1. Introduction
In recent years, human activities have caused a significant release of gaseous pollutants into the environment. These pollutants include volatile organic compounds (VOCs), nitrogen oxides (NO
x), sulfur oxide (SO
x) and particulate matter, which have resulted in severe environmental issues
[1]. These harmful substances can negatively impact human health, compromising the immune system and leading to conditions such as skin diseases, asthma, chronic respiratory diseases, cardiovascular diseases, and cancer. Shockingly, air pollution has been linked to approximately 26,000 to 48,000 deaths in European countries alone
[2]. In addition, these pollutants can also negatively impact plant growth, water and soil quality, and lead to ecosystem collapse, as well as contribute to climate change and global warming issues
[3]. Given the gravity of the situation, extensive research and environmental remediation measures are currently underway to address these concerns.
photocatalytic technology has been widely recognized for its potential to treat air pollutants
[4]. This innovative technology works by converting harmful gases into harmless substances, effectively reducing the harmful impacts of air pollution
[5]. Unlike conventional treatment methods, photocatalytic technology has low energy consumption and secondary pollution, in addition, photocatalysts are usually renewable and low-toxicity, which provide better environmental sustainability
[6]. Additionally, photocatalysis has a wide range of applicability and can be used to treat a variety of pollutants, including nitrogen dioxide, volatile organic compounds, formaldehyde, benzene, etc. [
4].
Based on these advantages, photocatalytic technology has been widely used in various fields, such as construction materials, air purifiers, and wastewater treatment. Especially in the field of building materials, photocatalytic building materials have become a new type of building material, and their potential in mitigating air pollution has received widespread attention [
7]. Photocatalytic building materials are capable of converting harmful gases, such as VOCs, NO
x and SO
x, into harmless substances through photocatalytic reactions. Additionally, they can decompose bacteria, viruses, and other microorganisms, improving indoor air quality. In recent years, many countries and regions have started to use photocatalytic building materials to combat air pollution. For example, in Japan, photocatalytic building materials accounted for 60% of the photocatalytic market sales in 2003 [
7]. They have developed a range of photocatalytic building materials by adding TiO
2 nanoparticles to glass, ceramics, and mortar to achieve photocatalytic functions of building materials, such as self-cleaning, antibacterial, and air purification [
8]. In China, many high-rise buildings and public places, including hospitals, schools, outdoor buildings, and roads, have begun using photocatalytic building materials to purify air and improve the indoor environment.
TiO
2 has received widely attention due to its simple preparation process, high stability, low toxicity and chemical inertness. [
9]. TiO
2-based photocatalytic building materials exhibit excellent photocatalytic performance and stability, effectively converting harmful substances in the air into harmless substances under light irradiation. Thus, their applications are of significant importance. Many methods have been studied for preparing TiO
2 nanoparticles, including sol-gel, hydrothermal [
10], vapor phase deposition [
11], and others [
12]. All of these methods can produce nanoscale TiO
2 particles, thereby improving the specific surface area and reaction activity of photocatalysts. In addition, photocatalytic building materials can be prepared by loading TiO
2 onto porous materials, which can improve the stability and mechanical properties of the photocatalytic materials and increase their reactivity [13, 14]. This preparation method is also widely used in the preparation of catalytic materials.
In recent years, TiO
2-based photocatalytic building materials have been widely investigated [14, 15]. However, TiO
2 has a low photocatalytic efficiency due to the fact that only 4% of UV light can be absorbed, additionally, the fast rate of light-induced electron-hole pair complexation leads to the low photocatalytic efficiency of ordinary TiO
2, which greatly limits its practical applications. In order to improve the TiO
2 photocatalytic efficiency, researchers have employed various strategies, such as surface chemical structure modification and loading onto nanomaterials to form composites [
16]. Moreover, other factors need to be considered in the preparation of TiO
2-based building materials, including the size of catalyst nanoparticles, structural stability, light-absorbing properties, catalytic activity, and mechanical strength, to ensure their long-term and effective operation. What is more, TiO
2-based building materials in the actual operation are practically optimized and adjusted for specific conditions, such as the angle of installation of the building materials, light conditions, pollutant types, concentrations, rainfall, etc., to achieve the best photocatalytic effect.
