Evaluation of Reducing NO and SO2 Concentration in Nano SiO2-TiO2 Photocatalytic Concrete Blocks.

The use of titanium dioxide in concrete block pavements is a promising approach to reduce air pollution in the roadside. When TiO2 is used as an additive of cement concrete or mortar, it is not dispersed uniformly due to agglomeration between particles causing the degradation of photocatalytic reaction. To improve the photocatalytic performance of TiO2, the Nano SiO2-TiO2 (NST) has been developed by coating TiO2 with SiO2 as a support using the sol-gel method. The environmental performance of concrete blocks incorporating NST as an additive was evaluated using both laboratory and full-scale chamber experiments. It was observed from laboratory environment chamber testing that the NO reduction efficiency of concrete blocks with 4% NST ranged from 16.5 to 59.1%, depending on the UV intensity. Results of the full-scale chamber test on NST concrete blocks indicated that the NO and SO2 reduction efficiencies were 22.3% and 14.4% at a 564 W/m2 of solar radiation, respectively. It was found that the increase in UV intensity and solar radiation had a positive effect on decreasing NO and SO2 concentration. In the future, the NST will be applied at in-service photocatalytic block pavements to validate the environmental performance in field conditions.

1. Introduction

With economic development led by rapid industrial growth, the air pollution has been steadily increasing, due to soot and sulfur oxides from factories and vehicle exhaust emissions, and it has become a rising common interest around the world [1,2]. As for the primary air pollutant NOx, road and non-road mobile pollutant sources account for the most proportion at 59%. NOx emitted from road mobile sources such as vehicles and stationary sources including industrial factories power generation facilities is a harmful air pollutant; NO emitted from vehicles is especially a serious problem in metropolitan areas [3,4,5]. In this regard, it is necessary to develop measures to reduce the NOx, including NO and NO2, from on-road mobile sources for the entire society.

The titanium dioxide (TiO2), one of the photocatalytic compounds, has various strengths, including physical and chemical stability, excellent acid resistance, alkali resistance, UV protection, dispersibility, durability, and high reactivity and activity [6]. TiO2 absorbs ultraviolet rays with a wavelength of 400 nm or less and is separated into high-energy electrons (e−) and holes (h+), which react with surface adsorbed oxygen and water to form active species, such as superoxide anions (O2−) and hydroxyl radicals (OH−), respectively. Due to the strong oxidizing power of the active species, TiO2 can decompose air pollutants, have a sterilization effect, and remove and absorb harmful gases [7]. It is expected that concrete products with excellent performance can be produced by mixing TiO2 with mortar and concrete. When it comes to road structures, it will be very effective in preventing air pollution, as TiO2 directly adsorbs and removes harmful gases emitted from vehicles. Its very large, specific surface area will maximize photocatalytic efficiency [8,9,10,11]. When the concrete material with TiO2 is applied to the road facilities, it will be very effective in reducing air pollution by directly absorbing and removing the harmful gases from vehicle emissions [12,13]. For this reason, Japan, Hong Kong, and some European countries use TiO2 for road structures and concrete blocks in removing air pollutants. In Italy, when photocatalytic (TiO2) cement was applied to the concrete block pavement of Borgo Palazzo Street in Bergamo, air pollution in the area was reduced by 30–40%. In Belgium, TiO2 block pavement was constructed over an area of 10,000 m2 in the Antwerp area, and air pollution decreased by about 20% one year after the construction. In Japan, TiO2 concrete block pavement was applied on an area of 50,000 m2 in Osaka, Chiba, Chigasaki, and Saitama-Shintoshin. As a result of the study, it was found that the photocatalytic pavements can remove 15% of NOx emitted from vehicles in motion and they have a higher NOx decomposition effect than roadside trees [12,14]. The use of higher content TiO2 in concrete material can interrupt the hydration reaction of cement, thus degrading the concrete’s strength [4]. When the TiO2 particles inside the concrete is not exposed to light sources or exhaust gases, it is difficult to trigger a photocatalytic reaction [15,16]. In particular, TiO2 of nano size with a large specific surface area was not dispersed due to agglomeration between particles, but rather was present as aggregates on the surface of the concrete block, thereby reducing the photocatalytic reaction [17].

