Adsorption Kinetics of The Photocatalytic Reaction o - 2023 - Construction and B
Adsorption Kinetics of The Photocatalytic Reaction o - 2023 - Construction and B
Adsorption Kinetics of The Photocatalytic Reaction o - 2023 - Construction and B
Review
A R T I C L E I N F O A B S T R A C T
Keywords: Nano-TiO2 cement-based materials have been widely used as green building materials due to their effective
Nano-TiO2 cement-based materials photocatalytic ability to degrade air pollutants. The photocatalytic reaction adsorption kinetics can accurately
Photocatalytic reaction describe the photocatalytic reactions of nano-TiO2 cement-based materials. In this paper, the photocatalytic
Adsorption
reaction mechanism and adsorption kinetics of nano-TiO2 cement-based materials have been introduced. The
Kinetic models
mechanisms of the effect of environmental factors such as the nano-TiO2 photocatalytic activity, TiO2 content,
reactant concentration, relative humidity, and light intensity on the photocatalytic reaction of nano-TiO2
cement-based materials have been analyzed in order to obtain an effective way to improve the photocatalytic
performance. Finally, a comparative analysis of the various types of photocatalytic adsorption kinetic models has
been carried out to provide a reference for establishing models with wider applicability in engineering.
* Corresponding author.
E-mail address: [email protected] (Y.-R. Zhao).
https://doi.org/10.1016/j.conbuildmat.2023.130462
Received 28 July 2022; Received in revised form 29 November 2022; Accepted 17 January 2023
Available online 19 February 2023
0950-0618/© 2023 Elsevier Ltd. All rights reserved.
Z.-M. Jia et al. Construction and Building Materials 370 (2023) 130462
natural environment, and the photocatalytic performance of these ma both the adsorption process and photocatalytic reaction, the advantages,
terials will be affected by the combined effect of multiple factors upon shortcomings, and applicability of these models have been compared
changes in geography, season, and use. The changes in the surface and summarized from the viewpoints of the adsorption mode and
photocatalytic activity and adsorption–desorption efficiency of cement- influencing factors. The results of this paper provide not only effective
based materials can reflect the changes in the photocatalytic perfor suggestions to improve the preparation process and photocatalytic
mance of nano-TiO2 cement-based materials [30,31]. Therefore, study performance of nano-TiO2 cement-based materials, but also provide a
ing the photocatalytic adsorption kinetic behavior of nano-TiO2 cement- reference for establishing photocatalytic adsorption kinetic models with
based materials using different factors and analyzing the photocatalytic wider applicability and more comprehensive considerations. In addi
adsorption kinetic mechanism in real working environments is an tion, the research described in this paper is of great significance to
effective way to improve the photocatalytic performance. The photo promote the scientific research and engineering applications of green
catalytic kinetic model is a mathematical approach to quantitatively and environmentally-friendly cement-based materials.
describe the relationship between the influencing factors and photo
catalytic degradation efficiency, which can be used to explore the pho 2. Principles of the photocatalytic reaction of cement-based
tocatalytic performance of nano-TiO2 cement-based materials under materials
different experimental environments. Moreover, the kinetic mechanism
of the adsorption process can be analyzed and the optimal kinetic pa Fig. 1(a) shows that the holes (h+) and highly reactive electrons (e–)
rameters under the environmental conditions can be obtained for en generated by nano-TiO2 on the surface of cement-based materials under
gineering applications. The kinetic models used for photocatalytic UV light irradiation are captured by water and oxygen molecules
reactions have been widely studied. The Langmuir–Hinshelwood (L–H) adsorbed on the surface of these materials. Hydroxyl (⋅OH) and super
model is a kinetic model that considers both the adsorption process and oxide (O2⋅–) radicals with strong oxidizing properties are then gener
the photocatalytic reaction, which has been extensively used to describe ated, which undergo redox reactions with the reactant molecules
the photocatalytic adsorption kinetic behavior of nano-TiO2 cement- adsorbed on the surface of the cement-based materials. Cement-based
based materials. materials are porous materials with complex internal pore morphol
In this paper, we analyze and summarize the mechanism of the ogies and contain microcracks. Fig. 1(b) shows the photocatalytic re
photocatalytic adsorption kinetics of nano-TiO2 cement-based materials action of nano-TiO2 cement-based materials is a continuous process of
under different influencing factors. For the kinetic models considering intermolecular adsorption-surface reaction-desorption, which can be
Fig. 1. Schematic diagram of the photocatalytic reaction mechanism of nano-TiO2 cement-based materials [131].
