Journal of Sol-Gel Science and Technology 33, 93–97, 2005 c 2005 Springer Science + Business Media, Inc.
Manufactured in The United States.
ZrO2 and Cu/ZrO2 Sol–Gel Materials Spectroscopic Characterization
´ ´ T. LOPEZ, M. ALVAREZ AND R. GOMEZ Department of Chemistry, Universidad Aut´ onoma Metropolitana-Iztapalapa, P.O. Box 44-534, M´ exico, D. F. 09340
D.H. AGUILAR AND P. QUINTANA Department of Applied Physics, Cinvestav-IPN, Unidad M´ erida, A.P. 73. Cordemex, 97310, M´ erida, Yucat´ an, M´ exico
Abstract. Copper-doped zirconia (1% mol) and zirconia powders were prepared by the sol–gel process, using zirconium n -butoxide and copper nitrate as precursors. The resulting xerogels are nanocrystalline and exhibit different properties from the corresponding microcrystalline materials. The copper nitrate salt was dissolved and cogelled in situ at the initial stage of the reaction. The properties of the resulting materials were studied by XRD, FTIR and UV-Vis. The as-prepared samples were amorphous and crystallized to the tetragonal zirconia phase at 400◦ C. At temperatures higher than 600◦ C, the monoclinic phase was also obtained. No evidence of discrete crystalline copper compounds was observed, consistent with good dispersion of the dopant. Several bands were observed by FTIR in the 4400–3000 cm−1 region, which diminishes in intensity and shifted to higher wavenumbers with heating. The bandgap energy ( E g ) was strongly modulated by the presence of the dopant and heating temperature, with increasing temperature leading to a corresponding decrease in E g . Keywords: copper-zirconia sol–gel, copper-zirconia band gap, copper-zirconia XRD, copper-zirconia FTIR
The performance of heterogeneous catalysts depends on their structure and stability . Zirconia exhibits many desirable structural and electronic properties, and has been used in many applications, in particular as a catalyst support. Depending on the preparation method and thermal treatment, monoclinic, tetragonal, cubic, or a mixture of these phases can be obtained, although the tetragonal form generally exhibits better catalytic properties. Zirconia is a suitable support for transition metals such as Cu, and Cu/ZrO2 has so far been prepared by precipitation, coprecipitation or impregnation of preshaped zirconia carriers with appropriate salt solutions . The sol–gel method has attracted considerable attention for the preparation of metallic catalysts, since the constituents are mixed in a molecular scale and gener-
ates a uniform distribution of the metal upon the support . Wombach et al.  shown that supported copper is a good catalyst for several reactions, including CO2 hydrogenation and combustion. Sun and Sermon investigated sol–gel derived Cu/ZrO2 catalysts and showed that the dopant can be present in two forms: surface aggregates and dispersed Cu(II) in ZrO2 substitutional sites . This phenomenon generates metal-support and ion-ion interactions and favors the formation of oxygen vacancies, leading to ionic conduction . It is well known that zirconia is an insulating material but sol–gel zirconia and doped zirconia behave as semiconductors with some photochemical properties. In the present work, zirconia was doped in situ with Cu(NO3 )2 . It is believed that most of the copper will be dispersed in the form of nanosized particles on the zirconia’s surface, although a small amount is introduced into the zirconia network . In this work, zirconia and
No evidence of discrete crystalline copper compounds was observed.2◦ (2θ ) can be seen (Fig. the crystallite size varied between 9 and 12 nm for both samples.3◦ (2θ ). 3. Typical reactions that occur during the co-gelation of zirconium n -butoxide and copper nitrate are illustrated in Fig. with the intensity of the characteristic peak at 28. X-Ray Diffraction. indicating the formation of the monoclinic phase. and then annealed in air for 4 h at 200. At 600◦ C. X-Ray Diffraction. structural and optical properties of the solids. with Cu Kα radiation and a graphite monochromator. 2(b)).1.
