gels
Article
Hydrophobic Modification of ZrO2-SiO2 Xerogel and Its
Adsorption Properties to Rhodamine B
Yan Liu and Jing Yang *
Citation: Liu, Y.; Yang, J.
Hydrophobic Modification of
ZrO2 -SiO2 Xerogel and Its
Adsorption Properties to Rhodamine
B. Gels 2022, 8, 675. https://doi.org/
10.3390/gels8100675
Academic Editor: Ashleigh Fletcher
Received: 21 September 2022
Accepted: 17 October 2022
Published: 20 October 2022
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4.0/).
Gels 2022, 8, 675. https://doi.org/10.3390/gels8100675
School of Urban Planning and Municipal Engineering, Xi’an Polytechnic University, Xi’an 710048, China
* Correspondence: 20020706@xpu.edu.cn
Abstract: Zirconium nitrate pentahydrate (Zr(NO3 )4 ·5H2 O) and tetraethyl orthosilicate (TEOS) are
used as the zirconium source and silicon source, respectively, and methyltriethoxysilane (MTES)
as the hydrophobic modifier; the hydrophilic and hydrophobic ZrO2 -SiO2 xerogels were prepared
successfully. The xerogels were characterized using Fourier transform infrared spectra (FTIR), X-ray
diffraction (XRD), scanning electron microscopy (SEM), and N2 adsorption–desorption measurement.
The adsorption mechanism of hydrophobic ZrO2 -SiO2 xerogels to RhB was described by the kinetic
and adsorption isotherms. The results showed that the introduction of Si-CH3 groups can make
the average pore size, BET surface area, and total pore volume of ZrO2 -SiO2 xerogel increase. The
hydrophobic ZrO2 -SiO2 xerogel displays an adsorption capacity of 169.23 mg·g−1 for RhB dye at
25 ◦ C and pH = 3. The adsorption process of hydrophobic ZrO2 -SiO2 xerogel to RhB followed a
pseudo–second-order kinetic model. Fitting results from the D–R model of adsorption indicate that
the adsorption of RhB onto the hydrophobic ZrO2 -SiO2 xerogels is mainly physical, accompanied by
a spontaneous heat absorption process. The regeneration and recycling properties of hydrophobic
xerogels were investigated, and their recoverability and reusability were demonstrated.
Keywords: methyl-modified; hydrophilic; hydrophobic; adsorption; rhodamine B; kinetic; adsorp-
tion isotherms
1. Introduction
Rhodamine B (RhB) (its structure is shown in Figure 1) is a basic cationic dye that was
used in large quantities as a food additive and was later banned from the food industry
because of experimental evidence of its carcinogenicity. However, RhB is still widely used
in laboratories, the paper industry, the textile printing and dyeing industry, colored glass,
specialty fireworks, and other industries [1]. These industries produce large amounts of
RhB dye wastewater, which, if not properly treated, can cause great harm to human health
and the ecological environment. Thus, it is important to seek an efficient and econom-
ical method for the treatment of dye wastewater represented by RhB [2]. Furthermore,
due to the continuous industrial demand for RhB and the increased difficulty in treating
RhB-containing dye wastewater, there is an increasing interest in its degradation and re-
moval [3–6]. To our knowledge, there were many treatment methods [7–11] implemented
for removing the eco-toxic dyes from aqueous solutions, therein including coagulation,
chemical oxidation, photodegradation, membrane filtration, and adsorption. Among these
methods, adsorption was deemed to be a high-efficiency and low-cost technology for
removing those hazardous impurities from aqueous solutions. The high effectiveness
and wide availability of an adsorbent make it very attractive for dye removal from the
water environment. By far, for its low cost and energy consumption, adsorption was fre-
quently chosen in the separation process [12–14]. High-performance adsorption materials
mainly included activated carbon, nanometallic oxide, graphene, zeolite, “Greek coffee”
grounds, etc.
https://www.mdpi.com/journal/gels
 Gels 2022, 8, x FOR PEER REVIEW 2 of 19

Gels 2022, 8, 675 2 of 19

materials mainly included activated carbon, nanometallic oxide, graphene, zeolite, “Greek
coffee” grounds, etc.

Figure1.1.Molecular
Figure Molecularstructural
structuralmodels
modelsofofRhB.
RhB.

Zirconia(ZrO
Zirconia (ZrO22),),one
oneofofthe
theimportant
importanttransition
transitionmetalmetaloxides,
oxides,has hasreceived
receivedconsider-
consider-
ableattention
able attentionfor forits
itswide
wideapplications
applicationsin inoxygen
oxygensensors,
sensors,fuel fuelcellcellelectrolytes,
electrolytes,catalysts,
catalysts,
andcatalytic
and catalyticcarriers,
carriers,andandmetal-oxide-semiconductor
metal-oxide-semiconductor devices devices due dueto toaahigh
highnumber
numberofof
active
activesites
sitesononthetheZrO
ZrO22 surface,
surface, good
good strength,
strength, large
large pore
pore size,
size, and
and high
high chemical
chemical stability,
stability,
etc.
etc.[15].
[15].TheTheaddition
additionof ofmetal
metaloxides
oxides[16,17]
[16,17]can
canprovide
provideadsorption
adsorptionsites sitesfor
forthe
thereactants
reactants
and
andimprove
improvethe theadsorption
adsorptionperformance,
performance,and andalso
alsoincrease
increasethe theanti-pollution
anti-pollutionproperties.
properties.
Ali
Alietetal.al.[18]
[18]prepared
preparedZrO ZrO2 2/CeO adsorbent materials
/CeO22 adsorbent materialsfor forthetheadsorption
adsorptionof ofacid
acidgreen
green1
1dye
dyeusingusinga aco-precipitation
co-precipitationmethod. method. Lin et al. [19] synthesized
Lin et al. [19] synthesized ZrO2/carbon ZrO 2 /carbon aerogel
aerogel (CA)
(CA) composites
composites with with different
different amounts amounts of monoclinic
of monoclinic and tetragonal
and tetragonal ZrO2 crystallites.
ZrO2 crystallites. The ad-
−1
The adsorption
sorption capacity capacity
of ZrOof ZrOmaterials
2/CA 2 /CA materials for cationic
for cationic RhB dyes RhBis dyes
95.42 ismg· 95.42 SiO·2gis a.
g −1. mg
SiO 2 is a material
porous porous material
with low with low density,
density, good thermal
good thermal stability,stability, chemically
chemically stablestable prop-
properties,
erties, and excellent
and excellent adsorption
adsorption properties,properties, and isused
and is widely widelyas ausedcarrierasxerogel
a carrier forxerogel for
adsorption
adsorption [20,21]. Shishmakov et al. [22] synthesized ZrO
[20,21]. Shishmakov et al. [22] synthesized ZrO2-SiO2 xerogels through the hydrolysis of a
2 -SiO 2 xerogels through the
hydrolysis
mixture ofof a mixture of tetrabutoxyzirconium
tetrabutoxyzirconium and tetraethoxysilane
and tetraethoxysilane in a desiccatorin inaa desiccator
vapor of a in a
15%
vapor of a 15% aqueous
aqueous NH3 atmosphere. Viter NH 3 atmosphere. Viter [23] synthesized mixed
[23] synthesized mixed oxide dry gels of ZrO2-SiO2 from oxide dry gels of
ZrO
ZrOCl2 -SiO 2 from
2-8H
ZrOCl2 -8H2 O and tetraethylorthosilicate
2O and tetraethylorthosilicate [Si(OEt)4] by the [Si(OEt) 4 ] by
sol–gel the sol–gel
method. Themethod.
synthe-
The
sized gels had a substantially increased porosity with specific surface areas of areas
synthesized gels had a substantially increased porosity with specific surface of
140–630
140–630 2
m ·pore− 1
g and pore volumes of 0.087–0.441 3 − 1
cm ·g et .al.Huang et al. [24]a prepared
m2·g−1 and volumes of 0.087–0.441 cm3·g−1. Huang [24] prepared SiO2-ZrO2
axerogel
SiO2 -ZrO 2 xerogel using TEOS as a
using TEOS as a silicon source and ZrO(NO) silicon source and ZrO(NO)
3·2H2O as Zr source. 3 · 2H2 OItsasspecific
Zr source.
sur-
2 −1 600 ◦ Cwith
Its specific
face surfaceup
area reached areato reached
525.6 m2up ·g−1 to
after 600m°C·gheatafter
525.6 treatment, heatan treatment,
average
3 ·g−1 and an RhB adsorption
with size
pore an
average pore size of
of 8.5 nm and a pore volume 8.5 nm and a pore volume of 1.16 cm
of 1.16 cm3·g−1 and an RhB adsorption capacity of about 119
capacity
mg·g−1 atofpH about 119 mg
= 4 and ·g−1 attime
a contact pH =of44and h. a contact time of 4 h.
So far, studies on hydrophilic ZrO2 -SiO2 xerogels are relatively common [25], however,
So far, studies on hydrophilic ZrO2-SiO2 xerogels are relatively common [25], how-
when preparing ZrO2 -SiO2 xerogels, a large amount of -OH groups are generated during
ever, when preparing ZrO2-SiO2 xerogels, a large amount of -OH groups are generated
the hydrolysis of TEOS, which can easily cause shrinkage or even cracking during the syn-
during the hydrolysis of TEOS, which can easily cause shrinkage or even cracking during
thesis of composite xerogels and destroy their pore structure and affecting the adsorption
the synthesis of composite xerogels and destroy their pore structure and affecting the ad-
performance. In this regard, the modification of hydrophilic ZrO2 -SiO2 composite xerogels
sorption performance. In this regard, the modification of hydrophilic ZrO2-SiO2 composite
with methyl hydrophobicity is a worthwhile approach to explore. For this reason, in this
xerogels with methyl hydrophobicity is a worthwhile approach to explore. For this reason,
paper, the hydrophobic modification was performed by introducing methyl groups based
in this paper, the hydrophobic modification was performed by introducing methyl groups
on the synthesis of hydrophilic ZrO2 -SiO2 composite xerogels, and the characterization
results of two samples and different influencing factors on the adsorption performance of
RhB were compared.
Gels 2022, 8, 675 3 of 19

For this, RhB was selected as the adsorbent and hydrophilic and hydrophobic ZrO2 -SiO2
xerogels were prepared in this paper. The xerogels were characterized by FTIR, XRD, SEM, and
N2 adsorption–desorption. The adsorption performance of the hydrophilic and hydrophobic
ZrO2 -SiO2 xerogels on RhB was analyzed under the influence of different dosages, pH, and
adsorption times and temperatures. In addition, the adsorption kinetics and adsorption
isotherms of hydrophobic ZrO2 -SiO2 xerogel were investigated. Prepare for the removal of
more diverse dyes in the future.