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divided into the following steps: (1) The reactants pass through the 3.2. TiO2 content on the surface of cement-based materials
surface of the cement-based materials, (2) the reactant molecules are
adsorbed, (3) the reactants diffuse internally through the pores and The photocatalytic reaction mainly occurs on the surface layer of
cracks of the cement-based materials, (4) the photocatalytic reaction cement-based materials. Therefore, a high loading and uniform distri
occurs under light conditions to produce new substances, (5) the prod bution of TiO2 nanoparticles on the surface of cement-based materials
ucts are desorbed from the surface of the photocatalyst, and (6) the re will increase the frequency of collisions between the reactant and
action products diffuse to the external space [13,14]. catalyst molecules, which significantly improves the efficiency of the
Fig. 1(b) shows the nano-TiO2 particles on the surface of cement- photocatalytic reaction. Increasing the doping amount of nano-TiO2 is
based materials receive higher photon energy and generate more the most effective way to increase the content of nano-TiO2 on the
electron-hole pairs when directly irradiated with UV light, generating surface of cement-based materials. However, nano-TiO2 has the char
more ⋅OH for redox reactions with the reactant molecules adsorbed on acteristics of high specific surface area and strong interactions between
the TiO2 surface. From the above analysis, it is clear that the photo particles, so when the doping amount is too large, agglomeration will
catalytic reaction mainly occurs on the surface of cement-based mate occur, resulting in an uneven distribution of nano-TiO2 on the surface of
rials, and the photocatalytic performance mainly depends on the the cement-based materials [36–38], which in turn affects the photo
number of highly reactive radicals generated on the surface and the catalytic efficiency. Moreover, the agglomeration of nano-TiO2 can also
number of adsorbed reactant molecules. Therefore, the photocatalytic adversely affect the mechanical properties and durability of cement-
performance of nano-TiO2 cement-based materials is closely related to based materials. Therefore, most researchers control the amount of
the nano-TiO2 photocatalytic activity, nano-TiO2 content on the mate nano-TiO2 doping to be within 10 %, as shown in Table 1. To reduce the
rial’s surface, reactant concentration, and environmental factors (light agglomeration phenomenon and improve the uniform distribution of
intensity and temperature). nano-TiO2 on the cementitious surface, researchers have improved the
nano-TiO2 dispersion process used during the preparation of cement-
3. Factors affecting the photocatalytic reaction based materials. For example, Yousefi and Othman et al. [39,40] have
used ultrasonic waves to significantly improve the dispersion and sta
3.1. Photocatalytic activity of TiO2 bility of nano-TiO2 in the cement slurry. It has also been shown [40–42]
that surfactants, such as polycarboxylate superplasticizer (PCE) and
The photocatalytic activity is key for the photocatalytic reactions of polyacrylic acid (PAA), have a positive effect on the dispersion of nano-
cement-based materials, which directly affects the reaction rate constant TiO2 in solution; the effect of PAA on the dispersion of nano-TiO2 in the
(k) and adsorption equilibrium constant (K). The photocatalytic activity cement slurry is more significant. Based on the above analysis, nano-
of TiO2 is affected by various factors, such as its crystal structure and TiO2 can be dispersed in a solution using both ultrasonic waves and
particle size. There are three main crystal structures of TiO2 found in surfactants in order to ensure the uniform dispersion and stability of
nature: rutile, anatase, and brookite [15,16], as shown in Fig. 2. nano-TiO2 in cement-based materials.
Brookite TiO2 is unstable and is easily converted into rutile TiO2. Rutile In addition, some other researchers have improved the content and
TiO2 exhibits poor adsorption ability toward O2 and small specific sur uniform distribution of nano-TiO2 on the surface of cement-based ma
face area, and the photogenerated electrons and holes are easily terials by optimizing the nano-TiO2 doping method used. Table 1 shows
recombined to adversely affect its photocatalytic activity. Therefore, the the commonly used methods are the internal doping method and
photocatalytic activity of rutile is significantly lower than that of external doping and coating method. Only the nano-TiO2 particles on
anatase. Therefore, anatase TiO2 is mainly used in cement-based mate the surface of the cementitious material can participate in the photo
rials. However, it was found that anatase nano-TiO2 would exhibit better catalytic reaction when using the internal doping method, and most of
photocatalytic performance compared to anatase TiO2 with larger par the remaining nano-TiO2 particles are found inside the cement-based
ticle size [17]. material, which cannot come in contact with light and participate in
Due to the disadvantages of its high electron-hole recombination rate the photocatalytic reaction. Therefore, the efficiency of nano-TiO2 uti
and large forbidden band width, nano-TiO2 can only absorb UV light, lization in this method is low. Although the external doping and coating
which accounts for 5 % of all solar radiation, limiting its photocatalytic method has a simple process and higher TiO2 utilization, maintaining
activity. Therefore, researchers have reduced the forbidden band width, the photocatalytic durability of the resulting cement-based material is a
promoted the separation of TiO2 photogenerated carriers, and reduced problem that needs to be solved. Researchers have studied toward a
the carrier recombination rate using photosensitization [19], ion doping solution to this problem. Zouzelka et al. [44] found that the use of a
[20,21], noble metal modification [22,23], and the construction of commercial photocatalytic coating protector (FN2) was efficient in
semiconductor heterojunctions [24,25], which in turn improved its removing nitrogen oxides (NOx) from polluted air even after two years of
photocatalytic activity. In summary, nanoscale anatase TiO2 is suitable operation under harsh conditions. Xu et al. [43] have used another
as a photocatalyst in cement-based materials and its crystal structure can approach and prepared a nano-TiO2 coating for cement-based materials,
be modified to improve the photocatalytic activity. which resembles a multilayer cast, with high photocatalytic efficiency
and better durability.
