Exchange of a Tetrapositive Cation into a Zeolite and a New Inorganic

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The Journal of Physical Chemistry

Exchange of a Tetrapositive Cation into a Zeolite and a New Inorganic Scintillator. I. Crystal Structures and Scintillation Properties of Anhydrous Zr1.7Tl5.4Cl1.7–LTA and Zr2.1Tl1.6Cl3.0–LTA

Joon Young Kim,† Jeong Min Park,‡ Hong Joo Kim,‡ Nam Ho Heo,*† and Karl Seff§

†

Laboratory of Structural Chemistry, Department of Applied Chemistry,

College of Engineering, Kyungpook National University, Daegu 702-701, Korea ‡

Department of Physics, College of Natural Science,

Kyungpook National University, Daegu 702-701, Korea §

Department of Chemistry, University of Hawaii,

2545 The Mall, Honolulu, Hawaii 96822-2275, U. S. A.

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(abstract) A new inorganic scintillator has been prepared by the assembly of thallium, zirconium, and chloride ions in a zeolite. Also, for the first time, a 4+ cation has been exchanged directly into

a

zeolite.

From

|Na12(H2O)x|[Si12Al12O48]-A

(zeolite

LTA),

|Zr1.7Tl5.4Cl1.7|[Si13.5Al10.5O48]-A and |Zr2.1Tl1.6Cl3.0|[Si17.4Al6.6O48]-A were prepared by the thallous ion exchange (TIE) method: fully dehydrated Tl12-A was treated with ZrCl4 (g, 3.7 x 103 Pa) at 553 K and 623 K, respectively. Their crystal structures were determined by single-crystal crystallography using synchrotron X-radiation and their compositions were partially confirmed by SEM-EDX analyses. Their structures were refined in the space group Pm 3 m (a = 12.125(1) and 11.945(1) Å) with all unique data to the final error indices R1 = 0.047 and 0.075 for the 680 and 380 reflections for which Fo > 4σ(Fo), respectively. Extraframework Zr4+ and Zr2+ ions had replaced some of the Tl+ ions in Tl12-A. Some Zr4+ ions are 4-coordinate with three bonds to framework oxygen atoms and one to a Cl- ion; others are 5-coordinate, bonding to two Cl- ions. Tetrahedral Zr2+ was found as ZrCl42- in |Zr2.1Tl1.6Cl3.0|[Si17.4Al6.6O48]-A; each of its Cl- ions bonds linearly to a Zr4+ ion, which in turn bonds linearly to another Cl- ion to form Zr5Cl810+ clusters centered in and extending out of the sodalite cavities. The Tl+ ions are in the large cavities.

The X-ray induced

emission spectrum of Zr,Tl,Cl-A has a broad band between 330 nm and 750 nm, peaking at 490 nm. The integrated light yield observed for Zr,Tl,Cl-A powder is about five times greater than that of anthracene, a well documented scintillator.

This strong

radioluminescence appears to be due to the simultaneous presence of Zr and Tl within the zeolite. Keywords: VPIE (vapor phase ion exchange), extraframework Zr4+ cation, scintillator, radioluminescence, crystallography, single crystal

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1. INTRODUCTION 1.1. New Inorganic Scintillators.

During the last several decades, new inorganic

scintillating materials have been extensively studied for a variety of applications such as precision calorimetry in high-energy physics, medical imaging, and homeland security.1-3 Nanoparticle based scintillating materials have attracted special attention due to their wide range of applications including some in medicine. For example, Scaffidi et al. demonstrated that psoralen-functionalized nanoscintillators were capable of killing or inhibiting the growth of cells upon X-ray excitation.4 Photoluminescent zeolites containing extraframework species such as silver,5,

6

cerium/terbium,7 gallium,8 bismuth,9, 10 cadmium treated with H2S,11 and rare-earth cations with organic photosensitizers12 have been reported. All were excited by ultraviolet,5-8, 11, 12 visible,9, 10 or near infrared radiation,9, 10 none by X-rays. Zeolites were seen to fluoresce upon irradiation with beta rays. Renschler et al. first suggested this in 1989.13 J. T. Gill et al. found that rare-earth exchanged zeolites fluoresced when irradiated with beta rays from tritium and suggested that this effect could be used to build zeolite-based tritium lamps.14

Campi et al. proposed zeolite-based monitoring

systems for tritiated water.15 We propose that zeolites tailored by ion exchange with heavy metal ions could be strong scintillators, possibly leading to new radiation detection materials and applications.



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They can be expected to be more durable than organic-based scintillatiors in applications involving high energy electrons or ionizing radiation. In this study, the properties of a zeolite containing Zr4+ and Tl+ are explored.

1.2. Zr4+ Based Luminescent Materials. Many Zr4+ compounds such as ZrP2O7,16 Li2ZrO3,16 Zr(HPO4)2H2O,17 and ZrO218 doped with metal cations such as europium,16 ruthenium,17 and erbium18 have been studied for their photoluminescent properties. Similar work was done using a zirconium barium fluoride glass (ZBLA) doped with chromium.19 Based on recent reports by Allendorf et al. of several metal-organic framework (MOF) scintillating materials,20, 21 Wang et al. proposed highly efficient X-ray scintillators by the synergistic assembly of MOFs composed of heavy metal clusters (M6(µ3-O)4(µ3OH)4(carboxylate)12 where M = Hf or Zr) and luminescent organic bridging ligands.22 However, considering their scintillation efficiencies, light yield, decay time, wavelength, and durability, further work is needed if better organic scintillators are to be prepared by this method.

1.3. Extraframework Zr4+ Ions in Zeolites.

Although numerous studies of the

preparation, characterization, and catalytic applications of zeolites with Zr4+ incorporated into their frameworks have been reported,23-28 these ions have never been ion exchanged to extraframework positions within zeolites.

This is because it is difficult to do by

conventional liquid phase ion exchange (LPIE). Because of its high charge and relatively


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small size (r = 0.79 Å),29 Zr4+ hydrolyzes strongly in solution,30 leading to high concentrations of H+ which can exchange into the zeolite and, if the zeolite has a high aluminum content, destroy it.30 The hydroxide ions produced by this hydrolysis will cause Zr4+ to precipitate directly from the exchange solution unless the pH is kept very low. These hydroxide ions might also accompany Zr4+ into the zeolite as Zr(OH)n(4-n)+. Other 4+ cations, Pb4+ 31, 32 and Ce4+,33 have been found at exchangeable positions in zeolites. In neither case had they been exchanged into the zeolite. Instead Pb2+ and Ce3+ were exchanged into the zeolite from aqueous solution and were oxidized in subsequent steps.

1.4. Objectives and Methodology. The objectives of this work were (1) to achieve a high degree of Zr4+ exchange into a high alumina zeolite by bypassing the problems of hydrolysis, and (2) to learn the positions and coordination environments of the Zr4+ ions within the zeolite. After it was seen that the products scintillated in the X-ray beam, a third objective arose, that of examining their scintillation properties, relating them if possible to structure. It was hoped that the first objective could be achieved by using the thallous ion exchange (TIE) method.34 TIE is a two-step vapor phase ion exchange (VPIE) method; in the second step an anhydrous Tl+-exchanged zeolite is treated with the vapor of volatile compound of the incoming metal ion. It is easy to design the reaction so that the Tl-



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containing product is also volatile, and therefore easily and quantitatively removable, leaving behind the pure zeolite product. This is an additional advantage of TIE. In this work, zeolite A (LTA) would first be fully Tl+ exchanged from aqueous solution and fully dehydrated.35 Then, because the vapor pressure of ZrCl4(s) is substantial at temperatures where zeolite A is stable, e.g., 1.7 x 105 Pa at 623 K,36, 37 it was hoped that TIE would proceed as follows, per unit cell: Tl12–A + 3ZrCl4(g) → Zr3–A + 12TlCl(g)

(1)

Zr4+ would be readily identifiable crystallographically because its ionic radius and scattering power are very different from those of any of the other ions in Tl12-A.

2. EXPERIMENTAL SECTION 2.1. Synthesis.

Large colorless single crystals of zeolite A (LTA, A; 4A,

|Na12(H2O)x|[Si12Al12O48]–LTA, Na12–A·xH2O, Na12–A, or Na–A) were synthesized by J. F. Charnell38 in G.T. Kokotailo's laboratory.

