Separation and Purification Technology 142 (2015) 251–257

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Separation and Purification Technology

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

Acid-treated g-C3N4 with improved photocatalytic performance in the

reduction of aqueous Cr(VI) under visible-light
Yongcai Zhang ⇑, Qian Zhang, Qiwei Shi, Zhenyu Cai, Zhanjun Yang
Jiangsu Key Laboratory of Environmental Material and Environmental Engineering, School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, China

a r t i c l e i n f o a b s t r a c t

Article history: An alternative simple, economical and efficient acid-soaking method was proposed to improve the activ-
Received 17 May 2014 ity of g-C3N4 for photocatalytic reduction of aqueous Cr(VI) in this work. The improvement was achieved
Received in revised form 19 December 2014 simply by soaking g-C3N4 (which was obtained by heating melamine in air at 550 °C for 4 h) in 5 mol/L
Accepted 22 December 2014
HNO3 or HCl aqueous solution for 2 h (the HNO3 and HCl-treated samples were denoted as g-C3N4AHNO3
Available online 12 January 2015
and g-C3N4AHCl, respectively). The compositions, structures, Brunner–Emmet–Teller (BET) specific sur-
face areas, Zeta potentials and optical properties of g-C3N4, g-C3N4AHNO3 and g-C3N4AHCl were charac-
Keywords:
terized by X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy,
Graphitic carbon nitride
Acid-soaking treatment
field emission scanning electron microscopy, N2 adsorption/desorption isotherms, Zeta potential analyzer
Photocatalytic reduction and UV–vis diffuse reflectance spectroscopy. The photocatalytic properties of g-C3N4, g-C3N4AHNO3 and
Hexavalent chromium g-C3N4AHCl were tested in the reduction of aqueous Cr(VI) under visible-light (k > 420 nm) irradiation. It
was observed that both g-C3N4AHNO3 and g-C3N4AHCl exhibited higher photocatalytic activity than
g-C3N4. The higher photocatalytic activities of acid-treated samples may be attributed to their larger
BET specific surface areas, positive surface charges and larger adsorption capacities for Cr(VI).
Furthermore, the soaking treatment with 5 mol/L HNO3 aqueous solution can not only remove the Cr(III)
species deposited on the surface of g-C3N4AHNO3 after use in photocatalytic reduction of aqueous Cr(VI),
but also enhance the photocatalytic efficiency of g-C3N4AHNO3 in reuse.
Ó 2015 Elsevier B.V. All rights reserved.

1. Introduction photocatalysis technology in treating large-scale Cr(VI)-containing

Hexavalent chromium (Cr(VI)) is a common pollutant in the
effluents from chromate-related industries [1–6]. It is highly toxic
and highly mobile in water, and can cause great harm to the envi-
ronment and human health [1–6]. Hence, it is obliged to develop
effective, economical and environmental-friendly methods of
treating Cr(VI)-containing wastewaters. Photocatalytic reduction
has now been considered as a promising method of treating
Cr(VI)-containing wastewaters [7–14], due to its distinguished
characteristics such as (i) low cost, (ii) good ability to use ‘‘free’’,
infinite, clean and safe solar energy, (iii) no use and no release of
other undesirable chemicals, e.g., less solid wastes (iv) reusability,
and (v) the reduced product, Cr(III) is much less toxic than Cr(VI)
and can be easily precipitated in aqueous solution (K > sp (Cr(OH)3) =
6.3  10 31) and treated as a solid waste. However, by now, the
lack of efficient, stable, nontoxic and inexpensive visible-light-
active photocatalysts hinders the practical application of
⇑ Corresponding author. Tel.: +86 18952568061.
E-mail address: zhangyc@yzu.edu.cn (Y. Zhang).
wastewaters.
Recently, g-C3N4 has attracted great research interest as a
promising metal-free visible-light-activated photocatalyst,
because of its simple preparation and low cost [15], high thermal
and chemical stability, semiconductivity and medium bandgap of
about 2.7 eV [15–20]. Considering the conduction band potential
of g-C3N4 ( 1.3 V versus NHE [15]) is more negative than the stan-
dard reduction potentials of Cr(VI)/Cr(III) (1.33 V versus NHE) and
Cr(VI)/Cr(V) (0.55 V versus NHE) (semiconductor-mediated photo-
catalytic reduction of Cr(VI) under normal illuminations occurs
through three consecutive one-electron transfer steps, ending in
Cr(III). The first electron transfer step (Cr(VI) + eCB = Cr(V)) was
generally considered as the rate-determining one [21]), the photo-
catalytic reduction of Cr(VI) over g-C3N4 should be thermodynam-
ically allowed. In fact, the use of g-C3N4 as photocatalyst in the
reduction of aqueous Cr(VI) under UV and visible light irradiation
have also been studied in some cases [22–24]. However, pure
g-C3N4 suffered from low photocatalytic activity resulted from
the fast recombination of photogenerated electrons and holes as
well as relatively low photoresponse [22–26]. Hence, many
researchers have turned to exploit various strategies to enhance

