Microporous cobalto- and zincophosphates with the framework-type of cancrinite

Bieniok, Anna; Brendel, Uwe; Paulus, E. F.; Amthauer, Georg

doi:10.1127/0935-1221/2005/0017-0813

Cited by 10 publications

(9 citation statements)

References 8 publications

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“…K + , Cs + , Rb + ) is still poor, as well as their behavior under T or P. This configuration is shown only by tiptopite (which contains K + ) among the mineralogical species, but the synthesis of several Cs-cancrinites has successfully been reported (e.g. Colella and de' Gennaro 1989;Norby et al 1991;Lee et al 2000;Fechtelkord et al 2001;Bieniok et al 2005;Gatta and Lee 2008), whose thermal (and compressional) stability is still unknown. The confinement of Cs + (or Rb + ) cations inside the can units, with their small effective pore widths (sensu Baerlocher et al 2007), suggests the potential application of cancrinite-group minerals as nuclear waste storage materials, as recently reported for other classes of microporous materials (e.g.…”

Section: Discussionmentioning

confidence: 99%

Cancrinite-group minerals: Crystal-chemical description and properties under non-ambient conditions—A review

Gatta¹,

Lotti

2016

American Mineralogist

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This is a review of the thermal and compressional behavior of cancrinite-group minerals with a description of the mechanisms, at the atomic scale, that govern their (P,T)-induced structure evolution. The open-framework structure of this group of feldspathoids is characterized by the [CAN] topology, which contains large parallel channels (confined by 12-membered rings of tetrahedra), surrounded by columns of cages. At least two structural "subgroups" can be identified according to the nature of the constituents filling the cages, irrespective of the channel population.The minerals of the "cancrinite subgroup" show [NaH 2 O] + clusters into the cages and those of the "davyne subgroup" contains [CaCl] + clusters. Beside a similar bulk compressibility and expansivity at room conditions for all the minerals of the group, a different elastic anisotropy, coupled with different deformation mechanisms of the tetrahedral framework, were found to be mainly controlled by the nature of the population filling the cages. The role played by the channel populations appear being secondary. These experimental findings allow us to provide a model of the structure evolution in response to the different cage content, i.e. NaH 2 O + and CaCl + .The high-temperature studies of the hydrous members of the cancrinite subgroup reveal a slow dehydration process, often irreversible at the time-scale of the experiments and leading to quasi-anhydrous high-temperature forms which keep their crystallinity even up to 800-900 K (at room P). The experiments at high pressure on the cancrinite-group minerals show a high-P stability, at least up to 7-8 GPa (at room-T), which is quite surprising if we consider their microporous nature. The P-induced stability is the effect of a pronounced structural flexibility, which in turn is based mainly on tilting of rigid tetrahedra around O atoms that behave as hinges. The character and the mechanisms that govern the (P,T)-induced P6 3 -to-P6 3 /m phase transition in the compounds of davyne subgroup are also discussed.

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Section: Discussionmentioning

confidence: 99%

Cancrinite-group minerals: Crystal-chemical description and properties under non-ambient conditions—A review

Gatta¹,

Lotti

2016

American Mineralogist

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“…Finally, three 4-MR ladder-like chains form a hexagonal column (Figure c). The basic building unit of the hexagonal column is the [4 6 6 2 6] cage of two 6-MRs at the top and bottom and six 4-MRs and three 6-MRs on the sides, that is, a so-called ε -cage (Figure d) . The ε -cage columns are interconnected, forming 12-membered ring (12-MR) channels with a diameter of 8.46 Å parallel to the c axis.…”

Section: Resultsmentioning

confidence: 99%

“…The thermal behavior of CLNZP is quite different from the compound containing OH – groups and H 2 O molecules, such as Cs-Na cancrinite {Na 6 (OH) 2 (H 2 O) 2 }Cs 2 [ZnPO 4 ] 6 with the same CAN-type open framework structure. It lost more than 9 wt % after calcination in the same temperature range because of the condensation of OH – groups and H 2 O molecules located in the 12-MR channels …”