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Table 1
Comparison of preparation processes of nano-TiO2 cement-based materials.
Type of Nano TiO2 dosage range(%) Dispersion Method Nano TiO2 doping method Range of 28d compressive strength Reference
substrate of substrates (MPa)
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3.4. Light intensity most researchers is a UV lamp, as shown in Table 2. Current studies
[50,76,77] have shown that the photocatalytic reaction rate increases
Light is one of the conditions required for the occurrence of photo with an increase in the UV radiation intensity, as shown in Fig. 5. The
catalytic reactions. Nano-TiO2 has a high photocatalytic activity in the higher the intensity of UV radiation, more e– and h+ are generated via
UV region (200–400 nm). Therefore, the type of light source used by photoexcitation and captured by water and oxygen molecules adsorbed
on the surface to produce more ⋅OH and O2⋅–, which will accelerate the
rate of the redox reactions on the photocatalyst surface. The relationship
Table 2
between light intensity and the photocatalytic reaction rate constant (k)
A comparison and analysis of the experimental reactants and parameters.
(see section 4.3 for details) is shown in Eq. (1) [78]:
Reactant parameters Analysis Notes Reference
1 α
Name Initial Flow = +β (1)
k I 1/2
concentration rate(L/
min)
where I is the light intensity and α and β are constants. From Eq. (1), it is
NOx 20 ppm 1–5 Increasing the gas [27] obvious that as the light intensity increases, the reaction rate constant
flow rate leads to a
increases and the photocatalytic efficiency of cement-based materials
decrease in the NOx
degradation rate. increases.
However, several studies have shown that there are limits to the
NOx 0.15–2 ppm 0.5–9 Increasing the NO [50]
effect of light intensity on the photocatalytic reaction. At low light in
flow rate and initial tensities, there is a positive linear correlation between the light intensity
NO concentration and NOx degradation efficiency. When the light intensity is high, the
are detrimental to NOx removal efficiency slowly increases upon increasing the light in
the NOx
tensity [50]. This has been attributed to the increase in the number of
photocatalytic
degradation rate. excited reaction sites formed on the surface of nano-TiO2 as the light
intensity increases. However, the number of reaction sites is ultimately
limited and cannot generate more reaction sites upon further increasing
NOx 10 ppm 1–5 A higher NOx [68]
photocatalytic the light intensity [68,71]. In addition, the coupling effects of multiple
degradation factors need to be considered due to the complex environment in which
efficiency is cement-based materials are used. Casagrande [68] investigated the ef
observed at lower
fects of relative humidity and light intensity on the photocatalytic re
gas flow rates.
action. The results showed that the effect of relative humidity on the
photocatalytic reaction was greater than that of the light intensity. In
NOx 0.1–1.0 ppm 1–5 A lower initial NO [73]
addition, the radiation intensity had almost no effect on the NOx
concentration leads
to a higher NOx degradation efficiency when the relative humidity was > 50 %, as shown
degradation rate, but in Fig. 6. Therefore, choosing an appropriate light intensity can effec
at very low initial NO tively improve the photocatalytic performance of nano-TiO2 cement-
concentrations, the
based materials.
photocatalytic
reaction rate
increases upon
increasing the 3.5. Relative humidity
concentration.
In the photocatalytic process, ⋅OH generated from water vapor is the
NOx 50–2000 ppb 1–5 An increase in the [95] main oxidizing agent in the photocatalytic reaction. Therefore, changes
initial NO in the relative humidity can have an impact on the photocatalytic re
concentration and
action. It has been found that in the relative humidity range of 10–90 %,
flow rate gradually
decreases the NOx
the photocatalytic degradation efficiency of formaldehyde initially
degradation rate, but
the reaction rate
increases.
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3.6. Temperature
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Fig. 8. (a) Hydrophobic TiO2 coating before UV irradiation and (b) superhydrophilic TiO2 coating under UV irradiation [72].
have almost no effect on the photocatalytic performance. This shows TiO2 cement-based materials is greater than that of temperature. When
that the competitive adsorption of water molecules will attenuate the the nano-TiO2 cement-based material is in dry weather conditions, the
effect of temperature change on the adsorption capacity of TiO2. effect of temperature on the photocatalytic performance follows the
Therefore, the effect of humidity on the photocatalytic reaction of nano- above rules, and the suitable temperature range can be determined
Table 3
Comparison of the test environment parameters.
