materials

Review
Carbon Gels-Modified TiO2: Promising Materials for
Photocatalysis Applications
Dongge Ma 1, * , Jundan Li 1 , Anan Liu 2 and Chuncheng Chen 3
1 School of Science, Beijing Technology and Business University, Beijing 100048, China;
1930102009@st.btbu.edu.cn
2 Basic Experimental Center for Natural Science, University of Science and Technology Beijing, Beijing 100083,
China; liuanan@ustb.edu.cn
3 Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences,
Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China; ccchen@iccas.ac.cn
* Correspondence: madongge@btbu.edu.cn; Tel.: +86-010-68985573




Received: 25 March 2020; Accepted: 2 April 2020; Published: 8 April 2020


Abstract: Carbon gels are a kind of porous organic polymer, which play pivotal roles in electrode,
supercapacitor, hydrogen storage, and catalysis. Carbon gels are commonly prepared by the condensation
of resorcinol and formaldehyde. The as-prepared polymers are further aged and sintered at a high
temperature in an inert atmosphere to form cross-linked and intertwined porous structures. Owing
to its large specific area and narrow pore size distribution, this kind of material is very appropriate for
mass transfer, substrate absorption, and product desorption from the pores. In recent years, carbon
gels have been discovered to function as effective hybrid materials with TiO2 for photocatalytic
applications. They could act as efficient deep-traps for photo-induced holes, which decreases the
recombination probability of photo-induced carriers and lengthens their lifetime. In this mini-review,
we will discuss the state-of-the-art paragon examples of carbon gels/TiO2 composite materials applied
in photo(electro)catalysis. The major challenges and gaps of its application in this field will also
be emphasized.

Keywords: carbon gels; photocatalysis; photo-induced carrier separation; pollutants degradation

1. Introduction
Nowadays, environmental pollution and energy shortage are two main crises facing the whole
world. The excessive utilization of fossil fuels produces various pollutants, which was discharged
into water and air environments. There is an urgent need for the use of green and renewable energy
resources for human society. Sunlight, considered as an inexhaustible and environmentally friendly
energy source, has aroused the attention from both academics and industries. As Fujishima and
Honda first reported TiO2 could be used to catalyze the water-splitting process evolving hydrogen and
oxygen under sunlight illumination in 1972 [1], and Carey et al. initially used TiO2 photocatalysis as an
advanced oxidation technique for the removal of pollutants in aqueous solution [2,3], photocatalysis has
been developed rapidly and becomes the focus of various disciplines including catalysis [4–7], materials
chemistry [8–10], environmental chemistry [11], energy chemistry [12,13], surface chemistry [14–16],
and processing chemistry and chemical engineering [17,18]. Among various photocatalysts, TiO2 being
extremely stable under light irradiation, highly acidic, and basic conditions; non-toxic, earth-abundant,
and easily-recyclable; and reusable without much loss of activity, has been profoundly investigated
from the 1970s up till now [19–27]. Moreover, with the high photo-induced hole oxidation potential
(Evb + = 2.7 V vs. NHE (Normal Hydrogen Electrode) at pH = 7); the ability to produce similarly highly
oxidative OH• radicals (E = 2.8 V vs. NHE), H2 O2 , and HOO•; and the appropriate photo-induced

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Materials 2020, 13, 1734 2 of 15

conduction band electron reduction potential (E = −0.5 V vs. NHE at pH = 7), which could be easily
trapped by dioxygen generating superoxide radical anion, all of these reactive oxygen species, along
with the photo-induced holes on TiO2 surface, could almost decompose all the organic pollutants
by unselective thorough mineralization with sequential hydrogen abstraction; halogen abstraction;
and addition to R•, C=C, and C≡C bonds until all the organic pollutants finally transform to CO2 ,
H2 O, and inorganic ion species [7,11,28]. Although TiO2 photocatalysis has garnered a plethora
of successful examples in water environment remediation applications [29–33], there are still gaps
and shortcomings that need to be overcome for TiO2 photocatalysis to be applied in real industrial
processes. The following main issues need to be addressed. Firstly, owing to the wide band gap
(Eg = 3.2 eV for anatase and 3.0 eV for rutile), TiO2 -based nanomaterial could only be excited under UV
(ultra-violet) irradiation (λ < 387.5 nm). This means that only less than 5% of the solar spectrum energy
could be utilized by TiO2 photocatalysis. Approximately 95% of the solar energy is wasted as heat.
Furthermore, current TiO2 photocatalysis displays a low quantum yield, even in UV spectrum. Poor
photon energy to chemical energy efficiency is obtained for the existing TiO2 system. The quantum
yield is in the range below 20%. The poor photocatalysis performance of TiO2 is attributed to the
following factors: (1) poor visible-light absorption, (2) facile hole-electron recombination, and (3) poor
adsorption and catalytic activity towards non-polar and hydrophobic compounds. To overcome these
obstacles, various strategies have been developed. Metal and non-metal atoms [34] doping such as
Fe [35], Cu [36], Ni [37] and N [38–40], C [41], and S [42], which could introduce extra traps below
the bottom of the conduction band and the top of the valence band, were incorporated in lowering
the band gap to facilitate visible-light absorption ability [43]. However, the addition of these dopant
atoms could in another way decrease its photocatalytic efficiency, as the trapping sites would also be
the recombination sites for electrons and holes. Coupling other photocatalysts with TiO2 to construct
heterojunction structure is another approach to improve TiO2 photocatalysis performance. A number
of inorganic and organic semiconductor photocatalysts, including CdS [44], BiVO4 [45], AgBr [46],
RGO [47], and g-C3 N4 [48], have been combined with TiO2 to generate a hybrid photocatalyst system,
which displays excellent performance for various photocatalytic applications including water-splitting,
CO2 reduction, water and air decontamination, and organic synthesis [49–52].
Carbon gels, as a kind of aerogels, were discovered as early as 1931 by Kistler [53]. The author
successfully prepared the gels using the supercritical liquid evaporation method, which guaranteed that
the jelly internal structure did not experience either change or shrinkage. This is a milestone discovery
for colloid chemistry. However, the synthesis and preparation of carbon gels was not rediscovered
and researched until more than half a century later. Pekala and co-workers innovatively developed
the four-step procedure to synthesize resorcinol–formaldehyde (RF) gels as shown in Figure 1 [54].
Firstly, resorcinol and formaldehyde were polycondensed in an alkaline solution. Then, the as-formed
RF mixtures were subjected to aging conditions at 85 ◦ C for several days. Later, the acid-treatment
and solvent-exchange processes were required before the key critical-point drying procedure. Finally,
CO2 was introduced to flow in and replace the residue solvent molecules at 45 ◦ C. The dried RF
gels were characterized by various techniques to prove the existence of the organic aerogel structure.
This example resembles the renaissance of organic carbon gels [55–59]. Nowadays, carbon gels have
been extensively investigated and applied in hydrogen and methane storage [60–69], electric energy
storage [70–73], thermal transport [74,75], and catalysis [76–78]. Carbon gels have been demonstrated as
ideal materials for these applications owing to their large specific surface area, high electric conductivity,
and porous structure [79,80]. These features would also be critical merits for catalyst and co-catalyst
materials for photocatalysis applications [81,82]. Carbon gels have been successfully incorporated
into TiO2 photocatalysis to improve the overall performance for photocatalytic water-splitting and
environment remediation [83]. This review will discuss the state-of-the-art paragon examples of carbon
gels-modified TiO2 -nanomaterials including the preparation, characterization, and activity of these
composite photocatalysts. Furthermore, the gaps and challenges of this area will also be outlined.
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Figure
Figure 1. Aschematic
1. A schematic diagram
diagram of theof the reaction
reaction of and
of resorcinol resorcinol and formaldehyde
formaldehyde to
to synthesize carbon
synthesize carbon
aerogel. Copied aerogel.
with Copied
permission fromwith permission1989
[54], Copyrights from [54], Copyrights
Springer [54]. 1989 Springer
[54].
2. Carbon Gels-Modified TiO2 Photocatalysis
2. Carbon Gels-Modified
Owing to their largeTiO2 Photocatalysis
specific surface area, ordered porous structure, and high electric conductivity,
carbon
Owing gelstohave
theirbeen applied
large specific in various
surface fields
area, including
ordered porous hydrogen storage, and
structure, electrode
high materials,
electric
and heterogeneous catalyst support. Although carbon gels are often
conductivity, carbon gels have been applied in various fields including hydrogen storage, electrode used as conductive materials,
they alsoand
materials, can heterogeneous
be used to constructcatalyst a composite semiconductor
support. Although carbon photocatalyst
gels are often with
usedTiOas
2 . conductive

