Construction and Building Materials 221 (2019) 375–383

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Influence of TiO2 incorporation methods on NOx abatement in

Engineered Cementitious Composites
Mingfeng Xu a,b, Yi Bao b,c, Kai Wu a, Tian Xia b, Herek L. Clack b, Huisheng Shi a, Victor C. Li b,⇑
a
School of Materials Science and Engineering, Tongji University, Shanghai 201804, China
b
Department of Civil and Environmental Engineering, University of Michigan, Ann Arbor, MI 48109, USA
c
Department of Civil, Environmental and Ocean Engineering, Stevens Institute of Technology, Hoboken, NJ 07030, USA

h i g h l i g h t s

Effect of three TiO2 incorporation methods on photocatalytic (PC) efficiency of ECC is studied.

Effect of three TiO2 incorporation methods on mechanical properties of ECC is studied.

Porous microstructure promotes the PC efficiency by increasing the exposure surface of ECC.

Alkaline environment of ECC consumes nitrate acid and promotes PC reactions.

a r t i c l e i n f o a b s t r a c t

Article history: Titanium dioxide (TiO2) nanoparticles have been incorporated in concrete to impart photocatalytic (PC)
Received 22 November 2018 properties, such as the self-cleaning and air purification functionalities, which are dependent on PC reac-
Received in revised form 9 April 2019 tions near the exterior surfaces of the concrete exposed to light. This study experimentally investigates
Accepted 5 June 2019
the effect of three TiO2 incorporation methods and surface patterns on the air-purifying functionality
Available online 18 June 2019
and mechanical properties of PC Engineered Cementitious Composites (PC-ECC). The air-purifying func-
tionality was evaluated by measuring the nitrogen oxides (NOx) concentration change with the presence
Keywords:
of PC-ECC plate specimens exposed to ultraviolet (UV) irradiation; uniaxial tensile and four-point bend-
Air purification
Engineered Cementitious Composites (ECC)
ing tests were conducted to evaluate the tensile and flexural properties of the PC-ECC plates; scanning
Functionally graded electron microscopy (SEM) was used to characterize the surface morphology of the plates; energy disper-
Nitrogen oxides sive spectroscopy (EDS) was used to map the element distribution on the surface. Test results indicate
Photocatalytic that the amount of TiO2 nanoparticles is reduced by 90% when TiO2 is incorporated through a thin layer
Surface on the exterior surface of the ECC plate, while PC functionality and mechanical properties are retained.
Incorporating TiO2 through polyurethane coating reduces the NOx abatement efficiency by 70–80%, com-
pared with directly mixing the TiO2 nanoparticles in ECC. The reduced PC efficiency is attributed to the
dense microstructure and low alkali content of the coating. This study advances the fundamental knowl-
edge for designing functionally graded PC concrete with optimized PC efficiency and mechanical
properties.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction fied in World Health Organization’s Air Quality Guideline [4]. As

Air pollution has been a serious environmental concern in many
major cities worldwide as a result of human activities. Although
different measures have been taken, such as issuing emission con-
trol policies [1] and using emission reduction devices [2,3], 95% of
the world’s population still live in areas where the PM2.5 (fine par-
ticles smaller than 2.5 lm) exceeds the limit (10 mg/m3) as speci-
⇑ Corresponding author.
E-mail address: vcli@umich.edu (V.C. Li).
one of the major precursors of PM2.5 formation, nitrogen oxides
(NOx) in air are responsible for many environmental, economic
and health concerns [5]. A plausible approach to alleviate air pollu-
tion is to impart air-purifying functionality into construction mate-
rials that are widely spread and closely tied with human activities.
One paradigm is to incorporate titanium dioxide (TiO2) in concrete,
which is commonly used in long-lasting and large-volume engi-
neering structures, such as buildings, pavements, bridges, etc. Con-
crete has substantial interaction with urban air pollutants due to
their large surface areas and locations within cities. Photocatalytic

https://doi.org/10.1016/j.conbuildmat.2019.06.053
0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.
376 M. Xu et al. / Construction and Building Materials 221 (2019) 375–383