In recent years, the nanotechnology has been dramatically developed through the continuous improvements in the production and characterization of solid materials [18,19,20,21,22]. The performance of solid materials is greatly affected by its surface and electronic properties when size is reduced to the nanoscale [23,24,25,26]. In particular, the aggregates are easily formed since nanomaterials have a large specific surface area and great unsaturated bonds when its size gets smaller [27,28]. Therefore, nano-sized TiO2 materials could not produce a sufficient effect with mortar and concrete as it exists as aggregates.

In order to improve the aggregation of nano-sized TiO2 in the binder, the nano-sized TiO2 interface should be deformed. Coating SiO2 as a support can create Ti-O-Si bonds on the nano TiO2 interface [29,30]. This type of chemical bonding can bring more negative charges to the surface of TiO2, which helps dispersion in water-based bonds on the electrostatic repulsion reaction. Accordingly, the dispersing force in the binder can be improved by decreasing the reduction of agglomerates. In addition, adding SiO2 as a support to cement is expected to create a pozzolanic reaction, improving concrete properties [31,32,33,34,35].

In order to solve the problems mentioned above, the SiO2-TiO2 material has been developed by coating TiO2 with SiO2 as a support using the sol-gel method. The developed Nano SiO2-TiO2 material was used to fabricate the concrete blocks. The environmental performance of the concrete blocks was evaluated based on the ability to remove air pollutants using laboratory and full-scale environmental chamber experiments.

2. Background

Photocatalyst

The utilization of TiO2 on pavement and road facilities has a significant effect on reducing NO, a primary source of fine particulate matter [36,37,38,39,40]. NO is considered the primary pollutant, which is mainly introduced into the atmosphere directly from high-temperature combustion in transport and industrial activities, whereas NO2 is considered a secondary pollutant, since it is mostly formed in the atmosphere due to the interaction between NO with O2 or O3 and/or sunlight. Photocatalysts are capable of decomposing various numbers of oxides and organic compound pollutants that cause health and environmental problems. The governing decomposition mechanism involves the generation of radicals due to the irradiation to the photocatalyst substance, and subsequently, converting pollutants into harmless compounds [36].

The photocatalytic process of TiO2 is described in nine reactions [41]. This process begins with irradiating UV light to the TiO2. When the TiO2 absorbs an equal or higher energy than the band gap, an electron is transferred from the valence band to the conduction band. The band gap energy of TiO2 in its anatase phase, which is mainly used as a photocatalyst, is 3.2 eV. (Equation (1)).

In this reaction, holes (h+), which has great reducing power, reacts with water (H2O) to generate hydroxyl radical (OH∙) (Equation (2)), which also presents high oxidizing power. Meanwhile, electrons (e−) accomplish the reduction of oxygen (O2) molecules to produce superoxide anion (O2−), which is very effective on pollutant’ degradation (Equation (3)). Thus the O2− produced reacts with H+ to dissociate in water to form HO2∙. (Equation (4)).

The mechanism by which O2− and OH− produced by the above reaction react with NOx and are removed is as follows.

According to Equations (5) and (6), OH∙ produced by the photocatalytic reaction reacts with NOx, NO, NO2, etc. to finally produce HNO3. The HNO3 is water-soluble and can be easily removed from the photocatalyst surface by an external environment, such as rain. The O2− generates HO2∙ by the reaction of Equation (4), and HO2 reacts with NO according to Equations (7) and (8) to finally produce HNO3.

In addition, in the NOx environment, as shown in Equation (9), NOx molecules react with O2− to generate NO3−, which effectively affects the removal of nitrogen oxides [42]. Similarly, purification of SO2 is as follows:

As shown in Equations (10)–(12), sulfuric acid (H2SO4) production from SO2 oxidation proceeds through a series of radical reactions. The HSO3 radical then rapidly reacts with molecular oxygen (O2) to yield SO3. SO3 reacts with atmospheric moisture (H2O) to form H2SO4. The finally produced H2SO4 can be easily removed from the photocatalytic surface by external environments, such as rain.

3. Materials and Experiment Method

3.1. Materials

3.1.1. Nano SiO2-TiO2

In order to improve the photocatalysis efficiency of TiO2, the TiO2 material had been developed as an anatase crystal phase with a larger specific surface area and excellent photodissociation. Various attempts had been made, including sputtering, which was a process in which TiO2 was directly and physically coated on a proper solid support. Although the specific surface area of TiO2 was large, it was difficult to achieve a proper photocatalytic effect due to aggregation of nano-sized particles in the mixture with a binder. To solve these problems, the Nano SiO2-TiO2 (NST) had been developed using the Sol-gel method in this study.