materials, they also can be used to construct a composite semiconductor photocatalyst with TiO2. to
In 2010, Zhao and co-workers firstly used carbon gels to modify the TiO 2 photocatalyst
improve
In 2010,its adsorption
Zhao and and conductivity
co-workers firstlyperformance
used carbon [84]. They
gels preparedthe
to modify a TiOTiO2 /carbon aerogel (CA)
2 photocatalyst to
photoelectrode
improve material.
its adsorption andThe CA was synthesized
conductivity performance by the base-catalyzed
[84]. They prepared polycondensation
a TiO2/carbon aerogelbetween
resorcinol and formaldehyde. The as-synthesized wet gels were
(CA) photoelectrode material. The CA was synthesized by the base-catalyzed polycondensationinitially solvent-exchanged by acetone
between resorcinol and formaldehyde. The as-synthesized wet gels were initiallyat
to replace water. The organic gel was transformed to CA by heating in an argon atmosphere
950 ◦ C. The CA material
solvent-exchanged by acetonewastoimmersed
replace water. into theThesol–gel
organic process
gel was of transformed
TiO2 formation. to CA Thebyas-formed
heating
mixed TiO /CA was sintered at different high temperatures to yield
in an argon 2atmosphere at 950 °C. The CA material was immersed into the sol–gel process of the final photoelectrode material.
TiO2
Various characterization
formation. The as-formed techniques
mixed TiO2such /CA wasas scanning
sinteredelectronic
at differentmicroscopy (SEM), X-ray
high temperatures diffraction
to yield the
(XRD), Raman spectrometry, and N isothermal adsorption and desorption
final photoelectrode material. Various characterization techniques such as scanning electronic
2 experiments were applied
to determine
microscopy the X-ray
(SEM), morphology (as shown
diffraction (XRD), in Figure
Raman 2), crystal structure,
spectrometry, and porosity
and N2 isothermal property.
adsorption
and TiO2 /CA photoelectrode
Thedesorption experiments were possesses
applied bothtoexcellent
determine photocatalytic
the morphology properties owingintoFigure
(as shown the anatase
2),
TiO semiconductor photoresponsive component and outstanding
crystal2 structure, and porosity property. The TiO2/CA photoelectrode possesses both excellent electrochemical properties of CA
material, suchproperties
photocatalytic as its extremely
owinghigh to the conductivity,
anatase TiO low electrochemical impedance, and large specific
2 semiconductor photoresponsive component
surface
and area. Thus,
outstanding the TiO2 /CAproperties
electrochemical photoelectrode of CAdemonstrated
material, such much
as itshigher photocurrent
extremely density and
high conductivity,
degradation efficiency for highly opaque methylene blue wastewater
low electrochemical impedance, and large specific surface area. Thus, the TiO2/CA photoelectrode under a −0.6 V potential bias
and 365 nm light
demonstrated much irradiation compared with
higher photocurrent the TiO
density 2 /ITO
and photoelectrode.
degradation The authors
efficiency for highlyattributed
opaque the
high efficiency to the following factors. Firstly, applying −0.6 V bias
methylene blue wastewater under a −0.6 V potential bias and 365 nm light irradiation compared would form an electrical double
layer
with thebetween
TiO2/ITO thephotoelectrode.
electrode and bulk Thesolution, causing thethe
authors attributed pollutants methylene
high efficiency blue,
to the which possesses
following factors.
positive charges, to adsorb on TiO /CA electrode surface. The excellent
Firstly, applying −0.6 V bias would form an electrical double layer between the electrode and bulk
2 conductivity of CA materials
would enhance
solution, causing the the electrosorption
pollutants methylene processblue,
and which
the large specific positive
possesses surface area would
charges, to promote
adsorb on the
dispersion of TiO nano-crystallite on the electrode film. The
TiO2/CA electrode2 surface. The excellent conductivity of CA materials would enhance theelectrosorption effect would increase the
transparency of
electrosorption the opaque
process wastewater,
and the large specific whichsurface
would area greatly increase
would the photocatalytic
promote the dispersion degradation
of TiO2
efficiency of TiO .
nano-crystallite on2 the electrode film. The electrosorption effect would increase the transparency of
the opaque wastewater, which would greatly increase the photocatalytic degradation efficiency of
TiO2.
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Figure 2. Scanning
Figure electronic
2. Scanning microscopy
electronic microscopy(SEM) imagesofofcarbon
(SEM) images carbon aerogel
aerogel (CA)
(CA) (A ×500,
(A ×500, B B
Figure 2. Scanning electronic microscopy (SEM) images of carbon aerogel (CA) (A × 500, B × 80 k)
×80and
×80 k) and
k) TiO2/CA TiO2/CA
and TiO2/CA (C ×500, D ×80 k, E ×450
(C ×500, D ×80 k, E ×450 k). Copied with the permission from [84],
Copied with the permission from [84],
(C × 500, D × 80 k, E × 450 k). Copied with the permission from [84], Copyrights 2010
Copyrights
Copyrights 2010 2010
ACS ACS [84].
[84].
ACS [84].
In 2011, Wu and co-workers reported that mesoporous and macroporous carbon aerogels
In In
2011,
2011,WuWuandand co-workers reported that
co-workers reported thatmesoporous
mesoporousand and macroporous
macroporous carbon
carbon aerogels
aerogels could
could couple with TiO2 to construct a hybrid CA/TiO2 composite photocatalyst [85]. The composite
could couple
couple with with
TiO TiO
to 2 to construct
construct a hybrid a hybrid
CA/TiO CA/TiO
composite2 composite photocatalyst
photocatalyst [85]. The [85].
compositeThe composite
photocatalyst
photocatalyst 2was prepared by a sol–gel process 2 mixing Ti(iPrO)4 with CA in an alcoholic solution.
photocatalyst
wasThepreparedwasbyprepared
as-prepared a CA
sol–gel by a sol–gel
was process
sintered mixing
process
at 400 °CTi(iPrO)
mixing
under N 4 2with Ti(iPrO)
CA in an
atmosphere.
4 with
Two
CA insolution.
alcoholic an alcoholic
CA materials withThe
solution.
as-prepared
different
The as-prepared
CApore
wasdiameters CA
sintered at was sintered
◦
400hybridized
were at
C underwith 400 °C under
N2 atmosphere. N
TiO2. The oneTwo2 atmosphere.
withCA Two CA materials
materialsstructure
mesoporous with different with
displayedpore different
diameters
much
pore
werediameters
hybridized
higher were
activity onhybridized
with Thewith
TiO2 . orange
methyl one TiO
with2. mesoporous
The compared
degradation one with mesoporous
structure
with structure
displayed
pristine TiO much
2 and displayed
TiOhigher
2/CA with muchon
activity
methyl orange degradation compared with pristine TiO2 and TiO2 /CA with macroporous structure
higher activity
macroporous on methyl
structure asorange
shown degradation
in Figure 3. By compared
analyzing with
XRD pristine
(X-ray TiO
diffraction),
2 and
SEM TiO /CA
(scanning
2 with
electron
macroporous microscopy),
as shown instructure
Figure 3.asBy and
shown BET (Brunner-Emmet-Teller
in Figure
analyzing XRD3.(X-ray
By analyzing measurements)
XRD SEM
diffraction), (X-ray experimental
diffraction),
(scanning results, the
SEM microscopy),
electron (scanning
andauthors
electron determinedand
microscopy),
BET thatBET
(Brunner-Emmet-Teller the (Brunner-Emmet-Teller
mesoporous
measurements) structure of TiO 2/CA125 photocatalyst
measurements)
experimental authorspromoted
results, theexperimental thethat
results,
determined thethe
substrates adsorption and products desorption because of the suitable pore size. The micropores
mesoporous structure of TiO2 /CA125 photocatalyst promoted the substrates adsorption and products
authors determined that the mesoporous structure of TiO 2 /CA125 photocatalyst promoted the
could not accommodate the considerably large methyl orange dye molecule entering the pore,
substrates
desorption adsorption
because of and
theproducts desorption
suitable pore size. The because of the
micropores suitable
could pore size. The
not accommodate themicropores
considerably
while the macropore is too large to confine the dye molecule inside the pore for effective adsorption
could
large not accommodate the considerably large methyl orange dye molecule entering the pore,
andmethyl
surfaceorange dye molecule
photocatalytic reaction. entering the pore, while the macropore is too large to confine the
while the macropore is too large to confine the dye molecule inside the
dye molecule inside the pore for effective adsorption and surface photocatalytic reaction.pore for effective adsorption
and surface photocatalytic reaction.

Figure 3. The photocatalytic degradation curves of methyl orange dye over TiO2 and
TiO2/CA photocatalysts. Copied with the permission from [85], Copyrights 2011 Elsevier
[85].
Thephotocatalytic
Figure3.3.The
Figure photocatalytic degradation
degradationcurves
curvesof of
methyl orange
methyl dye over
orange TiO2 and
dye over TiO2TiO 2 /CA
and
photocatalysts. Copied with the permission from [85], Copyrights 2011 Elsevier [85].
TiO2/CA photocatalysts. Copied with the permission from [85], Copyrights 2011 Elsevier
[85].
 Materials 2020, 13, 1734 5 of 15
Materials 2019, 12, x FOR PEER REVIEW 5 of 15

In In
2011,
2011,Zhao
Zhaoand
and co-workers reported
reportedthat that CA/TiO
CA/TiO 2 hybrid
2 hybrid material
material couldcould
act asact as promising
a very a very
promising
candidate candidate for a photocatalysis
for a photocatalysis enhancedenhanced electroadsorption
electroadsorption (PES)-based (PES)-based dye pollutant
dye pollutant elimination
elimination process
process [86]. They[86]. They prepared
prepared the CA/TiO the CA/TiO2 by
2 electrode electrode
dispersingby dispersing the as-prepared
the as-prepared CA material CAinto
material into titania sol–gel.
titania tetrabutylate tetrabutylate sol–gel. was
The CA material Thesynthesized
CA material from the was synthesized from
poly-condensation the
of resorcinol
poly-condensation
and formaldehyde, of resorcinol and formaldehyde,
the displacement the displacement
of water by immersing of water
in acetone, by immersing
and final in
sintering under
acetone, and final sintering under argon at a high temperature forming the
argon at a high temperature forming the final porous aerosol microstructure. The morphology, surface final porous aerosol
microstructure.
composition,The andmorphology,
properties were surface composition,
characterized by and
SEM, properties
EDS (Energy were Dispersive
characterized by SEM,
Spectroscopy),
EDS (Energy Dispersive Spectroscopy), TG/DTA (Thermogravimetric
TG/DTA (Thermogravimetric Analysis/Differential Thermal Analysis), BET, EIS (Electrochemical Analysis/Differential Thermal
Analysis),
Impedance BET, EIS (Electrochemical
Spectroscopy), Impedance Furthermore,
and Raman spectrometry. Spectroscopy), the and Raman
material spectrometry.
demonstrated excellent
Furthermore,
alizarin redthe (AR)material demonstrated
dye pollutant eliminationexcellent
abilityalizarin red (AR) adsorption,
by combining dye pollutant elimination
electroadsorption,
ability
and by combining adsorption,
photocatalysis electroadsorption,
in a three-in-all strategy. In a 400 andmg/Lphotocatalysis in a three-in-all
high concentration strategy.
AR pollutant In
solution,
a 400
the mg/L
hybridhigh concentration
material exhibitedAR pollutant
97.3% TOC (Totalsolution,
Organicthe hybrid
Carbon)material
removalexhibited
in 240 min 97.3% TOCPES
for the
(Total Organic
process Carbon) removal
in comparison with 59% in 240
in theminphotocatalysis
for the PES process process in comparison
without applied with 59% field
electric in theand
photocatalysis process withoutprocess
22% in the electrosorption appliedwithout
electric illumination.
field and 22%Not in the electrosorption
only did it possessprocess
high AR without
removal
illumination.
efficiency, Not onlymaterial
but this did it possess high ARvery
also exhibited removal
goodefficiency, but this material
stability, providing 92.3% AR alsoremoval
exhibited after
very good stability, providing 92.3% AR removal after five cycles. Moreover,
five cycles. Moreover, the authors proposed a mechanism for the synergistic effect of photocatalysis the authors proposed
a mechanism for the synergistic
and electrosorption as shown effect of photocatalysis
in Figure 4. The adsorbed anddyeelectrosorption as shown
molecules labile bondsinwereFigure 4.
initially
Thecleaved
adsorbed viadye molecules labile bonds
single-electron-transfer by TiOwere 2
initially
photo-induced cleaved via
hole single-electron-transfer
species or hydrogen by TiO
abstraction 2 by

