A molecular sieve, i. e. a material which is porous at the molecular level, has a three dimensional open framework providing cages or pores or, alternatively, gaps between adjacent layers. Depending upon the pore size or the interlayer spacing, molecular sieves are categorised into three groups: (1) microporous materials having a pore size or interlayer spacing of less than 20A (2 x 10-9m); (2) mesoporous materials having a pore size or interlayer spacing of from 20A to 50A (2 x 10~9m to 5 x 10~9m); and (3) macroporous materials having a pore size or interlayer spacing of greater than 50A (5 x 10~9m);. For convenience, however, molecular sieve materials are sometimes referred to as"microporous"even though they may have a pore size or interlayer spacing of more than 20A (2 x 10-9m);. Thus, the term"microporous"should not in all contexts be interpreted as being restricted to materials having a pore size or interlayer spacing of less than 20A (2 x 10-9m).

Intense interest, both academic and industrial, in the synthesis of new open framework materials (e. g. microporous materials) has stemmed from their great utility as catalysts, sorbents, ion-exchange reagents and as host materials for inclusion complexes (P B Venuto Microporous Mater. 1994,2,297). This has stimulated the search for new materials with novel layered and open-framework structures. Following the synthesis of microporous aluminophosphates in 1982, much interest has focused on the synthesis of other microporous metal phosphates. Research into the synthesis of metal phosphates has been driven by three main potential advantages that they have over aluminosilicate zeolites. Firstly, the ability of main group and transition metals to exist in five, six, seven or higher co-ordination environments, as opposed to zeolites and aluminophosphates which only contain tetrahedrally co-ordinated units, allows the synthesis of new more complex framework architectures. Secondly, the sheer number of different possible elements that may be incorporated into a phosphate framework means the potential for the synthesis of new materials is huge. Finally, the incorporation of transition metals capable

of existing in a variety of different oxidation states within an open-framework structure offers the possibility of combining the shape-selectivity of zeolites with the catalytic, magnetic and photo-chemical properties associated with d-block elements. These potential advantages have led many groups to study the synthesis of these materials over recent years, and a vast number of different metals have been incorporated into microporous phosphate frameworks, including Be, Ga, In, Mo, V, Zn, Co, Cr, Mn and Fe.

Many of these materials have unusual structures and properties.

Molecular sieve materials are generally synthesised under hydrothermal conditions in the presence of organic molecules which act as templates in the crystal growth process (see R M Barrer,"Hydrothermal Chemistry of Zeolites", Academic Press, 1982).

Actinide-containing molecular sieves are described in an International patent application No. WO 98/50307 entitled"Actinide-Containing Molecular Sieves"in the name of British Nuclear Fuels plc et al. The content of International application No. WO 98/50307 is intended to be included in this application. However, WO 98/50307 has the same filing date as the priority date for the present application. The molecular sieves described in WO 98/50307 contain an actinide in combination with atoms selected from the group consisting of oxygen, fluorine, phosphorus, transition metals and mixtures thereof. The actinide is preferably uranium. The molecular sieve material may contain a template species, which suitably comprises an organic template molecule and/or a cationic metal species; it may also contain water. Additionally, it may contain a dopant, usually in a minor amount; suitable dopants include transition metals to modify the catalytic properties of the materials. Preferred molecular sieves comprise layered structures in which layers containing actinide in combination with atoms selected from the group consisting of oxygen, fluorine, phosphorus, transition metals and mixtures thereof have organic templates and/or cationic metal species located between them. In one class of materials, the layers consist essentially of an actinide species and an oxoanion (preferably a phosphate, notably orthophosphate, or a transition metal oxoanion); in this class, the actinide may usually be represented as an oxo ion, especially an oxocation. In another class of materials, the layers consist essentially of actinide and fluorine.

Many of the actinide-containing molecular sieves, therefore, have an actinide/phosphorus/ oxygen framework, which may additionally contain fluorine and/or a dopant. Others of the molecular sieves have an actinide/fluorine framework and yet others have an actinide/non-actinide metal/oxygen framework.

A suitable strategy for making actinide-containing molecular sieves, especially for making the phosphorus-containing materials, is to adapt the techniques used previously to synthesise microporous metal phosphates, and make use of the same types of templating agents that have proved so successful in the synthesis of zeolites and other types of molecular sieve materials. In preferred embodiments, the synthesis mixture consists of four components: an actinide source, a phosphorus source, water and an organic template.

The concept of a template as a species which acts as a structure directing agent during the crystallisation of molecular sieves is not completely understood, but their use is very familiar in the synthesis of open framework materials. Generally, the actinide source, phosphorus source and water are mixed, the templating reagent added and then the resulting mixture is heated under autogenous hydrothermal conditions at temperatures of at least 100°C (and often of >150°C) to 175°C or sometimes more, for a prolonged duration typically of less than 24 hours to several days.