(PC) concrete doped with TiO2 has shown great promise in NOx tion methods on the photocatalytic and mechanical properties of
abatement due to PC reactions [6–9]. In PC concrete under UV light ECC remain unclear.
irradiation, a valence band electron is promoted to the conduction In this study, three TiO2 incorporation methods are experimen-
band, creating an electron-hole pair and further generating highly tally investigated in terms of the NOx abatement efficiency and
active hydroxyl radicals (OH) that can convert NOx to less toxic mechanical properties of ECC plate specimens. The air-purifying
species such as nitrate ions [10]. Nitrate can dissolve in water, functionality was evaluated by measuring the concentration
washed away by rain, and finally utilized by plants [11]. It was change of nitrogen oxides (NOx) in a chamber where PC-ECC plates
reported that NOx abatement rates in TiO2 functionalized concrete were exposed to ultraviolet (UV) irradiation; uniaxial tensile and
pavements in the Netherlands [12] and France [13] were up to 45% four-point bending tests were conducted to evaluate the tensile
and 82%, respectively. and flexural properties of the PC-ECC plates; scanning electron
Engineered Cementitious Composites (ECC) is a family of high- microscopy (SEM) was used to characterize the surface morphol-
performance fiber-reinforced cementitious composites with ogy of the plates; energy dispersive spectroscopy (EDS) was used
extreme tensile ductility and strain-hardening behavior accompa- to map the element distribution on the surface. This study com-
nied by multiple cracking and tight crack width (typically less than pares different TiO2 incorporation methods in ECC and provides
100 lm) [14,15]. The tensile strength and strain capacity could insights into approaches to increase the cost efficiency while main-
impressively attain up to 18 MPa and 8%, respectively [15]. These taining the mechanical and photocatalytic properties.
properties have demonstrated values in enhancing structural resi-
lience and durability [14,16]. To date, ECC has been applied in var- 2. Experimental program
ious types of engineering structures in different countries.
Examples include (1) high-rise buildings in Japan, (2) link slabs 2.1. Materials
in bridge decks in the United States and Italy, (3) a composite
bridge deck in Japan, (4) repair material of the Mitaka Dam in The raw materials include the Type I Portland cement (C), fly
Japan, (5) tunnel linings in South Korea, (6) buildings in China, ash (FA), TiO2 nanoparticles, finely ground quartz sand (S), Polyvi-
and so on [17]. Recently, TiO2 nanoparticles have been incorpo- nyl alcohol (PVA) fiber and tap water (W). Cement and fly ash were
rated in ECC to impart the PC functionalities, such as the self- used as the binder (B), and their chemical and physical properties
cleaning function [18] and air-purifying properties [19]. The photo- are listed in Table 1. Particle size distribution of cement and fly ash
catalytic ECC (PC-ECC) holds promise for applications in engineer- is shown in Fig. 1. Finely ground quartz sand (F75) was adopted as
ing structures located in heavily air-polluted areas. These include, fine aggregate. The TiO2 nanoparticles (Aeroxide P25Ò) consisted of
for example, pedestrian bridges deck, paving block/slab, or other 81% anatase and 19% rutile, with an average particle size of 21 nm.
coating systems for pavements or roads (overlays, white topping,
etc.) [10,20,21]. To develop the PC-ECC, TiO2 nanoparticles are used
to impart the desired photocatalytic properties. However, the
incorporation of TiO2 nanoparticles may affect the other properties Table 1
of ECC, such as the tensile and compressive strengths and the ten- Chemical composition and physical properties of cement and fly ash.
sile ductility, due to multiple mechanisms, such as the ‘‘site effect” Composition and property C FA
of the nanoparticles with large specific surface. There is a need to
SiO2 (%) 19.51 38.35
develop ECC mixtures that have retained unique mechanical prop- Al2O3(%) 3.19 17.37
erties and photocatalytic functions. Fe2O3(%) 2.93 7.88
The incorporation of TiO2 nanoparticles may increase the mate- CaO (%) 63.50 24.01
rial cost. To enhance cost-efficiency, it is needed to investigate MgO (%) 2.90 3.86
SO3(%) 4.23 3.30
methods to incorporate TiO2. The most straightforward way is to Na2O (%) 0.07 1.23
introduce the TiO2 nanoparticles during concrete mixing as an K2O (%) 0.76 1.20
additive [7–9,12,22–24]. With a porous microstructure, concrete TiO2 (%) 0.28 1.84
has advantages to serve as the host of TiO2, because concrete pro- Loss of ignition (%) 2.60 0.88
Density (g/cm3) 3.15 2.71
vides an enlarged surface area that facilitates production of hydro-
xyl radicals that come into contact with NOx in air [24]. Since the
TiO2 nanoparticles must be exposed to UV light to initiate the PC
reactions, interior TiO2 particles are shielded and thus less reactive.
Therefore, the intermixing method is effective yet inefficient in
terms of the material consumption and PC efficiency. An alterna-
