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Toward the design of Zn–Al and Zn–Cr LDH

wrapped in activated carbon for the solar assisted
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Cite this: RSC Adv., 2016, 6, 83196

de-coloration of organic dyes
Shahid Ali Khan,ab Sher Bahadar Khan*ab and Abdullah M. Asiriab

Received 24th April 2016
Accepted 6th August 2016
DOI: 10.1039/c6ra10598j
www.rsc.org/advances
Designing of materials for the extraction of organic toxins are the critical factors for environmental
remediation. In the present study, a layered double hydroxide (LDH) of the binary compounds Zn–Al
and Zn–Cr wrapped in activated carbon were synthesized through the co-precipitation method. These
catalysts were characterized by FESEM, XRD, EDS, XPS, FTIR, PL and DRS. These catalyst were
evaluated for the adsorption-assisted photodegradation of acridine orange (AO), malachite green (MG),
crystal violet (CV), congo red (CR) and methyl orange (MO) dyes. The adsorption-assisted
photodegradation was studied in four different parameters: dark, visible, ultraviolet and sunlight
exposure conditions. Under various light effects, AO was selectively removed and Zn–Al/C-LDH
showed stronger activity then Zn–Cr/C-LDH. Both catalysts showed approximately 90% removal
efficiency of AO in sunlight. PL and DRS data showed prominent bands for the respective catalysts in
the visible region. Zn–Al/C-LDH and Zn–Cr/C-LDH showed band gaps of 2.97 eV and 2.91 eV,
respectively. Zn–Al/C-LDH showed very good recyclability and durability until the fourth cycle and still
remained active after the fourth cycle as compared to Zn–Cr/C-LDH, which also showed good
recyclability until the fourth cycle, but remained inactive after the fourth cycle. It was also observed
that the specific light intensity and the substrate-catalyst specificity required equal consideration
during the development of these new catalysts.

industries, which play a signicant role in the economy and

1. Introduction
In ancient times, people tried to make their environment and
surroundings gorgeous and attractive using dyes. However,
these dyes are carcinogenic and mutagenic to aquatic life and
human health. The removal of organic pollutants from waste
water is certainly related to the quality of life. In the last few
decades, there has been a growing demand for the removal of
mutagenic and carcinogenic compounds from industrial and
domestic effluents.1,2 These organic pollutants have several
disorders on human health and other organisms. For
instance, a minute quantity of organic toxins in the water
were reported to cause endocrine disorders, chronic injuries
and develop injurious pathogen resistivities.3 Nevertheless,
besides these injurious worries to organisms and environ-
mental threats, dye industries have contributed major roles
in the progress and prosperity of a country. Synthetic dyes are
used for various purposes in various industries worldwide.
The highest amount of dyes were used by the textile
a
Chemistry Department, Faculty of Science, King Abdulaziz University, P. O. Box
80203, Jeddah 21589, Saudi Arabia. E-mail: sbkhan@kau.edu.sa; Tel:
+966-593709796
b
Center of Excellence for Advanced Materials Research, King Abdulaziz University, P.
O. Box 80203, Jeddah 21589, Saudi Arabia
progress of a country.4,5 The use of large amounts of synthetic
dyes in various industries signicantly increases environ-
mental pollution. Dumping of the untreated dyes, or other
waste materials, in water is cheaper compared to the treat-
ment of these water materials prior to sending into water
sources. It seems that, on one side, textile industries
contributed to the growth of a country, but on the other side,
it uses a large amount of chemical substances that nally
pour into water resources and causes severe health issues.
Due to these untreated chemicals, our water resources have
become contaminated and therefore, affect the ecosystem
and aqueous life. It was estimated that about 2–50% of
various dyes that are applied in textile processing are even-
tually dumped into water resources.6 Similarly, certain other
industries, such as plastic, paper, food, textile and cosmetic
industries, also use high amounts of dyes.1 These dye-stuffs
makes the water colorful at a very small concentration,
which make a foam-like layer on the surface, and thus
prevent the passage of sunlight and oxygen into the water;
and therefore, disturbs the biological phenomena of organ-
isms, which eventually causes the death of aquatic ora and
fauna. 4 Literature surveys have revealed that trace amounts of
dyes in the water is a severe threat for the environment,
animals, plants and human health.1 Furthermore, most of