2. Experimental Section
2.1. Sol Preparation
2.1.1. Preparation of ZrO2 Sol
The ZrO2 sols were prepared by sol–gel method using zirconium nitrate pentahy-
drate (Zr(NO3 )4 ·5H2 O, Tianjin Fuchen Chemical Reagent Co., Ltd., Tianjin, China) as the
precursor and oxalic acid (C2 H2 O4 ·2H2 O, p.a. grade, Tianjin Hedong Hongyan Chemical
Reagent Co., Ltd., Tianjin, China) as the solvent. A certain amount of Zr(NO3 )4 solution
was added to the three-mouth flask, and 0.2 mol·L−1 of C2 H2 O4 solution was added to the
Zr (NO3 )4 solution drop by drop with the volume ratio of Zr(NO3 )4 /C2 H2 O4 = 3/2. After
the temperature of the water bath reached 50 ◦ C, 30% (v/v) of propanetriol (GL, p.a. grade,
Tianjin Kemiou Chemical Reagent Co., Ltd., Tianjin, China) was added drop by drop and
stirred strongly for 3 h, and the clarified and transparent ZrO2 sol was obtained after aging
at 25 ◦ C for 12 h.
For the ZrO2 sol, the reactions are as Formulas (1)–(3):

Zr(NO3 )4 + 4H2 O → Zr(OH)4 + 4HNO3 (1)

≡ Zr-OH + OH-Zr ≡ → Zr-O-Zr ≡ +H2 O (2)

Zr(OH)4 + 2C2 H2 O4 ≡ →= Zr(C2 O4 )2 + 4H2 O (3)

2.1.2. Preparation of Hydrophilic SiO2 Sol

The molar composition of chemical regents preparing the hydrophilic SiO2 sol was
TEOS:MTES:EtOH:H2 O:HNO3 = 1.0:0.8:8.0:0.72:0.085. Ethyl orthosilicate (TEOS, p.a. grade,
Xi’an chemical reagent Co. Ltd., Xi’an, China) and anhydrous ethanol (EtOH, p.a. grade,
Tianjin Branch Micro-Europe Chemical Reagent Co., Ltd., Tianjin, China) were mixed as a
hydrophilic solution and placed in an ice water bath. The mixture of H2 O and nitric acid
(HNO3 , p.a. grade, Sichuan Xilong Reagent Co., Ltd., Xilong, China) was added dropwise
under a magnetic stirrer for 30 min. After the dropwise addition, the mixture was stirred at
reflux for 3 h at 60 ◦ C and cooled to obtain the hydrophilic SiO2 sol.

2.1.3. Preparation of Hydrophobic SiO2 Sol

Methyltriethoxysilane (MTES, grade 98%, Hangzhou Guibao Chemical Co. Ltd.,
Hangzhou, China) was used as a hydrophobic agent, and according to the molar ratio
of TEOS:MTES:EtOH:H2 O:HNO3 = 1.0:0.8:8.0:0.72:0.085, it was first mixed completely
with MTES, TEOS, and EtOH, placed in an ice-water bath, and stirred fully under a
magnetic stirrer for 30 min before adding dropwise H2 O and nitric acid mixture, and after
the dropwise addition, it was stirred at 60 ◦ C under reflux for 3 h and cooled to obtain
methyl-modified hydrophobic SiO2 sol.

2.1.4. Preparation of Hydrophilic and Hydrophobic ZrO2 -SiO2 Sols

According to the Zr/Si molar ratio of 0.15, a mixture of ZrO2 sol was added drop by
drop into the freshly prepared SiO2 sols and methyl-modified SiO2 , respectively. After
stirring strongly for 60 min at 25 ◦ C, the hydrophilic ZrO2 -SiO2 and hydrophobic ZrO2 -SiO2
sols were obtained, respectively.
The co-hydrolysis and condensation reactions of TEOS and MTES are as Formulas (4)–(9):
Gels 2022, 8, 675 4 of 19

Hydrolysis reactions:

Si(OCH2 CH3 )4 + nH2 O → Si(OCH2 CH3 )4−n (OH)n + nCH3 CH2 OH (4)

CH3 -Si(OCH2 CH3 )3 + nH2 O → CH3 -Si(OCH2 CH3 )3−n (OH)n + nCH3 CH2 OH (5)
Condensation reactions:

≡ SiOCH2 CH3 + HO-Si ≡ → Si-O-Si ≡ + CH3 CH2 OH (6)

≡ Si(CH3 )-OCH2 CH3 + HO-Si ≡ → Si(CH3 )-O-Si ≡ + CH3 CH2 OH (7)

≡ Si-OH + HO-Si ≡ → Si-O-Si ≡ +H2 O (8)
≡ Si(CH3 )-OH + HO-Si ≡ → Si(CH3 )-O-Si ≡ +H2 O (9)
The reactions between ZrO2 and hydrophilic SiO2 , hydrophobic SiO2 sols are as
Formulas (10) and (11):

Zr-OH + HO-Si → Zr-O-Si + H2 O (10)

Zr-OH + CH3 CH2 O-Si → Zr-O-Si + CH3 CH2 OH (11)

2.2. Preparation of Xerogels

The as-prepared ZrO2 , hydrophilic and hydrophobic SiO2 , and hydrophilic and
hydrophobic ZrO2 -SiO2 sols were placed in the Petri dishes, respectively, and dried at
50 ◦ C. The formed gels were ground into powders and then roasted in a program-controlled
high-temperature furnace at 400 ◦ C for 2 h under N2 atmosphere with a heating rate of
1 ◦ C·min−1 .

2.3. Characterization
FTIR spectra were recorded on a PerkinElmer Spotlight 400 and Frontier spectrometer
and KBr pellets were prepared and taken over a wavelength range of 400–4000 cm−1 . XRD
patterns were performed on a RigakaD/max 2200 X-ray diffractometer, using CuKα radia-
tion and scanning 2θ from 4 to 90◦ , operated at 40 kV and 40 mA. The JSM-6700F SEM was
used to investigate the morphology of the samples. X-ray photoelectron spectroscopy (XPS)
was used to analyze the surface chemical composition of the hydrophilic and hydrophobic
ZrO2 -SiO2 xerogels. (ESCALAB250xi, Thermo Scientific, Waltham, MA, USA). The pressure
in the analysis chamber was maintained at 3.0 × 10−7 Pa. The binding energy values were
referenced to the C (1 s) line situated at 284.6 eV. N2 absorption–adsorption isotherms and
pore size distributions were obtained from the ASAP2020 Plus automatic analyzer, mi-
cromeritics. Molecular structure models were constructed using ChemDraw software 18.0
(PerkinElmer Corporation, Waltham, MA, USA, Software license: Sijie Marking Software
Co., Ltd., Suzhou, China).

2.4. Water Adsorption Measurement

To examine the hydrophobicity of the two ZrO2 -SiO2 xerogels, the hydrophilic and hy-
drophobic ZrO2 -SiO2 samples were aged in a constant temperature and humidity chamber
of 25 ◦ C and 75% RH. During the aging period, the samples were weighed, and the mass
changes and water adsorption were calculated.

2.5. Adsorption Performance Test

The effects of adsorption time, adsorption temperature, dosage, and pH on the removal
of RhB were investigated by adsorption experiments. A certain amount of rhodamine B
(RhB, Relative molecular weight (Mw) = 479.01, λmax = 552 nm, Tianjin Comio Chemical
Reagent Co., Ltd., Tianjin, China) dye was dissolved in deionized water to prepare a
Gels 2022, 8, 675 5 of 19

standard solution of 140 mg·L−1 . The Zeta potential of the xerogels was measured using a
Nano-ZS tester manufactured in the UK and the average of three measurements was taken.
The hydrophilic and hydrophobic ZrO2 -SiO2 xerogels (0.01, 0.05, 0.1, 0.15, 0.2 g) were
separately dispersed in the above RhB solution (50 mL) under vigorous stirring (700 rpm). The
adsorption experiments were conducted at 25, 35, and 45 ◦ C, respectively. The solid–liquid
mixture was separated by centrifugation. The liquid phase was analyzed using a UV-V
spectrophotometer at a wavelength of 554 nm. The RhB concentrations were then calculated
from the calibration curve.
The adsorption amount qe of RhB by the hydrophilic and hydrophobic ZrO2 -SiO2
xerogels ate calculated by Equation (12):

(C0 − Ce )V
qe = (12)
W
The removal rate of RhB in water is calculated by Equation (13):

C0 − Ce
R= × 100% (13)
C0

where C0 and Ce (mg·L−1 ) is the initial and equilibrium concentration of RhB, respectively.
V (L) is the volume of the solution. W (g) is the dry mass of the xerogels.

2.6. Desorption Performance Test

The hydrophilic and hydrophobic ZrO2 -SiO2 xerogels were rinsed with anhydrous
ethanol at room temperature, and the process was repeated 6 times for multiple cycles of
adsorption and desorption to test the reproducibility of the prepared xerogel adsorbents.