Experimental environment parameters Conclusions Reference
2
Light source wavelength Light intensity (W/m ) Relative Temperature
range (nm) Humidity(%) (℃)
254 68.9 10–90 25 The formaldehyde photocatalytic efficiency first increases and then [62]
decreases upon increasing the relative humidity and was best at 50
% RH.
315–400 6 0–90 23 At low initial reactant concentrations (260 ppb), an increase in the [74]
humidity had a negative effect on the degradation of the benzene
system. An increase in the initial reactant concentration to 2600 ppb
was optimal at ~ 50 % RH.
315–400 7.8 0–70 25 The adsorption capacity was negatively exponentially related to the [91]
relative humidity in the photocatalytic process.
315–400 10–40 35–65 23 The concentration of nano-TiO2 on the mortar surface has a lower [68]
effect on the photocatalytic process when the relative humidity is >
60 %. The NOx degradation efficiency increased with an increase in
the UV-A radiation intensity.
315–400 10–40 30–70 20 The NOx degradation rate increases with an increase in the light [27]
intensity, but there was an extreme value for the light intensity
effect. After exceeding the extreme value, further increasing the
light intensity has no effect on the photocatalytic reaction. An
increase in the relative humidity leads to a decrease in the NOx
degradation rate.
300–400 2–11 10–70 – When the light intensity increases, the NOx degradation rate [92]
increases.
When the relative humidity increases, the NOx degradation rate
decreases.
100–800 0.3–3 10–80 25 The UV intensity was positively correlated with both the NO and [50]
NOx removal rates. Upon increasing the relative humidity, the NOx
removal efficiency initially increases, reaches its peak value, and
then decreases.
High-pressure mercury High-pressure mercury – 25–60 In a certain range, the higher the light intensity and temperature, the [89]
lamp, fluorescent lamp, lamp > fluorescent lamp > higher the photocatalytic degradation efficiency. However, the
natural light natural light magnitude of the temperature effect on the photocatalytic
performance was small.
– – 10–90 10–50 A small variation in NOx adsorption and degradation with [94]
temperature was observed at a constant relative humidity. However,
the photocatalytic adsorption of the intermediate nitrite product
increases upon increasing temperature.
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Therefore, increasing the nano-TiO2 content and uniformity of distri Because the reaction rate and the adsorption equilibrium are con
bution on the surface of cement-based materials is beneficial to improve stant during the same photocatalytic reaction, only the effect of the
the effect of light intensity. In the actual service process, cement-based reactant concentration on the photocatalytic rate is considered in the
materials will encounter complex, variable and uncontrollable above model; the effects of changes in the other reaction parameters on
external environment. The effects of temperature and humidity on the the photocatalytic reaction rate are not considered. Wang [105] intro
photocatalytic efficiency of nano-TiO2 cement-based materials have duced parameters characterizing the changes in the reaction environ
both positive and negative effects. Therefore, the focus of the next ment with time based on a first-order kinetic equation, and the values
research is to firstly determine the suitable range of working environ obtained by fitting the experimental data were used to analyze the
ment parameters through mechanism analysis, and secondly to study photocatalytic reaction rate.
how to maintain the photocatalytic efficiency of cement-based materials k− k(1+t)α
in different external environments for a long time will be. Ct = C 0 e 1+α (8)
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effects of other influencing factors (e.g., temperature, relative humidity, equilibrium constant (K) does not accurately describe the changes in the
etc.) on the photocatalytic efficiency. adsorption capacity and adsorption mode, and the L–H model does not
successfully describe the effect of the adsorption capacity on the pho
4.2. Photocatalytic kinetic model considering the adsorption mode tocatalytic efficiency.
Table 4 compares and analyzes the common photocatalytic models
The L–H model assumes that the adsorption process is thermody that consider the adsorption mode. Pan et al. [106] introduced the
namically reversible when an ideal adsorption–desorption equilibrium concept of metastable equilibrium adsorption (MEA) theory into the
state is reached in the gas–solid and solid–liquid phases. At this time, the photocatalytic degradation kinetics and established an improved MEA-
adsorption equilibrium constant (K) is generally considered to be the L–H model, which can describe the effects of the adsorption amount and
ratio of the reactant adsorption density to the nano-TiO2 concentration adsorption bond strength on the degradation rate during the photo
when the adsorption equilibrium state is reached, which can describe catalytic reaction. Vorontsov et al. [107,108] investigated the FTIR
the effect of reactant adsorption on the photocatalytic efficiency [124]. spectra of acetone adsorbed on the surface of nano-TiO2 and found that
However, the adsorption density at the adsorption equilibrium state in two adsorption sites (Ti4+ and OH) exist on the surface of nano-TiO2,
the actual photocatalytic reaction process may be the total concentra both of which obey the L–H adsorption mode. However, the adsorption
tion of several reactants, corresponding to different adsorption modes equilibrium and reaction rate constants at the two adsorption sites were
and adsorption equilibrium states. Therefore, the adsorption significantly different. Therefore, Vorontsov established a two-site L–H
Table 4
Comparison of the photocatalytic kinetic models used to consider the modes of adsorption.
