Photocatalytic roads: from lab tests to real scale applications
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- Boonen, E. & Beeldens, A. Eur. Transp. Res. Rev. (2013) 5: 79. doi:10.1007/s12544-012-0085-6
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This paper gives an overview of our research on photocatalytic concrete, which exhibits air purifying properties. Under the action of sunlight, a catalyst present at the surface of the material is activated, enabling degradation of pollutants from the surroundings and transformation to less harmful products. It is a promising technique to reduce a number of air contaminants, especially at sites with a high level of pollution: highly trafficked canyon streets, road tunnels, etc. In addition, the combination with cement offers some synergistic advantages, as the reaction products can be adsorbed at the surface and subsequently washed away by rain. However, the great potential of this emerging technology is hampered by the lack of uniform testing methods at European level to evaluate the photocatalytic activity.
Laboratory research is undertaken at BRRC to compare existing methods and draw up recommendations for future standards. Furthermore, translation of lab testing towards results in situ remains critical to demonstrate the effectiveness on larger scale. In this perspective, several trial applications have recently been initiated in Belgium to asses the “real life” behavior.
The paper gives a short overview of the photocatalytic principle and the application in concrete, as well as some main results of the laboratory research recognizing the important parameters that come into play. In addition, the implementation efforts of some recent realizations in Belgium will be presented.
Already some very promising results towards air purification have been obtained. Nevertheless, further validation, also with modeling, is necessary to extrapolate the findings and enable a judicial implementation of photocatalytic road materials across the globe.
KeywordsConcrete roads Air (de-) pollution Heterogeneous photocatalysis Titanium dioxide Nitrogen oxides
Emission from the transport sector has a particular impact on the overall air quality because of its rapid rate of growth: goods transport by road in Europe (EU-27) has increased by 31 % (period 1995–2009), while passenger transport by road in the EU-27 has gone up by 21 % and passenger transport in air by 51 % in the same period . The main emissions caused by motor traffic are nitrogen oxides (NOx), hydrocarbons (HC) and carbon monoxide (CO), accounting for respectively 46 %, 50 % and 36 % of all such emissions in Europe ann. 2008 .
These pollutants have an increasing impact on the urban air quality. In addition, photochemical reactions resulting from the action of sunlight on NO2 and VOC’s (volatile organic compounds) lead to the formation of ‘photochemical smog’ and ozone, a secondary long-range pollutant, which impacts in rural areas often far from the original emission site. Acid rain is another long-range pollutant influenced by vehicle NOx emissions and resulting from the transport of NOx, oxidation in the air into NO3- and finally, precipitation of nitric acid with harmful consequences for building materials (corrosion of the surface) and vegetation.
The European Directives  impose a limit to the NO2 concentration in ambient air of maximum 40 μg/m3 NO2 (33 ppbV) averaged over 1 year and 200 μg/m3 (163 ppbV) averaged over 1 h. These limit values gradually decreased from 50 and 250 in 2005 to the final limit in 2010.
Heterogeneous photocatalysis is a promising method for NOx abatement. In a first part of this paper, the principle of photocatalytic materials will be elaborated, followed by a description of the past laboratory research indicating important influencing factors for the purifying process. Next, an overview of the results regarding the first pilot project in Antwerp  is given, and finally, different applications in Belgium that have recently been started, will be discussed.
2 Heterogeneous photocatalysis, a process for air purification
Heterogeneous photocatalysis with titanium dioxide (TiO2) as catalyst is a rapidly developing field in environmental engineering, as it has a great potential to cope with the increasing pollution. The impulse for the use of TiO2 as photocatalyst was given by Fujishima and Honda in 1972 . They discovered the hydrolysis of water in oxygen and hydrogen in the presence of light, by means of a TiO2-anode in a photochemical cell. In the eighties, organic pollution in water was also decomposed by adding TiO2 and under influence of UV-light (with wave lengths lower than 387 nm). The application of TiO2, in the photoactive crystal form anatase, as air purifying material originated in Japan in 1996 (see e.g. ). Since then, a broad spectrum of products appeared on the market for indoor use as well as for outdoor applications. Regarding traffic emissions, it is important that the exhaust gases stay in contact with the active surface during a certain period. The geometrical situation, the speed of the traffic, the speed and direction of the wind, the temperature, all influence the final reduction rate of pollutants in situ.
In the case of concrete pavement blocks [7, 8], the anatase is added to the wearing layer of the pavers which is approximately 8 mm thick. The fact that the TiO2 is present over the whole thickness of this layer means that even if some abrasion takes place by the traffic, new TiO2 will be present at the surface to maintain the photocatalytic activity. Another, similar application consists of using a double layered concrete with addition of TiO2 (in the mass and/or as dispersion on the surface) to the top layer, which will be discussed later on. The use of TiO2 in combination with cement leads to a transformation of the NOx into NO3-, which is adsorbed at the surface due to the alkalinity of the concrete . Thus, a synergetic effect is created in the presence of the cement matrix, which helps to effectively trap the reactant gases (NO and NO2) together with the nitrate salt formed. Subsequently, the deposited nitrate will be washed away by rain.
Up till now, UV-light (in the UV-A spectrum) was necessary to activate the photocatalyst. However, recent research indicates a shift towards the visible light . This means that applications in tunnels and indoor environments become more realistic. Especially the application in tunnels is worth looking at due to the high concentration of air pollutants at these sites. One of the projects in Belgium is focusing on this subject .
3 Laboratory results: parameter evaluation
In general, it can be stated that the efficiency towards the reduction of NOx increases with a longer contact time (larger surface area, lower air velocity, smaller height of air flow, higher turbulence at the surface), a lower relative humidity and a higher intensity of incident light. These are the conditions at which the risk of ozone formation in summer is the largest: high temperatures, no wind and no rain. At these days, the photocatalytic reaction will be more pronounced.