As for starting materials, TTIP [Titanium Isopropoxide; Ti(OC3H7)4] (Sigma-Aldrich, Seoul, Korea) was used as the precursor of TiO2; TEOS [Tetraethyl Orthosilicate; Si(OC2H5)4] (Sigma-Aldrich, Seoul, Korea) as the precursor of SiO2; nitric acid (HNO3) (Sigma-Aldrich, Seoul, Korea) as the catalyst; and ethanol (EtOH) and iso-propanol (IPA) as the solvent (Sigma-Aldrich, Seoul, Korea). The NST was processed as shown in Figure 1, and the physical properties of the NST were shown in Table 1.

Figure 1

Production process of NST [43].

Table 1

Physical properties of NST.

Density(g/cm3)	Surface Area (m2/g)	Particle Size(nm)	Pore Volume(cm3/g)	Pore Size(Å)	pH
2.4	337	6.3~11.5	0.31	52	6~6.5

TEOS and EtOH were stirred at a molar ratio of 1:1, at 600 rpm or higher, for one hour.

HNO3 and distilled water were stirred at a molar ratio of 1:150, at 600 rpm or higher, for one hour.

The solutions prepared in steps 1 and 2 were stirred at 600 rpm or higher for five hours.

TIP and IPA were stirred at a molar ratio of 1:1 at 600 rpm or higher for one hour.

The solutions prepared in steps 3 and 4 were mixed and stirred at 800 rpm for 24 hours.

The mixture prepared in step 5 was refluxed at 80 °C for six hours.

The prepared NST slurry was washed and filtered for neutralization.

The NST slurry was dried at 80 °C for 48 hours.

Heat treatment was applied to the dried NST at 450 °C for six hours.

The heat-treated NST was ground.

The main performance of NST developed according to the existing research results were as follows [43]: Figure 2, Figure 3 and Figure 4 presented the results of the SEM (Akishima, Tokyo, Japan), XRD (Bruker-AXS, Shibuya, Tokyo, Japan), and UV-Vis (Gangnam, Seoul, Korea) analysis for NST with optimum mix proportion. It was found from Figure 2 that there was only the peak of anatase phase with excellent photocatalysis. However, the peaks of the rutile and brookite phases were not observed, because SiO2 with relatively better thermal properties interrupted the phase transition during the heat treatment process. Results of the SEM analysis in Figure 3 showed no aggregation of NST or single phases of TiO2 or SiO2.

Figure 2

XRD pattern of NST.

Figure 3

SEM images of NST: (a) NST (10,000×); (b) NST (50,000×).

Figure 4

UV-Vis absorbance of NST.

As shown in Figure 4, it was well known that TiO2 was activated in the wavelength range below 380 nm to act as a photocatalyst. The UV/Vis spectrophotometer testing was conducted to analyze the absorption spectra of NST. Test results showed that UV absorption peak of NST was found in the ultraviolet range below 380 nm, with much higher absorption than general TiO2.

3.1.2. Cement

The cement used for this study was ordinary Portland cement (OPC) (Hanil, Seoul, Korea), which had a density of 3.14 g/cm3 and Blaine fineness of 3,492 cm2/g. The physical and chemical properties of OPC were as shown in Table 2.

Table 2

Physical and Chemical properties of OPC.

Density(g/cm3)	BlaineFineness(cm2/g)	Chemical Properties (%)
		SiO2	Al2O3	Fe2O3	CaO	MgO	SO3	Ig.loss
3.14	3,492	21.1	4.65	3.14	62.8	2.81	2.1	2.18

3.1.3. Silica Sand

The fine aggregate used in this study, silica sand (Hanil-Eco, Gongju, Korea), was used instead of general natural fine aggregate, and the physical properties of silica sand were shown in Table 3.

Table 3

Physical properties of silica sand.

Type	Density (g/cm3)	Diameter ofParticle (mm)	Absorption (%)	SiO2 Content (%)
#4	2.61	0.8∼1.18	0.8	97.2

3.1.4. Aggregate

The coarse aggregate used in this study was crushed stone (Hanil-Eco, Gongju, Korea). The grain size of the aggregate was 5 to 8 mm, and the physical properties of the coarse aggregate were shown in Table 4.