3. Results and Discussion

3.1. FTIR Analysis
The functional groups of ZrO2 , hydrophilic and hydrophobic SiO2 , and hydrophilic
and hydrophobic ZrO2 -SiO2 xerogels were investigated using FTIR spectra, shown in
Figure 2. In Figure 2, the absorption peak at around 3449 cm−1 is the stretching and
bending vibration of the -OH group caused by the absorption of water, the characteristic
peak at 1634 cm−1 is caused by the Si-OH bonds [26] of the xerogel, the peaks located
around 790 cm−1 are related to the stretching vibration of the Si-O bond [27], and these
sets of absorption peaks co-occur in the hydrophilic and hydrophobic SiO2 , hydrophilic
and hydrophobic ZrO2 -SiO2 xerogels. As can be seen in Figure 2, the absorption peak of
Si-O-Si in hydrophilic and hydrophobic SiO2 xerogels is 1050 cm−1 [28]. In hydrophilic and
hydrophobic ZrO2 -SiO2 xerogels, the absorption peaks of Zr-O-Si appeared at 1100 cm−1 ,
and the absorption peak at 1110 cm−1 is due to the presence of Zr perturbing the three-
dimensional asymmetric stretching vibrations of Si-O-Si forming a Zr-O-Si bond, indicating
the chemical bonding of SiO2 to ZrO2 particles [29]. The methyl hydrophobic modification
of the xerogel is achieved by depleting the -OH group in the Si-OH bond on the xerogel
surface and introducing the hydrophobic group -CH3 to form the Si-CH3 bond. Compared
with SiO2 and hydrophilic ZrO2 -SiO2 , the hydrophobic SiO2 and ZrO2 -SiO2 exhibited -CH3
absorption peak at 2971 cm−1 and Si-CH3 absorption peak at 1277 cm−1 , indicating the
successful modification of the methyl hydrophobic groups. The characteristic peaks of -OH
and Zr-OH can be seen in ZrO2 xerogel at 3400 cm−1 and 1410 cm−1 , respectively, along
with an absorption peak of Zr-O at 447 cm−1 . In addition, it can be seen from Figure 2
that the absorption peaks at 3449 cm−1 and 1634 cm−1 of hydrophobic xerogel are slightly
weaker than hydrophilic xerogel, whereas the presence of this indicates the consumption
of -OH and the formation of Si-CH3 . According to infrared spectrum analysis, combined
with the reaction equations, there are Si-O-Si, Zr-O-Si, Si-OH, Zr-OH, and Zr-O groups on
the surfaces of hydrophilic and hydrophobic ZrO2 -SiO2 xerogels. In addition, the surface
of the hydrophobic ZrO2 -SiO2 sample also contains Si-CH3 groups.
 weaker than hydrophilic xerogel, whereas the presence of this indicates the consumption
of -OH and the formation of Si-CH3. According to infrared spectrum analysis, combined
with the reaction equations, there are Si-O-Si, Zr-O-Si, Si-OH, Zr-OH, and Zr-O groups on
Gels 2022, 8, 675 the surfaces of hydrophilic and hydrophobic ZrO2-SiO2 xerogels. In addition, the surface
6 of 19
of the hydrophobic ZrO2-SiO2 sample also contains Si-CH3 groups.

Figure 2. FTIR spectra comparison of (a) ZrO , (b) hydrophilic SiO2 , (c) hydrophobic SiO2 ,
Figure 2. FTIR spectra comparison of (a) ZrO2, (b)2 hydrophilic SiO2, (c) hydrophobic SiO2, (d) hy-
(d) hydrophilic
drophilic ZrO2,2and
ZrO2-SiO -SiO(e)
2, and (e) hydrophobic
hydrophobic ZrO
ZrO2-SiO 2 -SiO2 xerogels.
2 xerogels.

3.2. Phase Structure Analysis

3.2. Phase Structure Analysis
Figure 3 shows the XRD patterns of ZrO2 , hydrophilic and hydrophobic SiO2 , and
Figure 3and
hydrophilic shows the XRD ZrO
hydrophobic patterns of ZrO2, hydrophilic and hydrophobic SiO2, and
2 -SiO2 xerogels. The tetragonal phase ZrO2 diffraction
hydrophilic
peaks at 2θ = 30.57, 35.26, 50.41, and 60.63◦ can beThe
and hydrophobic ZrO 2-SiO2 xerogels.
seentetragonal
in ZrO2 . In phase ZrO2 diffraction
the hydrophilic and
peaks at 2θ = 30.57, 35.26, 50.41, and 60.63° can be seen in ZrO
hydrophobic SiO2 , and hydrophilic and hydrophobic ZrO2 -SiO2 xerogels, the distinctive 2. In the hydrophilic and

hydrophobic
diffraction peaks SiO2,alland hydrophilic
appear between and
2θ hydrophobic ZrO2to
= 20~30◦ , related -SiO
the2 xerogels,
presence the distinctive
of amorphous
diffraction peaks all appear between 2θ = 20~30°, related to the
SiO2 . In contrast, the silicon diffraction peak of the hydrophilic and hydrophobic SiO2 presence of amorphous
SiO 2. In contrast,
xerogels appears at the2θsilicon
= 20.88diffraction
◦ , whereaspeak of the diffraction
the silicon hydrophilicpeaks and of hydrophobic
the hydrophilicSiO 2
xerogels appears at 2θ = 20.88°, whereas the silicon diffraction
◦
and hydrophobic ZrO2 -SiO2 xerogels appear at 2θ = 24.08 , mainly because the introduced peaks of the hydrophilic
and hydrophobic
zirconium ZrO2-SiOsome
atoms replaced 2 xerogels
siliconappear
atoms at and
2θ =formed
24.08°, mainly
the Zr-O-Sibecause the introduced
bonds, which lead
zirconium
to a decrease atoms replaced
in SiO 2
some
content, silicon
the atoms
crystal and formed
diffraction peaks the Zr-O-Si
move to bonds,
a larger which
angle.lead
In
to a decreaseand
hydrophilic in SiO 2 content, the
hydrophobic ZrO crystal
2 -SiO 2diffraction
xerogels, peaks
because moveof theto a larger
formation angle.
of In hy-
Zr-O-Si
drophilic
bonds, the and hydrophobic
tetragonal t-ZrOZrO 2-SiO2 xerogels, surfaces
2 crystallographic because of the formation
appear of Zr-O-Sipeaks
in the diffraction bonds,at
the 30.57◦ , 50.41
2θ =tetragonal t-ZrO◦ , 2and 60.63◦ [30]. However,
crystallographic surfaces appear in the of
the intensity diffraction peaks at
the diffraction peak2θ is
=
30.57°, 50.41°, and 60.63° [30]. However, the intensity of the diffraction
weak and the dispersion broadens, indicating that the nuclei of t-ZrO2 are produced with peak is weak and
the dispersion
relatively broadens, indicating
low crystallinity [31]. Comparingthat thebefore
nucleiand
of t-ZrO 2 are
after the produced with
modification, relatively
the structures
low
of thecrystallinity [31]. Comparing
xerogels phases were similarbefore and theand after the peaks
diffraction modification,
did not the
differstructures of the
significantly.
xerogels
Thephases
surfacewerechemicalsimilar and the diffraction
composition peaks did not
of the hydrophilic and differ significantly.
hydrophobic ZrO2 -SiO2
xerogels was analyzed by XPS as shown in Figure 4. Figure 4a shows that the Si 2p
spectra of the hydrophilic ZrO2 -SiO2 sample consist of the main component with a binding
energy of 103.69 eV due to the Si-O species on the sample surface. The Si 2p spectra of the
hydrophobic ZrO2 -SiO2 sample contain two peaks as shown in Figure 4b. It is reasonable
to assign the peak lying at the binding energy of about 103.72 eV mainly to the Si-O species,
and the peak lying at the binding energy of around 101.79 eV to the Si-CH3 . It is seen
that the chemical environment of the Si on the two sample surfaces changes significantly
with the addition of MTES during the sol preparation. Compared with the hydrophilic
Gels 2022, 8, 675 7 of 19

sample, the morphology of the Si 2p peak of hydrophobic ZrO2 -SiO2 xerogel changed
significantly, and the Si 2p spectral peak became wider and moved to the direction of low
Gels 2022, 8, x FOR PEER REVIEW 7 of 19
bond energy, which indicated that the chemical bond structure of Si 2p changed significantly
after hydrophobic modification by methyl and the bond energy of Si decreased.

Figure 3. XRD pattern of (a) ZrO2, (b) hydrophilic SiO2, (c) hydrophobic SiO2, (d) hydrophilic ZrO2-
SiO2, and (e) hydrophobic ZrO2-SiO2 xerogels.

The surface chemical composition of the hydrophilic and hydrophobic ZrO2-SiO2

xerogels was analyzed by XPS as shown in Figure 4. Figure 4a shows that the Si 2p spectra
of the hydrophilic ZrO2-SiO2 sample consist of the main component with a binding energy
of 103.69 eV due to the Si-O species on the sample surface. The Si 2p spectra of the hydro-
phobic ZrO2-SiO2 sample contain two peaks as shown in Figure 4b. It is reasonable to as-
sign the peak lying at the binding energy of about 103.72 eV mainly to the Si-O species,
and the peak lying at the binding energy of around 101.79 eV to the Si-CH3. It is seen that
the chemical environment of the Si on the two sample surfaces changes significantly with
the addition of MTES during the sol preparation. Compared with the hydrophilic sample,
the morphology of the Si 2p peak of hydrophobic ZrO2-SiO2 xerogel changed significantly,
and the Si 2p spectral peak became wider and moved to the direction of low bond energy,
which indicated
Figure3.3. XRD
that the chemical
XRD pattern of
bond structure of2, (c)
Si 2p changed significantly after hy-
Figure of (a)
(a)ZrO
ZrO2,2(b)
, (b)hydrophilic
hydrophilicSiO
SiO hydrophobic
2 , (c) SiOSiO
hydrophobic 2, (d),hydrophilic ZrO2-
2 (d) hydrophilic
drophobic modification by methyl and the
SiO2, and (e) hydrophobic ZrO2-SiO2 xerogels. bond energy of Si decreased.
ZrO2 -SiO2 , and (e) hydrophobic ZrO2 -SiO2 xerogels.

The surface chemical composition of the hydrophilic and hydrophobic ZrO2-SiO2

xerogels was analyzed by XPS as shown in Figure 4. Figure 4a shows that the Si 2p spectra
of the hydrophilic ZrO2-SiO2 sample consist of the main component with a binding energy
of 103.69 eV due to the Si-O species on the sample surface. The Si 2p spectra of the hydro-
phobic ZrO2-SiO2 sample contain two peaks as shown in Figure 4b. It is reasonable to as-
sign the peak lying at the binding energy of about 103.72 eV mainly to the Si-O species,
and the peak lying at the binding energy of around 101.79 eV to the Si-CH3. It is seen that
the chemical environment of the Si on the two sample surfaces changes significantly with
the addition of MTES during the sol preparation. Compared with the hydrophilic sample,
the morphology of the Si 2p peak of hydrophobic ZrO2-SiO2 xerogel changed significantly,
and the Si 2p spectral peak became wider and moved to the direction of low bond energy,
which indicated that the chemical bond structure of Si 2p changed significantly after hy-
drophobic modification by methyl and the bond energy of Si decreased.
Figure 4. Si 2p spectra of XPS analysis for the (a) hydrophilic and (b) hydrophobic ZrO2 -SiO2 xerogels.
Figure 4. Si 2p spectra of XPS analysis for the (a) hydrophilic and (b) hydrophobic ZrO 2-SiO2 xero-

gels.
3.3. Pore Structure Analysis
Figure 5 shows the molecular structure of ZrO2 , SiO2 , hydrophobic SiO2 , hydrophilic
ZrO2 -SiO2 , and hydrophobic ZrO2 -SiO2 . Figure 6 shows the N2 adsorption–desorption
curves of hydrophilic and hydrophobic ZrO2 -SiO2 xerogels. From Figure 6, the isotherms
of hydrophilic and hydrophobic ZrO2 -SiO2 xerogels showed the type IV isotherms of
Brunauer–Deming–Deming–Teller (BDDT) classification, which exhibited a microporous
structure at P/P0 < 0.4 and a hysteresis loop near P/P0 = 0.4, indicating the presence
of mesopores in the xerogels. It can be seen from Figure 6 that the N2 adsorption of
hydrophobic ZrO2 -SiO2 xerogel is greater than that of hydrophilic ZrO2 -SiO2 . Compared

