Supporting Information

Visible-Light-Activated Black Organotitanias: How

Synthetic Conditions Influence Their Structure and
Photocatalytic Activity
Jesffls Jimnez-Lpez, Noemi Linares, Elena Serrano,* and Javier Garca-Martnez*[a]

cplu_201800054_sm_miscellaneous_information.pdf
Supporting Information Visible-light activated black organotitanias: How synthesis conditions influence…

Visible-light activated black organotitanias: How synthesis conditions

influence their structure and photocatalytic activity

J. Jiménez-López,[a,b] N. Linares,[a] E. Serrano,*[a] J. García-Martínez*[a]

[a] Laboratorio de Nanotecnología Molecular, Departamento de Química Inorgánica, Universidad de Alicante, Ctra. San
Vicente-Alicante s/n, E-03690 Alicante, Spain. elena.serrano@ua.es, j.garcia@ua.es; www.nanomol.es

[b] Current address: Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and technology
(BIST), Av. Països Catalans, 16, E-43007, Tarragona, Spain

Table of contents

1. Experimental Section…………………………………………………………………………………………………… 1

2. Results and Discussion………………………………………………………………………………………………… 2

2.1. Crystal structure characterization and textural properties…………………………………………………… 2

2.1.1. Effect of the volume of water for samples using a molar ratio of EtOH/TBOT= 41……………………… 2

2.1.2. Effect of the volume of water for samples prepared using a molar ratio of EtOH/TBOT= 12………….. 4

2.1.3. Effect of crystallization time at 80ºC…………………………………………………………………………….. 6

2.2. Photocatalytic activity………………………………………………………………………………………………… 8

1. Experimental Section

XRD analyses were carried out in order to study the crystalline structure of the materials. XRD measurements were carried out with a
Bruker D8-Advance diffractometer (operating at 40 kV and 40 mA), using a CuKα radiation (λ = 1.54056 Å). The samples were scanned
from 20º to 60° (2θ), at a scanning rate of 0.05 min-1. Lattice spacing (d101) of samples was calculated using Eq. Bragg. The average
crystallite size, referred as crystalline domain size, was determined from the broadening of the main reflections of anatase by Scherrer’s
formula:

D (nm) = K  /  cos  (1)

where K is the form factor (0.93),  is the full width at half the maximum intensity after subtraction of the instrumental noise, and  is the
diffraction angle. The degree of crystallinity was followed by analyzing the ratio between the intensity of the (101) peak at any crystallization
time/water volume with respect the maximum of the respective intensity peak of the control titania. For some samples, the degree of
crystallinity was determined with respect to 100% crystalline CaF2 samples using XRD diffractograms of physical mixtures titania/CaF2
50/50 wt% (see Figure S7), following the Jensen’s method.[1] According to this method, the amount of crystalline anatase for these mixtures
can be calculated using the equation (1):

Anatase (%) = (Aanatase, 101 / ACaF2, 220) / 1.25 x 100 (2)

where Aanatase, 101 and ACaF2, 220 are the areas determined from the (101) and (220) peaks of anatase and CaF2 in the XRD spectra of their
physical mixture, respectively, and 1.25 is the value of the ratio between the areas of the same peaks when a pure anatase crystalline
titania sample is used determined by Jensen et al. [1] Since rutile has not been detected by XRD and the amount of brookite in all the samples
is too small as to performed any calculations, the percentage of crystallinity (wcrys) and amorphous phases in these samples has been
estimated by assuming 100% anatase phase.

The incorporation of PPD in the titania samples was evaluated by FTIR and XPS spectroscopy techniques, and the content of the organic
compound in the final titania material was analyzed by TG analyses carried out in a Mettler Toledo TG-ATD (TGA/SDTA851e/sf/110). The

