Microchemical Journal 133 (2017) 1–12

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Microchemical Journal

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

Enhanced self-cleaning properties of N-doped TiO2 coating for

Cultural Heritage
L. Bergamonti a, G. Predieri b, Y. Paz c, L. Fornasini d, P.P. Lottici d, F. Bondioli a,⁎
a
Department of Engineering and Architecture, University of Parma, Parco Area delle Scienze 181/a, 43124 Parma, Italy
b
Department of Chemistry, Life Sciences and Environmental Susteinability, University of Parma, Parco Area delle Scienze 17/a, 43124 Parma, Italy
c
Department of Chemical Engineering, Technion-Israel Institute of Technology, 32000 Haifa, Israel
d
Department of Mathematical, Physical and Computer Sciences, University of Parma, Parco Area delle Scienze 7/a, 43124 Parma, Italy

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

Article history: Nanostructured TiO2 is the most widely studied photocatalytic material and is used in self-cleaning coatings in
Received 5 January 2017 buildings and for Cultural Heritage applications. To extend the photocatalytic activity of nanocrystalline titania
Received in revised form 3 March 2017 into the visible spectral range, doping of titania by non-metal elements as N, C, F and S is currently widely inves-
Accepted 3 March 2017
tigated. Here we report tests on carbonatic Travertine stones coated with two self-cleaning coatings based on N-
Available online 6 March 2017
doped TiO2 nanoparticles. The two coatings, both obtained by sol-gel synthesis, differ by their titanium precur-
Keywords:
sors and nitrogen sources. The obtained nanoparticles were characterized by X-ray diffraction, UV–VIS absorp-
Photocatalytic TiO2 tion, Raman and X-ray photoelectron spectroscopies. The harmlessness of the coatings is demonstrated by
Self-cleaning colorimetric analysis and by capillary absorption measurements. The self-cleaning properties of the treated
Travertine stones were evaluated by the measurement of water contact angle and of organic dyes degradation as a function
Sol-gel of UV–VIS light irradiation time. The results confirm that the synthesized nanoparticles were successfully doped
N-doped TiO2 with nitrogen, allowing a photocatalytic activity, even in the visible range, comparable or better than that shown
by P25 Evonik commercial product. A comparison between coating where the dopants are introduced by an acid-
ic process and coating doped using urea as the nitrogen source revealed higher activity for the former. The impor-
tance of the nature of the dye in the evaluation of the self cleaning properties is discussed.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction
Stone-based historic monuments, buildings and sculptures, are fac-
ing deterioration processes of constituent materials that have a power-
ful impact on their cultural, social and economic values [1]. Because of
air pollution [2], acid rain [3], soluble salts [4,5] and biodegradation [6,
7], these cultural heritage objects undergo the risk of being irreparably
lost. The degradation processes of natural and artificial stone artifacts
depend on the nature of the constituent materials and on the character-
istics of the environment. The actions of the chemical agents, and in par-
ticular of the atmospheric pollutants, are very dangerous on limestones
and calcarenites (mainly composed of carbonates), frequently used as
building materials [8–11]. These agents cause high levels of sulfate
and nitrate depositions, with development of black crusts that acceler-
ate the stone decay and produce an aesthetically unacceptable staining
of the stone surfaces [12–15]. For these reasons, it is necessary to re-
move soiling material to slow down the deterioration processes and to
improve the appearance and the aesthetic quality of the buildings. It
should be emphasized, however, that stone cleaning is an irreversible
⁎ Corresponding author.
E-mail address: federica.bondioli@unipr.it (F. Bondioli).
and expensive intervention and the use of detergents could cause
changes in the aesthetic aspect and the formation of by-products that
could be harmful for the objects as well as to the environment [16,17].
To limit these invasive interventions, it is necessary to perform preven-
tive and long-lasting actions. The possibility to obtain building materials
with self-cleaning surfaces is a current topic of great interest, especially
for exterior surfaces exposed to environmental pollutants, atmospheric
precipitations and human damages [18–20]. Self-cleaning behavior of a
solid surface refers to the capability to remove pollutants under natural
environments. There are two ways to obtain this result: to design hy-
drophilic surfaces or to achieve hydrophobic structures. In the first
case the water contact angle (WCA) is close to zero, hence water
forms a uniform surface film, which prevents the soil clinging to sub-
strate [21–23]. In the second case the surface is highly hydrophobic
(WCA N 90°), so that the water drops roll over the surface while sweep-
ing dirt away [23,24]. Self-cleaning surfaces can be also obtained by syn-
ergistic action of superhydrophilic and photocatalytic materials to
transform pollutants into harmless species [25–27].
Titanium dioxide (TiO2) is the most attractive photocatalyst for air
and wastewater purification and is extensively used for oxidative and
reductive removal of organic contaminants [28–31]. The use of titanium
dioxide (TiO2) for photocatalytic self-cleaning of building materials has

