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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.
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 Nano ZS90, and UV–vis diffuse reflectance spectra (The United
example, Dong et al. reported that carbon self-doping or incorpora- States Varian Cary 5000 UV–Vis–NIR spectrophotometer).
tion of formate anions could improve the photocatalytic activity of
g-C3N4 in Cr(VI) reduction under visible light irradiation [23,24]. 2.3. Photocatalytic tests
However, their modification strategies required extra hydrother-
mal treatment in tailor-made autoclaves at 200 °C or 150 °C for Photocatalytic properties of the products were tested in the
24 h, which are complex, time-consuming, uneconomical and reduction of aqueous Cr(VI) under visible-light (k > 420 nm) irradi-
inappropriate for industrial production. Although some other sim- ation in custom-made photochemical reactor (Supplementary
pler strategies such as thermal oxidation etching [25] and ultra- materials, Fig. S1). Prior to illumination, 300 mL of 50 mg/L
sound-assisted liquid exfoliation from bulk g-C3N4 into ultrathin K2Cr2O7 aqueous solution with the addition of 300 mg of photocat-
g-C3N4 nanosheets [26], have also been proposed, the yields of alyst and 1.0 mL of 100 mg/mL citric acid aqueous solution was
the resultant products were very low, for instance, only around ultrasonically dispersed for 5 min and magnetically stirred for
6 wt% g-C3N4 was left by thermal oxidation etching at 500 °C for 30 min in dark to ensure the adsorption–desorption equilibrium
2 h [25], and only about 15 wt% g-C3N4 could be exfoliated after between photocatalyst and Cr(VI). During illumination, about
intense ultrasonic treatment for 16 h [26]. Therefore, there is still 4 mL of suspension was taken from the reactor at a scheduled
a need to explore economical and efficient ways to improve the interval and filtered with pore size = 0.22 lm cellulose acetate
photocatalytic activity of g-C3N4. membrane filter to separate the photocatalyst. The Cr(VI) contents
Herein, an alternative simple, economical and efficient acid- in the filtrates were determined using the diphenylcarbazide color-
soaking method was proposed to enhance the photocatalytic activ- imetric method with a detection limit of 0.005 mg/L [27,28].
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
2.4. Determination of Cr(VI) using the diphenylcarbazide colorimetric
soaking it in 5 mol/L HNO3 or HCl aqueous solution for 2 h. The
method [27,28]
photocatalytic properties of the acid-treated products were tested
in the reduction of aqueous Cr(VI) under visible-light (k > 420 nm)
1.0 mL of sample was mixed with 9.0 mL of 0.2 mol/L H2SO4 in a
irradiation.
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
2. Experimental
was allowed to stand for 15 min to ensure full color development.
Using the reagent blank solution (that is, the solution contains all
K2Cr2O7 was a guaranteed reagent, melamine was chemically
the other substances, except for Cr(VI)) as reference, the absor-
pure, whereas all the other chemicals were analytically pure.
bance of the colored Cr(VI)–diphenylcarbazide complex solution
50 mg/L K2Cr2O7 aqueous solution (pH = 5.3) was prepared by dis-
was then measured at kmax = 540 nm.
solving 500 mg of K2Cr2O7 in 10.0 L of deionized water.
2.2. Characterization
Intensity (a. u.)
g-C3N4-HCl
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, g-C3N4-HNO3
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 g-C3N4
X-ray spectroscopy (FESEM and EDX, Japan Hitachi S-4800 FESEM
configured with a Noran energy dispersive X-ray analyzer), N2 10 20 30 40 50 60 70 80
adsorption (The United States Micromeritics Instrument Corpora- 2θ (deg.)
tion TriStar II 3020 surface area and porosity analyzer), Zeta poten-
tial analyzer (The United Kingdom Malvern Instruments Zetasizer 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
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.)