2.1.1.

Tl-A.

Single

crystals

of

fully

Tl+-exchanged

zeolite

A

(|Tl12(H2O)y|[Si12Al12O48]–LTA, Tl12–A, or Tl–A) were prepared by allowing 0.10 M aqueous TlC2H3O2 (Strem Chemicals, 99.999%) to flow past single crystals of Na-A in Pyrex capillaries at 294 K for 24 h. This and similar procedures had been shown to be suitable for the preparation of the fully Tl+-exchanged zeolites Tl-A,35, 39, 40 Tl-X,41, 42 and


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Tl-Y.43, 44 A powder sample of Tl-A was prepared by the batch method. Na-A powder (1.0 g, Aldrich, < 5 microns) was stirred in 100 mL of 0.1 M TlC2H3O2 (a two-fold excess) as described above for 24 h. This was repeated two times with fresh solution.

2.1.2. Crystal 1 (Zr1.7Tl5.4Cl1.7-A). A hydrated crystal of Tl-A was fully dehydrated at 673 K at 1 x 10-4 Pa for 48 h. It was then exposed to ZrCl4(g) (Aldrich, ampule, 99.99%, 3.7 x 103 Pa in equilibrium with ZrCl4(s) at 523 K)37 at 553 K for 48 h. Within the reaction vessel the vapor pressure of the product TlCl(g) in equilibrium with TlCl(s) at 523 K would be 6.1 x 10-2 Pa,45 about 105 less than that of ZrCl4(g), even less if insufficient TlCl was produced for TlCl(s) to condense. The crystal was then heated under vacuum at 553 K for additional 24 h to distill away any excess ZrCl4 and TlCl that might be near the crystal or loosely held within. After being allowed to cool to room temperature, the capillary containing the crystal was sealed off under vacuum from the reaction vessel. The product crystal was seen under the microscope to be transparent, but with numerous white sparkling crystallites within its volume and a white powder on its surface.

2.1.3. Crystal 2 (Zr2.1Tl1.6Cl3.0-A). Crystal 2 was prepared as described in Section 2.1.2 except that the reaction and final bake-out were done at a higher temperature, 623 K. It looked the same as crystal 1.



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2.1.4. Zr,Tl,Cl-A Powder. About 0.07 g of Tl-A powder (Section 2.1.1) was placed in a thin walled Pyrex tube 2 mm in diameter and was dehydrated under the same conditions used to dehydrate the Tl-A single crystals (Section 2.1.2). It was then allowed to react with ZrCl4(g) as described for crystal 2 (Section 2.1.3). After being allowed to cool to room temperature, it was sealed off under vacuum. It was white as above.

2.1.5. Anhydrous Zeolites. All zeolite samples studied in this report were anhydrous unless otherwise stated.

2.2. X-Ray Diffraction.

Diffraction intensities for the two single crystals were

measured with synchrotron X-radiation via a silicon(111) double crystal monochromator at the Pohang Accelerator Laboratory (PAL), Pohang, Korea (crystal 1), and the Photon Factory (PF), Tskuba, Japan (crystal 2). The ADSC Q210 program at PAL (crystal 1) and the ADX Q315 program at PF (crystal 2) were used for data collection by the omega scan method. Highly redundant data sets were harvested by collecting 72 sets of frames for each crystal with a 5o scan and an exposure time of 1 s per frame. The basic data files were prepared using the programs HKL3000 (PAL) and HKL2000 (PF).46 The reflections were indexed by the automated indexing routine of the DENZO program.46 These were corrected for Lorentz and polarization effects; negligible corrections for crystal decay were also applied. The space group Pm 3 m, standard for zeolite A unless high precision is warrented, was determined by the program XPREP.47 Additional experimental data are presented in


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Table 1.

2.3. SEM-EDX Analysis. After diffraction data collection, crystal 2 was removed from its capillary (exposed to the atmosphere). It was attached to a sample holder with carbon tape for scanning electron microscopy energy dispersive X-ray (SEM-EDX) analysis. Its composition was determined using a Versa 3D FIB (focused ion beam) within an Ametek EDX spectrometer and a FE (field emission) scanning electron microscope at 294 K and 1 x 10-3 Pa with a beam energy of 20 keV and current of 1 nA. The SEM-EDX results show that zirconium and thallium are both present (Table 2 and Figure 1). The composition of crystal 2 is in general agreement with that determined crystallographically (Table 2), except for the aluminum content (see Section 6.2).

2.4. X-Ray and UV Induced Luminescence. During the experimental steps prior to the collection of diffraction intensities, we were surprised to see that both Zr,Tl,Cl-A crystals luminesced bright sky blue upon synchrotron X-irradiation (13.8 keV, 350 mA, 293 K). We had not seen this before in our experience with many zeolite crystals. This luminescence was immediate when the beam was turned on and ended immediately when it was turned off. The scintillation properties of Zr,Tl,Cl-A upon X-irradiation were explored further. First CCD images of crystals 1 and 2 were obtained using synchrotron X-radiation (as above) at the PF.

Then CCD images of the Zr,Tl,Cl-A powder were obtained using



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synchrotron X-radiation (17.7 keV, 350 mA, 293 K) at the PAL.

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X-ray induced

luminescence spectra of powders of Zr,Tl,Cl-A, Tl-A, ZrCl4, and anthracene were recorded at 293 K with a QE 65000 spectrometer (Ocean optics, 100 kV, 2 mA). Finally, the luminescence intensity of the Zr,Tl,Cl-A powder was measured at 293 K with various X-ray tube voltages and currents. The UV photoluminescence of the Zr,Tl,Cl-A powder was studied with an Agilent Technologies Cary Eclips fluorescence spectrometer with a xenon flash lamp. The optical decay time was measured by directly coupling the vessel containing the Zr,Tl,Cl-A powder via an acryl block to the entrance window of the photomultiplier tube (PMT, H6610). A 266 nm pulsed laser (MPL-F-266 nm-20 mW-11031584) with a pulse duration of 7 ns was used for the excitation of the sample. The pulse shape of the PMT output was directly registered with a 1 GHz digital oscilloscope (WaveRunner 610zi) and the decay time was calculated from that.48 Finally, in order to examine the effect of exposure to the atmosphere, the tip of the capillary containing crystal 2 was broken. Air entered immediately and additional water vapor could diffuse in. Some luminescence remained after 6 h, but after 12 h it was all gone. Also the single-crystal diffraction peaks had been replaced by diffraction rings, indicating that the zeolite crystal had decomposed.

3. STRUCTURE DETERMINATION 10 ACS Paragon Plus Environment

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3.1. Procedures Common to Both Crystals. Full-matrix least-squares refinements (SHELXL2013)49 were done on F2 using all unique reflections measured for both crystals. They were initiated with the atomic parameters of the framework atoms [(Si,Al), O1, O2, and O3] in dehydrated |Na12|[Si12Al12O48]-A.50 Fixed weights were used initially. The initial refinements with anisotropic thermal parameters for all framework atoms converged to the high error indices (defined in the footnotes of Table 1) R1/R2 = 0.54/0.87 and 0.33/0.70 for crystals 1 and 2, respectively (steps 1 in Tables 3a and 3b). The detailed progress of structure determination as subsequent peaks were found on difference Fourier functions and identified as extraframework atoms are presented in Table 3. The final weights were assigned using the formula w = 1/[σ2(Fo2) + (aP)2 + bP] where P = [max(Fo2,0) + 2Fc2]/3; a and b are refined parameters whose final values are given in Table 1.

3.2. Procedures Unique to Crystal 1 (Zr1.7Tl5.4Cl1.7-A). The near final refinement of crystal 1 with anisotropic thermal parameters at all positions (Table 3a, step 6) led to convergence with R1/R2 = 0.049/0.143. The ratio of the occupancies at Zr11 and Cl11, 1.80(5)/1.25(9) = 1.44(11), and the Zr11-Cl11 bond length, 2.097(17), indicate that the Clions at C11 bond to Zr4+ ions at Zr11. Therefore, the occupancy ratio of Zr11/Cl11 was constrained to be 1.0, its maximum structurally acceptable value.