tive method is to disperse TiO2 in a coating material and apply
the coating to the exterior concrete surface exposed to light irradi-
ation. Typical coating substrates include water [25,26] and organic
paints such as polyurethane [27,28], epoxy [29], ethoxysilane [30],
etc. In the case of concrete as a structural material, water is inap-
propriate as the host of TiO2, because of insufficient bond between
TiO2 and hardened concrete after water vaporization. While
organic paints provide adequate bond, knowledge on the PC effi-
ciency and long-term durability are insufficient. Another paradigm
is to use multilayer concrete with the top layer containing TiO2 [6].
However, the interlayer bond strength and its implications for the
load-carrying capacity are unclear. A weak interlayer bond may
result in delamination and greatly compromise the mechanical
performance and long-term durability of the multilayer concrete.
Although there are various methods to incorporate TiO2 nanoparti- Fig. 1. Particle size distribution shows that the mean diameters of the cement and
cles in mortar or concrete, the effects of different TiO2 incorpora- fly ash are 17.7 lm and 36.2 lm, respectively.
 M. Xu et al. / Construction and Building Materials 221 (2019) 375–383
The micromorphological structure of TiO2 nanoparticles examined
using a transmission electron microscope (TEM, model: JEM-
2100F) is shown in Fig. 2. The PVA fiber (Kuraray Co. Ltd) has a sur-
face oil coating of 1.2% by weight; its detailed properties are shown
in Table 2.
Table 3 lists two ECC mixtures, designated as R-ECC and T5-ECC.
The R-ECC mixture does not contain any TiO2 and is used as the ref-
erence ECC mixture [31,32]; in the T5-ECC mixture, the binder was
partially replaced with TiO2 nanoparticles at a percentage of 5 that
has previously been proven to optimally balance the photocatalytic
and mechanical properties [33]. To ensure good dispersion of TiO2
nanoparticles and PVA fibers, a polycarboxylate-based superplasti-
cizer (SP) was used. The SP content was determined through the
flow table test [34] to make the mixtures achieve a slump spread
of 165 mm ± 5 mm. The PVA fiber content was set at 2% by volume
Fig. 2. Transmission electron microscope (TEM) image shows morphology of TiO2
nanoparticles dispersed in alcohol solution.
Table 2
Nominal properties of PVA fibers.
Length (mm) Diameter (lm) Elongation (%)
12 39 6 1300
Table 3
Mixture proportions.
Designation C FA
R-ECC 1 2.2
T5-ECC 1 2.2
*
Binder (B) includes cement (C), fly ash (FA) and TiO2.
Fig. 3. Schematic of three TiO2 incorporation methods to prepare PC-ECC: (a) intermix (ECC-I), (b) multilayer (ECC-M), (c) coating (ECC-C).
377
of the mixture. Except for the fiber content, the other ratios in
Table 3 are all by mass.
2.2. Specimens
Plate specimens measuring 76.2 mm in width, 304.8 mm in
length and 12.7 mm in thickness were prepared to test the NOx
abatement and mechanical properties. The three TiO2 incorpora-
tion methods are designated as intermix, multilayer, and coating,
as depicted in Fig. 3(a) to 3(c) to prepare PC-ECC. In Fig. 3(a), the
T5-ECC is used to cast the intermixing plate specimen (ECC-I). In
Fig. 3(b), the T5-ECC is applied on top of the R-ECC, forming a
functionally-graded structure (ECC-M). In Fig. 3(c), a transparent
polyurethane (PU) is used to prepare PC coating (ECC-C), in which
the PU was partially replaced by 5% TiO2 nanoparticles (by mass)
and applied as thin layer (0.25 mm ± 0.05 mm) on the top surface
of R-ECC. The TiO2 replacement content in ECC-C is made consis-
tent with that in T5-ECC, so that the mass ratio of TiO2/binder on
the surface of ECC-C and T5-ECC is roughly comparable.
Table 4 lists the specimens fabricated using the three different
TiO2 incorporation methods. For ECC-M, this study investigates
two thickness ratios, the ratios of T5-ECC layer thickness to the
total thickness, which are 0.1 (ECC-M0.1) and 0.4 (ECC-M0.4). To
study the effect of alkali on NOx abatement, three paint substrates
are investigated: (1) ECC-CP, with 5% TiO2 and 95% PU (mass ratio),
(2) ECC-CW, with 5% TiO2, 47.3% PU and 47.3% deionized water
(W), and (3) ECC-CS, with 5% TiO2 + 47.3% PU + 47.3% sodium
hydroxide (NaOH) solution (concentration: 1 mol/L).
The specimen ECC-I was directly cast in the mold for plate spec-
imens. The specimens ECC-M0.1 and ECC-M0.4 were cast in two
steps. The T5-ECC was placed at the bottom of the mold, and then,
the R-ECC layer was placed on top of the T5-ECC, both at fresh
state. After casting, the ECC specimens were placed on a vibration
table at moderate intensity for 30 s for better consolidation. The
molds were covered using a plastic sheet and cured in mold for
24 hours (h). After demolding, all specimens were cured in air at
a relative humidity of 55 ± 5% at 20 ± 1 °C until 28 days (d). The
Density (kg/m3) Young’ modulus (GPa) Normal strength (MPa)
42.8 1600
TiO2/B* W/B S/B SP Fiber (vol.%)
0.00 0.25 0.36 0.006 2
0.05 0.25 0.36 0.029 2
378 M. Xu et al. / Construction and Building Materials 221 (2019) 375–383

