Chemical Engineering Journal 358 (2019) 1539–1551

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Chemical Engineering Journal

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

A multifunctional gelatin-based aerogel with superior pollutants adsorption, T

oil/water separation and photocatalytic properties
Jingxian Jiang, Qinghua Zhang , Xiaoli Zhan, Fengqiu Chen
⁎

Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, College of Chemical and Biological Engineering, Zhejiang University,
Hangzhou 310027, PR China

HIGHLIGHTS GRAPHICAL ABSTRACT

• Aganic-inorganic
multifunctional gelatin-based or-
composite aerogel
was fabricated.
• This aerogel could realize oil/water
separation with high selectivity.
• This aerogel removed Cu (II) ions,
anionic and cationic dyes with good
reusability.
• Uniformly dispersed TiO nano-
2
particles endowed aerogel with pho-
tocatalytic property.
• This work offered new avenue to the
treatment of wastewater with complex
composition.

ARTICLE INFO ABSTRACT

Keywords: Designing multifunctional adsorbents that can satisfy sophisticated requirements in complex water treatment
Gelatin-based organic-inorganic composite fields remains challenging these days. In this work, an original and environment-friendly gelatin-based organic-
aerogel inorganic composite aerogel equipped with integrative functions was fabricated through facile methods. The
Organic dyes removal uniform dispersion of TiO2 nanoparticles was successfully achieved in the three-dimensional structure of the
Copper ions adsorption
composite aerogel, and the branched polyethyleneimine (PEI) was cross-linked onto it through the effect of
Oil/water separation
Photocatalysis
glutaraldehyde. The gelatin/TiO2/PEI (GTP) aerogel had a hierarchical porous structure and a superamphiphilic
Reusability surface, which endowed it with excellent oil/water separation properties, for both oil/water free mixtures and
oil-water emulsions. Both cationic (methylene blue and crystal violet) and anionic (congo red and methyl or-
ange) organic dyes could be adsorbed by the GTP aerogel with good adsorption capacity. It was noteworthy that
the GTP aerogel was capable of realizing dye degradation because of its photocatalytic performance.
Furthermore, this composite aerogel was able to remove copper ions from aqueous solutions with high capacity
and good reusability. The regeneration of the GTP aerogel was realized by methanol and EDTA for dyes and
copper ions respectively. Combined with comprehensive functions including oil/water separation, organic dyes
adsorption, copper ions removal and photocatalytic property, the bio-based organic-inorganic composite GTP
aerogel holds great promise for practical usage in water remediation, especially in the treatment of polluted
water with complex components.

⁎
Corresponding author.
E-mail address: qhzhang@zju.edu.cn (Q. Zhang).

