Patent Description:
Pollutants with a potential hazard for the environment and humans enter the aquatic environment through different channels. Examples of such pollutants are organic compounds, dyes and pharmaceutically active ingredients.

Process water from textile finishing, chemical, petrochemical and pharmaceutical production as well as wastewaters from hospitals or the like may contain contaminants which are not available for biological water treatment. These contaminants require a pre-treatment prior to the introduction to a biological water treatment.

Advanced oxidation methods such as the combined use of UV radiation and oxidizing agents (such as e.g. hydrogen peroxide) have been used in such cases. UV treatment is also used in the treatment of wastewaters in textile finishing processes or for the treatment of washing liquors in exhaust gas washers.

All the known methods are based on using radiation from high energy radiation sources outside the visible spectrum of sunlight, i.e. UV-light below <NUM> and use preferably UV-active photoctalytic materials based on titanium dioxide due to the ready availabilty and low costs of titanium dioxide. However, the efficiency of titanium dioxide is not satisfactory in a number of cases.

<NPL>) describe the polyoxometalate (POM) photocatalysis for decontaminating the aquatic environment. It is outlined that POMs, upon excitation with near-visible or UV-light , become powerful oxidizing reagents which are capable of destroying a great variety of organic pollutants in aqueous systems. Photolysis of POMs with visible and near UV light results in the formation of an excited state acting as a strong oxidant that oxidizes and in many cases, mineralizes (i.e. decompose to carbon dioxide and water) organic substrates including organic pollutants. Keplerate type POMs are not envisaged.

A polyoxometalate (abbreviated POM) is a polyatomic ion, usually an anion, that consists of three or more transition metal oxyanions linked together by shared oxygen atoms to form closed <NUM>-dimensional frameworks. The metal atoms are usually group <NUM> (Mo, W) or less commonly group <NUM> (V, Nb, Ta) transition metals in their high oxidation states.

Polyoxomolybdates, i.e. polyoxometalates based on Mo as transition metal have been described in great variety in the literature. The most common unit for polymolybdates is the octahedral {MoO<NUM>} unit, often distorted by the Mo atom being off-centre to give one shorter Mo-O bond. Some polymolybdates contain pentagonal bipyramidal units.

Polyoxomolybdates containing a pentagonal {(Mo)Mo<NUM>} building block, comprising a central pentagonal bipyramidal {MoO<NUM>} group with six surrounding {MoO<NUM>} octahedra is one such example described in the literature.

The highly symmetric [(pent)<NUM>(link)<NUM>] type spherical clusters, such as the {Mo<NUM>} type nanospheres, are comprised of <NUM> pentagonal {(Mo)Mo<NUM>} groups (pent) connected by <NUM> {Mo<NUM>} groups acting as linkers (link).

The number twelve, an emblem of icosahedral symmetry, is significant in the context of two Platonic solids: the icosahedron and dodecahedron, the latter having <NUM> faces, the former having <NUM> vertices.

The linker in these systems (the Mo group) may be replaced by other metal atoms such as Fe, Cr or V, leading to POMs commonly designated by the formulae Mo<NUM>Fe<NUM>, Mo<NUM>Cr<NUM> and Mo<NUM>V<NUM> and commonly referred to as Keplerate molecules.

Keplerates are a class of high-symmetry molecules. Some of the metals lie on the vertices of a Platonic solid (e.g. cube, octahedron, tetrahedron, icosahedron ) and the others on the vertices of an Archimedian solid (e.g. a cuboctahedron).

Keplerate type polyoxymolybdates Mo<NUM>Fe<NUM> have first been synthesized and described by Prof. Müller and his group at the University of Bielefeld around <NUM> and a number of reviews authored or co-authored by Prof. Müller relating to polyoxomolybdates have been published (e.g. <NPL>) or <NPL>). The use of Keplerate type POMs for decontaminating the aquatic environment has not been described or suggested in reported reviews.

<NPL>) discloses the degradation of Rhodamine B with a polyoxomolybdate Mo<NUM>Fe<NUM> under ultraviolet radiation.