Table 4

Physical properties of aggregate.

Grading (mm)	Density (g/cm3)	Unit Weight (kg/m3)	Absorption (%)	Ratio ofAbsoluteVolume (%)
5~8	2.75	1.510	0.84	52

3.2. Production of Concrete Block

As a result of testing the mortar mixed with NST, the flow rate of the mortar decreased, and the strength increased as the NST replacement rate increased. The increase in the strength could be attributed to the pozzolan reaction of SiO2, the nucleation and filling effects of NST, and the formation of pores smaller than 50 nm within the mortar matrix. Accordingly, 4% was found to be the optimal amount of NST to mix in order to obtain the target strength and flow value without using excessive chemical admixture.

Table 5 showed the mix proportions of the concrete blocks prepared in this study. The concrete block consisted of surface and concrete layers. As for the surface layer of the concrete block, which was 8 mm high, 4% of NST was applied to the mixture. For the 52 mm concrete layer, 5–8 mm aggregates were used. As shown in Figure 5, they were made into a standard square of 200 × 200 × 60 mm using equipment for manufacturing concrete blocks.

Table 5

Mix proportion of concrete block.

Type	Gradingof Agg.	W/B(%)	Thickness(mm)	Mix Proportioning (Ratio)
				OPC	NST	Aggregate
SurfaceLayer	Silica sandNo. 4	25	8	1	0.04	3
Type	Grading of Agg.	W/B (%)	Target Void Ratio (%)	Unit Weight (kg/0.7m3)
				OPC	Water	Aggregate
ConcreteLayer	5∼8 mm	25	6	413	95	1876

Figure 5

Manufacture of the concrete blocks: (a) material preparation; (b) manufacture; (c) block production; and (d) concrete block.

3.3. Experimental Program

3.3.1. Laboratory Experiment

A laboratory experiment was conducted to assess the capacity of the concrete block with NST to remove the NOx pollutants. The laboratory testing device (Ecotech, Knoxfield, Australia) with environment chamber was manufactured to evaluate the photocatalytic efficiency of concrete block specimens. The test setup was adapted from ISO 22197-1 (2007): “Test method for air-purification performance of semiconducting photocatalytic materials-Part1: Removal of Nitric Oxide” and UNI 11247: 2010: “Determination of the degradation of nitrogen oxides in the air by inorganic photocatalytic materials: continuous flow test method”. The developed experimental setup consisted of a pollutant source (gas cylinder of NO), zero air source, adjustable valves, humidifier, calibrator, photoreactor, and chemiluminescent NOx analyzer, as shown in Figure 6 and Figure 7.

Figure 6

Schematic representation of the experimental setup.

Figure 7

Laboratory experiment with environment chamber.

The calibrator controlled the NOx concentration flowing into the environment chamber, and a pressure gauge and a valve were in place to control NOx inflow. A T-shaped connector before the photoreactor was linked to the NOx analyzer to measure the concentration in the inlet. A gas mixture of NOx and zero air filled the photoreactor at the controlled humidity, flow, and NOx concentration.

The chamber’s photoreactor (500 × 500 × 500 mm) was fully sealed to maintain the controlled environment. All tests were performed at a temperature of 25 ± 2 °C and a humidity level of 40 ± 5%. UV light was placed above the photoreactor to simulate for photocatalysis.

The concrete block was placed in the center of the photoreactor, and the concentration of NOx was set to be 1.00 ppm by adding a gas mixture of NOx and zero air before the testing. The light source of the UV lamp was irradiated under three conditions of 10, 20, and 30 W/m2 for more than five hours to measure changes in the NOx concentration at one-minute intervals.

3.3.2. Full-Scale Environment Chamber Experiment

The full-scale environment chamber (KICT, Yeoncheon, Korea) had been constructed to evaluate the air pollutant reduction technologies on the roadside at the Korea Institute of Civil Engineering and Building Technology (KICT) near Yeoncheon, Korea (Figure 8). The chamber was a tunnel in shape, with a width of 11.4 m, a length of 22.8 m, and a height of 6.0 m. The total volume of this chamber was 1000 m3. This chamber was fabricated from transparent ETFE (Ethylene Tetrafluoroethylene) film to enable natural sunlight and ambient temperatures to govern the photochemical reactions occurring inside the chamber. The ETFE film was selected as the membrane material for the full-scale chamber structure because of its lightweight, high tensile strength, good durability, and high solar transmittance [44,45]. A previous study proved that ETFE films could supply sufficient natural sunlight for the photochemical reaction in the environment chambers, at an average of approximately 89% natural sunlight transmission at 300–1000 nm [46].

