# Variable temperature 29Si MAS NMR studies of titanosilicate TS-1

A. Tuel, Y. Ben Taarit

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A. Tuel, Y. Ben Taarit. Variable temperature 29Si MAS NMR studies of titanosilicate TS-1. Journal of the Chemical Society, Chemical Communications, 1992, pp.1578-1580. 10.1039/C39920001578. hal-00006294

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Distributed under a Creative Commons CC BY 4.0 - Attribution - International License
Variable Temperature <sup>29</sup>Si MAS NMR Studies of Titanosilicalite TS-1

A. Tuel* and Y. Ben Taarit

*Institut de Recherches sur la Catalyse, CNRS, 2, Avenue A. Einstein, 69626 Villeurbanne Cedex, France*

Variable temperature <sup>29</sup>Si MAS NMR spectroscopy has been used to correlate the monoclinic–orthorhombic transition temperature of titanosilicalite TS-1 with the Ti content.

The titanium molecular sieve TS-1 is a zeolite of the pentasil
family where a fraction of the Si⁴⁺ ions are replaced by Ti⁴⁺
ions.¹ It has been found to be a remarkable catalyst for the
oxidation of various organic substrates with hydrogen perox-
ide.² Although framework titanium ions are thought to be the

active sites,³ the nature of these centres is far from fully
elucidated. In a sustained effort to prove the framework
nature of the titanium ions, a number of physico-chemical
characterizations have been used.⁴

In particular, TS-1 shows a characteristic IR pattern similar
<table><caption>**Table 1** Designation, unit cell composition and symmetry of the different samples</caption><thead><tr><th>Designation</th><th>Unit cell composition<sup>a</sup></th><th>Symmetry at room temp.<sup>b</sup></th></tr></thead><tbody><tr><td>TS(0)</td><td>Si<sub>96</sub>O<sub>192</sub></td><td>M</td></tr><tr><td>TS(1)</td><td>Si<sub>95.59</sub>Ti<sub>0.41</sub>O<sub>192</sub></td><td>M</td></tr><tr><td>TS(2)</td><td>Si<sub>95.15</sub>Ti<sub>0.85</sub>O<sub>192</sub></td><td>M</td></tr><tr><td>TS(3)</td><td>Si<sub>94.75</sub>Ti<sub>1.25</sub>O<sub>192</sub></td><td>O</td></tr><tr><td>TS(4)</td><td>Si<sub>94.25</sub>Ti<sub>1.75</sub>O<sub>192</sub></td><td>O</td></tr></tbody></table>

<sup>a</sup> The chemical compositions were obtained for calcined samples by usual analytical methods. Crystal size and morphology did not depend on the Si/Ti ratio. All samples were highly crystalline as shown by IR spectroscopy and XRD. The absence of non-framework TiO<sub>2</sub> was revealed by UV spectra recorded on a Perkin-Elmer Lambda 9 UV-VIS spectrometer. <sup>b</sup> Estimated from XRD patterns (peak at 2θ = 24.4°) recorded on a Philips PW 1710 diffractometer using Cu-Kα radiation. M = monoclinic, O = orthorhombic.

<figure><img src="image_2.png" /><figcaption>**Fig. 1** <sup>29</sup>Si NMR spectra of sample TS(3) recorded at different temperatures. Spectra were recorded on a Bruker MSL 300 FT NMR spectrometer equipped with a double-bearing variable temperature MAS probehead. This equipment allowed us to work in the temperature range 173–373 K. Before acquisition, the system was left for 30 min in order to stabilize and homogenize the temperature. Spectra were collected using a classical 90° acquisition sequence. Samples were typically spun at 4 kHz. In order to minimize the effect of varying relaxation times with temperature, spectra were recorded with 20 s delay time between each scan. In most cases, 100 FID were accumulated. All chemical shifts were referenced with respect to SiMe<sub>4</sub>.</figcaption></figure>

to that of silicalite and, in addition, a new absorption at 960 cm<sup>-1</sup>. This band, whose intensity is proportional to the Ti content of TS-1, has been attributed to a stretching mode of a [SiO<sub>4</sub>] unit bonded to a Ti<sup>4+</sup> ion.<sup>5</sup>

<sup>29</sup>Si MAS NMR spectra of calcined TS-1 exhibit a broad peak around -116 ppm vs. SiMe<sub>4</sub>, whose intensity increases with increasing Ti content of the zeolite.<sup>6</sup> This peak has been interpreted as arising from distorted Si–O–Si bonds resulting from the presence of Si–O–Ti linkages.<sup>7</sup>

As one might conclude, none of these spectral observations could be considered as clear-cut evidence for the framework siting of titanium. This is particularly the case as Conner *et al.*<sup>8</sup> reported that such a band could also be observed in the <sup>29</sup>Si

<figure><img src="image_3.png" /><figcaption>**Fig. 2** Variation of the monoclinic to orthorhombic transition temperature as a function of the Ti content in the zeolite. The dashed area corresponds to ambient temperature (290–300 K).</figcaption></figure>

NMR spectra of silicalite or ZSM-5 samples, provided that the latter were recorded at temperatures over 320 K.<sup>8</sup>

Our purpose is to unveil a clear relationship between the nature and content of the substituting element and the transition temperature between monoclinic and orthorhombic symmetries. Such a relation would then be useful as a quantitative and qualitative tool to investigate the extent of isomorphous substitution.

