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Air Purification Performance of Photocatalytic Concrete Paving applied sciences Article Air Purification Performance of Photocatalytic Concrete Paving Blocks after Seven Years of Service Hubert Witkowski 1,*, Wioletta Jackiewicz-Rek 2, Karol Chilmon 2, Janusz Jarosławski 3, Anna Tryfon-Bojarska 4,5 and Arkadiusz G ˛asi´nski 6 1 Department of Building Physics and Building Materials, Lodz University of Technology, 90-924 Lodz, Poland 2 Faculty of Civil Engineering, Warsaw University of Technology, 00-637 Warsaw, Poland; [email protected] (W.J.-R.); [email protected] (K.C.) 3 Institute of Geophysics, Polish Academy of Science, 01-452 Warsaw, Poland; [email protected] 4 Skanska CDE, CEE Market, 00-877 Warsaw, Poland;[email protected] 5 SGH Warsaw School of Economics, 02-554 Warsaw, Poland 6 Institute of Ceramics and Building Materials, 02-676 Warsaw, Poland; [email protected] * Correspondence: [email protected]; Tel.: +48-502-746-797 Received: 28 March 2019; Accepted: 15 April 2019; Published: 26 April 2019 Abstract: This paper presents the results of laboratory tests on photocatalytic pavement blocks from a bicycle lane in Poland after seven years of service. Air purification performance was tested on dusty and clean samples using different light sources and setups, with non-laminar gas circulation. Secondary Electrons Secondary Ions (SESI) and InLens detectors combined with SEM–EDS and X-ray analyses were applied to confirm the presence of TiO2 in the studied blocks. The obtained results show that TiO2 was present in the form of agglomerates with a diameter of 0.25–5 µm and was bonded to the cement matrix components. The tested samples still maintained nitric oxide (NO) removal capability with a NO reduction rate of 4–45%, depending on light source and surface cleanliness. Keywords: photocatalytic concrete pavement; NO reduction; SEM analysis 1. Introduction The problem of deteriorating air quality in urban areas has become one of the major challenges of recent times. With the rapid growth of metropolises, the problem of airborne pollution increases [1]. Considerable attention is therefore given to solutions that may reduce the concentration of harmful compounds, such as nitrogen oxides (NOx), in the air. Short-term exposure to nitrogen dioxide (NO2) leads to irritation of the upper respiratory tract, and long-term exposure to NO2 leads to chronic diseases. Nitric oxide (NO) is significantly less harmful to human health, however, in contact with air it oxidizes to form NO2. The use of photocatalytic concrete in urban areas can contribute to a reduction in the concentration of NOx in the air. Concrete is the most common construction material in use, hence its adoption to reduce the concentration of NOx is a very promising solution. The implementation of photocatalytic cement-based materials has been the subject of a number of research projects and applications across Europe and North America [2–6]. The photocatalytic properties of these materials are provided by the use of TiO2 nanoparticles in cement, or in surface suspension. The mechanism of the photocatalytic reaction of TiO2 has been described by Fujishima and Honda [7]. When TiO2 (semiconductor) is illuminated with high-energy photons, whose energy is equal to or greater than semiconductor band–gap energy, electrons transfer from the valence band to the conduction band. This starts a series of oxidation–reduction reactions with substances adsorbed on the semiconductor surface, which leads to the creation of hydroxyl radicals (OH) (Figure1). Appl. Sci. 2019, 9, 1735; doi:10.3390/app9091735 www.mdpi.com/journal/applsci Appl. Sci. 2019, 9, x FOR PEER REVIEW 2 of 10 to the conduction band. This starts a series of oxidation–reduction reactions with substances adsorbed on the semiconductor surface, which leads to the creation of hydroxyl radicals (OH) (FigureAppl. Sci. 1).2019 , 9, 1735 2 of 9 Figure 1. Photocatalyticprocess scheme [8]. Figure 1.Photocatalyticprocess scheme [8]. The following process of NOx reduction can be illustrated with the following equations: The following process of NOx reduction can be illustrated with the following equations: hV, TiO2 + NO + OH , NO2 + H (1) −−−−−−−! NO + OH NO +H (1) hV, TiO2 + , NO2 + OH NO 3− +H (2) NO +OH−−−−−−−! NO +H (2) On a concrete surface, NO is created, which reacts with the cementitious compounds of concrete. On a concrete surface, NO3− 3− is created, which reacts with the cementitious compounds of concrete.Products Products of this reaction of this (nitric reaction soils) (nitric are removedsoils) are byremoved rainwater by fromrainwater the concrete from the surface. concrete As surface. a result Asof thisa result reaction, of this the reaction, concentration the concentration of nitric oxides of nitr in theic oxides vicinity in of the the vicinity surface of is the reduced, surface and is reduced, the effect andof air the purification effect of air is purification observed. is observed. The photocatalytic properties of concrete with the addition of TiO