http://dx.doi.org/10.1016/j.microc.2017.03.003
0026-265X/© 2017 Elsevier B.V. All rights reserved.
2 L. Bergamonti et al. / Microchemical Journal 133 (2017) 1–12
started already in the early 1990s [32], nevertheless, its use for
protecting objects of cultural heritage is relatively new [33–38], and is
characterized by an increasing number of studies concerning environ-
mental sustainability and potential human health risks [39,40].
TiO2 is present in nature in three crystalline phases: rutile (thermo-
dynamically the most stable), anatase and brookite. Both rutile and an-
atase phases show photocatalytic reactivity but anatase seems to
exhibit better photocatalytic performances than rutile [29]. Briefly,
photocatalysis is based on the generation of electron–hole pairs in
TiO2 semiconductor upon irradiation with light. Electrons are created
in the conduction band, leaving holes in the valence band: both charges
participate in redox reactions with adsorbed organic species and
adsorbed molecular oxygen and water [41] through formation of active
radicals. The main obstacle for practical application of TiO2 has to do
with the large band-gap of the photocatalyst (~ 3.0 eV for rutile and
~3.2 eV for anatase), meaning that the processes require UV light irradi-
ation, that corresponds to only 4–8% of the incident solar flux [42,43].
Many methodologies have been employed to increase the light absorp-
tion towards the visible range (longer wavelengths) and to improve the
photocatalytic performances of TiO2: sensitization with organic dyes
[44], deposition of noble metal ions on the TiO2 surface [45–49], doping
with transition metals [50–53], doping with non-metals (such as N, P, C,
S) [54–57]. The term “doping” is used loosely for describing the addition
of foreign atoms into lattice, surface or interstitial sites. Compared to the
other non-metal elements, nitrogen seems to be the most attractive be-
cause of its comparable atomic size with that of oxygen, small ionization
energy and stability [57–61]. Nitrogen can be used as a dopant in the al-
teration of the band-gap of TiO2 introducing filled N2p states above the
TiO2 valence band, which decrease the apparent gap of TiO2 down to
≈ 2.5 eV [54]. In addition, N-doping may form oxygen vacancies that
may red-shift absorption [62] or enhance the photocatalytic efficiency
by electron trapping, slowing down the recombination of
photogenerated electrons and holes [63–65].
The incorporation of nitrogen into TiO2 structure has been reported
via substitutional (replacement of oxygen) or interstitial (addition of ni-
trogen into the TiO2 lattice) solid solution formation [66,67]. To incorpo-
rate nitrogen into TiO2 various chemical and physical techniques have
been developed, such as ammonolysis, sol-gel, hydrothermal and
solvothermal reactions, sputtering, ion implantation and high energy
milling with an organic compound [43,68,69]. Among these, the sol-
gel method is the most used to obtain the desired doping level and
nanoparticle size distribution, thanks to the easy control of the synthesis
conditions (type of solvents, pH, temperature, etc.). As a nitrogen
source, aliphatic amines, nitrate and ammonium salts, nitrides, urea,
ammonia have been used [54,70].
The present work aimed to synthesize N-doped TiO2 powders by a
sol–gel method and to extend the photocatalytic activity of TiO2 into
the visible light region, thus obtaining a better photocatalytic efficiency.
Nano-sized doped titania samples were obtained using different N
sources (ammonia/nitric acid and urea). The self-cleaning photocatalyt-
ic properties of the N-doped TiO2 coatings were verified on Travertine
samples, one of the most famous Italian stones, extensively used since
the Roman age. For this purpose, the degradation of two organic dyes,
usually employed in staining/cleaning tests over building materials
[71–73] was studied. It is known that under UV–VIS light, dyes may un-
dergo photolysis and also can sensitize TiO2, injecting an electron into
its conduction band. The self-sensitization of the organic dyes in the vis-
ible region undoubtedly complicates the interpretation of the
photodegradation mechanisms [74,75], but, for sake of comparison,
we followed the tests which are commonly employed for building ma-
terials. The use of organic dyes is simplified with respect to other
“test” pollutants (e.g. stearic acid) and enables to verify by simple color-
imetric methods the photodegradation of the stains on the stones up to
the restoration of the original aesthetical appearance. In addition, dyes
have complex photodegradation mechanistic pathways and an accurate
determination of photocatalytic efficiencies is a very difficult task. For
this reason, the discussion about the photocatalytic activity on a
model pollutant should be made with due consideration [74]. The effi-
ciency of a photocatalyst has to be referred to the specific dye
employed: the photodegradation kinetics cannot be generalized to dif-
ferent dyes and the test is useful only for a comparison of the
photodegradation efficiency for that particular dye and between differ-
ent coatings in specific experimental conditions [76].
Static water contact angle (CA) tests were carried out in order to de-
termine also the effects on TiO2 treated surfaces of the hydrophilicity in-
duced by the light irradiation, while capillary water absorption and
colorimetric study were employed to verify the harmlessness of the N-
TiO2 coatings on the physical and aesthetical properties of the treated
stones [77].
2. Experiment
2.1. Synthesis of nitrogen-doped TiO2 nanoparticles
Chemicals and materials used for the synthesis were titanium(IV)
oxysulfate (TiOSO4, Aldrich), titanium (IV) tetraisopropoxide (TTIP, Al-
drich), urea (NH2CONH2, Aldrich), nitric acid (HNO3, 65%, Carlo Erba),
ammonium hydroxide (NH4OH, 26%, Carlo Erba). All reagents and
Aeroxide P25 (Evonik) were used as received without any further
purification.
Two different N-doped TiO2 sols (0.1 M), henceforth called N-TiA
and N-TiU, were obtained.
N-TiA was synthesized starting from titanium(IV) oxysulfate,
TiOSO4 (1 × 10−2 mol), hydrolyzed in 100 ml distilled water at 40 °C.
After cooling, NH4OH was slowly added dropwise to the solution, up
to pH ≈ 7. The obtained amorphous precipitate was separated by cen-
trifugation and washed repeatedly with distilled water to remove the
sulfate ions (as confirmed by BaCl2 test). The powder was suspended
in 100 ml of distilled water, followed by peptization with HNO3 to ob-
tain pH ≈ 1.5.
N-TiU sol was synthesized using tetraisopropoxide, TTIP, as a precur-
sor and urea as a complexing agent and nitrogen source: 0.1 mol of TTIP
were hydrolyzed in 10 ml of isopropanol. After vigorous stirring for
15 min, 40 ml of distilled water were slowly added to hydrolyze the pre-
cursor. 0.01 mol of urea were solubilized in 50 ml of water and then
added to Ti solution under vigorous stirring. The slurry was stirred at
room temperature for 1 h to favor the complete hydrolysis of the alkox-
ide. After these procedures, both N-TiA and N-TiU sols were stirred vig-
orously at room temperature for 30 min and refluxed at 100 °C for 3 h to
induce the crystallization. The resulted N-TiA sol had a pale-yellow color
and was very stable at a final pH of 1.6, while the N-TiU suspension,
characterized by a final pH of 8.3, was light yellow and quite unstable.
2.2. Characterization of the titania samples
To characterize the titania powders, small amounts of both sols were
centrifuged at 1000 rpm, repeatedly washed with distilled water and fi-
nally dried at 30 °C for 24 h. Room-temperature X-ray powder diffrac-
tion patterns were collected in the range 10°–60° by Thermo ARL
X'TRA X-ray diffractometer with Si–Li detector, using CuKα radiation
at 40 kV and 40 mA, at 0.2° scan rate (in 2θ). Measurements were per-
formed on samples spread on a conventional glass sample holder. The