http://dx.doi.org/10.1016/j.seppur.2014.12.041
1383-5866/Ó 2015 Elsevier B.V. All rights reserved.
252 Y. Zhang et al. / Separation and Purification Technology 142 (2015) 251–257
the photocatalytic activity or photoresponse of g-C3N4 [22–26]. For
example, Dong et al. reported that carbon self-doping or incorpora-
tion of formate anions could improve the photocatalytic activity of
g-C3N4 in Cr(VI) reduction under visible light irradiation [23,24].
However, their modification strategies required extra hydrother-
mal treatment in tailor-made autoclaves at 200 °C or 150 °C for
24 h, which are complex, time-consuming, uneconomical and
inappropriate for industrial production. Although some other sim-
pler strategies such as thermal oxidation etching [25] and ultra-
sound-assisted liquid exfoliation from bulk g-C3N4 into ultrathin
g-C3N4 nanosheets [26], have also been proposed, the yields of
the resultant products were very low, for instance, only around
6 wt% g-C3N4 was left by thermal oxidation etching at 500 °C for
2 h [25], and only about 15 wt% g-C3N4 could be exfoliated after
intense ultrasonic treatment for 16 h [26]. Therefore, there is still
a need to explore economical and efficient ways to improve the
photocatalytic activity of g-C3N4.
Herein, an alternative simple, economical and efficient acid-
soaking method was proposed to enhance the photocatalytic activ-
ity of g-C3N4. The g-C3N4 was synthesized by heating melamine in
air at 550 °C for 4 h, and its modification was achieved simply by
soaking it in 5 mol/L HNO3 or HCl aqueous solution for 2 h. The
photocatalytic properties of the acid-treated products were tested
in the reduction of aqueous Cr(VI) under visible-light (k > 420 nm)
irradiation.
2. Experimental
K2Cr2O7 was a guaranteed reagent, melamine was chemically
pure, whereas all the other chemicals were analytically pure.
50 mg/L K2Cr2O7 aqueous solution (pH = 5.3) was prepared by dis-
solving 500 mg of K2Cr2O7 in 10.0 L of deionized water.
2.1. Synthesis and modification
3000 mg of melamine was placed into a corundum crucible
with a cover. They were heated in a program control chamber elec-
tric furnace at 550 °C for 4 h. The average rate of temperature
increase from room temperature to 550 °C was 4 degrees per min-
ute, and after the calcination at 550 °C for 4 h, the resultant powder
was cooled to room temperature naturally. The resultant powder
(which was denoted as g-C3N4) was soaked in 80 mL of 5 mol/L
HCl or HNO3 aqueous solution for 2 h, then washed with deionized
water and absolute ethanol, and finally dried in air at 80 °C for
12 h. For the convenience of description, the products treated with
5 mol/L HNO3 and HCl were denoted as g-C3N4AHNO3 and
g-C3N4AHCl, respectively. The yields of g-C3N4, g-C3N4AHNO3
and g-C3N4AHCl were about 42%, 41% and 40%, respectively, with
reference to the starting melamine.
2.2. Characterization
The product was characterized by X-ray diffraction (XRD, Ger-
man Bruker AXS D8 ADVANCE X-ray diffractometer), Fourier trans-
form infrared spectroscopy (FTIR, The United States Varian Cary
670 FT-IR spectrometer), X-ray photoelectron spectroscopy (XPS,