photo-induced hole species or hydrogen abstraction by hydroxyl radicals

hydroxyl radicals and other reactive oxygen species (ROS), and the dye molecule radical cations and other reactive oxygen
species
were (ROS), and theand
hydroxylated dyemineralized
molecule radical
step by cations
step via were hydroxylated
radical addition, and
atommineralized
abstraction,stepand bybond
stepcleavage
via radical addition, atom abstraction, and bond cleavage mechanism.
mechanism. The photo-induced electrons were extracted to the other electrode by circuit The photo-induced
electrons were
to inhibit extracted to recombination,
hole-electron the other electrode andby thuscircuit to inhibit
improve hole-electron recombination,
the mineralization efficiency. Owing and to
thustheimprove
excellenttheporosity
mineralization efficiency. Owing
and conductivity, CA could to theact excellent porosity adsorbent
as very effective and conductivity, CA
and electrode
could act as very effective adsorbent and electrode materials. Under applied
materials. Under applied positive potential, negative-charged dye-molecules would be attracted to positive potential,
negative-charged dye-molecules
the positive electrode, would
enhancing be attracted
adsorption. Theto the
TiOpositive electrode, enhancing adsorption.
2 photocatalyst mineralized the dye, which
Theavoided
TiO2 photocatalyst mineralized
saturated adsorption of CAthematerial,
dye, which whileavoided saturated
CA adsorbed and adsorption
enriched dye of pollutant
CA material,to keep
while CA adsorbed and enriched dye pollutant to keep high pollutant concentration
high pollutant concentration on the TiO2 surface to make the photocatalytic reaction proceed rapidly. on the TiO 2

surface to make the

Photocatalysis andphotocatalytic
electroadsorptionreaction proceed rapidly.
synergistically ensuredPhotocatalysis
highly efficient and electroadsorptiondye
high-concentration
synergistically ensured highly efficient high-concentration dye solution decontamination,
solution decontamination, which is important not only in academics, but also in industrial engineering. which is
important not only in academics, but also in industrial engineering.

Figure 4. 4.Mechanism
Figure Mechanism of photocatalysis
of photocatalysis enhanced
enhanced electroadsorption
electroadsorption (PES) (PES) degradation
degradation ofred
of alizarin
alizarin red on
(AR) dye (AR) TiO2 /CA
the dye on the TiO2/CA photoelectrode.
photoelectrode. Copied with theCopied withfrom
permission the permission from2011
[86], Copyrights
Elsevier
[86], [86]. CB:
Copyrights Conduction
2011 Elsevier Band. VB: Conduction
[86]. CB: Valence band.Band. VB: Valence band.

Furthermore,
Furthermore, Zhao
Zhao andand co-workers
co-workers discovered
discovered thatTiO
that TiO 2 /CA
2/CA
materialcould
material couldhave
havethe
thecapacity
capacity to
act as
to act asan
aneffective photoelectrode
effective to extend
photoelectrode the TiO
to extend absorption
the2 TiO spectrum to the visible-light region and
2 absorption spectrum to the visible-light

region and mineralize Rhodamine 6G dye pollutants under visible-lightinirradiation

mineralize Rhodamine 6G dye pollutants under visible-light irradiation an aerobicincondition under
an aerobic
−0.9 V bias [87]. They figured out that H 2 2 out that H2O2 was generated on the electrode surface of
condition under −0.9 V bias [87]. They figuredO was generated on the electrode surface by the reduction
by the reduction of dioxygen. Further, the in-situ generated H2O2 coordinated with TiO2, forming a
 Materials 2020, 13, 1734 6 of 15
Materials 2019, 12, x FOR PEER REVIEW 6 of 15

dioxygen. Further,
visible-light responsivethe in-situ
surfacegenerated
Ti–peroxide H2 Ocomplex.
2 coordinated
Upon with TiOirradiation,
light 2 , forming athisvisible-light responsive
surface complex
surface Ti–peroxide complex. Upon light irradiation, this surface complex
was excited and injected electrons to the TiO2 conduction band. The conduction band electrons’ was excited and injected
electrons tosurface
decomposed the TiOadsorbed
2 conduction H2Oband. The conduction band electrons’ decomposed surface adsorbed
2 to hydroxyl radicals. The hydroxyl radicals that possess strong
H O
oxidative
2 2 to hydroxyl radicals. The hydroxyl
ability (E1/2 = 2.4 V vs NHE) can radicals that possess
be directly applied strong oxidative ability
to mineralize (E1/2 =This
pollutants. 2.4 V
mechanism was shown in Figure 5. To demonstrate the efficiency of this photoelectrocatalysis 5.
vs. NHE) can be directly applied to mineralize pollutants. This mechanism was shown in Figure
To demonstrate
system, the efficiency6G
azo dye Rhodamine of was
this photoelectrocatalysis system, azo
applied as a model pollutant indye
the Rhodamine
activity test.6GThe
wasresults
applied
as a model pollutant in the activity test. The results showed that, upon
showed that, upon –0.9 V bias and visible-light irradiation (λ > 420 nm), the TiO2/CA photocathode–0.9 V bias and visible-light
irradiation
could (λ > 420 nm),
reach removal efficiency for2 /CA
the TiO photocathode
Rhodamine 6G atcould
90.3%reach
and removal
TOC at 83.3%efficiency for min.
in 300 Rhodamine
GC-MS6G
at 90.3% and TOC at 83.3% in 300 min. GC-MS (Gas Chromatography-
(Gas Chromatography- Mass Spectroscopy) and HPLC (High-performance Liquid Chromatography) Mass Spectroscopy) and HPLC
(High-performance Liquid Chromatography) tracing of intermediates
tracing of intermediates indicated that less intermediates were generated under indicated that less intermediates
were generated under
photoelectrocatalytic photoelectrocatalytic
conditions than under conditions
traditionalthanphotocatalytic
under traditional photocatalytic
conditions. This conditions.
catalyst
This catalyst system demonstrated excellent pollutant removal efficiency
system demonstrated excellent pollutant removal efficiency and low energy consumption. and low energy consumption.
More
More importantly,
importantly, this example
this example provided provided
us a newus a new approach
approach to explore
to explore thethe visible-light
visible-light responsive
responsive
unconventional
unconventional TiO
TiO 2 -based
2-based
photocatalytic
photocatalytic materials.
materials.

Figure
Figure5.5.Mechanism
Mechanism of ofin-situ
in-situinduced
induced visible-light
visible-light photoelectrocatalysis
photoelectrocatalysis from molecular
from molecular oxygen on
oxygen on carbon aerogels-supported TiO
carbon aerogels-supported TiO2 . Copied with the permission from [87], Copyrights 2011 ACS[87],
2 . Copied with the permission from [87].
Copyrights 2011 ACS [87].
Zhao and co-workers reported that TiO2 nanorod cluster (NRC) material could be loaded on
Zhaoaerogel
carbon and co-workers reported that TiO2 nanorod
by a hydrothermal/calcination method [88]. cluster
The(NRC) material
as-prepared TiOcould be loaded
2 NRC/CA on
composite
carbon
materialaerogel
could by a hydrothermal/calcination
be used as photocathode for themethod [88]. The
decomposition andas-prepared
mineralization TiOof2 aNRC/CA
notorious
composite
pollutantmaterial could They
p-nitroaniline. be used as photocathode
compared the pollutant forremoval
the decomposition
efficiency and and mineralization
activity of TiO2 NRC/CA of a
notorious
with TiOpollutant p-nitroaniline.
2 NRC/graphite material.They Thecompared the pollutant
results indicated that TiOremoval
2 NRC/CA efficiency
materialand activity
could of
provide
TiO 2 NRC/CA
superior 98.2%withPNATiO(p-Nitroaniline)
2 NRC/graphite material. The results
removal efficiency inindicated that TiO
180 min under 2 NRC/CA irradiation
visible-light material
could
with provide
−0.6 V bias superior 98.2% PNA
in comparison (p-Nitroaniline)
with 79.8% removal efficiency
for TiO2 NRC/graphite. From variousin 180characterization
min under
visible-light
experiments, irradiation
the authorswith −0.6 Vthe
ascribed bias in comparison
higher efficiency ofwithTiO2 79.8%
NRC/CA for to
TiOthe2 NRC/graphite. From
CA’s three-dimensional
various characterization
structure, which provided experiments, the authors
greater surface area and ascribed the higher efficiency
larger conductivity. More TiOof 2 TiO NRC/CA
photocatalyst
2 to
could
thebeCA’s three-dimensional
loaded on CA rather than structure, which
on graphite. provided
Further, moregreater
H2 O2surface area and
and hydroxyl largercould
radicals conductivity.
be formed
More TiO2 photocatalyst
on electrode surface. Owingcould to be
theloaded
greateron CAofrather
level than onmore
TiO2 loading, graphite.
surface Further, morecomplex
Ti–peroxide H2O2 and and
hydroxyl radicals could be formed on electrode surface. Owing to the greater
photocurrent could be yielded under visible-light irradiation. All these factors made TiO2 NRC/CA level of TiO 2 loading,
more surface
excellent Ti–peroxide
photocathode complex
materials and photocurrent
for p-nitroaniline could
pollutants be yielded Moreover,
mineralization. under visible-light
the authors
irradiation.
proposed the Alldecomposition
these factorspathwaysmade TiO for2thisNRC/CA excellent photocathode
photoelectrocatalytic system as shown materials
in Figurefor 6.
p-nitroaniline
They discovered pollutants
the new mineralization.
important intermediatesMoreover, the authors proposed
1,2,4-trihydroxybenzene duringthe the
decomposition
decomposition
pathways
processesfor this photoelectrocatalytic
of p-nitroaniline and reasonably system as shown
explained in Figure 6. mechanism.
its mineralization They discovered the new
important intermediates 1,2,4-trihydroxybenzene during the decomposition processes of
p-nitroaniline and reasonably explained its mineralization mechanism.
 Materials 2020, 13, 1734 7 of 15
Materials 2019, 12, x FOR PEER REVIEW 7 of 15