This refinement

converged quickly with unchanged R values and no noticeable changes to the other



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occupancies (Tables 3 and 4). At a late stage of refinement, two minor peaks were found in a difference Fourier function, one near each of the 6-ring oxygen positions, O2 and O3. They were introduced as O2' and O3'; the peak at O3' was larger. After refinement the distances of these positions from the two original oxygen positions were O2-O2’ = 0.31(4) Å and O3-O3’ = 0.26(6) Å (Table 5a). It might be expected that the highly charged Zr4+ cations would affect the positions of the 6-ring oxygen atoms to which they bind (O3 or O3', to be decided), and in turn those of the remaining 6-ring oxygens (O2 or O2'), and perhaps in turn the adjacent O1 oxygen atoms. This effect should be greatest for the 6-ring oxygens and less for the O1 atoms because they are farther from the Zr4+ ion. Also the effect at O1 is more difficult to assess because many O1 atoms bridge between non-equivalent 6-rings, a result of the partial Zr4+ occupancy of the 6-rings. Therefore no attempt was made to separate O1 into two or more positions. Because O3' was closer to Zr11 and O2' was farther from Zr11, as would be expected for a small 4+ cation, the occupancies at O3' and O2' were fixed to be three times that at Zr11.

The occupancies at O3 and O2 were constrained to decrease in a

complementary manner. This refinement quickly converged with no noticeable change to the R values (Table 3a, steps 7 and 9). More detailed descriptions of framework geometry are presented in Section 4.1.

3.3. Procedures Unique to Crystal 2 (Zr2.1Tl1.6Cl3.0-A). The near final refinement of


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crystal 2 with anisotropic thermal parameters at all non-framework and framework positions (Table 3b, step 7) led to convergence with R1/R2 = 0.132/0.445. The occupancies of the ions at Cl12, Zr12, and Cl13 were all about four times that at Zr1. In addition, these positions were all located on 3-fold axes with acceptable Zr1-Cl12, Cl12-Zr12, and Zr12-Cl13 bond lengths, indicating the presence of a large Zr5Cl810+ cluster centered in and extending through 6-rings out of the sodalite cavity. When their occupancies were constrained to be Zr1:Cl12:Zr12:Cl13 = 1:4:4:4, the refinement converged quickly and the error indices decreased (step 9 in Table 3b). Furthermore, the ratio of the occupancies Zr11/Cl11 = 0.61(16)/0.41(20) = 1.49(20), and the Zr11-Cl11 bond length, 1.89(5) Å, indicate that the ions at Cl11 are bonded to Zr11 as seen in crystal 1. Zr11/Cl11 was therefore constrained to be 1.0 as in crystal 1 (step 9 in Table 3b). As in Section 3.2, minor peaks were found in a difference Fourier function near O2 and O3. They were introduced as O2' and O3'. As in crystal 1, the peak at O3' was larger. After refinement their distances to the O2 and O3 positions are O2-O2’ = 0.38(5) Å and O3-O3’ = 0.603(17) Å (Table 5b). As before O2' and O3' were introduced with occupancies fixed to be three times the sum of those at Zr11 and Zr12, and the occupancies at O2 and O3 were constrained to decrease complementarily. This led to a further decrease in the error indices: R1/R2 = 0.075/0.235 (Table 3b, steps 9 and 11).

3.4. Other Crystallographic Details. The final structural parameters are presented in



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Table 4 and selected interatomic distances and angles are given in Table 5. The positional and thermal parameters at Si and Al were constrained to be equal. Atomic scattering factors for neutral atoms were used and all were modified to account for anomalous dispersion.51, 52 Additional crystallographic details are given in Table 1.

4. DESCRIPTION OF THE STRUCTURES 4.1. Framework Geometry. The mean T-Oi (i = 1-3) bond lengths, 1.666 Å for crystal 1 and 1.636 Å for crystal 2, are both shorter than the mean (1.675 Å) of the Si4+-O (1.61 Å) and Al3+-O (1.74 Å) bonds in dehydrated Ca-LSX53 and hydrated Na-A.54 This is attributed to the silicon enrichment of the zeolite framework (see Section 6.2). Nonetheless, the T-O3’ bond lengths (1.77 Å for crystal 1 and 1.86 Å for crystal 2) are noticeably longer than any of the T-Oi bonds (Table 5). This is seen because the Zr4+ ions bonding to O3' draw bonding electron density from the O3'-T bonds (Table 5). To a lesser degree, the TO2' bonds are also lengthened. The Zr4+ ions have distorted the 6-rings that they occupy, pulling the three O3' oxygen atoms to which they bond inward. By the rotations that this brings to the participating TO4 units, the O2' atoms have to a lesser degree moved outward (see Figures 2 and 3).

4.2. Extraframework Ions. The oxidation states of the zirconium and thallium ions were assigned primarily on the basis of their ionic radii. Consideration was also given to


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their coordination numbers and environments (cations with smaller coordination numbers generally bond more closely to their ligands55, 56). The results are tabulated in Table 6. In crystal 1, the Zr4+ ions are all equivalent; the same is true for the Cl- ions. Crystal 2, however, with its greater Zr4+ content, is more complex: two kinds of Zr4+ and three kinds of Cl- are found.

4.2.1. Zr4+ Ions. Per unit cell of crystal 1, 1.67(4) Zr4+ ions at Zr11 lie on 3-fold axes near 6-rings. Each extends just a little, 0.36 Å, into large cavity from the (111) plane of its three 6-ring O3’ oxygen atoms (Figures 3 and 4). Each is 4-coordinate, bonding to the three O3’ framework oxygens and one Cl- ion at Cl11. The Zr11-O3' bond length, 2.01(6) Å, is perhaps shorter than the sum of Zr4+ and O2- ionic radii,29 0.79 + 1.32 = 2.11 Å, as might be expected because of the low coordination number at Zr4+.55, 56 Zr11-Cl11, 2.097(17) Å, is very much shorter than their sum, 0.79 + 1.81 = 2.60 Å,29 presumably because Cl11 binds to no other atom. Per unit cell of crystal 2, only 0.72(2) Zr4+ ions are found at Zr11. Each extends further, 0.68 Å, into sodalite cavity from the (111) plane of its three 6-ring O3’ oxygen atoms (Figures 5 and 6). These Zr4+ ions are again 4-coordinate, each bonding to three O3’ framework oxygens and one Cl- ion at Cl11 (Table 5). The Zr11-O3' bond length, 1.825(23) Å, is clearly shorter than the sum of Zr4+ and O2- ionic radii, 2.11 Å,29 while Zr11-Cl11, 1.89(6) Å, is again very much shorter than the corresponding sum, 2.60 Å,29 for the same



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reasons given for crystal 1. The remaining 1.12(2) Zr4+ ions in crystal 2 lie on the 3-fold axes at Zr12 near 6-rings. Each extends 0.58 Å into large cavity from the (111) plane of its three O3' oxygen atoms (Figure 7). Each of these Zr4+ ions is 5-coordinate, bonding to three O3’ framework oxygens and two Cl- ions at Cl12 and Cl13 with Zr4+-Cl- distances of 1.81(4) and 2.105(16) Å, respectively. The Zr4+-O3' bond lengths in crystal 2, Zr11-O3' = 1.825(23) Å and Zr12O3' = 1.767(16) Å, are both shorter than in crystal 1, 2.01(6) Å. This may be a consequence of the different Tl+ occupancies in the two crystals, 5.4 in crystal 1 but only 1.6 in crystal 2. Tl+ ions draw charge from the zeolite framework.

4.2.2. Zr2+ Ions. In crystal 2, 28(4)% of the sodalite cavities are centered by Zr2+ ions at Zr1 (Figure 7). Each of these is 4-coordinate tetrahedral, bonding to four Cl- ions at Cl12 on 3-fold axes at 2.74(5) Å. This bond is far longer than any of the other Zr-Cl bonds in either structure and longer than the sum of the Zr4+ and Cl- radii, 2.60 Å.29 It is closer to the Zr2+-Cl- bond lengths found in the bridging Zr2+–Cl- bonds in Na4Zr6Cl16Be, 2.771(3) and 2.773(3) Å,57 K3Zr6Cl15Be, 2.703(1) Å,58 and KZr6Cl15C, 2.725(2) Å.59 Zr2+ might have formed by the decomposition of ZrCl4(g), ZrCl4 → ZrCl2 + Cl2, within the zeolite at 623 K.

