The Preparation and Characterization of an X-Type Zeolite

An Experiment in Solid-state Chemistry

Kenneth J. Balkus, Jr., and Kieu T. Ly University of Texas at Dallas, Richardson, TX 75083-0688 Topics in solid-state chemistry are often neglected in undergraduate laboratories partly because there are relatively few experiments that capture the attention and imagination of students. The advent of high-Tc superconductors that provide dramatic yet simple experiments (1) has increased interest in solid-state materials. We have been part of a movement to introduce solid-state chemistry topics in the advanced undergraduate labs. We report an undergraduate experiment based on the syntheiis and charactrrrzat~on o f m X-twe -. zmlite (21. The synthetic X-type zeolite has the faujasite structure (3) shown below. Faujasite is the naturally occurring, but rare, mineral. The general formula is M,i,(A102),(Si02)~9~.n where n = 77-96 and x = valence of M. The faujasite structure wnsists of ten cages connected by hexagonal prisms or double six-ring (D6R)units. The P cages are oRen called sodalite cages because the structure of the zeolite sodalite (3) contains eight of these truncated octahedra connected through the four rings. The vertices in Figure 1 represent either tetrahedral A1 or Si atoms with the 0 atoms omitted f ~ r ~ c l a r i t y This . structure transcribes a sphere of about 12 Awhich we designate a s the supercage. The 12 ring apertures to the a or supercage are about 7.4 A in diameter. These dimensions allow only certain molecules to be adsorbed by the zeolite. I n this experiment we will probe the pore size by monitoring the adsorption of various molecules. If we view zeolite as a micropourous silicate in which the Si4+ has been partially substitued with A13t then we realize that for every A13+there must be an equal number of positive charges added for balance. The cations that compensate for the
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positive trivalent charge on Al can be virtually any electropositive element, from protons to lanthanides. These cations can he located throughout the structure. I n fact, there are more cation sites than cations. In this experiment we will prepare the sodium form ofan X-tvoezenlite.Thesodium ionscan then brexchanged with othk; metal ions such a s cobalt(I1). We have found the X-type zeolite can be prepared during a typical lab period and later characterized by infrared spectroscopy, ion exchange, and adsorption. Preparation of NaX Many variables can influence zeolite synthesis: temperature, pH, crystallization time, order of mixing, amount of Si, Al, Na, and HzO. Zeolite NaX is a metastable phase, meaning that other types of zeolites such a s P, A, or sodalite may form if this recipe is not followed carehlly. The procedure detailed below should produce highly crystalline NaX within a normal lab period (2-4 h) without detectable contamination from other phases. The first procedure is to prepare sodium silicate and sodium aluminate separately. The sources of silicon and aluminum can vary, but we have found that silica gel (Aldrich)and aluminumisopropoxide (Aldrich)are suitable starting materials. Since this experiment requires working under alkaline conditions, plasticware should be used. I'olypropylene bottles shouldbe used for the rnstallizatiun berausr 1hc.v are generdly autoclavnble. Sote: Polyethyl1 1 crick and leak.) ene bottles $ The sodium silicate is prepared by adding 3.0 g of silica gel, 2.4 g of sodium hydroxide, and 6 mL of deionized water to a 250-mL plastic beaker. This mixture is swirled until the solids are completely dissolved. The sodium aluminate solution is prepared simultaneously by adding 6.9 g of aluminum isopropoxide, 2.4 g of sodium hydroxide, and 9 mL of deionized water to a 250-mL plastic beaker. The mixture is stirred with gentle heating (below 80 ' C ) in a water bathuntil the solids are dissolved (about 10 min) and a clear gel is formed. A watch glass placed over the beaker should prevent loss ofwntcr. (Note: The isopropanol furmed during i h e hydrolysis of aluminum isopropoxide will evaporate or form droplets a t the surface. There is no need to separate the alcohol from the gel.) When both solutions are a t room temperature, the aluminate solution is added to the silicate solution. An additional 27 mL of water is added

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Figure 1. Structure of zeolite X.