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)
(a)
g-C3N4-HCl
Absorbance
g-C3N4-HNO3
g-C3N4
(b)
1/2
(αhν) g-C3N4-HCl
g-C3N4-HNO3
g-C3N4
1.0
between photocatalyst and Cr(VI) can be achieved after their mix- After g-C3N4AHNO3 was used in photocatalytic reduction of
ing for 15 min. Nevertheless, g-C3N4AHNO3 and g-C3N4AHCl had aqueous Cr(VI) under visible-light irradiation for 270 min, it was
larger adsorption capacities for Cr(VI) than g-C3N4, for instance, recovered by centrifugation, washed with deionized water and
the equilibrium adsorption capacities of g-C3N4, g-C3N4AHNO3 ethanol, dried at 80 °C for 12 h. Such recovered g-C3N4AHNO3 (g-
and g-C3N4AHCl for Cr(VI) were about 2.1%, 4.1% and 4.2%, respec- C3N4AHNO3-A1PU) displayed a slightly green surface color, and
tively. In the presence of mere g-C3N4AHCl, the decrease of Cr(VI) its XPS characterization suggested the presence of Cr(III) species,
concentration was negligible at pH = 5.3 or quite slow at pH = 3.2 such as Cr(OH)3. The deposition of Cr(III) species on the surface
under visible-light (k > 420 nm) irradiation (Fig. 6a), meaning that of g-C3N4AHNO3-A1PU can occupy the photocatalytically active
photocatalytic reduction of aqueous Cr(VI) cannot proceed effi- sites, leading to serious deactivation of the photocatalyst. Conse-
ciently in the presence of mere g-C3N4. The reasons accounting quently, the photocatalytic activity of g-C3N4AHNO3-A1PU
for this phenomenon may be explained as follows. For semicon- (Fig. 7(2nd, no HNO3-treated)) was much lower than that of fresh
ductor (e.g., g-C3N4 in this work)-mediated photocatalytic reduc- g-C3N4AHNO3 (Fig. 7(1st)). In order to remove the Cr(III) species
tion of Cr(VI) in water in the absence of any additional hole from the surface of g-C3N4AHNO3-A1PU and regenerate the lost
scavengers, the photogenerated electrons in the conduction band activity, the treatment of g-C3N4AHNO3-A1PU by soaking it in
of semiconductor can reduce Cr(VI), whereas the photogenerated 5 mol/L HNO3 aqueous solution was tried. The results indicated
holes in the valence band of semiconductor are generally con- that the 5 mol/L HNO3-soaking treatment can not only effectively
sumed in the oxidation of water to oxygen. Of the two half reac- remove the Cr(III) species from the surface of g-C3N4AHNO3-A1PU
tions occurred during the photocatalytic reduction of Cr(VI) in (Fig. 8), but also greatly enhance its photocatalytic activity in the
water in the absence of any additional hole scavengers, water oxi- next reuse (Fig. 7(2nd, HNO3-treated)). However, the treatment
dation is considered a more complicated process that involves with 5 mol/L HCl aqueous solution cannot remove completely the
four-electron transfer and reaction [21]. Accordingly, water oxida- deposited Cr(III) species from the surface of g-C3N4AHCl-A1PU
tion is the rate-determining half-reaction for the photocatalytic (which denoted the photocatalyst recovered after the first cycle
reduction of Cr(VI) in water in the absence of any additional hole photocatalytic use of g-C3N4AHCl), thus the 5 mol/L HCl-treated
scavengers [21]. Thus, it is difficult to achieve the effective separa- g-C3N4AHCl-A1PU (Fig. 9(2nd, HCl-treated)) exhibited lower
tion of electron–hole pairs and photocatalytic reduction of Cr(VI) in photocatalytic efficiency than g-C3N4AHCl (Fig. 9(1st)).
the absence of any additional hole scavengers. Nonetheless, the
efficiency of the photocatalytic reduction of Cr(VI) in water can 1.0 g-C3N4-HNO3 + CA, pH = 3.2
be greatly improved by adding some organic compounds as hole
2nd, no HNO 3-treated
scavengers [21]. As can be seen from Fig. 6a, in the presence of both 1st
photocatalyst (e.g., g-C3N4, g-C3N4AHNO3 or g-C3N4AHCl) and CA, 0.8
2nd, HNO 3-treated
Cr(VI) concentration decreased quickly under visible-light 3rd, HNO3-treated
(k > 420 nm) irradiation. The photocatalytic activities of g-C3N4, 0.6 4th, HNO3-treated
Ct/C0
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
Survey N 1s C=N-C
N-(C)3
Intensity (a. u.)
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.)
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) 251–257 257
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