The United States Thermo-VG Scientific ESCALAB 250 XPS system,
Al Ka radiation and adventitious C 1s peak (284.8 eV) calibration),
field emission scanning electron microscopy and energy dispersive
X-ray spectroscopy (FESEM and EDX, Japan Hitachi S-4800 FESEM
configured with a Noran energy dispersive X-ray analyzer), N2
adsorption (The United States Micromeritics Instrument Corpora-
tion TriStar II 3020 surface area and porosity analyzer), Zeta poten-
tial analyzer (The United Kingdom Malvern Instruments Zetasizer
Nano ZS90, and UV–vis diffuse reflectance spectra (The United
States Varian Cary 5000 UV–Vis–NIR spectrophotometer).
2.3. Photocatalytic tests
Photocatalytic properties of the products were tested in the
reduction of aqueous Cr(VI) under visible-light (k > 420 nm) irradi-
ation in custom-made photochemical reactor (Supplementary
materials, Fig. S1). Prior to illumination, 300 mL of 50 mg/L
K2Cr2O7 aqueous solution with the addition of 300 mg of photocat-
alyst and 1.0 mL of 100 mg/mL citric acid aqueous solution was
ultrasonically dispersed for 5 min and magnetically stirred for
30 min in dark to ensure the adsorption–desorption equilibrium
between photocatalyst and Cr(VI). During illumination, about
4 mL of suspension was taken from the reactor at a scheduled
interval and filtered with pore size = 0.22 lm cellulose acetate
membrane filter to separate the photocatalyst. The Cr(VI) contents
in the filtrates were determined using the diphenylcarbazide color-
imetric method with a detection limit of 0.005 mg/L [27,28].
2.4. Determination of Cr(VI) using the diphenylcarbazide colorimetric
method [27,28]
1.0 mL of sample was mixed with 9.0 mL of 0.2 mol/L H2SO4 in a
10.0 mL volumetric flask. Subsequently, 0.2 mL of freshly prepared
0.25% (weight/volume) diphenylcarbazide in acetone was added to
the volumetric flask. After the mixture was shaken for about 30 s, it
was allowed to stand for 15 min to ensure full color development.
Using the reagent blank solution (that is, the solution contains all
the other substances, except for Cr(VI)) as reference, the absor-
bance of the colored Cr(VI)–diphenylcarbazide complex solution
was then measured at kmax = 540 nm.
3. Results and discussion
The XRD patterns of g-C3N4, g-C3N4AHNO3 and g-C3N4AHCl are
shown in Fig. 1. All the three samples display two XRD peaks at
about 13.0° and 27.3°, which are consistent with the XRD patterns
of g-C3N4 reported in the literatures [29–33]. The XRD peak at
27.3° is corresponding to the interplanar stacking of the conjugated
aromatic systems and can be indexed as the (0 0 2) crystal plane of
g-C3N4 [29–33]. The XRD peak at 13.0° is corresponding to the in-
plane ordering of tri-s-triazine units and can be indexed as the
(1 0 0) crystal plane of g-C3N4 [29–33].
The g-C3N4, g-C3N4AHNO3 and g-C3N4AHCl have similar FTIR
spectra, as shown in Fig. 2. The absorption peak at around
813 cm 1 is attributed to the breathing mode of the triazine units
(002)
(100)
Intensity (a. u.)
g-C3N4-HCl
g-C3N4-HNO3
g-C3N4
10 20 30 40 50 60 70 80
2θ (deg.)
Fig. 1. XRD patterns of g-C3N4, g-C3N4AHNO3 and g-C3N4AHCl.
 Y. Zhang et al. / Separation and Purification Technology 142 (2015) 251–257 253