Table 4
List of investigated PC-ECC specimens.

Designation Incorporation method Topping material Substrate material Thickness ratio

ECC-I Intermix T5-ECC (5% TiO2) T5-ECC 1.00
ECC-M0.1 Multilayer T5-ECC (5% TiO2) R-ECC 0.10
ECC-M0.4 Multilayer T5-ECC (5% TiO2) R-ECC 0.40
ECC-CP Coating 5% TiO2 + 95% PU R-ECC 0.02
ECC-CW Coating 5% TiO2 + 47.3% PU + 47.3% W R-ECC 0.02
ECC-CS Coating 5% TiO2 + 47.3% PU + 47.3% NaOH solution R-ECC 0.02

specimens ECC-CP, ECC-CW, and ECC-CS were fabricated in two to NOx gas and UV irradiation. The uneven top (casting) surfaces of
steps. First, the R-ECC base was cast in the mold for plate specimen. the plate specimens and side surfaces of each specimen were
After the base hardened at 28 d, the PC coating was applied using a sealed using a low-viscosity epoxy before the NOx abatement test.
paint brush. Special attention should be paid to the preparation of The surface was pre-illuminated under two UV lamps (overall
the coating material, in particular, dispersion of the TiO2 nanopar- intensity: 10 W/m2) for 48 h to remove potential contamination
ticles. For ECC-CP, the TiO2 nanoparticles were dispersed in PU via on the surface.
ultrasonication for 60 minutes (min). For ECC-CW and ECC-CS, the Before the abatement test, NOx continuously flowed through
TiO2 nanoparticles were added in the water or NaOH solution, fol- the test setup for 2 h in darkness until its concentration stabilized
lowed by ultrasonication for 15 min, and then added to PU and at 1 ppm. This is done to saturate the adsorption of NOx by the con-
ultrasonicated for 60 min. tainer and specimen. A first-order kinetic model that considers the
Cube specimens with a 50 mm side length were cast using mor- gas flow rate (Q, L/min), initial NOx concentration (C0, ppm) and
tar that had the same mixture proportion as the R-ECC and T5-ECC reactor volume (V, L) is used to describe the NOx abatement reac-
but did not contain any PVA fiber. At the age of 28 days, a coating tions and quantify the reaction rate and efficiency:
layer was added on the top of the R-ECC cubic specimen, using the
same preparation procedure as ECC-CP, ECC-CW and ECC-CS. The dC
QC 0  QC  kCV ¼ V ð1Þ
four cube specimens in total were prepared for characterization dt
of the material microstructures.
where C (unit: ppm) is the NOx concentration at time t (unit: s); k is
the reaction rate constant (min1). Integrating Eq. (1) over time
2.3. Test methods gives Eq. (2):
 