<NPL>) disclose the use of a polyoxomolybdate Mo<NUM>(Mo<NUM>)<NUM> for the degradation of Rhodamine B under ultraviolet radiation.

<CIT> also discloses the use of a polyoxomolybdate Mo<NUM>(Mo<NUM>)<NUM> for the degradation of Rhodamine B under ultraviolet radiation.

It was an object of the present invention to provide a new use of Keplerate type polyoxomolybdates for the decontamination of aquatic environments.

This object has been achieved with the use in accordance with claim <NUM> and the process in accordance with claim <NUM>.

Preferred embodiments of the present invention are described in the dependent claims and in the detailed description hereinafter.

In accordance with the present invention Keplerate type polyoxomolybdates (POMs) of the structure Mo<NUM>Fe<NUM> in combination with electromagnetic radiation are used for decontaminating aquatic environments from inorganic and organic pollutants.

The term Keplerate, when used herein is used to designate molecular structures that contain Platonic and Archimedian solids (spanned by equivalent sets of atoms) according to the principle one inside another like in Russian dolls.

Keplerate type poyloxomolybdates suitable for the use in accordance with the present invention have been described in the literature, e.g. in <NPL>), <NPL>) and <NPL>) to give only a few examples.

All the Keplerate type polyoxomolybdates for use in the present invention may be represented by the general structure pent<NUM>link<NUM> wherein pent designates a pentagonal (Mo)Mo<NUM> unit and link is Fe. The pentagonal groups are linked by the linkers.

The core structure of the POMs used in accordance with the present invention comprising Fe is an icosidodecahedron. The magnetic ions Fe occupy the vertices of said icosidodecahedron. An icosidodecahedron comprises <NUM> pentagons (formed by the Mo(Mo<NUM>) units and <NUM> triangles (formed by the linker atoms Fe).

The POMs used in accordance with the present invention, formed by <NUM> pentagonal Mo(Mo<NUM>) units linked by <NUM> mono- or dinuclear linkers comprise a nanoscaled capsule cavity and <NUM> size-tunable specific nanopores of the type [FenOn] (for example with n= <NUM> or <NUM>) which can act as substrate specific receptors. The cavity can even house smaller polyoxometalates to form a supramolecular nanocomposite. Since Fe is a ferromagnetic metal molecular nanoantiferromomagnets are obtained.

The nano-objects of the type Mo<NUM>Fe<NUM> can be crosslinkled in a solid state reaction to form layers by following an inorganic polycondensation reaction.

Freshly filtered crystals show a rapid water loss and the possibility to form a related one-dimensional chain (paramagnetic Keplerate necklaces) from sperical nanospheres also exists.

Inside the cavities, which can be hydrophilic or hydrophobic, different types of reactions can be performed at well defined sites.

The POMs use in accordance with the present invention thus are interesting because of their stability, size, solubility, giant cavities, nanosized changeable pores, unique surfaces, unusual electronic structures and the abundance of magnetic centres (since Fe is a ferromagnetic metal) in a variety of topologies. Most of the clusters can be manipulated whilst keeping the robust nanoscopic oxymolybdate skeleton intact. Encapsulation of the giant clusters with surfactants allows one to produce films and monolayers.

Further information on the properties of POMs used in accordance with the present invention is given in<NPL> and in <NPL>).

General information for the synthesis of Keplerate POMs can also be found in the supporting information of <NPL>).

Processes for the synthesis of the POMs used in accordance with the present invention have been described in <NPL>), <NPL>), and <NPL>).

In accordance with a preferred embodiment Fe is FeIII.

A particularly preferred polyoxomolybdate in accordance with the present invention is.

MoVI <NUM>FeIII<NUM>O<NUM>(CH<NUM>COO)<NUM>{MoVi<NUM>O<NUM>(H<NUM>O)<NUM>{H<NUM>MoVI<NUM>O<NUM>(H<NUM>O)}(H<NUM>O)<NUM>]x.