Figure
Figure6.6.Mechanism
Mechanism of the decomposition
of the decomposition of intermediates
of intermediates in TiOin2 nanorod
TiO2 nanorod cluster
cluster (NRC)/CA
(NRC)/CA photoelectrocatalysis over p-nitroaniline pollutants. Copied with the
photoelectrocatalysis over p-nitroaniline pollutants. Copied with the permission from [88], Copyrights
permission from
2013 Elsevier [88], Copyrights 2013 Elsevier [88].
[88].

ShiShi
andand co-workers
co-workers discovered
discovered thatthat
TiOTiO 2 photocatalytic
2 photocatalytic activity
activity of of
DMP DMP (dimethyl
(dimethyl phthalate)
phthalate)
degradationcould
degradation could be be enhanced
enhancedbyby hybridizing
hybridizinga CAa material and constructing
CA material secondarysecondary
and constructing hydrophilic
pores [89].pores
hydrophilic They [89].
synthesized TiO2 /CA composite
They synthesized TiO2/CAphotocatalysts with differentwith
composite photocatalysts CA pore diameters.
different CA pore They
discovered
diameters. thatdiscovered
They materials comprising
that materials CA with 9.3 nm mesopores
comprising CA with 9.3 exhibited the highest
nm mesopores photocatalytic
exhibited the
degradation
highest efficiency,
photocatalytic while CA with
degradation smaller while
efficiency, pore diameters
CA withof 3.4 andpore
smaller 4.3 nm generated
diameters ofinferior
3.4 andresults
4.3
nmeven compared
generated with the
inferior pristine
results evenTiO 2 photocatalyst.
compared with theContact angle
pristine TiOanalysis and DMPContact
2 photocatalyst. adsorptionangletests
indicated
analysis andthat
DMP CA-9.3 possessed
adsorption tests the least ability
indicated to adsorb
that CA-9.3 DMP owing
possessed the leastto its larger
ability to wettability
adsorb DMP and
hydrophilicity.
owing to its largerHowever,
wettabilityasand TiOhydrophilicity.
2 nanoparticles dispersed
However, asin both
TiO 2 inner and
nanoparticles outer space
dispersed of
in CA-9.3,
both
photo-induced
inner and outer space electrons on thephoto-induced
of CA-9.3, outer surface migrated
electrons onto the
the inner
outer surface
surface through
migratedCA conductive
to the inner
porousthrough
surface structure, CA inhibiting electron-hole
conductive porous recombination and improving
structure, inhibiting the charge
electron-hole separation process.
recombination and
improving the charge separation process. Thus, the generation of hydroxyl radicals by by
Thus, the generation of hydroxyl radicals by photo-induced holes on the outer surface was enhanced
this effect, which
photo-induced holesincreased the DMP
on the outer surfacephotodegradation
was enhanced rate.
by Moreover,
this effect,the generation
which rate the
increased of hydroxyl
DMP
radical by other routes
photodegradation was also increased.
rate. Moreover, the generationIn the rate
innerofspace of hydrophilic
hydroxyl radical bysecondary
other routespore, dioxygen,
was also
photo-electrons,
increased. In the innerand space
water ofmolecules
hydrophilic weresecondary
enriched by thisdioxygen,
pore, micro-reactor. This encapsulation
photo-electrons, and water effect
enhancedwere
molecules the hydroxyl
enrichedradical
by thisgeneration
micro-reactor.by theThis
dioxygen reduction route
encapsulation effect in comparison
enhanced thewith the lack
hydroxyl
of porous
radical structure
generation of pristine
by the dioxygenTiOreduction
2 . This mechanism was illustrated
route in comparison withinthe Figure
lack 7.
of porous structure
of pristine TiO2. This mechanism was illustrated in Figure 7.
 Materials 2019, 12, x FOR PEER REVIEW 8 of 15

Materials 2020, 13, 1734 8 of 15

Materials 2019, 12, x FOR PEER REVIEW 8 of 15

Figure 7. Schematic illustration of dimethyl phthalate (DMP) degradation in TiO2/CA-9.3

under light irradiation. The red ring describes the reactions occurring in the secondary
pores. The processes include the following: (I) on the external surface, OH• formation
with
Figure 7.HSchematic
Figure O Schematic
27. reduction and oxidation;
illustration
illustration of
of dimethyl
dimethyl (II)phthalate
the photoelectrons
phthalate (DMP)
(DMP) generated
degradation
degradation in TiOin2on
TiO the
/CA-9.3 external
2/CA-9.3
under light
surface migrate
irradiation. The to
red the
ring internal
describes surface
the reactions through
occurring the
in carbon
the layer;
secondary
under light irradiation. The red ring describes the reactions occurring in the secondary (III)
pores. on
The the
processesinternal
include
surface,
theThe
pores. the
following: photoelectrons
(I) oninclude
processes the externalaresurface,
the trapped
following: by(I)
OH• Oon
2 to produce
formation
the with H2O
external O2•−; (IV) HOc
reduction
surface, and are
OH• generated
oxidation;
formation (II) the
with the participation
withphotoelectrons
H2O reduction generated of H 2O
and oxidation; and O
on the external •− and (V) DMP is oxidized by active HO• on both the
(II) surface
2 migrate to the internal
the photoelectrons generatedsurface
on through the carbon
the external
external and oninternal •− ; (IV)
layer;
surface (III)
migrate the the surface.
to internal internal Copied
surface, with the permission
the photoelectrons
surface through carbonfrom
are trapped
the by O2[89],
layer; Copyrights
to(III)
produce
on O the 2016HOc
2 internal RSCare
•−
[89].
generated with the participation
surface, the photoelectrons are trapped of H 2 O and
by O22 to produce O2 ; (IV) HOc are generated the
O and (V) DMP is•−oxidized by active HO• on both
withexternal and internalofsurface.
the participation H2O and Copied
O2•− with the permission
and (V) from [89],
DMP is oxidized byCopyrights
active HO• 2016
onRSC
both[89].
the
Wang
external and
and co-workers
internal reported
surface. that
Copiedthat Ce-doped
with TiO 2/CA could be applied as potent visible-light
the permission from [89],
Wang
responsive and co-workers
electrosorptive reported
photocatalytic Ce-doped
materials TiOfor2 /CA could beCopyrights
4-chlorophenol applied as 2016
potent
degradation
RSC
visible-light
[90]. They
[89].
responsive electrosorptive photocatalytic materials for 4-chlorophenol degradation [90]. They discovered
discovered that cerium doping could introduce defect sites above the top of the valence band
that ceriumTiO
red-shifting doping could introduce defect sites above the top of the valence band red-shifting TiO
2 absorption spectrum from 387 nm to 532 nm. Furthermore, carbon aerogel was 2
Wang and co-workers reported that Ce-doped TiO2/CA could be applied as potent visible-light
absorption
hybridized spectrum
with Ce-TiO from 387 nm to 532 nm. Furthermore, carbon aerogel was hybridized with
2 photocatalyst by an impregnation method. The as-synthesized
responsive electrosorptive photocatalytic materials for 4-chlorophenol degradation [90]. They
Ce-TiO
Ce-TiO2/CA 2 photocatalyst by an impregnation method. The as-synthesized Ce-TiO2 /CA 0.6 material was
discovered thatmaterial
cerium was dopingusedcould
as photoelectrode
introduce defectto degrade 4-chlorophenol
sites above the top of under
the valence V bias
bandand
used
500 WasXenon
photoelectrode to degrade 4-chlorophenol
lamp irradiation. under 0.6 V biastimes
and 500 W Xenon lamp irradiation.
red-shifting TiO2 absorption spectrumThis frommaterial
387 nm to exhibited
532 nm. 75 Furthermore, larger photocurrent
carbon aerogel was than
This
Ce-TiO material exhibited 75 times larger photocurrent than Ce-TiO
2/FTO (fluorine-doped tin oxide), which was ascribed2 to the lesser electron-hole
/FTO (fluorine-doped tin oxide),
hybridized with Ce-TiO2 photocatalyst by an impregnation method. The as-synthesized
which was ascribed
recombination rate byto thetheCAlesser
porouselectron-hole
structure, recombination
which facilitated rate
thebycharge
the CA porous structure,
separation processes, which
as
Ce-TiO 2/CA material was used as photoelectrode to degrade 4-chlorophenol under 0.6 V bias and
facilitated
mentioned the
above.charge separation
Furthermore, processes,
for the as mentioned
4-chlorophenol above.
(4-CP) Furthermore,
degradation, for
Ce-TiO the 4-chlorophenol
2/CA generated
500 W Xenon lamp irradiation. This material exhibited 75 times larger photocurrent than
(4-CP)
97.3%
Ce-TiO
degradation,
4-CP removal in 4.5 h,2 /CA
Ce-TiO generated
in sharp 97.3%
contrast 4-CP
with removal
65.4% in 4.5 h,
for Ce-TiO
2/FTO (fluorine-doped tin oxide), which was ascribed to the lesser electron-hole
in sharp contrast with 65.4%
2/FTO under other identical
for Ce-TiO2 /FTO under
photoelectrochemical other identical
conditions. Thisphotoelectrochemical
enhancing conditions.
effectthe was This enhancing effect was
recombination rate by the CA porous structure, which facilitated chargemainly
separation because
processes, of asthe
mainly because
highly-developed of the highly-developed
porous structure porous structure
and excellent conductivity, and excellent conductivity,
whichCe-TiO
were 2pivotal which were
for 4-CP
mentioned above. Furthermore, for the 4-chlorophenol (4-CP) degradation, /CA generated
pivotal forand 4-CP adsorption and the charge separationprocesses.
and migration processes. This mechanism was
97.3% 4-CP removal in 4.5 h, in sharp contrast with 65.4% for Ce-TiO2/FTO under other identical in
adsorption the charge separation and migration This mechanism was illustrated
illustrated
Figure 8. in Figure 8.
photoelectrochemical conditions. This enhancing effect was mainly because of the
highly-developed porous structure and excellent conductivity, which were pivotal for 4-CP
adsorption and the charge separation and migration processes. This mechanism was illustrated in
Figure 8.