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these dyes are non-biodegradable and carcinogenic, which
comes into the water cycle, and thereby affects human health
directly or indirectly.7
Dye removal and water purication are considered as some
of the fundamental concerns for researchers.4,8–10 Dyes should
be removed before discharge into the water in order to protect
living organisms and human health. Various technologies have
been administered by the scientic community for water puri-
cation. For instance, activated carbon, chitosan, biodegrada-
tion, adsorption, coagulation and membrane technologies have
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been used; however, adsorption and degradation are the most
effective, cheap and robust methods.11–13
In this study, we synthesized layered double hydroxides
(LDHs) of Zn–Al/C-LDH and Zn–Cr/C-LDH for dye removal.
Both catalysts showed a prominent response for acridine
orange (AO) removal from the effluent under solar, visible
and ultraviolet light contact, as well as in dark conditions.
LDH has received much attention in the scientic eld due to
its varied catalytic application. For instance, various Zn-
based LDHs have been used for dye degradation in the
literature. For instance, copper phthalocyanine-immobilized
Zn/Al-LDH was used for the degradation of methylene blue
(MB) dye under solar light irradiation14 and Zn–Cr-LDH
under visible light irradiation has been used for the degra-
dation of organic pollutants.15 Similarly, several metals like
Co, Ni, Cu and Zn/Cr-LDH have been used for the photo-
catalytic degradation of methyl orange (MO).16 LDHs belong
to inorganic nanostructured materials. LDH has a brucite-
like structure with positively charged cations at the top of
the layered structure and negatively charged anions are
present in the interlayers. The interlayer anions mostly
contain CO32
, NO31
, SO42
and Cl1
along with water
molecules.17 The interlayers of LDH are attached to each
other through hydrogen bonding. These are present in the
literature that these H-bonding are due to the presence of
H2O molecules inside the brucite interlayers. It is repre-
sented through the general formula [MII III z+ n