Figure 4. Si 2p spectra of XPS analysis for the (a) hydrophilic and (b) hydrophobic ZrO2-SiO2 xero-
 ZrO2-SiO2, and hydrophobic ZrO2-SiO2. Figure 6 shows the N2 adsorption–desorption
curves of hydrophilic and hydrophobic ZrO2-SiO2 xerogels. From Figure 6, the isotherms
of hydrophilic and hydrophobic ZrO2-SiO2 xerogels showed the type IV isotherms of
Brunauer–Deming–Deming–Teller (BDDT) classification, which exhibited a microporous
Gels 2022, 8, 675 structure at P/P0 < 0.4 and a hysteresis loop near P/P 0 = 0.4, indicating the presence of
8 of 19
mesopores in the xerogel. It can be seen from Figure 6 that the N 2 adsorption of hydro-
phobic ZrO2-SiO2 xerogel is greater than that of hydrophilic ZrO2-SiO2. Compared with
hydrophilic
with ZrOZrO
hydrophilic 2-SiO2, the N2 adsorption of hydrophobic ZrO 2-SiO2 xerogel is increased
2 -SiO2 , the N2 adsorption of hydrophobic ZrO2 -SiO2 xerogel increased
by 30.96%. Figure 77shows
by 30.96%. Figure showsthe thepore
poresize
sizedistributions
distribution of of the
the hydrophilic
hydrophilic andand hydrophobic
hydrophobic
ZrO 2-SiO2 xerogels. In Figure 7, it can be seen that the pore size distribution of hydrophilic
ZrO2 -SiO2 xerogels. In Figure 7, it can be seen that the pore size distribution of hydrophilic
andhydrophobic
and hydrophobicZrO ZrO-SiO 2-SiO2 xerogels are similar, and the pore distribution ranges from
2 2 xerogels are similar, and the pore distribution ranges from the
the micropore to the mesoporous
micropore to the mesoporous region. region. In graph,
In the the graph, the total
the total porepore volume,
volume, specific
specific sur-
surface
face area,
area, and pore
and pore size sizeof the of the hydrophobic
hydrophobic ZrOZrO 2-SiO2 xerogel are greater than those of the
2 -SiO2 xerogel are greater than those of the
hydrophilic ZrO 2 -SiO 2 xerogel, mainly
hydrophilic ZrO2 -SiO2 xerogel, mainly because the because the bond
bond lengths
lengths ofofSi-CH
Si-CH33 groups
groups ininthe
the
hydrophobic ZrO -SiO xerogel are longer than those of Si-OH in
hydrophobic ZrO2 -SiO2 xerogel are longer than those of Si-OH in hydrophilic ZrO2 -SiO22
2 2 hydrophilic ZrO 2 -SiO
xerogel(Figure
xerogel (Figure5),
5),thethebondbondlengths
lengthsof ofSi-C
Si-C(1.88
(1.88Å) Å )and
andC-H
C-H(1.1
(1.1Å)
Å )are
arelonger
longerthan
thanthose
those
of Si-O (1.65 Å ) and O-H (1.01 Å ),
of Si-O (1.65 Å) and O-H (1.01 Å), respectively.respectively.

Figure 5. Molecular structural models of (a) ZrO2, (b) hydrophilic SiO2, (c) hydrophobic SiO2, (d)
Figure 5. Molecular structural models of (a) ZrO2 , (b) hydrophilic SiO2 , (c) hydrophobic SiO2 ,
hydrophilic ZrO2-SiO2, and (e) hydrophobic ZrO2-SiO2 xerogels.
(d) hydrophilic ZrO2 -SiO2 , and (e) hydrophobic ZrO2 -SiO2 xerogels.

The pore structure parameters of hydrophilic and hydrophobic ZrO2 -SiO2 xerogels
are shown in Table 1. The average pore size, BET surface area, and total pore volume of
hydrophobic ZrO2 -SiO2 xerogel are larger than those of hydrophilic ZrO2 -SiO2 xerogel.
Compared with the hydrophilic ZrO2 -SiO2 xerogel, the specific surface area and pore
capacity of the hydrophobic ZrO2 -SiO2 xerogel sample increased by 62.76% and 59.26%,
respectively. Generally speaking, the adsorption performance of an adsorbent depends
mainly on its surface properties and the BET surface area, whereas a larger BET surface
area and a suitable pore size are more favorable [27] for the adsorption of dye molecules.
The hydrophobic xerogel was more advantageous.
Gels 2022, 8, 675 9 of 19
Gels
Gels 2022,
2022, 8, 8, x FOR
x FOR PEER
PEER REVIEW
REVIEW 9 9ofof1919

Figure
Figure
Figure 6.6.6.
TheThe
NN
The N22adsorption-desorption
2 adsorption-desorption isotherms
isotherms
adsorption-desorption for
for
isotherms the
the
for (a)
(a)
the hydrophilic
hydrophilic and
and (b)
(b)
(a) hydrophilic hydrophobic
hydrophobic
and ZrO
ZrO 2- 2-
(b) hydrophobic
SiO
SiO xerogels.
ZrO2 xerogels.
2
2-SiO xerogels.
2

Figure
Figure 7. The corresponding pore size distribution curves forfor
thethe
(a)(a)
hydrophilic andand
(b) (b)
hydrophobic
Figure 7.7.
TheThe corresponding
corresponding pore
pore size
size distribution
distribution curves
curves for the hydrophilic
(a) hydrophilic and (b) hydropho-
hydropho-
ZrO
bic 2 -SiO
ZrO 2 xerogels.
-SiO xerogels.
bic ZrO2-SiO2 xerogels.
2 2

Table 1. Pore structure parameters of the hydrophilic and hydrophobic ZrO2 -SiO2 xerogels.
TheThepore
porestructure
structureparameters
parametersofofhydrophilic
hydrophilicand andhydrophobic
hydrophobicZrO ZrO 2-SiO
2-SiO 2 xerogels
2 xerogels

Samples are
are shown
shown
BET ininTable
Surface Table(m
Area 1.1.2The
·gThe ) average
−1average poresize,
pore
Average size, BETsurface
PoreBET
Size surfacearea,
(nm) area,and
Vand totalpore
total porevolume
total (STP) (cm ·g )
3 volume
−1 ofof
hydrophobicZrO
hydrophobic ZrO 2-SiO
2-SiO 2 xerogel
2 xerogel arelarger
are largerthan
thanthose
thoseofofhydrophilic
hydrophilicZrO ZrO 2-SiO
2-SiO 2 xerogel.
2 xerogel.
hydrophilic ZrO2 -SiO2 310.13 2.16 0.27
hydrophobic ZrO2 -SiO2 Comparedwith
Compared withhydrophilic
504.78 hydrophilicZrO ZrO 2-SiO
2-SiO 2 xerogel,
2 xerogel, thespecific
2.35 the specificsurface
surfaceareaareaand andpore
0.43 porecapacity
capacity
of the hydrophobic ZrO -SiO xerogel sample were increased
of the hydrophobic ZrO2-SiO2 xerogel sample were increased by 62.76% and 59.26%, re-
2 2 by 62.76% and 59.26%, re-
spectively.Generally
spectively. Generallyspeaking,speaking,the theadsorption
adsorptionperformance
performanceofofananadsorbent adsorbentdepends depends
3.4. SEM Analysis
mainlyononitsitssurface
mainly surfaceproperties,
properties,especially
especiallythe theBET
BETsurface
surfacearea,
area,whereas
whereasa alarger largerBET BET
The area
surface SEMand images of hydrophilic sizeand hydrophobic ZrO[27]
2 -SiO 2 xerogels are shown in
surface area and a asuitable
suitable poresize
pore aremore
are morefavorable
favorable [27] for
for theadsorption
the adsorption ofofdyedye
Figure 8. In
molecules.The Figure 8, it
Thehydrophobic can
hydrophobicxerogelobviously be
xerogelwas seen
wasmorethat the particle
moreadvantageous.
advantageous. size of hydrophobic ZrO 2 -SiO 2
molecules.
xerogel is larger than that of the hydrophilic sample. As described in the pore structure
analysis,
Table
Table 1.1.
thisstructure
Pore
Pore
is a result
structure of the introduction
parameters
parameters ofof
of Si-CH
thehydrophilic
the hydrophilic and
and
groups,
3 hydrophobicin which
hydrophobic ZrO
ZrO
the2 bond
2-SiO
2-SiO
lengths of
2 xerogels.
xerogels.
Si-C and C-H are longer than those of Si-O and O-H, respectively.
Samples
Samples BETSurface
BET SurfaceArea Area(m (m 2· g2·g)−1) Average
−1 AveragePore PoreSize
Size(nm)
(nm) VV (STP)(cm
(STP)
total
total (cm g3·
3· g)−1)
−1

hydrophilicZrO
hydrophilic ZrO 2-SiO
2-SiO 2 2 310.13
310.13 2.16
2.16 0.27
0.27
hydrophobicZrO
hydrophobic ZrO 2-SiO
2-SiO 2 2 504.78
504.78 2.35
2.35 0.43
0.43
 3.4. SEM Analysis
The SEM images3.4. SEM Analysis
of hydrophilic and hydrophobic ZrO2-SiO2 xerogels are shown in
Figure 8. In Figure 8, itThe
canSEMobviously
images be seen that the
of hydrophilic andparticle size ofZrO
hydrophobic hydrophobic ZrOare
2-SiO2 xerogels 2- shown in
Figure
SiO2 xerogel is larger 8. In
than Figure
that 8, it
of the can obviously
hydrophilic be seen
sample. Asthat the particle
described sizepore
in the of hydrophobic
struc- ZrO2-
SiO xerogel is larger than that of the hydrophilic sample. As
ture analysis, this is a result of the introduction of Si-CH3 groups, in which the bond
Gels 2022, 8, 675 2 described in the pore
10struc-
of 19
ture analysis, this is a result of the introduction
lengths of Si-C and C-H are longer than those of Si-O and O-H, respectively. of Si-CH 3 groups, in which the bond

lengths of Si-C and C-H are longer than those of Si-O and O-H, respectively.