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measurements were carried out under nitrogen/oxygen atmosphere (4:1) from room temperature to 900 ºC, with a heating rate of 10 ºC
min-1. The morphology of these titanias was investigated by transmission electron microscopy (TEM) using a JEM-2010 microscope (JEOL,
200 kV, 0.14 nm of resolution). Samples for TEM studies were prepared by dipping a sonicated suspension of the sample in ethanol on a
carbon-coated copper grid. The digital analysis of the TEM micrographs was performed using Gatam DigitalMicrographTM 1.80.70 for GMS
1.8. Porous texture was characterised by N2 physisorption experiments at 77 K in an AUTOSORB-6 apparatus and the results were
analysed using the software package AUTOSORB1 (Quantachrome Corporation). The samples were previously degassed for 5 h at 373 K
at 5x10−5 bars. BET surface areas were estimated by using multipoint BET method, using the adsorption data in the relative pressure (P/P0)
range of 0.05–0.30. The pore size distribution was obtained by NL-DFT from the adsorption branch of the N2 isotherms. As expected for
these materials, the micropore volume, estimated from the t-plot method, was determined to be zero and thus the mesopore volume can
be directly read from the isotherms at relative pressure of 0.9. These values are in good agreement with those obtained from the adsorption
branch of the nitrogen isotherm using the NL-DFT method, where the volume was measured at the plateau of the cumulative adsorption
pore volume plot. The X-ray Photoelectron Spectroscopy (XPS) analyses were carried out in a VG-MicrotechMultilab instrument, using
MgK-alpha radiation of energy 1253.6 eV and pass energy of 50 eV. The pressure during the data acquisition was 5*10 -7 Pa. A careful
deconvolution of the spectra was made and the areas under the peaks were estimated by calculating the integral of each peak after
subtracting a Shirley background and fitting the experimental peak to a combination of Lorentzian/Gaussian lines of 30-70 % proportions.
XPS spectra were analysed by referencing the binding energies to both the C1s line at 284.6 eV from adventitious carbon and Ti2p line at
458.5 eV. The band gap of the titania materials was estimated by DRUV measurements. DRUV spectra were carried out in air at room
temperature in the wavelength range 800-200 nm using a Shimadzu UV-2401 PC spectrophotometer with BaSO4 as the reference material.
For the estimation of the band-gap, the reflectance data were converted into the equivalent absorption coefficient using the Kubelka-Munk
formalism, equation (3):

F(R´) = [1-(R´)]2/2(R´) (3)

where R´ is the reflectance value obtained directly from the spectrophotometer. Band gap calculations are based on the [F(R’)h]n/2 versus
photon energy (h) plot (Tauc plots). XPS spectra of these materials were obtained in the −10 to 2 eV region to calculate the position of the
maximum of their valence bands. Both techniques, i.e. DRUV and XPS in the valence band region, were combined to determine the
maximum of the conduction band position of the titania materials and to obtain the density of states (DOS) scheme.

Photocatalytic activity. The photocatalytic activity of the synthesized materials was evaluated in the degradation reaction of Rhodamine
6G in aqueous solution under UV or visible radiation. For a typical UV light degradation test, an aqueous suspension of Rhodamine 6G
(5x10-5 M, 100 ml) with 0.15 g L-1 of as-synthesized catalyst was stirred during 30 min in the dark, to achieve the adsorption/desorption
equilibrium of the dye on the catalyst surface. Afterwards, this suspension was irradiated with UV light using a photochemical reactor system
with a 125 W medium-pressure Hg lamp located in cooled, double-walled quartz, immersion well. The concentration of the dye was
monitored by UV-Vis spectroscopy analysis in the 700-300 nm wavelength range, using a Jasco V-650 UV-vis spectrophotometer. As
several intermediate species can appear during the photodegradation process, the total concentration of Rhodamine species was estimated
based on the maximum absorbance observed in the 490 to 530 nm range. The pseudophotocatalytic constants of the reaction were
determined from the average of a minimum of three runs. In all cases, the plot of ln(C0/C) vs irradiation time (t), where C0 and C are the
initial concentration and the concentration measured during the reaction, respectively, could be adjusted to a linear fit, which means a
pseudo-first reaction order, from which the pseudophotocatalytic constants were estimated. For the experiments under visible light, a
similar procedure was followed, but using a 400 W medium-pressure Hg lamp located in a double-walled Pyrex immersion well, cooled with
a 2 M solution of NaNO2 (UV cut-off filter > 400 nm). In these experiments, the concentration of catalyst used was 0.4 g L-1. For comparison
purposes, the photocatalytic activity of the commercial titania P25 (Aeroxide P25, Across organics) was also assessed. For samples
irradiated with UV light, a total organic carbon analyser (TOC 500A, Shimazu) was used in order to determinate the TOC content of the
synthesized samples before and after bleaching of the sample. A calibration curve using Rhodamine 6G with different concentrations was
used for determining TOC contents of samples.