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crystal zatlon mlxtJre recordeo as Figwe 2 FT-IR speclra of zeol~fe KBr pellets taken alter 0 2, 3 and 4 n. to the gel and stirred with either a spatula or stir bar until the mixture appears homogenous. The gel may take on a variety of appearances, but the initial eelatinous mixture will usuallv ouicklv form a suspension of white solids. This mixture is quickly transferred to a . oolwroovlene ". ." screw cao bottle. sealed and laced in an oven a t about 90 "C. All students should place their samples in the oven at the same time to minimize the fluctuation in temperature from opening the oven door. The reaction time will depend on the lab period. The best results are obtained a t 3 4 h, but reasonably crystalline zeolites can be isolated after only 2 R h. Alternatively, the crystallization can be followed by I spectroscopy to achieve the optimal yield (vide infra). After 2 4 h the mixture is cooled to room temperature, and the solution is neutralized by washing with much water. This is best accomplished by transferring the mixture to a beaker, then diluting with water, followed by suction filtration and further washings. If the high-pH zeolite solution is transferred directlv to a Buchner funnel or frit, contamination may result from dissolution of the oaoer or frit. The white zeolite crvstals mav be air-dried or bvkdried until the next lab period wbkn the yield of hydrated NaX zeolite may be calculated.

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have access to this technique. However, ifXRD is available, students should be referred to JCPDS file no. 38, 237 to obtain a standard pattern for NaX (4). The most reliable alternative is infrared s~ectrosco~v (5). which we can use to identify the zeolite and estima't;, the crvstallinitv. Fimre 2 shows a series of s ~ e c t r recorded a bv a student durGg the preparation of zeolite X, using KF; oellets. (Note: Excessive minding of samdes should be avoided.) We are examininithe mid-IR region only because the adsorbed water in the zeolite masks the OH reeion. Without an expensive vacuum IR cell, very little information can be obtained from this region. At 1 2 0 M 0 0 cn-' there are many bands associated with different Si and A1 tetrahedra vibrational modes. The spectrum for the initial amorphous aluminosilicate gel (0 h) is a series of broad, featureless bands. There is a correlation between this broadness and crystallinity: As crystallinity increases, the bands become more narrow and better defined. The 4 h spectrum is of a 100% crystalline sample. A comparison with the starting gel reveals several bands and shoulders have grown in. These have been classified as external linkaees or structure-sensitive vibrations. The appearance of th&e bands coincides withformation of the three-dimensional framework. The location of these bands will shift to higher frequencies as the SiIAl ratio of the product zeolite increases, but students can use these spectra as a guide. In Figure 2 the main asymmetric stretch is a t 982 m-' with a shoulder at 1053 cm-'. The symmetric stretches occur at 748 and 670 m-' with a weak shoulder at 689 cm-'. The band a t 560 cm-' is associated with the double 6 rings that connect the sodalite cages. A TO4 bending vibration occurs at 456 m-'. If an impurity phase did hystallize, it should be fairly easy to identify by IR. The key area to monitor is the double-ring region. Common phases that might appear as impurities include zeolites P and sodalite which both lack double-ring structural units (3).Therefore, there should be no IR bands near 560 em-' for these phases. Zeolite P has a characteristic band at 600 cn-'; sodalite, at 660 cm-'. If zeolite A were an imouritv the double-rinevibration would shift to a lower wave number (about 550-cm-') relative to X-tvoe zeolites because it has double four-ring units instead of D ~ units. R
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Ion-Exchange Properties

Characterization of NaX Probably the best way to identify the zeolite phase and evaluate the degree of crystallinity is by X-ray powder diffraction. We followed this experiment using XRD and found that highly crystalline NaX can be prepared after only 2 h. More crystalline zeolites were obtained after 4 h. Unfortunately, many undergraduate chemistry labs do not 876
Journal of Chemical Education