reflections of powdered crystalline silicon were used for 2θ calibration.
X-ray diffraction patterns were compared with the standard anatase
and brookite diffractograms (reference of anatase JCPDS card #21-
1272 and brookite JCPDS card #29-1360 and rutile JCPDS card #76-
1940).
The average diameter of the crystallites was estimated by the
Scherrer equation from the line broadening of the main diffraction
peaks:
D ¼ kλ=βcosθ ð1Þ
 L. Bergamonti et al. / Microchemical Journal 133 (2017) 1–12
where D is the average crystal diameter (nm), k is the shape factor (usu-
ally taken = 0.89 for spherical particles), λ = 0.15406 nm is the Cu-Kα
X-ray wavelength, β is the full width at half-maximum (FWHM) inten-
sity of the diffraction peak and θ is the Bragg diffraction angle [78].
Non-polarized Raman scattering measurements were carried out in
a nearly backscattered geometry using a Jobin Yvon LabRAM micro-
spectrometer (300 mm focal length spectrograph) equipped with an in-
tegrated Olympus BX40 microscope. Spectra were recorded at room
temperature. The powder samples were irradiated with 632.8 nm line
(nominal 15 mW He–Ne laser excitation). The spectral resolution was
about 1.5–2 cm−1. The Rayleigh radiation was blocked by an edge filter
and the backscattered Raman light was dispersed by a 1800 grooves/
mm holographic grating on a Peltier cooled CCD, consisting of an array
of 1024/256 pixels. The entrance-slit width was fixed at 100 μm. The
laser power on the sample was adjusted at b2 mW by means of a series
of density filters to avoid any damage to the samples or uncontrolled
thermal effects. Spectra were collected using both ×100 and long work-
ing distance × 50 microscope objectives. Typical exposures were
10–60 s, repeated three to five times. The system was regularly calibrat-
ed using the 520.6 cm−1 Raman band of silicon or by means of reference
emission lines of Ar or Cd light sources. The data analysis was performed
by LabSpec built-in software.
Specific surface areas were determined by the classical Brunauer–
Emmett–Teller (BET) procedure with a Micromeritics Pulse Chemisorb
2705 analyzer using nitrogen at 77 K (single point method). Prior to
measuring, the samples (150 mg) were outgassed under helium flow
at 473 K for 2 h.
UV–VIS diffuse reflectance spectroscopy (DRS) measurements on
TiO2 powdered samples were carried out by a Varian 2390 spectropho-
tometer equipped with an integrating sphere. The spectra were record-
ed in reflectance mode at room temperature, with BaSO4 as reference,
scanning in the 250–800 nm wavelength range. Absorption coefficients
and energy gaps were calculated based on Kubelka–Munk treatment
[79] and Tauc's plots [80].
TiO2 samples were investigated by XPS using a Thermo Scientific
Sigma Probe, hemispherical energy analyzer and a monochromatic Al
Kα source (hν = 1486.6 eV). The powders were attached onto a carbon
tape. The signal from the C1s peak at 285 eV was taken as internal con-
trol, to account for charging effects. The samples were first scanned in
fast mode, where the signal is collected in a wide angle (from 24° to
84° relative to the sample's normal). Then specific elements were
scanned more precisely in a slower mode. Here, the signal was collected
from a narrower window (from 24° to 38° degrees relative to the nor-
mal). This corresponds to a bulk-emphasizing measurement. A step
size of 1 eV was used for survey scanning, whereas for the acquisition
of specific peaks the step size was 0.05 eV. The lateral size of the beam
was 200 μm by 400 μm, which is large enough to average over local var-
iations among particles.
2.3. Stone characterization and sols application
Travertine stone is a sedimentary stone formed by deposition of
CaCO3 generated from thermal sources and directly from the upper
mantle [13]. The stone is characterized by parallel layer, typical struc-
ture of the sedimentary rock. The samples used in this study (Fig. 1)
present layers with massive and laminated structures. The massive
type is characterized by small pores irregularly distributed while the
laminated type presents large and irregular pores parallel to bedding
[81]. Travertine is a highly heterogeneous stone, and a single stone
block can contain several different facies. The porosity is mainly inter-
crystalline and intergranular and, according to the technical specifica-
tion, in our samples is 8.3% on average. Macropores up to centimeter
size give to the stones the classical vacuolar structure.
Due to the heterogeneity of Travertine stone, the samples were cho-
sen so as to have, for each coating, the same number of samples with
massive and layered structure. The selection of the samples was done
3
also by measuring the apparent density (2270 ± 54 kg/m3). The tests
were performed on the parallel face to the plane of sedimentation.
The N-TiA and N-TiU sols and the P25 0.1 M dispersion were applied
on stones by brush. The amount of titania per unit surface (mg/cm2)
was calculated from the dried weight of the stone samples before and
after the application of the coating: 0.19 ± 0.01 mg/cm2 for N-TiA,
0.26 ± 0.01 mg/cm2 for N-TiU and 0.22 ± 0.1 mg/cm2 for P25.
To evaluate the changes of the stone surface appearance due to the
TiO2 coatings according to UNI EN 15886:2010 norms [82], colorimetric
analysis was performed by a Techkon Spectrodens colorimeter using
D65 illuminant (daylight standard) and 10° viewing angle geometry.
The results on nine regions of a few mm2 of each specimen before and
after treatment were averaged on five samples. Color differences were
measured in the CIELab and CIELCH spaces, that better represent
human sensibility [83]. In the CIELab space L∗ values range from 0 to
+100 (black-white) and represents the lightness, while a* (opponent
red-green) and b* (opponent yellow-blue) are the chromatic coordi-
nates. In the CIELCH space, the attributes of chroma, C* =
(a*2 + b*2)1/2, and hue, h* = tan−1(b*/a*), represent the color purity
or saturation and the hue of the saturated color, respectively.
The colorimetric changes ΔE*, ΔC* and ΔH*, due to TiO2 applications
with respect to the uncoated stone, were evaluated by:
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2
ΔE ¼ ΔL2 þ Δa2 þ Δb
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ð2Þ
ΔH ¼ ΔE2 −ΔC 2 −ΔL2
ΔC  ¼ C r− C s
where C∗r and C∗s are the chroma of uncoated and coated samples,
respectively.
Changes in C* and h* are more sensitive to changes of a* or b* coor-
dinates, depending on the original color of the material. Travertine is a
yellowish stone characterized by b* values higher than a*: in our case,
L* = 81.6, a* = 1.9, b* = 9.6. In the evaluation of the treatment's effects
it should be taken into account that C* is strongly influenced by the co-
ordinate b*, whereas h* is very sensitive to changes in a*.
The microstructure of the stone surfaces before and after the coat-
ings was examined by a Scanning Electron Microscope Jeol JSM 6400
equipped with an Oxford Instruments Link Analytical Si(Li) Energy Dis-
persive System detector (SEM-EDS). The data analysis was performed
by INCA built-in software. The microanalyses were carried out with re-
spect to calcium as reference.
For the water capillary absorption tests, five samples for each coating
were employed, following UNI EN 15801:2010 recommendation [84].
After coating, the samples were dried at 60 °C in a ventilated oven,
until reaching mass difference b 0.1% between two measurements, at
24 h intervals. The specimens were then placed on blotting paper satu-
rated with demineralized water, with the TiO2 coated side facing down-
wards. The water level was maintained constant throughout the test.
Specimens were weighed at regular time intervals and at subsequent
Fig. 1. Typical Travertine structure in the direction perpendicular to the sedimentation
plane: the difference between a) massive and b) laminated structures is evident.
4 L. Bergamonti et al. / Microchemical Journal 133 (2017) 1–12