Figure 8. SEM comparison of (a) hydrophilic ZrO2-SiO2, (b) hydrophobic ZrO2-SiO2 xerogels.
Figure 8. SEM comparison
Figure 8. of
SEM(a)comparison
hydrophilic ofZrO 2-SiO2, (b) hydrophobic
(a) hydrophilic ZrO2 -SiO2 , (b) ZrO 2-SiO2 xerogels.
hydrophobic ZrO2 -SiO2 xerogels.
3.5. Water Absorption Analysis
3.5. Water Absorption Analysis
3.5. Water Absorption Analysis
The water absorption of hydrophilic and hydrophobic ZrO 2-SiO2 xerogels was ana-
The water absorption of hydrophilic and hydrophobic ZrO2 -SiO2 xerogels was an-
alyzed, shown
lyzed,
The water absorption shown ininFigure
Figure9.9.As
of hydrophilic shown
and
As in Figure
hydrophobic
shown in Figure 9,ZrO
with the increase
-SiO
9, 2with 2 xerogels
the in aging
increase was time,time,
ana-
in aging the water
the
absorption
lyzed, shown in Figure 9. As of the
shown two inZrO
Figure
2 -SiO 9,
2 samples
with thegradually
increase increased.
in aging
water absorption of the two ZrO2 -SiO2 samples gradually increased. It reached its satu- It reached
time, the its
watersaturated state
afterZrO
absorption of the rated
two 6 d,2and
state afterthe
-SiO 26
saturated
samples
d, and the water
gradually
saturated absorption
increased. was
water absorptionIt about
reached 10.55%
was its and10.55%
5.33%state
saturated
about for the
and hydro-
5.33% for
philic and hydrophobic samples, respectively. Compared with the hydrophilic ZrO 2-SiO2
after 6 d, and thethe hydrophilic
saturated water and hydrophobic
absorption was samples, respectively.
about 10.55% Compared
and 5.33% with
for the the hydrophilic
hydro-
xerogel,
ZrO the water absorption of the hydrophobic sample decreased by 49.5%. The water
philic and hydrophobic 2 -SiO 2 xerogel,
samples, the water absorption
respectively. Compared of the
with hydrophobic
the hydrophilicsampleZrO decreased
2-SiO2 by 49.5%.
absorption
The of porous
water absorption materials is
of porous materialsrelated to their
is relatedhydrophobicity
to their and specific
hydrophobicity surface area.
and specific
xerogel, the water absorption
In general,
of the hydrophobic sample decreased by 49.5%. The water
surface area. more hydrophilic
In general, surfaces and
more hydrophilic larger and
surfaces specific
largersurface
specificareas correspond
surface areas cor-to
absorption of porous materials
greater water is related to
absorption. Astheir
shown hydrophobicity
in Table 1, the and specific
specific surface area.
respond to greater water absorption. As shown in Table 1, surface area surface
the specific of the hydrophobic
area of the
In general, morehydrophobic
hydrophilic
ZrO 2-SiO2 xerogelsurfaces
ZrO2 -SiOis largerandthan larger
that specific surface areas
of the hydrophilic correspond
one. This means that to the intro-
2 xerogel is larger than that of the hydrophilic one. This means
greater water absorption.
duced
that As shown
theSi-CH 3 bonds
introduced in inTable
Si-CH 1, the in
the3 bonds
hydrophobicspecific
the ZrO surface
2-SiO2 area
hydrophobic xerogel
ZrOof the
have hydrophobic
higher hydrophobicity
2 -SiO2 xerogel have higher
ZrO2-SiO2 xerogelhydrophobicity
is larger
than thanthan
the Si-OH thattheof
bonds, the
which hydrophilic
can lead to lessone.
waterThis means
absorption.
Si-OH bonds, which can lead to less water absorption. that the intro-
duced Si-CH3 bonds in the hydrophobic ZrO2-SiO2 xerogel have higher hydrophobicity
than the Si-OH bonds, which can lead to less water absorption.

Figure9.9.Water
Figure Waterabsorption
absorptiondiagram
diagramofofhydrophilic
hydrophilicZrO
ZrO 2-SiO
2 -SiO andhydrophobic
2 2and hydrophobicZrO
ZrO 2-SiO
2 -SiO xerogels.
2 2xerogels.

3.6. Adsorption Performance Studies

3.6.1. Effect of Adsorption Time and Temperature
Figure
Figure 9. Water absorption 10 shows
diagram the effect ofZrO
of hydrophilic the2-SiO
adsorption capacity of hydrophilic
2 and hydrophobic and hydrophobic
ZrO2-SiO2 xerogels.
ZrO2 -SiO2 xerogel with the change in adsorption time and adsorption temperature. As
shown in Figure 10, the hydrophobic xerogel exhibited rapid adsorption during the first
 3.6. Adsorption Performance Studies
3.6.1. Effect of Adsorption Time and Temperature
Gels 2022, 8, 675 Figure 10 shows the effect of the adsorption capacity of hydrophilic and hydrophobic 11 of 19
ZrO2-SiO2 xerogel with the change in adsorption time and adsorption temperature. As
shown in Figure 10, the hydrophobic xerogel exhibited rapid adsorption during the first
30 min, after which it was basically in adsorption equilibrium. The hydrophilic xerogel
30 min, after which it was basically in adsorption equilibrium. The hydrophilic xerogel was
was basically in adsorption equilibrium at 120 min. The adsorption amounts of hydro-
basically in adsorption equilibrium at 120 min. The adsorption amounts of hydrophilic
philic and hydrophobic xerogels increased by 10.88 mg·−g1−1 and 15.18 mg·g−−11with increas-
and hydrophobic xerogels increased by 10.88 mg·g and 15.18 mg·g with increasing
ing temperature, respectively, and reached the maximum adsorption amount at 45 °C.◦In
temperature, respectively, and reached the maximum adsorption amount at 45 C. In
addition, the adsorption capacity of the hydrophobic xerogel was increased by 70.3% rel-
addition, the adsorption capacity of the hydrophobic xerogel was increased by 70.3%
ative to thattoofthat
relative hydrophilic ZrO2-SiO
of hydrophilic xerogel.
ZrO22-SiO The results showed that the hydrophobic
2 xerogel. The results showed that the hydrophobic
xerogel had a superior adsorption effect on
xerogel had a superior adsorption effect on the the RhBRhB
solution. As seen
solution. in Figure
As seen 10, 10,
in Figure the the
adsorption
adsorptionprocess of of
process hydrophobic
hydrophobic ZrO
ZrO2-SiO2 on RhB was endothermic, and in general,
2 -SiO2 on RhB was endothermic, and in general, the
the normal
normal adsorption
adsorption process
processisisexothermic.
exothermic.However,
However,ififthe
theadsorption
adsorptionprocess
processisisinfluenced
influ-
enced by intraparticle diffusion, the adsorption capacity will increase with temperature
by intraparticle diffusion, the adsorption capacity will increase with temperature due to the
dueheat
to the heat absorption
absorption of the diffusion
of the diffusion process
process [27]. This[27].
means This
thatmeans that increasing
increasing the
the temperature
temperature increases the diffusion rate of adsorbent RhB molecules between
increases the diffusion rate of adsorbent RhB molecules between the outer boundary layer the outer
boundary
and thelayer
innerand the of
pores inner
the pores of the hydrophobic
hydrophobic ZrO2-SiO
ZrO2 -SiO2 xerogel, 2 xerogel,
thus thusthe
increasing increasing
adsorption
the capacity
adsorption capacity of hydrophobic
of hydrophobic ZrO2 -SiO2 . ZrO 2 -SiO 2 .

Figure 10. Effect

Figure of hydrophilic
10. Effect and hydrophobic
of hydrophilic ZrO2-SiO
and hydrophobic ZrO22xerogels at various
-SiO2 xerogels adsorption
at various temper-tem-
adsorption
atures (a) 25 °C,
peratures (a)(b)2535◦°C, and35
C, (b) (c)◦45
C, °C on (c)
and the45
adsorption capacity
◦ C on the of RhBcapacity
adsorption (pH = 7, of
RhB concentration
RhB (pH = 7, RhB
= 140 mg·L−1).
concentration = 140 mg·L−1 ).

As the
As thehydrophobic
hydrophobicZrOZrO
2-SiO 2 xerogel
2 -SiO contains
2 xerogel methyl
contains groups
methyl on its
groups onsurface, the the
its surface, RhBRhB
surface is also
surface richrich
is also in methyl groups
in methyl groups(Figure 1), making
(Figure the hydrophobic
1), making xerogel
the hydrophobic similarly
xerogel similarly
soluble withwith
soluble RhBRhBandand
providing
providing a better adsorption
a better adsorptioneffect. Therefore,
effect. the the
Therefore, hydrophobic
hydrophobic
ZrOZrO
2-SiO xerogel was chosen for the subsequent experiments.
2 -SiO2 xerogel was chosen for the subsequent experiments.
2