2. Results and Discussion

2.1. Crystal structure characterization and textural properties

2.1.1. Effect of the volume of water for samples using a molar ratio of EtOH/TBOT= 41

XRD analysis. It should be noted that in all the materials prepared in this work an additional diffraction peak of very low intensity
appears in both TiO2 and TiO2-PPD at 2θ = 30.7º, which corresponds to the (121) peak of brookite. The 100% intensity (101) peak
of anatase overlaps with the 100% intensity (120) and the 80% intensity (111) peaks of brookite (JCPDS cards No. 21-1272 and
29-1360, respectively). Given the overlapping between the main peaks of both crystalline phases, as well as the very low intensity
of the 2θ = 30.7º peak, quantitative analysis of this peak was not possible. A simple comparison between the integrated intensities
of the (121) peak of brookite and the (101) peak of anatase gives a brookite content of only ca. 4% after 24 h of crystallization at
80ºC. Thus, the main phase in both the control titania and the black organotitanias herein synthesized is anatase.

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Supplementary Table S1. Structural and textural parameters of control titanias as a function of the volume of water
added during the hydrolysis step for samples prepared using a molar ratio of EtOH/TBOT= 41 (35 ml EtOH per gram of
titania).

VH2O [ml] VH2O / VEtOH H2O/ TBOT[a] DXRD[b] [nm] I101/Imax [b] SBET[c] [m2 g-1] Vt[c] [cm3 g-1] dp[c] [nm]

5 0.14 19 n.c. n.c. 460 0.25 2.6

10 0.29 38 5.6 0.9 315 0.25 4.2

20 0.57 76 5.0 1.0 280 0.31 5.0

40 1.14 152 5.4 1.0 --- --- ---

60 1.71 228 --- --- --- --- ---

125 3.57 467 5.1 1.0 275 0.35 5.5

[a] Water-to-titania molar ratio. [b] Crystalline domain size (DXRD) and the intensity of (101) peak normalized with respect
to the maximum intensity of the (101) peak of the control TiO2, from XRD measurements. n.c.: non crystalline. [c] BET
surface area (SBET), total pore volume at P/P0 = 0.9 (Vt) and interparticle pore size (dp) from N2 adsorption/desorption
isotherms at 77K.

125 ml
40 ml
20 ml VH2O
10 ml
5 ml
I / a.u.

20 30 40 50 60
2 / 

Supplementary Figure S1. XRD patterns of control titanias, TiO2, as a function of the volume of water added during the hydrolysis step for samples prepared
using a molar ratio of EtOH/TBOT= 41 (35 ml EtOH per gram of titania).

Raman analysis. The Raman spectra of both the control titania and TiO2-PPD match well with the characteristic peaks of anatase
presenting Raman shifts of 147 (Eg), 197 (Eg), 398 (B1g), 513 (A1g, B1g doublet) and 637 cm-1 (Eg) (Figure S2). Nonetheless, there
is a shift of the most intense vibrational mode of anatase from the theoretical value of 144 cm -1 to 147 cm-1 (and 151 cm-1) for control
(and black) titania. Theoretical shifts of the Eg mode of anatase and the A1g mode of brookite are 144 and 154 cm-1, respectively
(the presence of rutile was discarded, based on both the Raman spectra and the XRD results already shown). [2] However, it has
been previously reported that the intensity of the Eg mode of anatase is strongly damped in mixtures of anatase and brookite in
comparison with their higher wavenumber modes, even when only traces of brookite are present in the mixture. [2] Taking into
account the high intensity of the band at 147 (151) cm -1 in the Raman spectra shown in Figure S2, although the shifts of the most
intense peak could be ascribed to the presence of brookite, the main phase in both the control titania and the black organotitanias
is anatase.