24 h intervals until t = tf, when the difference between two consecutive
weighing was b1% of the initial weight of the specimen. The amount of
absorbed water Qi at time ti was calculated by Q i ¼ Mi −M
A , M0 being the
0
The photocatalytic oxidation reactions were performed under the
Osram ultra-Vitalux lamp. The test was made also under visible light ir-
radiation, adding a low-energy 400 nm cutoff filter. A further test was

mass of the dry specimen, Mi the mass at time ti and A the area in contact made with a LED at 405 nm. In Fig. 2 are reported the emission spectra
with the wet paper. of the light sources and the absorption spectra of MeO and RhB.
The calculated values of Qi were reported (in kg/m2) as a function of Three coverings of the dyes' solution (about 1.5 ml, 1 mM) were ap-
the square root of time t1/2
i . The absorption coefficient (AC) and the rel-
plied by a brush on the surface of the stone samples. After each covering
ative capillary index (RCI) were also reported. AC (in kg/(m2s1/2) was step, the stones were kept to dry in ventilated oven at 50 °C for 60 min.
evaluated as the slope of the curve Qi at low times (b30 min), where The coating degradation activity on the dyes was evaluated by color-
the amount of the absorbed water vs. t1/2 should be approximately lin- imetric measurements on nine control points for each stained sample
ear according to the most used model for the capillarity absorption [85]. surface (three samples for each type) using the Techkon Spectrodens
The RCI parameter is defined [38,86] as the ratio between the area colorimeter. Assuming as reference the starting value of the color pa-
under the Qi curve for the treated stone, (Qi)tr, and for the untreated rameters measured on the stained stone, the color variation was moni-
one, (Qi)unt: tored over the irradiation time. A normalized chroma change, ΔCn, at
different exposure times, t, was obtained by the chromatic coordinates
a*(t) and b*(t) as follow:
t
∫ 0f ðQ i Þtr dt
RCI ¼ ð3Þ vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
t
∫ 0f ðQ i Þunt dt u 
uða ðt Þ−a ð0ÞÞ2 þ ðb ðt Þ−b ð0ÞÞ2
ΔC n ¼ t  2    2 ð4Þ
aC −a ð0Þ þ bC −b ð0Þ
representing the water absorption capability of a given coated sample
versus the control.
where a∗C and b∗C are measured on clean stones before the staining with
dyes [38]. This function should reach 1 after the complete dye
2.4. Photoinduced properties
degradation.