1
x M x (OH) 2 ] (A )z/
n $yH 2 O where M and M
II III
are di- and trivalent cations, while
An
is the counter anion present in the interlayer of these
brucite-like sheets.18–22 LDH is a novel nanosorbent and has
been applied largely in catalysis, adsorption, degradation,
extraction and many other elds.23 A wide range of tunable
metal ions can be used in LDH without changing the struc-
tural characteristics and the exchangeable anions between
the interlayers, which makes LDH a suitable candidate for
catalysis.
2. Experimental
2.1 Chemicals and reagents
Chemicals such as NaOH, NH4OH and nitrate and chloride salts
of Al, Zn and Cr in the form of Al(NO3)3$9H2O, Zn(NO3)2$6H2O,
ZnCl2 and CrCl2 were purchased from Sigma-Aldrich, Ireland.
The double distilled water was puried through a Millipore-Q
machine present in the department of chemistry at the King
Abdulaziz University, Saudi Arabia.
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2.2 Synthesis of Zn–Al/C-LDH
The LDH nanostructures were wrapped in activated carbon
through a co-precipitation method, as reported in our previous
papers.24,25 Salts of Al(NO3)3$9H2O and Zn(NO3)2$6H2O were
mixed in 1 : 3 molar ratio. Prior to mixing, each salt was well
dispersed in double distilled water and with respect to molar
ratio of salt, 10 wt% of activated carbon was added to the
solution mixture and was dispersed by magnetic stirring. Aer
mixing, NaOH solution (0.1 M) was added to basify the solution
in a dropwise fashion to obtain pH 9 by continuously scruti-
nizing the pH of the solution. The stated reaction mixture was
heated on a hot plate at 60  C and le overnight with contin-
uous stirring. The supernatant was drawn off and the precipi-
tate was separated and washed with a C2H5OH : H2O mixture
(8 : 2) thrice. The product was then put overnight in an oven at
50  C for drying and stored in clean tubes. The Zn–Cr/C-LDH
was prepared by a similar method but the chloride salt of Cr
and Zn was used instead of the nitrate salts.
2.3 Adsorption-assisted photodegradation procedure
Initially, the ratio of the catalyst to dye was xed under visible
light irradiation at 400 watt. The optimized amount, 10 mg of
the respective catalyst, was added in 100 mL of 0.025 mmol
solution of acridine orange (AO), malachite green (MG), crystal
violet (CV), methyl orange (MO) and congo red (CR) dyes. By the
addition of the catalyst, the decrease in dye concentration was
determined through a UV-vis spectrophotometer, while the dye
removal efficiency (R. E.) (%) was determined through the
following equation:
R. E. (%) ¼ (C0
Ct)/C0  100 ¼ (A0
At)/A0  100 (1)
where C0 is the original concentration of the dye solution at
time ¼ 0, Ct is the concentration of dye solution containing
catalyst aer time ¼ t. Similarly, A0 is the absorbance of the
original concentration of the dye solution at time ¼ 0; whereas,
At is the absorbance of dye solution containing catalyst aer
time ¼ t. 3 mL of the aliquots were taken periodically and
monitored for the decrease in concentration through a UV-vis
spectrophotometer. AO showed an absorbance maxima at lmax
¼ 490 nm while MG at 620 nm, CV at 590 nm, CR at 500 nm and
MO at 464 nm.
2.4 Instrumental analysis and characterization
Crystal morphology and crystallinity of the synthesized catalysts
were examined through powder X-ray diffractometry (PXRD)
with a Ka radiation (l ¼ 0.154 nm) source (Thermo Scientic).
FT-IR was used for the determination of functional groups in
the synthesized catalyst (Thermo Scientic). Field emission-
scanning electron microscopy (FESEM) on a JEOL (JSM-7600F,
Japan) was used for the morphology and average size while
elemental analysis was scrutinized through energy dispersive X-
rays spectrometry (EDS) from an Oxford-EDS system. The X-ray
photo electron spectroscopy (XPS) was recorded on Thermo
Scientic K-Alpha KA1066 spectrometer (Germany) in the range
of 0 to 1350 eV. Photoluminescence (PL) emission spectra were
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veried at 320 nm excitation wavelength with a uorescence
spectrouorophotometer (RF-5301 PC, Shimadzu, Japan). The
solid state UV-vis diffuse reectance spectroscopy (DRS) was
documented by a PerkinElmer UV-vis diffuse reectance spectro-
photometer. The photocatalytic reaction was monitored through
an Evolution 300 UV-vis spectrophotometer (Thermo scientic).
The effect of visible and ultraviolet light on the adsorption–
degradation process of the dyes, with respective catalyst, were
observed under a visible light lamp (400 watt, OSRAM), an ultra-
violet lamp (Smiec, Shanghai China, 230 V and 11 watt), normal-
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day sunlight and under completely dark conditions.
3. Results and discussion
