Journal of Colloid and Interface Science 540 (2019) 237–246

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Journal of Colloid and Interface Science

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

Regular Article

Constructing high-efficiency photocatalyst for degrading ciprofloxacin:

Three-dimensional visible light driven graphene based NiAlFe LDH
Jianxing Liang, Ying Wei, Yan Yao, Xiaoke Zheng, Jing Shen, Guangyu He ⇑, Haiqun Chen ⇑
Key Laboratory of Advanced Catalytic Materials and Technology, Advanced Catalysis and Green Manufacturing Collaborative Innovation Center, Changzhou University,
Changzhou, Jiangsu Province 213164, China

g r a p h i c a l a b s t r a c t
Proposed mechanism for the photocatalytic degradation of CIP in the presence of NiAl0.85Fe0.15 LDH/RGO25.

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

Article history: A three-dimensional (3D) graphene based photocatalyst, consisting of Fe(III)-doped NiAl layered double
Received 24 September 2018 hydroxide (NiAlFe LDH), was prepared via a simple one-step hydrothermal approach for the first time.
Revised 2 January 2019 The growth of NiAlFe LDH nanoplates and the reduction of graphene oxide were accomplished simulta-
Accepted 3 January 2019
neously during hydrothermal process without adding toxic reductant and toxic solvent. No complex and
Available online 6 January 2019
time-consuming preparation steps were needed. The structural characterization shows that NiAlFe LDH
nanoplates with a size of 100–150 nm vertically grow on the reduced graphene oxide (RGO) sheet, form-
Keywords:
ing a unique 3D structured graphene based photocatalyst (NiAlFe LDH/RGO). The photocatalyst was
Three-dimensional graphene based
photocatalyst
applied for the first time to remove ciprofloxacin (CIP) in wastewater under visible-light illumination.
Layered double hydroxide Interestingly, after incorporating with an appropriate amount of Fe3+ and RGO, the NiAl LDH shows
Photocatalytic degradation improved photocatalytic degradation performance in comparison with reported photocatalysts. The reac-
Ciprofloxacin tion rate in the presence of NiAlFe LDH/RGO is respectively 2.4 and 7.3 times faster than that in the pres-
Visible light ence of NiAl0.85Fe0.15 LDH and NiAl LDH, demonstrating that the addition of Fe3+ and RGO can improve
synergistically the photocatalytic performance of the nanocomposite. Moreover, the photocatalytic
mechanism of the 3D NiAlFe LDH/RGO photocatalyst was also investigated in detail.
Ó 2019 Elsevier Inc. All rights reserved.

1. Introduction

Water pollution has become a serious environmental issue

⇑ Corresponding authors. influencing our health [1,2]. Photocatalysis has aroused extensive
E-mail addresses: hegy@cczu.edu.cn (G. He), hqchenyf@hotmail.com (H. Chen). attention of researchers for its application in removing organic