The wetting degree of the stone surface and its light induced changes
3. Results and discussion
were assessed by the values of water contact angle (WCA). Measure-
ments of the static contact angles were performed by OCA 20 apparatus
3.1. TiO2 powders characterization
(DataPhysic Instrument GmbH) using the sessile drop method, in accor-
dance to UNI EN 15802:2010 [87] standard rules. A water drop with vol-
The specific surface area of the powder, as determined by the BET
ume of 3 μl was placed on the surface by a needle: CA measurements
isotherm, was 260 m2/g and 230 m2/g for N-TiA and N-TiU, respectively,
were made on the drop profile 15 s after its deposition, every 30 min,
more than four times larger than that of commercial TiO2 powder
up to 2 h. The reported values are an average of 12 + 12 measurements
(Evonik, Aeroxide P25) [88], generally considered one of the most active
taken on two stone specimens for each treatment (N-TiA, N-TiU, P25)
TiO2-based products for dye photodegradation. These results of specific
and for the untreated reference.
surface areas confirm those obtained previously for undoped titania
Contact angles measurements were repeated also on samples irradi-
powders prepared by the authors using a similar sol-gel method [37].
ated by a UV–VIS Osram ultra-Vitalux (300 W, 280–800 nm spectral
The XRD patterns of P25, N-TiA and N-TiU are shown in Fig. 3. The
range emission). The distance between the lamp and the stone samples
anatase, rutile and brookite percentage in the powders was calculated
was kept at 14 cm to achieve an irradiance power in the UV range of
by the integrated diffraction peak intensities, according to the method
about 3.5 mW/cm2.
proposed by Zhang and Banfield [89]. As expected, P25 is characterized
Methyl orange (MeO) and rhodamine B (RhB), extensively
by the presence of anatase, as main phase, and rutile, as secondary
employed in various applications, were used to evaluate the photocata-
phase (Fig. 3a). The rutile weight fraction, WR, was determined by:
lytic efficacy of the N-doped TiO2 coatings on stained stone samples.
MeO is an anionic azo-dye frequently used in titration as pH indicator:
at pH b 3.1 is red, until pH 4.4 is orange (pKa = 3.8) and at pH N 4.4 is AR
WR ¼ ð5Þ
clearly yellow. When dissolved in water exhibits a broad peak at ðkA AA þ AR Þ
about 465 nm, typical of a substituted azo-benzene.
RhB is a cationic red dye of the xanthene class, often used as a tracer where AA and AR are the integrated intensities of the (101) anatase main
dye and in biology as a staining fluorescent dye. The pH value of a water peak and of the (110) rutile peak, respectively, and kA = 0.884 is a coef-
solution of RhB is 4.3. Rhodamine B exists, in the 1–13 pH range, in two ficient determined by calibration. In the insert of Fig. 3a the
principal forms, i.e. cationic (RhB+) or zwitterionic (RhB±), with its deconvolution employed to determine the rutile WR fraction is report-
absorption maximum close to 551–553 nm. ed: in good agreement with the commonly reported values WR =

Fig. 2. (a) Emission spectra of the blue LED and of the Osram ultra-Vitalux lamp, with and without UV filter; (b) absorption spectra of methyl-orange and rhodamine B dyes.
 L. Bergamonti et al. / Microchemical Journal 133 (2017) 1–12 5

0.21 ± 0.02 [88]. A rough estimation of the nanocrystals size by the

Scherrer formula gives 17 ± 4 nm for anatase and 25 ± 4 nm for rutile.
In the case of N-TiA and N-TiU, the observed diffraction peaks can be
perfectly indexed by diffraction planes of tetragonal anatase (marked
with A). Besides, a small diffraction peak of the brookite phase (marked
with B), is observed at 2θ = 30.81°. The main diffraction peak of anatase
(101) at 2θ = 25.28° overlaps with the (120) and (111) reflections of
brookite at 2θ = 25.34° and 2θ = 25.69°, respectively. The weight frac-
tion of brookite phase, WB, was calculated using the integrated intensi-
ties AA of the (101) anatase peak and AB of the (121) brookite peak, by:

kB AB
WB ¼ ð6Þ
ðkA AA þ kB AB Þ

where kB is equal to 2.721 [89]. In the inserts of Fig. 3b and c the

deconvolution employed to determine the anatase/brookite phase con- Fig. 4. Raman spectra of TiO2 nanopowders: the wavenumbers of the main anatase peaks
are shown. A, B and R indicate features of anatase, brookite and rutile phases, respectively.
tent were reported. In the fitting procedure with lorentzian or pseudo-

Fig. 5. UV–VIS absorption spectra of N-TiA and N-TiU doped TiO2 and of the reference P25.
Fig. 3. XRD pattern of P25 (a), N-TiA (b), N-TiU (c): (A) anatase. (R) rutile, (B) brookite. In (a) Log(1/R) versus λ (R is the reflectance); (b) Kubelka-Munk F(R) function vs. photon
the inserts: (a) fit of the main anatase-rutile and (b, c) anatase-brookite peaks. energy, hv; (c) Tauc's plot (hνF(R))1/2 vs. photon energy, hv.
6 L. Bergamonti et al. / Microchemical Journal 133 (2017) 1–12
Voigt functions, it was assumed that (120), (111), and (121) brookite
peaks have the same peak broadening, while their intensities, according
to the JCPDS card no. 29-1360, were fixed by the ratios 100/80/90, re-
spectively. The percentage fraction of anatase and brookite were esti-
mated 82% and 18% for N-TiA and 92% and 8% for N-TiU, respectively.
Finally, the line broadening of the main diffraction peak (101) of anatase
was used to determine the crystallite size of the particles: 4.5 ± 1.0 nm
and 8.5 ± 1.2 nm in N-TiA and N-TiU, respectively, significantly lower
than that of P25.
Raman spectroscopy is very sensitive to the crystallinity and micro-
structure of TiO2 and is largely applied to discriminate the local order
characteristics of TiO2. In Fig. 4 the Raman spectra of both N-TiA and
N-TiU nanopowders were compared with that of P25. The spectra of
both N-doped powders show five high-intensity Raman peaks, ob-
served at 151–153 cm−1, 204 cm− 1, 398 cm− 1, 512 cm−1, and
635 cm−1, corresponding to the characteristic Eg, Eg, B1g, A1g(B1g), and
Eg Raman modes of the TiO2 anatase structure, respectively. Moreover,
some features from the brookite phase, also evidenced by XRD data,
are observed at 246–318/324–366 cm−1. The Raman spectrum of P25,
a mixture of anatase (~80%) and rutile (~20%) according to the XRD re-
sults, shows weak features of rutile, hardly visible on the intense ana-
tase spectrum. It is well-known that the most intense mode at
143 cm−1 in crystalline anatase shows increasing broadening and a
shift towards higher wavenumbers, as the particle size decreases [90].
The broadening (FWHM: 14 cm−1 in P25, 26 cm− 1 in N-TiU and
33 cm−1 in N-TiA) and the shift (from 143 cm−1 to 150 cm− 1 up to
155 cm−1) observed in these N-doped samples, which are only margin-
ally due to the brookite contribution, are compatible with anatase
nanocrystals of 5–10 nm size [91] in good agreement with the XRD re-
sults, where N-TiA shows larger linewidths than N-TiU.
The UV–VIS absorption of a semiconductor is described by the ener-
gy gap value, Eg, corresponding to a strong increase in the absorbance,
due to the excitation of valence-band electrons into the conduction
band. Since the UV–VIS spectra of the powdered catalysts were record-
ed in diffuse-reflection mode, the diffuse reflectance, R, was directly
Fig. 6. XPS peaks of Ti2p and N1s in N-TiU (A and B) and in N-TiA powders (C and D).
obtained from the output of the spectrometer. The band gap energy
was estimated by the Kubelka–Munk (KM) function: the absorption co-
efficient, K, and the scattering coefficient, S, are related at each wave-
length to the KM function by the following [92]:
 