2.3.1. NOx abatement test C t
The test set-up for NOx abatement evaluation is a continuous
¼ exp  þ Y0 ð2Þ
C0 B
reaction system, as shown in Fig. 4. The inlet gas contained
10 ppm NO (Airgas Inc, US), using N2 as the balance gas. Pressur-
Q V Q
ized lab air was used to dilute the NO from 10 ppm to 1 ppm in A¼1 ;B¼ ; Y0 ¼ ð3Þ
Q þ kV Q þ kV Q þ kV
the mixing chamber. Concentrations of NO, NO2, and the sum of
them, NOx concentration, were continuously measured using a A, B, and Y0 are model parameters that are functions of the flow
chemiluminescence NOx analyzer (model: ECO PHYSICS CLD 64) rate Q, reactor volume V and reaction rate constant k.
during the test. The flow rate was 1 L/min. The light intensity on Among the three model parameters, Y0 is a dimensionless resid-
the surface of specimen was 20 W/m2; the relative humidity in ual concentration index that represents the ratio of residual NOx
the reactor was 30% ± 2%; the temperature was 20 °C ± 2 °C; the concentration to its initial concentration in steady state (time
pressure was 1 atm. approaching infinity). Therefore, g in Eq. (4) represents the PC effi-
Only the flat smooth surface of the specimen (the surface in ciency that describes the percentage of reacted NOx. For a specific
contact with the smooth bottom surface of the mold) was exposed reaction with fixed flow rate (Q) and volume (V), the reaction rate

Fig. 4. Experimental setup for the NOx abatement test where the specimen is exposed to UV irradiation as NO gas flows through the reactor.
 M. Xu et al. / Construction and Building Materials 221 (2019) 375–383
constant (k) is determined through regression analysis using
experimental data of C(t).
g ¼ ð1  Y 0 Þ  100%
2.3.2. Flexural and tensile tests
Four-point bending test was conducted to evaluate the flexural
properties of the plate specimens under displacement control at a
constant displacement rate of 0.5 mm/min [35]. The test setup is
shown in Fig. 5(a). The span length was 228.6 mm, and the loading
span was 101.6 mm. The flexural strength was calculated using
Eq. (5):
6M u
fu ¼ 2
bh
where fu represents the flexural strength (MPa); Mu represents the
bending moment (Nm); b and h are the width (76.2 mm) and depth
(12.7 mm) of the slab, respectively.
In the testing of ECC-M0.4, the T5-ECC layer was at the bottom
subjected to tensile stresses. In the testing of ECC-M0.1, both sce-
narios (T5-ECC at the bottom and top) were tested. For the coating
specimens (ECC-CP, ECC-CW and ECC-CS), considering the very
thin coating, flexural and tensile tests were not conducted. The
mechanical properties of the coated specimens were considered
the same as those of the intermix specimen (ECC-I).
Plate specimens were also prepared for uniaxial tensile test.
Thin aluminum plates of size 51 mm  76 mm were epoxied to
both ends of the plate specimens to minimize possible stress con-
centrations from gripping fixtures of the tensile test system (Fig. 5
(b). Four specimens were fabricated and tested for each case. The
uniaxial tensile test was performed at a constant displacement rate
of 0.5 mm/min, in accordance with [36]. Two linear variable dis-
placement transducers (LVDT-1 and LVDT-2) were deployed on
each side of the specimen to measure length change in the gauge
length (about 80 mm). The exact gauge length was measured using
a caliber. The applied tensile force was measured using a load cell
(capacity: 100 kN) embedded in the load frame.
2.3.3. Microstructure characterization
To characterize the morphology and element distribution on
the surface of the PC-ECC specimens exposed to NOx, samples mea-
suring 10 mm  10 mm  10 mm were cut from the surface of the
specimen. Microscopic analysis was conducted using a SEM
(model: FEI Nova NanoSEM 450) with an accelerated voltage of
15 kV. The sample was coated with a thin layer of carbon conduct-
Fig. 5. Mechanical test set-up: (a) flexural and (b) uniaxial tensile test.
379
ing film for conduction. Energy dispersive spectrometry (EDS) was
applied to map elements (Ti, Ca, and Na) in T5-ECC, ECC-CP, ECC-
CW and ECC-CS. The magnification was 100,000, with an area of
ð4Þ
3 lm  4 lm. The scanning time was about 15 min for each EDS
scan.
3. Results and discussion
3.1. Mechanical properties
Fig. 6 (a) and 6(b) respectively show the tensile and flexural test
results of the intermix and multilayer specimens. All the investi-
gated specimens show strain hardening behavior and the tensile
ð5Þ ductility beyond 3.0% (Fig. 6(a)). After first cracking, the ECC con-
tinues to bear higher loads. During the strain hardening stage, vol-
umetric inelastic strain deformation that is analogous to plastic
yielding of ductile metal is revealed, accompanied by multiple
microcracks. Similarly, in Fig. 6(b), the investigated ECC specimens
exhibits deflection hardening behavior: the flexural stress
increases up to 14–16 MPa with the mid-span deformation
increased to 20–25 mm. T5-ECC has been tailored with optimized
tensile property and photocatalytic function based on the design
of reference ECC [33]. With 5% TiO2, the tensile and flexural prop-
erties of T5-ECC are not obviously distinct from R-ECC. The tensile
and flexural properties of the multilayer specimens are comparable
with those of the intermix R-ECC and T5-ECC specimens. The rea-
sons for this phenomenon lie in the following two aspects: (1) The
incorporation of TiO2 did not significantly change the mechanical
properties of the ECC. The tensile strain capacity and the mid-
span deflection of ECC-I with 5% TiO2 are 3.0% and 23.0 mm,
respectively, which are comparable with those of the reference
ECC andT5-ECC. (2) The specimens were prepared using fresh mix-
tures and no obvious flaws or defect were observed at the interface
between reference and photocatalytic layers (see Fig. 6(c), thus
resulting in ‘‘wet joint” between the different mixtures.
3.2. NOx abatement
Fig. 7(a) and 7(b) show the NOx abatement test results of the
intermix specimen. The NOx concentration is shown to rapidly
reduce to 0.05 ppm (5% of the initial concentration) within 5 min
after the UV lights were turned on (Fig. 7(a)), due to the PC reac-
tions in the presence of the ECC-I (T5-ECC) specimen under UV
irradiation. The NOx concentration remained stabilized at
0.05 ppm until t = 67 min, when the UV lights were turned off. Dur-
380 M. Xu et al. / Construction and Building Materials 221 (2019) 375–383