3.1 Structural characterization of catalyst
The average size and morphology of the catalysts were scruti-
nized through FESEM. The FESEM images show that both
Fig. 1 FESEM images of Zn–Al/C-LDH (a–d) and Zn–Cr/C-LDH (e–h) nanosheets.
Fig. 2 EDS spectra and plot images of Zn–Al/C-LDH (a–c) and Zn–Cr/C-LDH (d–f) nanosheets.
83198 | RSC Adv., 2016, 6, 83196–83208
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catalysts were grown in the form of sheets. In case of Zn–Al/C-
LDH, the sheets were made by the aggregation of approxi-
mately 14 nm particles, as shown in Fig. 1a–d, while Zn–Cr/C-
LDH sheet contains mixed particles and blocks which on
aggregation makes Zn–Al/C-LDH nanostructure. On average,
the particle size in Zn–Cr/C-LDH sheets were 10 nm while
blocks were approximately 50 nm, as indicated in Fig. 1e–h.
The EDS spectra show C, O, Al and Zn elements in Zn–Al/C-
LDH (Fig. 2a and b) and also conrmed the C, O, Cr and Zn
elements in Zn–Cr/C-LDH (Fig. 2c and d). The EDS data reects
that the synthesized catalysts contain C, Al, Cr, O and Zn
elements in the respective catalysts. C, O, Al and Zn are present
9.08, 41.29, 13.85 and 27.47 weight% in Zn–Al/C-LDH; while C,
O, Cr and Zn are present 9.18, 25.52, 21.42 and 42.88 weight% in
Zn–Cr/C-LDH.
FTIR analysis was recorded for functional group conrma-
tion in the synthesized catalysts. Absorption peaks at 423 to 830
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cm
1 conrmed the presence of O–M–O and M ¼ O bonds in
Zn–Al/C-LDH and Zn–Cr/C-LDH catalysts.26 A sharp peak at
1355 cm
1 corresponded to the presence of NO31
in Zn–Al/C-
LDH and Cl1
in Zn–Cr/C-LDH. These sharp peaks suggested
that the synthesized catalyst have LDH morphology. A broad
peak for OH1
at 3425 cm
1 was exhibited in both catalysts,
suggesting the presence of H2O in the interlayer of the LDH.26
Furthermore, the broadening of this peak suggested the pres-
ence of hydrogen bonding between the water molecules in the
interlayer morphology of LDH. This peak is recognized as the
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O–H stretching vibration in the brucite-like layers.27,28 The
absorption at 1637 cm
1 was attributed to the OH bending
vibration in Zn–Al/C-LDH and Zn–Cr/C-LDH. The FTIR analysis
conrmed the LDH nature of the synthesized catalysts, as
shown in Fig. 3a.
The PXRD pattern displayed peaks for metal oxide and LDH
in Zn–Al/C-LDH and Zn–Cr/C-LDH. The diffraction peaks at 2q
¼ 10.8 (003), 23.0 (006) and 33.4 (012) appeared in Zn–Al/C-
LDH. Similarly, the peaks at 2q ¼ 11.4 (003), 23.4 (006) and
34.4 (012) suggested the formation of Zn–Cr/C-LDH. The XRD
spectra displayed the characteristic peaks at 10.8 and 11.5 for
Zn–Al/C-LDH and Zn–Cr/C-LDH, respectively, conrming the
LDH nature of these catalysts. Similarly, a doublet at 2q ¼ 60–
Fig. 3 FT-IR spectrum (a) and powder XRD spectrum (b) of Zn–Al/C-LDH and Zn–Cr/C-LDH nanosheets.
Fig. 4 XPS spectrum of Zn–Al/C-LDH (a) and Zn–Cr/C-LDH (b) nanosheets.
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62 (110 and 113) in both catalysts further supported the LDH
nature of the Zn–Al/C-LDH and Zn–Cr/C-LDH catalysts. The
XRD patterns propose the presence of NO31
and Cl1
anion
intercalation in the inner layer of the LDH in the respective
catalysts. The remaining XRD peaks in Zn–Al/C-LDH and Zn–
Cr/C-LDH correspond to the presence of Al and Zn doped
oxides and Cr and Zn doped oxides, respectively.29,30 It was
concluded from the FTIR and XRD data that the respective
catalysts were grown in mixed metal oxide and LDH
morphologies. Fig. 3b presents the XRD data for both
catalysts.
The binding energy of both catalysts were determined
through XPS, as indicated in Fig. 4a and b. The peak appeared at
288 eV conrm the presence of carbon (C, 1s) while peaks for Zn
(2p3/2, 2p1/2) were appeared at 1000 and 1047 eV and Al (2p, 2s)
appeared at 91.8 and 141.7 eV in Zn–Al/C-LDH.31,32 Similarly,
Zn–Cr/C-LDH catalyst showed Zn (2p3/2, 2p1/2) at 1000 and 1047
eV and Cr 2p3/2 at 586 eV while C 1s was appeared at 285 eV. This
conrms that the respective catalysts were composed of C, Al, O,
Cr and Zn elements.
The band gap was determined through solid state UV-vis
DRS. Zn–Al/C-LDH (Fig. 5a and b) and Zn–Cr/C-LDH (Fig. 5c
and d) showed a band gap of 2.97 and 2.91 eV, respectively. The
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low band gap suggested that both catalysts would work in the
visible light range.
The PL spectra were obtained by excitation at 320 nm for
both catalysts and recorded from 350–800 nm. Both catalysts
showed intense peaks in the visible range at 625 nm, as indi-
cated in Fig. 6. Again the PL also suggested that both catalysts
would work in the visible light range.

