Supplementary Information

ETS-10 Modified with CuxO Nanoparticles and Their Application for the
Conversion of CO2 and Water into Oxygenates

Eliane R. Januário,a Ana F. Nogueirab and Heloise O. Pastore*,a

a
Grupo de Peneiras Moleculares Micro e Mesoporosas and
b
Laboratório de Nanotecnologia e Energia Solar, Instituto de Química,
Universidade Estadual de Campinas, 13083-970 Campinas-SP, Brazil

Photocatalytic reactor

a) b)

c) d)

Figure S1. Reactor for photocatalytic reactions: (a) top view of the reactor with 50 mL total capacity; (b) glass support
of powder and liquid water; (c) side view of the reactor; (d) reactor inside the solar simulator. Maximum temperature
was 333 K.

_________________________________________
*e-mail: gpmmm@iqm.unicamp.br
Analytical curve of methanol

Equation y = a + b*x
60000 Adj. R-Square 0,9999
Value Standard Error
50000 B Intercept 122,34748 103,98642
B Slope 192,73526 0,78058

40000

30000

Area
20000
Methanol curve
Fit linear
10000

0 50 100 150 200 250 300

[ ] ppm

Figure S2. Calibration curve of methanol solutions obtained experimentally by gas chromatography-flame ionization
detector (GC-FID).

High resolution transmission electron microscopy (HRTEM)

(a) (b)

5 0 n m 5 0 n m

Figure S3. High resolution transmission electron micrographs of (a) Cu2O nanoparticles and (b) CuO nanoparticles.

Direct band gap estimations by Tauc equation

The absorption spectra can be used to estimate the energy gap of the materials through Tauc’s formula: 1

(αhν)νη = B h0 Eg) (S1)

where B is a constant related to the material; hν is the photon energy in eV, h is Planck’s constant; ν is the frequency of
the photon; Eg is the optical band gap in eV, η is an exponent that can take a value = 2 for a direct transition; α is the
absorption coefficient and the value is proportional to the F(R ∞) = Kubelka Munk function. Moreover, the most
common method to calculate the band gap energy (Eg) involves plotting (a hn) n vs. (hn), as shown in Figure S4.
 2,50E+012

ETS-10
2,00E+012

1,50E+012


h
1,00E+012

5,00E+011

3.8 eV
0,00E+000
0 1 2 3 4 5 6
Energy (eV)

7,00E+010
1,20E+011 NP Cu2O NP CuO
6,00E+010
4,00E+012
ETS-10/Cu2O
1,00E+011 3,50E+012
5,00E+010
3,00E+012
8,00E+010
4,00E+010
2,50E+012




h
h


h
6,00E+010 2,00E+012
3,00E+010

1,50E+012
4,00E+010 2,00E+010
1,00E+012
2,00E+010 1,00E+010
2.2 eV 2.3 eV 5,00E+011
3.6 eV
0,00E+000 0,00E+000
0,00E+000
0 1 2 3 4 5 6 0 1 2 3 4 5 6
0 1 2 3 4 5 6
Energy (eV)
i Energy (eV)
Energy (eV)

3,50E+012 ETS-10/CuO
3,00E+012

2,50E+012

2,00E+012

h

1,50E+012

1,00E+012

5,00E+011

3.7 eV
0,00E+000
0 1 2 3 4 5 6
Energy (eV)

Figure S4. Direct band gap estimations of Cu2O, CuO nanoparticles, titanosilicate ETS-10, ETS-10/Cu2O and
ETS-10/CuO by Tauc equation.

Gas phase chromatographic analysis

The gas phase was analyzed using a GC with TCD detector to determine O2, CO and CO2.
 ETS-10 Cu2O (5% m/m)

100 cps CO2

O2

Time= 0h

Abundance (a.u.) Time= 2h

Time= 20 h

0 2 4 6 8
Retention time (min)

O evolution after 20 h of irradiation

2
Gas Peak area Area / %
O 800.01483 12.22865
2
CO 5742.12207 87.77135
2
Figure S5. Chromatograms of photocatalytic reaction applying the catalyst ETS-10/Cu2O obtained by GC-TCD
analysis and relative areas. Gas carrier: He; isotherm: 100 °C.

Possible mechanisms of acetic acid formation

Srinivas et al.2 proposed the mechanism for acetic acid formation in reaction media, associated to formic acid
and methanol formation in contact of catalyst and irradiation, as follow:

(S2)

Acetic acid formation occurs also by glyoxal pathway from CO 2 to CH4. This mechanism was proposed by
Shkrob et al.3 using EPR technique. Methyl radicals can also be formed from acetaldehyde along a different pathway if
the aldehyde is oxidized to acetic acid.
Figure S6. Possible pathways to acetic acid during photocatalytic reactions.

Catalytic activity

The catalytic activity can be calculate by equation:4,5

R = [Product] / time[catalyst] (S3)

where [Product] are given in μmol or ppm.

For example:
ETS-10/CuO = R = [120] / (20 × 0.050) = 120 mol (mol h)-1
Then, we divided the mol number of products for mol number of photoactive material on photocatalyst.
120 × 10-6 mol / (3.14 × 10-5 mol) = 3.82 molproduct (molcatalyst h)-1

References

1. Tahir, M.; Amin, N. S.; Energy Convers. Manage. 2013, 76, 194.
2. Srinivas, B.; Shubhamangala, B.; Lalitha, K.; Reddy, P. A. K.; Kumari, V. D.; Subrahmanyam, M.; De, B. R.;
Photochem. Photobiol. 2011, 87, 995.
3. Dimitrijevic, N. M.; Shkrob, I. A.; Gosztola, D. J.; Rajh, T.; J. Phys. Chem. C 2012, 116, 878.
4. Habisreutinger, S. N.; Schmidt-Mende, L.; Stolarczyk, J. K.; Angew. Chem., Int. Ed. 2013, 52, 7372.
5. Slamet; Nasution, H. W.; Purnama, E.; Kosela, S.; Gunlazuardi, J.; Catal. Commun. 2005, 6, 313.