https://doi.org/10.1016/j.jcis.2019.01.011
0021-9797/Ó 2019 Elsevier Inc. All rights reserved.
238 J. Liang et al. / Journal of Colloid and Interface Science 540 (2019) 237–246
pollutants in water, such as antibiotic residues, because of its low
energy-consumption and environmental friendliness [3–5].
As dramatic progress being achieved in nanoscience and nan-
otechnology, various kinds of nanophotocatalysts have been devel-
oped, including metal oxide, metal sulfide, layered double
hydroxide, etc. [6–13]. Among them, layered double hydroxide
(LDH) is regarded as a promising kind of photocatalyst, owing to
its unique layered structure and tunable composition [14,15].
Lately, series of LDHs used as efficient photocatalysts in the treat-
ment of water pollution have been reported [16,17]. However, pris-
tine monolayer LDH has poor charge mobility and high density of
surface charge, which respectively gives rise to prompt recombina-
tion of photogenerated electron-hole pairs and easy aggregation of
LDH nanoplates, reducing its photocatalytic activity [18–20].
Therefore, strategies have been explored to improve the photocat-
alytic activity of LDH.
Metal elements doping, one of the typical strategies, is exten-
sively used to enhance the photocatalytic activity of LDH [21]. Par-
ida et al. reported a co-precipitation approach to fabricate Cu/Cr
LDH doped with Co2+, which showed excellent photocatalytic per-
formance towards the degradation of malachite green under sun-
light illumination [22]. Other metal elements, such as Tb, Fe, Ce
and Ni, were also doped with LDH to improve its photocatalytic
activity [23–26]. Among those metal elements, Fe has attracted
extensive attention due to its low cost, nontoxicity and unique
electronic configuration [27]. For example, Mantilla et al. prepared
Fe3+ doped ZnAl LDH by co-precipitation method, which exhibited
great photocatalytic activity for the degradation of 2, 4-
dichlorophenoxyacetic acid [28]. Although metal element doping
can inhibit the recombination of photogenerated electron-hole
pairs therefore improving the activity of the photocatalysts, the
aggregation of LDH nanoplates remains a serious problem.
Graphene, a two-dimensional carbon material, has been widely
served as an ideal carrier for nanoplates, owing to its superior elec-
tron mobility as well as large specific surface areas [29,30]. The
coupling of LDHs with graphene was reported to be able to effec-
tively facilitate the separation of photogenerated electron-hole
pairs in nanocomposites and suppress the aggregation of LDH
nanoplates [31–33]. Hwang et al. reported a ZnCr LDH-graphene
nanohybrid, which was prepared by electrostatically derived self-
assembly and exhibited great photocatalytic activity on O2-
generation [34]. Li et al. spent 24 h fabricating a hybrid nanocom-
posite, ZnCr LDH/RGO, using co-precipitation method, which dis-
played a promoted photocatalytic activity toward the
degradation of RhB [35]. Nevertheless, the preparation of graphene
based LDH (LDH/graphene) photocatalysts through electrostatic
self-assembly or co-precipitation is complex. Multiple preparation
steps and long synthetic time are required. Hence, exploiting a
facile method to prepare LDH/graphene photocatalysts is meaning-
ful. Apart from that, a structural change might also be meaningful
in terms of enhancing the catalytic activity of the nanocomposite.
LDH/graphene photocatalysts with LDH nanoplates horizontally
deposited on the graphene sheets have been reported [33–35]. If
the LDH nanoplates can be vertically deposited onto graphene
sheets to form a three-dimensional (3D) LDH/graphene photocata-
lysts, a larger specific surface area, more adsorption and active
sites, and less aggregation of LDH can definitely be obtained,
thereby an improved photocatalytic activity.
In our previous work, we have investigated in detail the prepa-
ration of graphene and dedicated to developing a variety of meth-
ods to fabricate graphene-based photocatalysts [19,36–40]. Based
on our research results, we prepared, for the first time, a 3D NiAlFe
LDH/RGO photocatalysts via a simple one-step hydrothermal
method. Neither complex nor time-consuming preparation steps
are needed. It costs only half of the time that Li et al. spent with
just one preparation step required [35]. Moreover, no toxic
chemical reductants or additional toxic solvents were used. Struc-
tural characterization proves that both the vertical growth of
NiAlFe LDH nanoplates on the surface of graphene and the reduc-
tion of graphene oxide are accomplished simultaneously during
hydrothermal process. Moreover, the as-prepared 3D NiAl0.85Fe0.15
LDH/RGO25 was applied, also for the first time, in degrading CIP
under visible light illumination, where remarkable photocatalytic
performance with good stability was observed. The degradation
rate constant in the presence of NiAl0.85Fe0.15 LDH/RGO25 is 2.4
and 7.3 times higher than that in the presence of NiAl0.85Fe0.15
LDH and pristine NiAl LDH, respectively. More importantly, the
performance of NiAl0.85Fe0.15 LDH/RGO25 is superior to that of some
photocatalysts previously reported [19].
2. Experimental section
2.1. Experimental reagents
Natural graphite powder (99.85%, 500 mesh), Ni(NO3)2
6H2O, Al
(NO3)3
9H2O, Fe(NO3)3
9H2O and CON2H4 were purchased from
Sinopharm Chemical Reagent Co., Ltd. All reagents were analytical
reagent (AR) and used as received without further purification.
Graphite oxide (GO) was fabricated by Hummers method [41].
2.2. Preparation of NiAl1-XFeX LDH/RGO nanocomposites
NiAl1-XFeX LDH nanocomposites with a varying molar ratio of Fe
(X = 0, 0.05, 0.1, 0.15, 0.2 and 0.3, respectively) and NiAl0.85Fe0.15
LDH/RGOY with a diverse mass ratio of RGO (Y = 0, 5, 15, 25 and
35 wt%, respectively) were prepared by a facile hydrothermal
method. The preparation process is demonstrated in Scheme 1.
The representative preparation procedure of NiAl0.85Fe0.15 LDH/
RGO25 is as follow: 0.29 g of Ni(NO3)2
6H2O, 0.16 g of Al(NO3)3-