https://doi.org/10.1016/j.cej.2018.10.144
Received 17 July 2018; Received in revised form 15 October 2018; Accepted 18 October 2018
Available online 19 October 2018
1385-8947/ © 2018 Elsevier B.V. All rights reserved.
J. Jiang et al.
1. Introduction
Water, the source of life, plays a decisive role in the existence and
development of human society. However, global water pollution has
become a much more severe issue nowadays [1]. The increasingly de-
veloped agriculture and industry, the rapidly growing population and
the accelerating modernization lead to the discharge of a large amount
of wastewater with sophisticated composition [2]. Organic dyes, heavy
metal ions, and oils make it more laborious to well dispose the waste-
water [3]. Owning to the intricate organic structure, dyes like methy-
lene blue (MB) and methyl orange (MO) are difficult to biodegrade
[4,5]. Additionally, there are a variety of heavy metal ions in polluted
water. They are toxic and even radioactive, and inclined to accumulate
in animal body through food chains in ecosystem [6–8]. The existence
of heavy metal ions lays heavy burden on the environment [9–11]. Oily
wastewater imposes great threats to aquatic organisms and water
safety, further threatening human survival [12,13]. Given all that, en-
ormous efforts have been made to remove complex pollutants from
water system, including precipitation, filtration, adsorption, membrane
separation, combustion, electro-dialysis and reverse osmosis [14,15].
Among these techniques, adsorption has been recognized as one of the
most efficient methods due to its easy operation, convenience and ef-
fectiveness. Many adsorbents like clay, coal ash, bentonite, activated
carbon and synthesized polymer are utilized to realize water remedia-
tion [16–19]. But the single-function nature, low adsorption capacity,
poor recyclability and limited efficiency greatly impede their pace of
large-scale utilizations [20].
Aerogels, the typical three-dimensional (3D) porous materials, are
considered as one of the most attractive adsorbents, because of their
low density, large surface area, high porosity, bigger adsorption capa-
city, self-supporting configuration and good mechanical properties
[21–23]. In contrast to aerogel adsorbents derived from metal oxides,
graphene and carbon nanotubes, bio-based aerogels are more cost-ef-
fective, sustainable and environmentally friendly [24–27]. Besides,
biomass materials have abundant reactive groups in their molecular
chains, which give them more opportunities to realize surface mod-
ification [28–30]. Therefore, bio-based aerogels have attracted in-
tensive attentions and many efforts have been dedicated to offer spe-
cific performance to aerogels aimed at the treatment of wastewater with
complicated composition [24,31–33]. Naturally abundant biomass
cellulose, lignin and chitosan are widely utilized as starting materials to
fabricate aerogel skeletons [34–39]. Various methods have been em-
ployed to endow original aerogels with fascinating performances.
Chemical vapor deposition (CVD), surface grafting, surface coating,
physical blending and other methods are utilized to change the che-
mical and physical properties of original 3D porous materials to obtain
adsorbents with superhydrophobicity/superoleophilicity, underwater
superoleophobicity, or special adsorption sites for organic dyes and
heavy metal ions [6,28,40–44]. The incorporating of inorganic nano-
particles into 3D skeleton can combine the remarkable advantages of
both 3D framework and inorganic components, and thereby get a class
of adsorbents with multifunctional characteristics [45,46]. Recent work
has shown that inorganic particles like Fe3O4, TiO2, Ag2O, SiO2, etc. can
be employed to provide aerogels with magnetism, catalytic character-
istic or special wettability [41,47–49]. However, the fabrication of or-
ganic-inorganic composite aerogels is challenging. On account of phase
separation, it is difficult to get organic-inorganic composite aerogels
with inorganic nanoparticles firmly bonded and evenly dispersed on/in
the organic skeleton [50]. Generally, composite aerogels possessed
multiple functions are usually fabricated through sophisticated proce-
dures, which are time/money-consuming. Preparing organic-inorganic
composite aerogels with excellent comprehensive properties via facile
routines still remains challenging. Therefore, designing bio-based
composite aerogels with multiple functions and exploring their usage in
wastewater treatment have a practical significance. To the best of our
knowledge, reports about bio-based adsorbents with integrative
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Chemical Engineering Journal 358 (2019) 1539–1551
functions inclusive of pollutants adsorption, oil/water separation (for
both oil/water free mixtures and oil-water emulsions) and photo-
catalytic property were rare.
Gelatin, a well-known bio-based protein, can be easily found in
animal skin, bone and myolemma [28]. It has been extensively used in
food, chemical engineering and pharmaceutical industries due to its low
cost, biocompatibility and biodegradability [40]. Gelatin has abundant
hydroxyl, carboxyl and amino groups in its molecule chains, offering it
with easy gelation and functionalization. Gelatin can be set as the
starting material to build 3D structures. Porous gelatin networks have
been developed for tissue engineering, flame retarding, oil/water se-
paration and pollutants adsorption, separately [28,51–54]. Here in this
work, a gelatin-based organic-inorganic composite aerogel equipped
with heavy metal ions adsorption, dyes adsorption and degradation,
and oil/water separation properties was fabricated. Gelatin was chosen
as the 3D scaffold material and TiO2 nanoparticles were dispersed in the
gelatin skeleton. Then the branched polyethylenimine (PEI) was
crosslinked onto it through the effect of glutaraldehyde. After a freeze-
drying process, the composite gelatin-based aerogel (GTP aerogel) was
finally prepared. The GTP aerogel could adsorb both anionic and ca-
tionic dyes, and the adsorption mechanism was revealed. The photo-
degradation of organic dyes under UV light could be realized. Besides, it
was able to remove copper ions from aqueous solutions with a fairly
high capacity and reusability. What’s more, the oil/water separation for
both oil/water free mixtures and oil-water emulsions with high se-
lectivity could be achieved by this composite aerogel. Hence, this work
will provide new insights into engineering reliable multifunctional bio-
based adsorbents for water remediation.
2. Experimental procedure
2.1. Materials
Gelatin was obtained from Sinopharm Chemical Reagent. Titanium
oxide nanoparticles (TiO2; anatase; purity 99.8%, average crystal
size = 25 nm) and branched ethylene imine polymer (PEI)
(MW = 70000, 50% w/v in water) were purchased from Aladdin Co.,
Ltd. Glutaraldehyde solution (25%), ammonium sulfate, nitric acid,
sodium hydroxide, sodium chloride, toluene, Tween 60, crystal violet,
methylene blue, copper chloride dehydrate (CuCl2·2H2O) were bought
from Sinopharm Chemical Reagent. Methyl orange and congo red were
offered by Aladdin Co., Ltd. Methanol and ethylenediamine tetraacetic
acid disodium salt (EDTA) were got from Sinopharm Chemical Reagent.
Deionized water was used in the whole experimental process.
Additionally, all the reagents were used as received.
2.2. Preparation of gelatin/TiO2/PEI (GTP) composite aerogels
Gelatin powders (10 g) were added into deionized water (190 g) and
stirred continuously at 60 °C to form a transparent homogeneous solu-
tion of 5 wt% [28,51]. TiO2 nanoparticles (0.2 g) were blended into this
aqueous solution and stirred for 6 h at 60 °C until the solution turned
milk white. The resulting solution was poured into molds and then
