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Supporting Information for

The effect of nature and location of defects on bandgap


narrowing in black TiO2 nanoparticles
Alberto Naldoni,* Mattia Allieta, Saveria Santangelo, Marcello Marelli, Filippo Fabbri,
Serena Cappelli, Claudia L. Bianchi, Rinaldo Psaro, and Vladimiro Dal Santo*

[*] Dr. A. Naldoni, Dr. R. Psaro, Dr. V. Dal Santo,


CNRIstituto di Scienze e Tecnologie Molecolari, Via C. Golgi 19, Milano 20133, Italy
E-mail: a.naldoni@istm.cnr.it; v.dalsanto@istm.cnr.it;
Fax: +39-02-50314405; Tel: +39-02-50314428
Dr. M. Allieta, S. Cappelli, Prof. C. L. Bianchi
Dipartimento di Chimica Fisica ed Elettrochimica, Universit degli Studi di Milano,
Via Golgi 19, Milano 20133, Italy
Dr. M. Marelli
CNRIstituto di Scienze e Tecnologie Molecolari,
Via Fantoli 15/16, Milano 20138, Italy
Prof. S. Santangelo
Dipartimento di Meccanica e Materiali, Universit Mediterranea di Reggio Calabria, Loc. Feo di Vito,
89122 Reggio Calabria, Italy
Dr. F. Fabbri
IMEM-CNR Institute, Parco Area delle Scienze 37/A , 43100 Parma, Italy.

Contents
1. Preparation of TiO2 samples

2. Structural and electronic characterization methods

3. Figures

4. Tables

5. References

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1. Preparation of TiO2 samples


A commercial amorphous TiO2 (NanoActive, NanoScale Corporation, USA) was used as precursor. Small
amounts of the amorphous powder (up to 300 mg) were initially treated under vacuum (10-5 mbar) and then
heated at 200C under flowing O2 for 1 h, in order to oxidize and favor the desorption of molecular species
adsorbed onto the surface of the metal oxide. After the sample reached RT, the obtained TiO2 (TiO2 ox200) was
subjected to different thermal treatments: oxidation in flowing O2 at 500 C for 1 h (white TiO2), or reduction in
H2 flow at 400 C (TiO2 red400), 450 C (TiO2 red450), and 500 C (black TiO2) for 1 h. In order to study the
influence of precursor crystallinity, we reduced (H2 flow) for 1 h at 500 C the already crystalline P25 Degussa
and white TiO2. All thermal treatments were carried out using a heating rate of 10 C/min. The sample cooling
was performed under inert gas flow by placing the reactor outside the furnace, or turning off the furnace and
leaving the reactor inside it. A cooling rate of approximately 50 C/min and 2 C/min was obtained in the two
cases, respectively.

2. Structural and electronic characterization methods


X-ray powder diffraction (XRPD): Preliminary powder diffraction measurements were performed on all
prepared samples using a Siemens D500 diffractometer operating at 40 kV and 30 mA and at Cu K radiation
source. Data were collected using a scan rate of 1.25 deg/min and a step size of 0.02 deg.
Synchrotron X-ray powder diffraction (SXRPD): White TiO2 and black TiO2 samples were investigated also by
SXRPD. Data were collected at ID31 high-resolution powder diffraction beam-line of the European Synchrotron
Radiation Facility (ESRF, Grenoble). The powdered samples were loaded in 1 mm diameter kapton capillaries
and spun during measurements to guarantee a well powder randomization. A wavelength of = 0.354130(1)
was selected and diffracted intensities were collected at room temperature in the 0< 2 < 60 range for a total
counting time of 40 minutes for each sample. The XRPD patterns were analyzed with the Rietveld method as
implemented in the GSAS software suite of programs,1 which feature the graphical interface EXPGUI.2 Starting
structural models for anatase and rutile TiO2 phases were taken from [3] and [4], respectively. The background
was fitted by Chebyshev polynomials. Absorption correction was performed through the Lobanov empirical
formula [5] implemented for the Debye-Scherrer geometry. In the last refinement cycles, scale factor(s), cell
parameters, positional coordinates, isotropic thermal parameters and occupation factor for all the atoms, as well
as background and line profile parameters, were allowed to vary.
The average particle size was estimated from the synchrotron diffraction pattern using the Williamson Hall
(WH) plot method. WH method considers the broadening of the peaks mainly induced by the size and strain
contributions. From the peak width data as a function of diffraction angles it is then possible to determine the
dimension (DV) and the strain parameter () according to the relation:

obs

inst cos = / DV + 4 sin

(1)