<NUM><NUM>O which has been described in <NPL>).

Other examples of Keplerate POMs not used in the present invention are Na<NUM>K<NUM>[(VO)[(MoVI)MoVI<NUM>O<NUM>(H<NUM>O)<NUM>{MoVI)MoVI<NUM>O<NUM>(H<NUM>O)<NUM>(SO<NUM>)<NUM>{VIVO(H<NUM>O)<NUM><NUM>{VIVO}<NUM>({KSO<NUM>)<NUM>)<NUM> X <NUM><NUM>O(Mo<NUM>V<NUM>) and [{Na(H<NUM>O)<NUM>}[MoVI<NUM>CrIII<NUM>O<NUM>(CH<NUM>COO)<NUM>(H<NUM>O)}]<NUM> x <NUM><NUM>O (Mo<NUM>Cr<NUM>). Information on their synthesis is given in <NPL>) to which reference is made for further details.

The polyoxomolybdates are used for the decontamination of aqueous environments from organic and inorganic pollutants.

In principle any kind of aquatic environment can be treated with the POMs in accordance with the present invention, i.e. there are no specific limitations in this regard.

It has been found advantageous in certain cases to treat aquatic environments selected from process waters of textile finishing, dye production, chemical synthesis, petrochemical synthesis or pharmaceutical synthesis or from waste water collecting systems in urban environments or hospitals in accordance with the present invention.

Process waters from textile finishing, chemical, petrochemical and pharmaceutical production may contain contaminants which cannot be removed by biological or chemical water treatment and which possess a hazard for the environment. By treating this kind of aquatic environments with POMs in accordance with the present invention, it is possible to remove the contaminants to a significant degree and thus to eliminate or at least to reduce the risk associated with such contaminants in aqueous media.

The pollutants may be inorganic or organic in nature and can be e.g. pharmaceutically active ingredients, agriculturally active ingredients, peptides or aromatic compounds, preferably pharmaceutically or agriculturally active ingredients. Another group of pollutants are dyes.

One of the advantages in accordance with the present invention is the fact that the pollutants in many cases are basically mineralized, i.e. decomposed to carbon dioxide and water. Known oxidative processes in certain cases decompose the pollutant to intermediate or decomposition products still posing a hazard. It is obvious that a decomposition of the entire carbon chain to carbon dioxide and water eliminates any potential issue with intermediate or decomposition products and thus the use in accordance with the present invention provides an important benefit over known processes in this regard.

Just by way of example, the use in accordance with the present invention may be applied to aquatic envornments containing as pollutants urea, ureic acid, phenanthrolines, peptides, bacteria, benzene, pyrene, acetonitrile, hematoporphyrins, melamine, fluorinated organic compounds such as pentafluophenol, nitrogen containing aromatic compounds such as p-nitrophenol, triethanolamine or dyes such as potassium ferrocyanate, methylene blue, crystal violet, Fe(III)phthalocyanine chloride or methylviologen.

As stated above, this list is only exemplary; there is no specific limitation as the POMs oxidize a vast majority of organic and inorganic pollutants.

In accordance with a preferred embodiment, the POMs are used in combination with an oxidizing agent.

Suitable oxidizing agents are e.g. hydrogen peroxide, oxygen, or persulfates, of which the latter are preferred. Particularly, the alkali metal and the alkaline earth metal persulfates such as sodium persulfate, potassium persulfate or calcium persulfate are preferred due to their good availability. The skilled person will select the suitable oxidzing agent based on his professional experience and on the specific intended application.

The weight ratio of the POMs to the oxidizing agent is in the range of from <NUM>:<NUM> to <NUM>:<NUM>, preferably in the range of from <NUM>:<NUM> to <NUM>:<NUM>.

The electromagnetic radiation has a wavelength exceeding <NUM>, preferably exceeding <NUM>. Particularly preferred is electromagnetic radiation in the range of from <NUM> to <NUM>, i.e. radiation in the visible range of the spectrum.