4.2.3. Tl+ Ions. About 5.4 Tl+ ions per unit cell were found at two positions in crystal 1 (Figure 4), while only about 1.6 were present at one position in crystal 2 (Figure 6). They are all in the large cavities, opposite 6-rings and on or near the 8-rings (Table 4). These


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positions are very similar to those in previously reported Tl-A structures.35, 60, 61

4.2.4. Cl- Ions. In crystal 1, 1.67(4) Cl- ions per unit cell at Cl11 are in the sodalite cavities. Each bonds to a Zr4+ ion at Zr11. In crystal 2, this occupancy is less, 0.72(2). Another 1.12(2) Cl- ions at Cl12 are in the remaining sodalite cavities, and each of them forms a linear bridge between Zr1 (Zr2+) and Zr12 (Zr4+). Finally, 1.12(2) Cl- ions at Cl13 are in large cavities, each bonding to a Zr4+ ion at Zr12. The Cl13-Zr12-Cl11 angle is 180o (Figure 7).

4.2.5. Zr5Cl810+ Clusters. The 0.28(1) Zr2+ ions per unit cell at Zr1, at the very centers of the sodalite cavities of crystal 2, do not bond to the zeolite framework. Instead, each bonds tetrahedrally to four Cl- ions at Cl12. Each of these Cl- ions bonds to a 6-ring Zr4+ ion (Zr12) on the same 3-fold axis, and each of these Zr4+ ions, in turn, bonds to a Cl- ion at Cl13 on the same 3-fold axis in the large cavity. Accordingly, 28% of the sodalite cavities contain a Zr5Cl810+ cluster centered in and extending out of them (Figure 7). Halide ions often bridge between Zrn+ ions.57-59

4.3. Charge balance.

The sum of the charges of the extraframework cations and

anions per unit cell are 10.5+ and 6.7+ for crystals 1 and 2, respectively (see Table 6). For both crystals, this diminished charge (reduced from 12.0+ in Na-A) is attributed to the dealumination of the zeolite framework (Section 6.1), as reported by Anderson and Klinowski for zeolites treated with SiCl4(g).62

Consistent with this are the unit cell



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parameters of the two Zr,Tl,Cl-A crystals, a = 12.125(1) and 11.945(1) Å, which are noticeably smaller than the ca.-12.2 Å value commonly found for dehydrated mono- and dipositive cation exchanged zeolites A. Crystal 2, with its greater loss of Al, has the smaller unit cell. Structures richer in Si have smaller unit cells because Si-O is shorter than Al-O (Section 4.1).

4.4. Verification of Atomic Composition by SEM-EDX Analysis.

The atomic

composition of crystal 2 was confirmed using energy dispersive X-ray analysis (SEM-EDX) (Table 2). Considering the relatively large estimated standard deviations (esds) in the EDX analysis, due in part to the zeolite decomposition to be expected in the electron beam and the possible decomposition of the zeolite upon exposure to atmosphere, acceptable agreement is seen for each element except Al (see Section 6.1). Finally, as is often the case due to contamination, a Na peak is present at 1.04 keV in the EDX analysis although it was not found crystallographically. It cannot be from the ZrCl4 reagent because NaCl (10.4 ppm) is not volatile at 553 K, nor from the Tl12-A because Tl+ exchange was complete.35

5. SCINTILLATION PROPERTIES OF Zr,Tl,Cl-A Crystals 1 and 2 fluoresce bright sky blue when irradiated by synchrotron X-rays (Figures 8b and 8d). The X-ray induced emission spectrum of the similarly prepared Zr,Tl,Cl-A powder sample consists of a broad band between 330 nm and 750 nm, peaking at


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490 nm (Figure 9a). Under the same measurement conditions, neither Tl+-exchanged zeolite A nor ZrCl4(s) showed any radioluminescence (Figure 9a). The general features of the emission spectrum of the Zr,Tl,Cl-A powder are similar to those commonly seen in Tl+doped CsI,63 NaI,63 and KX (X = Cl, Br, and I).64 The integrated light yield observed for Zr,Tl,Cl-A powder is about five times greater than that of anthracene, a commercially available scintillator whose light yield is well documented (Table 7 and Figure 9b).22, 65 The UV photoluminescence of the Zr,Tl,Cl-A powder sample consists of a broad emission band located between 390 nm and 550 nm, peaking at 474 nm for an excitation wavelength of 280 nm (Figure 10a). Note that this maximum is close to that seen upon Xirradiation, 490 nm. The optical decay time of the Zr,Tl,Cl-A powder was determined by fitting the recorded pulse shape information with a two-component exponential function, y = A1exp(t/τ1) + A2exp(-t/τ2) + y0, where the y and y0 are luminescence intensities, A1 and A2 are constants, t is time, and τ1 and τ2 are decay times (Figure 10b). The presence of two rather slow decay times, 0.92 µs (47%) and 2.24 µs (53%) (Figure 10b), may indicate that a spinforbidden intersystem cross relaxation,1,5 such as a triplet-singlet transition in the case of Tl+, is occurring in Zr,Tl,Cl-A (see Section 6.2). Similar long decay times were seen in other Tl+-containing materials such as Tl+-doped CsI (information from Saint-Gobain Ceramics & Plastics, Inc). The luminescent area of the Zr,Tl,Cl-A powder, r = 134 µm, was about seven times



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greater than that of the synchrotron X-ray beam (elliptical, ca. 80 x 120 µm) at the PAL (Figure 11b). This is probably because the luminescence emitted by each microcrystal was scattered by others. The Zr,Tl,Cl-A powder was further exposed to X-rays of various energies and intensities (50 to 100 kV, 1 and 2 mA). The radioluminescence intensities observed at 490 nm seem to be directly proportional to the X-ray intensities and to increase more than linearly with increasing X-ray energies. No noticeable deterioration was seen (Figure 11c). This indicates that Zr,Tl,Cl-A is robust and suggests that it could be used to detect a variety of high energy radiations.

6. DISCUSSION When Tl-A was treated with ZrCl4(g) at 553 K, about 54% of the Tl+ ions were replaced by Zr4+ and Cl- ions (crystal 1). When this was done at 623 K, 87% of the Tl+ ions were replaced by Zr4+, Zr2+, and Cl- ions (crystal 2). Both Zr,Tl,Cl-A compositions are strongly radioluminescent at 293 K.

6.1. Net Reactions. The sum of the charges of the extraframework ions (Zr2+, Zr4+, and Cl-) is 10.5+ and 6.7+ per unit cell for crystals 1 and 2, respectively. Therefore, for charge balance, the frameworks should have charges of 10.5- and 6.7-, respectively, per unit cell.

This indicates that framework dealumination, as was seen with SiCl4(g) treated


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zeolites,62 has occurred. In crystals 1 and 2, 1.5 and 5.3 Al3+ ions were lost per unit cell, respectively. There are not enough Cl- ions present to write reactions where Al3+ leaves the zeolite as Al2Cl6(g) and Tl+ leaves only as TlCl(g), so it appears that at least some of those elements were lost as Tl2O and Al2O3. Assuming that the reaction products are Tl2O(g) and Al2O3(s), the following reactions can be written. They are not quite balanced with respect to oxygen, and they do not account for the reduced number of unit cells (due to the reorganization of the structure). Crystal 1: |Tl+12|[Si12Al12O48]12--LTA + 1.67ZrCl4(g) → |Zr4+1.67Tl+5.44Cl-1.67|[Si13.5Al10.5O48]-LTA + 5.06TlCl(g) + 0.75Tl2O(g) + 0.75Al2O3(s)

(2)

Crystal 2: |Tl+12|[Si12Al12O48]12--LTA + 2.12ZrCl4(g) → |Zr4+1.84Zr2+0.28Tl+1.58Cl-2.96|[Si17.3Al6.7O48]-LTA + 5.02TlCl(g) + 2.7Tl2O(g) + 2.7Al2O3(s) + 0.28Cl2(g)

(3)

Al2O3(s) on the surface of crystal 2 would account for the undiminished Al content observed by SEM-EDX (Table 2).