Figure
Figure 8. Schematics
Schematics of mechanism
of the the mechanism 2 /carbon
of Ce-TiOof Ce-TiO 2/carbon
aerogel aerogel
electrode in theelectrode in the
photoelectrocatalytic
photoelectrocatalytic degradation
degradation of 4-chlorophenol of Copied
pollutant. 4-chlorophenol pollutant.
with the permission fromCopied with the
[90], Copyrights 2018
permission from [90], Copyrights 2018 Elsevier [90].
Elsevier [90].
Figure 8. Schematics of the mechanism of Ce-TiO2/carbon aerogel electrode in the
Szilágyi and co-workers reported an atomic-layer-deposition (ALD) method to prepare
photoelectrocatalytic degradation of 4-chlorophenol pollutant. Copied with the
resorcinol–formaldehyde aerogel (RFA) and resorcinol–formaldehyde carbon aerogel (RFCA)/TiO2
permission from [90], Copyrights 2018 Elsevier [90].
Materials 2019, 12, x FOR PEER REVIEW 9 of 15

Szilágyi and co-workers reported an atomic-layer-deposition (ALD) method to prepare

Materials 2020, 13, 1734 9 of 15
resorcinol–formaldehyde aerogel (RFA) and resorcinol–formaldehyde carbon aerogel (RFCA)/TiO2
composite photocatalysts [91]. They initially prepared RFA and RFCA by the modified Pekala’s
three-step
composite method; the first [91].
photocatalysts step to synthesize
They initiallyRF hydrogel,
prepared RFAtheand
second
RFCAstepby dry RF hydrogel
the modified in
Pekala’s
supercritical
three-step condition
method; the forming RFA,toand
first step the last step
synthesize to yield RFCA
RF hydrogel, by sintering
the second step dryRFARFunder a N2 in
hydrogel
atmosphere at a high temperature. The as-synthesized RFA and RFCA were
supercritical condition forming RFA, and the last step to yield RFCA by sintering RFA under a N2 utilized as substrates
foratmosphere
ALD of TiO at2 aathigh
80 °C and 250 °C.The
temperature. TiOas-synthesized
2 prepared at 80 RFA°C and
wasRFCA
amorphous, while that
were utilized at 250 °Cfor
as substrates
wasALDcrystalline.
of TiO2 at Furthermore,
80 ◦ C and 250 the◦ C.
authors conducted
TiO2 prepared at the
80 ◦photo-degradation
C was amorphous,experiments
while that atof methyl
250 ◦ C was
orange dye. Surprisingly, they discovered that RFCA/amorphous TiO
crystalline. Furthermore, the authors conducted the photo-degradation experiments of methyl orange 2 exhibited better
photocatalytic activity
dye. Surprisingly, theythan RFCA/crystalline
discovered TiO2. Further,
that RFCA/amorphous TiO2 the RFCAbetter
exhibited material without activity
photocatalytic TiO2
deposition exhibited the best photocatalytic activity towards methyl orange
than RFCA/crystalline TiO2 . Further, the RFCA material without TiO2 deposition exhibited the best degradation. These
results were shown
photocatalytic in Figure
activity towards9. The authors
methyl ascribed
orange these unconventional
degradation. These results results to the in
were shown fact that 9.
Figure
theThe
oxide deposition
authors ascribed reduced the surface area
these unconventional and to
results thethefunctional group
fact that the content
oxide of RFCA,
deposition reducedthusthe
blocking and decreasing the activity sites. The ALD treatment at a higher
surface area and the functional group content of RFCA, thus blocking and decreasing the activity temperature more
significantly deteriorated
sites. The ALD treatment theatRFCA
a higherporous structuremore
temperature and significantly
decreased itsdeteriorated
functional group
the RFCAcontents.
porous
This report and
structure wasdecreased
interesting, demonstrating
its functional group that amorphous
contents. carbonaceous
This report material
was interesting, such as
demonstrating
resorcinol–formaldehyde
that amorphous carbonaceous carbon material
aerogel such
couldasnot only exhibit semiconductive
resorcinol–formaldehyde photocatalytic
carbon aerogel could not
activity, but also
only exhibit generate higher
semiconductive ability towards
photocatalytic organic
activity, but pollutant degradation
also generate undertowards
higher ability illumination
organic
than traditional metal-oxide materials.
pollutant degradation under illumination than traditional metal-oxide materials.

Figure
Figure9.9.Photocatalytic resultsofof(A)
Photocatalytic results (A) resorcinol–formaldehyde
resorcinol–formaldehyde aerogelaerogel
(RFA) (RFA) and its
and its composite,
composite, (B) resorcinol–formaldehyde
(B) resorcinol–formaldehyde carbon aerogelcarbon
(RFCA)aerogel (RFCA) and
and its composites, andits(C)composites, and
specific surface area
(C)and
specific
heatingsurface areadata
corrected andofheating
RFCA andcorrected data of RFCA
its composites. Copiedand
with itsthe
composites.
permissionCopied
from [91],
Copyrights
with 2019 Elsevier
the permission from[91].
[91], Copyrights 2019 Elsevier [91].

The performance
The performance of the of the state-of-the-art
state-of-the-art examples
examples of TiO /CA2 /CA
of 2TiO photo(electro)catalysis
photo(electro)catalysis is summarised
is summarised
in Table
in Table 1. 1.

Table Summary ofofphoto(electro)catalytic

Table1.1. Summary performance
photo(electro)catalytic performance /carbon
of TiO2of aerogel (CA)
TiO2/carbon materials
aerogel (CA)for
pollutants
materials forremoval. NRC,removal.
pollutants nanorod cluster; RFCA, resorcinol–formaldehyde
NRC, nanorod carbon aerogel.
cluster; RFCA, resorcinol–formaldehyde
carbon aerogel.
Removal Rate
Catalyst Condition Pollutant Ref.
Constant
365 nm UV-irradiation under Methylene Blue
TiO2 /CA
Catalyst Condition Pollutant 10−3 min−1
10.27 ×Removal Rate [84]
Ref.
−0.6 V bias (150 mg/L)
Methyl Orange
TiO2 /CA 125 300 W Hg lamp −3 −1
46.2 × 10 Constant
min [85]
(10 mg/L)
80 W UV light (320–400 nm, Alizarin Red
TiO2 /CA 9.24 × 10−3 min−1 [86]
peak at 365 nm) 0.6 V bias (400 mg/L)
TiO2/CA 365 nm300
UV-irradiation under nm) Methylene
W Xe lamp (420–800 Blue (150
Rhodamine 6G mg/L) 10.27 × 10−3 84
TiO2 /CA 2 3.61 × 10−3 min−1 [87]
100
−0.6 V bias −0.9 V bias
mW/cm (50 mg/L) min−1
500 W Xe lamp (peak at p-Nitroaniline
TiO2 NRC/CA 23.1 × 10 min−1
−3 [88]
420 nm) −0.6 V bias (150 mg/L)
300 W Xe lamp (320–700 nm Dimethyl phthalate
2 /CA-9.3
TiO125 −3 min−1−3
12.6 × 1046.2 [89]
TiO2/CA 300 W
peak at Hg
420 lamp
nm) 85 mW/cm2 Methyl (2 Orange
mg/L) (10 mg/L) × 10 85
4-Chlorophenol
9.24 × 10−3 min
−1
Ce-TiO2 /CA 500 W Xe lamp 0.6 V bias min−1 [90]
(100 mg/L)
2 parallel UV lights Methyl Orange
RFCA/TiO2 /80 ◦ C 3.3 × 10−3 min−1 [91]
(18 W UV-A blacklights) (8 × 10−5 mol/L)
Materials 2020, 13, 1734 10 of 15

Besides the activity improvements of the TiO2 /CA photo(electro)catalyst, its life cycle assessment
(LCA) of the environmental impacts should also be considered. Although we lack the data of the
environmental effects of the CA synthesis and the hybrid process of TiO2 and CA nano-materials,
according to the previously reported LCA of environmental impacts for seven different fabrication
routes of TiO2 nanomaterials by mass unit, surface-area unit, and photocatalytic activity unit [92], or the
reported LCA cradle to gate environmental impacts of five different non-doped and metal-doped TiO2
nanomaterials prepared by the sol–gel method by the function unit of photocatalytic carbamazepine and
methyl orange degradation [93], we can infer that the TiO2 /CA photo(electro)catalyst will generate more
environmental impacts because the fabrication of CA materials requires an intensive energy-input process
and the use of a considerable amount of organic precursor resorcinol and formaldehyde, while the use of
formaldehyde will contribute to environmental concern. Further, during the photo(electro)catalytic
process of pollutant removal, the added bias would generate much greater consumption of electricity
energy. However, the greatly enhanced pollutants removal efficiency would come as a trade-off to the
added extra environment impacts for TiO2 /CA materials compared with non-doped TiO2 photocatalysts.
Further, a thorough investigation using quantitative software to assess the environmental impacts
of the TiO2 /CA photo(electro)catalyst “from cradle to grave” based on the function unit of the
photo(electro)catalytic removal of certain organic pollutants by LCA should be conducted in the future.