maintained in a 4 °C refrigerator for the initial gelation. After 2 h of
gelation, these gelatin hydrogels were soaked into (NH4)2SO4 solution
(150 mL) with a concentration of 20 wt% at 4 °C for 24 h. Subsequently,
the obtained hydrogels were immersed in 150 mL of PEI solution (di-
luted 10 times with deionized water) for 24 h. And glutaraldehyde so-
lution was used as the crosslinking agent. The prepared gelatin hy-
drogels were pre-cooled in a −20 °C refrigerator for 6 h and then were
freeze-dried in a lyophilizer for 48 h to get the GTP composite aerogels
[28,51].
2.3. Characterization
The attenuated total reflection/Fourier transform infrared (ATR-
J. Jiang et al.
FTIR, Nicolet 5700, ThermoFisher) was applied to investigate the
chemical structure of the prepared aerogels. The spectral range was
400–4000 cm−1, and 32 scans were taken for each spectrum with a
resolution of 4.0 cm−1. And ZnSe was used as the optical crystal. The
microstructure and morphology of aerogels were observed using scan-
ning electron microscopy (SEM). The SEM was operated on an S-570
scanning electron microscope (Hitachi) with an accelerating voltage of
5 kV. All the aerogel samples to be tested should be treated by gold
sputtering in advance. SEM-EDX (Energy dispersive X-ray,
GENESIS4000, EDAX, USA) mapping was employed to investigate the
presence and dispersion of TiO2 nanoparticles in GTP aerogel structure.
The surface wettability of GTP aerogels was studied by sessile drop
contact angle analysis with a contact angle instrument (KSV Co., Ltd.)
at room temperature. A mercury porosimeter (AutoPore Ⅳ 9500,
Micromeritics, USA) was applied to measure the porosity and total pore
area of the GTP aerogel. Optical microscopy images of the emulsion
before and after separation were taken by a Nikon ECLIPSE E200 op-
tical microscope. Droplet size distribution was measured by a dynamic
light scattering (DLS) measurement (Zetasizer Nano ZS, Malvern, UK).
2.4. Oil/water separation performance
The GTP aerogel was fixed in the filtering apparatus to investigate
its oil/water separation properties, for both oil/water mixtures se-
paration and oil-in-water emulsions separation. A mixture of hexane
(dyed with Sudan I) and water with a volume ratio of 1:1 was prepared.
Identically, another mixture of dichloromethane (dyed with Sudan I)
and water with a volume ratio of 1:1 was also prepared. The GTP
aerogel was first pre-wetted by water, and then 200 mL of the mixture
of hexane and water was poured into the upper receiver of the filtering
apparatus. To separate the mixture of dichloromethane and water, the
aerogel was pre-wetted with dichloromethane in advance.
Subsequently, 200 mL of the mixture of dichloromethane and water was
poured into the filtering apparatus. The whole separation process was
solely driven by gravity. When the separation process was completed,
the filtrate was gathered from the upper and lower receivers respec-
tively. In order to investigate the stability of the GTP aerogel, n-hexane/
HNO3 (1 M), n-hexane/NaOH (1 M) and n-hexane/NaCl (3.5 wt%)
mixtures were also prepared, respectively. And the separation processes
were carried out the same as described above.
The oil-in-water emulsion was prepared by mixing 5 mL of toluene
with 150 mL of water (containing 0.2 wt% Tween 60). Then the
emulsion was poured into the upper receiver of the filtering apparatus
mentioned above. The oil concentrations of the original oil-in-water
emulsion and the filtrate were measured by a UV–vis spectro-
photometer at λ = 261 nm (for toluene). The separation efficiency was
calculated by the oil rejection coefficient R (%) as follows:
Cf
R(%) = 1 × 100%
C0 (1)
where C0 and Cf are the oil concentrations of the original oil-in-water
emulsion and the filtrate, respectively [34].
2.5. Adsorption experiments of dyes
The dye adsorption tests were performed using methylene blue
(MB), congo red (CR), crystal violet (CV) and methyl orange (MO) as
model pollutants. These experiments were operated in a 100 mL flask at
room temperature with continuous stirring. A piece of prepared aerogel
(∼0.30 g) was placed into the dye solution (50 mL with a certain
concentration). Here, dye solutions with different concentrations of 10,
20, 50, 100, 200, 300, 500 mg/L were used as polluted wastewater.
Each dye removal test was continued for 10 h to reach adsorption
equilibrium. Then the aerogel was taken out from the aqueous solution
by tweezers. The initial and equilibrium concentrations of dyes were
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Chemical Engineering Journal 358 (2019) 1539–1551
detected by an UV–vis spectrophotometer at λ = 664 nm (for MB),
590 nm (for CV), 465 nm (for MO) and 500 nm (for CR). The adsorption
capacity (qe, mg g−1) was calculated through the difference in the in-
itial and final concentrations of dye solution, and the calculation
equation was defined as follows:
Ci Ce
qe = V
(2)
m
−1
where ci and ce (mg L ) are the initial and equilibrium concentrations
of the dye solution, m (g) is the weight of the aerogel adsorbent, and V
(L) is the volume of the dye solution.
Adsorption kinetic tests were carried out with an initial concentra-
tion of 100 mg/L. Samples were taken at different time intervals (5 min,
15 min, 30 min, and 60 min). The concentrations of samples were de-
termined by the abovementioned method. Then the real-time adsorp-
tion capacity of the aerogel adsorbent can be calculated by Eq. (2).
2.6. Adsorption experiments of Cu (II) ions
Adsorption test of Cu (II) ions was conducted in a 100 mL flask at
room temperature under continuous stirring. The initial concentrations
of Cu (II) ion solutions were set as 10, 20, 50, 100, 200, 500 ppm, re-
spectively. A piece of the prepared aerogel (∼0.025 g) was immersed
into 50 mL of Cu (II) ion solution for 24 h to ensure the equilibrium
adsorption was achieved. Then the saturated adsorbent was removed
from the aqueous solution. And the Cu (II) ion solution after adsorption
was collected. The concentration of solutions before and after the ad-
sorption test was analyzed by inductively coupled plasma optical
emission spectrometer (ICP-OES). The adsorption capacity was also
defined as Eq. (2).
2.7. Regeneration and reusability of the GTP aerogel
The used GTP aerogel (after adsorption of dyes) was placed into
50 mL of methanol to get rid of the absorbed dyes at room temperature.
This process should be repeated three times. Then the GTP aerogel was
rinsed with deionized water several times to get the aerogel ready for
next adsorption test.
The used GTP aerogel (after adsorption of copper ions) was put into
50 mL of 0.05 mol/L EDTA solution three times to remove the absorbed
copper ions from the GTP aerogel at room temperature. Then the
deionized water was used to rinse the GTP aerogel to make it suitable
for next adsorption experiment towards copper ions.
2.8. Modeling of isotherm and kinetic for adsorption on the GTP aerogel
In order to investigate the adsorption process of the GTP aerogel in
detail, adsorption isotherms and kinetics were studied both for dyes and
copper ions adsorption. Two mainly used models, the Langmuir model
and the Freundlich model, were employed to fit with the adsorption
data to study the adsorption isotherms.
The Langmuir model is expressed as:
ce c 1
= e +
qe qm KL qm (3)
The Freundlich model is defined as:
1
lnqe = lnKF + lnce
n (4)
where ce (mg/L) is the concentration of dyes or Cu (II) ions in ad-
sorption equilibrium; qe (mg/g) is the adsorption capacity in equili-
brium; qm (mg/g) is the maximum adsorption capacity under ideal
conditions; 1/n is an empirical parameter in Freundlich model that
indicates the adsorption capacity; KL and KF are constants of the
Langmuir and Freundlich equations respectively.
The pseudo-first order kinetic model (Eq. (5)) and the pseudo-