Also, the unusual appearance of both crystals,

transparent with white crystallites within them and a white powder on their surfaces, is consistent with the formation of Al2O3. Although the vapor pressure of Tl2O(s) is very low at the reaction temperatures used (1.0 x 10-7 Pa at 553 K and 8.5 x 10-6 Pa at 623 K66), it appears to have been high enough for Tl2O (black) to have vaporized away. Another explanation for the reduction of the negative charge of the zeolite framework



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could have been the replacement of Al3+ by Zr4+. This, however, would have led to increases in the unit cell size because Zr4+ (r = 0.79 Å)29 is larger than Al3+ (r = 0.51 Å);29 instead a monotonic decrease is seen with increasing Zr content. Also, peaks for framework zirconium ions were not seen on difference Fourier functions, and the addition of zirconium to the present tetrahedral framework sites was unsuccessful in least squares refinement.

6.2. Radioluminescence. The partial exchange of Zr4+ into a Tl+-exchanged zeolite has produced a zeolite with strong scintillation properties. It is generally understood that the luminescence of Tl+-doped CsI67 is due to the interaction of Tl+ with holes (h+) and electrons (e-) produced by high energy radiation as follows. h+ + Tl+ → Tl2+, Tl2+ + e- → (Tl+)*, and (Tl+)* → Tl+ + phonons + photon

(4)

e- + Tl+ → Tl0, h+ + Tl0 → (Tl+)*, and (Tl+)* → Tl+ + phonons + photon

(5)

The h+'s and e-'s formed in the zeolite framework by high energy irradiation68 might undergo similar processes in Zr,Tl,Cl-A, together with trapping and recombination, to produce the observed radioluminescence. However, Liu et al. suggested that, unlike the 'hyperthermal' electrons, the (trapped) holes in the zeolite framework should not react with Tl+,69 indicating that oxidation processes like h+ + Tl+ → Tl2+ (first step in (4)) and h+ + Tl0 → (Tl+)* (second step in (5)) should not be observed in zeolites. The absence of noticeable luminescence from Tl-A upon X-irradiation verifies that expectation (Figure 9a, Section 5).


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Therefore, the holes and electrons needed for the observed radioluminescence of Zr,Tl,Cl-A might not have come from the zeolite framework but from another source such as the Zr species in Zr,Tl,Cl-A. In crystal 1, ZrCl3+ may be the source of the electron and hole pairs which could effectively move to the Tl+ luminescence center by the reaction sequences (4) and (5) without trapping. In crystal 2 and the identically prepared powder, Zr5Cl810+ may perform that function. Alternatively, a partial relaxation of the spin-orbit interaction for the spin-forbidden transition from the triplet excited state, 3P0,1 (6s16p1), to the singlet ground state, 1S0 (6s2), of the Tl+ activator by the nearby polarizable Zr4+ and Zr2+ ions may have made this forbidden conversion possible.70 This is another, perhaps more plausible, explanation for the absence of noticeable luminosity from Tl-A and the strong luminescence seen from Zr,Tl,Cl-A. Accordingly, it appears that the simultaneous presence of Zrn+ and Tl+ ions is necessary for the observed fluorescence to occur. Furthermore, the breadth of the emitted spectra from Zr,Tl,Cl-A (Figures 9a and 10a) and its decay time (Figure 10b) are very similar to those of Tl+-doped CsI,63 suggesting that their scintillation mechanisms are similar. The loss of X-ray luminosity by Zr,Tl,Cl-A upon hydration may be due to the hydrolysis of the Zr4+ ions. Zeolite A, a high alumina zeolite, is sensitive to acid, so the many H+ ions produced by this hydrolysis could have led to the destruction of zeolite framework. As poduct phases formed, the Zr and Tl ions are unlikely to have remained in close proximity as they were in the zeolite, disrupting the hole and electron transfer



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pathways responsible for X-ray luminosity. These results suggest that many other zeolite scintillators, tunable to specific applications, can be prepared by exchanging appropriate metal cations into zeolites. They suggest that similarly prepared high silica zeolites might continue to scintillate after hydration.

Studies in progress are aimed at exploring these possibilities and at

understanding the scintillation mechanisms.

7. SUMMARY A new kind of inorganic scintillator has been prepared by the assembly of Zr4+, Zr2+, Tl+, and Cl- ions in a zeolite. Zr1.7Tl5.4Cl1.7-A and Zr2.1Tl1.6Cl3.0-A were prepared by the thallous ion exchange reaction of fully dehydrated Tl12-A with 3.7 x 103 Pa of ZrCl4(g) at 553 K and 623 K, respectively. Their crystal structures were determined by single-crystal crystallography and their compositions were partially confirmed by SEM-EDX analyses. The structures showed that some Tl+ ions had been replaced by extraframework Zr4+, Zr2+, and Cl- ions, and that the zeolite framework had lost Al to become enriched in Si. The Zr4+ ions are all in 6-rings where they bond to three framework oxygen atoms and one, sometimes two, Cl- ions. Tetrahedral Zr2+ ions center Zr5Cl810+ clusters in Zr2.1Tl1.6Cl3.0-A. Tl+ ions occupy 6-ring and 8-ring positions in the large cavities.

Upon exposure to X-

radiation, Zr,Tl,Cl-A luminesces with a broad emission band between 330 nm and 750 nm,


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peaking at 493 nm. The integrated light yield observed for Zr,Tl,Cl-A powder is about five times greater than that of anthracene, a well documented scintillator.65

This strong

radioluminescence appears to be due to the simultaneous presence of Zr and Tl within the zeolite.

■ ASSOCIATED CONTENT Supporting Information. Observed and calculated structure factors squared with esds. This information is available free of charge via the Internet at http://pubs.acs.org. ■ AUTHOR INFORMATION Corresponding Author * Tel.: +82 53 950 5589; Fax: +82 53 950 6594; E-mail address: [email protected] ■ ACKNOWLEDGEMENT We gratefully acknowledge the Photon Factory, High Energy Accelerator Research Organization, KEK, Tsukuba, Japan and the Pohang Light Source, Korea, for the use of their diffractometer and computing facilities. This work was supported by a National Research Foundation of Korea (NRF) grant (No. NRF-2014R1A2A1A11054075) funded by the Korean government (MSIP).