In accordance with a particularly preferred embodiment, the radiation used is sunlight in which case the term solar photocatalysis is used. This embodiment has the advantage that, compared to radiation of other wavelenghts, no energy consuming source for the radiation is necessary as the light of the sun which is abundantly available. Compared to processes where UV radiation with wavelengths of less than <NUM> is necessary and for which specific radiation sources are necessary requiring external energy supply for the generation of the radiation, the use in accordance with the present invention provides the benefit of realizing significant energy savings and the independency of any expensive energy infrastructure.

In accordance with a particularly preferred embodiment, a Keplerate type polyoxomolybdate as described hereinbefore in combination with an oxidizing agent and electromagnetic radiation with a wavelength exceeding <NUM>, preferably in the range of from <NUM> to <NUM>, is used.

A further embodiment of the present invention relates to a process for the decontamination of aquatic according to the appended claim <NUM> environments wherein a Keplerate type polyoxomolybdate of the structure Mo<NUM>M<NUM> wherein M is Fe, is supported on a solid support and the aqueous medium flows over the loaded carrier while being irradiated with the electromagnetic radiation (e.g. visible sun light) and persulfate is added to the aqueous medium. The electromagnetic radiation has a wavelength exceeding <NUM>, preferably exceeding <NUM> and up to <NUM>.

The solid support for the POMs is not subject to particular limitations and may be chosen from any suitable material which enables immobilization of the POM in a manner which allows a liquid ( the aquatic envireonment) to flow over the supported POM without destructing the structure. The skilled person will chose suitable supports based on his professional knowledge and the specific application situation.

The use in accordance with the present invention allows the decontamination of aquatic environments in an energy saving and economically viable process, in particular when using sunlight as the source of the electromagnetic radiation.

It has been found that most organic and inorganic pollutants can be removed to a degree of <NUM> % or more, preferably <NUM> % or more and most preferably of <NUM>% or more in a time period of from <NUM> to <NUM> and in particular of from <NUM> to <NUM> hours at ambient conditions, i.e. in a temperature range of from <NUM> to <NUM>, preferably of from <NUM> to <NUM>.

The concentration of the pollutants is in the range of from <NUM> to <NUM> ppm.

One advantage of the use in accordance with the invention, as mentioned earlier, is the fact that the pollutants are basically converted to harmless products, i.e. the organic backbone structure is efficiently degraded to give primarily carbon dioxide and water as final degradation products which are easy to treat/remove and do not pose health hazards.

The following examples show the broad versatility of the use in accordance with the present invention and of the process in accordance with the invention.

<NUM>,<NUM> Mo<NUM>Fe<NUM>, synthesized in accordance with <NPL>), <NUM> grams of sodium persulfate, <NUM> of water and the substrate to be treated in accordance with the data given in Table <NUM> were irradiated in a quartz glass reactor with a Xe-lamp using a filter excluding radiation of wavelengths of less than <NUM> (thereby filtering out the UV radiation). The decomposition of the substrate was monitored by measuring the CO<NUM> evolution at the upper end of the reactor with CG/MS. In addition, for some of the experiments, chromatographic (HPLC) or spectrophotometric (UV/VIS) measurements were carried out to show the degradation of the substrates. Table <NUM> shows the results obtained.

The results show that the use of POM in accordance with the present invention can be successfully applied to a great variety of different pollutants.

Claim 1:
Use of Keplerate type polyoxomolybdate Mo<NUM>Fe<NUM> in combination with electromagnetic radiation having a wavelength exceeding <NUM>, preferably exceeding <NUM>, and persulfate as the oxidizing agent for decontaminating aqueous media from inorganic and organic pollutants, characterized in that the weight ratio of Keplerate to persulfate is in the range of from <NUM>:<NUM> to <NUM>:<NUM>; the concentration of pollutant in the aqueous medium is in the range of from <NUM> - <NUM> ppm;
irradiation with electromagnetic radiation is conducted in a temperature range of from <NUM> to <NUM>; and
the duration of irradiation with electromagnetic radiation is in the range of from <NUM> to <NUM> hours.