9H2O and 0.03 g of Fe(NO3)3
9H2O are dissolved in a 20 mL of
aqueous ethanol solution (VC2 H5 OH =VH2 O ¼ 1). The obtained solution
is then added dropwise under vigorous stirring to a GO suspension,
which is prepared by ultrasonically dispersing 1.64 g of GO colloid
(2.6 wt%) in 40 mL of aqueous ethanol solution. After stirring for
3 h, 0.48 g of urea, dissolved in 20 mL of aqueous ethanol solution,
is added and stirred for another 1 h. The mixed suspension is then
transferred into a 100 mL Teflon-lined autoclave and kept at 120 °C
for 12 h. After that, the as-prepared black product is filtered and
rinsed with distilled water and ethanol before dried in a vacuum
oven at 60 °C for 12 h.
For comparison, the above procedure was carried out in the
absence of Fe3+ to obtain NiAl LDH/RGO25 nanocomposite, and in
the absence of metal ions to obtain RGO. Besides, NiAl0.85Fe0.15
LDH (75 wt%) and 25 wt% of RGO were mechanically mixed and
denoted as NiAl0.85Fe0.15 LDH + RGO25.
2.3. Characterization of NiAl0.85Fe0.15 LDH/RGO nanocomposites
The crystal structures of the as-prepared samples were identi-
fied by X-ray diffraction (XRD) with Bruker D8 Advance X-ray pow-
der diffractometer by Cu Ka radiation (k = 0.154178 nm). The X-ray
photoelectron spectra (XPS) were obtained by an RBD upgraded
PHI-5000C ESCA system (Perkin-Elmer) with Mg Ka source
(hv = 1253.8 eV). The Fourier transform infrared (FTIR) spectra of
the samples were recorded on a Nicolet 370 spectrometer. Raman
spectra of the as-prepared nanocomposites were acquired using a
Renishaw in Via Reflex Raman microprobe. The morphological
properties were investigated by field emission scanning electron
microscopy (FE-SEM) (S-900 microscopy) and transmission elec-
tron microscopy (TEM) (JEM-2100 microscope), respectively. And
the metal composition was determined with an energy dispersive
 J. Liang et al. / Journal of Colloid and Interface Science 540 (2019) 237–246
Scheme 1. Illustration of the preparation process of NiAlFe LDH/RGO nanocomposite.
X-ray spectrometer (EDS). The Brunauer-Emmet-Teller (BET)
specific surface area of the as-prepared samples were measured
on ASAP2010C surface aperture adsorption instrument by nitrogen
physisorption at 77 K. The optical absorption properties of the pho-
tocatalysts were investigated using a UV–vis diffuse reflectance
spectrophotometer (Shimadzu, Japan) equipped with an integrat-
ing sphere in the range of 200–800 nm and BaSO4 powder as a
reflectance standard. Photoluminescence (PL) spectra of the sam-
ples were performed on a Jobin Yvon SPEX Fluorolog 3P spectrom-
eter. Electrochemical impedance spectra (EIS) were recorded on a
CHI920 workstation.
2.4. Photocatalytic performance measurement
Catalytic performance of the as-prepared photocatalysts was
appraised by degrading CIP under visible-light illumination at
25 °C. The photocatalytic experiments were performed using a
500 W xenon lamp equipped with a UV cutoff filter (k > 420 nm).
10 mg of photocatalyst was added into 40 mL of CIP solution
(10 mg
L1) in a quartz tube and vigorously stirred in dark for
30 min to reach complete adsorption-desorption equilibrium of
CIP on the as-prepared photocatalysts. Then, the reaction solution
was illuminated under visible-light irradiation. 3 mL of aliquots
were collected at time interval of 30 min and centrifuged. The con-
centration change of CIP in the supernatant was detected using an
UV–vis spectrophotometer.
Fig. 1. (A) XRD patterns of NiAl LDH, NiAl0.85Fe0.15 LDH, NiAl0.85Fe0.15 LDH/RGO25 and RGO. (B) Wide-scan XPS spectrum of NiAl0.85Fe0.15 LDH/RGO25. (C) C 1s, (D) Ni 2p, (E) Al
2p and (F) Fe 2p core-level XPS spectra of NiAl0.85Fe0.15 LDH/RGO25.
239
3. Results and discussion
3.1. Characterization of NiAl0.85Fe0.15 LDH/RGO nanocomposites
The XRD patterns of NiAl LDH, NiAl0.85Fe0.15 LDH and NiAl0.85-
Fe0.15 LDH/RGO25 are shown in Fig. 1A. NiAl LDH, NiAl0.85Fe0.15
