Journal of Hazardous Materials 394 (2020) 122554

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Journal of Hazardous Materials

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

Efficient recovery of Cu(II) by LTA-zeolites with hierarchical pores and their T

resource utilization in electrochemical denitrification: Environmentally
friendly design and reutilization of waste in water
Jiacheng Li, Miao Li*, Qinan Song, Sai Wang, Xiaofeng Cui, Fang Liu, Xiang Liu
Scholl of Environment, Tsinghua University, 30# Shuangqing Road, Hai Dian Distract, Beijing, 100086, China

GRAPHICAL ABSTRACT

Recovery of Cu(II) by mesoporous LTA with high efficiency and their further utilization as cathode for NO3− reduction.

ARTICLE INFO ABSTRACT

Editor: Daniel C.W. Tsang Water pollution seriously endangers human health and the environment. Here we prepared and tested meso-
Keywords: porous LTA zeolites for the adsorption of Cu(II) from aqueous media and the captured copper was further used
Cu(II) for electrochemical nitrate reduction. The prepared hierarchically porous LTA exhibited a high capacity
Nitrates (341.5 mg g−1) for Cu(II) adsorption, following the pseudo-second-order kinetic and Freundlich adsorption
Resource reuse isotherm models well. The Cu-LTA sample was characterised by various analytical methods, and Cu(I) species
LTA zeolite were identified as the active sites for nitrate electrochemical reduction. Based on the spectral characterization
Electrocatalysis and reducibility, strong metal-support interaction was found between copper and LTA, which is beneficial to the
Wastewater
dispersion of active sites and their contacts with nitrates. In total, 10.1 g-N-NO3 g−1-Cu was reduced over the Cu-
LTA-modified cathode in a three-electrode system with high N2 selectivity (92.1 %). Compared to purely mi-
croporous zeolites, mesoporous LTA has a higher capacity for Cu(II) removal and nitrate reduction. The me-
soporous structure allows easy access to the inner active sites with low diffusion resistance. The low Tafel slope
and high current density confirm the high activity of the mesoporous Cu-LTA, making it a promising and effi-
cient material for the removal and reuse of heavy metal ions.

⁎
Corresponding author.
E-mail address: miaoli@tsinghua.edu.cn (M. Li).

https://doi.org/10.1016/j.jhazmat.2020.122554
Received 10 January 2020; Received in revised form 14 March 2020; Accepted 16 March 2020
Available online 18 March 2020
0304-3894/ © 2020 Elsevier B.V. All rights reserved.
J. Li, et al.
1. Introduction
Rapid urbanisation and industrialisation has resulted in a vast in-
crease in the amount of wastewater generated each year. This waste-
water represents a threat to both human health and the environment
(Cheng et al., 2018; Qin et al., 2019). Nitrates and heavy metals are the
most common inorganic contaminants in water. The former comes
mainly from fertilisers and urban sewage. Nitrates can cause infant
methemoglobinemia or adult gastrointestinal diseases and the US En-
vironmental Protection Agency has set a maximum permissible limit in
drinking water of 50 mg L−1 (Garcia et al., 2018). Consequently, the
removal of nitrates from wastewater has been intensely investigated,
especially electrochemical denitrification. This process is of particular
interest because it is space-saving, robust, durable, and easy to operate
(Su et al., 2019; Martinez et al., 2017; Reyter et al., 2010; Su et al.,
2016). Electrode plays a key role in the electrochemical system and the
chemically modified electrode shows good prospect in treatment of
wastewater (Motahare et al., 2018; Wu et al., 2019). Heavy metals are
also released in large quantities in wastewater, especially copper,
without treatment. Cu(II) is an intransigent toxin that accumulates in in
living organisms and it can damage the biological retreatment systems
in water (Wu et al., 2018). In humans, copper causes kidney and liver
damage, and the USEPA has set the drinking water limit to 1.3 mg L−1
(Chávez et al., 2015). Fortunately, many techniques have been devel-
oped to remove heavy metals from wastewater, but, to date, the
treatment of Cu(II) is mainly based on precipitation, membrane se-
paration, electrodialysis, ion exchange, and adsorption (Ge et al., 2015;
Zhang et al., 2016).
In view of waste utilisation, an ideal wastewater treatment process
should not only allow the efficient removal of Cu(II) but also enable its
recovery because copper is a valuable transition metal. In electro-
chemical remediation methods, the cathode material plays the key role
in determining the activity of nitrate electrocatalytic reduction, and
copper is regarded as an optimal cathode materials because of its low
cost, high conductivity, and high catalytic activity (Reyter et al., 2011;
Bae et al., 2007).
Heavy metals could be simply and effectively recovered by ad-
sorption (Pei et al., 2010). Many efforts have been devoted to improve
the performance of adsorbents (Maedeh et al., 2015; Hamid et al.,
2017). Specially, zeolites are widely used for removal of water cationic
pollutants due to their unique properties. As adsorbents, zeolites are
highly efficient, negative charges of frameworks, and they have been
investigated intensely over the last fifty years (Lupulescu et al., 2013; Li
et al., 2017; Hong et al., 2019). Their basic tetrahedral units were
connected by channels with different dimensions (Alireza et al., 2013),
which enables them good ion exchange ability. Moreover, they can be
further modified by other functional groups with high selectivity to
heavy metal ions removal (Marzieh and Alireza, 2020; Motahare et al.,
Scheme 1. Recovery of Cu(II) by mesoporous LTA with high efficiency and their further utilization as cathode for NO3− reduction.