3. Conclusions
We have outlined the state-of-the-art examples of carbon aerogels materials hybridized with
TiO2 applied as both catalysts for photoelectrochemical cells and photocatalysts for environmental
pollutants degradation. Although still in its blossoming stage in comparison with other traditional
inorganic metal oxides, metal chalcogenides, and surface plasmonic metallic photocatalysts and
photo-electrocatalysts, CA-modified TiO2 material still exhibited miscellaneous advantages. Firstly,
carbon aerogels modification could greatly increase the surface area of TiO2 owing to the great porosity
and highly-developed hierarchical porous structures. The increase of surface area would enhance the
adsorption of pollutants on TiO2 . Furthermore, the introduction of porous structure would enhance
electron-hole pair separation by the facilitated TiO2 photoelectron transfer between inner surface and
outer surface in the interconnected pore structure. Secondly, owing to CA’s excellent conductivity,
upon hybridization with CA, TiO2 semiconductive material became much more conductive, and the
electron-transfer impedance was greatly reduced. This effect was crucial for the increase of photocurrent
during the photoelectrochemical degradation of organic pollutants. Last, but not least, the doping of
carbon aerogel would introduce defect sites in TiO2 bulk solid, thus generating a dopant energy level
in the top of the valence band and in the bottom of the conduction band, thus providing the narrower
band gap for more efficient photon absorption. This would generate an apparent red-shift phenomenon
for TiO2 , extending its absorption limit from 387 nm to approximately 532 nm. Compared with other
crystalline carbonaceous materials, metal oxides, metal chalcogenides, and metal surface plasmonic
photocatalysts, CA/TiO2 photocatalysts still have a long way to proceed for more mature applications
in environment remediation. The main limitations and challenges for CA/TiO2 photocatalysts include
the following aspects. Initially, the degradation efficiency should be further improved to fulfill the
requirements of practical use in industry wastewater treatment. To meet this end, an elaborate, intricate,
and novel synthesizing method should be developed. Much higher performance of hydroxyl radical
generation and pollutants adsorption should be achieved. Secondly, in order to improve the activity of
the composite photocatalyst, the mechanism of how the photoelectrons, photo-induced holes, dioxygen,
water, organic pollutants, and the degradation intermediates interacted in the composite photocatalyst,
and in particular, how the porous structure influenced the whole photocatalytic process should be
more clearly demonstrated. We do believe that if these issues can be resolved successfully, the future
of CA/TiO2 photocatalysis would be promising.
Materials 2020, 13, 1734 11 of 15

Author Contributions: Conceptualization, D.M.; writing—original draft preparation, D.M.; writing—review and
editing, D.M., A.L. and C.C.; Literature search: D.M. and J.L. supervision, D.M.; funding acquisition, D.M. and
A.L. All authors have read and agreed to the published version of the manuscript.
Funding: This work was supported by the National Natural Science Foundation of China (21703005) and the
fundamental research funds for the central universities (FRF-TP-18-104A1).
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Fujishima, A.; Honda, K. Electrochemical Photolysis of Water at a Semiconductor Electrode. Nature 1972,
238, 37–38. [CrossRef] [PubMed]
2. Carey, J.H.; Lawrence, J.; Tosine, H.M. Photodechlorination of PCB’s in the presence of titanium dioxide in
aqueous suspensions. Bull. Environ. Contam. Toxicol. 1976, 16, 697–701. [CrossRef] [PubMed]
3. Frank, S.N.; Bard, A.J. Heterogeneous photocatalytic oxidation of cyanide ion in aqueous solutions at
titanium dioxide powder. J. Am. Chem. Soc. 1977, 99, 303–304. [CrossRef]
4. Inoue, T.; Fujishima, A.; Konishi, S.; Honda, K. Photoelectrocatalytic reduction of carbon dioxide in aqueous
suspensions of semiconductor powders. Nature 1979, 277, 637–638. [CrossRef]
5. Ishitani, O.; Inoue, C.; Suzuki, Y. Photocatalytic reduction of carbon dioxide to methane and acetic acid by an
aqueous suspension of metal-deposited TiO2 . J. Photochem. Photobiol. A Chem. 1993, 72, 269–271. [CrossRef]
6. Yu, J.; Low, J.; Xiao, W.; Zhou, P.; Jaroniec, M. Enhanced Photocatalytic CO2 -Reduction Activity of Anatase
TiO2 by Coexposed {001} and {101} Facets. J. Am. Chem. Soc. 2014, 136, 8839–8842. [CrossRef]
7. Ma, D.; Liu, A.; Li, S.; Lu, C.; Chen, C. TiO2 photocatalysis for C–C bond formation. Catal. Sci. Technol. 2018,
8, 2030–2045. [CrossRef]
8. Chen, X.; Mao, S.S. Titanium Dioxide Nanomaterials: Synthesis, Properties, Modifications, and Applications.
Chem. Rev. 2007, 107, 2891–2959. [CrossRef]
9. Zhang, H.; Liu, G.; Shi, L.; Liu, H.; Wang, T.; Ye, J. Engineering coordination polymers for photocatalysis.
Nano Energy 2016, 22, 149–168. [CrossRef]
10. Xiong, F.; Yu, Y.-Y.; Wu, Z.; Sun, G.; Ding, L.; Jin, Y.; Gong, X.-Q.; Huang, W. Methanol Conversion into
Dimethyl Ether on the Anatase TiO2(001) Surface. Angew. Chem. Int. Ed. 2015, 55, 623–628. [CrossRef]
11. Chen, C.; Ma, W.; Zhao, J. Semiconductor-mediated photodegradation of pollutants under visible-light
irradiation. Chem. Soc. Rev. 2010, 39, 4206. [CrossRef] [PubMed]
12. Li, H.; Shang, J.; Ai, Z.; Zhang, L. Efficient Visible Light Nitrogen Fixation with BiOBr Nanosheets of Oxygen
Vacancies on the Exposed {001} Facets. J. Am. Chem. Soc. 2015, 137, 6393–6399. [CrossRef] [PubMed]
13. Li, X.; Yu, J.; Jaroniec, M.; Chen, X. Cocatalysts for Selective Photoreduction of CO2 into Solar Fuels. Chem. Rev.
2019, 119, 3962–4179. [CrossRef] [PubMed]
14. Heller, A. Chemistry and Applications of Photocatalytic Oxidation of Thin Organic Films. Accounts Chem.
Res. 1995, 28, 503–508. [CrossRef]
15. Kikuchi, Y.; Sunada, K.; Iyoda, T.; Hashimoto, K.; Fujishima, A. Photocatalytic bactericidal effect of TiO2 thin
films: dynamic view of the active oxygen species responsible for the effect. J. Photochem. Photobiol. A Chem.
1997, 106, 51–56. [CrossRef]
16. Saito, T.; Iwase, T.; Horie, J.; Morioka, T. Mode of photocatalytic bactericidal action of powdered semiconductor
TiO2 on mutans streptococci. J. Photochem. Photobiol. B Boil. 1992, 14, 369–379. [CrossRef]
17. Bet-Moushoul, E.; Mansourpanah, Y.; Farhadi, K.; Tabatabaei, M. TiO2 nanocomposite based polymeric
membranes: A review on performance improvement for various applications in chemical engineering
processes. Chem. Eng. J. 2016, 283, 29–46. [CrossRef]
18. Sheikh, M.; Pazirofteh, M.; Dehghani, M.; Asghari, M.; Rezakazemi, M.; Valderrama, C.; Cortina, J. Application
of ZnO nanostructures in ceramic and polymeric membranes for water and wastewater technologies: A review.
Chem. Eng. J. 2019, 123475, 123475. [CrossRef]
19. Fujishima, A.; Zhang, X.; Tryk, D. TiO2 photocatalysis and related surface phenomena. Surf. Sci. Rep. 2008,
63, 515–582. [CrossRef]
20. Ma, D.; Zhai, S.; Wang, Y.; Liu, A.; Chen, C. TiO2 Photocatalysis for Transfer Hydrogenation. Molecules 2019,
24, 330. [CrossRef]
Materials 2020, 13, 1734 12 of 15