4 Pilot project in Antwerp
Besides the tests in the lab, on site measurements were also carried out. Since no reference measurements without photocatalytic material (prior to the application) exist, the interpretation of these results is rather difficult. Especially the influence of traffic, wind speed, light intensity and relative humidity are playing an important role. Detailed results can be found in . In brief, the field measurements suggested a decrease in NOx concentration at the sites with photocatalytic materials, where a levelling out of the peaks is visible. In any case, precaution has to be taken with the interpretation of data since these results are momentary and limited over time. But, at least, they give an indication of the efficiency of the photocatalytic pavement materials in situ, and a basis to work on for future applications.
5 Recent photocatalytic applications in Belgium
5.1 Life+-Project PhotoPAQ
5.2 INTERREG Project ECO2PROFIT
The broad environmental sustainability project ECO2PROFIT deals with the reduction of the emission of greenhouse gasses and sustainable production of energy on industrial estates in the frontier area between Flanders and Holland. To reach these goals, several tangible demonstration projects have been planned on industrial sites in Belgium and the Netherlands.
For the application of photocatalytic materials in a concrete road (and in general for any other type of application) a fundamental choice can be made between: mixing in the mass (TiO2 in cement) and/or spraying on the surface (dispersion of TiO2). The former has the advantage of a more durable action since the TiO2 will continuously be present, even after wearing of the top layer. On the other hand, the initial cost will be higher (higher TiO2 content, necessity for double layered concrete) and only the TiO2 at the surface will be active. In contrast, dispersing at the surface of a TiO2 solution will provide a more direct action, and a lower initial cost (e.g. “ordinary” cement). In this case however, the longevity of the photocatalytic action could be questioned because of loss of adhesion to the surface in time. This fundamental choice was also investigated within the research programme.
Effect of different materials in the mass
Effect of different dispersions on the surface
Influence of curing compound
Influence of curing and/or storing conditions
Effect of surface finishing
Simulation of durability
Apparently, the curing compound will initially inhibit the photocatalytic reaction, most likely because it is shielding off the active components from the pollutants in the air. Consequently, it is probable that the curing must disappear from the surface (normally after 1–2 months open to traffic and weathering) before the TiO2 will reach its optimal air purifying performance. In case of a TiO2 spray, this also means that it is best to apply the photocatalytic dispersion some time after the curing compound to have the best effect. Further measurements “on site” (see below) are planned to reveal the short and long term effect of the curing compound on the photocatalytic performance.
Besides the curing compound, also the storage and curing conditions of the concrete play a role, although to a lesser extent compared to the former. The effect is most pronounced in the case of absence of a curing compound, where it can be seen that more humid conditions have an adverse effect on the photocatalytic efficiency. This is related to the relative humidity conditions at the surface of the concrete and the competition effect between water and pollutants as described above. Moreover, the hardening process of the concrete will slightly differ depending on the curing conditions which could in turn affect the porosity of the surface and hence, also the photocatalytic action. This could be important in practice, because it is obviously hard to control these hardening conditions in situ.
The photocatalytic efficiency decreases by about 10 % after the brushing/washing operation. This demonstrates once again the need to assess the durability of these photocatalytic materials in situ and to check to longevity of the action after several years of service life.
In conclusion, the effect of the curing compound, curing conditions and surface finish has been clearly clarified, as well as the durability of the photocatalytic action in the lab. Based on these results and the optimization of the concrete composition, a proper selection of photocatalytic materials and of application procedures could be made, for the construction of double layered, photocatalytic concrete roads on the industrial zone “Den Hoek 3” in Wijnegem. A final choice has been made for the use of TiO2 integrated in the cement, plus afterwards a surface application of a TiO2 suspension, to be able to evaluate both types of applications and their durability.
6 Conclusions and perspectives
The use of photocatalytic pavement materials in order to minimize the air pollution by traffic is applied more frequently on site in horizontal as well as in vertical applications, also in Belgium. Laboratory results indicate a good efficiency towards the abatement of NOx in the air by using photocatalytic materials. Also, the durability of the photocatalytic action remains intact. However, the relative humidity is an important parameter which may reduce the efficiency on site. If the RH is (too) high, the water will be adsorbed at the surface and prevent the reaction with the pollutants.
Measurements on site in the past indicated a decrease of the pollution peaks due to the presence of the photocatalyst. Repeated measurements in the laboratory on photocatalytic concrete pavement blocks confirm the efficiency over time, even after more than 5 years of service life. Although a reduction in efficiency is evident due to the deposition of nitrate on the surface, the original efficiency can be regained by washing the surface.
The translation from the laboratory results to the “real” site efficiency is still a difficult factor, because of the great number of parameters involved. Hence, there is still a need for large scale projects to demonstrate the effectiveness of photocatalytic materials on site, including also other positive effects (O3, VOC’s, PM…). To this purpose, two recent applications have also been started up in Belgium, which show already some very promising results. Here, the influence of several parameters (curing compound, surface finish, weathering conditions) affecting the photocatalytic activity in a practical case of road construction has been assessed to guarantee an optimal implementation. Furthermore, the best results will be achieved by modeling the environment, validating the model by measurements and implementing the different parameters to asses the real life effect (e.g. ). One must bear in mind that photocatalytic applications are only effective in case of good contact between pollutants and the active surface. Parameters as wind, street configuration and pollution source play an important role.
The authors wish to thank IWT Flanders (Institute for the Promotion of Innovation by Science and Technology in Flanders), Life+ and EFRO (European Union), and INTERREG for the (financial) support of the different projects.
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