The synthetic technique may use fluoride as a mineralising agent. The use of fluoride as a mineralising agent in hydrothermal syntheses was originally pioneered by Flanigen and Patton as a new method of synthesising zeolites (E. M. Flanigen, R. L. Patton U. S., 1978).

The technique was then further developed by Guth and Kessler (J. L. Guth, H. Kessler, R.

Wey; Stud. Surf. Sci. Catal. J. L. Guth, H. Kessler, J. M. Higel, J. M.

Lamblin, J. Patarin, A. Sieve, J. M. Chezcau, R. Wey; ACS Symp. Ser. 1989,398,17). Replacement of OH-ions by F-ions allows the crystallisation of zeolites to be performed in neutral or acidic conditions which, in turn, allows the synthesis of heteroatom (e. g. B, Al, Fe, Ga, Ti) substituted high silica zeolites. These cannot be synthesised under high pH conditions because many transition metal ions are not stable under such conditions.

Of most importance to the present invention, however, is the application of the fluorine method to the synthesis of microporous metal phosphates, since the use of fluorine appears to aid the crystallisation of metal phosphates.

Hydrothermal synthesis using fluorine and phosphate may also be used to synthesise the actinide/fluorine frameworks. Such procedures suitably use U308, H3P04, HF and a template as the starting materials.

According to the present invention we provide a method of synthesising a di-peroxy species comprising oxidising a carbonyl moiety in the presence of a molecular sieve.

The present invention provides a method for synthesising di-peroxy compounds, that is, compounds containing a functional group of the formula I; The"zig-zag"lines indicate that the di-peroxy group is not restricted as to the moieties bonded to it.

Usually, however, the starting compound is an aldehyde, e. g. an alkanal or a ketone, e. g. an alkanone. The alkyl moieties joined to the carbonyl groups of such compounds may contain, for example, up to 6 carbon atoms but more often 1,2,3 or 4 carbon atoms.

Thus a preferred di-peroxy compound is of the formula II;

Where R', R2, R3 and R4, which may be the same or different, are each hydrogen or alkyl Cl to 6.

In a preferred embodiment only one of R'and R2 and only one of R3 and R4 are hydrogen, the remainder being alkyl Cl to 6.

The starting compound may be an aldehyde and preferred aldehydes are alkyl Cl to 6 aldehydes such as propionaldehyde. A preferred ketone is acetone.

Thus, the most preferred di-peroxy compound is of formula III; The method usually uses a peroxide as an oxidant. Any conventionally known peroxides may be used or, alternatively ozone may be used as an oxidant. If preferred peroxide is hydrogen peroxide.

More specifically, the method of the invention comprises reacting a carbonyl species with an oxidant in the presence of a molecular sieve.

The molecular sieve usually contains a transition metal e. g. Mo or W, an actinide or both when an actinide is present, it is preferably U. Additionally or alternatively, it may contain other metals, for example Ga. Some contain Al. The metal is most likely to be present in an oxidised state. When an actinide is present, such as uranium, it is likely to be in its most highly oxidised state eg U (VI).

One class of molecular sieve contains oxoanions, notably phosphorus oxanions. A preferred phosphorus oxoanion is orthophosphate; others include P03F2-, PO3 and organophosphonates (i. e. RPO3 moieties in which R is an organic group, especially methyl or other alkyl, including for example linear, branched and cyclic alkyl structures).

Oxoanions may be protonated in whole or in part, or unprotonated; the location of protons is however difficult to determine. Molecular sieves containing mixed phosphorus oxoanions of empirical formula P2 °5 are preferred.

The molecular sieves may contain transition metal oxoanions (e. g. molybdate or tungstate) as well as cationic metal species (especially Ut22+) and, optionally, phosphorus oxoanions.

The molecular sieves may be doped with transition metals or other dopants.

Certain of the molecular sieves contain fluorine, optionally together with phosphorus or other oxoanions. Actinide/fluorine molecular sieves are one preferred class.

Particularly preferred molecular sieves have actinide/P/O frameworks, where U (especially U (VI)) is the preferred actinide. Phosphorus: actinide ratios of from 1: 1 to 4: 1 are preferred, especially ratios in the order of 2: 1 (e. g. from 1.5: 1 to 2.5: 1, particularly about 1.7: 1 to about 2.3: 1). An exemplary material having a P: O ratio of about 1.7: 1 has a synthesis gel composition containing 1 P205 : 1. 2 UO2 (NO3) 3. The frameworks are normally layered structures.

The molecular sieves are usually mesoporous. They typically contain organic templates, especially primary, secondary or tertiary amines or quaternary ammonium ions in cages,

pores or interlayer gaps. C8-C, alkylamines, notably dodecyclamine, are preferred templates.

More generally, any molecular sieve material described in the aforementioned International Patent application may be used, notably those of Genus 1, as illustrated by Examples 1 to 4 of the International application.

