ti Ti/IrO2–Pt 36 cm2 50 250 20 2 h, 32% 2 h, 32% [41]
Ti Ti/IrO2–Pt 40 cm2 100 200 20 3 h, 30% 3 h, 10% [25]
Cu/Zn Ti/IrO2–Pt 36.5 cm2 50 250 20 2 h, 72% 2 h, 72% [41]
Cu/Zn Ti/IrO2–TiO2–RuO2 100 cm2 60 – 25 6 h, 96% 6 h, 32% [48]
Cu/Zn Ti/IrO2–Pt 50 cm2 100 400 40 3 h, 83% 3 h, 78% [50]
Ti/Fe2O3 Ti/Ir–Ru 16 cm2 100 90 10 3 h, 99% 3 h, 50% [51]
Ti/Co3O4 Ti/Ir–Ru 16 cm2 100 90 10 3 h, 99% 3 h, 65% [51]
BDD BDD 70 cm2 500 – 40 4 h, 96% 4 h, 87% [47]

BDD represents boron-doped diamond, three equal compartments are used

25 benefit for the oxidation of the by product, i.e., ammonia-

N to nitrogen and therefore enhancing the nitrate removal
Current efficiency / %

20 efficiency. The current efficiency for nitrate removal on this

combined anodes is 24.5%. The membrane-free system effi-
15
ciently reduces the operation cost and simplifies the opera-
tion procedure.
10 Acknowledgements  This work was financially supported by Natural
Science Foundation of Zhejiang Province (No. LY18E010005), Tal-
5 ent Project of Zhejiang Association for Science and Technology (No.
2017YCGC015).

0 Compliance with Ethical Standards 

Ti/I Ti/R Ti/I
rO2 uO2 rO2
-Ti/
RuO
2 Conflict of interest  The authors declare that they have no conflict of
interest.
Fig. 5  The current efficiencies for nitrate removal with different
anodes after electrolysis for 7 h
References
1. Rivett MO, Buss SR, Morgan P, Smith JW, Bemment CD (2008)
4 Conclusion Water Res 42:4215–4232
2. Chan TY (2011) Toxicol Lett 200:107–108
A combined anode, Ti/IrO2 (0–3.5 h)–Ti/RuO2 (3.5–7 h) is 3. Garcia-Segura S, Lanzarini-Lopes M, Hristovski K, Westerhoff P
proposed to remove high concentration of nitrate by a step- (2018) Appl Catal B 236:546–568
4. Jia YH, Tran HT, Kim DH, Oh SJ, Park DH, Zhang RH, Ahn DH
wise method. Results shown that the total nitrogen removal (2008) Bioprocess Biosyst Eng 31:315–321
efficiency is as high as 85% when the initial nitrate-N con- 5. Winkler M, Coats ER, Brinkman CK (2011) Water Res
centration is 500 mg L−1. This is because that the Ti/RuO2 45:6119–6130
anode has higher activity for chlorine evolution, which is of 6. Epsztein R, Nir O, Lahav O, Green M (2015) Chem Eng J
279:372–378