Model Name Adsorption Theoretical basis Research content Feature analysis Reference
type
MEA-L–H model Solid-liquid L–H model assumptions. To investigate the effect of the The Keq parameter describes the
[106]
phase Sub-stable equilibrium adsorption adsorption bond strength or adsorption magnitude of adsorption and the Kme
Gas-solid (MEA) theory. mode on the kinetic behavior of parameter describes the strength of the
phase photocatalytic adsorption. adsorption bond. Thus, the adsorption
equilibrium constantK = Keq × Kme . The
results show that the photocatalytic
degradation rate of H-acid on the TiO2
surface is more influenced by Keq and the
two parameters are influenced by the
adsorption mode. However, the model
kinetic parameters (Keq and Kme ) were
obtained by fitting the experimental data
and the applicability of the model under
other environmental conditions needs to
be verified.
L–H two-site Gas-solid Two types of adsorption sites exist on To investigate the effects of reactant The model defines the adsorption [107,108]
adsorption model phase the TiO2 surface (surface hydroxyl adsorption and the reaction rate on the equilibrium constants (K1 and K2) and
(⋅OH) and Ti4+ ions) and each obeys different adsorption sites on the TiO2 the reaction rate constants (k1 and k2),
the assumptions of the L–H model. surface on the kinetic behavior of respectively, according to the different
photocatalytic adsorption. adsorption amounts and reaction rates at
the two adsorption sites on the TiO2
surface. However, the model assumes a
unimolecular layer adsorption model
based on the L–H model and does not
consider the competitive adsorption
between the reactant molecules.
Competitive Gas-solid The model is based on the L–H model To investigate the effect of the The model is semi-empirical and semi- [109]
adsorption model phase assumptions. However, competitive adsorption amount of intermediate theoretical and can accurately predict the
for L–H adsorption of the intermediates is products on the TiO2 surface on the photocatalytic degradation efficiency of
intermediates considered. kinetic behavior of photocatalytic acetone. However, the types of
adsorption. intermediates in the photocatalytic
process need to be determined and their
adsorption equilibrium constants need to
be determined by fitting a large amount
of experimental data.
L–H bimolecular Solid-liquid The model is based on the L–H model To investigate the effect of As described in section 4.2, the three [111,112]
adsorption model phase assumptions. However, it is intermolecular interactions on the types of bimolecular adsorption models
Gas-solid considered that there is an interaction adsorption sites on the TiO2 surface on are classified according to the
phase between the reactant molecules the kinetic behavior of photocatalytic intermolecular interactions on the
during the adsorption process. adsorption. adsorption sites on the TiO2 surface.
These models can explain the mechanism
of the interactions of the reactant
molecules in the adsorption process and
are widely used to describe the kinetic
behavior of photocatalytic adsorption in
different environments. However, the
models do not consider the differences
between the different adsorption sites on
the TiO2 surface.
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model to describe the photocatalytic degradation behavior of acetone photocatalytic reaction process.
using nano-TiO2. Some gaseous reactants will generate intermediate In summary, these models are improved theoretical models of
products during the photocatalytic degradation process that are adsor adsorption kinetics based on the L–H model, which are mainly used to
bed on the catalyst surface. These intermediates will affect the adsorp study the kinetic behavior of the adsorption process on the surface of
tion of the reactants. For example, phenol will generate four cement-based materials during the photocatalytic reaction. As shown in
intermediates during the photocatalytic degradation process, namely Table 4, we can judge the adsorption mode of photocatalytic reaction
catechol, hydroquinone, light ketone, and organic acid. Therefore, according to the type of reactants. Then, we can choose the corre
Ibrahim’s improved L–H model considers the effect of the intermediates sponding model to study the adsorption kinetic mechanism. However, in
adsorbed on the catalyst surface on the photocatalytic efficiency [109]. the service environment of cement-based materials, the process of
Fig. 1(a) shows that during the photocatalytic reaction, nano-TiO2 photocatalytic degradation of multiple reactants can exist on the ma
promotes the adsorbed oxygen and water molecules on the surface to terial surface at the same time. Therefore, the model needs to consider
form ⋅OH and O2⋅− after absorbing photon energy. The redox reaction multiple adsorption modes and establish a photocatalytic kinetic model
then occurs with the reactants adsorbed on the surface [110]. From this, that can characterize multiple adsorption modes. Although these models
it is clear that oxygen, water, and various reactant molecules will be consider the effects of the adsorption mode and adsorption capacity on
adsorbed on the surface of nano-TiO2 during the photocatalytic reaction. the photocatalytic performance, they do not mention the influence of
Consequently, three adsorption modes exist between the molecules as various reaction environment factors. The environment of nano-TiO2
follows: cement-based materials in service is complex and variable, and the
photocatalytic process is also affected by relative humidity and light
(1) The molecules do not react with each other and adsorb on intensity. Therefore, it is important to study the photocatalytic adsorp
different adsorption sites. tion kinetic model considering the effects of these factors.