3.2 Adsorption-assisted photodegradation

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Adsorption-assisted photodegradation phenomena of two

anionic dyes (CR and MO) and three cationic dyes (AO, MG and
CV) were studied (Fig. 7–19, Tables 1 and 2).
3.2.1 Effect of visible light. Prior to sunlight exposure, the
effects of visible light on the degradation of CR, MO and AO
were studied. Solar light intensity is variable from day to day,
and even on the same day. Therefore, initially these three dyes Fig. 6 Comparison of PL spectra of Zn–Al/C-LDH and Zn–Cr/C-LDH.
were checked under a xed intensity of 400 watt visible light
exposure. Initially, 100 mg of Zn–Al/C-LDH and Zn–Cr/C-LDH
were added to 100 mL of 0.025 mmol AO dye and the dye the degradation of AO as compared to CR and MO, as shown in
degraded approximately to 80% and 59% in one hour, as shown Fig. 10. Both catalysts were selective for AO removal. Interest-
in Fig. 18a and b for Zn–Al/C-LDH and Zn–Cr/C-LDH, respec- ingly, aer 15 min, the removal efficiency of Zn–Al/C-LDH and
tively. The amount of catalyst was decreased and an optimized Zn–Cr/C-LDH against AO was 42.3% and 15.5% while CR was
amount (10 mg) of the respective catalyst was used against the removed only 12.8% and 5.3% and MO 1.9% and 1.0%,
degradation of 100 mL of 0.025 CR, MO and AO dyes. As the respectively. These results showed the selective degradation of
reaction proceeded, 3 mL aliquots of each dye were taken and AO by both catalysts compared to CR and MO. The % removal
the change in original concentration was periodically moni- efficiency (R. E.) increases directly with the increase in contact
tored through UV-vis. Both catalysts showed superior activity for

Fig. 5 Diffuse reflectance spectra of Zn–Al/C-LDH (a) and Zn–Cr/C-LDH (c). Band gap of Zn–Al/C-LDH (b) and Zn–Cr/C-LDH (d).

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Fig. 7 Adsorption-assisted photodegradation of AO under visible light (400 watt) with A1, A3 and without catalyst, concentration decrease of AO
(a) and % removal of AO (b). AO, acridine orange; A1, Zn–Al/C-LDH; A3, Zn–Cr/C-LDH; WOC, without catalyst and VL, visible light exposure.

Fig. 8 Adsorption-assisted photodegradation of CR under visible light (400 watt) with A1 and A3: concentration decrease of CR (a) and %
removal of CR (b). CR, congo red dye; A1, Zn–Al/C-LDH; A3, Zn–Cr/C-LDH; WOC, without catalyst and VL, visible light exposure.

time. For instance, aer 200 min the R. E. of Zn–Al/C-LDH
against AO and MO were 61.1% and 10.7%, respectively,
compared to Zn–Cr/C-LDH, which were 36.5% and 6.6%,
respectively. But at the same time, Zn–Cr/C-LDH degraded the
CR dye a little higher then Zn–Al/C-LDH with a R. E. of 23.0%
and 19.7%, respectively. The decrease in concentration by
applying the formula C0
Ct/C0 and R. E. of AO is depicted in
Fig. 7a and b, CR (Fig. 8a and b) and MO (Fig. 9a and b). The
progressive decrease in color change of AO with both catalysts is
depicted in Fig. 19. It was concluded that, under visible light
exposure, the Zn–Al/C-LDH showed a dominant catalytic
performance for AO and MO while Zn–Cr/C-LDH showed a little
higher degradation efficiency for CR (Fig. 10).
3.2.2 Dye selectivity. Under visible light exposure (400
watt), AO was selectively removed by both catalysts compared to
CR and MO (Fig. 11a and b). This showed that both catalysts
were selective for cationic dyes. The better selectivity of AO is
due to the carboxylic group (COOH) present in activated carbon,
which facilitated the interaction of AO (cationic nature) to the
negatively charged COOH group. Among the three dyes, AO
showed better selectivity and was further selected for solar light
effects.
3.2.3 Effect of solar light. The effect of solar light was
studied in normal day sunlight exposure. The normal day
sunlight exposure means “the intensity of sunlight at that
specic day”. Primarily, adjusted doses of 10 mg of the
respective catalysts were used against 100 mL of 0.025 AO, as in
the visible light exposure tests. As the reaction proceeded, 3 mL
aliquots were taken periodically from the reaction mixtures and
the decrease in concentration of dye solutions was observed by
UV-vis. Aer the rst 15 min of the experiment, the R. E. of AO
by both catalysts were 27.9%. This indicated that, at the start of
the experiment, both catalysts show the same trend and the
same catalytic activity. However, by increasing the exposure
time, the degradation process was increased and aer 200 min,
the R. E. of AO by Zn–Al/C-LDH and Zn–Cr/C-LDH were 89.4%