This paper reviewed recent advances in TiO2-based building materials for air purification. We discussed various preparation techniques for producing TiO2-based building materials, including sol-gel, hydrothermal, spray-drying, anodic oxidation, and microwave-assisted methods. In addition, to solve the problems of aggregation of TiO2 nanomaterials in suspension, poor adsorption ability, wide band gap, and high recombination rate, we discussed the strategies to improve the catalytic efficiency of TiO2-based building materials. Finally, based on practical application cases, we discussed the effectiveness of photocatalytic building materials in practical applications, the key factors affecting the catalytic efficiency as well as the limitations and future development trends of photocatalytic building materials.The purpose of this paper is to provide an effective reference for the development of highly efficient and stable photocatalytic building materials, and to improve the public's awareness of green buildings.
3. The Study Status of TiO2-Based Photocatalytic Building Materials
In recent years, there has been significant progress in the field of TiO
2 photocatalytic construction. TiO
2 has garnered considerable attention as a photocatalyst for organic pollutant degradation because of its chemical stability, low cost, and compatibility with most building materials
[24]. In fact, studies have shown that TiO
2 can react with metal oxides in cement to form stable compounds, such as CaTiO
3, which possesses a band gap energy of 3.5 eV and an isoelectric point pH of 3
[25].
Table 1 shows some of the studies on the addition of TiO
2-based nanomaterials to building materials to remove airborne pollutants respectively.
Researchers have developed various TiO
2 catalysts with different morphological designs, including nanoparticles, nanotubes, hollow fibers, and mesoporous materials, to improve their photocatalytic performance
[26]. Recent studies have extensively investigated the relationship between TiO
2 crystallinity, crystal phase, crystal size, surface area, pore structure, pore size, and its photocatalytic and adsorption capacities
[27]. The use of photocatalysts with building materials began in the early 1990s and since then TiO
2-modified building materials have been used for a variety of purposes such as environmental pollution remediation, self-cleaning and self-disinfection
[7]. TiO
2 is a versatile material that can be used both as a photocatalyst and as a structural component. This has led to its widespread use in a variety of building materials, both for exteriors and interiors, including cement mortars, exterior wall tiles, paving blocks, glass, and PVC fabrics. TiO
2-based photocatalytic building materials offer significant advantages and have great potential for a wide range of applications. These materials are compatible with conventional building materials such as cement, without altering any of their original properties. Additionally, they are effective even in ambient atmospheric environments with weak solar radiation
[28]. A growing number of research findings proved the viability of the technology in the construction industry. Cárdenas et al. [
29] conducted a study demonstrating that TiO
2 nanoparticles are highly efficient photocatalysts in cement paste, and the photocatalytic activity increased proportionally with the percentage of TiO
2 addition. Their findings revealed that cement paste containing 5% TiO
2 exhibited the highest NO
x removal rate. Additionally, Cheung et al.
[30] developed photocatalytic building materials by combining TiO
2 with local waste materials, such as cement, crushed glass, and sand, for NO degradation. Intriguingly, they discovered that lower density materials with higher porosity were more effective for NO degradation when mixed with less cement. Furthermore, Demeestere et al.
[31] reported that roofing tiles and corrugated sheets containing TiO
2 displayed remarkable photocatalytic activity by effectively removing toluene. They suggested that incorporating TiO
2 into building materials for photocatalytic materials has the potential to significantly contribute to air purification.
In summary, TiO2 shows great promise for photocatalytic building applications due to its high photocatalytic activity, compatibility with traditional building materials and effectiveness in ambient atmospheric environments under weak solar radiation.. However, the efficiency of low-cost TiO2-based building materials remains unsatisfactory, especially under visible-light or solar-light irradiation due to the wide band gap of TiO2 (3.2 eV). Consequently, the development of narrow band gap and efficient photocatalysts is essential for practical applications.
4. Preparation of TiO2 Photocatalytic Building Materials
The production of TiO2 photocatalytic construction materials involves several stages, such as selecting the suitable TiO2 nanoparticles, fabricating the construction materials, and integrating the nanoparticles into the materials. Several approaches have been documented in literature for the creation of TiO2 photocatalytic construction materials, which include sol-gel, hydrothermal, and spray-drying methods.
4.1. Sol-Gel Method
The sol-gel technique is a widely employed method for creating TiO2 photocatalytic construction materials. This approach involves the synthesis of TiO2 nanoparticles by hydrolyzing the titania salt in a solvent and incorporating a stabilizer to prevent the aggregation of the nanoparticles. The ensuing solution is then combined with a construction material such as concrete or gypsum and allowed to dry. This method results in nanoparticles that are uniform in size and shape, thereby increasing the photocatalytic efficiency of the construction material.