One of the characteristic properties of zeolites is their ability to ion-exchwe cations. The combinationof Si4+ and A13+ results in a deficiency of positive charge which is balanced by exchangeable cations. In a simple test we can determine if the above product has ion-exchange capabilities. In a 250-mL Erlenmeyer flask dissolve 0.1 g of cobalt chloride in about 100 mL of deionized water. Then add 1g of the product zeolite and stir until the pink solution is decolorized.Times will vary, but heating greatly facilitates this process, so complete exchange can be accomplished in less than anhour. After filtration, wash with water and test the washings for NaCl with a AgN03 solution. If the zeolite is pink and if the filtrate is colorless but contains NaC1, the product has ion-exchange properties. Ideally two Na+ions will exchange for every COZ+, as shown in eq 1. In reality a stoichiometric exchange is unlikely because different cobalt species are possible. For example, a Cl- or OH- ligand might be coordinated to the metal ion, with one Na+ exchanged, to maintain electroneutrality. One can imagine how this ion-exchange property could be exploited commerciallyto soften water or to remove toxic or radioactive metal ions from water.

Adsorption Properties If the Co(I1)-exchanged zeolite is allowed to air-dry, it remains a pink powder, but if the students heat the zeolite crystals they will eventually turn blueviolet. This change in color results from dehydration of the zeolite and illustrates t h e adsorption properties of zeolites. A suprisingly large amount of water can he adsorbed by X-type zeolites: Thermogravimetric measurements indicate as much a s 25% by weight. This hydrophilicity is related to the large internal surface area and the polarizing ability of the zeolite cages. Given these strong adsomtion urouerties we can now probe thedimrnsion;bfthe zholite pores by varyingth~size of the adsorbinr! molecule. The ahovo strurture of zeolite X would indicatethat molecules smaller than about 7.4 should he adsorbed. We can use the kinetic diameter (2) to decide if a molecule will fit through the zeolite pores. For example, water has a kinetic diameter of 2.65 A, benzene, 5.85 A. We already know water is adsorbed, but we can test to see if benzene is adsorbed. Place about 50 mg of dehydrated zeolite into a 1/2-dram vial or small test tube. Then carefully weigh the vial avoiding fingerprints and place it inside a larger vial. Place both vials uncapped into a larger vial or beaker that can be covered tightly. Place a few milliliters of benzene into the largest vial and cover. After a n hour or so remove the vial containing the zeolite and weigh.

A weight change indicates that benzene was adsorbed and the pmduct must have pores with diameters of 6 A or more. This experiment can be repeated with other molecules provided they have significant vapor pressure. Given the uniform pore distribution of zeolites one can see how these materials wuld be used a s molecular sieves to adsorb or exclude molecules by size.
Conclusion The synthesis of an X-type zeolite is a relatively simple experiment in solid-state chemistry. I t allows the students to prepare a commercially important material and thenuse its physical properties a s a probe of molecular structure. The synthesis of this zeolite fmm such simple starting materials is fascinating, and it is fun to realize that ion-exchange and selective adsorption studies easily relate the synthetic product to the interesting three-dimensional structure of Figure 1. Acknowledgment We thank the Robert A. Welch Foundation and the donors of the Pretroleum Research Fund administered by the American Chemical Society for financial support. Literature Cited
1. Forerample,seeJue~gen~gen,F.H.;EUls.A.B.:DiecLmann,G.H.:Perkins,R.I. JCham. Edue. 1987.64.851. 2. For an overview of zeolites, see Breck, D. W. &di& Molecuior Siew6; Wiley: New York, 1974. 3. Meier,W.M.;Olson,D.H.AllasofZ~di~SL~ucfunTyp~s;Butteteorth:London,1988. 4. Pmddd D~ffficfion Pila lhorganjr): JCPDS-International Centre for Diffraction Data: Swarthmare. PA. 5. Flanken, E. M. in Zeolite Chemistry ond Cafalys&;ACS Monograph No. 171,1976, SO.

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