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Fig. 9Adsorption-assisted photodegradation of MO in visible light (400 watt) with A1 and A3: concentration decrease of MO (a) and % removal
of MO (b). MO, methyl orange dye; A1, Zn–Al/C-LDH; A3, Zn–Cr/C-LDH; WOC, without catalyst and VL, visible light exposure.
and 87.4%, respectively. Again, both catalysts indicated
approximately the same activity in solar light against AO. The
UV-vis graph, decrease in dye concentration and percent R. E. of
AO in solar light is depicted in Fig. 12a–d.
We observed that the R. E.s of both catalysts against AO
(cationic dye) were higher in solar light compared to visible
light. So, we decided to check the catalytic activity of both
catalysts against other cationic dyes, such as MG and crystal
violet CV, to evaluate the solar light effect on the nature of
cationic dyes. Similarly, 10 mg of the adjusted dose of both
catalysts were used against the degradation of 100 mL of 0.025
mmol MG and CV. The Zn–Al/C-LDH catalyst showed 52%
degradation in 200 min compared to 22% R. E. of Zn–Cr/C-LDH
for CV. Similarly, Zn–Al/C-LDH removed 70% MG in 200 min
compared to Zn–Cr/C-LDH, which showed only 20% R. E. under
the same conditions. Both catalysts showed stronger
Fig. 10 % removal of AO, CR and MO by Zn–Al/C-LDH (A1) and Zn–
Cr/C-LDH (A3) catalysts.
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performance for AO and predominantly degraded AO over MG
and CV in solar light. From this experiment, it was concluded
that, among the cationic dyes, AO is again selectively removed
over CV and MG. The % R. E. of CV and MG with the respective
catalysts are indicated in Fig. 13a and b.
3.2.4 Effect of ultraviolet light. As we observed from the
above experiment, AO was removed preferentially with both
catalysts over the other stated dyes; therefore, we selected AO for
further study under ultraviolet light and dark conditions.
The effect of ultraviolet light was studied against AO removal
with both catalysts under 230 volts (11 watt) and keeping the
same conditions as for solar and visible light. The adjusted dose
of 10 mg of the respective catalysts were used against the
removal of 100 mL of 0.025 mmol AO. Under ultraviolet light
exposure, Zn–Al/C-LDH removed AO aer the rst 15 mint to
8.5% while Zn–Cr/C-LDH to 7.5%. However, aer 200 min, the
R. E. of AO by Zn–Al/C-LDH and Zn–Cr/C-LDH was 36.3% and
29.1%, respectively. Again Zn–Al/C-LDH showed dominant
catalytic performance over Zn–Cr/C-LDH under ultraviolet light
exposure. The decrease in concentration and R. E. of AO by both
catalysts are presented in Fig. 14a and b.
3.2.5 Effect of dark conditions. Prior to the effect of
sunlight and ultraviolet light, the effect of dark conditions was
studied to know if the adsorption or degradation, or both
phenomena, occurs simultaneously. The experiment was per-
formed carefully by providing completely dark conditions. The
same procedure was followed for the dark as described above
for visible light. 10 mg of the respective catalysts were used
against the removal of 100 mL 0.025 mmol solution of AO.
During dark conditions, the adsorption phenomenon was
observed with both catalysts. Aer the rst 15 min, the
adsorption efficiency of Zn–Al/C-LDH was 11.3% as compared
to 10.0% in Zn–Cr/C-LDH against AO. However, with increasing
contact time, the adsorption was increased for both catalysts.
For instance aer 200 min, the adsorption of Zn–Al/C-LDH was
35.1% and Zn–Cr/C-LDH was 26.6%. The results favor again the
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Fig. 11 Selective removal of AO under visible light using Zn–Al/C-LDH (a) and Zn–Cr/C-LDH (b).

Fig. 12 Adsorption-assisted photodegradation UV-vis spectra of AO under sunlight irradiation with A1 (a) and A3 (b). Concentration decrease of
AO (c) and % removal of AO (d). AO, acridine orange; A1, Zn–Al/C-LDH; A3, Zn–Cr/C-LDH and S, normal day sunlight.