LDH and NiAl0.85Fe0.15 LDH/RGO25 all display characteristic peaks
of (0 0 3), (0 0 6), (0 1 2), (0 1 5), (0 1 8), (1 1 0) and (1 1 3) planes,
which are similar to standard NiAl hydrotalcite (JCPDS No. 15-
0087), demonstrating that the hydrotalcite structure is success-
fully prepared by the hydrothermal method [42]. However,
NiAl0.85Fe0.15 LDH shows weaker characteristic peak intensity in
comparison with NiAl LDH. It may be because an isomorphic sub-
stitution of Fe3+ for Al3+ causes the lattice distortion, leading to
lower crystallinity and stability [23,24,43]. Further broadened
and weakened diffraction peaks are observed in the XRD pattern
of NiAl0.85Fe0.15 LDH/RGO25, which indicates that the introduction
of graphene affects the nucleation and crystal size of NiAl0.85Fe0.15
LDH nanoplates [19,44,45]. The crystallite size ofNiAl0.85Fe0.15 LDH
and NiAl0.85Fe0.15 LDH/RGO25 was calculated respectively by Scher-
rer equation to be 10.2 and 8.95 nm, which further confirms that
the introduction of graphene results in the formation of smaller
NiAl0.85Fe0.15 LDH plates in the composite. Moreover, no character-
istic peak of RGO (0 0 2) can be found in the XRD pattern of
NiAl0.85Fe0.15 LDH/RGO25, which is because RGO sheets can be
effectively exfoliated hydrothermally, leading to the decline of
structural integrity [44,46,47].
240 J. Liang et al. / Journal of Colloid and Interface Science 540 (2019) 237–246
The wide-scan XPS spectrum of NiAl0.85Fe0.15 LDH/RGO25 shown
in Fig. 1B confirms the presence of C, O, Ni, Al and Fe elements. The
C 1s high-resolution spectrum of the nanocomposite is presented
in Fig. 1C. Peaks at about 284.8, 286.0, 287.5 and 289.1 eV can be
attributed to C@C, CAO, CAOAC, and OAC@O, respectively [48–
50]. The peak intensity of the carbons in oxygen-containing func-
tional groups in NiAl0.85Fe0.15 LDH/RGO25 are apparently lower
than that in GO, confirming that GO is reduced to RGO during
hydrothermal reaction [51]. The spectra of Ni 2p, Al 2p and Fe 2p
are presented in Fig. 1D, E and F, respectively. The peaks shown
in Fig. 1D at 856.3 and 874.1 eV can be ascribed to Ni 2p3/2 and
Ni 2p1/2. In addition, two shakeup satellite peaks located at 862.5
and 879.9 eV are detected, which provides an evidence for the
presence of Ni2+ [52,53]. Fig. 1E demonstrates the existence of
Al3+ in the nanocomposites [54]. The peaks of Fe 2p3/2 and Fe
2p1/2 are found at 712.5 and 725.3 eV (Fig. 1F), corresponding to
Fe3+ [19,55].
FTIR spectra of NiAl LDH, NiAl0.85Fe0.15 LDH, NiAl0.85Fe0.15 LDH/
RGO25 and GO are illustrated in Fig. 2A. FTIR spectra of NiAl LDH
and NiAl0.85Fe0.15 LDH show almost analogous absorption peaks
in the range of 1000–4000 cm1. The peak centered at approxi-
mately 1629 cm1 represents the bending mode of interlayer
water molecules [46,56]. The relatively intensive absorption peak
at approximately 1363 cm1 can be ascribed to the asymmetrical
stretching vibration of carbonate (CO2 3 ) anions in LDH [57,58].
Absorption peaks appeared in the range of 500–600 cm1 are
assigned to the vibrations of metal–oxygen bonds in the hydrotal-
cite [31,44]. In the FTIR spectrum of GO, the peaks located at 3410,
2918, 2850, 1716 and 1622 cm1 are attributed to the stretching
vibration of OAH, the anti-symmetrical of CH2, the symmetrical
vibration of CH2, the stretching vibration of C@O and the stretching
vibration of C@C, respectively [38,40]. The absorption peaks
appeared at 1380 and 1090 cm1 can be interpreted as the bending
vibration of CAO [59]. Nonetheless, the absorption peaks correlat-
ing with the oxygen-containing functional groups disappear or
weaken in the spectrum of NiAl0.85Fe0.15 LDH/RGO25, indicating
the reduction of GO in the nanocomposites after the hydrothermal
reaction [44,60]. Notably, the absorption peaks of metal-oxygen
(500–600 cm1) in the NiAl0.85Fe0.15 LDH/RGO25 shifts to higher
wavenumber compared with those of pristine NiAl0.85Fe0.15 LDH,