2
Journal of Hazardous Materials 394 (2020) 122554
2017; Alireza et al., 2013). When modified by transition metals, such as
Cu, Ni, and Zn, zeolites could have many new properties in practical
application (Javad et al., 2016; Alireza et al., 2010; Hadis and Alireza,
2017a,b). For example, the strong electric field strength of zeolite helps
separation of electron/hole pairs, having bright future in photocatalysis
(Hadis and Alireza, 2017a,b; Majid et al., 2016). In addition, zeolites
could also be used to modify electrodes, which show different charge
transfer pathways (Tahmineh et al., 2019).
The removal efficiency of Cu(II) by Si/Al-containing zeolites is
mainly determined by their ion exchange ability. Zeolites with high Al/
Si ratios and high sodium contents should, in theory, have larger Cu(II)
adsorption capacities. Faujasite (FAU) and tschernichite (LTA) type
zeolites are two kinds of typical zeolites with low Si/Al ratio (about
1:1), exhibiting both high cation exchange capacity and adsorption
performance. In difference, FAU zeolite has 12-membered-ring (MR)
pores and the sodalite (sod) cages are connected by a double-6-MR,
while the LTA zeolite has 8-MR pores and the sod cages are connected
by a double-8-MR. However, the adsorption of Cu(II) in micropores is
typically hindered by the mass transfer resistance because of the limited
pore size. Thus, the inner Na+ ions of zeolites cannot be substituted by
Cu(II) through ion exchange. As a crucial step in our design process, we
chose to introduce mesoporous channels to the microporous structure
to promote the contact of Cu(II) and the inner adsorption sites. The
abundant mesoporous channels resulted in the utilisation of the entire
zeolite surface, both interior and exterior. Compared with that of the
bulk zeolite, the Cu(II) removal efficiency was improved on mesoporous
zeolite. Therefore, we designed a LTA/FAU zeolite with micro/meso-
pores for the adsorption of Cu(II) from wastewater and subsequently
tested the copper-containing zeolites as a cathode material for nitrate
electroreduction (Scheme 1). Thus, Cu(II)-contaminated water can
purified by the mesoporous zeolite, which has a very high adsorption
capacity, and the copper can be reused to remove nitrate from water.
Crucially, for the subsequent nitrate electroreduction process, the
copper must be evenly distributed on the zeolites by adsorption.
Characterisation of the samples revealed that the multiple micro- and
mesopores channels in the zeolites improved the dispersion of Cu, thus
improving the utilisation and contact between nitrates and Cu active
sites in the electroreduction process and making the copper adsorption
step a low-cost, effective, and convenient catalyst preparation process.
2. Experimental section
Three LTA samples were prepared: Z1, a conventional microporous
zeolite, and Z2 and Z3, which contained mesopores. Z1 was prepared
using a standard method starting from fumed silica, whereas Z2 and Z3
were prepared from phenylaminopropyl trimethoxysilane (PHAPTMS)-
functionalised fumed silica, which is known to produce a mesoporous
structure. More details on the synthesis procedures and
J. Li, et al.
Fig. 1. (A) XRD Patterns of different zeolites. (B) N2-sorption results of different zeolites, (C) Micro- and (D) Meso-pore size distribution of different zeolites.
characterizations can be found in the Supporting materials.
3. Results and discussion
3.1. Characterization of zeolites
X-ray diffraction (XRD) patterns of the prepared samples were ob-
tained, and these show that the all peaks of the as-synthesised Z2 and
Z3 samples match the standard XRD pattern of LTA-type of zeolite well
(Fig. 1(A)). In contrast, the Z1 sample was identified as mixed phase of
LTA and FAU by XRD. Zeolites with uniform structure have their typical
diffraction peaks under X-ray (Alireza et al., 2011a, 2011b, 2012, 2013;
Narges and Alireza, 2020). The LTA zeolite shows diffraction peaks at
2θ = 7.2°, 10.2°, 12.5°, 16.1°, 21.6°, 24.0°, 26.1°, 27.1°, 29.9°, 30.8°,
32.5° and 34.2°, which could be ascribed to crystallite planes of (200),
(220), (222), (420), (600), (622), (640), (642), (644), (660), (840), and
(664) (JCPDS No. 39-0222). The diffraction peaks of FAU zeolite at 2θ
values of 6.1°, 10.0°, 11.7°, 15.5°, 18.4°, 20.1°, 21.0°, 23.3°, 23.6°, 26.7°,
30.3°, 31.0°, and 37.4° can be indexed as the planes of (111), (220),
(311), (331), (511), (440), (531), (533), (622), (642), (660), (751), and
(1022) (JCPDS No. 38-0237), correspondingly.
The modification of fumed silica by PHAPTMS affected the crystal
structure by accelerating the formation of a pure LTA phase. N2-mul-
tipoint Brunauer–Emmett–Teller (BET) analysis (Table S1) indicated
that the surface area of the zeolites increased by six times when using
the PHAPTMS-modified SiO2. The organosilane is randomly in-
corporated into the zeolite crystal in the hydrothermal process and
works as a mesostructure-directing agent. Generally, ionic small mo-
lecules could be used as organic templates for the generation of me-
sopores during the crystallization of zeolite. The N2-sorption result of
the Z1 sample (Fig. 1(C)) shows typical characteristic of a microporous
material with a type-I isotherm according to previous study (Brunauer
et al., 1938; Zhan et al., 2002).
N2-sorption measurements of the Z2 and Z3 samples reveal type-IV
isotherms with a combination of H2 and H4 hysteresis loops above a
relative pressure of 0.4. The channels are connected, and both wedge-
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Journal of Hazardous Materials 394 (2020) 122554
shaped and ink-bottle mesopores exist in the samples (Broekhoff et al.,
1968). The different pore sizes and volumes of zeolites could affect their
performance for the adsorption of Cu(II) during wastewater treatment.