Fig. 6. Mechanical testing results: (a) tensile stress-strain curves; (b) flexural stress-deflection curves; (c) cross section of R-ECC, ECC-I and ECC-M specimen
(12.7 mm  30 mm). All the specimens demonstrate strain-hardening behavior and high tensile ductility. The multilayer specimens have comparable tensile and flexural
properties with the intermix specimen.

Fig. 7. NOx abatement test results of intermix specimens: (a) NO, NO2 and NOx concentration (sum of NO and NO2) concentration changes under different exposure
conditions of T5-ECC; (b) NOx abatement in three different scenarios. T5-ECC is effective in NOx abatement under UV irradiation.

ing the stabilized period, the NOx concentration is negligible. Then,
the NO2 concentration gradually returned to 1 ppm until
t = 200 min in the absence of UV exposure. Fig. 7(b) plots the
change of NOx concentration in three different scenarios. In Sce-
nario 1 (blank), no ECC specimen was placed in the reactor. The
NOx concentration remains at 1 ppm. In Scenario 2 (R-ECC), an
ECC specimen without any TiO2 was placed in the reactor. The
NOx concentration slowly decreased by 6% at 15 min. In Scenario
3 (T5-ECC), PC-ECC specimen with 5% TiO2 nanoparticles was
placed in the reactor. The NOx concentration quickly dropped from
1 ppm to 0.05 ppm. The comparison of three scenarios confirms
that the T5-ECC is effective in NOx abatement.
The NOx abatement curves of the multilayer specimens (ECC-
M0.1 and ECC-M0.4) are comparable with that of the intermix
specimen (ECC-I), as shown in Fig. 8(a). As the thickness ratio
increases from 0.1 to 0.4, there is negligible change in the NOx
abatement result, indicating that a very thin layer (1.3 mm) of
T5-ECC on the exterior surface is effective for the PC functionality.

Fig. 8. NOx abatement test results of multilayer specimens: (a) NOx abatement of multilayer specimens is comparable with that of ECC-I; (b) multilayer specimens have less
TiO2 consumption yet sustained NOx abatement efficiency.
 M. Xu et al. / Construction and Building Materials 221 (2019) 375–383 381

