Solid State Sciences 8 (2006) 337–341 www.elsevier.com/locate/ssscie A new addition to the Phillipsite family of molecular sieves: A divalent metal-ion-framework substituted microporous aluminophosphate (DAF-8) Philip A. Barrett a , Gopinathan Sankar a,∗ , Richard Stephenson a , C. Richard A. Catlow a , John Meurig Thomas a , Richard H. Jones b , Simon J. Teat c a The Davy Faraday Research Laboratory, 21, Albemarle Street, London W1S 4BS, UK b School of Chemistry and Physics, University of Keele, Keele, Staffordshire, ST5 5BG, UK c CCLRC Daresbury Laboratory, Daresbury, Warrington, Cheshire WA4 4AD, UK Available online 2 March 2006 Abstract By adding substantial amounts of either Co(II) or Zn(II) salts to a gel composed of Al 2 O 3 ,P 2 O 5 and the organic template 1,4-diamino- cyclohexane, the tendency to yield layered aluminophosphates (AlPOs) is tilted in favour of the production of three-dimensional microporous MAlPOs: in particular, phase-pure samples of a novel Phillipsite structure (designated Davy–Faraday number 8, DAF-8) are formed.  2006 Elsevier SAS. All rights reserved. 1. Introduction The growing importance [1–5] of framework-substituted metal-ion (M) variants of microporous aluminophosphates (MAlPOs), especially in the context of catalysis [3–5], has prompted us to prepare new molecular sieve solids possess- ing small to medium size apertures. Such solids may func- tion as shape-selective catalysts (if stable upon removal of the structure-directing organic templates) both in acid-catalysed dehydrations, alkoxylations, or isomerisations [6–8] and in the aerial regio-functionalisation of alkanes [5,9–12]. When, for example, Zn 2+ ions are incorporated isomorphously in place of Al 3+ during the synthesis of the MAlPOs the solid is converted to a Bronsted acid form by simply burning away the organic template. Similarly, Co 2+ may be elevated to Co 3+ state by calcination in air after driving away the structure-directing or- ganic template, thereby producing powerful selective oxidation catalysts for a variety of alkanes, linear or cyclic. The eight- membered rings which constitute the apertures of MAlPO-18 and MAlPO-34 are especially useful in the regioselective ter- minal oxyfunctionalisation of n-alkanes [5,10,12]. Previously, we have pursued two distinct procedures in syn- thesising new, framework-substituted MAlPOs: one based on * Corresponding author. E-mail address: sankar@ri.ac.uk (G. Sankar). accumulated chemical experience in judging which organic template to use, the other relies more on a computer algorithm (such as Zebedde [13]). Whereas DAF-1, -2, -3, -4 (DAF-4 is a cobalt aluminophosphate with LEV framework, were synthe- sised by rational design of organic template molecule; indepen- dent computational work from the RI group [13] identified the same template methyl cyclohexylamine as the best structure directing agent for the production of Levyne structure) were prepared by the former approach, DAF-5 relied mainly on a computational choice of template. Here, in this work, we again use the former approach. We have long realised that small cyclic amines can effec- tively direct the formation of small-pore cage structures. For example, cyclohexylamine is used to prepare chabazite related MAlPO, SAPO or MAPSO materials [14–16]. However, it was found that, in the absence of heteroatoms (Si 4+ , Co 2+ , etc.), a layered type aluminophosphate structure is formed instead [16]. Thus it appears that the introduction of hetero-atoms, such as Co 2+ in the synthesis gel directs the formation of a three- dimensional structure. We have capitalised upon this fact and chose 1,4-diaminocyclohexane, since it has been shown that it directs the formation of a layered aluminophosphate [17]. Here we report the synthesis and structure of a new hetero-atoms (Co 2+ or Zn 2+ ) substituted (in place of Al 3+ ) microporous ma- terial which has a Phillipsite structure (PHI, IZA code [18]) as revealed by micro single crystal diffraction technique. 1293-2558/$ – see front matter  2006 Elsevier SAS. All rights reserved. doi:10.1016/j.solidstatesciences.2006.02.009