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2002, 106, 4578. 40. Heo, N. H.; Kim, S. H.; Choi, H. C.; Jung, S. W.; Seff, K., Crystal Structure of IndiumExchanged Zeolite A Containing Sorbed Disulfur. J. Phys. Chem. B 1998, 102, 17. 41. Heo, N. H.; Park, J. S.; Kim, Y. J.; Lim, W. T.; Jung, S. W.; Seff, K., Spatially Ordered Quantum Dot Array of Indium Nanoclusters in Fully Indium-Exchanged Zeolite X. J. Phys. Chem. B 2003, 107, 1120. 42. Heo, N. H.; Jung, S. W.; Park, S. W.; Park, M.; Lim, W. T.; Seff, K., Crystal Structures of Fully Indium-Exchanged Zeolite X. J. Phys. Chem. B 2000, 104, 8372. 43. Jeong, G. H.; Lee, Y. M.; Kim, Y.; Vaughan, D. E. W.; Seff, K., Single Crystal Structure of Fully Dehydrated Fully Tl+-Exchanged Zeolite Y, |Tl71|[Si121Al71O384]-FAU. Microporous Mesoporous Mater. 2006, 94, 313. 44. Seo, S. M.; Lee, O. S.; Kim, H. S.; Bae, D. H.; Chun, I. J.; Lim, W. T., Determination of Si/Al Ratio of Faujasite-type Zeolite by Single-crystal X-ray Diffraction Technique. Singlecrystal Structures of Fully Tl+- and Partially K+-exchanged Zeolites Y (FAU), |Tl71|[Si121Al71O384]-FAU and |K53Na18|[Si121Al71O384]-FAU. Bull. Korean Chem. Soc. 2007, 28. 45. International Series on Materials Science and Technology; Pergamon International Library: Elmsford, NY, 1979; Vol. 24, p 374. 46. Otwinowski, Z.; Minor, W., Processing of X-ray Diffraction Data Collected in Oscillation Mode. Methods Enzymol. 1997, 276, 307. 47. XPREP, Version 6.12, Program for Automatic Space Group Determination; Bruker AXS Inc.: Madison, WI, 2001. 48. Kim, H.; Annenkov, A.; Boiko, R.; Buzanov, O.; Chernyak, D.; Cho, J.; Danevich, F.; Dossovitsky, A.; Rooh, G.; Kang, U., Neutrino-Less Double Beta Decay Experiment Using Ca MoO Scintillation Crystals. IEEE Trans. Nucl. Sci. 2010, 57, 1475-1480. 49. Sheldrick, G. M., A Short History of SHELX. Acta Crystallogr., Sect. A 2007, 64, 112122. 50. Yanagida, R. Y.; Amaro, A. A.; Seff, K., Redetermination of the Crystal Structure of Dehydrated Zeolite 4A. J. Phys. Chem. 1973, 77, 805-809. 51. Cromer, D. T., Anomalous Dispersion Corrections Computed from Self-Consistent Field Relativistic Dirac-Slater Wave Functions. Acta Crystallogr. 1965, 18, 17. 52. International Tables for X-ray Crystallography; Kynoch Press: Birmingham, 1974; Vol. IV; p 148. 53. Vitale, G.; Bull, L. M.; Morris, R. E.; Cheetham, A. K.; Toby, B. H.; Coe, C. G.; Mac Dougall, J. E., Combined Neutron and X-ray Powder Diffraction Study of Zeolite Ca LSX and a 2H NMR Study of Its Complex with Benzene. J. Phys. Chem. 1995, 99, 16087-16092. 54. Fischer, R. X.; Sehovic, M.; Baur, W. H.; Paulmann, C.; Gesing, T. M., Crystal Structure and Morphology of Fully Hydrated Zeolite Na-A. Z. Kristallogr. 2012, 227, 438-445. 55. Shannon, R. D.; Prewitt, C. T., Effective Ionic Radii in Oxides and Fluorides. Acta Crystallogr., Sect. B 1969, 25, 925. 56. Jia, Y. Q., Crystal Radii and Effective Ionic Radii of the Rare Earth Ions. J. Solid State Chem. 1991, 95, 184. 57. Ziebarth, R. P.; Corbett, J. D., New Layered Phases Achieved with Centered Zirconium Chloride Clusters. The Stoichiometry Zr6Cl16. Inorg. Chem. 1989, 28, 626-631. 58. Ziebarth, R. P.; Corbett, J. D., Cluster Framework Structures and Relationships. Two Compounds with a New Connectivity, K2Zr6Cl15B and K3Zr6Cl15Be. J. Am. Chem. Soc. 1988, 110, 1132-1139. 59. Ziebarth, R. P.; Corbett, J. D., Cation Distributions within a Cluster Framework. Synthesis and Structure of the Carbon-and Boron-Centered Zirconium Cluster Compounds KZr6Cl15C and CsKZr6Cl15B. J. Am. Chem. Soc. 1987, 109, 4844-4850. 60. Riley, P. E.; Seff, K.; Shoemaker, D. P., Crystal Structures of Hydrated and Dehydrated


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Thallium-Exchanged Zeolite A. J. Phys. Chem. 1972, 76, 2593-2597. 61. Firor, R. L.; Seff, K., Near-Zero-Coordinate Thallium(I). The Crystal Structures of Hydrated and Dehydrated Zeolite A Fully Exchanged with TlOH. J. Am. Chem. Soc. 1977, 99, 4039-4044. 62. Anderson, M. W.; Klinowski, J., Zeolites Treated with Silicon Tetrachloride Vapour. Part 1.-Preparation and Characterisation. J. Chem. Soc., Faraday Trans. 1 1986, 82, 1449-1469. 63. Aitken, D.; Beron, B.; Yenicay, G.; Zulliger, H., The Fluorescent Response of NaI (Tl), CsI (Tl), CsI (Na) and CaF2 (Eu) to X-rays and Low Energy Gamma Rays. IEEE Trans. Nucl. Sci. 1967, 14, 468-477. 64. Edgerton, R.; Teegarden, K., Emission Spectra of KCl: Tl, KBr: Tl, and KI: Tl at 300, 80, and 12° K. Phys. Rev. 1963, 129, 169. 65. Helfrich, W.; Schneider, W., Recombination Radiation in Anthracene Crystals. Phys. Rev. Lett. 1965, 14, 229. 66. Cubicciotti, D., Thermodynamics of Vaporization of Thallous Oxide. High Temp. Sci. 1970, 2, 213. 67. Gwin, R.; Murray, R., Scintillation Process in CsI (Tl). II. Emission Spectra and the Possible Role of Self-Trapped Holes. Phys. Rev. 1963, 131, 508. 68. Zhang, G.; Liu, X.; Thomas, J. K., Radiation Induced Physical and Chemical Processes in Zeolite Materials. Radiat. Phys. Chem. 1997, 51, 135-152. 69. Liu, X.; Zhang, G.; Thomas, J. K., Spectroscopic Studies of Electron Trapping in Zeolites: Cation Cluster Trapped Electrons and Hydrated Electrons. J. Phys. Chem. 1995, 99, 10024-10034. 70. G. Blasse; B.C. Grabmaier, Luminescent Materials. Springer: New York, 1994.



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TABLE 1. Experimental Conditions and Crystallographic Data crystal 1 (Zr1.7Tl5.4Cl1.7-A) crystal cross-section (mm) 0.070 + Tl ion exchange (T (K), h, mL) 294, 24, 5 dehydration of Tl-Y (T (K), h, P (Pa)) 673, 72, 1.5 x 10-4 reaction of Tl-Y with ZrCl4 (T (K), h, P (Pa)) 553, 72, 3.7 x 103 X-ray source PLS(2D-SMC)a wavelength (Å) 0.7000 detector ADSC Quantum-210 crystal-to-detector distance (mm) 63 data collection temperature (T (K)) 294(1)

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crystal 2 (Zr2.1Tl1.6Cl3.0-A) 0.080 294, 24, 5 673, 72, 1.5 x 10-4 623, 72, 3.7 x 103 PF(BL-5A)b 0.9000 ADSC Quantum-315r 60 294(1)

Pm 3 m, 221 Pm 3 m, 221 space group, No. unit cell constant, a (Å) 12.125(1) 11.945(1) maximum 2θ for data collection (deg) 66.79 72.95 no. of reflections measured 40,516 22,366 no. of unique reflections measured, m 747 442 no. of reflections with Fo > 4σ(Fo) 680 380 no. of variables, s 51 56 data/parameter ratio, m/s 14.6 7.9 weighting parameters: a, b 0.073, 4.214 0.151, 2.216 c d final error indices: R1 , R2 0.047, 0.144 0.075, 0.235 goodness of fite 1.18 1.14 a Beamline 2D-SMC at the Pohang Light Source, Korea. bBeamline BL-5A at the Photon Factory, Japan. c R1 = Σ|Fo - |Fc||/ΣFo; R1 is calculated using only those reflections for which Fo > 4σ(Fo). dR2 = [Σw(Fo2 Fc2)2/Σw(Fo2)2]1/2 is calculated using all unique reflections measured. eGoodness of fit = (Σw(Fo2-Fc2)2/(ms))1/2.


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TABLE 2. Crystal Composition (Atomic %) by Crystallographic (SXRD) and SEM-EDX Analyses crystal 2 (Zr2.1Tl1.6Cl3.0-A) element SXRD SEM-EDXa Si

22.18

17.1(9)

Al O

8.33 61.01

16.5(8)b 56(5)

Zr Tl

2.69 2.02

3.28(16) 3.8(4)

Cl 3.76 2.94(20) The zeolite crystal can be expected to have suffered some decomposition due to the action of the electron beam and upon subsequent exposure to the atmosphere. This can be a significant source of error. b See Section 6.1. a



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TABLE 3. Steps of Structure Determination as Non-framework and Minor Framework Atomic Positions Were Found step Zr1

Zr11

1c 2 3 4 5d 6e 7f 8 9

1.37(9) 1.49(10) 1.80(5) 1.70(4) 1.72(4) 1.67(4)

1c 2 3 4 5d 6 7e 8 9h 10 11

2.6(3) 1.81(11) 1.57(11) 1.26(10) 1.33(7) 0.65(15) 0.61(16) 0.71(2) 0.74(2) 0.72(2)

0.22(2) 0.23(2) 0.23(3) 0.28(1) 0.29(1) 0.28(1)

Zr12

1.44(10) 1.66(11) 1.21(8) 1.12(7) 1.10(7) 1.12(7) 1.11(3) 1.16(2) 1.12(2)

number of ions or atoms per unit cella a. crystal 1 (Zr1.7Tl5.4Cl1.7-A) Cl11 Cl12 Cl13