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151 (A+B?)

147 (A+B?)
I / a.u.

197 (A)

637 (A)
513 (A)
398 (A)

TiO2 -PDD

Control TiO2

100 200 300 400 500 600 700 800 900 1000
-1
Raman shift / cm

Supplementary Figure S2. Raman spectra of a black organotitania (TiO2-PPD, blue line) and control TiO2 (TiO2, black dashed line) for samples prepared
using a molar ratio of the synthesis gel: 1 TiO2/0.1 PPD/228 H2O/41 EtOH. Spectra have been vertically shifted for clarity (A: anatase; B: brookite).

A) B) 2.4
2.0
125 ml 125 ml
60 ml 40 ml
2.0
1.6 40 ml 20 ml VH2O
VH2O
20 ml 10 ml
dV(log d) / cm g STP
dV(log d) / g cm STP

10 ml 5 ml
1.6
5 ml
-1

1.2
-3

1.2

0.8
0.8

0.4
0.4

0.0 0.0
1 10 100 1 10 100
dp / nm dp / nm

Supplementary Figure S3. Pore size distribution of TiO2-PPD black organotitanias (A) and control TiO2 (B) as a function of the volume of water added during
the hydrolysis step for samples prepared using a molar ratio of EtOH/TBOT= 41 (35 ml EtOH per gram of titania).

2.1.2. Effect of the volume of water for samples prepared using a molar ratio of EtOH/TBOT= 12

125 ml
60 ml
VH2O
40 ml
20 ml
I / a.u.

20 30 40 50 60
2 / 

Supplementary Figure S4. XRD patterns of control titanias as a function of the volume of water added during the hydrolysis step for samples prepared using
a molar ratio of EtOH/TBOT = 12 (10 ml EtOH per gram of titania).

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Supplementary Table S2. Structural and textural parameters of TiO2-PPD black organotitanias in comparison with the control titanias
(TiO2) as a function of the volume of water added during the hydrolysis step for samples prepared using a molar ratio of EtOH/TBOT= 12
(10 ml EtOH per gram of titania).

VH2O [ml] VEtOH [ml] VH2O / VEtOH H2O/ TBOT [a] DXRD[b] [nm] I101/Imax [b] SBET[c] [m2 g-1] Vt[c] [cm3/ g-1] dp[c] [nm]

TiO2-PPD

20 10 2 76 5.1 0.9 250 0.42 6.1

40 10 4 152 5.1 0.9 252 0.42 7.0

60 10 6 228 5.1 0.9 235 0.41 7.8

125 10 12.5 467 4.9 0.9 255 0.44 7.9

TiO2

20 10 2 76 5.4 1.0 249 0.45 5.6

40 10 4 152 5.0 1.0 280 0.35 5.4

60 10 6 228 5.1 1.0 --- --- ---

125 10 12.5 467 4.9 1.0 240 0.30 5.4

[a] Water-to-titania molar ratio. [b] Crystalline domain size (DXRD) and the intensity of (101) peak normalized with respect to the maximum
intensity of the (101) peak of the control TiO2, from XRD measurements. [c] BET surface area (SBET), total pore volume at P/P0 = 0.9 (Vt)
and interparticle pore size (dp) from N2 adsorption/desorption isotherms at 77K.

A) 2.0
125 ml
60 ml
40 ml VH2O
1.6
20 ml
dV(log d) / cm g STP

1.2
-1
3

0.8

0.4

0.0
1 10 100
dp / nm
B) 400 C) 2.0
125 ml 125 ml
350
40ml VH2O 40 ml VH2O
20ml 1.6 20 ml
300
dV(log d) / cm g STP
V / cm g STP

250
1.2
-1
-1

200
3

150 0.8

100
0.4
50

0 0.0
0.0 0.2 0.4 0.6 0.8 1.0 1 10 100
P/P0 dp / nm

Supplementary Figure S5. (A) Pore size distribution of TiO2-PPD black organotitanias, (B) N2 adsorption/desorption isotherms at 77 K and (C) the
corresponding pore size distribution of control TiO2 as a function of the volume of water added during the hydrolysis step for samples prepared using a molar
ratio of EtOH/TBOT = 12 (10 ml EtOH per gram of titania).