(2) The molecules do not react with each other, but compete for the
same adsorption sites.
4.3. Adsorption kinetic models considering the effect of a single factor
(3) The molecules react with each other and compete for the same
adsorption sites.
In order to investigate the effect of a single reaction environmental
factor on the photocatalytic reaction, some researchers have established
Based on the above analysis, many researchers have improved the
photocatalytic adsorption kinetic models using the single factor effect,
L–H model and established the L–H bimolecular adsorption model (as
as shown in Table 5. From Section 3.4, the relative humidity has both
shown in Table 4). The L–H bimolecular adsorption model can not only
promoting and inhibiting effects on the photocatalytic adsorption ki
characterize the effect of the adsorption amount on the photocatalytic
netics of nano-TiO2 cement-based materials. Therefore, the adsorption
rate using the adsorption equilibrium constant, but also reflect the effect
kinetic model considering the effect of humidity needs to explain the
of the different adsorption modes and adsorption amounts on the
following aspects of the photocatalytic adsorption kinetics mechanism:
Table 5
Comparison of the photocatalytic reaction adsorption kinetics models considering the influence of a single factor.
Model Adsorption Adsorption model type Influencing Feature analysis Reference
Name type Factors
Zhang Gas-solid Semi-empirical L–H Humidity Equation (9) shows the reaction rate constant can be defined in the model as a [113]
phase adsorption model function of the relative humidity and the photocatalytic reaction rate constant is
linearly related to the inverse of the relative humidity. However, the model does
not consider the effect of the competing adsorption of water molecules on the
photocatalytic adsorption kinetics.
Yu Gas-solid L–H bimolecular adsorption Humidity The model considers the existence of the competing adsorption of water [114]
phase model molecules and VOC gas molecules in the photocatalytic reaction, but does not
consider the effect of the relative humidity on the reaction rate and change in the
adsorption constants during the competing adsorption process.
Serhane Gas-solid L–H bimolecular adsorption Humidity The model defines two types of adsorption constants considering the competitive [115]
phase model adsorption of water molecules and VOC gases: 1) the adsorption equilibrium
constant of water molecules and reactants and 2) the competitive adsorption
equilibrium constant. The results show that the optimal relative humidity range is
from 35 to 45 %.
Devahasdin Gas-solid L–H bimolecular adsorption Humidity NOx photocatalytic adsorption degradation model considering the competitive [116]
phase model, adsorption relationship between water molecules and NO, as well as the effect of
Competitive adsorption intermediates on the kinetics of the photocatalytic adsorption process.
model for L–H intermediates
Li Solid-liquid L–H model Light intensity Only considering the effect of light intensity, the adsorption equilibrium constants [78]
phase and reaction rate constants are all functions of the light intensity, which requires a
large amount of experimental data to be fitted.
Vanesa Gas-solid Empirical model Light intensity The model does not consider the effects of the intermediate products and
[117]
phase competing adsorption of water molecules. However, the irradiation uniformity of
the photocatalyst surface is considered and the local surface photon absorption
rate (ea,s ) is calculated. The model is an empirical formula with several kinetic
parameters obtained by fitting the experimental data. The applicability of the
model to other reactants (e.g., VOC gases) needs to be verified.
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Table 6
Comparison of photocatalytic reaction adsorption kinetics model considering the influence of multiple factors.
Model Reactants Influencing factors Model experimental conditions Feature analysis Reference
Name
Yu Formaldehyde Reactant concentration, Formaldehyde concentration: 170–900 Based on the four-variable adsorption kinetic [83]
relative humidity, ppb, relative humidity: 10–70 %, UV model, effective optimization measures to increase
temperature, and light intensity: 0.21–0.90 mW/cm2, and the photocatalytic reaction rate in winter and
intensity temperature: 15–45 ℃ summer were proposed.
John. C Trichloroethylene Light intensity and TiO2 Nano-TiO2 concentration: 0.1–2 mg/L, The model fits well with the experimental results in [119]
(TCE) content TCE concentration: 750–8500 μg/L, and the applicable range, but the accuracy of the
UV intensity: 83.2–743.2 mW/L. prediction of the photocatalytic degradation
efficiency for compounds outside the applicable
range and other types of compounds needs to be
verified.
Puma Trichloroethylene Reactant concentration, TCE concentration: 0–8 μmol, flow rate: The model is able to predict the photocatalytic [125]
(TCE) relative humidity, and light 4 L/min, water vapor concentration: degradation rate of TCE on the TiO2 surface and
intensity 0–1000 μmol, and UV light intensity: propose a method to estimate the kinetic
15.5 W/m2. parameters, which is applicable to the prediction of
the TCE photocatalytic degradation efficiency in
reactors with different geometries. However, the
accuracy of the model to characterize the
photocatalytic adsorption kinetics of other types of
compounds needs to be verified.