Fig. 8(b) shows that the TiO2 consumption can be greatly reduced
(by 90%) by using the functionally-graded structure, without com-
promising the NOx abatement functionality. The total cost of pho-
tocatalytic ECC can be largely reduced using the multilayer
preparation method, while the mechanical property and photocat-
alytic function are retained.
Fig. 9(a) to 9(c) show the NOx abatement curves of ECC-CP, ECC-
CW, and ECC-CS, respectively. The three figures show consistent
trends of the NOx concentration that decreases under the UV irra-
diation. However, compared with the intermix and multilayer
specimens, the concentration decreasing rates of the coated speci-
mens are significantly lower, and the stabilized NOx and NO2 con-
centrations are much higher. Among the three specimens, ECC-CS
demonstrates the highest reaction rate and the lowest stabilized
NOx and NO2 concentrations, followed by ECC-CW, suggesting that
the alkali content has a positive effect on the NOx abatement. Due
to the addition of water, ECC-CW has a more porous microstruc-
ture than that of ECC-CP with pure PU coating matrix, and thus
has a slightly higher NOx abatement efficiency than ECC-CP. After
the UV lamps were turned off, the NOx and NO concentrations
gradually returned to the initial concentrations.
Table 5 lists the curve fitting results of the NOx abatement tests
of the investigated specimens. The NOx abatement results of the
specimens are analyzed using the first-order kinetic model. The
key model parameters are determined through regression analysis
based on Eq. (2). The multilayer PC-ECC specimens (ECC-M0.1 and
ECC-M0.4) have comparable high NOx abatement efficiencies with
intermix PC-ECC (ECC-I), followed by ECC-CS, ECC-CW and ECC-CP.
The PC efficiency of the coated specimens is about 70–80% less
than that of the intermix and multilayer specimens with T5-ECC
directly exposed to UV irradiation, likely due to the denser
microstructure of PU. The reaction rate constant (k) of the PC-
ECC prepared by three methods follows the same trend as the PC
efficiency (Table 5). The PC reaction rates of the intermix and mul-
tilayer specimens are about 20 times higher than that of the coated
specimens.
Another interesting observation from Fig. 9 is the high residual
NO2 concentration during the reaction. This phenomenon can be
ascribed to the accumulation of HNO3 on the coating surface dur-
ing the photocatalytic reaction [23,37]. Basically, the degradation
of nitrogen oxides by photocatalysis can be summarized in Eq.
(6). Eq. (6) ensures a gradual accumulation of HNO3 on the surface
of the specimen. The HNO3 in turn prompts the conversion of NO to
NO2 via the reaction in Eq. (7). Consequently, the TiO2 nanoparti-
cles act to mediate the oxidation of NO to NO2. In this case, high
amount of NO2 is left in the coating PC-ECC system (Fig. 9(a) and
Fig. 9(b)), for the lack of certain alkali to consume HNO3 and pre-
vent its accumulation.
TiO2 ;UVA
2NO þ 1:5O2 þ H2 O ! 2HNO3 ð6Þ
TiO2 ;UVA
2HNO3 þ NO ! 3NO2 þ H2 O ð7Þ
Concrete with a base environment is considered beneficial to
mitigating this unwanted effect, by readily reacting with the
HNO3 and preventing the above highly undesirable reaction in
Eq. (4) [38,39]. Therefore, in the cases of intermix and multilayer
PC-ECC specimens, NO2 concentration is negligible (see Fig. 6(a)).
This argument also explains why ECC-CS containing NaOH has a
greater reaction rate and a lower stabilized NO2 concentration,
compared with ECC-CP and ECC-CW. With reaction going on, NaOH
on the coating surface of the ECC-CS specimen was gradually con-
sumed by HNO3, accompanied by the reduction of the PC efficiency
and reaction rate constant.
3.3. Element mapping
The morphology and elements distribution of the T5-ECC and
three coated PC-ECC are shown in Fig. 10. T5-ECC demonstrates
the most porous microstructure and is beneficial for the PC reac-
tions [8]. The porous microstructure promotes not only access of
pollutants but also formation of more hydroxyl radicals as well

Fig. 9. NOx abatement results of surface coated ECC specimens: (a) ECC-CP; (b) ECC-CW; (c) ECC-CS. All show relatively poor NOx abatement performance compared with the
intermix and multilayer specimens (Fig. 8). Obviously higher NO2 concentrations than in T5-ECC system were also observed due to the accumulation of HNO3 on the coating
surface of ECC-CP and ECC-CW with low alkali content.

Table 5
NOx abatement results based on first order kinetic model.

Designation Curve fitting equation g (%) k (min1) R2

R-ECC C/C0 = 0.06exp(0.11) + 0.94 6.0 0.081 0.800
ECC-I C/C0 = 0.95exp(0.66 t) + 0.05 95 0.631 0.997
ECC-M0.1 C/C0 = 0.96exp(0.63 t) + 0.04 96 0.601 0.998
ECC-M0.4 C/C0 = 0.95exp(0.59 t) + 0.05 95 0.571 0.994
ECC-CP C/C0 = 0.11exp(0.03 t) + 0.89 11 0.001 0.904
ECC-CW C/C0 = 0.12exp(0.03 t) + 0.88 12 0.001 0.927
ECC-CS C/C0 = 0.22exp(0.06 t) + 0.78 22 0.031 0.969
382 M. Xu et al. / Construction and Building Materials 221 (2019) 375–383

Fig. 10. SEM and EDS images of the mixtures. The images have the same magnification (5000).

