Synthesis and Characterization of Titania-Graphene Nanocomposites

SAND2009-7446C

Carlos A. Chavez,1 Timothy N. Lambert,1* Bernadette Hernandez-Sanchez,2 Ping Lu,3 Andrea Ambrosini,1 Thomas A. Friedman,4 Timothy J. Boyle,2 and David R. Wheeler5
Sandia National Laboratories, PO Box 5800, MS 0734, Albuquerque, New Mexico, 87185.
Department of: 1Fuels and Energy Transitions, 2Ceramics and Inorganic Materials, 3Materials Characterization, 4Nanomaterials Science, 5Biosensors and Nanomaterials
Email: cachav@sandia.gov, *tnlambe@sandia.gov

Titania-Graphene Hybrid Composites

Abstract

Titania-graphene-oxide composites have been prepared

Our Approach Powder X-ray Stirred reactions results
utilizing the hydrolysis of titanium tetrafluoride to form the Scanning in the intercalation of
ceramic at low temperature in the presence of aqueous Diffraction (PXRD) Electron Microscopy (SEM) TiO2 between GO sheets
suspensions of graphene oxide (GO). In most cases, the resulting TiF4 10.0 GO
0.01 M 0.02 M

Intensity (a.u.)
7500
composite is isolated by a simple filtration and washing protocol. Synthesis Plan GO-TiO2 (0.04 M)
60 oC
8.0

6.0 d001 GO BET Surface Area

5000
Our approach utilizes the
4.0 @ 10.2 GO: 39 m2/g
oven or
Titania-reduced-graphene-oxide composites were prepared hydrolysis of titanium(IV)
2.0

hot plate 2500 x10^3 GO-TiO2 (0.04 M): 71 m2/g

fluoride7 in the presence of
5 6 7 8 9 10 11 12 13 14 15 16

by reducing a suspension of a pre-made ceramic-GO composite aqueous graphene oxide (GO)

0
20 30 40 50 60 70 80
GO-TiO2 (0.08 M): 121 m2/g
chemically with hydrazine hydrate, or by thermal treatment of dispersions to form TiO2-GO 2-Theta(°) GO-TiO2 (0.08 M): 81 m2/g
TiO2-GO composites at 800 oC. composites.8,9,10 TiO2-GO 600
Low Conc. RGO: 459 m2/g

Intensity (a.u.)
500

TiO2-GO composites were TiO2-GO

These composites have been characterized by SEM, TEM, XRD, BET, then chemically reduced with oC
400
N2 Adsorption/Desorption
100 300
hydrazine hydrate11
Raman, SAED and EDS. The synthesis and materials (N2H4• H2O) or thermally to N2H4•H2O
200
GO-TiO2 (0.08 M) 0.08 M
100 0.16 M
characterization efforts to date are presented. form the reduced graphene Or 0
10 20 30 40 50 60 70 80
oxide composites, termed 2-Theta(°)
TiO2-CRGO or TiO2-TRGO Thermally
@ 800 -
300

Intensity (a.u.)
High Conc.
1100 0C 250
TiO2-GO
200

150

Goals
100

TiO2-RGO
50
0
20 30 40 50 60 70 80

• Synthesize TiO2-Graphene composites 2-Theta(°)

Non-stirred reactions result in self-
TiO2 Anatase (JCPDS file no. 21-1272) TiO2 particle morphology
• Fully characterize these composite materials Transmission assembly of TiO2-GO sheets is concentration
• Examine possible applications of these composites Electron Microscopy (TEM) dependant

211/105 Energy Dispersive X-Ray Spectroscopy (EDS) TiO2-RGO

Introduction
200
Surface Chemically reduced
GO-TiO2 TRGO-TiO2
bound F
Graphene nanosheets are of considerable scientific and
103/004
w/ N2H4•H2O
technological interest due their potential applications in structural, Raman Spectroscopy
101
thermal, electronic and various other nanotechnologies.1-4 Loss of surface
bound fluorine Thermally reduced
Graphene, is a two dimensional macromolecule comprised of a on TiO2 in TiO2-
Eg @ 1000 oC
carbon layers with one atomic thickness. Theoretically it has a RGO
surface area of ~ 2630 m2/g.5 Chemical exfoliation of graphite, to
A1g
form graphene oxide, followed by chemical reduction (i.e. B1g *
hydrazine) is the dominant route to graphene like materials in the D G
literature.6 The marriage of inorganic ceramic materials with *
graphene could allow for the preparation of a new class of nano-
hybrid materials with interesting properties. We have recently
gained interest in preparing ceramic-graphene nanocomposites for Eg
CRGO-TiO2

a number of applications, including the mechanical reinforcement of Top-Left: TiO2-GO with GO G-band, GO D-band 1250

Intensity (a.u.)
Silica due to etching

Intensity (a.u.)
1000
A1g and TiO2 Eg/A1g/B1g. Initial sample was TiO2-
elastomers, electrical energy storage materials, and as catalysts in The particles are crystalline in nature. Bright- B1g
GO from 0.08 M TiF4.
of glassware.
1000
750

field TEM: Seed-like shapes and faceted 750

UV wastewater treatment. structures are observed. Dark-field TEM: the Bottom-Left: Raman on TiO2-CRGO also 500
500

Here we present our synthesis of TiO2-GO from the composites are composed of smaller confirms anatase. Inset: Increase in 250 250

nanoparticles that are crystallographically asymmetry and D/G ratio for TiO2-CRGO
hydrolysis of TiF4 and its subsequent chemical and thermal aligned. Selected Area Electron Diffraction
D G (black line) is consistent with reduction of
0
20 30 40 50 60 70 80 90 100
0
20 30 40 50 60 70 80 90 100

reduction to give TiO2-RGO. We also investigate the physiochemical (SAED): is consistent with Anatase phase as GO.11
*
2-Theta(°) 2-Theta(°)
determined by XRD
properties of our ceramic-graphene composites. Left: Chemically reduced composites
(TiO2-CRGO) retain anatase phase.
Right: Thermally reduced (TiO2- time )
(increasing
TRGO) partially transforms into rutile
phase.