Figure 8

KICT Full-Scale Environment Chamber.

The environment chamber was divided into reference and testing chambers. The membrane layer was installed in the middle of chamber for perfectly blocking the transportation of aerosol and gas materials between the two chambers. The test data measured in the reference chamber was used to determine the wall loss rates and leakage rates of gaseous reactants and particles. It was applied to calibrate the measurement data in the testing chamber for the analysis. The temperature and humidity control systems were implemented at each chamber to maintain the designed environment condition. A total of 16 sensors at different heights were installed to monitor the temperature and relative humidity data inside the chamber during the testing.

The testing was conducted to determine NO/SO2 reduction efficiency of concrete blocks with TiO2 application using a full-scale environment chamber. The chamber was purged with rural background air prior to the experiment. The diesel and gasoline exhaust gas were generated from a 2010 Hyundai Star Rex (Hyundai, Ulsan, Korea) and 2019 Sonata engine (Hyundai, Ulsan, Korea), which were run under idling conditions. An air fan was used to uniformly diffuse the exhaust gas inside the chamber within a short period of time.

A total of 50 concrete blocks were placed at the center of the testing chamber with 4m2 of coverage area. The concrete blocks were exposed to natural sunlight for photocatalytic reaction by removing the aluminum cover after ensuring an equilibrium condition. The environment parameters such as temperature, relative humidity, and solar radiation were monitored during the testing at one-minute intervals.

4. Test result

4.1. Laboratory Experiment

Figure 9 illustrated the variation of NOx concentration during the laboratory environment chamber test for the concrete block sample treated with 4% of NST replacement rate under 30W/m2 of UV intensity. The inlet concentration reached equilibrium at 1 ppm before the light was turned on. After turning on the UV light, a fast drop of NO and NOx concentration in the outlet was exhibited, and the NO2 was produced from the NO oxidation. The light and gas supply were turned off after five hours of testing. For the test condition shown in Figure 9, the use of NST photocatalyst had a NO reduction of 59.1%, and the overall NOx reduction was 51.8%.

Figure 9

Variation of NOx concentrations during the experiment (UV intensity = 30 W/m2).

Figure 10 presented the effects of UV light intensity on NOx reduction efficiency. Results presented in Figure 10 showed that the NO/NOx reduction efficiency doubled with an increase of 10 W/m2 in UV intensity. As a result of the experiment, the concrete blocks using NST were capable of reducing the NOx concentration through photocatalysis. This fact proved that NST does not penetrate the cement pores and was evenly dispersed in the surface layer of the concrete blocks, since negative charges were formed due to the Ti-O-Si bond and activated interface.

Figure 10

Effects of UV light intensity on NOx reduction efficiency.

4.2. Full-Scale Environment Chamber Experiment

Figure 11 illustrated the variation of NO concentration measured in reference and testing chambers during the full-scale experiment for the concrete block specimens treated with TiO2 material. As shown, the NO concentration rapidly increased in both chambers, by injecting the exhaust gas for roughly 40 min, until NO concentration inside the chamber reached approximately 800 ppb. After stopping the gas injection, it took 20 min to ensure equilibrium conditions inside the chambers. Once the concrete blocks were exposed to natural sunlight in the testing chamber, a fast drop of NO concentration was exhibited due to the photocatalytic reaction of TiO2 material. To determine NO/SO2 reduction efficiency of TiO2 concrete blocks in the environment chamber, two hours of measured data were compared between the reference and testing chambers. The measured data in the reference chamber was used to calculate the absolute reduction of NO/SO2 concentration by considering wall loss and leaking phenomenon. The testing was conducted at different weather conditions and times to investigate the effects of solar radiation on NO/SO2 reduction efficiency.

Figure 11

Variation of NO concentrations during the experiment.

Figure 12 compared the nitrogen oxide (NO) concentration data measured from the reference and testing chambers for different levels of solar radiation. For the reference chamber, it was observed from test results that the NO concentration decreased linearly with time at 0.5~1 ppb/min.