The sol-gel technique boasts a significant benefit in its cost-effectiveness, as well as its capacity to maintain precise control over the chemical composition of its products by employing a low reaction temperature. Furthermore, the sol-gel method yields nanoparticles that are uniform in both size and shape, thereby intensifying the photocatalytic activity of the building material. Nonetheless, this method is relatively slow and may produce nanoparticles that lack stability
[43].
It is worth noting that the sol-gel method can be used as a forming material in the manufacture of ceramics and can be used as an intermediate between metal oxide films in a variety of applications. Although the sol-gel method is a cost effective way of producing nanoparticles of uniform size and shape that can enhance the photocatalytic activity of building materials, it is a relatively slow process and the resulting nanoparticles can have low stability.
4.2. Hydrothermal Method
The hydrothermal method involves the synthesis of TiO2 nanoparticles in an aqueous solution under high pressure and temperature. In this method, the precursor solution is placed in a sealed vessel and heated to a high temperature, which promotes the formation of nanoparticles. The resulting nanoparticles are then mixed with the building material and allowed to dry. The advantage of the hydrothermal method is that it produces nanoparticles with a high surface area, which enhances the photocatalytic activity of the building material.
The hydrothermal method is one of the most commonly used methods for the synthesis of TiO
2 nanostructures. It has several advantages over other methods, such as appropriate crystallization temperatures, environmental friendliness, controlled reaction conditions, low energy consumption and low cost. Hydrothermal synthesis is a simple and effective method for the synthesis of TiO
2 nanostructures. It involves the use of alkali solutions such as lithium hydroxide, sodium hydroxide and potassium hydroxide as solvents
[44]. The concentration of the base solution used has an effect on the crystallinity, agglomeration ratio, particle size and specific surface area of the resulting TiO
2 phase
[44]. NaOH is the most commonly used solvent in material preparation techniques
[45]. However, the use of other alkali solutions (e.g. KOH) has been shown to affect the morphology and crystal structure of TiO
2 nanostructures obtained by hydrothermal methods
[45]. The use of different TiO
2 precursors as non-homogeneous photocatalysts can also affect the morphology of TiO
2 nanostructures obtained by hydrothermal methods
[46]. The photocatalytic performance of the synthesised TiO
2 products at different NaOH concentrations was evaluated by the toxic NO
x gas removal efficiency. The nanostructured TiO
2 samples prepared at higher NaOH concentrations showed higher nitrogen removal efficiency than the TiO
2-P25 precursor
[47]. In summary, the hydrothermal method is an effective way to synthesise TiO
2 nanoparticles with high specific surface area, enhancing the photocatalytic activity of the building materials. The use of different alkali solutions and TiO
2 precursor pairs can both affect the morphology and crystal structure of the materials. This affects the efficiency of TiO
2-based building materials in degrading pollutants.
4.3. Spray-Drying Method
The spray-drying method involves the synthesis of TiO2 nanoparticles by spraying a TiO2 precursor solution into a hot drying chamber. The hot air evaporates the solvent, leaving behind the nanoparticles, which are then collected and mixed with the building material. This method has several advantages:
Production of nanoparticles with a narrow size distribution to enhance the photocatalytic activity of building materials.
An efficient and scalable method for producing nanoparticles with a uniform distribution.
Allows the phase composition, crystal size and surface area of nanoparticles to be adjusted.
Although spray drying is an efficient and scalable method for the synthesis of TiO
2 nanoparticles, it has a number of limitations. One of the main disadvantages is that the method is highly dependent on the nature of the parent ion solution, such as its viscosity, surface tension and concentration. If the precursor solution is not properly formulated, the resulting nanoparticles may be of poor quality or not form at all
[48]. In addition, the method requires a large amount of energy to operate, which can increase production costs.
In conclusion, the preparation of TiO2 photocatalytic building materials involves the selection of appropriate nanoparticles, the preparation of the building materials, and the incorporation of the nanoparticles into the materials. Various methods have been reported in the literature for the preparation of TiO2 photocatalytic building materials, including sol-gel, hydrothermal, and spray-drying methods. These methods produce nanoparticles with different properties, which can affect the photocatalytic activity of the building materials. Therefore, the selection of an appropriate method depends on the specific requirements of the application.