3.2. Removal experiments
As shown in Fig. 2, the mesoporous structured LTA (Z3) was found
to has the highest adsorption saturation value for Cu(II)
(327.5 mg g−1). While the saturation adsorption value for Z1 and Z2
were 296.5 and 323.0 mg/g, respectively. Pseudo-first- and second-
order kinetics models were employed to study the kinetics of Cu(II)
removal (Maryam et al., 2015; Sahar et al., 2017). The removal of Cu
(II) by all zeolites reached equilibrium in 40 min and the experimental
data could be fitted well to the pseudo-second-order kinetic model with
high correlation coefficients (R2 = 99.74–99.97 %). (Figs. 2(B) and S1).
The high R2 also implies that there were more adsorption sites than
metal ions adsorbed. Compared to the microporous Z1 sample, the
mesoporous Z2 and Z3 samples had higher Cu(II) capacities. Thus, the
Cu(II) removal efficiency was obviously improved by the mesopores,
which accelerated the mass transfer of Cu(II) in zeolites for exchange
with Na+ ions in the interior. The hydrated radius of Cu(II) is 0.419 nm,
whereas the sodalite cages and α-cages in LTA have diameters of 0.6
and 1.1 nm, respectively (Eglal et al., 2015; Wu et al., 2014). To ac-
celerate the adsorption of Cu(II) on the Si-O-Al six-membered-rings of
sodalite, a wider channel (mesopore) is vital for increasing the Cu(II)
removal efficiency. Consequently, by using the mesoporous LTA
sample, a very high Cu(II) removal efficiency was achieved, and a
comparison of the Cu(II) adsorption capacity by the different ad-
sorbents is summarised in Table S1. Two typical adsorption isotherm
models were employed to simulate the Cu(II) adsorption data, and the
Freundlich model was found to give the best fit (Figs. 2(C) and S2),
indicating that the process is governed by chemical adsorption.
To examine the capacity of the Z3 sample for Cu(II) in practical use,
the effects of interfering ions, such as K+, Ca2+, and Mg2+, was in-
vestigated (Fig. 2(D)). The addition of competing ions in increasing
molar ratios reduced the Cu(II) adsorption capacity. Compared with
J. Li, et al.
Fig. 2. (A) Adsorption of Cu(II) as a function of time, (B) Adsorption Kinetics model of the pseudo-second-order equation in linear form, (C) Freundlich adsorption
isotherm plots for adsorption of Cu(II) on different zeolites, (D) The effects of coexisting metal ions and practical water on Cu(II) adsorption.
those of the pure Cu(II) solution, the maximum and minimum Cu(II)
capacities fell to 99.0 % and 70.5 % for the molar ratios of K+/Cu2+ =
1/2 and Ca2+/Cu2+ = 2/1, respectively. Moreover, the effect of in-
terfering compounds on Z3 was investigated by using a Cu(II) solution
containing water obtained from Beijing (PB) and Changzhou (PC), two
representative large cities in the north and south of China, respectively.
The Cu(II) capacity increased by 1.3 and 1.1 times in PB and PC, re-
spectively, which could be caused by the higher pH of these water
sample. The existing state of Cu (II) varies with the pH value, Cu(OH)2
could form as solid precipitates in high pH value (> 8) and more
amounts of Cu(II) were removed consequently. The results also indicate
that Z3 is a promising material for real-world applications.
3.3. Characterization of Cu/zeolites
On the basis of the transmission electron microscopy (TEM) images
of zeolites after Cu(II) adsorption and H2 reduction (Fig. 3), the Z1
sample has few mesopores, but the Z2 and Z3 samples contain some
mesopores inside the LTA zeolite, which is consistent with the N2-
sorption results. In addition, copper nanoparticles were observed
widely dispersed over all of the zeolite samples. Further, the Cu2O
(200) facet was the main exposed surface.
Fourier transform infrared (FT-IR) spectra of the reduced catalysts
were obtained to investigate the chemical environment of the Cu-zeo-
lites (Fig. 4(A)). The two peaks at around 465 and 1000 cm−1 are as-
cribed to the Si/Al-O bending and asymmetric stretching vibrations,
respectively. The peak at 620 cm−1 lies in the fingerprint region of LTA,
which is consistent with the standard LTA structure and the XRD re-
sults. In addition, the shoulder peaks at 675 cm−1 and the broad peak at
1040 cm−1 are caused by copper phyllosilicate (Hasan et al., 2012;
Hoffmann et al., 2010; Song et al., 2017), indicating a strong
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Journal of Hazardous Materials 394 (2020) 122554
interaction between the copper and the zeolite. The three peaks at high
wavenumbers (> 3400 cm−1) correspond to OH vibrations. The band
at 3650 cm−1 caused by CueO also lied in this region (Chávez et al.,
2015), indicating the presence of Cu2O species in catalysts.
A comparison of the UV–vis diffuse reflectance spectroscopy in
Fig. 4(B) reveals the dispersion effect of the zeolites on Cu(II) via ad-
sorption. All the Cu-zeolite samples showed sharp bands at about
220 nm, which are caused by charge transfer between the oxygen in
zeolite and Cu2+/Cu+ species (Wang et al., 2013). That also indicates a
strong interaction between zeolites and copper nanoparticles. In con-
trast, no peak was detected around 780 nm, which is usually caused by
the d-d transitions of Cu(II) (Wang et al., 2015). In contrast, the SiO2
(fumed silica)-supported copper sample has a broad peak at this region,
implying the oxide state of copper. Because these samples were reduced
at the same temperature (453 K) and only the Cu-zeolites indicate the
presence of low-valent copper (Cu(0)/Cu(I)), we concluded that the
dispersion of Cu(II) on the LTA(FAU) zeolite is much higher compared
than that on SiO2. The mesoporous LTA zeolite with a low Si/Al ratio
could not only remove Cu(II) from wastewater but also resulted in an
even dispersion via adsorption. Cu(II) ions could coordinate with the
single six-membered-rings (S6Rs) in the LTA, which improves the cat-
alytic performance of the copper catalyst for nitrate removal.