strongest adsorption capacity of Zn–Al/C-LDH as compared to
Zn–Cr/C-LDH for AO in dark conditions. The decrease in
concentration and R. E. of AO by both catalysts are presented in
Fig. 15a and b.
Here, we conclude the above experiments: the adsorption
phenomenon was observed in dark conditions and
adsorption-assisted photodegradation occurs under visible,
ultraviolet, and sunlight exposure conditions. Although the %
R. E. in the dark and ultraviolet light is approximately same;
however, in the dark conditions the dyes are removed through
adsorption, and in the ultraviolet light conditions, by
adsorption-assisted photodegradation. The metal oxide inu-
enced the degradation phenomenon as it worked efficiently in
ultraviolet light.33 Similarly, both catalysts removed the dye
through adsorption-assisted photodegradation in visible and
solar light conditions. The adsorption-assisted

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Fig. 13 % removal of CV and MG under sunlight irradiation with A1 and A3. A1, Zn–Al/C-LDH; A3, Zn–Cr/C-LDH and S, normal day sunlight.
Fig. 14 Adsorption of AO under ultraviolet light by A1 and A3: concentration decrease of AO (a) and % removal of AO (b). AO, acridine orange
dye; A1, Zn–Al/C-LDH; A3, Zn–Cr/C-LDH and U, ultraviolet light.
photodegradation proceeded rst by adsorbing the dyes onto
the surface of the catalyst and then degradation occurs. It was
also found that, for all the dyes in all condition except the CR
dye, Zn–Al/C-LDH showed a stronger activity compared to Zn–
Cr/C-LDH. However, Zn–Cr/C-LDH showed a little higher effi-
ciency for CR dye then Zn–Al/C-LDH under visible light
conditions.
3.2.6 Kinetics of the above experiments. The decrease in
reactant concentration, or increase in product concentration
with time, is called the rate of reaction. Here, we determined the
rate of reaction from the decrease in concentration by applying
a pseudo-rst order reaction (ln Ct/C0) rate law as depicted in
Fig. 16. As AO is selectively extracted, the equation is applied on
the removal of AO. It was found that Zn–Al/C-LDH showed the
highest rate in all experiments, as discussed above for AO, and
this data is shown in Table 1. Zn–Al/C-LDH and Zn–Cr/C-LDH
showed approximately the same rate in solar light exposure,
which were 1.1  10
2 and 1.0  10
2 mol L
1 min
1, respec-
tively, as shown in Table 1. Under visible light conditions, the
rate of AO removal by Zn–Al/C-LDH (2.8  10
3 mol L
1 min
1)
83204 | RSC Adv., 2016, 6, 83196–83208
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was higher compared to Zn–Cr/C-LDH (1.4  10
3 mol L
1
min
1). Similarly, the rate of Zn–Al/C-LDH was also higher in
the dark and ultraviolet light conditions compared to Zn–Cr/C-
LDH.
3.3 Plausible mechanism of adsorption-assisted
photodegradation of dyes
During photodegradation of the dyes, the electrons in the
valance band of Zn (Zn–Al/C-LDH) absorbed visible light of
appropriate frequencies and were promoted to the conduc-
tion, band leaving an electron deciency (h+) in the valance
band.34 The electron in the conduction band is taken up by the
Al atom, thus preventing it from recombination. At the same
time, the dyes are also excited to a higher energy state by the
promoting of an electron from the HOMO to the LUMO aer
receiving an appropriate amount of energy.9 Some of these
dyes are adsorbed while the remaining are degraded by reac-
tive oxygen species (O2c
, cOH) generated in the system during
the redox reaction. Probably, the superoxide oxygen and
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Fig. 15 Adsorption of AO under dark conditions by A1 and A3: concentration decrease of AO (a) and % removal of AO (b). AO, acridine orange
dye; A1, Zn–Al/C-LDH; A3, Zn–Cr/C-LDH and D, dark conditions.

Fig. 16 Langmuir adsorption isotherm of AO with catalyst A1 and A3 under solar (S) and visible light (VL).

Fig. 17 Plausible mechanism for adsorption-assisted photodegradation of dyes using Zn–Al/C-LDH.