Tl1

Tl2

3.44(22) 3.23(12) 2.55(7) 2.64(7) 2.67(2) 2.69(2) 2.68(2) 2.68(2)

2.90(10) 2.45(7) 2.59(7) 2.77(3) 2.75(3) 2.82(3) 2.76 (3)

1.62(11) 1.60(9) 1.56(8) 1.52(8) 1.54(4) 1.70(4) 1.58(4)

1.63(24) 1.25(9) 1.70(4) 1.72(4) 1.67(4) b. crystal 2 (Zr2.1Tl1.6Cl3.0-A)

0.41(20) 0.71(2) 0.74(2) 0.72(2)

1.6(3) 1.7(4) 1.11(3) 1.16(2) 1.12(2)

1.34(23) 2.62(22) 1.91(17) 1.79(18) 1.88(18) 1.11(3) 1.16(2) 1.12(2)

a

error indicesb

4.2(14) 5.01g

R1 0.54 0.30 0.17 0.128 0.116 0.0485 0.0486 0.0455 0.0473

R2 0.87 0.70 0.54 0.454 0.437 0.1431 0.1467 0.1348 0.1441

3.9(18) 5.52i

0.33 0.30 0.24 0.22 0.17 0.139 0.132 0.125 0.085 0.067 0.075

0.70 0.69 0.62 0.59 0.52 0.465 0.445 0.438 0.281 0.214 0.235

O2’

O3’

8.4(13) 5.01g

8.3(21) 5.52i

Numbers in parentheses are the estimated standard deviations (esds) in the units of the least significant figure given for the corresponding parameter. bDefined in footnotes to Table 1. cOnly framework atoms which were refined anisotropically. dAn extinction parameter (EXTI) was introduced and refined. eA twoparameter weighting system was applied. After that all atoms were refined anisotropically. fThe occupancies of Zr11 and Cl11 were constrained to be equal. g The occupancies at O2' and O3' were fixed to be three times the occupancy of Zr11, each of them was refined anisotropically. hThe constraint, occupancy at Zr1:Cl12:Zr12:Cl13 = 1:4:4:4, was applied to the Zr5Cl810+ cluster. After that occupancies of Zr11 and Cl11 were constrained to be equal. iThe occupancies at O2' and O3' were fixed to be three times the occupancies at Zr11 + Zr12, and each was refined anisotropically.

32


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TABLE 4. Positional, Thermal, and Occupancy Parametersa atom Wyckoff position position

x

y

z

U11 or Uisob

U22

U33

U23

U13

U12

occupancyc varied constrained fixed

a. crystal 1 (Zr1.7Tl5.4Cl1.7-A) 219(5) 203(5) 145(5) 22(3) 0d 0d 24 d d 579(32) 590(33) 177(18) 0 0 0d 12 513 (61) 185(48) 185(48) 20(50) 0d 0d 6.99e 390(66) 136(52) 136(52) 18(59) 0d 0d 5.01e 316(20) 316(20) 389(59) 75(25) 75(25) 92(22) 18.99e 547(191) 547(191) 257(151) -141(142) -141(142) 102(175) 5.01e 776(31) 776(31) 776(31) 386(31) 386(31) 386(31) 1.80(5) 1.67(4)f 329(4) 329(4) 329(4) -16(2) -16(2) -16(2) 2.67(2) 2.68(2) 1075(18) 339(11) 638(38) -168(18) 0d 0d 2.77(3) 2.76(3) 513(29) 513(29) 513(29) 21(28) 21(28) 21(28) 1.25(9) 1.67(4)f b. crystal 2 (Zr2.1Tl1.6Cl3.0-A) T 24(k) 0d 18260(13) 36746(13) 569(11) 514(11) 454(10) 21(6) 0d 0d 24 d d d d O1 12(h) 0 20447(94) 50000 1947(111) 1309(84) 542(40) 0 0 0d 12 O2 12(i) 0d 28961(151) 28961(151) 1386(173) 490 (74) 490 (74) 59 (101) 0d 0d 6.48g O2’ 12(i) 0d 31237(159) 31237(159) 620(94) 486(83) 486(83) -113(75) 0d 0d 5.52g O3 24(m) 10376(66) 10376(66) 32952(105) 923(51) 923(51) 1163(95) -183(47) -183(47) 332(59) 18.48g O3’ 24(m) 13612(111) 13612(111) 30813(188) 394(54) 394(54) 376(71) 76(47) 76(47) -9(66) 5.52g d d d Zr1 1(a) 0 0 0 781(38) 0.23(3) 0.28(1)h Zr11 8(g) 15875(131) 15875(131) 15875(131) 691(65) 691(65) 691(65) 113(71) 113(71) 113(71) 0.61(16) 0.72(2)f Zr12 8(g) 22019(43) 22019(43) 22019(43) 618(22) 618(22) 618(22) 85(23) 85(23) 85(23) 1.12(7) 1.12(2)h d d d Tl2 24(l) 5852(87) 45138(55) 50000 2475(131) 791(38) 1482(71) 0 0 -149(41) 1.52(8) 1.58(4) Cl11 8(g) 6730(256) 6730(256) 6730(256) 994(120) 994(120) 994(120) -19(145) -19(145) -19(145) 0.41(20) 0.72(2)f Cl12 8(g) 13256(221) 13256(221) 13256(221) 787(131) 787(131) 787(131) 118(123) 118(123) 118(123) 1.7(4) 1.12(2)h Cl13 8(g) 32193(66) 32193(66) 32193(66) 581(44) 581(44) 581(44) -167(36) -167(36) -167(36) 1.88(18) 1.12(2)h a 5 4 Positional parameters x 10 and thermal parameters x 10 are given. Numbers in parentheses are the estimated standard deviations (esds) in the units of the least significant figure given for the corresponding parameter. bThe anisotropic temperature factor is exp[-2π2a-2(U11h2 + U22k2 + U33l2 + 2U12hk + 2U13hl + 2U23kl)]. cOccupancy factors are given as the number of atoms or ions per unit cell. dExactly, by symmetry. eThe occupancies at the O2’ and O3’ atoms were fixed to be three times the occupancies of Zr11. In addition the occupancies of O2 + O2’, and O3 + O3’ were fixed to be 12 and 24. fThe occupancies of Zr11 and Cl11 were constrained to be equal. gThe occupancies at the O2’ and O3’ atoms were fixed to be three times the occupancies at Zr11 + Zr12, respectively. In addition the occupancies at O2 + O2’ and O3 + O3’ were fixed to be 12 and 24. hThe constraint, occupancy at Zr1:Cl12:Zr12:Cl13 = 1:4:4:4, was applied to the Zr5Cl810+ cluster. T O1 O2 O2’ O3 O3’ Zr11 Tl1 Tl2 Cl11

24(k) 12(h) 12(i) 12(i) 24(m) 24(m) 8(g) 8(g) 24(k) 8(g)

0d 0d 0d 0d 11224(94) 12067(356) 20115(49) 25889(5) 0d 10203(64)

18295(8) 21684(53) 29069(104) 30888(142) 11224(94) 12067(356) 20115(49) 25889(5) 43996(27) 10203(64)

36926(8) 50000d 29069(104) 30888(142) 33753(130) 31995(479) 20115(49) 25889(5) 47306(16) 10203(64)

33



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TABLE 5. Selected Interatomic Distances (Å) and Angles (deg)a distances a. crystal 1 b. crystal 2 Zr1.7Tl5.4Cl1.7-A Zr2.1Tl1.6Cl3.0-A T-O1 1.6498(19) 1.6046(24) O1-T-O2 O1-T-O2’ T-O2 1.629(3) 1.581(4) O1-T-O3 T-O2’ 1.706(8) 1.684(10) O1-T-O3’ average T-O2 1.661 1.628 O2-T-O3 T-O3 1.666(5) 1.621(4) O2-T-O3’ T-O3’ 1.77(3) 1.859(9) O2’-T-O3 average T-O3 1.688 1.676 O2’-T-O3’ O3-T-O3 mean 1.666 1.636 O3’-T-O3’ mean Zr11-O3 2.266(15) 2.241(13) Zr11-O3’ 2.01(6) 1.825(23) T-O1-T T-O2-T 2.904(10) 2.913(21) T-O2’-T Zr11…O2 3.214(24) T-O3-T Zr11…O2’ 3.083(15) T-O3’-T Zr12-O3 2.361(11) mean Zr12-O3’ 1.767(16) O3-Zr11-O3 Zr11-Cl11 2.097(17) 1.89(6) O3’-Zr11-O3’ Zr1-Cl12 Zr12-Cl12 Zr12-Cl13