in these samples may be originated from the adventitious oxygen-

g-C3N4-HCl ous species, such as surface adsorbed H2O [37–40]. The C 1s XPS
spectra of the three samples display two peaks at (i) 284.8 eV
and (ii) 288.1–288.2 eV (Fig. 3), which can be assigned to (i)
CAC in graphite and adventitious carbon and (ii) sp2-bonded C
Transmittance

g-C3N4-HNO3 in N-containing aromatic rings (NAC@N) [37–40], respectively.

g-C3N4
4000 3500 3000 2500 2000
Wavenumber (cm )
Fig. 2. FTIR spectra of g-C3N4, g-C3N4AHNO3 and g-C3N4AHCl.
[34–36]. The absorption peaks observed in the range of 1200–
1700 cm 1 are corresponding to the typical stretching modes of
CN heterocycles [34–36]. The absorption bands between 3000
and 3500 cm 1 can be ascribed to the uncondensed amine groups
and surface adsorbed water molecules [34–36].
The surface elemental composition and chemical states of
g-C3N4, g-C3N4AHNO3 and g-C3N4AHCl were further analyzed by
XPS. The survey XPS spectra (Fig. 3) reveal that g-C3N4 and
g-C3N4AHNO3 contains C, N and O components, whereas
g-C3N4AHCl contains C, N, O and Cl components. The O contaminants
The N 1s XPS spectra of the three samples can be deconvoluted
into three peaks at (i) 398.6–398.7 eV, (ii) 400.0 eV and (iii)
401.1 eV (Fig. 3), which can be assigned to (i) sp2-hybridized N
in C@NAC, (ii) tertiary N bonded to C in the form of NA(C)3 and
(iii) CANAH which might be related to the structural defects
and incomplete condensation in the polymerization process
[37–40], respectively. Besides, the surface N/C ratios in
g-C3N4, g-C3N4AHNO3 and g-C3N4AHCl were determined to be
1500 1000 500
-1
1.21, 1.32 and 1.28, respectively. The above XPS results further
demonstrated the formation of graphite-like sp2-bonded graphitic
carbon nitride [37–39]. The Cl 2p XPS spectrum of g-C3N4AHCl
displays two peaks at about 197.9 and 199.6 eV, which can be
assigned to Cl 2p3/2 and Cl 2p1/2 of Cl chemically adsorbed by
g-C3N4AHCl [41].
The FESEM images of g-C3N4, g-C3N4AHNO3 and g-C3N4AHCl
are shown in Fig. 4(a), (b) and (c), respectively. As can be seen
from Fig. 4(a), (b) and (c), all the three samples comprise aggre-
gates of stacked lamellas. Nevertheless, there seems to be some
fractures in the stacked lamellar textures of g-C3N4AHNO3 and
g-C3N4AHCl.
The BET specific surface areas of g-C3N4, g-C3N4AHNO3 and
g-C3N4AHCl were determined to be 8.526, 9.929 and 10.156 m2/g,
respectively, by N2 adsorption/desorption isotherms.
N 1s

C=N-C
Survey N 1s
NH N-(C)3
C 1s
O 1s

g-C3N4-HCl
Cl 2p

g-C3N4-HCl
Intensity (a. u.)
Intensity (a. u.)

g-C3N4-HNO3 g-C3N4-HNO3

g-C3N4 g-C3N4

1000 800 600 400 200 0 404 402 400 398 396
Binding energy (eV) Binding energy (eV)

C 1s N=C-N2
Cl 2p3/2
Cl 2p
Intensity (a. u.)