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where obs and inst are the observed and instrumental integral breadths of the reflection collected at . To
evaluate the instrumental integral breadths as a function of we employed a diffraction pattern collected on Si
standard sample.
Figure S3 (a) and (b) shows the WH plots related to white and black sample, respectively. Note that, since few
peaks related to the rutile phase are well separated, the WH method was applied only to the anatase TiO2 phase
in the black sample. For the rutile a single peak method (i.e., Scherrer equation) was used to estimate DV using
the (110) reflection.
High-resolution transmission electron microscopy (HRTEM) analysis: dimension, morphology, and exposed
facets of investigated nanocrystals were evaluated by HRTEM. Samples were finely ground using an agate
mortar and then dispersed in isopropanol in an ultrasonic bath. A drop of the suspension was gently deposited
on a holey-carbon film supported on a copper 300 mesh grid. The specimen, after solvent evaporation, was
inserted in the column of a ZEISS LIBRA 200FE HRTEM. TEM micrographs were taken, spanning wide
regions of all examined samples in order to provide a truly representative and statistical map of TiO2 powders.
Parallel electron energy loss spectra were collected with the ZEISS on-column Omega filter system coupled
with the high resolution CCD camera.
Micro-Raman analysis: Raman scattering excited at 2.41 eV (514.5 nm) was measured using a microscope
(Olympus BX40, X50 objective) coupled to a double monochromator (Jobin Yvon Ramanor U-1000) and a
photomultiplier (Hamamatsu R943-02) operating in photon-counting mode. In order to minimize heating of the
sample a low laser-power (3 mW at its surface) was chosen. A sufficient S/N ratio was obtained using an
acquisition time of 30 s. Further details about instrumentation utilized and spectra-fitting procedure are reported
elsewhere.6
Cathodoluminescence spectroscopy (CL): emission spectra were acquired by using a commercial
GatanMONOCL2 system mounted on a S360 Cambridge Stereoscan scanning electron microscope. The system
was equipped with a grating and a multi-alkali photomultiplier sensitive in the range 350 830 nm (3.6 eV - 1.5
eV). The spectra were collected with an accelerating voltage of 10 kV, a beam current of 75 nA and a spectral
resolution of 9 nm (about 70 meV).
Diffuse reflectance UVvis (DRUV-vis) analysis: spectra of carefully ground powders were measured on a
Thermo Scientific spectrophotometer (Evolution 600), which was equipped with a diffuse reflectance accessory
PrayingMantis sampling kit (Harrick Scientific Products, USA). A Spectralon disk was used as reference
material for background measurement. All the samples were measured under ambient conditions.
X-ray photoelectron spectroscopy (XPS): spectra were acquired in an M-probe apparatus (Surface Science
Instruments). The source was a monochromatic Al K radiation (1486.6 eV). The binding energy (BE) was
corrected for specimen charging by referencing the C 1s peak to 284.6 eV. For the background subtraction the
Shirleys method was used.7 The relevant fittings were performed using only Gaussian line shapes, without BE
or FWHM (full width at half maximum) constraints. The accuracy of the reported BE can be estimated to be
0.1 eV.
Electron paramagnetic resonance spectroscopy (EPR): spectra were recorded at RT and 100K on a continuous
wave X-band Bruker E500 spectrometer equipped with a standard rectangular cavity (ER4102ST) at a
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microwave power of 6.36 mW. Microwave frequencies were measured with a Hewlett Packard frequency
counter and the magnetic field was calibrated by using the g-value of a solid DPPH standard. P25 shows no EPR
signal (data not reported). This means that neither pure anatase nor pure rutile can account for the EPR peaks
observed in the black TiO2 sample (see manuscript).

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3. Figures

Figure S1: SXRPD pattern and picture of white TiO2.