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2.1.3. Effect of crystallization time at 80ºC for samples prepared using only 20 ml of water and 10 ml of
ethanol per gram of titania

Supplementary Table S3. Structural and textural parameters of control TiO2 prepared at 80ºC using different crystallization
times. Molar ratio of the synthesis gel: 1 TiO2 /76 H2O/12 EtOH.

Sample tcrys [a] (h) d101[b ][nm] DXRD[b] [nm] I101/Imax [b] SBET[c] [m2 g-1] Vt[c] [cm3 g-1] dp[c] [nm] Eg[d] [eV]

TiO2--0 0 n.c. n.c. n.c. 430 0.33 2.5 3.3

TiO2-4 4 0.35 4.1 0.6 270 0.36 5.1 ---

0.7
TiO2-6 6 0.35 4.0 --- --- --- 3.2

0.8
TiO2-12 12 0.35 4.6 262 0.36 5.5 3.1

0.8
TiO2-14 14 0.35 5.0 273 0.36 5.5 3.1

TiO2-24 24 0.35 5.4 1.0 249 0.45 5.6 3.2

[a] Crystallization times at 80ºC. [b] Lattice spacing (d101), crystalline domain size (DXRD) and ratio between the intensity of (101)
peak normalized with respect to the maximum intensity of the (101) peak of the control TiO2, from XRD measurements. n.c.: non
crystalline [c] BET surface area (SBET), total pore volume at P/P0 = 0.9 (Vt) and interparticle pore size (dp) from N2
adsorption/desorption isotherms at 77K. [d] Band gap from the DRUV measurements.

B)
24 h
14 h
12 h tcrys
6h
4h
0h
I / a.u.

20 30 40 50 60
2 / 

Supplementary Figure S6. XRD patterns of control TiO2 as a function of the crystallization time (tcrist) at 80ºC (molar ratio of the synthesis gel: 1 TiO2/76 H2O/12
EtOH).

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A) B)
CaF2 CaF2
CaF2
Intensity / a.u.

Intensity / a.u.
A CaF2 A

A A A

20 30 40 50 60 20 22 24 26 28 30 32
2 2

Supplementary Figure S7. (A) XRD pattern of a physical mixture of TiO2-PPD black organotitania and CaF2 (50/50 wt%) for a black organotitania prepared
using a molar ratio of the synthesis gel: 1 TiO2:0.1 PPD:76 H2O:12 EtOH. (B) The corresponding deconvolution of the XRD pattern in the 2 = 22º – 30º region.
Black line corresponds to the experimental data (A: anatase; B: brookite).

A) 2.0
0h 12 h
2h 14 h
1.6 4h 24 h
6h
-1
dV(log d) / cm g
-3

1.2

0.8

0.4

0.0
1 10 100
dp / nm

B) 400 C) 2.0
200 0h 12 h
350 2h 14 h
V / cm g STP)

1.6 4h 24 h
300 150 6h
-1

dV(log d) (cm g )
-3

-1
V / cm g STP

250
-3

100 1.2
-1

200
-3

0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

P/P0
150 0.8
0h
100 4h
12 h 0.4
50 14 h
24 h
0 0.0
0.0 0.2 0.4 0.6 0.8 1.0 1 10 100
P/P0 dp (nm)

Supplementary Figure S8. (A) Pore size distribution of TiO2-PPD black organotitanias, (B) N2 adsorption/desorption isotherms at 77 K, and (C) the
corresponding pore size distribution of control titanias TiO2 as a function of the crystallization time (tcrist) at 80ºC. Molar ratio of the synthesis gel: 1 TiO2:0.1
PPD:76 H2O:12 EtOH.

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A) B)
C)
Ti 2p Ti 2p Ti 2p

TiO2 (24 h) TiO2 (24 h)

TiO2-PDD (24 h)
TiO2-PDD (24 h)

Intensity / a.u.
Intensity / a.u.
Intensity / a.u.

