The speciation and structure of Cu ions and complexes in chabazite (SSZ-13) zeolites, which are relevant catalysts for nitrogen oxide reduction and partial methane oxidation, depend on material composition and reaction environment. Ultraviolet-visible (UV-Vis) spectra of Cu-SSZ-13 zeolites synthesized to contain specific Cu site motifs, together with ab initio molecular dynamics and time-dependent density functional theory calculations, were used to test the ability to relate specific spectroscopic signatures to specific site motifs. Geometrically distinct arrangements of two framework Al atoms in six-membered rings are found to exchange Cu 2+ ions that become spectroscopically indistinguishable after accounting for the finite-temperature fluctuations of the Cu coordination environment. Nominally homogeneous single Al exchange sites are found to exchange a heterogeneous mixture of [CuOH] + monomers, O- and OH-bridged Cu dimers, and larger polynuclear complexes. The UV-Vis spectra of the latter are sensitive to framework Al proximity, to precise ligand environment, and to finite-temperature structural fluctuations, precluding the precise assignment of spectroscopic features to specific Cu structures. In all Cu-SSZ-13 samples, these dimers and larger complexes are reduced by CO to Cu + sites at 523 K, leaving behind isolated [CuOH] + sites with a characteristic spectroscopic identity. The various mononuclear and polynuclear Cu 2+ species are distinguishable by their different responses to reducing environments, with implications for their relevance to catalytic redox reactions.
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Zeolite Adsorption of Chloride from a Synthetic Alkali-Activated Cement Pore Solution
This work presents experimental evidence that confirms the potential for two specific zeolites, namely chabazite and faujasite (with a cage size ~2–13 Å), to adsorb small amounts of chloride from a synthetic alkali-activated cement (AAC) pore solution. Four synthetic zeolites were first exposed to a chlorinated AAC pore solution, two faujasite zeolites (i.e., FAU, X-13), chabazite (i.e., SSZ-13), and sodium-stabilized mordenite (i.e., Na-Mordenite). The mineralogy and chemical composition were subsequently investigated via X-ray diffraction (XRD) and both energy- and wavelength-dispersive X-ray spectroscopy (WDS), respectively. Upon exposure to a chlorinated AAC pore solution, FAU and SSZ-13 displayed changes to their diffraction patterns (i.e., peak shifting and broadening), characteristic of ion entrapment within zeolitic aluminosilicate frameworks. Elemental mapping with WDS confirmed the presence of small amounts of elemental chlorine. Results indicate that the chloride-bearing capacity of zeolites is likely dependent on both microstructural features (e.g., cage sizes) and chemical composition.
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- Award ID(s):
- 1604457
- PAR ID:
- 10100958
- Date Published:
- Journal Name:
- Materials
- Volume:
- 12
- Issue:
- 12
- ISSN:
- 1996-1944
- Page Range / eLocation ID:
- 2019
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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