K 1−R2
F ðRÞ ¼ KM ¼ ¼ ð7Þ
S 2R
Under the assumption that S does not depend on the wavelength,
the KM function can be taken as proportional to the absorption coeffi-
cient. Eg can be roughly calculated by the Tauc's plot, (hνK)n ∝
(hνF(R))n ∝ (hν–Eg), assuming an indirect band gap (i.e. n = 1/2), as
known for anatase, by fitting the linear part of the curve and extrapolat-
ing the hν value for F(R) = 0.
In Fig. 5(a–c) the plots obtained by UV–VIS Diffuse Reflectance Spec-
troscopy (DRS) for the N-doped TiO2 powders and the reference P-25
are reported. Both N-TiA and N-TiU showed a light absorption increase
towards the visible range relative to P25. The band gaps obtained from
Tauc's plots were 3.25, 3.10 and 3.02 eV for P25, N-TiU, N-TiA, respec-
tively. The absorption enhancement in the visible-light range is in
good agreement with the yellowish color of both samples.
XPS measurements performed on both N-TiA and N-TiU powders
showed some differences between the two powders. Both samples re-
vealed the Ti2p doublet (2p3/2, 2p1/2), at binding energies of 458 eV
and 464 eV, which are typical for Ti4+ species in TiO2 (Fig. 6a, c) [93].
Nevertheless, the N-TiA powder revealed also the presence of a second
Ti2p doublet (Fig. 6c) of binding energy lower by 1.5 eV than that of
Ti4+ species in pristine TiO2. This suggests that unlike in the N-TiU pow-
der, where all the titanium atoms are in the same environment as in
TiO2, part of the titanium in the N-TiA samples experience a different
environment, leading to weaker binding of the core electrons to the ti-
tanium nucleus. The Ti peak in TiN was reported as located around
455 eV [94]: such a shift might indicate the presence of substitutional
nitrogen, provided that there is evidence also from the position of the
 L. Bergamonti et al. / Microchemical Journal 133 (2017) 1–12 7

nitrogen peak. Despite the inherent low intensity of the N1s peak, a
clear difference between N-TiU and N-TiA is observed. In the N-TiU sam-
ples, nitrogen peak is comprised of a single peak, centered at binding en-
ergy of 400 eV (Fig. 6b). In contrast, the nitrogen peak in the N-TiA
samples is broader and comprised of two peaks of equal contribution,
one at 400 eV and a second at 401 eV (Fig. 6d). Former work has claimed
that the binding energy of electrons in interstitial N in titania should be
around 400–401 eV and that, if nitrogen is in both interstitial and substi-
tutional position, the two peaks should be well resolved [95]. It should
be noted, however, that the N1s peak in TiN is 397 eV [94] and that
this value is slightly shifted to lower energies (by 0.5–1 eV), in the pres-
ence of oxygen, i.e. in TiOxNy [96]. Hence, the location of the nitrogen
peak seems to suggest the nitrogen is in interstitial positions in both
types of samples, with larger variety in the N-TiA samples. The exact na-
ture of the interstitial peak of nitrogen in titanium oxide is not clear and
was hypothesized as N2, NO− 3 or N\\H [97]. Indeed, another N1s peak
was found at 408 eV in some of the N-TiA samples, indicating the
presence of nitrate. An interesting XPS finding was the ratio between
the atomic concentration of oxygen to that of titanium, which was con-
siderably higher than 2 in all samples. This may be originated from the
presence of adsorbed oxygen-containing molecules at the surface. How-
ever, in that case, one could expect that the oxygen/titanium ratio in the
surface mode of operation would be higher than in the bulk mode, in
contrast to our measurements that showed almost no difference be-
tween the two modes of operation.
In conclusion, it is possible to say that the changes in the optical ab-
sorption of the N-doped photocatalysts can be ascribed to the introduc-
tion of localized N2p doping states near the valence band edge of TiO2.
While doping may introduce nitrogen atoms in both interstitial and
substitutional positions, our XPS results, corroborated with the absorp-
tion results, suggest that the nitrogen dopants in the N-TiA are likely to
reside in positions that affect the immediate environment of titanium
atoms, whereas nitrogen dopants in the N-TiU samples are mostly inter-
stitial and do not affect the local environment of the titanium atoms. At

Fig. 7. SEM images and EDS spectra on: (a) untreated, (b) N-TiA coated, (c) N-TiU coated and (d) P25 coated Travertine.
8 L. Bergamonti et al. / Microchemical Journal 133 (2017) 1–12

Fig. 8. Partial and total color differences of the Travertine coated with TiO2 with respect to the raw stone, without coatings.