13
Efficient Electrochemical Reduction of High Concentration Nitrate by a Stepwise Method 1223
7. Schoeman JJ, Steyn A (2003) Desalination 155:15–26
8. Kalaruban M, Loganathan P, Shim WG, Kandasamy J, Naidu G,
Nguyen TV, Vigneswaran S (2016) Sep Purif Technol 158:62–70
9. Terry PA (2009) Environ Eng Sci 26:691–696
10. Xie D, Li C, Tang R, Lv Z, Ren Y, Wei C, Feng C (2014) Electro-
chem Commun 46:99–102
11. Li M, Feng C, Zhang Z, Yang S, Sugiura N (2010) Bioresour
Technol 101:6553–6557
12. Martínez J, Ortiz A, Ortiz I (2017) Appl Catal B 207:42–59
13. Lange R, Maisonhaute E, Robin R, Vivier V (2013) Electrochem
Commun 29:25–28
14. Lan H, Liu X, Liu H, Liu R, Hu C, J Qu (2016) Catal Lett 146:
91–99
15. Szpyrkowicz L, Daniele S, Radaelli M, Specchia S (2006) Appl
Catal B 66:40–50
16. Lacasa E, Cañizares P, Llanos J, Rodrigo MA (2012) J Hazard
Mater 213–214:478–484
17. Ding J, Li W, Zhao Q-L, Wang K, Zheng Z, Gao Y-Z (2015) Chem
Eng J 271:252–259
18. Martin de Vidales MJ, Millán M, Sáez C, Cañizares P, Rodrigo
MA (2016) Electrochem Commun 67:65–68
19. Estudillo-Wong LA, Arce-Estrada EM, Alonso-Vante N, Manzo-
Robledo A (2011) Catal Today 166:201–204
20. Dima GE, de Vooys ACA, Koper MTM (2003) J Electroanal
Chem 554:15–23
21. Hu C, Dong J, Wang T, Liu R, Liu H, Qu J (2018) Chem Eng J
335:475–482
22. Soares OSGP, Órfão JJM, Pereira MFR (2008) Catal Lett
126:253–260
23. El-Deab MS (2004) Electrochim Acta 49:1639–1645
24. Polatides C, Kyriacou G (2005) J Appl Electrochem 35:421–427
25. Li M, Feng C, Zhang Z, Sugiura N (2009) Electrochim Acta
54:4600–4606
26. Reyter D, Bélanger D, Roué L (2010) Water Res 44:1918–1926
27. Yang C, Zhang QB, Gao MY, Hua YX, Xu CY (2016) J Electro-
chem Soc 163:D469–D475
28. Mattarozzi L, Cattarin S, Comisso N, Gerbasi R, Guerriero P,
Musiani M, Vázquez-Gómez L, Verlato E (2015) J Electrochem
Soc 162:D236–D241
29. Ghodbane O, Sarrazin M, Roué L, Bélanger D (2008) J Electro-
chem Soc 155:F117–F123
30. Soares OSGP, Órfão JJM, Pereira MFR (2010) Catal Lett
139:97–104
3 1. Dash BP, Chaudhari S (2005) Water Res 39:4065–4072
32. Kim K-W, Kim Y-J, Kim I-T, Park G, II, Lee E-H (2006) Water
Res 40:1431–1441
33. Li W, Xiao C, Zhao Y, Zhao Q, Fan R, Xue J (2016) Catal Lett
146:2585–2595
34. Diaz V, Ibanez R, Gomez P, Urtiaga AM, Ortiz I (2011) Water
Res 45:125–134
35. Vanlangendonck Y, Corbisier D, Van Lierde A (2005) Water Res
39:3028–3034
36. Kim KW, Kim YJ, Kim IT, Park GI, Lee EH (2006) Water Res
40:1431–1441
37. Paidar M, Bouzek K, Jelínek L, Mat Z (2004) Water Environ Res
76:2691–2698
38. Wu L-K, Liu X-Y, Hu J-M (2016) J Mater Chem A 4:11949–11956
39. APHA, WPCF AWWA (1998) Standard methods for the examina-
tion of water and wastewater. American Public Health Associa-
tion, Washington, DC
40. Rosero-Navarro NC, Pellice SA, Castro Y, Aparicio M, Duran A
(2009) Surf Coat Technol 203:1897–1903
41. Kuang P, Feng C, Li M, Chen N, Hu Q, Wang G, Li R (2017) J
Electrochem Soc 164:E103–E112
42. Su L, Li K, Zhang H, Fan M, Ying D, Sun T, Wang Y, Jia J (2017)
Water Res 120:1–11
43. Pletcher D, Poorabedi Z (1980) Cheminform 24:1253–1256
44. Katsounaros I, Kyriacou G (2007) Electrochim Acta
52:6412–6420
45. Li L, Liu Y (2009) J Hazard Mater 161:1010–1016
46. Pressley TA, Bishop DF, Roan SG (1973) Environ Sci Technol
6:622–628
47. Ghazouani M, Akrout H, Bousselmi L (2015) Desalin Water
Treatment 53:1107–1117
48. Fan N, Li Z, Zhao L, Wu N, Zhou T (2013) Chem Eng J 214:83–90
49. Barada Prasanna Dash SC (2005) Water Res 39: 4065–4072
50. Li M, Feng C, Zhang Z, Shen Z, Sugiura N (2009) Electrochem
Commun 11:1853–1856
51. Su L, Li K, Zhang H, Fan M, Ying D, Sun T, Wang Y, J Jia (2017)
Water Res 120: 1–11
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