4.4. Anodic Oxidation Method
The anodic oxidation technique represents an innovative method to generate photocatalytic building materials with TiO
2. This approach entails electrochemically oxidizing titanium metal or alloy in an electrolyte solution, which forms a porous TiO
2 layer on the surface. This resulting layer of TiO
2 can serve as a coating for a diverse range of construction materials, including but not limited to steel, aluminum, and glass. As a result of this method, TiO
2 nanoparticles are produced, which possess high porosity and surface area, as well as a morphology and crystallinity that can be adjusted, ultimately enhancing the photocatalytic efficacy of the building material
[49].
The anodic oxidation method presents certain advantages over alternative techniques, including a straightforward and eco-friendly process, direct formation of TiO
2 on the substrate without any binder, and a robust adhesion and durability of the coating. Nevertheless, this method is not without challenges, such as the necessity for high-quality titanium metal or alloy as the anode material, the complexity of maintaining uniformity and thickness of the TiO
2 layer, and the potential corrosion of the substrate by the electrolyte solution
[50].
4.5. Microwave-Assisted Method
The microwave-assisted method is a modern technique for synthesizing TiO
2 nanoparticles and integrating them into construction materials. This approach employs microwave radiation to heat and activate the titanium precursor and solvent in an enclosed vessel, producing TiO
2 nanoparticles. These particles are subsequently blended with a construction material such as cement or ceramic and cured under suitable conditions. The outcome of this method is TiO
2 nanoparticles with a high level of crystallinity and purity, as well as a narrow size distribution and a spherical shape, ultimately enhancing the photocatalytic efficacy of the construction material
[51].
The microwave-assisted method has several benefits over the other methods, such as a rapid and homogeneous heating process, a low energy consumption and environmental impact, and a facile control over the reaction parameters and product properties. However, this method also has some limitations, such as the requirement of special equipment and microwave-absorbing materials, the possible formation of hot spots and thermal gradients in the reaction vessel, and the difficulty in scaling up for industrial applications.
6. Application Status and Future Prospects of TiO2-Based Building Materials
Numerous practical applications have demonstrated the feasibility of integrating photocatalytic technology with building materials to achieve pollution and carbon reduction in buildings. In the preceding chapters, we discussed the preparation methods of photocatalytic building materials and the modification strategies of TiO2 to enhance the photocatalytc performance of TiO2-based building materials. In this chapter, we discussed some practical examples of photocatalytic building materials to further analyze the effectiveness and critical factors that influence the application of modified functional materials. Lastly, we discuss the limitations and future trends of photocatalytic construction in practice, aiming to deepen understanding of photocatalytic construction materials and provide a reference for the subsequent development of photocatalytic functional building materials.
6.1. Application Status and Key Influencing Factors of Photocatalytic Building Materials
After obtaining good results from laboratory-scale tests, the photocatalytic building materials have been used in practical applications, including office buildings, museums and transportation infrastructures.
Table 2 lists a number of demonstration projects using photocatalytic building materials. These materials have been employed in different countries such as China, Berlin, and the Netherlands, and have proven to be durable and effective through long-term field testing. For instance, the Toledo Specialist Hospital in Mexico City has employed tiles coated with TiO
2, produced by Elegant Decoration, a construction company based in Berlin. The photocatalytic façade was found to be effective in reducing pollution levels in the surrounding air, as confirmed by long-term field tests. Similarly, the Jubilee Church in Rome, Italy, features a TiO
2 coating on its façade, which has been shown to break down harmful pollutants like NO
x and VOCs into harmless compounds, while retaining the white appearance of the church and preventing the growth of vegetation. In addition, a segment of the north toll station of Nanjing Yangtze River Bridge, China, which spans an area of approximately 6000 m
2 and is situated in heavily polluted areas, employed loaded nano TiO
2 photocatalytic material. Researchers monitored pollutant levels in buildings within a few months and determined that the removal efficiency of NO
x exceeded 80%.
Despite the encouraging treatment outcomes of these demonstration projects, there are critical issues that must be addressed in the practical application of photocatalytic building materials. The first issue concerns the stability of the building's photocatalytic function. During the use of photocatalytic building materials, the material structure itself is insufficiently stable, leading to the deactivation of building materials. Moreover, during the degradation process of air pollutants, a significant number of intermediate products, such as VOCs by-products or airborne dust, accumulate on the surfaces of photocatalytic building materials, resulting in catalyst contamination and consequently, negatively impacting the building's photocatalytic function. Furthermore, the impact and quantification of production by-products have scarcely been reported. The environmental impact of the intermediate by-products produced during the degradation of pollutants in photocatalytic buildings remains unknown, and further research is needed to gain a deeper understanding of the impact of photocatalytic buildings on the environment.