any case, it should be noted that whether substitutional positioning of (RCI) and the capillary absorption coefficient AC30, evaluated as the
the nitrogen is a prerequisite for visible light activity [98] or not [99] is slope of the linear fit to the Qi curve vs. t1/2 in the first 30 min.
still a matter of controversy. Capillary test measurements are affected by experimental uncer-
tainty due to the non homogeneity of the stone samples of the order
3.2. Stone characterization of 2–4%: nevertheless, the overall capillary rise seems to be slightly im-
proved by both titania treatments with respect to untreated samples, as
The microstructure of the travertine samples, before and after the ti- shown in Fig. 9 for long-time test as well as evidenced by the RCI values.
tania treatments, was determined by SEM-EDS measurements (Fig. 7). The AC30 coefficient shows a significant improvement of capillary rise
The stones mainly consist of calcium carbonate (CaCO3) in calcite only for N-TiU coating compared to the untreated surface, while for N-
form. As clearly visible in Fig. 7a, the untreated stone shows both TiA and P25 coatings the decrease of capillary absorption was not clearly
micritic (crystals b 2 μm) and crystalline texture. The hexagonal crystals observed, suggesting similar behavior between treated and untreated
of calcite, grown inside the pores, are distinguishable. A homogeneous surfaces in short time.
and crack-free coating is observed for the N-TiA-coated surface
(Fig. 7b). In contrast, the N-TiU-coated surface (Fig. 7c) and P25- 3.3. Photoinduced activity of TiO2 coatings
coated surface (Fig. 7d) are less uniform and reveal micro crystalline ag-
gregates of TiO2. The wettability, measured by the water contact angle, is a very im-
The EDS spectra were recorded from the corresponding micrograph portant property depending on the chemical composition and the struc-
areas, showing the presence of titania in all the treated samples. SEM- ture of the solid surfaces. The static contact angle values measured
EDS measurements on the cross sections, not reported here, reveal a before light irradiation show (Fig. 10) significant differences between
limited (0.3 b μm) penetration depth for both treatments. treated and untreated stones. In particular, the N-TiA coating induces
To verify the preservation of the original appearance, color measure-
ments were performed on the surface of the stone samples before and
after the application of the treatments. In Fig. 8 the total (ΔE*) and par-
tial (ΔL*, ΔC* and ΔH*) color differences and the colorimetric coordinate
differences (Δa*, Δb*) are reported. The total color difference ΔE* after
the application of the N-TiA and N-TiU treatments is lesser than 3, a
value which is well below the acceptable limit in the field of cultural
heritage [71]. The commercial P25 coating gives a higher color differ-
ence (~3) and a decrease of color saturation with respect to the untreat-
ed stone, probably due to the larger particles' size and the higher
agglomeration degree as observed by SEM analysis. Analyzing the be-
havior of the color coordinates, it can be concluded that the color change
is due to the decrease of b* parameter, indicating a slight yellowing of
the stone.
The effects of the coating on the behavior of the stones in the pres-
ence of water were evaluated by comparative measurements of water
absorption by capillarity (Qi) on untreated and titania coated samples,
according to standard tests [84]. The Qi values (kg/m2) as a function of Fig. 9. Capillarity water absorption tests carried on Travertine samples treated with P25,
square root of time (s1/2) are shown in Fig. 9 prior to and after coating, N-TiA and N-TiU. Open circles: untreated stone; full circles: treated stone. Error bars are
for each type of samples. Table 1 reports the relative capillary index shown on the legend symbols.
 L. Bergamonti et al. / Microchemical Journal 133 (2017) 1–12
Table 1
Capillary absorption coefficient (AC30) and relative capillary index (RCI).
AC30 AC30
Before coating After coating
P25 0.016 ± 0.001 0.015 ± 0.002
N-TiA 0.014 ± 0.002 0.012 ± 0.001
N-TiU 0.009 ± 0.001 0.006 ± 0.001
an increase of the water contact angle approaching hydrophobicity (al-
most 100°). This behavior is probably due to the homogeneous, smooth
film formed by this treatment, as previously observed by SEM analysis.
The well-known UV photoinduced hydrophilicity of TiO2 coatings is
a fundamental side effect of photocatalytic self-cleaning surfaces [34].
During light irradiation, the contact angle of N-TiA and P25 treated
stones decreased while the CA of N-TiU and untreated stone (UT)
remained roughly the same. In particular, for N-TiA coating, after 2 h
of irradiation the contact angle fell drastically to b30°, well below the
P25 values. The change during irradiation in the shape of water droplets
on a Travertine sample, coated with N-TiA sol, is shown in Fig. 10b.
To compare the self-cleaning ability of the different titania coatings,
we have chosen to evaluate the photocatalytic activity on stained stones
by means of colorimetric measurements of the photodegradation of
both methyl orange (MeO) and rhodamine B (RhB) dyes under expo-
sure to UV–VIS and VIS illumination as explained in the experimental
section.
The normalized change in the Chroma ΔCn is reported as a function
of the irradiation time (in minutes): Fig. 11 shows the discoloration of
the dyes on untreated (UT) and treated Travertine samples, under dif-
ferent light sources, enabling a comparison between the N-doped TiO2
coatings N-TiA and N-TiU with commercial P25. On the untreated
stone, slow photodegradation of the dyes takes place even in the ab-
sence of catalyst under the different irradiation sources: 20–30% for
MeO and 15–30% for RhB, after about 3 h, with higher discoloration
under UV–VIS Osram lamp. This may be due to the natural self-fading
of the dyes when exposed to light irradiation [100].
Under UV–VIS irradiation the efficiency of MeO decomposition sig-
nificantly improved in the presence of the photocatalysts (Fig. 11a).
The fastest and most effective decomposition was obtained by N-TiA
treatment that, at the end of the experiment, decomposed almost 90%
of the dye. A 40% and 60% MeO discoloration was obtained by N-TiU
and P25 catalysts, respectively, in both cases higher than the self-
fading of the dye on the untreated stone.
Fig. 10. (a) Evolution of the contact angle as a function of the irradiation time (b) Photographs of the water droplets over a Travertine sample coated by N-TiA, taken at 0, 60 and 120 min