Fig. 11. Schematic illustrations of: (a) T5-ECC, and (b) PC-ECC coated with TiO2-doped PU paint under UV irradiation. The porous microstructure and alkaline environment of
T5-ECC promote formation of hydroxyl radicals and consumption of PC reaction products. Grey circles represent the hydration products in the hardened ECC matrix; the
spaces between the grey circles represent inter-particle pores.

as the contact of hydroxyl radicals with pollutants. In the element
distribution images, the brightness indicates the concentration of
certain element. The high brightness of Ca in T5-ECC and Na in
ECC-CS are in line with their high NOx abatement efficiency and
low NO2 production, corroborating that an alkali environment ben-
efits the PC reactions. The low brightness of Ti in ECC-CP is consis-
tent with its low NOx abatement efficiency and reaction rate
constant. Although the brightness of Ti in ECC-CW is comparable
with that in ECC-CS, the low alkaline content in ECC-CW and its
dense microstructure limit the NOx abatement efficiency.
A schematic illustration is presented to help interpret the NOx
abatement test results of T5-ECC and PC-ECC coated with TiO2-
doped PU paint, as shown in Fig. 11. Under UV irradiation, hydroxyl
radicals (OH) are produced around the TiO2 nanoparticles; the
hydroxyl radicals convert NOx into HNO3 (Eq. (6)). The highly por-
ous microstructure ensures full exposure of TiO2 nanoparticles to
UV irradiation and NOx by providing more surface area, therefore
producing more hydroxyl radicals and promoting the PC efficiency.
Moreover, the rich alkali of T5-ECC from cement hydration readily
consumes the accumulated HNO3 produced via the PC reaction in
Eq. (6) and generates a stable PC efficiency and reaction rate con-
stant. However, in PC-ECC coated with TiO2-doped PU paint, the
dense microstructure exposes less TiO2 nanoparticles ready for
PC reaction, and the lack of alkali on the coating surface results
in the accumulation of HNO3, generating low PC efficiency, slow
reaction rate, and worse, high NO2 during the PC reaction (Eq. (7)).
4. Conclusions
Based on the above experimental investigations and reaction
kinetic modelling, the following conclusions can be drawn.
 M. Xu et al. / Construction and Building Materials 221 (2019) 375–383

Photocatalytic (PC) abatement of NOx occurs within a thin
(<1.3 mm) layer of the exterior surface of PC-ECC. Increasing
the thickness of T5-ECC from 1.3 mm to 5.1 mm does not
change the PC efficiency and reaction rate. Thus, incorporating
TiO2 through the functionally-graded structure is effective to
reduce the consumption of photocatalyst with retained PC
property: the PC efficiency is 95–96%, reaction rate constant is
0.57–0.63 min1 and little NO2 is detected.

Incorporating PC property via polymer coating with TiO2
nanoparticles is less effective compared with intermix or multi-
layer method. With the same mass ratio of TiO2 on the surface,
the PC efficiency and reaction rate constant of the coated spec-
imens are 70–80% and 20 times lower than the ECC-I or ECC-M
specimens respectively. This is consistent with the relatively
dense microstructure of the polymer coating.

The low PC efficiency and reaction rate of the PC coating are
associated with the dense microstructure and lack of alkalinity
of the coating. While 1 mol/L NaOH solution was used to pre-
pare the coating to enhance the PC efficiency and reaction rate,
such enhancement was eliminated as alkaline was consumed
during the PC reactions. To effectively convert NOx to nitrate
without generating high NO2, conditions of porous substrate
and rich alkali are recommended.

The PC-ECC prepared by intermix or multilayer method has
intrinsic strain-hardening properties and high tensile ductility.
The tensile strain capacity is more than 3% and the mid-span
deflection at peak load under bending is over 20 mm.

The PC reactions of different specimens can be described using
first-order reaction model. The model parameters can be used
to quantify the PC efficiency and reaction rate.
Declaration of Competing Interest
None.
Acknowledgements
This study was partially funded by E. B. Wylie Collegiate Profes-
sorship of Civil Engineering at the University of Michigan – Ann
Arbor, China Scholarship Council (CSC), National Natural Science
Foundation of China (51608382), Natural Science Foundation of
Shanghai of China (17ZR1442000).
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