Section: Resultsmentioning

confidence: 99%

“…Based on the above criteria, {Na 6 (OH) 2 (H 2 O) 2 }Cs 2 [ZnPO 4 ] 6 with the CAN-type three-dimensional anionic framework crystallizing in a polar space group P 6 3 is chosen as the prototype to design new DUV NLO crystals with a bulk-crystal habit (Figure ). However, it is obvious that the existence of OH – and H 2 O groups in the 12-MR channels of the prototype has low thermal stability, which will affect the refractive index, transmittance, and SHG intensity of the materials.…”

Section: Resultsmentioning

confidence: 99%

“…To stabilize the non-centrosymmetric 3D framework, Li + cations are involved in the crystal structure as substitutions, which also can enhance SHG effects and transmittance at the DUV region. As a result, two new anhydrous zincophosphates with cancrinite (CAN)-type framework structures, namely, {(Li 6– x Na x O) A 2 }[(ZnPO 4 ) 6 ] ( A = Cs, Rb; x = 2–3) (designated as CLNZP for the cesium compound and RLNZP for the rubidium compound), were rationally designed by applying CAN-type zincophosphate {Na 6 (OH) 2 (H 2 O) 2 }Cs 2 [ZnPO 4 ] 6 as the prototype . Their crystal structure features the NCS CAN-type framework acting as the robust host and the heavy alkali metal cations and (Li 6– x Na x O) 4+ groups filling the ε -cage channels and 12-membered ring (12-MR) channels acting as the guest species to improve the SHG effect of compounds.…”

Section: Introductionmentioning

confidence: 99%

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Strategy for a Rational Design of Deep-Ultraviolet Nonlinear Optical Materials from Zeolites

Liu,

Tang,

Zhang

et al. 2023

Inorg. Chem.

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Deep-ultraviolet (DUV) nonlinear optical (NLO) materials play a crucial role in cutting-edge laser technology. In order to solve the serious layered growth tendency of the sole commercial DUV NLO crystal KBe 2 BO 3 F 2 (KBBF), developing alternative systems of compounds with bulk crystal habits has become an urgent task for practical applications. Herein, a novel strategy was developed by applying non-centrosymmetric (NCS) cancrinite (CAN)-type zincophosphates {Na 6 (OH) 2 (H 2 O) 2 }Cs 2 [ZnPO 4 ] 6 with bulk-crystal habits as the prototype to design new DUV NLO crystals. Two new anhydrous alkali zincophosphates, namely, {(Li 6 −x Na x O)A 2 }[(ZnPO 4 ) 6 ] (A = Cs, Rb; x = 2−3) crystallizing in the NCS hexagonal space group P6 3 (no. 173) with a CAN-type framework, were successfully synthesized via a modified fluoro-solvo-hydrothermal method by applying triethylamine (TEA) and concentrated NaF solution as a co-solvent. Interestingly, the rigidity of the NCS CAN-type framework acting as the host ensures the non-centrosymmetry of the resulting new compounds. Meanwhile, the replacement of water molecules by guest cationic species in the channels or cages can greatly improve the thermal stability of the resultant crystal and tune its NLO properties. The synergetic effect of the host framework and the guest species makes the two compounds transparent down to the DUV region (<200 nm) and exhibit SHG effects. Therefore, the proposed rational design strategy of applying the known zeotype NCS frameworks as prototypes together with the modified fluoro-solvo-hydrothermal method opens a great avenue for highly effectively exploring new DUV NLO materials.

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Crystal structure and chemical composition of compounds with CAN type zeolite frameworks

Baur¹,

Fischer

2017

Microporous and Other Framework Materials With Zeolite-Type Structures

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Microporous cobalto- and zincophosphates with the framework-type of cancrinite

Cited by 10 publications

References 8 publications

Cancrinite-group minerals: Crystal-chemical description and properties under non-ambient conditions—A review

Cancrinite-group minerals: Crystal-chemical description and properties under non-ambient conditions—A review

Strategy for a Rational Design of Deep-Ultraviolet Nonlinear Optical Materials from Zeolites

Crystal structure and chemical composition of compounds with CAN type zeolite frameworks

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