Intensity (a. u.)

g-C3N4-HCl C-C
Cl 2p1/2

g-C3N4-HNO3

g-C3N4-HCl

g-C3N4

292 290 288 286 284 206 204 202 200 198 196 194
Binding energy (eV) Binding energy (eV)

Fig. 3. XPS spectra of g-C3N4, g-C3N4AHNO3 and g-C3N4AHCl.

254 Y. Zhang et al. / Separation and Purification Technology 142 (2015) 251–257

(a)

g-C3N4-HCl

Absorbance
g-C3N4-HNO3
g-C3N4

200 300 400 500 600 700 800

Wavelength (nm)

(b)

1/2
(αhν) g-C3N4-HCl
g-C3N4-HNO3

g-C3N4

1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2

hν (eV)

Fig. 5. UV–vis diffuse reflectance spectra of g-C3N4, g-C3N4AHNO3 and g-C3N4AHCl

in the absorbance mode, and (b) Tauc plots for estimating the bandgap (Eg) values of
g-C3N4, g-C3N4AHNO3 and g-C3N4AHCl.

1.0

0.8 CA, pH=3.2

g-C3N4-HCl, pH = 5.3
Fig. 4. FESEM images of (a) g-C3N4, (b) g-C3N4AHNO3 and (c) g-C3N4AHCl. g-C3N4-HCl, pH = 3.2
0.6 g-C3N4 + CA, pH = 3.2
Light on
Ct/C0

g-C3N4-HNO3 + CA, pH = 3.2

g-C3N4-HCl + CA, pH = 3.2

The Zeta potentials of g-C3N4, g-C3N4AHNO3 and g-C3N4AHCl 0.4

dispersions in water were determined to be 19.3, +6.2 and
+9.8 mV, respectively, suggesting acid-soaking treatment had
changed g-C3N4 from negative to positive surface charges as a
result of protonation [41].
Fig. 5(a) shows the UV–vis diffuse reflectance spectra of g-C3N4,
g-C3N4AHNO3 and g-C3N4AHCl. All the three samples display obvi-
ous visible-light-absorbing ability with an absorption edge close to
500 nm. Using the Tauc plot approach [42–44], the bandgap (Eg)
values of g-C3N4, g-C3N4AHNO3 and g-C3N4AHCl were estimated
to be about 2.52, 2.49 and 2.47 eV (Fig. 5(b)), which fall within
the range of 2.1–2.8 eV reported for the Eg values of g-C3N4 with
different condensation degrees, C/N ratios and sizes [15–19,45–
47].
Fig. 6a shows the photocatalytic reduction of aqueous Cr(VI)
over g-C3N4, g-C3N4AHNO3 and g-C3N4AHCl in the presence of cit-
ric acid (CA) under visible-light (k > 420 nm) irradiation, as well as
the results from dark adsorption (without irradiation, but with
photocatalyst) and blank experiments (without photocatalyst,
but with irradiation). In the presence of mere CA, there was almost
no change in the Cr(VI) concentration under both the conditions of
0.2
0.0
-30 0 30 60 90 120 150 180 210 240 270 300
Time (min)
Fig. 6a. Photocatalytic reduction of aqueous Cr(VI) over g-C3N4, g-C3N4AHNO3 and
g-C3N4AHCl in the presence of citric acid (CA) under visible-light (k > 420 nm)
irradiation, as well as the results from dark adsorption (without irradiation, but
with photocatalyst) and blank experiments (without photocatalyst, but with
irradiation).
dark and visible-light (k > 420 nm) irradiation (Fig. 6a), implying
that Cr(VI) cannot be chemically reduced directly by CA. In the dark
adsorption experiments, the Cr(VI) concentration first decreased,
then kept constant after the mixing of photocatalyst (e.g., g-C3N4,
g-C3N4AHNO3 and g-C3N4AHCl) and Cr(VI) aqueous solution for
15 min, suggesting that the adsorption–desorption equilibrium
 Y. Zhang et al. / Separation and Purification Technology 142 (2015) 251–257 255