3.6.2.
3.6.2. Effect
Effect of Dosage
of Dosage
Figure
Figure 11 shows
11 shows the the adsorption
adsorption capacity
capacity for the
for the unitunit
massmass of RhB
of RhB by hydrophilic
by hydrophilic andand
hydrophobic
hydrophobic ZrO2-SiO ZrO -SiO xerogels
2 2 xerogels
2 with various dosages. It can be seen from Figure
with various dosages. It can be seen from Figure 11 that 11 that
the removal rate of both samples increased with the increase in the dosage, whereas the the
the removal rate of both samples increased with the increase in the dosage, whereas
maximum
maximum removal
removal raterate of the
of the hydrophobic
hydrophobic xerogel
xerogel waswas
23.03%23.03% higher
higher thanthan
thatthat of the
of the
hydrophilic
hydrophilic one.one. In addition,
In addition, the the adsorption
adsorption capacity
capacity for the
for the unitunit
massmass of both
of both xerogels
xerogels
reached the maximum value at the dosage of 0.01 g and decreased gradually with the the
reached the maximum value at the dosage of 0.01 g and decreased gradually with
increase
increase in dosage.
in dosage. When When the dose
the dose was increased
was increased fromg 0.01
from 0.01 g to
to 0.05 g, 0.05 g, the adsorption
the adsorption per
per unit mass decreased by 7.6 mg·g−1 and 8.3 mg·g−1 for hydrophilic and hydrophobic
xerogels, respectively. The total amount of adsorption increased with increasing dose,
whereas the adsorption per unit mass decreased gradually. The reason is that as the
amount of RhB remains unchanged, with the gradual increase in the amount of adsorbent,
the number of adsorption active sites in the system increases and the adsorption rate
accelerates, which leads to a decrease in the utilization of adsorption active sites per unit
 unit mass decreased by 7.6 mg·g−1 and 8.3 mg·g−1 for hydrophilic and hydrophobic xero-
gels, respectively. The total amount of adsorption increased with increasing dose, whereas
the adsorption per unit mass decreased gradually. The reason is that as the amount of RhB
Gels 2022, 8, 675 12 of 19
remains unchanged, with the gradual increase in the amount of adsorbent, the number of
adsorption active sites in the system increases and the adsorption rate accelerates, which
leads to a decrease in the utilization of adsorption active sites per unit mass of adsorbent,
mass of adsorbent,
resulting in a lowerresulting in aamount
adsorption lower adsorption amount
for unit mass. for unit mass.
The adsorption The adsorption
capacity for the unit
capacity for the unit mass
mass of hydrophobic ZrO2of hydrophobic
-SiO 2 xerogel wasZrO 2 -SiOthan
higher 2 xerogel
thosewas higher thanZrO
of hydrophilic those
2-SiOof2
hydrophilic ZrO -SiO xerogel because the introduced -CH group increased
xerogel because the introduced -CH3 group increased the specific surface area and the
2 2 3 the specific
surface
contact area
area and
withtheRhBcontact areaand
solution, with RhB
the solution,capacity
adsorption and the ofadsorption capacityxerogel
the hydrophobic of the
hydrophobic xerogel increased by 66.1% and 71.5% relative to the hydrophilic
increased by 66.1% and 71.5% relative to the hydrophilic at 0.01 g and 0.05 g, respectively.at 0.01 g
and 0.05 g, respectively. Therefore, the highest utilization rate was
Therefore, the highest utilization rate was achieved at the dosage of 0.05 g.achieved at the dosage
of 0.05 g.

Figure11.
11. Effect
Effect of
of hydrophilic
hydrophilicand
andhydrophobic
hydrophobicZrO 2-SiO2 xerogels on the adsorption capacity and
ZrO
Figure 2 -SiO2 xerogels on the adsorption capacity
removal rate for unit mass of RhB at various dosages (pH = 7, contact time = 120 min, RhB concen-
and removal rate for unit mass of RhB at various dosages (pH = 7, contact time = 120 min, RhB
tration = 140 mg·L−1; T = 25 °C).
concentration = 140 mg·L−1 ; T = 25 ◦ C).
3.6.3.Effect
3.6.3. Effectof ofpHpH
Inthe
In theadsorption
adsorptionexperiments,
experiments, the thesolution
solutionpH pHisisan animportant
importantfactor factorin incontrolling
controlling
the adsorption
the adsorption process
process and and may
mayhave havea agreat
greatinfluence
influence onon thethe
final adsorption
final adsorption effect, be-
effect,
cause it affects the surface charge of the adsorbent in the solution
because it affects the surface charge of the adsorbent in the solution as well as the degree ofas well as the degree of
ionization and molecular structure of the dyes [27]. The adsorption
ionization and molecular structure of the dyes [27]. The adsorption capacities of RhB for the capacities of RhB for
the hydrophilic
hydrophilic and hydrophobic
and hydrophobic ZrO22-SiO
ZrO2 -SiO 2 xerogels
xerogels at different
at different pH were pH shown
were shown in Fig-
in Figure 12.
Inure 12. In12,
Figure Figure 12, the variation
the variation of adsorption
of adsorption capacity for capacity
the two forsamples
the twoshowed
samplessimilar
showed sim-
trends.
ilar trends.
With With the
the increases increases
in pH value, in
thepH value, thecapacities
adsorption adsorption capacities
of RhB for theofhydrophilic
RhB for theand hy-
drophilic andZrO
hydrophobic hydrophobic
2 -SiO 2 ZrO
xerogels2 -SiO
tended
2 xerogels
to tended
decrease to decrease
gradually, gradually,
which had a which
maximumhad a
ofmaximum
52.42 andof169.23
52.42 and g−1 at mg·
mg·169.23 pHg=−13, at respectively.
pH = 3, respectively.
When the WhenpHthe valuepH increased
value increased
from
3from 3 to
to 11, the11, the adsorption
adsorption capacities
capacities of RhB of for
RhBthe forhydrophilic
the hydrophilic and and hydrophobic
hydrophobic sam-
samples
ples decreased
decreased by 55.5%by and
55.5% and respectively.
31.0%, 31.0%, respectively.
The effect The effect ofpH
of solution solution
on thepH zetaon the zeta
potentials
of the two of
potentials adsorbents is shown is
the two adsorbents in shown
Figurein 13.Figure
At pH 13.=At3–11,
pH =the3–11,twothe adsorbents
two adsorbents both
had
botha had
negative zeta potential
a negative and their
zeta potential absolute
and their values
absolute increased
values with with
increased the increasing
the increasingpH
value.
pH value.Furthermore,
Furthermore, the the
absolute
absolute value of of
value thethezeta
zeta potential
potentialofofthe thehydrophilic
hydrophilicsamplesample
was
wasgreater
greater than that that ofofthe
thehydrophobic
hydrophobicone oneatat thethe same
same pHpH value.
value. RhBRhB is a cationic
is a cationic basic
basic dye and its acid dissociation constant pKa is at about
dye and its acid dissociation constant pKa is at about 3.2. When pH = 3, the RhB 3.2. When pH = 3, theisRhB
pre-
issented
presented in cationic
in cationic and monomeric
and monomeric molecular
molecular form,isthere
form, there is electrostatic
electrostatic attraction attraction
existing
existing between RhB and the two adsorbents. Thus, the organic skeleton of RhB easily
can enter into the pores of the xerogels. When pH = 5–11, the RhB exists in the form of
zwitterions. At the time, they are not easy to enter into the pore structure. In the process of
adsorption of RhB by the adsorbents, the electrostatic mechanism is not only the mechanism
of dye adsorption in this system but also the interaction between the adsorbents and dye
molecules via hydrogen bonds and hydrophobic structures. The hydrophobic ZrO2 -SiO2
 between
betweenRhB RhBand
andthe
thetwo
twoadsorbents.
adsorbents.Thus,Thus,the theorganic
organicskeleton
skeletonofofRhB
RhBeasily
easilycancanenter
enter
into
intothe
thepores
poresof
ofthe
thexerogels.
xerogels.When
WhenpH pH==5–11,
5–11,thetheRhB
RhBexists
existsin
inthe
theform
formofofzwitterions.
zwitterions.
At
Atthe
thetime,
time,they
theyare
arenot
noteasy
easyto
toenter
enterinto
intothethepore
porestructure.
structure.In
Inthe
theprocess
processof
ofadsorption
adsorption
Gels 2022, 8, 675 of
ofRhB
RhBby bythe
theadsorbents,
adsorbents,thetheelectrostatic
electrostaticmechanism
mechanismisisnot notonly
onlythe
themechanism
mechanismof 13dye
of dye
of 19
adsorption
adsorptionin inthis
thissystem
systembutbutalso
alsothetheinteraction
interactionbetween
betweenthe theadsorbents
adsorbentsandanddyedyemole-
mole-
cules
culesvia
viahydrogen
hydrogenbonds
bondsandandhydrophobic
hydrophobicstructures.
structures.The Thehydrophobic
hydrophobicZrOZrO2-SiO
2-SiO2 2xero-
xero-
gel
gelhas
has the
thehydrophobic
hydrophobic Si-CH
Si-CH 3 3groups,
groups, whereas
whereas the
the hydrophilic
hydrophilic sample
sample
xerogel has the hydrophobic Si-CH3 groups, whereas the hydrophilic sample does not. This does
does not.
not. This
This
further
further increases the adsorption capacity of hydrophobic xerogel to RhB. Furthermore,the
further increases
increases the
theadsorption
adsorption capacity
capacity of
ofhydrophobic
hydrophobic xerogel
xerogel to
toRhB.
RhB.Furthermore,
Furthermore, the
the
results
results indicate
indicate that
that the
theacidic
acidicenvironment
environment is
is favorable
favorable for
forthe
theadsorption
adsorption
results indicate that the acidic environment is favorable for the adsorption of RhB by the of
ofRhB
RhB byby the
the
hydrophilic
hydrophilicand
hydrophilic andhydrophobic
and hydrophobicZrO
hydrophobic ZrO22-SiO
ZrO -SiO222xerogels.
2-SiO xerogels.
xerogels.

Figure
Figure12.
12.Adsorption
Adsorptioncapacities
Adsorption capacitiesof
capacities ofRhB
of RhBfor
RhB forthe
for thehydrophilic
the hydrophilicand
hydrophilic andhydrophobic
and hydrophobicZrO
hydrophobic ZrO2-SiO
ZrO 2-SiO 2 2xerogels
xerogelsatat
Figure 12. 2 -SiO2 xerogels at
different
differentpH
different pH(dosage
pH (dosage===0.05
(dosage 0.05g,g,
0.05 g,contact
contacttime
contact time==
time =120
120min,
120 min,RhB
min, RhBconcentration
RhB concentration==
concentration =140
140mg·
140 mgL·L
mg· , ,T
−1−1
L− , =T=25
1T °C).
=2525
°C).
◦ C).

Figure
Figure13.
Figure 13.Effect
13. Effectof
Effect ofsolution
of solutionpH
solution pHon
pH onthe
on thezeta
the zetapotentials
zeta potentialsof
potentials hydrophilic
ofhydrophilic
of and
hydrophilicand hydrophobic
andhydrophobic ZrO
ZrO22-SiO
hydrophobicZrO -SiO222
2-SiO

xerogels.
xerogels.
xerogels.

3.7.
3.7. AdsorptionKinetic
3.7.Adsorption KineticAnalysis
Analysis
The adsorption
The adsorption kineticanalysis
adsorptionkinetic analysisprocess
processisisdesigned
designedto to investigate
investigate
investigatethe the kinetics
kineticsand
and
mechanism of adsorption
mechanism of adsorption of
adsorption of RhB
of RhB by
RhB by hydrophobic
by hydrophobic ZrO
hydrophobic ZrO -SiO
ZrO22-SiO
2-SiO xerogel, and it includes
222 xerogel, and it includes
includes
pseudo–first-order
pseudo–first-orderdynamics,
pseudo–first-order dynamics,pseudo–second-order
dynamics, pseudo–second-order
pseudo–second-order dynamics,
dynamics,
dynamics, andandintra-particle
and intra-particlediffusion
intra-particle diffu-
diffu-
models.
sion The The
sionmodels.
models. experimental datadata
Theexperimental
experimental werewere
data fitted
were by aby
fitted
fitted kinetic
by sorption
aakinetic
kinetic sorptionmodel
sorption [32,33],
model
model which
[32,33],
[32,33], was
which
which
calculated and fitted using Equations (14) and (15). The fitting results are shown in Table 2
and Figure 14a–c.
Gels 2022, 8, x FOR PEER REVIEW 14 of 19

Gels 2022, 8, 675 was calculated and fitted using Equations (14) and (15). The fitting results are shown
14 of in
19
Table 2 and Figure 14a–c.