J. Jiang et al.
second order kinetic model (Eq. (6)) were applied to investigate ad-
sorption kinetics. The formulas were shown as follows:
K1 t
log(qe qt ) = logqe
(5)
2.303
t t 1 molecules was observed at 1447 cm−1. When TiO2 nanoparticles were
= +
qt qe K2 qe2 (6)
−1
where qt is the adsorption capacity at any time t; K1 (h ) and K2 (g/
mg/h) are the rate constants of the pseudo-first order kinetic model and
pseudo-second order kinetic model, respectively.
2.9. Photocatalytic activity measurements
The photocatalytic performance of the GTP aerogel was evaluated
by the photodegradation of MO (5 mg/L) under UV-light irradiation
(λ = 365 nm). The UV light was generated by a 100 W UV lamp
(Spectronics Co., USA). A piece of the GTP aerogel (0.40 g) was im-
mersed into 50 mL of MO solution in a 100 mL flask with continuous
stirring. At the same time, another identical piece of the GTP aerogel
was treated the same way. Simultaneously, one of the flasks was put
into the UV-light irradiation (20 cm below the UV lamp), and another
one was placed under the shading condition. The above operations
started at the same time. For a given time interval, 1.0 mL of MO so-
lution was sampled and determined by the UV–vis spectrophotometer
at the maximal absorption wavelength of MO (465 nm).
3. Results and discussion
3.1. Preparation and characterization of GTP aerogels
According to the procedures in part 2.2, the gelatin/TiO2/PEI
aerogel (GTP aerogel) was successfully fabricated. For the purpose of
enhancing the strength and stability of the virgin gelatin gel, an im-
mersing procedure in (NH4)2SO4 solution was performed during the
fabrication process of the GTP aerogel [55]. The concentration of the
original pure gelatin solution and the content of TiO2 nanoparticles as
well as the dispersing time length played vital roles in forming a
homogeneous aerogel with nanoparticles uniformly dispersed. A high
density of functional groups existed in the gelatin molecules, which
provided active sites for gelatin to integrate with other molecules and
nanoparticles to construct advanced materials. It is well known that
gelatin and TiO2 nanoparticles have a hydrophilic nature and the hy-
droxyl groups on TiO2 nanoparticle surface can react with amino
groups and hydroxyl groups in gelatin molecules with the help of glu-
taraldehyde. Detailed reaction mechanisms have been revealed by
published articles [56]. In addition, hydrogen bonding between TiO2
nanoparticles and gelatin molecules was of great significance in struc-
tural integrity and stability. When the concentration of gelatin was
lower than 5 wt%, the gelation process was difficult to realize and the
formed gel was unstable. When the concentration of gelatin was higher
than 5 wt%, the dispersion of TiO2 nanoparticles was hindered.
Therefore, in this work, a gelatin solution of 5 wt% and a TiO2 content
of 2 wt% (relatively to gelatin) were chosen as starting materials to
prepare the composite GTP aerogel. The blending process of TiO2 na-
noparticles was lasted for 6 h to guarantee the sufficient contact be-
tween nanoparticles and gelatin molecules, further promoting the uni-
formly dispersion of the TiO2 nanoparticles. The finally obtained GTP
aerogel had a density of 0.115 g/cm3. The porosity and total pore area
of the GTP aerogel were 75.37% and 9.56 m2/g, respectively.
Attenuated total reflection/Fourier transform infrared (ATR-FTIR)
spectroscopy was employed to investigate the chemical structure of the
gelatin (G) aerogel, gelatin/TiO2 (GT) aerogel and GTP aerogel. ATR-
FTIR spectra of these three kinds of aerogels are shown in Fig. 1. The
typical broad peak at 3301 cm−1 of the G aerogel was ascribed to the
NeH stretching vibration in gelatin molecules. Absorption peak at
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Chemical Engineering Journal 358 (2019) 1539–1551
1629 cm−1 in the spectrum of the G aerogel was derived from the C]O
stretching vibration of amide I. The peaks at 1537 and 1235 cm−1
corresponded to the bending vibrations of NeH groups and stretching
vibrations of C-N groups of amide II in gelatin molecules, respectively.
And the peak representing aliphatic CeH bending vibrations in gelatin
dispersed into the original aerogel, something different appeared in the
spectrum of the GT aerogel. The peak corresponding to NeH stretching
vibration was shifted to 3272 cm−1, and the peak was a little sharper in
comparison with that of the original gelatin aerogel. A minor shifting
from 1629 to 1623 cm−1 occurred in the spectrum of the GT aerogel. In
addition, a new peak was shown at 934 cm−1, which might be ascribed
to the combination of the Ti-O-Ti and Ti-O-C stretching vibrations
[50,57]. These differences between the spectra of GT and G aerogels
were indicative of the formation of the hydrogen bonding and chemical
bonding, which was attributed to the addition of TiO2 nanoparticles.
The coating of PEI molecules helped to introduce free amino groups to
the composite GTP aerogel. The spectrum of the GTP aerogel appeared
different compared to the spectra of GT and G aerogels. The enhance-
ment in intensities of peaks at 2914 and 2846 cm−1 which referred to
CeH groups seemed apparent. There are amino groups both in gelatin
and PEI molecules, the peaks at around 1400 to 1600 cm−1 that were
assigned to vibrations of NeH and C-N in PEI molecules were at the
similar positions in comparison with that of gelatin molecules. The peak
at 1040 cm−1 was ascribed to tertiary amine groups, confirming the
presence of the branched PEI in the fabrication process. These results
revealed the difference in chemical structures among G, GT and GTP
aerogels. The existence of hydrogen and chemical bondings helped to
realize the uniform dispersion of TiO2 nanoparticles. At the same time,
the integrity and stability of the composite aerogel were improved. The
coated PEI molecules introduced rich amino groups to the composite
GTP aerogels, and the cross-linking with glutaraldehyde further en-
hanced their stability.
Scanning electron microscopy (SEM) was utilized to determine the
morphologies of the prepared aerogels. Fig. 2 shows the SEM images of
GTP aerogels. The intrinsic gelation ability of gelatin makes it superior
material to form gels and aerogels with three-dimensional structure.
From the macroscopic perspective, original G aerogel and composite
GTP aerogel possessed self-supporting and three-dimensional porous
structures. Their stereostructure could be tuned by different molds used
in the fabrication process. As can be seen from Fig. 2a, original G
aerogel had honeycomb-like porous structure, and each pore had thin
walls surrounded. Pore walls of G aerogel exhibited a clean and flat
surface, indicative of a remarkable difference with that of GTP aerogels.
By blending with TiO2 nanoparticles and cross-linking with PEI mole-
cules, though the macroscopic three-dimensional structure changed
little, the microscopic morphology had become significantly different.
The coating and cross-linking of PEI molecules made a remarkable
difference in the morphologies between outer surface and inner part of
the composite GTP aerogel. Fig. 2d shows the outer surface of the GTP
aerogel, which revealed that original honeycomb-like pores were cov-
ered by a coating layer. When examined at high magnifications (Fig. 2e
and f), the coating layer was revealed to be a porous network composed
of interconnected pores in nanoscale. Apparently, this coating was de-
rived from the cross-linking of PEI molecules with gelatin molecules in
the outer surface of the G aerogel. However, the inner part of the GTP
aerogel maintained the honeycomb-like porous structure (Fig. 2g). TiO2
nanoparticles could be seen both in the aerogel skeleton and on the
surface of pore walls. These nanoparticles were dispersed uniformly