H2 temperature-programmed reduction (H2-TPR) profiles were ob-
tained to discriminate between Cu species formed when the Cu-zeolites
were reduced at different temperatures. It is well known that the re-
duction reactions of Cu(II) to Cu(I) and Cu(I) to Cu(0) usually occur in
the low and high temperature regions, respectively (Jo et al., 2016; Gao
et al., 2014, 2015). In our study, the Cu-zeolites show two major peaks
at 150–350 and 450–520 °C (Fig. 4(c)). These peaks are mainly caused
by the reduction of Cu(II) and Cu(I), respectively. Moreover, there are
two peaks in the low-temperature region (around 230 and 275 °C),
J. Li, et al.
Fig. 3. TEM images of Cu-Z1 (A) and corresponding Cu nanoparticles in high magnitution (B); TEM images of Cu-Z2 (C) and Cu-Z3 (D); TEM images of Cu-Z3 (E) and
corresponding EDS elemental mapping of Al, Si, O and Cu (F) (G).
which are ascribed to the reduction of Cu(II) on the surfaces or in the
inner pores of the zeolites. The relative area of the second peak in-
creased from Z1 to Z2 and the corresponding temperature decreases
from Z2 to Z3. With increasing mesopore volume from Z1 to Z3, the
reduction of Cu(II) in inner pores became easier because of the de-
creasing diffusion resistance of H2. In comparison, the reduction of Cu
(II) on SiO2 begins at a higher temperature. Owing to the SMSI effect,
Cu(II) species on zeolites are highly dispersed with low size, which
facilitate their reduction. But Cu(II) species on SiO2 tend to form large
particles, which need to be reduced at high temperature.
The chemical states of Cu on the different zeolites were determined
using X-ray photoelectron spectroscopy (XPS) focusing on the Cu 2p
signals (Fig. 4(D)). The two XPS peaks observed at binding energies of
932.8 and 952.7 eV correspond to Cu2p3/2 and Cu2p1/2, respectively,
indicating the presence of Cu(0) or Cu(I) (Dutta et al., 2017; Jeon et al.,
2018). Moreover, the binding energy of Cu2p3/2 at 936.0 eV suggests
the presence of copper phyllosilicate, which again suggests a strong
metal–support interaction of Cu-zeolites (Wang et al., 2015). The strong
interaction accelerates dispersion of Cu species in the electrode surface,
improving the availability of Cu. The high dispersion of Cu(0)/Cu(I)
couple on LTA surface catalyze the reduction of nitrates by mediating
the electron transfer as discussed below.
3.4. Electrochemical experiments
The recovered Cu-zeolites were further utilized in the preparation of
cathode. As is known, the chemically modified electrodes show good
catalytic performance in the treatment of wastewater (Mohammad
et al., 2014; Safoura et al., 2015; Tahmineh et al., 2018). The
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Journal of Hazardous Materials 394 (2020) 122554
electrocatalytic efficiencies of the different Cu-zeolite electrodes for
nitrate conversion and the corresponding product selectivities are
shown in Fig. 5(A). The maximum nitrate conversion (49.6 %) was
obtained over the Cu-Z3 sample after 24 h, and 10.1 g N-NO3− was
converted per gram of recovered copper.
Before the nitrate was reduced into nitrogen or ammonia at cathode
surface, it firstly transferred and adsorbed on the active sites of cathode
[36]. The superior activity of Cu-Z3 is caused by its two advantages: the
high loading of copper and multiple mesopores. The hydrated ionic
radii of nitrate is 0.340 nm, so nitrate cannot pass through the through
the four-membered-ring (MR) window (0.16 nm), six-MR window
(0.22 nm), and 8-MR window (0.41 nm) connecting the sodalite cages
or α-cages. Therefore, mesoporous channels are necessary to enable
contact between nitrates and interior active Cu(I) sites (Wu et al., 2014;
Banasiak et al., 2009). The diffusion resistance of nitrates on Cu-zeolites
with only micropores would be rather large, and the conversion is,
consequently, lower than that of the mesoporous sample.
In addition, the products reveal the high selectivity towards N2
(> 90 %), which is an ideal and innocuous product of nitrate reduction.
Generally, the product of the direct electroreduction of nitrate is NH4+.
Here, chlorides not only work as electrolyte but also participate in the
re-oxidation process at the anode. Chlorides are first oxidised to aqu-
eous chlorine and, then, active hypochlorite species (HOCl/OCl−) are
formed, thus oxidising the ammonia by-products to form N2. As sum-
marized in Table S3, the high nitrate conversion and nitrogen se-
lectivity enable practical water remediation.
Tafel plots and linear sweep voltammetry (LSV) curves were em-
ployed to evaluate the electrochemical properties of the Cu-zeolite
electrode. Tafel plots of the three samples were plotted (Fig. 5(B)), and
J. Li, et al.
Fig. 4. (A) The FTIR spectra of different Cu-zeolites. (B) UV–vis diffuse reflectance absorbance spectra of different Cu-zeolites. (C) H2-TPR results of different Cu-
zeolites. (D) XPS results of different Cu-zeolites.
the mesoporous Cu-LTA cathode had the lowest Tafel slope of 216.2 mV
dec−1. This could be correlated to the pore structure of zeolites, as
listed in Table S1 and shown in Fig. 1. Based on previous studies, suf-
ficient contact between active sites and reactants is beneficial to the
utilization of catalysts (Zhao et al., 2019). The plentiful pores and large
surface areas promote the fast mass transport and accelerate the cata-
lytic reaction (Li et al., 2018; Huang et al., 2019).