Figure S2: (a) DRUV-vis spectra of P25 Degussa (green solid line), white TiO2 (black line), black TiO2 (red
line), reduced P25 (green dashed line), reduced white TiO2 (black dashed line). The effects of 1h reduction at
500C under H2 flow on amorphous or already crystalline samples are notably different. In the first case, the
reduction process (giving black TiO2, red line) induced the red-shift of the UV absorption threshold and a high
absorption in the visible region (and the NIR region) that accounts for the black color of the powder.
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Differently, reduction of crystalline samples resulted in negligible absorption change. After the H2 treatment
both samples turned from white to a pale blue color with absorption spectra (reduced P25, green dashed line;
reduced white TiO2, black dashed line) resembling the reference ones (P25, green solid line; white TiO2, black
solid line, respectively). (b) DRUV-vis spectra of P25 Degussa (black solid line), white TiO2 (black dashed
line), TiO2 red400 (yellow dashed line), TiO2 red450 (green line), black TiO2 (red line).

Figure S3: XRPD patterns of all considered samples measured with a Siemens D500 diffractometer. From the
bottom to the top of the figure: NanoActive TiO2 was the precursor powder, TiO2 ox200 was obtained oxidizing
(O2 flow) Nanoactive TiO2 at 200C for 1h. The other samples were prepared starting from TiO2 ox200: white
TiO2 was obtained through an oxidizing treatment (O2 flow) at 500C for 1h; TiO2 red400, TiO2 red450, black
TiO2, were obtained applying a reducing treatment (H2 flow) for 1 h at 400C, 450C, 500C, respectively. P25
by Degussa was used as reference TiO2.

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Figure S4: The Williamson-Hall plots of the TiO2 anatase phase related to (a) white and (b) black samples,
respectively. In the panels the Miller index of the diffraction peaks used in the analysis, as well as parameters
obtained from the fitted lines (blue lines), are reported.

Figure S5: Results of decomposition of Micro-Raman spectrum of black TiO2 nanoparticles. Lorentzian Raman
line-shapes (dotted lines), superimposed to a Gaussian VO related photoluminescence (PL) band (dashed line,
centered at 2.35 eV), are used to reproduce the measured spectral profile (red circles). Inset: in order to evidence
the photoluminescence band the same spectral profile is re-plotted against energy expressed in eV. The high
crystallinity of the sample accounts for the high intensity of Raman features with respect to the PL band.

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Figure S6: Gaussian decomposition of the CL spectra reported in Figure 1c in the manuscript, for black TiO2
nanoparticles (a) and P25 powder (b). The decomposition procedure revealed that both the spectra were mainly
composed by three peaks centered at 2.77 eV, 2.63 eV and 2.36 eV. The spectrum of P25 showed an additional
faint shoulder on the high-energy side, at 3.25 eV. The calculation of the integrated intensity (not reported) of
the CL components evidenced that in black TiO2 the bands at 2.63 eV and 2.36 eV are more intense than in
P25. The higher intensities of these bands are related to the higher concentration of oxygen vacancy in black
TiO2 nanoparticles.

Figure S7: HRTEM micrograph of an aggregate of anatase white TiO2 crystallites viewed along the anatase
[010] lattice plane. Panels (a), (b), (c) show diffractograms obtained from the regions enclosed by the red boxes.

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Figure S8: HRTEM micrograph of a single nanocrystal of anatase viewed along the anatase [010] direction in
the P25 sample. The inset shows the diffractogram of the crystal.

Figure S9: HRTEM image of P25 TiO2. Panel (a) and (b) show the FFT obtained from the regions enclosed by
the red boxes. Panel (a) shows the diffractogram of a hexagonal single crystal of anatase viewed along the

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anatase [010] direction. Panel (b) indicates the presence of rutile and anatase phases. As shown by the HRTEM
image, the two contributes are obtained from different overlapped crystals.

Figure S10: HRTEM micrographs of black TiO2 nanocrystals along with their diffractograms (see inset).
Images (a) and (b) show two anatase single crystals with their characteristic outer disorder surface layer
indicated by black arrows. Differently, image (c) represents one rutile crystal superimposed to an anatase one.
This observation proves that anatase and rutile are present in separated nanocrystals.

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Figure S11: Comparison of fine structural features of EELS spectra of O-K edge for white (black line) and
black TiO2 (red line). In the black TiO2 spectrum, the superimposed features, indicated with an arrow, are due to
the presence of the rutile (R) phase in the sample.

Figure S12: EPR spectra of black TiO2 measured at 100 K. The strong EPR signal at about g = 1.957 is
characteristic of paramagnetic Ti3+ centers.