between photocatalyst and Cr(VI) can be achieved after their mix-
ing for 15 min. Nevertheless, g-C3N4AHNO3 and g-C3N4AHCl had
larger adsorption capacities for Cr(VI) than g-C3N4, for instance,
the equilibrium adsorption capacities of g-C3N4, g-C3N4AHNO3
and g-C3N4AHCl for Cr(VI) were about 2.1%, 4.1% and 4.2%, respec-
tively. In the presence of mere g-C3N4AHCl, the decrease of Cr(VI)
concentration was negligible at pH = 5.3 or quite slow at pH = 3.2
under visible-light (k > 420 nm) irradiation (Fig. 6a), meaning that
photocatalytic reduction of aqueous Cr(VI) cannot proceed effi-
ciently in the presence of mere g-C3N4. The reasons accounting
for this phenomenon may be explained as follows. For semicon-
ductor (e.g., g-C3N4 in this work)-mediated photocatalytic reduc-
tion of Cr(VI) in water in the absence of any additional hole
scavengers, the photogenerated electrons in the conduction band
of semiconductor can reduce Cr(VI), whereas the photogenerated
holes in the valence band of semiconductor are generally con-
sumed in the oxidation of water to oxygen. Of the two half reac-
tions occurred during the photocatalytic reduction of Cr(VI) in
water in the absence of any additional hole scavengers, water oxi-
dation is considered a more complicated process that involves
four-electron transfer and reaction [21]. Accordingly, water oxida-
tion is the rate-determining half-reaction for the photocatalytic
reduction of Cr(VI) in water in the absence of any additional hole
scavengers [21]. Thus, it is difficult to achieve the effective separa-
tion of electron–hole pairs and photocatalytic reduction of Cr(VI) in
the absence of any additional hole scavengers. Nonetheless, the
efficiency of the photocatalytic reduction of Cr(VI) in water can
be greatly improved by adding some organic compounds as hole
scavengers [21]. As can be seen from Fig. 6a, in the presence of both
photocatalyst (e.g., g-C3N4, g-C3N4AHNO3 or g-C3N4AHCl) and CA,
Cr(VI) concentration decreased quickly under visible-light
(k > 420 nm) irradiation. The photocatalytic activities of g-C3N4,
After g-C3N4AHNO3 was used in photocatalytic reduction of
aqueous Cr(VI) under visible-light irradiation for 270 min, it was
recovered by centrifugation, washed with deionized water and
ethanol, dried at 80 °C for 12 h. Such recovered g-C3N4AHNO3 (g-
C3N4AHNO3-A1PU) displayed a slightly green surface color, and
its XPS characterization suggested the presence of Cr(III) species,
such as Cr(OH)3. The deposition of Cr(III) species on the surface
of g-C3N4AHNO3-A1PU can occupy the photocatalytically active
sites, leading to serious deactivation of the photocatalyst. Conse-
quently, the photocatalytic activity of g-C3N4AHNO3-A1PU
(Fig. 7(2nd, no HNO3-treated)) was much lower than that of fresh
g-C3N4AHNO3 (Fig. 7(1st)). In order to remove the Cr(III) species
from the surface of g-C3N4AHNO3-A1PU and regenerate the lost
activity, the treatment of g-C3N4AHNO3-A1PU by soaking it in
5 mol/L HNO3 aqueous solution was tried. The results indicated
that the 5 mol/L HNO3-soaking treatment can not only effectively
remove the Cr(III) species from the surface of g-C3N4AHNO3-A1PU
(Fig. 8), but also greatly enhance its photocatalytic activity in the
next reuse (Fig. 7(2nd, HNO3-treated)). However, the treatment
with 5 mol/L HCl aqueous solution cannot remove completely the
deposited Cr(III) species from the surface of g-C3N4AHCl-A1PU
(which denoted the photocatalyst recovered after the first cycle
photocatalytic use of g-C3N4AHCl), thus the 5 mol/L HCl-treated
g-C3N4AHCl-A1PU (Fig. 9(2nd, HCl-treated)) exhibited lower
photocatalytic efficiency than g-C3N4AHCl (Fig. 9(1st)).
1.0 g-C3N4-HNO3 + CA, pH = 3.2
2nd, no HNO 3-treated
1st
0.8
2nd, HNO 3-treated
3rd, HNO3-treated
0.6 4th, HNO3-treated
Ct/C0