Table 2. Adsorption kinetic parameters of RhB on hydrophobic ZrO2-SiO2 xerogel at various tem-
Table 2. Adsorption kinetic parameters of RhB on hydrophobic ZrO2 -SiO2 xerogel at various temper-
peratures.
atures.
Temperature (K)
Kinetic Model Kinetic Parameters
Kinetic Model Kinetic Parameters 298.15 Temperature308.15
(K) 318.15
qe 298.15 169.23 308.15 170.05 318.15
178.98
qe K1 169.23 0.0068 170.05 0.0058 0.0075
178.98
Pseudo–first-order
K1 R2 0.0068 0.9112 0.0058 0.9886 0.0075
0.9768
Pseudo–first-order
R2 K2 0.9112 0.0083 0.9886 0.0063 0.9768
0.0071
Pseudo–second-order K2 0.0083 0.0063 0.0071
Pseudo–second-order R2 0.9805 0.9832 0.9961
R2 0.9805 0.9832 0.9961
Kdi Kdi 2.1038 2.1038 2.9532 2.9532 3.8449
3.8449
intra-particle
intra-particle diffusion
diffusion
R2 R2 0.9015 0.9015 0.9594 0.9594 0.9483
0.9483

Figure Adsorptionkinetics
14. Adsorption
Figure 14. kineticsofofRhB
RhB adsorbed
adsorbed byby hydrophobic
hydrophobic ZrO ZrO 2 -SiO
2-SiO 2 xerogel:
2 xerogel: (a) pseudo–
(a) pseudo–first-
first-order
order kinetickinetic
plots,plots, (b) pseudo–second-order
(b) pseudo–second-order kinetic
kinetic plots,plots, and
and (c) (c) intra-particle
intra-particle diffusion
diffusion plots plots
(dos-
age = 0.05
(dosage g, pH
= 0.05 g, =pH
3, =
RhB concentration
3, RhB = 140
concentration mg·mg
= 140 L−1,·L −1 , contact
contact time time
= 120=min, T = 298.15,
120 min, 308.15,
T = 298.15, and
308.15,
318.15
and K). K).
318.15

The calculation of the pseudo–first-order

pseudo–first-order dynamics
dynamics is
is given
given in
in equation:
equation:
ln(𝑞
lne(q−e 𝑞−t )q=
t ) ln
= 𝑞lne −
qe 𝐾
−1 𝑡K1 t (14)
(14)
The calculation of the pseudo–second-order dynamics is given in equation:
The calculation of the pseudo–second-order dynamics is given in equation:
𝑡 1 𝑡
= + (15)
𝑞tt 𝐾2 𝑞e21 𝑞e t
= + (15)
qt
The adsorption rate is usually controlledK2 q2eby membrane
qe diffusion, intra-particle dif-
fusion, or both of them. The first–second-order and pseudo–second-order kinetic models
The adsorption rate is usually controlled by membrane diffusion, intra-particle dif-
cannot determine the role of intra-particle diffusion in the adsorption dynamics process.
fusion, or both of them. The first–second-order and pseudo–second-order kinetic models
In order to identify whether the intra-particle diffusion is a rate-limiting step in the ad-
cannot determine the role of intra-particle diffusion in the adsorption dynamics process. In
sorption kinetics process or not, the experimental data is further fitted by the intra-particle
order to identify whether the intra-particle diffusion is a rate-limiting step in the adsorption
diffusion model [34], and the calculation formula is shown in (16):
kinetics process or not, the experimental data is further fitted by the intra-particle diffusion
model [34], and the calculation formula 𝑡 0.5 + 𝐶in (16):
𝑞t = 𝐾isdishown (16)
where t (min) is the adsorption time. qt q=e and qt +
Kdi t0.5 (mg·
C g ) are the adsorption capacities
−1 at
(16)
equilibrium and at time t, respectively. K1 (min−1) and K2 (g·mg−1·min −1) are the pseudo–
first-order
where t (min) and is pseudo–second-order
the adsorption time.adsorptionqe and qt (mg −1 ) are the
rate·gconstants (min −1), respectively.
adsorption capacitiesKdi
− 1 −1 · min −1 ) are
at equilibrium
(mg· g ·min ) is and time t, respectively.
theatintra-particle diffusionKrate1 (min
constant. 2 (g · mg the
) andCKrepresents greater the
effect
−1 −0.5

pseudo–first-order
of the boundary layer molecule diffusion. adsorption rate constants (min−1 ), respec-
andonpseudo–second-order
tively. Kdihigh − 1
·g ·min
(mgvalues − 0.5 C represents
The of R2 in) Table
is the 2intra-particle
indicate that diffusion rate constant.
the adsorption of RhB onto hydrophobic the
greater
ZrO2-SiO effect of thecan
2 xerogel boundary layer on molecule
be approximated diffusion. by a pseudo–second-order
more appropriately
The high values of R2 in Table 2 indicate that the adsorption of RhB onto hydrophobic
ZrO2 -SiO2 xerogel can be approximated more appropriately by a pseudo–second-order
kinetic model. According to the pseudo–second-order model, the boundary layer resis-
tance is not a rate-limiting step [35]. Moreover, the investigation of diffusion mechanism
Gels 2022, 8, x FOR PEER REVIEW 15 of 19

Gels 2022, 8, 675 15 of 19

kinetic model. According to the pseudo–second-order model, the boundary layer re-
sistance is not a rate-limiting step [35]. Moreover, the investigation of diffusion mecha-
nismthe
with with the intra-particle
intra-particle diffusion
diffusion model model is important.
is important. The The linear
linear fitting
fitting result
result is shown
is shown in
in Figure 14c. The linearity is attributed to the mesopores diffusion, which
Figure 14c. The linearity is attributed to the mesopores diffusion, which is an accessible is an accessible
siteof
site ofadsorption.
adsorption. TheThe fitted
fitted lines
lines did
did notnotpass
passthrough
throughthe theorigin;
origin;hence,
hence,thetheadsorption
adsorption
rateisisaffected
rate affectedbybyboth
bothintra-particle
intra-particlediffusion
diffusionandandfilm
filmdiffusion.
diffusion.In Inshort,
short,the
theadsorption
adsorption
of RhB
of RhB onto hydrophobic
hydrophobic ZrO ZrO22-SiO
-SiO2 2xerogel
xerogelisis
a complex
a complex process.
process.TheTherelated
relatedplots in Fig-
plots in
ure 14a–c
Figure indicate
14a–c thatthat
indicate thethe
RhBRhB adsorption
adsorption reaction proceeds
reaction through
proceeds throughthree steps:
three the first
steps: the
stagestage
first is the
is rapid adsorption
the rapid phase
adsorption of the
phase ofouter surface
the outer (film (film
surface diffusion), the second
diffusion), stage
the second
is theisslow
stage adsorption
the slow stage stage
adsorption (pore (pore
or intra-particle diffusion),
or intra-particle and the
diffusion), andthird stage stage
the third is the
isadsorption equilibrium
the adsorption stage which
equilibrium meansmeans
stage which the adsorption reactionreaction
the adsorption is no longer carried
is no longer
carried
out. out.

3.8.
3.8. Adsorption
AdsorptionIsotherm
IsothermAnalysis
Analysis
In order to understand
In order to understand the theinteractions
interactions of of
RhBRhB with
with the the hydrophobic
hydrophobic ZrO2ZrO
-SiO22-SiO
xero-
2
xerogel,
gel, the the Langmuir
Langmuir [36],[36], Freundlich
Freundlich [37][37]
andand Dubinin–Radushkevih
Dubinin–Radushkevih (D–R)
(D–R) models
models [38][38]
are
are
usedused at 298.15,
at 298.15, 308.15
308.15 andand 318.15
318.15 K,K,respectively.
respectively.To
Todescribe
describe the
the adsorption
adsorption behavior
behavior ofof
RhB onto the hydrophobic ZrO -SiO xerogel
RhB onto the hydrophobic ZrO2-SiO2 xerogel as follow:
2 2 as follow:
The
Thecalculation
calculationofofthe
theLangmuir
Langmuirmodel modelisisgiven
givenininEquation
Equation(17):
(17):
111 1 1
== + + 1 (17)
(17)
𝑞e
𝑞m 𝑏𝐶e 𝑞m
qe qm bCe qm
where b (L·mg−1) is the Langmuir constant. qm is the maximum monolayer adsorption ca-
(L·mg −1 ) is the Langmuir constant. q is the maximum monolayer adsorption
pacity b(mg·
where g−1), the Langmuir isotherm plots of m 1/qe versus 1/Ce are given in Figure 15a,
capacity −
·g 1 ), the
and the (mg
parameters Langmuir
are exhibitedisotherm
in Tableplots
3. of 1/qe versus 1/Ce are given in Figure 15a,
and the parameters are exhibited in Table 3.

Figure
Figure15.15.(a)
(a)Langmuir,
Langmuir,(b)(b)Freundlich
Freundlichand,
and,(c)(c)D–R
D–Radsorption
adsorptionisotherm
isothermofofRhB RhBonto
ontohydrophobic
hydrophobic
ZrO
ZrO22-SiO
-SiO22 xerogel
xerogel(dosage
(dosage==0.05
0.05g,g,pH
pH==3,3,RhB
RhBconcentration
concentration==140
140mg ·LL−−11 , contact
mg· contact time
time == 120
120 min,
min,
TT==298.15,
298.15,308.15
308.15and
and318.15
318.15K).
K).

Table3.3. Adsorption
Table isothermparameters
Adsorption isotherm parametersofofRhB
RhBonon hydrophobic
hydrophobic ZrO
ZrO 2 -SiO
2-SiO 2 xerogel
2 xerogel
at various
at various tem-
temperatures.
peratures.