The current density increases rapidly in the negative potential re-
gion (< 1.2 V) and the mesoporous Cu-LTA electrode showed a rela-
tively low overpotential compared with that of microporous Cu-LTA at
the same current density (Fig. 5(C)), also indicating the better elec-
trochemical activity of Cu-Z3 than Cu-Z1 and Cu-Z2. It is well known
that cyclic voltammograms (CVs) of electrode could be significantly
affected by the composition or concentration of the electrolytes and
scanning rates (Farzad et al., 2016, 2019; Tahmineh et al., 2019).
All CVs (Figs. 5(D) and S3(A) and (B)) show obvious peaks at
around -0.6 V, which were not caused by the reduction of electrolyte
but were ascribed to the reduction of Cu(I) to Cu(0) (Badea et al.,
2009). The CV results also offer some information about nitrate con-
version and reveal the reaction mechanism. The free electrons and H+
would contribute to the reduction of nitrogenous pollutants (Soumitra
et al., 2019). When nitrates adsorb on zero valent copper, the Cu(0)-
NO3− species are firstly formed (Shi et al., 2019). Then they react with
free H+ to from Cu(I)-NO2 species and H2O. The Cu(I)-NO2 could be
further reduced to Cu(0)-NO2 by free electrons. In this process, copper
is cycled between the states of Cu(I) and Cu(0). The Cu(0)-NO2 would
finally be reduced to Cu(0) and N2 with the help of H+ and electrons.
When nitrates were added, the cathode current increased obviously
in the region of −0.8 to −1.2 V (Fig. S3(C)). A high current density is
6
Journal of Hazardous Materials 394 (2020) 122554
beneficial for nitrate reduction, and nitrates are more easily reduced to
ammonia in this voltage region (Li et al., 2009a,b). Subsequently, am-
monia is further reoxidised to nitrogen at the anode, as discussed above.
4. Conclusions
In this work, hierarchical pores LTA zeolites were synthesized by a
facile hydrothermal method. The Z3 sample possessed the highest ca-
pacity for Cu(II) adsorption and electrocatalytic activity for nitrate re-
duction when used as a cathode material. In total, 341.5 mg g−1 Cu(II)
was adsorbed on the Z3 zeolite. After reduction, a total of 10.1 g-N-
NO3- g−1-Cu was reduced over the Cu-LTA-modified cathode in a three-
electrode system with high N2 selectivity (92.1 %). The definite im-
provements could be attributed to the unique structure of LTA having
multiple micro/mesopores. The low Si/Al ratio of LTA leads to its high
cation exchange capacity and adsorption performance. The mesoporous
LTA is suitable for both adsorption and electroreduction because of its
high ion-exchange capacity and adjustable structural properties.
The novelty of the work lies in not only the preparation of materials
with high pollutant removal ability but also in their further resourceful
utilization. For the first time, Cu(II) ions were recovered from synthetic
wastewater and reutilized as an efficient electrocatalyst for nitrate re-
duction. Moreover, SMSI effect between copper and zeolite was dis-
covered and Cu+ was found to be the active site for nitrate electro-
reduction.
In consequence, mesoporous LTA can be regarded as an ideal
‘bridge’ between Cu(II) recovery and nitrate electroreduction. Waste
recovery and resource utilisation is an environmentally friendly way to
solve the problems of heavy metal pollution. This work offer novel
J. Li, et al.
Fig. 5. (A) Comparison of electrocatalytic performance of different Cu-zeolites modified cathode in nitrates conversion and nitrogen as a function of time. (B) Tafel
plots and (C) Polarization curves of different Cu-zeolites modified cathode in 0.02 M NaCl and 50 mg/L NaNO3 solution. (D) Cyclic voltammetry at Cu-Z3 sample in
0.02 M NaCl or the mixture of 0.02 M NaCl and 50 mg/L NaNO3 electrolyte.
strategy to wastewater treatment. Many such ‘bridges’ are still required
for the removal of water pollutants and realise their reutilisation as a
promising supplement to the conventional water treatment processes.
CRediT authorship contribution statement
Jiacheng Li: Conceptualization, Methodology, Investigation,
Visualization, Writing - original draft, Writing - review & editing. Miao
Li: Supervision, Visualization, Resources, Funding acquisition, Writing -
review & editing, Project administration. Qinan Song: Formal analysis,
Investigation, Validation. Sai Wang: Validation, Investigation.
Xiaofeng Cui: Investigation. Fang Liu: Resources. Xiang Liu:
Resources, Project administration, Funding acquisition.
Declaration of Competing Interest
There are no conflict of interest to declare.
Acknowledgements
We acknowledge the National Natural Science Foundation of China
(No. 41977162) and National Water Pollution Control and Treatment
Science and Technology Major Project (2017ZX07202002) for the fi-
nancial support of this work.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jhazmat.2020.122554.
7
Journal of Hazardous Materials 394 (2020) 122554
References
Alireza, N.E., Atefeh, B., 2011. Surfactant modified ZSM-5 zeolite as an active component
of membrane electrode towards thiocyanate. Desalination 281, 248–256.
Alireza, N.E., Elahe, M., 2013. Hexadecylpyridinium surfactant modified zeolite A as an
active component of a polymeric membrane sulfite selective electrode. Mater. Sci.
Eng. C 33, 4751–4758.
Alireza, N.E., Mahshid, K., 2010. Photodecolorization of Eriochrome Black T using NiS-P
zeolite as a heterogeneous catalyst. J. Hazard. Mater. 176, 629–637.