have been proved in a number The photocatalytic properties of concrete with the addition of2 TiO2 have been proved in a numberof laboratory of laboratory studies [studies9–14]. The[9–14 results]. The ofresults a research of a research described described by Beeldens by Beeldens [15] indicated [15] indicated that the thatmajor the factors majora factorsffecting affecting the reaction the arereaction UV lightare UV intensity, light intensity, surface exposure surface exposure to UV light, to UV pollutant light, pollutantconcentration, concentration, ambient temperature, ambient temperature, and air flow and rate. air Asflow the rate. research As the showed, research the showed, best results the werebest resultsobtained were at high obtained UV intensity, at high withUV aintensity, temperature with above a temperature 25◦C, with above low relative 25°C, with humidity low andrelative low humidityair flow. and low air flow. AnotherAnother important important aspect aspect is is the the durability durability of of the the air purifying capacity capacity over over time, time, especially in in thethe case case of of pavement pavement materials materials exposed exposed to to abrasion abrasion and soil. A A case case study study of of a a street street in in Bergamo Bergamo [16] [16] indicatedindicated thatthat pavingpaving blocks blocks may may still still show show a satisfactory a satisfactory air purificationair purificati performanceon performance after after two yearstwo yearsof service. of service. The same The studysame alsostudy indicated also indicated that the ethffatectiveness the effectiveness of the blocks of the was blocks strongly was dependent strongly dependenton surface cleanliness.on surface cleanliness. Research showed Research that show the reductioned that the of NOxreduction was significantly of NOx was higher significantly on days higherwhen theon pavingdays when blocks the were paving cleaned. blocks were cleaned. Unfortunately,Unfortunately, the number of studies on on air air puri purificationfication performance performance over over time time is is very very limited, limited, particularly in in relation relation to to the the effectiveness effectiveness of of the the blocks blocks after after long-term long-term usage usage in in a a moderate moderate climate, climate, where pavement materials are are exposed exposed not not only only to to abrasion and and soil, soil, but but also also to cyclic freezing and thawingthawing through through the the presence of deicing salt. ThisThis paper paper presents presents the the results of laboratory te testssts on pavement blocks collected from from a a bicycle lanelane in in Zielona Zielona Gora Gora (Poland). (Poland). The The aim aim of of the the study study was was to to verify verify the the air air purification purification performance performance of of photocatalytic concrete paving blocks after long-termlong-term service (seven years) in a moderate climate. 2. Experimental Procedure 2. Experimental Procedure Laboratory tests were conducted on two 330 150 80 mm exposed aggregate pavement blocks Laboratory tests were conducted on two 330 × 150 ×× 80 mm exposed aggregate pavement blocks (Figure2) collected after seven years of service from a bicycle lane that runs along one of the main (Figure 2) collected after seven years of service from a bicycle lane that runs along one of the main roads in the city. The pavements blocks were collected from the 2m2 area of the bicycle lane. The top roads in the city. The pavements blocks were collected from the 2m2 area of the bicycle lane. The top layer (5 mm thick) of each sample was made of concrete containing CEM II/A–S 42.5 R (EN 197-1) layer (5 mm thick) of each sample was made of concrete containing CEM II/A–S 42.5 R (EN 197-1) with nano-TiO2. The pavement blocks were produced in accordance with the EN 1339:2005 standard. with nano-TiO2. The pavement blocks were produced in accordance with the EN 1339:2005 standard. The characteristic bending strength declared by the producer was 5.0 MPa (each single bending test resulted in no less than 4.0 MPa according to EN 1339:2005), and the declared water absorbability was less than 6%. Appl.Appl. Sci. Sci. 2019 2019, ,9 9, ,x x FOR FOR PEER PEER REVIEW REVIEW 33 of of 10 10 TheThe characteristic characteristic bending bending strength strength declared declared by by the the producer producer was was 5.0 5.0 MPa MPa (each (each single single bending bending test test resultedAppl.resulted Sci. 2019in in no ,no9, 1735lessless than than 4.0 4.0 MPa MPa according according to to EN EN 1339:2005), 1339:2005), and and the the declared declared water water absorbability absorbability3 of 9 waswas less less than than 6%. 6%. FigureFigure 2. 2. Photocatalytic Photocatalytic concrete concrete pavement pavement block. block. SamplesSamples werewere tested tested to to determine determinedetermine photocatalytic photocatalyticphotocatalytic activity activity with with a aa special specialspecial test testtest setup.
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