Figure 12

Comparison of NO concentrations measured in testing and reference chambers at different levels of solar radiation: (a) Average Solar Radiation = 564 W/m2; (b) Average Solar Radiation = 358 W/m2; and (c) Average Solar Radiation = 67 W/m2.

As shown in Figure 12, the NO concentrations in the testing chamber were significantly reduced after the application of natural sunlight at high levels of solar radiation. The difference in NO concentration measured in the testing and reference chambers gradually increased with time due to the continuous photochemical reaction. However, there were no differences in NO concentration between the testing and reference chambers at very low solar radiation, indicating that the average 67 W/m2 of solar radiation was not enough for activating a photocatalytic reaction of concrete blocks with TiO2 application.

Table 6 presented the absolute reduction and reduction efficiency of NO measured after two hours in three different solar radiation levels. At high levels of solar radiation, the absolute reduction and reduction efficiency of NO were 0.145 ppm and 22.3%, respectively. It was found from this table that NO reduction efficiency tended to increase as the level of solar radiation increased.

Table 6

Summary of NO Absolute Reduction and Reduction Efficiency.

Test ID	AverageSolar Radiation (W/m2)	AverageUV Intensity (W/m2)	NO Concentration (ppm)		AbsoluteReduction (ppm)	ReductionEfficiency (%)
			Reference Chamber	TestingChamber
1	564	30.2	0.6508	0.5056	0.1452	22.3
2	358	19.8	0.5883	0.5247	0.0636	10.8
3	67	2.9	0.5802	0.5768	0.0034	0.6

Figure 13 presented the comparison of SO2 concentrations measured in the testing and reference chambers. It was observed from this figure that the SO2 concentration in the testing chamber could be reduced using TiO2 at 358 and 564 W/m2 solar radiation. Similar to the NO measurement results, the SO2 reduction efficiency of concrete blocks with TiO2 applications tended to increase with an increase of solar radiation. It was also found from the test results that the reduction efficiencies of SO2 were slightly lower than those of NO at high solar radiation levels.

Figure 13

Comparison of SO2 concentrations measured in testing and reference chambers at different levels of solar radiation: (a) Average Solar Radiation = 564 W/m2; (b) Average Solar Radiation = 358 W/m2; and (c) Average Solar Radiation = 67 W/m2.

Table 7 presented the measured SO2 reduction efficiencies for the concrete block that was treated with TiO2. It was found that the use of TiO2 photocatalyst materials had an SO2 reduction of 14.4% at 564 W/m2 of average solar radiation.

Table 7

Summary of SO2 Absolute Reduction and Reduction Efficiency.

Test ID	AverageSolar Radiation (W/m2)	AverageUV Intensity (W/m2)	NO Concentration (ppm)		AbsoluteReduction (ppm)	ReductionEfficiency (%)
			Reference Chamber	TestingChamber
1	564	30.2	13.106	11.22	1.886	14.4
2	358	19.8	11.668	11.155	0.513	10.0
3	67	2.9	11.145	11.259	−0.114	−1.0

5. Conclusions

This study evaluated the environmental effectiveness of incorporating NST as an additive to concrete blocks. The NST coated with SiO2 as a support was prepared using the sol-gel method and blended with a conventional concrete binder at 4% of replacement rate for concrete blocks. Prepared concrete block samples were evaluated for the NOx reduction performance using laboratory and full-scale chamber experiments. Based on the results of the experimental programs, the following conclusions may be drawn:

(1) Based on the results of the laboratory chamber test, the concrete blocks using NST were effective in reducing NOx pollutants in the air stream. The NO reduction efficiency ranged from 16.5 to 59.1%, and the highest NO reduction efficiency was achieved with a UV intensity of 30 W/m2. The increase in UV intensity positively affected the effectiveness of the NOx reduction capacity.

(2) Results of the full-scale environmental chamber test showed that the concrete blocks with NST was effective in reducing NO and SO2 pollutants. The maximum environmental performance was achieved at a 564 W/m2 with NO and SO2 reduction efficiencies of 22.3% and 14.4%, respectively.

(3) In the future, the field application of NST as a road material is required to validate the NOx and SO2 reduction efficiencies by considering various influencing parameters. In order to improve the photocatalysis efficiency of TiO2, the TiO2 material has been developed as an anatase crystal phase with larger specific surface area and excellent photodissociation. Various attempts have been made, including sputtering, a process in which TiO2 is directly and physically coated on a proper and solid support.