Genus 1 defines materials containing actinide atoms together with phosphorus atoms or atoms of a first or second row transition metal.

The preferred actinide is uranium.

Examples of first or second row transition metals whose atoms may form part of the molecular sieve are chromium, vanadium, molybdenum and rhodium.

Preferably the molecular sieve includes atoms of phosphorus and it is preferred that the ratio of phosphorus to uranium atoms in the molecular sieve is in the range 0.1 to 10.

The molecular sieve may be made by any suitable method, for example by a method which comprises reacting together an actinide-containing reactant and a reactant containing phosphorus atoms or atoms of a first or second row transition metal, the reaction being conducted in the presence of a structure directing and/or pH modifying material referred to as a template.

Preferably the template is an organic compound. It is normally present in the reaction mixture in an amount up to 50% by weight, preferably from 2% to 20% by weight.

Preferred templates are primary, secondary or tertiary amines, alcohols and crown ethers.

As mentioned above, the molecular sieves are useful as catalysts, for instance, oxidation, epoxidation or hydroxylation catalysts. For example, a molecular sieve of the present invention is of use as a catalyst in the oxidation of toluene to the corresponding carboxylic acid.

In the case of the preparation of a molecular sieve which includes both uranium atoms and phosphorus atoms, the reactant may be any suitable uranium-containing material and any suitable phosphorus-containing material. The following table gives examples of reactants and the"normal"products of their reaction. However, it should be appreciated that, in the presence of the template molecules, molecular sieve materials are formed which may be related to the normal reaction products but are likely to include groups provided by the template molecules.

Preparation of Uranium-Phosphate Compounds "Normal"product Method of Preparation Hydrophosphites U (H, P02) 4 Precipitation of U (S04) 2 solution with H3P02<BR> <BR> UO2 (H2PO2) 2 Precipitation of UO22+ solution with HaH2PO2 Phosphites U (HP03) 2 Precipitation of U(SO4) 2 solution with Na2HP03<BR> <BR> U02HP03 Precipitation of UO22+ solution with<BR> <BR> Na2HP03 Metaphosphates U (P03) 4 HP03 (in CO, stream) passed over U02 at red heat UO2 (PO3) 2 Evaporate HN03 solution of UO2 (H2PO2) 2 and ignite Orthophosphates U3 (PO4) 4 Precipitation of UCl4 solution with Na3PO4 U (HP04) 2 Precipitation of UCl4 solution with Na2HP04 (UO2) 3 (PO4) 2 Addition of uranyl nitrate to phosphoric acid UO, HP04 Dilution of crystals formed from the above mixture Pyrophosphates UP207 Ignition of U (HP04) 2 ofNa4P2O7solutiontoUO22+(UO2)2P2O7Addition solution

In addition to the reactants mentioned in the above table, other uranium starting materials may be used. Examples are uranium fluorides such as UF4. The use of fluoride- containing starting materials in conjunction with mineralising agents such as HF and NH4F can yield Genus 1 molecular sieves.

When the reactants are mixed together, they typically form a gel which may be aged, preferably for a period up to three hours. The resulting gel may then be subjected to reaction in a sealed container at a temperature which is preferably between 100 and 200°C.

The reaction mixture includes water and the amount of water present will affect the structure of the molecular sieve which is formed.

The reaction conditions are not critical but the oxidation reaction is suitably performed under reflux. An aqueous reaction medium is typically used.

The diperoxy species may exist in one or more isomeric forms, eg where R', R2, R3 and R4 have the definitions given above.

EXAMPLE The following reaction was catalysed by a mesoporous uranium phosphate material representative of the actinide-containing molecular sieves described above. The material is a layered compound with dodecylamine intercalated between uranium phosphate layers. <BR> <BR> <P>The synthesis gel composition is: 1 P205 : 1.2UO2 (NOs) 3 lCI2H2sNH2: 80 H2O. The uranyl nitrate is made by dissolving UO2 in concentrated nitric acid; and the phosphorus source is phosphoric acid (85% in water).

The method for preparing the material involves adding the uranyl nitrate to the phosphoric acid and water, followed by stirring this into the dodecylamine. Age for 1 hour then put the gel into an autoclave 2/3 full heat at 100 °C for 24 hours. Quench, wash and filter to give a yellow solid. The procedure follows those of Examples 1 to 4 in WO 98/50307.

The reaction conditions are as follows: 0.1g of catalyst is added to Iml of organic substrate. 10 ml of hydrogen peroxide (30% aqueous solution) is added at the start and the mixture is refluxed for 4 hours. The product was analysed by GCMS and NMR.

Acetone reacted with the catalyst to form di-acetone peroxy species (yield 100%). This molecule is very unusual and has potential uses as a selective oxidant for fine chemicals manufacture. The reaction is shown below.