References Colloidal Properties Conclusions

1. Jang, B. Z.; Zhamu, A., J. Mater. Sci. 2008, 43 (15), 5092-5101. Zeta Potentials Dynamic Light Scattering We have demonstrated the ability to prepare TiO2-GO
2. Geim, A. K.; Novoselov, K. S., Nat. Mater. 2007, 6 (3), 183-191.
3. Katsnelson, M. I., Mater. Today 2007, 10 (1-2), 20-27. pH 4.44 pH 6.03 pH 7.00 pH 3.66 pH 4.48 pH 5.92 pH 3.60 pH 4.60 pH 5.88
composites via the hydrolysis of TiF4 at 60 oC in the
Increasing pH results
presence of an aqueous dispersion (~ 0.75 mg/mL) of
4. Rao, C. N. R.; Biswas, K.; Subrahmanyam, K. S.; Govindaraj, A., J. Mater. Chem. 2009, 19 (17), 2457-2469. 14 14
pH 7.95 pH 9.07 pH 10.41 pH 8.12 pH 9.20 pH 9.90 14 pH 6.80 pH 8.05 pH 9.17
5. Peigney, A.; Laurent, C.; Flahaut, E.; Bacsa, R. R.; Rousset, A., Carbon 2001, 39 (4), 507-514. in the repulsion of TiO2 pH 9.99
6. Park, S.; Ruoff, R. S., Nat. Nanotechnol. 2009, 4 (4), 217-224.
particles in dispersion.
12
GO
12
GO-TiO2 12 GO. This approach yielded highly faceted anatase
7. Liu, B.; Zeng, H. C., Chem. Mat. 2008, 20 (8), 2711-2718.
8. Williams, G.; Seger, B.; Kamat, P. V., ACS Nano 2008, 2 (7), 1487-1491.
10 10 (0.04 M) 10
GO-TiO2 nanocrystals, with petal-like morphologies on and
9. Peng, W. Q.; Wang, Z. M.; Yoshizawa, N.; Hatori, H.; Hirotsu, T., Chem. Commun. 2008, (36), 4348-4350. (0.08 M)
embedded between the graphene sheets. At higher GO
Intensity
Intensity

Intensity
8 8
10. Chu, Y. H.; Yamagishi, M.; Wang, Z. M.; Kanoh, H.; Hirotsu, T., Micropor. Mesopor. Mat. 2009, 118 (1-3), 496-502. 8
11. Stankovich, S.; Dikin, D. A.; Piner, R. D.; Kohlhaas, K. A.; Kleinhammes, A.; Jia, Y.; Wu, Y.; Nguyen, S. T.; Ruoff, R.
S., Carbon 2007, 45 (7), 1558-1565.
6 6 6 concentrations (ex. 1.5 mg/mL) with no stirring of the
12. Lambert, T.N.; Chavez, C.A.; Hernandez-Sanchez, B.; Lu, P.; Ambrosini, A.; Friedman, T.; Boyle, T.J.; Wheeler, D.R., 4 4 4 reaction media, long-range ordered assembly for TiO2-
Journal of Physical Chemistry C. 2009, Manuscript Submitted.
2 2 2
GO sheets was observed due to self-assembly. GO-TiO2
0 0 0
composites formed colloidal dispersions (~ 0.75
10 100 1000 10 100 1000 10 100 1000
mg/mL) at low concentrations in water with zeta
Acknowledgments GO and TiO2-GO retain
Graphene-oxide shows
Diameter (nm)
similar
Diameter (nm)
GO-TiO2 exhibits a pH dependence due to
Diameter (nm)
Higher loaded sample of GO-TiO2 shows
potentials and dynamic light scattering data explaining
these results.
particle size across entire pH range. aggregation of titania and graphene sheets. even more drastic dependence of pH. At
This work was partially funded by Sandia’s Laboratory Directed Research and Development (LDRD) a negative zeta Bimodal distribution with peaks at Particle size shifts at slight decrease of lower pH values there is a broad peak at
Program. Sandia is a multi-program laboratory operated by Sandia Corporation, a Lockheed-Martin Zeta potentials of () GO,
potential across entire 50-60 nm and ~300 nm. acidity at pH 3.66 from 800 nm to ~200 nm. 900 nm, which begins to shift to a lower Future Work
Company, for the United States Department of Energy’s National Nuclear Security Administration (+) TiO2-GO from 0.04 M
pH range. value as the pH is raised. This shift is
under Contract DE-AC04-94AL85000. TiF4, () TiO2-GO from 0.08
complete even as low as pH 5.9. • Adsorption studies with methyl orange dye and UV
M TiF4, () commercial
anatase TiO2 nanopowder. photocatalysis of RGO-TiO2 is planned.
• Mechanical testing will examine physical strength of
Sandia
National TiO2-GO nanocomposites.
Laboratories

*Zeta potentials and Dynamic Light Scattering measurements by Nelson Bell (SNL)