21. Ma, D.; Zhai, S.; Wang, Y.; Liu, A.; Chen, C. Synthetic Approaches for C-N Bonds by TiO2 Photocatalysis.
Front. Chem. 2019, 7, 635. [CrossRef] [PubMed]
22. Wang, Y.; Liu, A.; Ma, D.; Li, S.; Lu, C.; Li, T.; Chen, C. TiO2 Photocatalyzed C–H Bond Transformation for
C–C Coupling Reactions. Catalysts 2018, 8, 355. [CrossRef]
23. Lang, X.; Chen, X.; Zhao, J. Heterogeneous visible light photocatalysis for selective organic transformations.
Chem. Soc. Rev. 2014, 43, 473–486. [CrossRef] [PubMed]
24. Lang, X.; Ma, W.; Chen, C.; Ji, H.; Zhao, J. Selective Aerobic Oxidation Mediated by TiO2 Photocatalysis.
Accounts Chem. Res. 2013, 47, 355–363. [CrossRef]
25. Lang, X.; Zhao, J.; Chen, X. Cooperative photoredox catalysis. Chem. Soc. Rev. 2016, 45, 3026–3038. [CrossRef]
[PubMed]
26. Wang, Y.; Wei, Y.; Song, W.; Chen, C.; Zhao, J. Photocatalytic Hydrodehalogenation for the Removal of
Halogenated Aromatic Contaminants. ChemCatChem 2018, 11, 258–268. [CrossRef]
27. Wu, T.; Liu, G.; Zhao, J.; Hidaka, H.; Serpone, N. Mechanistic study of the TiO2 -assisted photodegradation of
squarylium cyanine dye in methanolic suspensions exposed to visible light. New J. Chem. 2000, 24, 93–98.
[CrossRef]
28. Teoh, W.Y.; Scott, J.A.; Amal, R. Progress in Heterogeneous Photocatalysis: From Classical Radical Chemistry
to Engineering Nanomaterials and Solar Reactors. J. Phys. Chem. Lett. 2012, 3, 629–639. [CrossRef]
29. Tan, T.T.Y.; Beydoun, D.; Amal, R. Photocatalytic Reduction of Se(VI) in Aqueous Solutions in UV/TiO2
System: Kinetic Modeling and Reaction Mechanism. J. Phys. Chem. B 2003, 107, 4296–4303. [CrossRef]
30. Augugliaro, V.; Camera-Roda, G.; Loddo, V.; Palmisano, G.; Palmisano, L.; Soria, J.; Yurdakal, S.
Heterogeneous Photocatalysis and Photoelectrocatalysis: From Unselective Abatement of Noxious Species
to Selective Production of High-Value Chemicals. J. Phys. Chem. Lett. 2015, 6, 1968–1981. [CrossRef]
31. Liu, G.; Wu, T.; Zhao, J.; Hidaka, H.; Serpone, N. Photoassisted Degradation of Dye Pollutants. 8. Irreversible
Degradation of Alizarin Red under Visible Light Radiation in Air-Equilibrated Aqueous TiO2Dispersions.
Environ. Sci. Technol. 1999, 33, 2081–2087. [CrossRef]
32. Serpone, N.; Emeline, A. Semiconductor Photocatalysis — Past, Present, and Future Outlook. J. Phys. Chem.
Lett. 2012, 3, 673–677. [CrossRef] [PubMed]
33. Wu, T.; Lin, T.; Zhao, J.; Hidaka, H.; Serpone, N. TiO2 -Assisted Photodegradation of Dyes. 9. Photooxidation
of a Squarylium Cyanine Dye in Aqueous Dispersions under Visible Light Irradiation. Environ. Sci. Technol.
1999, 33, 1379–1387. [CrossRef]
34. Choi, W.; Termin, A.; Hoffmann, M.R. The Role of Metal Ion Dopants in Quantum-Sized TiO2 : Correlation
between Photoreactivity and Charge Carrier Recombination Dynamics. J. Phys. Chem. 1994, 98, 13669–13679.
[CrossRef]
35. Zhu, J.; Chen, F.; Zhang, J.; Chen, H.; Anpo, M. Fe3+ -TiO2 photocatalysts prepared by combining sol–gel
method with hydrothermal treatment and their characterization. J. Photochem. Photobiol. A Chem. 2006, 180,
196–204. [CrossRef]
36. Valero, J.M.; Obregón, S.; Colón, G. Active Site Considerations on the Photocatalytic H2 Evolution Performance
of Cu-Doped TiO2 Obtained by Different Doping Methods. ACS Catal. 2014, 4, 3320–3329. [CrossRef]
37. Tang, J.; Grampp, G.; Liu, Y.; Wang, B.-X.; Tao, F.-F.; Wang, L.-J.; Liang, X.-Z.; Xiao, H.-Q.; Shen, Y.-M. Visible
Light Mediated Cyclization of Tertiary Anilines with Maleimides Using Nickel(II) Oxide Surface-Modified
Titanium Dioxide Catalyst. J. Org. Chem. 2015, 80, 2724–2732. [CrossRef]
38. Xing, M.; Zhang, J.; Chen, F. New approaches to prepare nitrogen-doped TiO2 photocatalysts and study on
their photocatalytic activities in visible light. Appl. Catal. B Environ. 2009, 89, 563–569. [CrossRef]
39. Asahi, R.; Morikawa, T.; Ohwaki, T.; Aoki, K.; Taga, Y. Visible-Light Photocatalysis in Nitrogen-Doped
Titanium Oxides. Science 2001, 293, 269–271. [CrossRef]
40. Khan, S.U.; Al-Shahry, M.; Ingler, W.B. Efficient Photochemical Water Splitting by a Chemically Modified
n-TiO2 . Science 2002, 297, 2243–2245. [CrossRef]
41. Shim, J.; Seo, Y.-S.; Oh, B.-T.; Cho, M. Microbial inactivation kinetics and mechanisms of carbon-doped TiO2
(C-TiO2 ) under visible light. J. Hazard. Mater. 2016, 306, 133–139. [CrossRef] [PubMed]
42. Umebayashi, T.; Yamaki, T.; Itoh, H.; Asai, K. Band gap narrowing of titanium dioxide by sulfur doping.
Appl. Phys. Lett. 2002, 81, 454–456. [CrossRef]
43. Daghrir, R.; Drogui, P.; Robert, D. Modified TiO2 For Environmental Photocatalytic Applications: A Review.
Ind. Eng. Chem. Res. 2013, 52, 3581–3599. [CrossRef]
Materials 2020, 13, 1734 13 of 15

44. Liu, S.; Zhang, N.; Tang, Z.-R.; Xu, Y.-J. Synthesis of One-Dimensional CdS@TiO2 Core–Shell Nanocomposites
Photocatalyst for Selective Redox: The Dual Role of TiO2 Shell. ACS Appl. Mater. Interfaces 2012, 4, 6378–6385.
[CrossRef] [PubMed]
45. Singh, A.P.; Kodan, N.; Mehta, B.R.; Held, A.; Mayrhofer, L.; Moseler, M. Band Edge Engineering in
BiVO4 /TiO2 Heterostructure: Enhanced Photoelectrochemical Performance through Improved Charge
Transfer. ACS Catal. 2016, 6, 5311–5318. [CrossRef]
46. Hirakawa, T.; Kamat, P.V. Photoinduced Electron Storage and Surface Plasmon Modulation in Ag@TiO2
Clusters. Langmuir 2004, 20, 5645–5647. [CrossRef]
47. Yu, H.; Xiao, P.; Tian, J.; Wang, F.; Yu, J. Phenylamine-Functionalized rGO/TiO2 Photocatalysts: Spatially
Separated Adsorption Sites and Tunable Photocatalytic Selectivity. ACS Appl. Mater. Interfaces 2016, 8,
29470–29477. [CrossRef]
48. Wang, X.-J.; Yang, W.-Y.; Li, F.-T.; Xue, Y.-B.; Liu, R.-H.; Hao, Y.-J. In Situ Microwave-Assisted Synthesis of
Porous N-TiO2 /g-C3 N4 Heterojunctions with Enhanced Visible-Light Photocatalytic Properties. Ind. Eng.
Chem. Res. 2013, 52, 17140–17150. [CrossRef]
49. Ma, D.; Liu, A.; Lu, C.; Chen, C. Photocatalytic Dehydrogenation of Primary Alcohols: Selectivity Goes
against Adsorptivity. ACS Omega 2017, 2, 4161–4172. [CrossRef]
50. Ma, D.; Yan, Y.; Ji, H.; Chen, C.; Zhao, J. Photocatalytic activation of pyridine for addition reactions: an
unconventional reaction feature between a photo-induced hole and electron on TiO2 . Chem. Commun. 2015,
51, 17451–17454. [CrossRef]
51. Liu, Y.; Zhang, M.; Tung, C.-H.; Wang, Y. TiO2 Photocatalytic Cyclization Reactions for the Syntheses of
Aryltetralones. ACS Catal. 2016, 6, 8389–8394. [CrossRef]
52. Cherevatskaya, M.; Neumann, M.; Füldner, S.; Harlander, C.; Kümmel, S.; Dankesreiter, S.; Pfitzner, A.;
Zeitler, K.; König, B. Visible-Light-Promoted Stereoselective Alkylation by Combining Heterogeneous
Photocatalysis with Organocatalysis. Angew. Chem. Int. Ed. 2012, 51, 4062–4066. [CrossRef] [PubMed]
53. Kistler, S.S. Coherent Expanded Aerogels and Jellies. Nature 1931, 127, 741. [CrossRef]
54. Pekala, R.W. Organic aerogels from the polycondensation of resorcinol with formaldehyde. J. Mater. Sci.
1989, 24, 3221–3227. [CrossRef]
55. Hanzawa, Y.; Kaneko, K.; Pekala, R.W.; Dresselhaus, M.S. Activated Carbon Aerogels. Langmuir 1996, 12,
6167–6169. [CrossRef]
56. Heinrich, T.; Klett, U.; Fricke, J. Aerogels?Nanoporous materials part I: Sol-gel process and drying of gels.
J. Porous Mater. 1995, 1, 7–17. [CrossRef]
57. Lee, K.T.; Oh, S.M. Novel synthesis of porous carbons with tunable pore size by surfactant-templated sol-gel
process and carbonisation. Chem. Commun. 2002, 2722–2723. [CrossRef]
58. Baumann, T.F.; Satcher, J.H. Homogeneous Incorporation of Metal Nanoparticles into Ordered Macroporous
Carbons. Chem. Mater. 2003, 15, 3745–3747. [CrossRef]
59. Baumann, T.F.; Satcher, J.H. Template-directed synthesis of periodic macroporous organic and carbon
aerogels. J. Non-Cryst. Solids 2004, 350, 120–125. [CrossRef]
60. Feaver, A.; Cao, G. Activated carbon cryogels for low pressure methane storage. Carbon 2006, 44, 590–593.
[CrossRef]
61. Zhang, S.; Gross, A.F.; Van Atta, S.L.; López, M.; Liu, P.; Ahn, C.C.; Vajo, J.J.; Jensen, C.M. The synthesis
and hydrogen storage properties of a MgH2 incorporated carbon aerogel scaffold. Nanotechnology 2009, 20,
204027. [CrossRef] [PubMed]
62. Lin, K.-S.; Mai, Y.-J.; Chiu, S.-W.; Yang, J.-H.; Chan, S.L.I. Synthesis and Characterization of Metal
Hydride/Carbon Aerogel Composites for Hydrogen Storage. J. Nanomater. 2012, 2012, 1–9. [CrossRef]
63. Utke, R.; Milanese, C.; Javadian, P.; Jepsen, J.; Laipple, D.; Karmi, F.; Puszkiel, J.; Jensen, T.R.; Marini, A.;
Klassen, T.; et al. Nanoconfined 2LiBH4 –MgH2 –TiCl3 in carbon aerogel scaffold for reversible hydrogen
storage. Int. J. Hydrog. Energy 2013, 38, 3275–3282. [CrossRef]
64. Gosalawit−Utke, R.; Nielsen, T.K.; Pranzas, K.; Saldan, I.; Pistidda, C.; Karimi, F.; Laipple, D.; Skibsted, J.;
Jensen, T.R.; Klassen, T.; et al. 2LiBH4 –MgH2 in a Resorcinol–Furfural Carbon Aerogel Scaffold for Reversible
Hydrogen Storage. J. Phys. Chem. C 2011, 116, 1526–1534. [CrossRef]
65. Tian, H.; Buckley, C.E.; Wang, S.; Zhou, M. Enhanced hydrogen storage capacity in carbon aerogels treated
with KOH. Carbon 2009, 47, 2128–2130. [CrossRef]
Materials 2020, 13, 1734 14 of 15