g-C3N4AHNO3 and g-C3N4AHCl were in an ascending order of g- 5th, HNO3-treated

C3N4 < g-C3N4AHNO3 < g-C3N4AHCl. The higher photocatalytic

0.4
activities of acid-treated samples may be attributed to their larger
BET specific surface areas, positive surface charges and larger
adsorption capacities for Cr(VI). 0.2
Fig. 6b shows the variation of UV–vis absorption spectra of
Cr(VI)–diphenylcarbazide complex solution (whose absorbance 0.0
intensity is in direct proportion to the Cr(VI) concentration) with
0 30 60 90 120 150 180 210 240 270
irradiation time during photocatalytic reduction of Cr(VI) over
g-C3N4AHCl. The peak intensity of the UV–vis absorption related Irradiation time (min)
to Cr(VI)–diphenylcarbazide complex at 540 nm decreased with
Fig. 7. Photocatalytic performance of g-C3N4AHNO3 in five successive cycles of
the increase of irradiation time, and disappeared after 240 min, photocatalytic use. Note: HNO3-treated = treated with 5 mol/L HNO3 aqueous
indicating that Cr(VI) had been photocatalytically reduced. solution after the former cycle photocatalytic use.

1.0
g-C3N4-HCl + CA, pH = 3.2
C
Irradiation time (min) Au
0.8 0 N
30
Absorbance

60
Au
0.6 90
g-C3N4 -HNO3 -A1PU-HNO3
Intensity (a. u.)

Au
120
150
180
0.4 210 g-C3 N4 -HNO3 -A1PU
240
Cr

0.2

g-C3 N4 -HNO3
0.0
400 450 500 550 600 650 700
Wavelength (nm) 0 2 4 6 8
Energy (keV)
Fig. 6b. Variation of UV–vis absorption spectra of Cr(VI)–diphenylcarbazide
complex solution (whose absorbance intensity is proportional to the Cr(VI) Fig. 8. EDX spectra of g-C3N4AHNO3, g-C3N4AHNO3-A1PU (g-C3N4AHNO3 after the
concentration) with irradiation time during photocatalytic reduction of Cr(VI) over first cycle photocatalytic use) and g-C3N4AHNO3-A1PU-HNO3 (g-C3N4AHNO3-A1PU
g-C3N4AHCl. treated with 5 mol/L HNO3 aqueous solution).
256 Y. Zhang et al. / Separation and Purification Technology 142 (2015) 251–257

1.0 photocatalytic reactions, centrifugation collection and 5 mol/L

g-C3N4-HCl + CA, pH = 3.2 HNO3-soaking treatment, the former cycle was conducted twice
2nd, no HCl-treated
in order to accumulate enough photocatalyst for the next reuse
0.8 2nd, HCl-treated
1st cycle. Fig. 7 shows the performance of g-C3N4AHNO3 in five suc-
cessive cycles of photocatalytic reduction of aqueous Cr(VI)
0.6 under visible-light (k > 420 nm) irradiation. As can be seen from
Ct/C0