Results and Discussion
The competition between hydrolysis and condensation strongly affects the composition. In general. HNO3 . (1): Eg = 1239 ∗ b −a (1)
where E g is in eV. Measurements were carried out using a Siemens model D-5000 diffractometer.2. FTIR. and b and a are obtained by a linear ﬁt. the crystallite size in the copper-doped samples was ca. copper doping promotes the formation of the monoclinic phase. 2. from the measured full-width at half-maximum of the 30. the relative abundance of the monoclinic phase is signiﬁcantly higher than observed in the undoped sample. 400. When zirconia is doped with 1% mol copper (Fig.1. respectively. and pressed into clear pellets for analysis. used as a catalyst. and UV-Vis spectroscopy to evaluate the effect of copper on the structural and electronic properties of zirconia. As the temperature increases. which disappeared when the annealing temperature was increased. Water (6 mL) and tert-butyl alcohol (61 mL. The band gap values were calculated by linearization of the slopes in the spectra for each sample using Eq. For the Cu/ZrO2 sample. To obtain the spectra. The evolution of the FTIR spectra as a function of annealing temperatures is illustrated in Fig. The Debye-Scherrer formula  was used to calculate the apparent crystallite size of the tetragonal phase.03◦ (2θ ) and a step time count of 1 s were employed. Samples was mixed with KBr (5% W). The bands in the 1300–1400 cm−1 range are attributed to C H scissor modes. it had increased to 16 and 18 nm for the undoped and doped samples. and all spectra were referenced to a 100% reﬂectance sample (MgO).2◦ (2θ ) increases up to four times compared to that in the undoped material. characteristics of Zr O bonds.3. J. Experimental Sample Preparation
3. FTIR Spectra. equipped with an integrating sphere.3◦ peak. A step size of 0.5H2 O was dissolved into the water. 600 and 800◦ C. 2(a)).1. was added to adjust the pH to 3.T Baker. self-supporting pellets were prepared. The catalysts were characterized by FTIR spectroscopy in a Paragon-1000 spectrophotometer. well-deﬁned peak at 31. XRD was used to detect the crystalline phases in the samples. The undoped zirconia sample was amorphous below 400◦ C.
copper-doped zirconia (Cu/ZrO2 ) materials were synthesized via the sol–gel method. 1(a) and (b). with a heating rate of 5◦ C per min. 0.7%). a small peak near 28.2045 g of Cu(NO3 )2 ·2. the presence of monoclinic zirconia is conﬁrmed by the appearance of a second. at this temperature. 2.
. 2. 2. The solution was heated at 70◦ C for 10 min. were mixed with continuous stirring over 10 min. At 3450 cm−1 . Reﬂuxing was then maintained until gelation occurred. Aldrich 80% in 1-butanol) was added drop-wise to the solution. All samples exhibited bands at 450– 520 cm−1 . and characterized by XRD. and crystallized to form the tetragonal phase at this temperature. 99. 10% larger than in the undoped material. The resulting samples were dried at 90◦ C. UV-Vis Spectra. a broad band is observed corresponding to O H stretching vibrations of molecular water (either free or H-bonded). Below 800◦ C. cooled to 60◦ C and zirconium (IV) n -butoxide (39 mL. The band proﬁle around 1630 cm−1 contains contributions from water (O H O bending mode) and nitrate species (O NO2
ZrO2 and Cu/ZrO2 xerogels were prepared by the sol–gel method. but at 800◦ C. 2. However.1. UV-Vis (diffuse reﬂectance) spectra were obtained with a Varian Cary-1 UVVis spectrophotometer. associated with organic residues which disappear when the materials were treated above 400◦ C.94
L´ opez et al. there is no signiﬁcant change in the crystalline phases observed below 800◦ C. FTIR Spectra.1. This indicates that at high temperatures.