proving that NiAl0.85Fe0.15 LDH/RGO is a composite rather than a
mechanically mixed mixture [47].
Two intense peaks at about 1362 cm1 and 1605 cm1 in the
Raman spectrum of GO (Fig. 2B) correspond respectively to the D
and G bands of carbon materials [57]. Shift of the D and G bands
to lower frequency (1347 and 1597 cm1, respectively) in the spec-
trum of NiAl0.85Fe0.15 LDH/RGO25 demonstrates that GO is reduced
to RGO after the hydrothermal treatment [59,61]. The intensity
ratio of D and G bands (ID/IG) of NiAl0.85Fe0.15 LDH/RGO25,
calculated to be 1.14, is much higher than that of GO (ID/
Fig. 2. (A) FTIR spectra of NiAl LDH, NiAl0.85Fe0.15 LDH, NiAl0.85Fe0.15 LDH/RGO25 and GO. (B) Raman spectra of GO, RGO and NiAl0.85Fe0.15 LDH/RGO25.
IG = 0.81), revealing further the reduction of GO in the formation
of NiAl0.85Fe0.15 LDH/RGO25. Besides, the results also strongly imply
that smaller but more numerous in-plane sp2 domains are formed
during the reduction of GO [44,62].
The morphology and microstructure of NiAl0.85Fe0.15 LDH and
NiAl0.85Fe0.15 LDH/RGO25 were investigated by SEM and TEM. As
shown in Fig. 3A and C, NiAl0.85Fe0.15 LDH nanoplates stack disor-
derly, whereas, after the introduction of graphene, NiAl0.85Fe0.15
LDH nanoplates deposit uniformly and almost vertically on RGO
sheets, forming a 3D structured NiAl0.85Fe0.15 LDH/RGO25
nanocomposite (Fig. 3B and 3D). Notably, the size of NiAl0.85Fe0.15
LDH nanoplates in the nanocomposites is approximately in the
range of 100–150 nm, which is smaller than that of pure NiAl0.85-
Fe0.15 LDH with no RGO integrated. A possible explanation is that
the integration of RGO decreases the agglomeration of NiAl0.85-
Fe0.15 LDH during hydrothermal process [32,45].
The EDS spectrum and elemental mapping of NiAl0.85Fe0.15 LDH/
RGO25 are shown in Fig. 3E. The EDS spectrum reveals that the
nanocomposite is comprised of C, O, Ni, Al and Fe elements (the
presence of Pt element comes from Pt substrate). The elemental
mapping indicates a uniform distribution of C, Ni, Al and Fe ele-
ments in the nanocomposites.
BET surface area and porous structure of NiAl0.85Fe0.15 LDH/
RGO25 were studied by nitrogen adsorption/desorption isotherm.
As shown in Fig. 3F, isotherms of all samples exhibit classical
IUPAC type IV shape with a distinct H3-type hysteresis loop in
the relative pressure range of 0.4–1.0, confirming the presence of
mesopores [34,53,63]. An average pore size of NiAl0.85Fe0.15 LDH/
RGO25 nanocomposites is calculated to be 4.11 nm according to
BJH equation (Fig. S1). The BET specific surface area of NiAl0.85Fe0.15
LDH/RGO25 (146.48 m2
g1) is noticeably larger than that of both
NiAl LDH (63.74 m2
g1) and NiAl0.85Fe0.15 LDH (86.82 m2
g1),
indicating that the introduction of RGO successfully inhibits the
agglomeration of LDH nanoplates and enlarges the specific surface
area of the nanocomposite. It’s worth mentioning that the 3D
NiAl0.85Fe0.15 LDH/RGO25 we prepared in this work has larger
specific surface area than that of the 2D NiAl LDH/Fe3O4-RGO we
reported previously (93.76 m2
g1) [19]. Generally speaking, larger
specific surface area leads to more sufficient exposure of active
sites, and allows more pollutant molecules to be adsorbed on the
surface of photocatalysts, which is conducive to the photocatalytic
degradation [25]. Therefore, enhanced photocatalytic activity of
the 3D NiAl0.85Fe0.15 LDH/RGO25 nanocomposite can be expected.
UV–vis diffuse reflectance spectra of NiAl LDH, NiAl0.85Fe0.15
LDH and NiAl0.85Fe0.15 LDH/RGO25 photocatalysts are presented
in Fig. 4. NiAl LDH has an intense absorption only in a narrow
region of 200–300 nm while NiAl0.85Fe0.15 LDH exhibits a relatively
stronger and much wider absorption peak in the range of
200–600 nm, which is ascribed to the d-d transition of Fe3+
[19,23,64]. In the meantime, the addition of graphene dramatically
 J. Liang et al. / Journal of Colloid and Interface Science 540 (2019) 237–246 241