(top to bottom).
9
The high photo-activity of the N-TiA coating is maintained also
blocking the UV portion by a filter, while both P25 and N-TiU do not in-
RCI (±0.02) duce appreciable changes in MeO discoloration with respect to the un-
treated stone, as evident in Fig. 11c.
0.93 The ΔCn curves for blue LED irradiation are reported in Fig. 11e: N-
0.96 TiA is again the most effective catalyst, photodegrading N 50% of the
0.84 MeO dye in 90 min, in spite of the slower kinetics under irradiation at
lower power with respect to the UV–VIS irradiation.
The effects of the photocatalysis on RhB are shown in Fig. 11b, d, f.
Under UV–VIS Osram irradiation (Fig. 11b) the degradation of the dye
is similar for all the treated surfaces and higher than for untreated
ones: 80% of discoloration is reached in 3 h.
Using UV filter (Fig. 11d) and LED (Fig. 11f) the photoactivity effi-
ciency of all TiO2 catalysts is moderate. The photo-cleaning induced on
stained surfaces by catalysts is faster during the first hour of irradiation
with respect to UT stones. With the UV filtered lamp the 40% of the RhB
cleaning is obtained only after about 3 h, whereas the same degradation
efficiency with the blue LED is obtained in about 7 h. On the untreated
stone the self-fading of the dye doesn't exceed the 15–20%.
Unlike MeO behavior, where the N-TiA coating, under visible light ir-
radiation, is clearly active, for RhB the different kinds of TiO2 seem to be
not particularly efficient.
The two dyes investigated in the photocatalytic tests behave in a
quite different manner during the discoloration. The difference of the
reactivities of the dyes could be due to their degree of adsorption on
TiO2, which depends both on the surface pH and on the ionization
state of the organic molecules [101]. It is known that at pH value less
than the Point of Zero Charge (PZC) of TiO2 (≈6.5) the surface is posi-
tively charged [78–100]. Therefore, one should expect that the methyl
orange anionic dye is better adsorbed on acid TiO2 (N-TiA) than on neu-
tral (P25) or basic (N-TiU) TiO2 [78]. This could explain the higher activ-
ity of the acid N-TiA compared to that of P25 and N-TiU in the photo-
degradation of MeO.
Rhodamine B is a cationic/zwitterionic dye and the adsorption most-
ly occurs at the basic/neutral TiO2 surfaces (negatively charged), like N-
TiU and P25 that indeed exhibit good photocatalytic performances, in
particular under UV–VIS irradiation. Nevertheless, also N-TiA has
proved to be very effective in RhB discoloration: this could be due to
the presence of the zwitterionic form of RhB, whose deprotonated car-
boxyl groups should make possible dye adsorption on N-TiA particles
[102].
Generally, in both dyes discoloration, the N-TiA revealed higher ac-
tivity: this result is correlated with the shifted absorption spectrum
10 L. Bergamonti et al. / Microchemical Journal 133 (2017) 1–12
and with the XPS results that indicated N doping in positions that direct-
ly affect the vicinity of the titanium atoms. The N atoms into TiO2 lattice
can form intermediate energy levels, leading to the narrow band gap of
TiO2.
In any case, the specimens treated with N-TiA or N-TiU show always
higher dye degradation than that obtained by P25, probably due to the
absorption at higher wavelengths.
4. Conclusions
Sol-gel N-doped TiO2-based photocatalytic coatings, prepared with
different Ti-precursors and N sources (N-TiA and N-TiU), were synthe-
sized, characterized and tested to evaluate their efficiency as self-
cleaning treatments for Travertine stone. The obtained TiO2 crystals
(anatase as main crystalline phase) have nanometric size. The presence
of nitrogen, that creates an enhancement in the visible-light absorption,
was confirmed by XPS analysis, which indicates that doping by an acidic
process (N-TiA samples) may yield nitrogen in substitutional positions
(or at least in positions that affect the immediate environment of
Fig. 11. Photocatalytic activity vs. time of P25, N-TiA and N-TiU coatings on methyl orange and rhodamine B under UV–VIS (a and b), UV-filter (c and d) and Blue LED irradiation (e and
f) measured by chromatic changes ΔCn of the stained stone.
titanium), whereas doping using urea as a nitrogen source usually yields
nitrogen in interstitial positions.
The coatings do not alter the aesthetic properties of Travertine stone
and slightly improve the resistance to the capillary water absorption. Both
treatments exhibit good photocatalytic activity under UV–VIS irradiation
in the discoloration of organic dyes such as methyl orange and rhodamine
B used as contaminants of the Travertine, even in the presence of potential
dye photosensitization effects. In particular, the photodegradation of MeO
by N-TiA is more efficient with respect to P25 and N-TiU whereas for RhB
no appreciable differences are found between the different treatments.
A more effective adsorption of the anionic MeO dye on the N-TiA
nanoparticles could explain this behavior.
By UV filtering or by using a blue-LED irradiation, the effectiveness of
N-TiA coating for MeO degradation is maintained, whereas, in the RhB
test, all treatments show a reduced activity.
The increase of the absorption in the visible range for the N-doped
TiO2 seems to be effective only for N-TiA with MeO. The results for rho-
damine B cannot definitely interpreted: this fact confirms the intrinsic
difficulties found when using dyes as model compounds for the deter-
mination of the photocatalytic activity [75].
 L. Bergamonti et al. / Microchemical Journal 133 (2017) 1–12
The UV photoinduced hydrophilicity, measured by the static water
contact angle as a function of irradiation time, is evident only in the
case of N-TiA coating that enhanced the wettability of the stone surfaces
improving the self-cleaning properties.
The results, due to the synergic effect of the anatase phase structure,
small crystallite size, high specific surface area and N-doping, highlight
the compatibility of the proposed treatments on the studied carbonatic
stone. Of the two tested treatments, N-TiA coating displays good self-
cleaning properties (hydrophilicity and photocatalytic activity), open-
ing interesting possibilities for building applications and in the cultural
heritage field.
Acknowledgments
Support from MAECI (project “NANO4HER, Nanotechnology at the
service of cultural heritage preservation”, Italy-Israel Scientific and Tech-
nological Cooperation, Ministry of Science) is gratefully acknowledged.
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