without heavy agglomeration, which was in favor of their photo-
catalytic property (Fig. 2h and i). Therefore, with facile fabrication, a
three-dimensional aerogel with hierarchical structure was built, and the
scales could vary from nanoscale to microscale, even centimeter scale.
The formation of the unique structure was attributed to the intrinsic
gelation ability of gelatin, the hydrogen bonding and chemical bonding
formed between molecules and the effect of additional crosslinking
J. Jiang et al.
Fig. 1. ATR-FTIR spectra of the G, GT and GTP aerogels, respectively.
agent.
3.2. Wettability of GTP aerogels
Wettability always has a big effect on the performance of materials.
As for an aerogel aiming to be used for oily wastewater treatment, its
surface wettability needs to be investigated in detail. Fig. 3 exhibits the
wetting behavior of water and oil (n-hexane) on the GTP aerogel, and
wettability of both the outer surface and the cross-section of the aerogel
was studied. In air, when water contacted with the outer surface of the
aerogel, the water droplet instantaneously spread out and permeated
into the aerogel within 0.136 s, and the water contact angle in air was
about 0° (Fig. 3a). Similarly, when the n-hexane droplet made contact
with the outer surface of the aerogel, the oil droplet spread out and
permeated into the aerogel swiftly, giving an oil contact angle in air of
0° (Fig. 3c). Though the water and oil contact angles on the cross-sec-
tion of aerogel were 0°, the permeation process was faster, always
Fig. 2. SEM images of aerogels: (a–c) G aerogel, (d–f) surface morphologies of the GTP aerogel, (g–i) cross-sectional morphologies of the GTP aerogel.
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Chemical Engineering Journal 358 (2019) 1539–1551
within 0.001 s (Fig. 3b and d), which could be ascribed to the super-
hydrophilic pore surface and larger pore size (Fig. 2g). Therefore, in air,
the GTP aerogel was superhydrophilic and superoleophilic, due to its
chemical composition and pore structures. In the water/oil/aerogel
three-phase system, things seemed different. The aerogel could not be
wetted by water when immersed in oil and could not be wetted by oil
when immersed in water. Water droplet maintained its quasi-spherical
state when it contacted the surface of the aerogel under oil (Fig. 3e),
which suggested the aerogel exhibited superhydrophobicity under oil.
Identically, the oil droplet showed a quasi-spherical shape on the sur-
face of the aerogel under water (Fig. 3f), indicative of a super-
oleophobic surface under water. When the contact angle test was per-
formed under oil, the oil trapped between the water and aerogel led the
aerogel to be superhydrophobic under oil. The water caught between
the oil and aerogel provided the aerogel with a superoleophobic surface
under water. Based on the reality shown in Fig. 3, the GTP aerogel
could be employed in oil/water separation in oil-rich or water-rich
J. Jiang et al.
conditions with good selectivity.
3.3. Oil/water separation properties of GTP aerogels
The disposal of oily wastewater is a refractory problem which needs
to be urgently solved. Techniques and materials to realize oil/water
separation or oil absorption have been developing with great concern.
The as-prepared GTP aerogel has the fascinating property to realize the
separation of oil/water free mixtures and oil-in-water emulsions. In
order to investigate the separation property of oil/water free mixtures,
the GTP aerogel was first fixed in a commonly used filter apparatus
which is shown in Fig. 4a and d. N-hexane/water mixture and di-
chloromethane/water mixture were prepared as shown in Fig. 4b and e,
and an apparent stratification phenomenon appeared on account of
their immiscibility and difference in density. The GTP aerogel pre-
wetted by water was used to separate n-hexane/water mixture. And it
took several minutes to complete the whole separation process which
was only driven by gravity. Water was penetrated through the GTP
aerogel and collected in the receiver beneath, while n-hexane was ob-
structed in the upper receiver. From the filtrate shown in Fig. 4c, it
could be found that almost no water droplet existed in the n-hexane
solution, and no n-hexane droplet appeared in water, suggesting that an
ultrahigh n-hexane/water mixture separation efficiency was obtained
for GTP aerogel. When GTP aerogel was applied to separate di-
chloromethane/water mixture, the aerogel should be pre-wetted by
dichloromethane in advance. The separation process is exhibited in
Fig. 4d, and the picture of the filtrate is demonstrated in Fig. 4f. The
water collected from upper receiver was clear and transparent, with no
oil droplet mixed in. The dichloromethane solution was also trans-
parent without water droplet. These two separation tests revealed that
the GTP aerogel could realize the separation of oil/water free mixture
with high efficiency. Because of the superhydrophilic and super-
oleophilic nature of the GTP aerogel, the aerogel was easily wetted by
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Chemical Engineering Journal 358 (2019) 1539–1551
Fig. 3. Wetting behavior of water and oil (n-
hexane) on the GTP aerogel. (a) (c) Water
and oil contact angles on the outer surface of
the GTP aerogel in air. (b) (d) Water and oil
contact angles on the cross-section of the
GTP aerogel in air. (e) Water contact angle
on the surface of the GTP aerogel in oil. (f)
Oil contact angle on the surface of the GTP
aerogel in water.
water and oil, which provided prerequisite for oil/water separation.
When aerogel was pre-wetted by water, the water absorbed in the GTP
aerogel was trapped into the porous structure of the aerogel and formed
a water film which was able to prevent oil from penetrating through the
aerogel [58]. Vice versa, when aerogel was pre-wetted by oil, oil ab-
sorbed in the aerogel formed oil layer to keep water droplet from
transiting through the aerogel. Therefore, the GTP aerogel was capable
of effectively separating oil and water as needed, which was of strong
significance in oil/water mixture treatment.
In order to investigate the chemical stability of the GTP aerogel, the
separation of the mixture of n-hexane and corrosive solution was car-
ried out [58]. GTP aerogels were pre-wetted by HNO3 (1 mol/L), NaOH
(1 mol/L) and NaCl (3.5 wt%) aqueous solutions, respectively. And
Fig. 5 shows the separation processes and results. Corrosive solutions
permeated through the GTP aerogels by the driving force of gravity,
while n-hexane was repelled and blocked in the upper receiver of the
apparatus. When the separation process was completed, no oil droplet
was observed in the collective corrosive solutions, and no water droplet
was observed in the collective oils. These results suggested that a high
separation efficiency of n-hexane/corrosive solution mixture could be
obtained by the GTP aerogels. And GTP aerogels could be utilized in
oil/water separation in the harsh environment.
Compared with oil/water free mixture, oil-water emulsion was
more intractable to treat due to its micro dimensions and good stability
[34]. The ability to separate oil-water emulsion can greatly enlarge the
application potential of the materials used for water treatment. In our
work, the toluene-in-water emulsion was prepared to measure the se-
paration performance of GTP aerogels. The separation apparatus was
the same as what is shown in Figs. 4 and 5, and the GTP aerogel was
pre-wetted by water. Separation results for the toluene-in-water emul-
sion are exhibited in Fig. 6. There was a significant difference in the
phase composition between the feed solution and the filtrate, as de-
monstrated by the optical microscopy images (Fig. 6a and c). Before
J. Jiang et al. Chemical Engineering Journal 358 (2019) 1539–1551

