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Data for A gel aging effect in the synthesis of open-framework gallium phosphates : structure solution and solid-state NMR of a large-pore, open-framework material
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Broom, Lucy K., Clarkson, Guy J., Guillou, Nathalie, Hooper, Joseph, Dawson, Daniel, Tang, Chiu, Ashbrook, Sharon Elizabeth and Walton, Richard I. (2017) Data for A gel aging effect in the synthesis of open-framework gallium phosphates : structure solution and solid-state NMR of a large-pore, open-framework material. [Dataset]
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Raw Data for A Gel Aging Effect in the Synthesis of Open-Framework Gallium Phosphates.ZIP - Published Version Download (46Mb) |
Abstract
The templated zeolite-analogue GaPO-34 (CHA structure type) crystallises from a gel precursor Ga2O3:2H3PO4:1HF:1.7SDA:70H2O (where SDA = structure directing agent), treated hydrothermally for 24 hours at 170 °C using either pyridine or 1-methylimizadole as SDA and one of either poorly crystalline ε-Ga2O3 or γ-Ga2O3 as gallium precursor. If the same gels are stirred for periods shorter than 2 hours but treated under identical hydrothermal conditions, then a second phase crystallises, free of GaPO-34. If β-Ga2O3 is used as a reagent only the second phase is found to crystallise, irrespective of gel aging time. The competing phase, which we denote GaPO-34A, has been structurally characterised using synchrotron powder X-ray diffraction for the pyridine material, GaPO-34A(pyr), and using single-crystal X-ray diffraction for the 1-methylimiazole material, GaPO-34A(mim). The structure of GaPO-34A(pyr), P1 @#x0305;, a = 10.22682(6) Å, b = 12.09585(7) Å, c = 13.86713(8) Å, α = 104.6531(4) °, β = 100.8111(6) °, γ = 102.5228(6) °, contains 7 unique gallium sites and 6 phosphorus sites, with empirical formula [Ga7P6O24(OH)2F3(H2O)2].2(C5NH6). GaPO-34A(mim) is isostructural but is modelled as a half volume unit cell, P1 @#x0305;, a = 5.0991(2) Å, b = 12.0631(6) Å, c = 13.8405(9) Å, α = 104.626(5) °, β = 100.346(5) °, γ = 101.936(4) °, with a gallium and a bridging fluoride partially occupied and two partially occupied SDA sites. Solid-state 31P and 71Ga NMR spectroscopy confirms the structural complexity of GaPO-34A with signals resulting from overlapping lineshapes from multiple Ga and P sites, while 1H and 13C solid-state NMR spectra confirm the presence of the protonated SDA and provide evidence for disorder in the SDA. The protonated SDA is located in 14-ring one-dimensional channels with hydrogen bonding deduced from the SDA nitrogens to framework oxygen distances. Upon thermal treatment to investigate SDA removal, structure collapse occurs, which may be due the large number of bridging hydroxides and fluorides in the as-made material, and the unequal amounts of gallium and phosphorus present.
| Item Type: | Dataset | ||||||||||||||||||||||||||||||
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| Subjects: | Q Science > QD Chemistry | ||||||||||||||||||||||||||||||
| Divisions: | Faculty of Science > Chemistry | ||||||||||||||||||||||||||||||
| Type of Data: | crystal structure, single crystal X-ray diffraction, NMR spectroscopy, NMR spectra, High resolution powder XRD, IR, NMR, Powder XRD, TGA-DSC-MS, Thermodiffraction, 31P, 71Ga, 1H, 13C | ||||||||||||||||||||||||||||||
| Library of Congress Subject Headings (LCSH): | Gallium -- Synthesis, Phosphates | ||||||||||||||||||||||||||||||
| Publisher: | University of Warwick, Department of Chemistry | ||||||||||||||||||||||||||||||
| Official Date: | 21 November 2017 | ||||||||||||||||||||||||||||||
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| Date of first compliant deposit: | 22 November 2017 | ||||||||||||||||||||||||||||||
| Status: | Not Peer Reviewed | ||||||||||||||||||||||||||||||
| Publication Status: | Published | ||||||||||||||||||||||||||||||
| Media of Output: | .zip; .dat; .xy; .prn; .png; .txt | ||||||||||||||||||||||||||||||
| Access rights to Published version: | Open Access | ||||||||||||||||||||||||||||||
| Description: | High resolution powder XRD Figure 2, IR Figure S3, NMR Figures 6,7 S4, Powder XRD Figure 1, Powder XRD Figure S1, Powder XRD Figure S5, TGA-DSC-MS Figure 8, Thermodiffraction Figure 9 |
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