Hunger NOx Reactant concentration and NO concentration: 0.05–5 ppm, flow The model can predict the NOx degradation [121,126]
flow rate, light intensity and rate: 1–5 L/min, light intensity: 1–10 W/ efficiency, calculate the reaction rate constant and
relative humidity m2, relative humidity: 10–70 %, adsorption equilibrium constant, and define the
temperature: 20 ℃. relationship between the relative humidity and
adsorption equilibrium constant.
Yu NOx Reactant concentration and NO concentration: 0.1–1 ppm, flow rate: The model considers the competing adsorption [123]
flow rate, relative humidity, 1–5 L/min, UV intensity: 1–13 W/m2, behavior of the intermediate NO2 product, which
light intensity, and TiO2 and relative humidity: 10–70 %. can explain the photocatalytic degradation
content mechanism of NO under indoor air conditions.
However, the accuracy of describing the kinetic
behavior of the photocatalytic adsorption of
organic pollutants, such as volatile organic
compounds (VOCs), indoors needs to be verified.
The main influencing factors to be considered are different for the The more influencing factors considered in the model, the more ac
different types of reactants studied. For example, inert intermediates are curate the prediction of the photocatalytic efficiency in an actual engi
generated during the photocatalytic degradation of benzene, which neering environment. For example, Yu’s model considered the effects of
cover the surface of the photocatalyst and affect the photocatalytic ef the pollutant concentration, pollutant flow rate, relative humidity, light
ficiency, while water can promote the decomposition of these in intensity, photocatalyst dosage, and reactor size on the photocatalytic
termediates, improving the photocatalytic efficiency. Doucet’s model performance, and the model prediction results were in good agreement
considered the relative humidity, benzene concentration, and flow rate with the experimental results [123]. Yu conducted an experimental
as the main influencing factors during the degradation of benzene [120]. study on the loading of nano-TiO2 on interior decorative walls and
Hunger’s model considered the external mass transfer and internal carried out the photocatalytic degradation of formaldehyde. A four-
molecular diffusion reactions of the pollutants. The model was improved variable model constructed on the basis of the three-variable model
by considering the relationship between the NO concentration, posi was established. Considering the effects of the following four factors:
tional competition between NOx and water molecules for adsorption, formaldehyde concentration, relative humidity, temperature, and UV
and the light intensity on the photocatalytic reaction. The relationships irradiation intensity, on the photocatalytic degradation of formalde
between the reaction rate and the light intensity and relative humidity hyde, the experimental results were in good agreement with those pre
were obtained as follows [121]: dicted [83].
{ From the discussion and analysis of the factors influencing the
photocatalytic reaction in Section 3, it is clear that there is an interaction
α8
k = α7 RH
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ (12)
k = α1 (− 1 + 1 + α2 E ) between different influencing factors on the kinetic behavior of photo
catalytic adsorption of nano-TiO2 cement-based materials. As
whereα1 ,α2 ,α7 ,α8 are fitting parameters, and E and RH are the light in mentioned in section 3.6 the mechanism of temperature effect on pho
tensity and relative humidity, respectively. tocatalytic reaction in humid weather conditions (relative humidity >
Shang’s model can be used to describe the competitive adsorption 50 %) is significantly different from that in dry weather conditions. In
behavior among three molecules (oxygen, water, and the reactant) and addition, it was mentioned in the discussion of section 3.4 that the light
the effect of the light intensity on the kinetic behavior of photocatalytic intensity had little effect on the photocatalytic performance of nano-
adsorption. By fitting the experimental data to obtain the constant term, TiO2 cement-based materials when the relative humidity was higher
the simplified equation was established as follows [122]: than 50 %. When considering the influence of multiple factors, there will
0.295Ch 0.0024CO2 be various interaction mechanisms among the factors. It is difficult to
Rh = 0.326I 0.58 ⋅ (13) quantitatively analyze the influence of a factor on the photocatalytic
1 + 0.295Ch + 0.098CW 1 + 0.0024CO2
12
Z.-M. Jia et al. Construction and Building Materials 370 (2023) 130462
performance and the interactions among the factors in the model. materials. However, they have both positive and negative ef
Therefore, most scholars currently use the introduction of empirical fects, which need to be considered in the experimental analysis.
parameters to modify the adsorption kinetic model of photocatalytic
reaction influenced by a single factor. This method can calculate the By comparing the classification of photocatalytic adsorption kinetic
photocatalytic efficiency of cement-based materials under the influence models, the following suggestions are provided to improve the function
of multiple factors. Also, the interrelationship between each factor and of each type of photocatalytic adsorption kinetic model used in engi
the adsorption equilibrium constant and the adsorption rate constant neering applications:
can be determined (e.g., Eqs. (12) and (13)). However, these empirical
parameters need to be determined by fitting a large amount of experi (1) Photocatalytic kinetic models considering the adsorption mode
mental data. If the influencing factors change significantly, it is also do not take the effects of environmental factors into account.