Alireza, N.E., Mehdi, K.S., 2013. Effective removal of Ni(II) from aqueous solutions by
modification of nano particles of clinoptilolite with dimethylglyoxime. J. Hazard.
Mater. 260, 339–349.
Alireza, N.E., Zohreh, B., 2011. A comparison between the efficiency of CdS nano-
particles/zeolite A and CdO/zeolite A as catalysts in photodecolorization of crystal
violet. Desalination 279, 146–151.
Alireza, N.E., Zohreh, B., 2012. Sunlight assisted photodecolorization of crystal violet
catalyzed by CdS nanoparticles embedded on zeolite A. Desalination 284, 157–166.
Badea, G.E., 2009. Electrocatalytic reduction of nitrate on copper electrode in alkaline
solution. Electrochim. Acta 54, 996–1001.
Bae, S.E., Stewart, K.L., Gewirth, A.A., 2007. Nitrate adsorption and reduction on Cu(100)
in acidic solution. J. Am. Chem. Soc. 129, 10171–10180.
Banasiak, L.J., Schäfer, A.I., 2009. Removal of boron, fluoride and nitrate by electro-
dialysis in the presence of organic matter. J. Memb. Sci. 334, 101–109.
Broekhoff, J.C.P., Boer, J.H.D., 1968. Studies on pore systems in catalysts: XI. Pore dis-
tribution calculations from the adsorption branch of a nitrogen adsorption isotherm
in the case of “ink-bottle” type pores Author links open overlay panel. J. Catal. 10,
153–165.
Brunauer, S., Emmett, P.H., Teller, E.J., 1938. Adsorption of gases in multimolecular
layers. J. Am. Chem. Soc. 60, 309–319.
Chávez-Guajardo, A.E., Medina-Llamas, J.C., Maqueira, L., Andrade, C.A.S., Alves, K.G.B.,
Melo, C.P., 2015. Efficient removal of Cr (VI) and Cu (II) ions from aqueous media by
use of polypyrrole/maghemite and polyaniline/maghemite magnetic nanocompo-
sites. Chem. Eng. J. 281, 826–836.
Cheng, C., Cai, Y., Guan, G., Yeo, L., Wang, D., 2018. Hydrophobic-force-driven removal
of organic compounds from water by reduced graphene oxides generated in agarose
hydrogels. Angew. Chem. Int. Ed. 57, 11177–11181.
Dutta, A., Rahaman, M., Mohos, M., Zanetti, A., Broekmann, P., 2017. Electrochemical
CO2 conversion using skeleton (Sponge) type of Cu catalysts. ACS Catal. 7,
5431–5437.
Eglal, M.M., Ramamurthy, A.S., 2015. Removal of Pb (II), Cd (II), Cu (II) and tri-
chloroethylene from water by Nanofer ZVI. J. Environ. Sci. Health Part A 50,
J. Li, et al.
901–912.
Farzad, A., Alireza, N.E., 2016. Considerable decrease in overvoltage of electro-catalytic
oxidation of methanol by modification of carbon paste electrode with Cobalt(II)-
clinoptilolite nanoparticles. Int. J. Hydrogen Energy 41, 6288–6299.
Farzad, A., Alireza, N.E., 2019. Considerable decrease in overvoltage of electrocatalytic
oxidation of methanol by modification of carbon paste electrode with Cobalt(II)-
clinoptilolite nanoparticles. J. Taiwan Inst. Chem. Eng. 104, 130–138.
Gao, F., Walter, E.D., Kollar, M., Wang, Y., Szanyi, J., Peden, C.H.F., 2014. Understanding
ammonia selective catalytic reduction kinetics over Cu/SSZ-13 from motion of the Cu
ions. J. Catal. 319, 1–14.
Gao, F., Washton, N.M., Wang, Y., Kollár, M., Szanyi, J., Peden, C.H.F., 2015. Effects of
Si/Al ratio on Cu/SSZ-13 NH3-SCR catalysts: implications for the active Cu species
and the roles of Brønsted acidity. J. Catal. 331, 25–38.
Garcia-Segura, S., Lanzarini-Lopes, M., Hristovski, K., Westerhoff, P., 2018.
Electrocatalytic reduction of nitrate: fundamentals to full-scale water treatment ap-
plications. Appl. Catal. B Environ. 236, 546–568.
Ge, Y., Cui, X., Kong, Y., Li, Z., He, Y., Zhou, Q., 2015. Porous geopolymeric spheres for
removal of Cu(II) from aqueous solution: synthesis and evaluation. J. Hazard. Mater.
283, 244–251.
Hadis, D., Alireza, N.E., 2017a. Comprehensive study on enhanced photocatalytic activity
of heterojunction ZnS-NiS/zeolite nanoparticles: experimental design based on re-
sponse surface methodology (RSM), impedance spectroscopy and GC-MASS studies.
J. Colloid Interface Sci. 490, 652–664.
Hadis, D., Alireza, N.E., 2017b. Increased photocatalytic activity of NiO and ZnO in
photodegradation of a model drug aqueous solution: Effect of coupling, supporting,
particles size and calcination temperature. J. Hazard. Mater. 321, 629–638.
Hamid, S., Alireza, N.E., 2017. An efficient modified zeolite for simultaneous removal of
Pb(II) and Hg(II) from aqueous solution. J. Mol. Liq. 230, 221–229.
Hasan, F., Singh, R., Webley, P.A., 2012. Formation of LTA zeolite crystals with multi-
hollow polycrystalline core–shell structure via aggregation–recrystallization route in
presence of emulsion droplets. Microporous Mesoporous Mater. 160, 75–84.