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Fig. 18 Catalytic activity and no. of cycles of A1 (a) and A3 (b) against AO. AO, acridine orange; A1, Zn–Al/C-LDHand A3, Zn–Cr/C-LDH in visible
light. Each cycle lasted for 1 h.

hydroxide free radical species (O2c
and cOH) are generated
from O2 and H2O respectively.35 The O2 is converted to O2c
by
receiving an electron, available from the conduction band of
Al, while cOH is generated from H2O reacting in the positive
hole (h+) of the Zn valance band. It might be possible that both
h+ in the valence band and e
in the conduction band move to
the surface defects of the catalyst where they produce the O2c

and cOH, which are the possible species for the mineralization
of dyes. The tentative mechanism for dye degradation is shown
in Fig. 17.
3.4 Recyclability of the catalyst
The catalytic recyclability of both catalysts were checked
under visible light rather than solar light because the
intensity of solar light was variable day to day, and even on
the same day. Therefore, we carried out the catalytic recy-
clability tests under visible light of 400 watt. For the recy-
clability of the catalyst, 100 mg of the respective catalyst were
added in 100 mL 0.025 mmol solutions of AO and checked
under the inuence of visible light (400 watt). Aer one hour,
a 3 mL aliquot was taken and monitored by UV-vis aer
carefully separating the catalyst. The recovered catalyst was
washed thrice with acetone and then quickly used in the next
cycle without any physical or chemical treatment. The
recovered catalyst was again added in 100 mL 0.025 mmol
solution of AO and kept under visible light for 1 hour expo-
sure. The same procedure was repeated four times for both
catalysts. During each cycle, the reaction lasted for 1 hour.
The Zn–Al/C-LDH indicated 78% removal efficiency in the
rst cycle and that decreased to 76%, 47% and 23% in
second, third and fourth cycles, respectively. However, Zn–Al/
C-LDH remained active aer the fourth cycle. Similarly, Zn–
Cr/C-LDH indicated 59% R. E. in the rst cycle and that
decreased to 45%, 23% and 15% in second, third and fourth
cycles, respectively. The result shows the strongest catalytic
performance of both the catalyst for dye removal as well as
best catalytic recyclability and durability. The catalytic recy-
clability of Zn–Al/C-LDH and Zn–Cr/C-LDH are shown in
Fig. 18a and b, respectively.
Table 1 Rates of reaction for both catalysts derived from the pseudo-
first order Langmuir adsorption isotherm model for adsorption-assis-
ted photodegradation of AOa

S. no. Catalyst Rate (mol L
1 min
1)

1 AO–A1–S 1.1  10
2

2 AO–A3–S 1.0  10
2
3 AO–A1–VL 2.8  10
3
4 AO–A3–VL 1.4  10
3
5 AO–A1–U 1.9  10
3
6 AO–A3–U 1.2  10
3
7 AO–A1–D 1.1  10
3
8 AO–A3–D 8.1  10
4
a
Fig. 19 Color change of AO dye with Zn–Al/C-LDH (a) and Zn–Cr/C- AO, acridine dye; A1, Zn–Al/C-LDH; A3, Zn–Cr/C-LDH; S, solar light;
LDH (b) under visible light illumination. VL, visible light; U, ultraviolet light and D, dark.

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Table 2 Structure of dyes used in the experiment

Entry Structure Dyes Nature Mol. mass (g mol
1)

1 Acridine orange (AO) Cationic 265.36

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2 Malachite green (MG) Cationic 364.911

3 Crystal violet (CV) Cationic 407.979

4 Congo red (CR) Anionic 696.66

5 Methyl orange (MO) Anionic 327.33

4. Conclusion LDH and mixed oxides. The Zn–Al/C-LDH and Zn–Cr/C-LDH

This study unveiled the removal of ve dyes (AO, CR, MO, MG
and CV) under visible, solar, ultraviolet light and dark condi-
tions through the synthesized Zn–Al/C-LDH and Zn–Cr/C-LDH.
The Zn–Al/C-LDH and Zn–Cr/C-LDH were grown in the form of
had band gaps of 2.97 eV and 2.91 eV, respectively, which
reects their better performance in the presence of visible light
and solar light. Dyes were removed through adsorption and
adsorption-assisted photodegradation. Complete adsorption
occurred in dark conditions and adsorption-assisted

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RSC Advances
photodegradation in ultraviolet, visible and solar light condi-
tions. During adsorption-assisted photodegradation, the dyes
were rst adsorbed onto the surface of the catalyst and then
degraded. It was also observed that the light intensity and the
substrate-catalyst specicity both required equal consideration
during the development of these new catalysts.
Conflict of interest
The authors conrms that the content of this manuscript have
Published on 08 August 2016. Downloaded by New York University on 05/09/2016 20:26:25.
conict of interest.
Acknowledgements
The authors highly acknowledge center of excellence for
advance material research king Abdulaziz University for
providing research facilities.
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