Fig. 4. Digital images of oil/water free mixture separation by GTP aerogel: (a–c) n-hexane/water mixture separation process and results (d–f) dichloromethane/water
mixture separation process and results. Dichloromethane and n-hexane were dyed with Sudan I in advance.

separation, the emulsion was a milky white solution with a wider
droplet size distribution range from 90 nm to 6438 nm. The filtrate
became transparent after separation and no oil droplets were observed
in the entire view (Fig. 6b and c). Only a strong DLS signal at around
10 nm was conspicuous for the filtrate, which was due to the existence
of the emulsifier (Fig. 6e) [59]. In addition, the oil rejection coefficient
R (%) was calculated as 99.72%, revealing the high separation effi-
ciency of the GTP aerogels.
3.4. Adsorption of dyes
Apart from oils, organic dyes are common pollutants in wastewater,
which are hard to degrade in nature surroundings, remarkably im-
posing heavy burdens on the properly treatment of wastewater.
Therefore, studying the properties of adsorption of dyes is of great
significance in the practical usage of newly prepared materials. In order
to confirm that the as-prepared GTP aerogel actually works in water
remediation, organic dyes were applied in the adsorption test.
Adsorption properties, isotherms, kinetics and mechanisms of GTP

Fig. 5. Digital images of separation processes of (a) hexane/HNO3 (1 mol/L) (b) hexane/NaOH (1 mol/L) (c) hexane/NaCl (3.5 wt%) by GTP aerogel. N-hexane were
dyed with Sudan I in advance.