Hoffmann, S.K., Goslar, J., Lijewski, S., Olejniczak, I., Jankowska, A., Werbińska, A.,
Kowalak, S., 2010. Sulfur pigments synthesized from zeolite LTA under vacuum and
in air. XRD and spectroscopic (UV-vis, FTIR, Raman, ESR, ESE) characterization. Ind.
Eng. Chem. Res. 49, 8192–8199.
Hong, M., Yu, L.Y., Wang, Y.D., Zhang, J., Chen, Z.W., Dong, L., Zan, Q.J., Li, R.L., 2019.
Heavy metal adsorption with zeolites: the role of hierarchical pore architecture.
Chem. Eng. J. 359, 363–372.
Huang, Z.H., Sun, F.F., Munkhbayar, B., Li, W.H., Li, H., Sun, Y., Zhao, Q., Liu, X., Ma,
T.Y., 2019. Zinc–nickel–cobalt ternary hydroxide nanoarrays for high-performance
supercapacitors. J. Mater. Chem. A 7, 11826–11836.
Javad, E.H., Alireza, N.E., 2016. Increased photocatalytic activity of Zn(II)/Cu(II) oxides
and sulfides by coupling and supporting them onto clinoptilolite nanoparticles in the
degradation of benzophenone aqueous solution. J. Hazard. Mater. 316, 194–203.
Jeon, H.S., Kunze, S., Scholten, F., Cuenya, B.R., 2018. Prism-shaped Cu nanocatalysts for
electrochemical CO2 reduction to ethylene. ACS Catal. 8, 531–535.
Jo, D., Ryu, T., Park, G.T., Kim, P.S., Kim, C.H., Nam, I.S., Hong, S.B., 2016. Synthesis of
high-silica LTA and UFI zeolites and NH3−SCR performance of their copper-ex-
changed form. ACS Catal. 6, 2443–2447.
Li, M., Feng, C.P., Zhang, Z., Sugiura, N., 2009a. Efficient electrochemical reduction of
nitrate to nitrogen using Ti/IrO2-Pt anode and different cathodes. Electrochim. Acta
54, 4600–4606.
Li, M., Feng, C.P., Zhang, Z., Lei, X., Chen, R., Yang, Y., Sugiura, N., 2009b. Simultaneous
reduction of nitrate and oxidation of by-products using electrochemical method. J.
Hazard. Mater. 171, 724–730.
Li, Y., Li, L., Yu, J.H., 2017. Applications of zeolites in sustainable chemistry. Chemistry 3,
928–949.
Li, H., Sun, Y., Yuan, Z.Y., Zhu, Y.P., Ma, T.Y., 2018. Titanium phosphonate based me-
tal–organic frameworks with hierarchical porosity for enhanced photocatalytic hy-
drogen evolution. Angew. Chem. Int. Ed. 57, 3222–3227.
Lupulescu, A.I., Kumar, M., Rimer, J.D., 2013. A facile strategy to design zeolite L crystals
with tunable morphology and surface architecture. J. Am. Chem. Soc. 135,
6608–6617.
Maedeh, B., Alireza, N.E., 2015. Enhanced removal efficiency of clinoptilolite nano-par-
ticles toward Co(II) from aqueous solution by modification with glutamic acid.
Colloids Surf. A: Physicochem. Eng. Asp. 479, 35–45.
Majid, B.M., Alireza, N.E., 2016. A comprehensive study on photocatalytic activity of
supported Ni/Pb sulfide and oxide systems onto natural zeolite nanoparticles. J.
Hazard. Mater. 318, 291–301.
Martinez, J., Ortiz, A., Ortiz, I., 2017. State-of-the-art and perspectives of the catalytic and
electrocatalytic reduction of aqueous nitrates. Appl. Catal. B Environ. 207, 42–59.
Maryam, H.C., Alireza, N.E., 2015. Clinoptilolite nano-particles modified with aspartic
acid for removal of Cu(II) from aqueous solutions: isotherms and kinetic aspects. New
J. Chem. 39, 9396–9406.
Marzieh, N.A., Alireza, N.E., 2020. A comprehensive study on the kinetics and thermo-
dynamic aspects of batch and column removal of Pb(II) by the clinoptilolite–glycine
adsorbent. Mater. Chem. Phys. 240, 122142–122157.
Mohammad, H.S.M., Alireza, N.E., 2014. Modification of carbon paste electrode with Ni-
Journal of Hazardous Materials 394 (2020) 122554
clinoptilolite nanoparticles for electrocatalytic oxidation of methanol. Electrochim.
Acta 147, 572–581.
Motahare, N., Alireza, N.E., 2017. High catalytic activity of Fe(II)-clinoptilolite nano-
particales for indirect voltammetric determination of dichromate: experimental de-
sign by response surface methodology (RSM). Electrochim. Acta 223, 47–62.
Motahare, N., Alireza, N.E., 2018. A sensitive and simple modified zeolitic carbon paste
electrode for indirect voltammetric determination of nitrate. Ionics 24, 2135–2145.
Narges, O., Alireza, N.E., 2020. Focus on scavengers’ effects and GC-MASS analysis of
photodegradation intermediates of sulfasalazine by Cu2O/CdS nanocomposite. Sep.
Purif. Technol. 235, 116228–116249.
Pei, Z.G., Shan, X.Q., Kong, J.J., Wen, B., Owens, G., 2010. Coadsorption of ciprofloxacin
and Cu(II) on montmorillonite and kaolinite as affected by solution pH. Environ. Sci.
Technol. 44, 915–920.
Qin, S.P., Yu, L.P., Yang, Z.J., Li, M.Y., Clough, T., Wrage-Mönnig, N., Hu, C.S., Liu, B.B.,
Chen, S.M., Zhou, S.G., 2019. Electrodes donate electrons for nitrate reduction in a
soil matrix via DNRA and denitrification. Environ. Sci. Technol. 534, 2002–2012.