needed to re-collect the experimental data to determine the empirical They are mainly used to study the influence of the adsorption
parameters. In summary, it is shown that although the more influencing mode and adsorption capacity of the reactants on the photo
factors considered in the model, the more accurate the prediction of catalytic performance of cement-based materials during the
photocatalytic efficiency during the actual service of cement-based photocatalytic process. Therefore, the adsorption mode should be
materials. But the more empirical parameters need to be determined determined according to the type of reactants, and an appropriate
will be more. Therefore, how to determine the interdependence of multi- photocatalytic kinetic model should be selected. The next step for
factor influencing parameters, such as the influence of humidity and researchers should be focused on establishing photocatalytic ki
temperature in the model, through mechanism analysis will be the focus netic models that can characterize a variety of adsorption modes.
of further in-depth research. (2) Single-factor photocatalytic adsorption kinetic models are used to
As shown in Table 6, the multifactor-influenced adsorption kinetic study the photocatalytic adsorption kinetic mechanism in regard
model can more accurately describe the photocatalytic adsorption ki the effect of a single factor on nano-TiO2 cement-based materials.
netic behaviors of nano-TiO2 cement-based materials during the service However, it is known that the mechanisms of some influencing
process when experiencing changes in degradant concentration, hu factors on the photocatalytic adsorption kinetics can be affected
midity, light intensity, temperature and other factors. And predict its by other environmental factors, as outlined in Section 3. How
photocatalytic efficiency. The most effective way to improve the pho ever, single-factor photocatalytic adsorption kinetic models
tocatalytic efficiency of nano-TiO2 cement-based materials can be ach cannot characterize these combined effects. Therefore, re
ieved by analyzing the coupled influence mechanism of multiple factors. searchers should investigate the relationship between the influ
However, these models are all semi-empirical and semi-theoretical with encing factors and study the photocatalytic adsorption kinetic
many kinetic parameter variables, which need to be determined by mechanism when multiple factors are combined. This could
fitting a large amount of experimental data. Moreover, the prediction establish a multifactor-influenced photocatalytic adsorption ki
results obtained using these models are good within a specific range of netic model that could be used to provide a theoretical basis for
experimental conditions. Therefore, further experimental validation is the photocatalytic performance.
needed for the prediction of the photocatalytic efficiency under other (3) The multifactor-influenced photocatalytic adsorption kinetic
environmental conditions. model can accurately describe the photocatalytic adsorption ki
netic behavior of nano-TiO2 cement-based materials in engi
5. Summary and prospects neering environments and predict their photocatalytic efficiency.
However, a large amount of data fitting is required to determine
According to the analysis of the factors influencing the adsorption the kinetic parameters in the model equations. Therefore, the
kinetics of photocatalytic reactions described in this review, the applicability of this type of model requires further validation.
following suggestions have been provided to improve the photocatalytic (4) Since the models summarized in this paper have been optimized
performance of nano-TiO2 cement-based materials: and improved based on the L–H model, none of them consider the
effect of the random distribution of nano-TiO2 on the surface of
(1) Nanoscale anatase TiO2 should be selected as a suitable photo cement-based materials on the photocatalytic efficiency. There
catalyst in cement-based materials. In addition, the photo fore, further studies on these models should consider the influ
catalytic activity can be improved by modifying the crystal ence of the content and distribution of nano-TiO2 on the
structure of TiO2. photocatalytic performance of cement-based materials.
(2) The dispersion process can improve the content and homogeneity
of TiO2 nanoparticles on the surface of cement-based materials. Declaration of Competing Interest
Ultrasonic treatment and surfactants are the two most common
and effective dispersion methods used to date. The authors declare that they have no known competing financial
(3) Optimizing the preparation process of nano-TiO2 cement-based interests or personal relationships that could have appeared to influence
materials. For the internal doping method, how to increase the the work reported in this paper.
nano-TiO2 content on the surface of cement-based materials is the
key issue. For the coating method, how to maintain the coating Data availability
photocatalytic durability is the key issue needing to be solved.
(4) The photocatalytic efficiency can be significantly improved when Data will be made available on request.
a low flow rate and high concentration of gas-phase reactants are
used. However, in an actual engineering environment, the con Acknowledgments
centration of reactants on the surface of cement-based materials
is difficult to control. Consequently, how to design the buildings’ This study was supported by the National Natural Science Founda
appearance so that the gas flow rate on the surface of cement- tion of China (Grant No. 12162025), Natural Science Foundation of
based materials can be reduced is a key issue to maintaining Inner Mongolia (Grant No.2021LHMS05010).
high photocatalytic efficiency.
(5) The relative humidity, temperature, and light intensity all affect
the photocatalytic performance of nano-TiO2 cement-based
13
Z.-M. Jia et al. Construction and Building Materials 370 (2023) 130462
14
Z.-M. Jia et al. Construction and Building Materials 370 (2023) 130462
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