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Figure S13: XPS spectra of the Ti 2p peak and O 1s peak for P25 Degussa (a and c) and black TiO2 (b and d),
respectively. Inside (c) the different atomic species present at the surface are indicated as OL = TiO2 lattice
oxygen and OOH = oxygen from OH species.

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4. Tables
Table S1: Refined structural parameters (phase composition and crystallite size) and optical bandgap of selected
TiO2 samples.

Samples

Phase composition
(%)

Crystallite size
(DV-nm)*

Optical Band
gap
(eV)

P25

80

20

25

3.25

TiO2 red400

100

3.05

TiO2 red450

100

3.05

White TiO2

See Table S2

3.15

Black TiO2

See Table S3

2.75

DV parameter was evaluated using Scherrer equation based on the (101) anatase reflections.

Table S2. Refined structural parameters and WH parameters for the anatase phase of white TiO2 sample. Spacegroup I41/amd. Atomic positions: Ti 4b (0 3/8), O 8e (0 z). Agreement factors are Rwp=0.0688, 2=1.691,
R(F2)=0.0484.
White TiO2 / Anatase phase
a/

3.78670(1)

c/

9.49890(1)

V/3

136.225(9)

z(O)

0.16620(7)

Uiso(Ti)

0.0051(1)

Uiso(O)

0.0077(3)

Occupation factor (Ti)

1.001(1)

Occupation factor (O)

0.990(2)

Phase fraction (%)

100

DV/nm

15.30
35

%
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Table S3. Refined structural parameters and WH parameters for the anatase phase of black TiO2 sample. Spacegroup I41/amd. Atomic positions: Ti 4b (0 3/8), O 8e (0 z). Refined structural parameters for rutile phase
are also reported. Space-group P42/mnm. Atomic positions: Ti 2a (0 0 0), O 4b (x x 0). The refined relative
weight fractions are also reported in the tables. Agreement factors are Rwp=0.0591, 2=1.607, R(F2)=0.0449.
Black TiO2 / Anatase phase
a/

3.78539(3)

a/

4.59513(4)

c/

9.51216(3)

c/

2.95999(4)

V/3

136.302(3)

V/3

62.501(1)

z(O)

0.1673(5)

x(O)

0.3037(2)

Uiso(Ti)

0.00581(6)

Uiso(Ti)

0.0065(2)

Uiso(O)

0.0054(1)

Uiso(O)

0.0094(4)

Occupation factor (Ti)

1.010(1)

Occupation factor (Ti)*

Occupation factor (O)

0.955(2)

Occupation factor (O)*

Phase fraction (%)

19

DV/nm**

~49

Phase fraction (%)

81

DV/nm

22.89
4

%
*

Black TiO2 / Rutile phase

Since during the refinement the occupation factors of Ti and O assumed values well above the unity with very large

standard deviations, we decided to fix these factors to 1.


**

DV parameter was evaluated using Scherrer equation based on the (110) rutile reflections.

Table S4: Binding energy of Ti 2p and O 1s peaks determined by XPS analysis.

Samples

B.E. (eV)
Ti 2p
2p3/2

2p1/2

P25

458.46

464.15

black TiO2

458.18

463.87

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B.E. (eV)
O 1s

529.68
531.24
529.40
530.83

5. Reference
[1] Larson, A. C.; Von Dreele, R. B. General Structural Analysis System (GSAS). Los Alamos National
Laboratory (LAUR) 2004, 25, 86.
[2] Toby, B. H. J. Appl. Cryst. 2001, 34, 210.
[3] Gonschorek, W. F.; Feld, R. Zeitschrift. fuer Kristallographie 1982, 161, 1.
[4] Burdett, J. K.; Hughbanks, T.; Miller, G. J.; Richardson J. W., Jr.; Smith, J. V. J. Am. Chem. Soc. 1987,
109, 3639.
[5] Lobanov, N. N.; Alte de Vega, L. 6th European Powder Diffraction Conference 1998, Abstract P12-16.
[6] Santangelo, S.; Messina, G.; Faggio, G.; Donato, A.; De Luca, L.; Donato, N.; Bonavita, A.; Neri, G. J.
Sol. St. Chem. 2010, 183, 2451.
[7] Cappelletti, G.; Ardizzone, S.; Bianchi, C. L.; Gialanella, S.; Naldoni, A.; Pirola, C.; Ragaini, V.
Nanoscale Res. Lett. 2009, 4, 97.

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