2.74(5) 1.81(4) 2.105(16)

Tl1-O3 Tl1-O3’

2.709(16) 2.50(6)

Tl2-O1 Tl2-O2 Tl2-O2’

2.745(7) 2.878(18) 2.57(3)

3.031(12) 3.25(3) 2.88(3)

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angles a. crystal 1 Zr1.7Tl5.4Cl1.7-A 110.3(3) 106.7(3) 110.8(6) 116.0(18) 109.1(6) 110.5(8) 111.5(6) 103.9(19) 110.6(6) 111.4(9) 110.1

b. crystal 2 Zr2.1Tl1.6Cl3.0-A 107.7(4) 103.3(4) 111.7(5) 115.1(8) 107.8(6) 91.0(6) 115.2(6) 97.2(6) 106.6(5) 103.3(8) 105.9

168.9(3) 162.2(13) 141.2(15) 143.0(10) 127 (4) 148.5

162.2(5) 162.1(18) 136.0(17) 144.1(8) 112.2(8) 143.3

118.36(22) 117.9(8)

116.6(5) 105.5(11)

O3-Zr12-O3 O3’-Zr12-O3’

107.7(4) 111.7(8)

O3-Tl1-O3 O3’-Tl1-O3’

91.8(5) 87.0(19)

O1-Tl2-O2 O2-Tl2-O2 O2’-Tl2-O2’

50.83(9) 108.42(15) 110.39(20)

51.03(10) 101.46(20) 102.41(22)

Cl12-Zr1-Cl12 109.47b 0.31(4) 0.38(5) Zr1-Cl12-Zr11 180.0c O2…O2’ 0.26(6) 0.603(17) Cl12-Zr11-Cl13 180.0c O3…O3’ a The numbers in parentheses are the estimated standard deviations (esds) in the units of the least significant digit given for the corresponding value. bThe tetrahedral angle by symmetry. cZr1-Cl12-Zr11Cl13 is linear by symmetry.


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TABLE 6. Unit Cell Charge Budget atom position ionsa occ.b

M-O,c Å

r,d Å

CNe

charge x occ.

a. crystal 1 (Zr1.7Tl5.4Cl1.7-A) 1.67(4)

2.01(6)

0.69

4

6.7+ f

Tl+

2.68(2)

2.709(16)

1.39

3

2.7+

+

2.76(3)

2.745(7)

1.43

2

2.8+

-

1.67(4)

1

1.7- f

Zr11

Zr

Tl1 Tl2 Cl11

Tl

4+

Cl

Σ charges 10.5+ b. crystal 2 (Zr2.1Tl1.6Cl3.0-A) Zr

2+

0.28(1)

Zr11

Zr

4+

0.72(2)

1.825(23)

Zr12

Zr4+

Zr1

4

0.6+

0.50

4

2.9+ f

1.12(2)

1.767(16)

0.45

5

4.5+

+

1.58(4)

3.031(12)

1.71

3

1.6+

Cl11

-

Cl

0.72(2)

1

0.7- f

Cl12

Cl-

1.12(2)

2

1.1-

Cl13

-

1.12(2)

1

1.1-

Tl2

Tl

Cl

Σ charges 6.7+ c. the

Zr5Cl810+

cluster in crystal 2

Zr1, Cl12, Zr5Cl810+ Σ charges 10+ Zr12, Cl13 a Extraframework ions. bOccupancy, ions per unit cell. cShortest M-O (metal ion to framework oxygen) bond lengths. dRadii of M ions obtained by subtracting 1.32 Å (the conventional radius of the oxide ion, ref. 29) from the shortest M-O bond lengths. eCoordination numbers. f The occupancies of Zr11 and Cl11 were constrained to be equal.



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TABLE 7. Light Yield Comparison sample

sample mass (mg)

density (g/cm3)

emission peak (nm)

ZrCl4b Tl-Ac

3.2 3.4

2.80 3.55

-

2.3 2.68 493 Zr,Tl,Cl-Ac d anthracene 2.9 1.28 447 a b c Integrated light yield. ZrCl4, Aldrich, 99.99%. Powder samples. commercially available scintillator whose light yield is well documented.


light yielda (anthracene = 100) -

516 100 d C14H10, Sigma, ≥99.0%, a

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(figure captions)

Figure 1. EDX spectrum (counts vs. photon energy in keV) of hydrated Zr2.1Tl1.6Cl3.0-A (crystal 2).

Figure 2. The 6-rings that are occupied by a Zr4+ ion are shown in red for each crystal. Superimposed upon them in blue for the purpose of comparison are the 6-rings that do not contain Zr4+. As can be seen, Zr4+ markedly distorts the 6-rings that it occupies. These drawings are only approximate because only a single T position was refined in each structure. It is a weighted average position for the Si and Al atoms in both rings.

Figure 3. A stereoview of a sodalite cavity with Zr4+ (Zr11), Tl+ (Tl1), and Cl- (Cl11) ions on 3fold axes of Zr1.7Tl5.4Cl1.7-A (crystal 1). The zeolite A framework is drawn with open bonds; solid bonds are used to show the coordination about the Zr4+ and Tl+ ions. Ellipsoids of 35% probability are shown.

Figure 4. A stereoview of the large cavity showing all extraframework Zr4+, Tl+, and Cl- ions of Zr1.7Tl5.4Cl1.7-A (crystal 1). See the caption to Figure 3 for other details.

Figure 5. A stereoview of a sodalite cavity with Zr4+ (Zr11) and Cl- (Cl11) ions on 3-fold axes of Zr2.1Tl1.6Cl3.0-A (crystal 2). See the caption to Figure 3 for other details.

Figure 6. A stereoview of the large cavity of Zr2.1Tl1.6Cl3.0-A (crystal 2). See the caption to Figure 3 for other details.



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Figure 7. A stereoview of the Zr5Cl810+ cluster in a sodalite cavity and extending into four adjacent large cavities (crystal 2). This cluster is held in place and stabilized by 12 bonds (thin solid lines) between its four Zr4+ ions (Zr12) and O3’ atoms of the zeolite framework.

Figure 8. CCD images of Zr,Tl,Cl-A crystals before being exposed to X-rays (a & c) and while being irradiated (b & d) with synchrotron X-rays (13.8 keV, 350 mA, 293 K).

Figure 9. (a) Emission spectra of Tl-A, ZrCl4(s), anthracene, and Zr,Tl,Cl-A powder upon irradiation with X-rays (Cu Kα at 100 kV, 2 mA). (b) Light yield comparison for Tl-A, ZrCl4(s), anthracene, and Zr,Tl,Cl-A powder upon irradiation with X-rays (Cu Kα at 100 kV, 2 mA) at 293 K. Arbitrary units are used for the intensities.

Figure 10. (a) Excitation (red line) and emission (blue line) spectra of Zr,Tl,Cl-A powder. (b) The luminescence decay time of Zr,Tl,Cl-A powder monitored at 266 nm (UV laser). The decay curve was fitted by two exponential functions, y = A1exp(-t/τ1) + A2exp(-t/τ2) + y0 (R2 = 0.99963). Arbitrary units are used for the intensities.

Figure 11. CCD images of Zr,Tl,Cl-A powder (a) before and (b) upon being irradiated with synchrotron X-rays (17.7 keV, 350 mA, 293 K). (c) Radioluminescence intensities (arbitrary units) of Zr,Tl,Cl-A powder with different tube currents and voltages at 293 K.


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Figure 1. Kim, Park, Kim, Heo, and Seff



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Note to editor: This stereoview is the correct width, ca. 4 1/4 inches black to black, for clearest viewing. This width is dictated by the average distance between adult human eyes. If it is enlarged it will not be viewable in stereo. If necessary to save journal space, it may be reduced to as little as one full column width, ca. 3 1/8 inches black to black.



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TOC Art


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Exchange of a Tetrapositive Cation into a Zeolite and a New Inorganic

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