TS-1 samples were synthesized following the method described by Kraushaar *et al.*<sup>9</sup> In order to obtain different Si/Ti ratios in the solid, the amount of tetraethylorthotitanate was varied in the synthesis mixture. As-synthesized solids were calcined in air at 550 °C for 5 h to remove the templating agent.

The unit cell composition and the crystal structure symmetry of the investigated samples are reported in Table 1. TiO<sub>2</sub>-free TS(1) to TS(4) samples are highly crystalline and show a typical IR absorption band at 960 cm<sup>-1</sup>. Samples TS(0) to TS(2) exhibit monoclinic symmetry at ambient temperature [from X-ray powder diffraction (XRD) patterns] whereas samples TS(3) and TS(4) have orthorhombic symmetry.

Fig. 1 shows typical <sup>29</sup>Si MAS NMR spectra of sample TS(3) recorded at different temperatures. At temperatures over 275 K, the spectra are similar to those reported in the literature for TS-1: namely a major resonance at -113 ppm associated with a more or less pronounced shoulder at -116 ppm. Below this temperature, the shoulder disappears and the spectra are similar to those of ZSM-5 recorded at room temperature. For the particular sample under investigation, the transition temperature, corresponding to the modifications in the NMR spectra, is centred around 275 K, i.e. slightly below ambient temperature. In contrast with silicalite,<sup>10</sup> we did not observe significant changes in the appearance of the <sup>29</sup>Si NMR spectra above and below the transition temperature, probably because of the large widths of the NMR peaks.

Each sample within the series exhibited similar behaviour; however, transition temperatures varied with the titanium content. Fig. 2 depicts the evolution of the monoclinic to orthorhombic transition temperature with the Ti content of the samples. The transition temperature of samples TS(0) to TS(4) decreased almost linearly with the Ti/Si ratio, as already observed for ZSM-5 on increasing the Al/Si ratio.<sup>11</sup> The transition temperature may also be affected by sorbed organic or inorganic species.<sup>12</sup> In the present work, careful monitoring of the synthesis parameters and post-synthesis treatment
prevented the deposition of non-framework material, as
proved by various means of characterization. Kokotailo *et
al.*¹¹ reported that the monoclinic angle β increased with Si/Al
ratios. Thus, β approaches 90° with increasing aluminium
content and temperature, until β becomes equal to 90°, at
which point the symmetry becomes orthorhombic.

High-resolution X-ray diffraction has also been used to
monitor the evolution of the transition temperature with the
degree of substitution. This technique allows the change in the
β angle to be followed by measuring the degree of separation
of the 313 and 313 reflections. As an example, Gabelica *et al.* ¹³
have shown that the monoclinic to orthorhombic temperature
varied linearly with the Ge content in Ge-substituted silical-
ites.

For TS-1, X-ray diffraction revealed that the monoclinic
symmetry, characteristic of pure silicalite at room temperat-
ure, persisted for calcined samples at room temperature up to
around 1 Ti per unit cell.⁶ Variable temperature ²⁹Si MAS
NMR data clearly show that our samples possess monoclinic
symmetry at ambient temperature for Ti content below 0.9 Ti
per unit cell (Fig. 2). This result is in good agreement with the
experimental observations reported previously.

We have thus shown that a reversible monoclinic to
orthorhombic transition could be observed for TS-1 samples
using variable temperature ²⁹Si MAS NMR spectroscopy and
that the presence of the NMR shoulder at –116 ppm vs. SiMe₄
is characteristic of substituted MFI-type zeolites having
orthorhombic symmetry. The corresponding temperature of
the transition decreased with increasing Ti content of TS-1, a
similar behaviour to that previously reported for ZSM-5.¹⁴

Therefore, it is possible to use this method to investigate the
extent of substitution in these materials. Indeed, the slope of
the linear plot may be expected to vary with the ionic radius of
the incorporated element.

References

1 US Pat. 4,410,501 (1983) to M. Taramasso, G. Perego and B. Notari.

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11 G. T. Kokotailo, L. Reikert and A. Tissler, in *Zeolites as Catalysts, Sorbents and Detergent Builders*, ed. H. G. Karge and J. Weitkamp, Proc. Int. Symp. Studies in Surface Science and Catalysis, Würzburg, FRG, Sept. 4–8, 1988, Elsevier, Amsterdam, 1989, vol. 46, p. 821.

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