This behavior is due to the transformation of the electrical properties of the solid. From the UV-Vis spectroscopic analysis.ZrO2 and Cu/ZrO2 Sol–Gel Materials Spectroscopic Characterization
Figure 1. which also decrease in intensity with increasing temperature. we expect that the powders obtained can be used as photocatalysts for the degradation of aromatics in waste water.17 at 200◦ C to 3. from an insulator to a semiconducting material. These values
are decreased signiﬁcantly on doping. it was observed that the E g values decreased with increasing temperature.25 eV being observed for the doped material after heating at 800◦ C. we observe that the bandgap for the undoped sample decreases from 4. as expected.74 eV at 800◦ C. UV-Vis Spectra. Sol–gel reactions: (a) hydrolysis reaction and (b) condensation reaction. 4. Therefore. with a value of 3.
antisymmetric stretch) . this will be the subject of future investigations.
. In Fig.
T. A. 5071 (1999). 159 (2002). Zm denotes peaks assigned to monoclinic zirconia. References
1. L. Ross. P. 57. Montes.
Figure 2. 161 (1992). and M. Acknowledgments We would like to acknowledge CONACyT for the grant given to M.D. with E g decreasing with increasing temperature.H.J. Chem. Wokaun. the lowest E g values are obtained. below 600◦ C the particle size of the tetragonal phase does not vary signiﬁcantly in either the doped or undoped zirconia. Villa. Wombach. we expect that this sample will ﬁnd potential applications as a photocatalyst. 1. Band gap ( E g ) values for ZrO2 and Cu/ZrO2 as a function of annealing temperature. while still retaining the tetragonal structure. Chem. J. 4.
The addition of copper in zirconia sol–gel processing promotes the formation of the monoclinic phase at higher temperatures. L´ opez. Tech. Alvarez (No.
Figure 3. J. Castro.
L´ opez et al. 127 (1990). Phys. Baiker. Phys. (c) 400. Since the copper-doped zirconia has a low E g value at 400◦ C. and J.171497). 600 or 800◦ C. FTIR spectra of Cu/ZrO2 samples: (a) as-prepared. Mat. Zamudio. 25. (d) 600. Chem. nevertheless. and A. Sol–Gel Sci. When copper is co-gelled with zirconia. T. E. Burggraaf. Van Ommen.M Doesburg. Appl.R. J.Catal. (b) 200.
.G.L. 2. Phys.B. Reyes. Maercera. and (e) 800◦ C. and C. M´ endez. XRD patterns for: (a) pure ZrO2 and (b) 1% mol Cu doped ZrO2 . 30. P.
4. Both samples were annealed at 400. A. The main effect of doping was observed in the band gap values. 3. J.
9. Bokhimi. L´ opez. Elements of X-ray Diffraction (Addison-Wesley. Portilla. M. M. N. Lin-Vien. 6. Novaro. Azomoza. Davis and M. Chem.B. Novaro. Pizoferrato. J. Non-Cryst. Sarcinelli. F. Non-Cryst. O.A. Colthup. 28 (1999). Tzompantzi. Lett. X. T. G´ omez. Pavesi. Sun and P. A. 2616 (1997). 10.ZrO2 and Cu/ZrO2 Sol–Gel Materials Spectroscopic Characterization
5. A. Morales. 316 (1999). Solid State Chem. G´ omez. p. et al. L´ opez. Catal. T. Capelleti. Bokhimi.. O. J. Baraldi. 29. P. and F. Morales. Solids 317. 177 (1996). B. J. and R. London. A. C. R. Solids. The Handbook of Infrared and Raman Characteristic Frequencies of Organic Molecules (Academic Press. 9. 8. Massachusetts. 135. M. Cullity.
. p. Casalboni. Prosposito.D. 7. D. 284. 1991). M. Y. K. R. 1978). 358. X. 201. 231 (2003). Sermon. and R. Chimal. Mora. 11. O. Tomozawa.M. Mater.