Reyter, D., Bélanger, D., Roué, L., 2010. Nitrate removal by a paired electrolysis on
copper and Ti/IrO2 coupled electrodes – influence of the anode/cathode surface area
ratio. Water Res. 44, 1918–1926.
Reyter, D., Bélanger, D., Roué, L., 2011. Optimization of the cathode material for nitrate
removal by a paired electrolysis process. J. Hazard. Mater. 192, 507–513.
Safoura, S., Alireza, N.E., 2015. Using of anionic adsorption property of a surfactant
modified clinoptilolite nano-particles in modification of carbon paste electrode as
effective ingredient for determination of anionic ascorbic acid species in presence of
cationic dopamine species. Electrochim. Acta 184, 371–380.
Sahar, F., Alireza, N.E., 2017. Synergistic effects of ion exchange and complexation
processes in cysteine-modified clinoptilolite nanoparticles for removal of Cu(II) from
aqueous solutions in batch and continuous flow systems. New J. Chem. 41,
3811–3820.
Shi, Y.J., Wu, Z.L., Huang, Y.H., Huang, C.P., 2019. Electrochemical nitrate reduction as
aff ;ected by the crystal morphology and facet of copper nanoparticles supported on
nickel foam electrodes (Cu/Ni). Appl. Catal. B: Environ. 257, 117909–117919.
Song, J., Wang, Y., Walter, E.D., Washton, N.M., Mei, D., Kovarik, L., Engelhard, M.H.,
Prodinger, S., Wang, Y., Peden, C.H.F., 2017. Toward rational design of Cu/SSZ-13
selective catalytic reduction catalysts: implications from atomic-level understanding
of hydrothermal stability. ACS Catal. 7, 8214–8227.
Soumitra, P., Swapna, C., Chanchal, C., Sounak, R., 2019. A hydrogen evolution reaction
induced unprecedentedly rapid electrocatalytic reduction of 4-nitrophenol over ZIF-
67 compare to ZIF-8. J. Electroanal. Chem. 853, 113545–113556.
Su, J.F., Ruzybayev, I., Shah, I., Huang, C.P., 2016. State-of-the-art and perspectives of
the catalytic and electrocatalytic reduction of aqueous nitrates. Appl. Catal. B
Environ. 180, 199–209.
Su, J.F., Kuan, W.F., Liu, H., Huang, C.P., 2019. Mode of electrochemical deposition on
the structure and morphology of bimetallic electrodes and its eff ;ect on nitrate re-
duction toward nitrogen selectivity. Appl. Catal. B Environ. 257, 117909–117919.
Tahmineh, T., Alireza, N.E., 2018. A comprehensive study on the kinetic aspects and
experimental design for the voltammetric response of a Sn(IV)-clinoptilolite carbon
paste electrode towards Hg(II). J. Electroanal. Chem. 829, 95–105.
Tahmineh, T., Alireza, N.E., 2019a. Sensitive voltammetric determination of bromate by
using ion-exchange property of a Sn(II)-clinoptilolite-modified carbon paste elec-
trode. J. Solid State Electrochem. 23, 143–157.
Tahmineh, T., Alireza, N.E., 2019b. Electrocatalytic determination of Hg(II) by the
modified carbon paste electrode with Sn(IV)-clinoptilolite nanoparticles.
Electrocatalysis 10, 466–476.
Wang, L., Gaudet, J.R., Li, W., Weng, D., 2013. Migration of Cu species in Cu/SAPO-34
during hydrothermal aging. J. Catal. 306, 68–77.
Wang, Z.Q., Xu, Z.N., Peng, S.Y., Zhang, M.J., Lu, G., Chen, Q.S., Chen, Y., Guo, G.C.,
2015. High-performance and long-lived Cu/SiO2 nanocatalyst for CO2 hydrogena-
tion. ACS Catal. 5, 4255–4259.
Wu, Z., Goel, S., Choi, M., Iglesia, E., 2014. Hydrothermal synthesis of LTA-encapsulated
metal clusters and consequences for catalyst stability, reactivity, and selectivity. J.
Catal. 311, 458–468.
Wu, H., Zheng, Z.K., Tang, Y.M., Huang, N.M., Rose, A., Lim, H.N., Ng, Y.H., 2018. Pulsed
electrodeposition of CdS on ZnO nanorods for highly sensitive photoelectrochemical
sensing of copper (II) ions. Sustain. Mater. Tec. e00075.
Wu, H., Tan, H.L., Toe, C.Y., Scott, J., Wang, L.Z., Rose, A., Ng, Y.H., 2019. Photocatalytic
and photoelectrochemical systems: similarities and differences. Adv. Mater.
1904717–1904738.
Zhan, B.Z., White, M.A., Lumsden, M., Neuhaus, J.M., Robertson, K.N., Cameron, T.S.,
Gharghouri, M., 2002. Control of particle size and surface properties of crystals of
NaX zeolite. Chem. Mater. 14, 3636–3642.
Zhang, N., Zang, G.L., Shi, C., Yu, H.Q., Sheng, G.P., 2016. A novel adsorbent TEMPO-
mediated oxidized cellulose nanofibrils modified with PEI: preparation, character-
ization, and application for Cu(II) removal. J. Hazard. Mater. 316, 11–18.
Zhao, Q., Naman, K., Ieuan, D.S., Graeme, H., Ma, T.Y., 2019. Vanadium(III) acet-
ylacetonate as an efficient soluble catalyst for lithium–oxygen batteries. Angew.
Chem. Int. Ed. 58, 12553–12557.