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J. Jiang et al. Chemical Engineering Journal 358 (2019) 1539–1551

Fig. 6. (a, c) Optical microscopy images of the feed and filtrate of the toluene-in-water emulsion. (b) Digital picture of the toluene-in-water emulsion before (left) and
after (right) filtration. (d, e) DLS data of the toluene-in-water emulsion before (d) and after (e) separation.

Fig. 7. (a) Adsorption isotherms of methylene blue (MB) for the GTP aerogel and G aerogel respectively. (b) Adsorption kinetics of MB for the GTP aerogel with an
initial concentration of 100 mg/L, inserting picture shows the color change of MB before and after adsorption process. (c) Adsorption data fitted with the Langmuir
model. (d) Adsorption data fitted with the Freundlich model. (e) Plot of the pseudo-first order kinetic model. (f) Plot of the pseudo-second order kinetic model.

aerogels were explored and discussed. The adsorption performance
towards methylene blue (MB) of GTP aerogels is shown in Fig. 7. The
effect of initial concentrations of MB on the adsorption capacity of as-
prepared aerogels is exhibited in Fig. 7a. With an increasing initial
concentration of MB solution, the adsorption capacity of the GTP
aerogel increased, and the adsorption capacity could reach to
40.07 mg/g at an initial concentration of 469 mg/L. Fig. 7a also shows
the adsorption capacity of the G aerogel, which was lower than that of
the GTP aerogel, suggesting that gelatin played a role in the adsorption
of MB with other effective components. When the initial concentration