In practice, photocatalytic building materials need to take into account a variety of factors, such as the catalyst, the installation environment and the building structure, to ensure that the photocatalytic building can operate in a stable and efficient manner. Therefore, photocatalytic building materials need to be selected from catalysts with high activity and stability, and their structures and morphologies need to be optimised to improve the degradation efficiency and stability of photocatalytic materials. To avoid the accumulation of intermediates and by-products, multifunctional catalysts, such as composites of TiO2 with other catalysts, can be tried to improve the catalytic activity and selectivity. Secondly, photocatalytic building materials need to be installed in a suitable environment to ensure their effective absorption of light and exposure in air. The location of the installation in the building, such as light openings, vents and walls, can also have a significant impact on the effectiveness of photocatalytic materials. When installing photocatalytic building materials, the reaction rate and light intensity of the material needs to be considered in order to achieve optimum degradation at the time and under the conditions of contact between the pollutant and the light. Finally, it is worth noting that photocatalytic building materials need to be matched to the structure of the building to ensure their effective application. The properties of photocatalytic building materials, such as light transmission, mechanical strength and durability, need to be taken into account during the building design phase. The coating and veneer materials on the building surface also need to be coordinated with the photocatalytic materials to ensure their degradation and aesthetics.
6.2. Future Perspective and Related Problem Discussions
In the future, the application of photocatalytic building materials in air pollution prevention is highly promising, as environmental protection awareness increases and technology advances. As urbanization accelerates, urban air pollution poses a significant threat to public health and quality of life. Therefore, using photocatalytic building materials in urban construction and planning can effectively enhance air quality. However, researchers are still exploring more efficient and stable photocatalytic building materials for better application in air pollution prevention and control. Both the government and enterprises should promote and apply photocatalytic building materials widely to maximize their environmental benefits. To better apply photocatalytic building materials in the real environment, the following technical challenges must be overcome:
Stability of photocatalytic materials: The stability of photocatalytic materials is critical in practical applications. It is important to study the stability of these materials, which undergo prolonged exposure to light and environmental factors, to improve their lifetime. Some factors that may affect the stability of photocatalytic materials include humidity, temperature, pH, pollutants, and microorganisms. Moreover, the photocatalytic materials may also degrade the substrates or binders that they are attached to, resulting in a reduction of mechanical strength and durability [
82]. Therefore, developing strategies to enhance the stability of photocatalytic materials and their substrates or binders is necessary for their long-term performance.
Photocatalytic reaction rate: The photocatalytic reaction rate is a key issue that affects the practical application of photocatalytic building materials. It is necessary to ensure that the reaction rate is fast enough to effectively degrade harmful substances in the air. Therefore, exploring different photocatalytic reaction mechanisms is necessary to increase the reaction rate. Some factors that may influence the reaction rate include light intensity, wavelength, catalyst loading, surface area, morphology, crystallinity, doping, and co-catalysts [
4]. Moreover, the reaction rate may also depend on the type and concentration of pollutants, as well as the presence of other substances that may interfere with the photocatalysis [
4]. Therefore, optimizing these factors to enhance the reaction rate is essential for achieving high efficiency and selectivity of photocatalysis.
Selectivity of photocatalytic materials: The selectivity of photocatalytic materials refers to their ability to selectively oxidize or reduce specific pollutants in the presence of other substances [
83]. Selectivity is important for achieving high efficiency and avoiding unwanted by-products or secondary pollution. However, most photocatalytic materials have low selectivity and tend to react with various organic and inorganic compounds in the air [
84]. This may lead to a decrease in photocatalytic activity and an increase in energy consumption. Therefore, designing and modifying photocatalytic materials with high selectivity for target pollutants is a key challenge for their application in air pollution control.
Economics of photocatalytic materials: The economics of photocatalytic materials involves the cost-effectiveness and feasibility of their production and application. The cost of photocatalytic materials depends on several factors, such as the type and amount of raw materials, the synthesis method, the fabrication process, the scale-up potential, and the maintenance cost. The benefits of photocatalytic materials depend on their performance, durability, environmental impact, and social acceptance [
58]. Therefore, evaluating and optimizing the economics of photocatalytic materials is essential for their widespread adoption and implementation in air pollution prevention.