66. Gross, A.F.; Vajo, J.J.; Van Atta, S.L.; Olson, G.L. Enhanced Hydrogen Storage Kinetics of LiBH4 in Nanoporous
Carbon Scaffolds. J. Phys. Chem. C 2008, 112, 5651–5657. [CrossRef]
67. Feaver, A.; Sepehri, S.; Shamberger, P.J.; Stowe, A.; Autrey, T.; Cao, G. Coherent Carbon Cryogel−Ammonia
Borane Nanocomposites for H2 Storage. J. Phys. Chem. B 2007, 111, 7469–7472. [CrossRef]
68. McNicholas, T.P.; Wang, A.; O’Neill, K.; Anderson, R.; Stadie, N.; Kleinhammes, A.; Parilla, P.; Simpson, L.;
Ahn, C.C.; Wang, Y.; et al. H2 Storage in Microporous Carbons from PEEK Precursors. J. Phys. Chem. C 2010,
114, 13902–13908. [CrossRef]
69. Kabbour, H.; Baumann, T.F.; Satcher, J.H.; Saulnier, A.; Ahn, C.C. Toward New Candidates for Hydrogen
Storage: High-Surface-Area Carbon Aerogels. Chem. Mater. 2006, 18, 6085–6087. [CrossRef]
70. Mayer, S.T.; Pekala, R.; Kaschmitter, J.L. The Aerocapacitor: An Electrochemical Double?Layer Energy?Storage
Device. J. Electrochem. Soc. 1993, 140, 446. [CrossRef]
71. Saliger, R.; Fischer, U.; Herta, C.; Fricke, J. High surface area carbon aerogels for supercapacitors. J. Non-Cryst.
Solids 1998, 225, 81–85. [CrossRef]
72. Long, J.W.; Dening, B.M.; McEvoy, T.M.; Rolison, D.R. Carbon aerogels with ultrathin, electroactive
poly(o-methoxyaniline) coatings for high-performance electrochemical capacitors. J. Non-Cryst. Solids 2004,
350, 97–106. [CrossRef]
73. Bordjiba, T.; Mohamedi, M.; Dao, L.H. Synthesis and electrochemical capacitance of binderless nanocomposite
electrodes formed by dispersion of carbon nanotubes and carbon aerogels. J. Power Sources 2007, 172, 991–998.
[CrossRef]
74. Worsley, M.A.; Satcher, J.H.; Baumann, T.F. Synthesis and Characterization of Monolithic Carbon Aerogel
Nanocomposites Containing Double-Walled Carbon Nanotubes. Langmuir 2008, 24, 9763–9766. [CrossRef]
75. Worsley, M.A.; Satcher, J.H.; Baumann, T.F. Enhanced thermal transport in carbon aerogel nanocomposites
containing double-walled carbon nanotubes. J. Appl. Phys. 2009, 105, 84316. [CrossRef]
76. Baker, W.S.; Long, J.W.; Stroud, R.M.; Rolison, D.R. Sulfur-functionalized carbon aerogels: a new approach
for loading high-surface-area electrode nanoarchitectures with precious metal catalysts. J. Non-Cryst. Solids
2004, 350, 80–87. [CrossRef]
77. Marie, J.; Berthon-Fabry, S.; Achard, P.; Chatenet, M.; Pradourat, A.; Chaînet, E. Highly dispersed platinum
on carbon aerogels as supported catalysts for PEM fuel cell-electrodes: comparison of two different synthesis
paths. J. Non-Cryst. Solids 2004, 350, 88–96. [CrossRef]
78. Du, H.; Li, B.; Kang, F.; Fu, R.; Zeng, Y. Carbon aerogel supported Pt–Ru catalysts for using as the anode of
direct methanol fuel cells. Carbon 2007, 45, 429–435. [CrossRef]
79. Lu, A.-H.; Spliethoff, B.; Schüth, F. Aqueous Synthesis of Ordered Mesoporous Carbon via Self-Assembly
Catalyzed by Amino Acid. Chem. Mater. 2008, 20, 5314–5319. [CrossRef]
80. Lin, C.; Ritter, J.A. Carbonization and activation of sol–gel derived carbon xerogels. Carbon 2000, 38, 849–861.
[CrossRef]
81. Nardecchia, S.; Carriazo, D.; Ferrer, M.L.; Gutiérrez, M.C.; Del Monte, F. Three dimensional macroporous
architectures and aerogels built of carbon nanotubes and/or graphene: synthesis and applications. Chem. Soc.
Rev. 2013, 42, 794–830. [CrossRef] [PubMed]
82. Ghosh, S.; Maiyalagan, T.; Basu, R.N.; Thandavarayan, M. Nanostructured conducting polymers for energy
applications: towards a sustainable platform. Nanoscale 2016, 8, 6921–6947. [CrossRef] [PubMed]
83. Yin, X.; Liu, Q.; Chen, Y.; Xu, A.; Wang, Y.; Tu, Y.; Han, W. Preparation, characterization and environmental
application of the composite electrode TiO2 -NTs/SnO2 -Sb with carbon aerogels. J. Chem. Technol. Biotechnol.
2019, 94, 3124–3133. [CrossRef]
84. Wu, M.; Jin, Y.; Zhao, G.; Li, M.; Li, N. Electrosorption-promoted Photodegradation of Opaque Wastewater
on A Novel TiO2 /Carbon Aerogel Electrode. Environ. Sci. Technol. 2010, 44, 1780–1785. [CrossRef] [PubMed]
85. Cui, H.; Zhao, Z.; Liang, Y.; Shi, J.; Wu, D.; Liu, H.; Fu, R. Influence of Carbon Aerogel (CA) Pore Structure
on Photodegradation of Methyl Orange over TiO2 /CA. Chin. J. Catal. (Chin. Version) 2011, 32, 321–324.
[CrossRef]
86. Jin, Y.; Wu, M.; Zhao, G.; Li, M. Photocatalysis-enhanced electrosorption process for degradation of
high-concentration dye wastewater on TiO2 /carbon aerogel. Chem. Eng. J. 2011, 168, 1248–1255. [CrossRef]
87. Jin, Y.; Zhao, G.; Wu, M.; Lei, Y.; Li, M.; Jin, X. In Situ Induced Visible-Light Photoeletrocatalytic Activity from
Molecular Oxygen on Carbon Aerogel-Supported TiO2 . J. Phys. Chem. C 2011, 115, 9917–9925. [CrossRef]
Materials 2020, 13, 1734 15 of 15

88. Wang, Y.; Zhang, Y.-N.; Zhao, G.; Wu, M.; Li, M.; Li, N.; Zhang, Y.; Zhang, Y. Electrosorptive photocatalytic
degradation of highly concentrated p-nitroaniline with TiO2 nanorod-clusters/carbon aerogel electrode under
visible light. Sep. Purif. Technol. 2013, 104, 229–237. [CrossRef]
89. Cui, H.; Liang, Z.-X.; Zhang, J.; Liu, H.; Shi, J. Enhancement of the photocatalytic activity of a TiO2 /carbon
aerogel based on a hydrophilic secondary pore structure. RSC Adv. 2016, 6, 68416–68423. [CrossRef]
90. Wang, Y.; Pan, Z.; Qin, D.; Bai, S.; Peng, Q. Preparation of Ce-TiO2 /carbon aerogel electrode and its
performance in degradation of 4-chlorophenol. J. Rare Earths 2018, 36, 374–378. [CrossRef]
91. Justh, N.; Mikula, G.J.; Bakos, L.P.; Nagy, B.; László, K.; Parditka, B.; Erdélyi, Z.; Takáts, V.; Mizsei, J.;
Szilágyi, I.M. Photocatalytic properties of TiO2 @polymer and TiO2 @carbon aerogel composites prepared by
atomic layer deposition. Carbon 2019, 147, 476–482. [CrossRef]
92. Wu, F.; Zhou, Z.; Hicks, A. Life Cycle Impact of Titanium Dioxide Nanoparticle Synthesis through Physical,
Chemical, and Biological Routes. Environ. Sci. Technol. 2019, 53, 4078–4087. [CrossRef] [PubMed]
93. Fernandes, S.; Esteves da Silva, J.C.G.; Pinto da Silva, L. Life Cycle Assessment of the Sustainability of
Enhancing the Photodegradation Activity of TiO2 with Metal-Doping. Materials 2020, 13, 1487. [CrossRef]
[PubMed]

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