Fig. 3. SEM images of (A) NiAl0.85Fe0.15 LDH and (B) NiAl0.85Fe0.15 LDH/RGO25. TEM images of (C) NiAl0.85Fe0.15 LDH and (D) NiAl0.85Fe0.15 LDH/RGO25. (E) EDS spectrum of
NiAl0.85Fe0.15 LDH/RGO25 and elemental mapping of C, Ni, Al and Fe of NiAl0.85Fe0.15 LDH/RGO25 (inset). (F) Nitrogen adsorption/desorption isotherms of (a) NiAl0.85Fe0.15 LDH/
RGO25, (b) NiAl0.85Fe0.15 LDH and (c) NiAl LDH.

3.2. Study on photocatalytic performance of NiAl1-XFeX LDH/RGO

nanocomposites

Degradation of CIP under visible-light irradiation was chosen to

Fig. 4. UV–vis diffuse reflectance spectra of NiAl LDH, NiAl0.85Fe0.15 LDH and
NiAl0.85Fe0.15 LDH/RGO25.
enhances the optical absorption of NiAl0.85Fe0.15 LDH/RGO25, espe-
cially in the visible light region [35,65]. Thus, effective and ade-
quate exploitation of visible light in photodegradation using
NiAl0.85Fe0.15 LDH/RGO25 as a photocatalyst is expected [40,66].
assess the catalytic performance of the as-prepared photocatalysts.
Fig. 5A shows the photocatalytic activity of NiAl1-XFeX LDH towards
the degradation of CIP under visible-light illumination at 25 °C.
With increasing the Fe content from 0 to 0.15, the photocatalytic
activity of the nanocomposite is enhanced. The key reason to
account for the enhancement is that Fe3+ ions serve as trapping
sites to capture the photogenerated electrons, suppressing the
recombination of the photogenerated electron-hole pairs thereby
extending their lifetime [64,67,68]. However, as the Fe content
exceeds 0.15, the photodegradation performance of the photocata-
lyst begins to decline. It may be because Fe3+ becomes a recombi-
nation center for the photogenerated electron-hole pairs where the
excess Fe3+ reacts with electrons it captures to generate Fe2+, which
reacts promptly with holes to regenerate Fe3+ [69,70]. So, the
NiAl0.85Fe0.15 LDH with the Fe content of 0.15 was chosen for the
subsequent performance evaluations.
The influence of RGO content on the photocatalytic degradation
of CIP over NiAl0.85Fe0.15 LDH/RGOY (Y = 0, 5, 15, 25 and 35 wt%,
242 J. Liang et al. / Journal of Colloid and Interface Science 540 (2019) 237–246

Fig. 5. (A) Effect of Fe content in NiAl1-XFeX LDH on photocatalytic degradation of CIP (X = 0, 0.05, 0.1, 0.15, 0.2 and 0.3, from a to f, respectively). (B) Effect of RGO content on
photocatalytic degradation of CIP over NiAl0.85Fe0.15 LDH/RGOY (Y = 0, 5, 15, 25 and 35 wt%, from a to e, respectively). (C) Pseudo-first-order kinetic for the photocatalytic
degradation towards CIP using NiAl LDH, NiAl0.85Fe0.15 LDH, NiAl LDH/RGO25, NiAl0.85Fe0.15 LDH + RGO25 and NiAl0.85Fe0.15 LDH/RGO25 as catalyst, respectively. (D) Cycling
experiment of photocatalytic degradation towards CIP over NiAl0.85Fe0.15 LDH/RGO25 under visible-light irradiation.

respectively) was also investigated. As can be seen from Fig. 5B, the
adsorption of NiAl0.85Fe0.15 LDH/RGOY towards CIP in the dark is
promoted as the RGO content is increased. It is because the intro-
duction of RGO offers NiAl0.85Fe0.15 LDH/RGOY larger specific sur-
face area in comparison with NiAl0.85Fe0.15 LDH and NiAl LDH,
promotes the p-interaction between RGO and CIP molecules, and
provides more sites to adsorb CIP [71,72]. After reaching
adsorption-desorption equilibrium, the reaction solution is illumi-
nated by visible light. Significantly increased photocatalytic degra-
dation efficiency of CIP is observed with increasing the content of
RGO in NiAl0.85Fe0.15 LDH/RGOY nanocomposite. The photocatalytic
degradation efficiency reaches 93% when the RGO content is raised
to 25 wt%. The possible reason is that the addition of RGO restrains
the aggregation of LDH nanoplates, and hinders effectively the
rapid recombination of photogenerated electron-hole pairs as well.
It is known that the adsorption of target molecules on photocata-
lyst is the prerequisite of photocatalytic degradation [40]. Thus,
the photocatalytic activity of the photocatalyst should be enhanced
when the adsorption increases with the increase of the RGO con-
tent in the photocatalyst [73]. Nevertheless, when the RGO content
surpasses 25 wt%, the photocatalytic performance of NiAl0.85Fe0.15
LDH/RGOY toward the degradation of CIP begins to decline, which
may be because the extra RGO wraps up the LDH nanoplates,
therefore, hinders the exposure of active sites in the photocatalyst
to CIP, leading to a declined photocatalytic performance.
Besides, the photocatalytic activity of different photocatalysts
on degrading CIP was investigated. As shown in Fig. S2, under
the same experimental condition, the photocatalytic efficiency of
the samples toward the degradation of CIP follows this order:
NiAl0.85Fe0.15 LDH/RGO25 (93%) > NiAl LDH/RGO25 (75%) > NiAl0.85-
Fe0.15 LDH + RGO25 (66%) > NiAl0.85Fe0.15 LDH (54%) > NiAl LDH
(31%). The order indicates that introducing Fe3+ and RGO signifi-
cantly improved the photocatalytic activity of the nanocomposite.
To further explore the photocatalytic degradation activity of the
prepared samples, pseudo-first-order kinetic equation
lnðC0 =Ct Þ¼ kt was used to fit the degradation of CIP (Fig. 5C),
where k is the photocatalytic reaction rate constant under
visible-light illumination, C0 and Ct are the concentration of CIP
when the irradiation time is 0 and t, respectively. The rate constant
in the presence of NiAl LDH, NiAl0.85Fe0.15 LDH, NiAl LDH/RGO25,
NiAl0.85Fe0.15 LDH + RGO25 and NiAl0.85Fe0.15 LDH/RGO25 are calcu-
lated to be 0.0022 min1, 0.0053 min1, 0.0092 min1,
0.0069 min1 and 0.0182 min1, respectively. Among all the sam-
ples, NiAl0.85Fe0.15 LDH/RGO25 exhibits excellent photocatalytic
activity with the highest reaction rate constant achieved, which
is 2.0, 3.4 and 8.3 times that achieved in the presence of NiAl
LDH/RGO25, NiAl0.85Fe0.15 LDH and NiAl LDH, respectively. The
above result demonstrates further that the synergistic effect
among Fe(III), NiAl LDH and RGO contributes to the enhancement
of the photocatalytic activity of NiAl0.85Fe0.15 LDH/RGO25.
More importantly, the superior catalytic activity of NiAl0.85Fe0.15
LDH/RGO25 on the photodegradation of CIP is highlighted when
compared with those of the photocatalysts previously reported
(Table 1) [19,57,74–78]. NiAl0.85Fe0.15 LDH/RGO25 reported in this
work either exhibits improved photocatalytic activity (in compar-
ison with NiAl LDH/Fe3O4-RGO) or shows comparable photocatalytic
activity but is prepared via cheaper, easier and more environmental-
friendly route (in comparison with CeO2-Ag/AgBr) [19,75]. It is also
proved that the photocatalytic performance of 3D LDH/RGO com-
posites is superior to that of the corresponding 2D ones.
The stability, i.e. reusability, is also of great significance to the
practical application of a catalyst. Therefore, five cycling tests were
carried out to appraise the stability of NiAl0.85Fe0.15 LDH/RGO25. As
shown in Fig. 5D, the photocatalytic activity of NiAl0.85Fe0.15 LDH/
RGO25 declines slightly after five consecutive photocatalytic degra-
dation of CIP under visible-light irradiation at 25 °C, demonstrating
a good stability.
3.3. Study on the mechanism of photocatalytic degradation
The photogenerated-charge transfer performance of as-
prepared photocatalysts was investigated via EIS. As shown in
 J. Liang et al. / Journal of Colloid and Interface Science 540 (2019) 237–246 243