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J. Jiang et al.
of MB was set as 100 mg/L, the effect of reaction time on the adsorption
capacity of the GTP aerogel is shown in Fig. 7b. The adsorption rate
increased rapidly at the beginning of the adsorption process, and gra-
dually slowed down along with the adsorption process went on, finally
reached to an equilibrium. At the very beginning of the adsorption
process, because of the abundant functional sites in the aerogel, the dye
molecules were adsorbed as soon as they contacted with the aerogel.
With the number of the adsorbed dye molecules on the aerogels en-
larged, free functional sites on the aerogel were limited, and the re-
pulsive force between the combined dye molecules and free molecules
became stronger, leading to a slower adsorption rate. The moment the
driving force and repulsive force reached a balance, the adsorption
equilibrium was achieved. The MB solution was changed from a very
dark blue to a light blue before and after the adsorption process as
shown in the inserting picture of Fig. 7b, indicating an efficient dye
adsorption process. Besides, as depicted in Fig. S1, the removal effi-
ciency could reach as high as 92.9% when adsorption equilibrium was
realized.
For the purpose of studying the adsorption mechanisms of GTP
aerogels, experimental data was used to fit with the Langmuir and
Freundlich isotherm model. Fitting results of the GTP aerogel are dis-
played in Fig. 7c and d. As illustrated in Fig. 7c, the Langmuir isotherm
had a correlation coefficient (R2) of 0.9975, showing that the experi-
mental data was in good agreement with the Langmuir isotherm model.
And from the Langmuir isotherm model, qm (the maximum adsorption
capacity), could be calculated as 81.41 mg/g, which was higher than
previously reported adsorbents such as graphene nanosheet/magnetite
composite (43.82 mg/g) and graphene-carbon nanotubes (65.79 mg/g)
[60,61]. And the Freundlich isotherm model had a correlation coeffi-
cient (R2) of 0.9842. The magnitude of n in the Freundlich equation
illustrates the adsorption ability, and if n is > 1, it will confirm a fa-
vorable adsorption condition [62]. The value of n was calculated as
1.392, revealing a well adsorption ability of the GTP aerogel. By com-
paring the fitting results of the two isotherm models, due to higher
value of R2, the adsorption of MB onto GTP aerogel was better fitted
with the Langmuir model than Freundlich model, indicative of a
monolayer adsorption. The adsorption kinetics were evaluated by using
pseudo-first order kinetic model and pseudo-second order kinetic
model. Fig. 7e and f show the fitting results of them. The higher cor-
relation coefficient (R2) of 0.9996 revealed that the experimental data
was in good accordance with the pseudo-second order kinetic model.
The adsorption capacities of different kinds of organic dyes for GTP
aerogel under different initial concentrations were investigated, and
results are shown in Fig. 8(a–c). All these three plots illustrated that
adsorption capacities increased with the increase of dyes initial con-
centrations. When the initial concentration was set as 100 mg/L, the
color changes of dyes before and after adsorption process could be
clearly seen in the inserting pictures in Fig. 8, which suggested a good
adsorption ability toward various organic dyes. The adsorption capa-
cities of GTP aerogels for CV, MO and CR were 64.31 mg/g, 85.21 mg/
g, 86.67 mg/g at an initial concentration of 500 mg/L. The property of
the GTP aerogel to adsorb diverse kinds of organic dyes are beneficial
for their usage in wastewater treatment with complex components.
Reusability is a vital prerequisite for practical usage of adsorbents.
Methanol was employed to use as the regeneration agent for GTP
aerogels. The MB molecules adsorbed on the saturated GTP aerogel
could be removed by methanol. After rinsed with deionized water for
several times, the regenerated GTP aerogel was used to carry out an-
other cycle of the adsorption process. The results of the cycling test are
shown in Fig. 8d. After five cycles of regeneration, the adsorption ca-
pacity remained 74.04% of the first cycle, indicating an excellent reu-
sability of the GTP aerogel. And dye molecules firmly combined onto
the GTP aerogel that could not be easily removed by ethanol were
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Chemical Engineering Journal 358 (2019) 1539–1551
attributed to the decrease of the adsorption capacity in the second to
fifth cycles.
The solution pH is an important factor that can affect the dye ad-
sorption behavior remarkably. The surface charge of the adsorbent, the
degree of ionization of dyes and the structure of dye molecules can vary
along with the changing of the pH value [63]. The effect of pH on the
adsorption of MB and CR dyes of the GTP aerogel over the range of 5–9
was investigated, and the results are shown in Fig. 9. The adsorption
capacity of MB increased with the increased pH values. But the ad-
sorption capacity of CR increased with the increase of pH values first,
and then decreased with the increase of pH values. The pH of zero point
charge of the GTP aerogel was around 5.16. For cationic MB, in the acid
solution, the GTP aerogel was protonated, the excessive H+ ions on the
surface of the aerogel compete with the MB molecules, leading to a
lower adsorption capacity. In the alkaline solution, the GTP aerogel was
deprotonated, the electrostatic attraction between the aerogel and the
cationic MB resulted in a higher adsorption capacity. For CR dye, whose
surface charge changes at the solution pH about 6.8, the adsorption
behavior seemed different [64]. In the alkaline conditions, the elec-
trostatic repulsion between the deprotonated aerogel and the anionic
CR molecules retarded the adsorption behavior. In the acid solution,
with the decrease of the pH values, the electrostatic repulsion between
the protonated GTP aerogel and the cationic CR molecules caused a
declined adsorption capacity. Therefore, the adsorption of cationic and
anionic dyes was greatly influenced by the change of pH values. The
electrostatic interactions between the dyes and aerogels also played an
important role in the adsorption property. The natural pH of MB solu-
tion is between 8 and 9, and the natural pH of CR solution is between 6
and 7. In this work, the adsorption of MB and CR on the GTP aerogel
was measured without the adjusting of solution pH. As can be seen from
Fig. 9, the GTP aerogel could favorably adsorb MB and CR dyes at their
natural pH values, respectively.
In order to further understand the mechanisms of organic dyes ad-
sorption on GTP aerogels, FTIR spectra of GTP aerogels before and after
adsorption are demonstrated in Fig. 10. In these two adsorption pro-
cesses, two pieces of the GTP aerogel were immersed in MB and CR dyes
(100 mg/L) respectively to reach adsorption equilibrium. After col-
lecting and drying, these two adsorbents were determined by FTIR. As
can be seen in Fig. 10, after dyes adsorption, the characteristic peaks in
the spectra of dye loaded GTP aerogels were slightly shifted to lower
wavenumbers. The peak at 1639 cm−1 that referred to the C]O
stretching vibration of amide I was shifted to 1629 cm−1 for GTP-MB
aerogel and 1626 cm−1 for GTP-CR aerogel. The NeH bending vibra-
tion peak which was at 1572 cm−1 almost disappeared in the spectra of
GTP-MB and GTP-CR aerogels. In addition, the peak at 1540 cm−1
shifted to 1533 cm−1 (GTP-MB) and 1537 cm−1 (GTP-CR). And the
peak that was assigned to CeH bending vibration shifted from
1453 cm−1 to 1450 cm−1 and 1447 cm−1 for GTP-MB and GTP-CR,
respectively. These variations in spectra illustrated the existence of
electrostatic and hydrogen bonding reactions between the functional
groups of dye molecules and GTP aerogels.
3.5. Adsorption of Cu (II) ions
The adsorption of Cu (II) ions on GTP aerogel was performed to
investigate its capability of dealing with heavy metal ions. Cu (II) ions
can form complexes of bright blue color with amino groups, which is
able to confirm the adsorption of Cu (II) ions in turn. Fig. 11a shows
how the equilibrium adsorption capacity changed with the initial
concentrations of Cu (II) ion solutions. In this test, Cu (II) ions solution
was used as prepared at a pH of 4.62 without further pH adjusting. The
plot revealed that the equilibrium adsorption capacity of the GTP
aerogel remarkably increased with the increase of initial concentrations
J. Jiang et al.
Fig. 9. Effect of pH values on the adsorption of MB and CR molecules of the
GTP aerogels at an initial solution concentration of 100 mg/g.
of Cu (II) ion solutions when the concentrations were less than 100 mg/
L. Subsequently, the increasing of the equilibrium adsorption gradually
slowed down. And the adsorption capacity at an initial concentration of
500 mg/L was 61.2 mg/g. This adsorption capacity for Cu (II) ion of the
GTP aerogel was higher than many other adsorbents reported in lit-
eratures, such as the immobilized Bacillus strain CR-7 biomass
(33.3 mg/g), the polyaniline and poly(acrylic acid) grafted sodium al-
ginate/gelatin adsorbent (53.7 mg/g), and the PEI-functionalized ion
imprinted hydrogel (40.0 mg/g) [65–67]. Fig. 11b and c exhibit the
fitting results of experimental data with the Langmuir model and
Freundlich model respectively. Result revealed that adsorption data
fitted better with the Freundlich model. PEI has many amino groups in
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Chemical Engineering Journal 358 (2019) 1539–1551
Fig. 8. Adsorption capacity under different
initial concentrations of (a) crystal violet
(CV); (b) methyl orange (MO); (c) congo red
(CR). (d) Reusability test of the GTP aerogel
for MB adsorption up to five cycles (effi-
ciencies: 100, 96.73, 76.08, 75.42, 74.04
(%)). Inserting pictures in (a–c) show the
color change of dyes before and after ad-
sorption progress.
Fig. 10. FTIR spectra of GTP aerogels before (GTP) and after dyes adsorption
(GTP-MB for MB adsorption and GTP-CR for CR adsorption).
its molecular chains, which favors the process of Cu (II) ion adsorption.
Besides, gelatin molecules have amino groups too, giving them some
adsorption ability. Fig. 11d depicts the relationship between the equi-
librium adsorption capacity of the GTP aerogel and the adsorption time
at a setting initial concentration of 500 mg/L. The adsorption rate was
large at the very beginning of the adsorption process, then decreased
gradually until the adsorption equilibrium was reached. Pseudo-first
order kinetic model and pseudo-second order kinetic model were em-
ployed to explore the adsorption kinetics of Cu (II) ions. As demon-
strated in Fig. S2 and Fig. 11e, adsorption kinetic data was fitted better
with the pseudo-second order kinetic model.
Cycling test was conducted to evaluate the reusability of the GTP
J. Jiang et al.
Fig. 11. (a) Adsorption isotherm of Cu (II) on GTP aerogel. Inserting photo shows GTP aerogel before and after the adsorption of Cu (II) ions with an initial
concentration of 100 mg/L. (b) Adsorption data fitted with the Langmuir model. (c) Adsorption data fitted with the Freundlich model. (d) Adsorption kinetics of the
GTP aerogel on Cu (II) ions with an initial concentration of 500 mg/L. (e) Plot of the pseudo-second order kinetic model. (f) Cycling test of the GTP aerogel for Cu (II)
ions adsorption up to five cycles (efficiencies: 100, 85.94, 85.69, 84.12, 76.58 (%)).
aerogel on Cu (II) ions adsorption. EDTA, a common used chelating
agent for metal ions, was utilized to realize the regeneration of satu-
rated GTP aerogels. After going through the regeneration process, the
“clean” aerogel was ready for next adsorption experiment. Fig. 11f
displays the resorption efficiency for 5 cycles of the regeneration pro-
cess, and the results revealed that the GTP aerogel possessed good
reusability. After the 5th cycle, the adsorption capacity of the GTP
aerogel still remained 76.58% of the first cycle.
3.6. Photocatalytic property of the GTP aerogel
Anatase TiO2 nanoparticles are commercially used as photocatalysts
for their well-known photocatalytic properties. TiO2 can generate
electron-hole pairs by the excitation of UV light. The photogenerated
electrons move from the valence band (VB) to the conduction band (CB)
of TiO2. The photogenerated electrons and holes can react with oxygen
(O2) and water (H2O) to form superoxide radical (O2%−) and hydroxyl
radical (HO·). These two kinds of radicals are highly effective in the
degradation of organic pollutants [41,50,68]. However, incorporating
TiO2 nanoparticles into functional materials always has problems such
as nanoparticles aggregation and unstable attachment, which could
inhibit their performance. In this work, the uniform dispersion of TiO2
nanoparticles was realized, which could be confirmed by SEM images
and elemental mapping images. In Fig. 12e, the homogeneous disper-
sion of Ti element is displayed, verifying the distribution of TiO2 na-
noparticles in the GTP aerogel. Because the TiO2 nanoparticles were
blended into the starting solution of the GTP aerogel, some of them
were encapsulated into the skeleton of the GTP aerogel, others were
exposed on the pore surfaces of the GTP aerogel. TiO2 nanoparticles
exposed onto the surface of pores had the access to contact with organic
dyes and could exert photocatalytic property under UV irradiation. In
addition, the exposed nanoparticles uniformly dispersed onto the sur-
face of pore walls without agglomeration (Fig. 2i), which was good for
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Chemical Engineering Journal 358 (2019) 1539–1551
the photocatalytic property of the GTP aerogel. However, nanoparticles
trapped into the aerogel skeleton could not be used to degrade organic
dyes. That is one main reason to explain the only 15% improvement
(Fig. 12h) in degradation result under the condition that TiO2 nano-
particles were homogeneously dispersed. Another reason is that the
relatively dense surface of the GTP aerogel inhibit the incoming of UV
light to some degree, making exposed TiO2 nanoparticles come into
contact with limited UV irradiation. Unfortunately, with these two
main reasons, the photocatalytic performance of the GTP aerogel was
confined. But the GTP aerogel did have photocatalytic property which
could play an auxiliary role in water treatment. In addition, the method
to realize the uniform dispersion of TiO2 nanoparticles, the dilemma we
met in constructing high-efficiency photocatalytic aerogels, will pro-
vide important references for designing multifunctional aerogels used
for water remediation.
4. Conclusions
In this work, an original gelatin-based multifunctional aerogel (GTP
aerogel) was fabricated through facile method including the preparing
of gelatin solution, TiO2 blending, PEI cross-linking and freeze-drying
procedures. The as-prepared GTP aerogels could realize excellent oil/
water separation for both oil/water free mixture and oil-water emulsion
with high selectivity, various organic dyes and Cu (II) ions adsorption
with good reusability and uniform dispersion of TiO2 nanoparticles. The
photocatalytic performance of the GTP aerogel could also play an
auxiliary effect in water treatment. The mechanism of organic dyes
adsorption might be ascribed to electrostatic and hydrogen bonding
interactions between dye molecules and GTP aerogel molecules. The
adsorption of Cu (II) ions on GTP aerogel was mainly attributed to the
complex formed by amino groups in the aerogel and Cu (II) ions.
Equipped with these integrative functions, the designed gelatin-based
aerogels promise to be reliable and competitive candidates in
J. Jiang et al.
Fig. 12. (a–e) Elemental mapping images of the GTP aerogel. (f) Overlapping of C, O, N, S, Ti elements. (g) EDS analysis of the GTP aerogel. (h) Photocatalytic result
of MO (5 mg/L) with/without using GTP aerogel.
wastewater remediation. This work will also provide new thoughts for
functions integration in environmentally friendly bio-based materials.
Conflict of interest
The authors declare no competing financial interest.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (No. 21776249, 21476195, and 21576236).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cej.2018.10.144.
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