Fig. 7, g-C3N4AHNO3 always exhibited higher photocatalytic

0.4
0.2
0.0
0 30 60 90 120 150
Irradiation time (min)
Fig. 9. Photocatalytic activities of g-C3N4AHCl (1st), g-C3N4AHCl-A1PU (g-C3N4-
AHCl after the first cycle photocatalytic use, (2nd, no HCl-treated)) and g-
C3N4AHCl-A1PU-HCl (g-C3N4AHCl-A1PU treated with 5 mol/L HCl, (2nd, HCl-
treated)).
The reusability of g-C3N4AHNO3 in photocatalytic reduction of
aqueous Cr(VI) was examined for five successive cycles in this
work. In each cycle, the dosage of photocatalyst was 300 mg, and
the photocatalytic reactions were conducted until the complete
reduction of Cr(VI). After each cycle photocatalytic use, the
g-C3N4AHNO3 was separated from aqueous suspension by centri-
fugation, soaked in 5 mol/L HNO3 for 6 h, washed with deionized
water and absolute ethanol, and dried at 80 °C for 12 h. Taking into
account the mass loss (<6.7%) of g-C3N4AHNO3 during each cycle
efficiency in the next reuse cycle, suggesting that the 5 mol/L
HNO3-soaking treatment can endow g-C3N4AHNO3 with good
reusability in photocatalytic reduction of aqueous Cr(VI).
The product recovered after the fifth cycle photocatalytic use of
g-C3N4AHNO3 (g-C3N4AHNO3-A5PU) was characterized by XPS.
The survey XPS spectrum of g-C3N4AHNO3-A5PU revealed the
presence of C, N, O and Cr elements (Fig. 10). The C 1s XPS spec-
180 210 240 270
trum displayed two peaks at 284.8 and 288.2 eV (Fig. 10), whereas
the N 1s XPS spectrum can be deconvoluted into three peaks at
398.8, 400.0 and 401.2 eV (Fig. 10), respectively. The binding ener-
gies of C 1s and N 1s of g-C3N4AHNO3-A5PU (Fig. 10) were almost
the same as those of fresh g-C3N4AHNO3 (Fig. 3), suggesting the
chemical states of the C and N components of g-C3N4AHNO3
remained unchanged after the fifth cycle photocatalytic use. The
binding energy of Cr 2p3/2 of g-C3N4AHNO3-A5PU was observed
at 577.3 eV (Fig. 10), which corresponded to Cr(III) [40]. This
suggested that Cr(VI) had been reduced to Cr(III) through
g-C3N4AHNO3-mediated photocatalytic reactions.
4. Conclusions
The treatment of g-C3N4 in 5 mol/L HNO3 or HCl aqueous solu-
tion can enhance its photocatalytic activity in the reduction of
N 1s

Survey N 1s C=N-C

N-(C)3
Intensity (a. u.)

Intensity (a. u.)

C 1s

NH
O 1s
Cr 2p

1000 800 600 400 200 0 404 402 400 398 396
Binding energy (eV) Binding energy (eV)

C 1s N=C-N 2 Cr 2p Cr 2p3/2
Intensity (a. u.)

Intensity (a. u.)

Cr 2p1/2

C-C

292 290 288 286 284 282 596 592 588 584 580 576 572
Binding energy (eV) Binding energy (eV)

Fig. 10. XPS spectra of g-C3N4AHNO3-A5PU (g-C3N4AHNO3 recovered after the fifth cycle photocatalytic use).
 Y. Zhang et al. / Separation and Purification Technology 142 (2015) 251–257
aqueous Cr(VI) under visible-light (k > 420 nm) irradiation. The
higher photocatalytic activities of acid-treated samples may be
attributed to their larger BET specific surface areas, positive surface
charges and larger adsorption capacities for Cr(VI). Furthermore,
the 5 mol/L HNO3 treatment can not only effectively remove the
deposited Cr(III) species from the surface of g-C3N4 after use in
photocatalytic reduction of aqueous Cr(VI), but also enhance the
photocatalytic efficiency of g-C3N4 in the reuses.
Acknowledgments
This work was financially supported by National Natural
Science Foundation of China (21475116) and the Priority Academic
Program Development of Jiangsu Higher Education Institutions.
Thanks also to The Testing Center of Yangzhou University for the
TEM and UV–vis characterization.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.seppur.2014.12.
041.
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