Table 1
Comparison of the photocatalytic activity of NiAl0.85Fe0.15 LDH/RGO25 with those of the photocatalysts previously reported.

Photocatalyst Mass (mg) Light source CIP Concentration/volume Degradation time/efficiency References
2a 1
g-C3N4/TiO2/kaolinite 200 90 mW
cm 10 mg
L /100 mL 4 h/92% [74]
CeO2-Ag/AgBr 50 300 Wb 10 mg
L1/150 mL 2 h/93% [75]
Ag QDs/BiOBr 50 300 Wa 10 mg
L1/1100 mL 3 h/79% [76]
BiOBr 20 400 Wc 5 mg
L1/140 mL 2.3 h/95% [77]
Ag3PO4-NPs/Cu-NWs 10 500 Wd 10 mg
L1/150 mL 2.5 h/85% [78]
NiAl LDH/Fe3O4-RGO 10 500 Wb 10 mg
L1/140 mL 2.5 h/91% [19]
ZnAl MMO/RGO 10 800 Wb 10 mg
L1/150 mL 2 h/91% [57]
NiAl0.85Fe0.15 LDH/RGO25 10 500 Wb 10 mg
L1/140 mL 2 h/93% This work
a
Light source: Xe lamp (k > 400 nm).
b
Light source: Xe lamp (k > 420 nm).
c
Light source: halogen lamp (k > 420 nm).
d
Light source: tungsten lamp (k > 420 nm).