Temperature
Temperature (K) (K)
Adsorption
Adsorption Isotherm Isothermal
Isotherm Isothermal Parameters
Parameters
298.15 298.15 308.15 308.15 318.15
318.15
b b 0.0031 0.0031 0.0039 0.0039 0.0042
0.0042
qm qm 139.77 139.77 154.64 154.64 173.53
173.53
Langmuir
Langmuir
R2 R2 0.9924 0.9924 0.9939 0.9939 0.9961
0.9961
RL RL 0.1231 0.1231 0.1191 0.1191 0.1123
0.1123
KF 18.1367 8.6576 8.3704
KF 18.1367 8.6576 8.3704
Freundlich 1/n 0.5138 0.7471 0.7789
Freundlich R2 1/n 0.8826 0.5138 0.9647 0.7471 0.7789
0.9631
E R2 4.0285 0.8826 4.1893 0.9647 0.9631
4.7584
D–R
D–R R2 E 0.9302 4.0285 0.9951 4.1893 0.8438
4.7584
Gels 2022, 8, 675 16 of 19

Dimensionless constant (RL ) [39] was used to identify the feasibility and favorability
of the adsorption process. RL is calculated in each case using the Equation (18):

1
RL = (18)
1 + bC0

The values of RL reveal that the isotherms are irreversible (RL = 0), unfavorable
(RL > 1), favorable (0 < RL < 1), or linear (RL = 1) [40].
The calculation of the Freundlich isotherm model is given in Equation (19):

1
ln qe = ln KF + ln Ce (19)
n

where KF (L·g−1 ) and n are the Freundlich constant related to adsorption capacity and
adsorption intensity, respectively. The Freundlich isotherm plots of lnqe versus lnCe are
shown in Figure 15b and the parameters are exhibited in Table 3.
In order to determine the type of adsorption reaction, the calculation of the Dubinin–
Radushkevich (D–R) isotherm model (Figure 15c) is given in Equations (20)–(22):

ln qe = ln qD − B·ε2 (20)

1
ε = RT ln (1 + ) (21)
Ce
1
E= √ (22)
2B
where qD is the theoretical saturation capacity, mg·g−1 . B is the adsorption energy con-
stant, mol2 ·J−2 . ε is the Polanyi potential energy, J·mol−1 . R is the ideal gas constant,
8.314 J·mol−1 ·K−1 . T is the thermodynamic temperature, K. E is the average adsorption
energy, kJ·mol−1 .
From Figure 15 and Table 3, it is seen that the Langmuir isotherm model is more
suitable for the RhB adsorption onto hydrophobic ZrO2 -SiO2 xerogel with R2 values greater
than 0.99 for both and that the adsorption process may be monolayer adsorption. Maximum
adsorption capacity increased with an increase in the temperature from 139.77 mg·g−1
to 173.53 mg·g−1 , revealing the endothermic nature of the adsorption process. As can be
seen in Table 3, for the dimensionless constants, RL values (0.1123~0.1231) are all less than
1, which indicates that RhB adsorption of hydrophobic ZrO2 -SiO2 xerogel is favorable.
In addition, the adsorption constant 0 < (1/n) < 1 of the Freundlich model indicates that
the hydrophobic ZrO2 -SiO2 xerogel has inhomogeneous surface properties and RhB is
easily adsorbed on the surface of the hydrophobic ZrO2 -SiO2 xerogel. With the increase
in adsorption temperature, the adsorption energy (E) increases. It is indicated that the
adsorption of RhB onto hydrophobic ZrO2 -SiO2 xerogel is an endothermic behavior. As
can be seen from Table 3, the calculated E values are found to be less than 8 kJ·mol−1 ,
indicating that the adsorption process is mainly physical adsorption [41]. The results of
this experiment also confirm the better prospect of hydrophobic ZrO2 -SiO2 composites for
the removal of dye wastewater.
Table 4 shows the comparison of Langmuir parameters for different adsorbents from
different researchers. From Table 4, it can be seen that the R2 of these adsorbent materials is
close to 1, which indicates that the adsorption is relatively good. The RL values are also
all less than 1, which indicates that the adsorption is irreversible. The data show that the
maximum adsorption capacity of the hydrophilic adsorbent in the fourth cited paper is
177.7 mg·g−1 , however, its equilibrium adsorption capacity is only about 120 mg·g−1 and
the preparation method is different, and the equilibrium adsorption capacity in this paper
is as high as 169.23 mg·g−1 . This means that the maximum adsorption capacity of the
hydrophobic SiO2 -ZrO2 xerogel prepared in this paper is higher than the average value of
 Gels 2022, 8, 675 17 of 19

Gels 2022, 8, x FOR PEER REVIEW 17 of 19

most adsorbents. Therefore, it indicates that the hydrophobically modified adsorbent in

this paper is successful.
Table 4. Langmuir parameters of materials for RhB adsorption from various researchers.
Table 4. Langmuir parameters of materials for RhB adsorption from various researchers.
Material Type R2 qm RL
Montmorillonite
Material Type [42] 0.9864
R 2 q42.19
m 0.309
RL
Kaolinite [14][42]
Montmorillonite 0.98
0.9864 46.08
42.19 0.94
0.309
Carbon xerogel
Kaolinite [14] [43] 0.9976
0.98 147.1
46.08 0.058
0.94
Hydrophilic
CarbonZrO 2-SiO2[43]
xerogel xerogel [24] 0.998
0.9976 177.7
147.1 0.843
0.058
Hydrophilic
Hydrophobic ZrO ZrO 2 -SiO
2-SiO 2 xerogel
2 xerogel
[24]work)
(this 0.998
0.9961 177.7
173.53 0.843
0.1123
Hydrophobic ZrO2 -SiO2 xerogel (this work) 0.9961 173.53 0.1123

4. Reusability of Xerogel Adsorbent

4. Reusability of Xerogel Adsorbent
In addition to the high adsorption capacity, the regeneration and recycling properties
In addition to the high adsorption capacity, the regeneration and recycling properties of
of the xerogel are important for a potential application. Figure 16 shows the recycling per-
the xerogel are important for a potential application. Figure 16 shows the recycling perfor-
formance of hydrophobic ZrO2-SiO2 xerogel at different recycling times. As shown in Fig-
mance of hydrophobic ZrO -SiO xerogel at different recycling times. As shown in Figure 16,
ure 16, the xerogel samples2 were2 easily separated from the RhB solution with ethanol.
the xerogel samples were easily separated from the RhB solution with ethanol. After ad-
After adsorption, the xerogel was washed with ethanol at room temperature and reused
sorption, the xerogel was washed with ethanol at room temperature and reused to adsorb
to adsorb RhB again. This regeneration procedure was repeated five times, and the ad-
RhB again. This regeneration procedure was repeated five times, and the adsorption capac-
sorption capacity of the hydrophobic ZrO2-SiO2 xerogel decreased from −1 169.23 mg·g−1 to
ity of the hydrophobic ZrO 2 -SiO2 xerogel decreased from 169.23 mg ·g to 115.74 mg·g−1 ,
115.74 mg·g−1, and the adsorption capacity decreased by 31.6%. The results show that the
and the adsorption capacity decreased by 31.6%. The results show that the hydrophobic
hydrophobic ZrO2-SiO2 xerogel has good reusability for the adsorption of RhB and can be
ZrO2 -SiO2 xerogel has good reusability for the adsorption of RhB and can be used repeatedly
used repeatedly many times.
many times.

Figure
Figure16.
16.Recycling
Recyclingperformance
performanceofofhydrophobic
hydrophobicZrO
ZrO2-SiO 2 xerogel
2 -SiO at at
2 xerogel different recycling
different times.
recycling times.

5.5.Conclusions
Conclusions
InInthis
this paper,
paper, thethe hydrophilic
hydrophilic andand hydrophobic
hydrophobic ZrOZrO 2 -SiO
2-SiO 2 xerogels
2 xerogels werewere prepared
prepared by
by the sol–gel method. The results showed that the hydrophobic
the sol–gel method. The results showed that the hydrophobic Si-CH3 groups Si-CH groups were
3 were intro-
introduced
duced by MTES by modification.
MTES modification.There areThere are Zr-O-Si,
Si-O-Si, Si-O-Si, Zr-O-Si,
Si-OH, Si-CHSi-OH, Si-CH , Zr-OH,
3, Zr-OH, 3and Zr-

O groups on the surfaces of hydrophobic ZrO2-SiO2 xerogel. The hydrophobichydrophobic

and Zr-O groups on the surfaces of hydrophobic ZrO 2 -SiO 2 xerogel. The ZrO2-SiO2
ZrO2 -SiO
xerogel has2 axerogel
larger has a larger
specific specific
surface area,surface
mean area,
pore meanand
size, porepore
size,volume.
and poreA volume.
high ad-A
high adsorption capacity of 169.23 mg · g −1 for the hydrophobic ZrO -SiO xerogel was
sorption capacity◦ of 169.23 mg·g−1 for the hydrophobic ZrO2-SiO2 xerogel 2 was2 achieved at

25achieved
°C and pH at 25= 3.CThe
andadsorption
pH = 3. Thedata
adsorption data fit
fit well with thewell with the pseudo–second-order
pseudo–second-order dynamics
dynamics model and the isothermal adsorption curve fitting showed that the adsorption
model and the isothermal adsorption curve fitting showed that the adsorption process of
process of hydrophobic ZrO -SiO2 on RhB was both monolayer adsorption and non-
hydrophobic ZrO2-SiO2 on RhB2was both monolayer adsorption and non-uniform adsorp-
uniform adsorption, and the isothermal adsorption model at different temperatures was
tion, and the isothermal adsorption model at different temperatures was consistent with
consistent with the Langmuir isotherm model. The results from the D–R model indicate
the Langmuir isotherm model. The results from the D–R model indicate the adsorption of
RhB by hydrophobic ZrO2-SiO2 xerogel is mainly physical adsorption, accompanied by a
Gels 2022, 8, 675 18 of 19

the adsorption of RhB by hydrophobic ZrO2 -SiO2 xerogel is mainly physical adsorption,
accompanied by a spontaneous endothermic process. In future work, we will further
investigate the adsorption performance of the hydrophobic ZrO2 -SiO2 xerogel to other
dyes and mixed dyes, comparing the similarities and differences in the adsorption of
single-component and multi-component dye molecules.

Author Contributions: Conceptualization, Y.L. and J.Y.; writing—original draft preparation, Y.L.
and J.Y.; funding acquisition, J.Y. All authors have read and agreed to the published version of
the manuscript.
Funding: This research was funded by the Scientific Research Project of Shaanxi province, China
[2022SF-287 and 2021GY-147].
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

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