466 464 462 460 458 456 466 464 462 460 458 456 466 464 462 460 458 456
Binding energy / eV Binding energy / eV Binding energy / eV

Supplementary Figure S9. XPS in the Ti2p region of: (A) the TiO2-PPD black organotitania (blue line) and the control titania, TiO2 (black dashed line), after
24 h of crystallization at 80ºC (molar ratio of the synthesis gel: 1 TiO2/0.1PPD/76 H2O/12 EtOH). Spectra have been vertically shifted for clarity. (B) and (C)
display the XPS spectra of the control titania and the black organotitania, respectively, showing both the raw data and the fitting of each of the doublet Ti2p 3/2
and Ti2p1/2.

3. Photocatalytic activity

A) B)
27
0 min EtOH/TBOT = 41
1.2 20 min
(20 - 125 ml H2O)
Absorbance / a.u.

40 min
60 min 24 EtOH/TBOT = 12
80 min 3.8 wt%
(12 - 24 h cryst. 80C)
1.0 100 min

21
-1
k ' x 10 / min

0.8 3.4 wt%

18 2.6 wt%
ln (C0/C)

450 480 510 540 570 600

3

4.8 wt%
0.6 Wavelength / nm
15
2.0 wt%
1.6 wt%
0.4 12
125 ml 2.0 wt%
60 ml 9
0.2 40 ml Control TiO2

20 ml 6
0.0
0 10 20 30 40 50 60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00
100
t / min max
crystallinity (I101/I101 x 100) / %
Supplementary Figure S10. (A) Photocatalytic activity of the TiO2-PPD black organotitanias in the degradation reaction of an aqueous solution of Rhodamine
6G (5 × 10−5 M) under UV-vis irradiation as a function of the volume of water added during the hydrolysis step for samples prepared using a molar ratio of
EtOH/TBOT= 41 (35 ml EtOH). (B) Representation of the pseudophotocatalytic constant (k´) of TiO2-PPD black organotitanias as a function of the PPD content
and crystallinity (defined as the intensity of the (101) peak normalized with respect to the maximum intensity of the (101) of the control titania) for samples
prepared using different water-to-ethanol volume ratio, water-to-titania precursor molar ratio and different crystallization times in comparison to the control
titania. The PPD content (wt%) for each of the organotitania is indicated in the plot.

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0.5
1.0

0.8
0.4 Black organotitania
0.6
P25
C/C 0

0.4
0.3
ln (C0/C)

0.2

0.0
0.2 1 2 3 4
t/h

0.1

0.0
0 50 100 150 200 250 300
t / min

Supplementary Figure S11. Photocatalytic activity of the TiO2-PPD black organotitania (prepared using 125 ml of water and a molar ratio of EtOH/TBOT=
41 and 24 h of crystallization at 80ºC) compared to the commercially available Aeroxide P25 in the degradation reaction of an aqueous solution of
Rhodamine 6G (5 × 10−5 M) under visible light irradiation.

References

[1] H. Jensen, K.D. Joensen, J.-E. Jørgensen, J.S. Pedersen, E.G. Søgaard, J. Nanopart. Res. 2004, 6, 519–526.
[2] a) L. Zhang, Z. Xing, H. Zhang, Z. Li, X. Zhang, Y. Zhang, L. Li, Wei Zheou, ChemPlusChem 2015, 80, 623 – 629; b) C.S. Campos, E.
R. Spada, F. R. de Paula, F. T. Reis, R. M. Faria, M. L. Sartorelli, J. Raman Spectrosc. 2012, 43, 433–438; c) W. Li, R. Liang, A. Hu, Z.
Huanga, Y. N. Zhou, RSC Adv. 2014, 4, 36959–36966; d) R.M. Kadam, B. Rajeswari, Arijit Sengupta, S.N. Achary, R.J. Kshirsagar, V.
Natarajan, Spectrochim. Acta A 2015, 137, 363–370; e) H. Li, M. Vrinat, G. Berhault, D. Li, H. Nie, P. Afanasiev, Mater. Res. Bull. 2013,
48, 3374–3382.

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