Fig. 6A, the Nyquist plot of NiAl0.85Fe0.15 LDH/RGO25 has the small-
est radius, which demonstrates that NiAl0.85Fe0.15 LDH/RGO25 pos-
sesses the smallest charge transfer resistance. Since low charge
transfer resistance is generally beneficial to the efficient separation
of photogenerated electron-hole pairs and charge transfer in semi-
conductor photocatalysts, the photocatalytic degradation activity
of NiAl0.85Fe0.15 LDH/RGO25 was dramatically improved, which
we believe is attributed to the doping of Fe3+ in NiAl LDH and
the coupling with RGO [51,79–81].
In addition, PL spectra were obtained to understand the separa-
tion and transfer of photogenerated charges in photocatalysts. As
shown in Fig. 6B, the emission peak of NiAl LDH explored at an
excitation wavelength of 340 nm appears at approximately
478 nm. NiAl0.85Fe0.15 LDH exhibits significantly depressed peak, Fig. 7. Photocatalytic degradation of CIP using NiAl0.85Fe0.15 LDH/RGO25 as photo-
which reveals that appropriate doping of Fe3+ reduces effectively catalyst in the presence of different radical scavengers under visible-light
illumination.
the recombination of photogenerated electron-hole pairs in
NiAl0.85Fe0.15 LDH [23,27]. No emission peak is observed for
NiAl0.85Fe0.15 LDH/RGO25, indicating that the addition of graphene directly oxidize CIP molecules adsorbed on the surface of NiAl0.85-
further depresses the recombination of photogenerated electron- Fe0.15 LDH/RGO25.
hole pairs, owing to its superior electron mobility [82,83]. The effi- On the basis of the above investigation, a possible mechanism
cient separation and transfer of photoinduced charges enhances for the photocatalytic degradation was proposed as illustrated in
significantly the photocatalytic performance of the catalyst under Scheme 2.
visible light irradiation. Electron-hole pairs are generated in NiAlFe LDH by visible-light
In order to explore further the mechanism for the photocat- illumination [84]. A part of photogenerated electrons generated in
alytic degradation over NiAl0.85Fe0.15 LDH/RGO25, the major active the valence band (VB) of NiAlFe LDH are trapped by the doped
oxidative species in the photodegradation were investigated as Fe3+. The other part of the photogenerated electrons are excited to
well (Fig. 7). Disodium ethylenediamine tetraacetate (EDTA-2Na), the conduction band (CB), and rapidly transferred to the surface of
benzoquinone (BQ) and isopropyl alcohol (IPA) were selected as RGO due to the superior electron mobility RGO possesses [85].
the scavenger of photogenerated hole (h+), superoxide radical Therefore, the rapid recombination of the photogenerated electrons
(O2) and hydroxyl radical (OH), respectively [13,51,82]. Signifi- in CB and holes in VB is suppressed [70,86]. Simultaneously, both the
cant decline of the photodegradation rate is observed after adding electrons trapped by Fe3+ and the electrons migrated to RGO react
EDTA-2Na and BQ, respectively, whereas, only a slight decrease of with O2 to generate O2, leaving holes in the VB of NiAlFe LDH
the photodegradation rate is observed in the presence of IPA. The [64,84]. Eventually, the CIP molecules adsorbed on the surface of
results prove that h+ and O2 are the major active oxidative species NiAlFe LDH/RGO are oxidized by the oxidative h+ and O2 [87,88].

Fig. 6. (A) EIS of NiAl LDH, NiAl0.85Fe0.15 LDH and NiAl0.85Fe0.15 LDH/RGO25. (B) PL spectra of NiAl LDH, NiAl0.85Fe0.15 LDH and NiAl0.85Fe0.15 LDH/RGO25.
244 J. Liang et al. / Journal of Colloid and Interface Science 540 (2019) 237–246
Scheme 2. Proposed mechanism for the photocatalytic degradation of CIP in the presence of NiAl0.85Fe0.15 LDH/RGO25.
4. Conclusions
In conclusion, a 3D NiAlFe LDH/RGO photocatalyst was suc-
cessfully synthesized for the first time, through an environmen-
tally benign and simple one-step hydrothermal method.
Structural characterization indicates that NiAlFe LDH nanoplates
grow perpendicularly on the RGO sheets, forming a 3D struc-
tured photocatalyst with large specific surface area. The 3D
NiAl0.85Fe0.15 LDH/RGO25 photocatalyst exhibits impressive pho-
tocatalytic performance and good stability toward the pho-
todegradation of CIP. 93% of CIP is removed after visible-light
illumination for 120 min at 25 °C in the presence of NiAl0.85Fe0.15
LDH/RGO25. The reaction rate constant is respectively 2.4 and 7.3
times higher than that in the presence of NiAl0.85Fe0.15 LDH and
pristine NiAl LDH. The improved photocatalytic performance is
attributed to the synergistic effect among Fe(III), NiAl LDH and
RGO in the nanocomposite, which is favorable to the separation
and transfer of photoinduced charges. Moreover, the perfor-
mance of the 3D NiAlFe LDH/RGO photocatalyst we prepared in
this work is better than that of the corresponding 2D ones pre-
viously reported for the degradation of CIP [19], which may be
because the 3D photocatalyst with large specific surface area
provides more active sites for the degradation. Radical scavenger
experiments confirmed that h+ and O2 are the major active
oxidative species here. Thus, this work provides a facile method
for the development of 3D visible light-driven graphene based
LDH photocatalysts for the photocatalytic degradation of CIP.
And further application of 3D graphene based LDH photocata-
lysts to the visible light-driven photocatalytic degradation of pol-
lutants in practical wastewater is worth exploring.
Acknowledgments
The authors are grateful for the financial support from National
Natural Science Foundation of China (No. 51572036, 51472035),
Changzhou Key Laboratory of Graphene-Based Materials for Envi-
ronment and Safety (CM20153006, CE20185043), and PAPD of
Jiangsu Higher Education Institution.
Appendix A. Supplementary material
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jcis.2019.01.011.
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