MXPA00000449A - Charge generators in heterolamellar multilayer thin films - Google Patents

Abstract

Multi-layered compositions having a plurality of pillared metal complexes disposed on a supporting substrate, the pillars comprising divalent electron acceptor moieties with a phosphonate or arsenate at each end. The pillars can be electron donating, electron accepting or charge generating in nature. Each layer of parallel pillars is separated by a layer of a group (IVA), (IVB), (IIIa) or (IIIB) metal or a lanthanide. The compositions can further comprise particles of at least one Group VIII metal at zero valence entrapped within each layer of the complex. The complexes can also incorporate"stalactites"and"stalagmites"of capped arsonato or phosphonato ligands interspersed with the pillars providing a series of interstices about each electron accepting group. The supporting substrate can be comprised of an organic polymer template. The complexes are useful for the conversion and storage of solar energy, for the production of photocurrents, and as catalysts for reduction reactions, for example, the production of hydrogen peroxide from oxygen and hydrogen gases, the production of H2 gas from water, and the reduction of ketones to form alcohols.

Description

LOAD GENERATORS IN THIN FILMS OF HETEROLAMINAR ULTICAPAS TECHNICAL FIELD The present invention relates to improved photovoltaic compositions, more particularly to thin films of multilayers, heterolaminars and methods for using them.

BACKGROUND OF THE INVENTION Solar energy can be used and stored by the efficient production of photo-induced, long-lasting charge separation - a state achieved in photosynthetic systems by the formation of a long-lived radical pair. A number of artificial systems have been reported to transfer efficiently experienced photochemical charge, unfortunately, the thermal backup electron sometimes transfers income in an appreciable ratio, which limits the utility of these systems. What is needed is a system that has photoinduced and efficient charge transfer, and forms a separate state of charge that is long-lived in the air. The charge separation in these systems typically involves a redox reaction between a photoexcited donor and a suitable acceptor, which results in the production of ion pairs illustrated by the formula: (1a) D + hv - > D * (1b) D * + A - > A "+ D + (2) D + + A"? D + A The cation and the anion generated in this way are better oxidants and reducing agents, respectively, either of the state molecules of neutral increase. For the harvest of the light placed in this system, the oxidation and reduction power of the photogenerated species must be used before the electrons are transferred backup (equation 2) that generates the starting materials. It is desirable to control this photochemically thermal velocity backup electron reaction transfer without production. One method has been incorporated into the donors and acceptors in the solid matrices. The design and characterization of chemically sensitive interfaces and thin films have focused on mimic attempts at the highly efficient processes observed in biological systems, many of which occur in membranes. In this way, an important goal in this area is the manufacture of an artificial system for the conversion of solar energy into chemical or electrical energy. This method for energy conversion can be taken in a number of ways, averaging the design of novel photovoltaic devices in search of an efficient and cost-effective method to photochemically convert liquid water to gaseous hydrogen and oxygen. The properly designated systems can use the photoinduced charge separation to generate a photocurrent. In a process to generate chemical energy, D + and A "are used to direct upward chemical reactions, such as oxidation and reduction of water, respectively.To generate electrical energy the same species can be used as the anode and cathode of a photocell. For any of these processes to be the efficient backup electron transfer (equation 2) they must be prevented.To slow the transfer of backup electron it is important to control the structural and electronic properties of the system. The objective is achieved by the fixed geometrical dispositions of electron donors, intermediate carriers and electron acceptors within the membrane.In artificial systems, electron donors and acceptors with selected redox potentials can be arranged in a geometry set using simple self-assembly techniques. Individuals in the separate state of charge have the appropriate potentials to carry out the reduction and oxidation of water. Unfortunately, these direct reactions are kinetically limited, such that catalysis is required to overcome kinetic barriers. The colloidal particles of platinum are ideal catalysts for the reduction of water to give H2. In the systems used for water photoreduction, the closed contact of the highly potential radicals formed in the compounds and the Pt particles is advantageous, due to the transfer of the electron from the reduced viologen to Pt particles must compete effectively with the backup electron transfer. These platinum particles may be present in the reaction solution, incorporated in the structure of the compositions or both. The compounds that can carry out the reduction reactions, use hydrogen gas as their reduction equivalents, are useful as catalysts for the conversion of mixtures of hydrogen and oxygen to hydrogen peroxide. Hydrogen peroxide is a very large volume chemical. The annual production in the United States is greater than 500 million pounds. The different processes have been patented for the production of hydrogen peroxide, which depends on the following two reactions. The objective is to promote the reaction (3) and to delay the reaction (4): (3) H2 + O2? H202 (4) H202 + H2? 2 H20 A number of catalysts for this conversion have been reported including homogeneous and heterogeneous catalysis.

The compositions of the present invention are capable of producing the state of photoinduced continuous charge separation that supplies the compositions useful in the conversion of solar energy and storage. Thin multilayer films of the present invention composed of donor and acceptor layers produce photocurrents when irradiated with light. In addition, the compositions allow the reduction of several metal ions to produce the zero valent metal in a colloidal form trapped in the matrices of the composition. These latter matrices contain the zero-valent metal that has a variety of uses such as in the decomposition of water to produce hydrogen gas and the detection of oxygen. In addition, zero-valent metal matrices can be used in catalysis, such as in the production of hydrogen peroxide and the oligomerization of methane to form high hydrocarbons.

BRIEF DESCRIPTION OF THE INVENTION The present invention provides multilayer compositions, each layer containing a plurality of "columns" comprising portions of electron divalent acceptor or donor with an osphonate or arsonate at each end. Each layer of parallel columns are separated by a layer of a group metal (IV A), (IV B), (III A) or (III B) or a lanthanide.

The complex may further comprise particles of at least one Group VIII metal at zero valence trapped within each layer of the complex. The complexes may also incorporate "stalactites" and "stalagmites" of blocked arsonate or phosphonate ligands scattered with the columns that provide a series of interstices around each electron that the group accepts. The donor or acceptor portion of each column layer can be selected independently of the other layers. Therefore the films can be homogeneous, where the donor / acceptor portion of each layer is the same; or heterogeneous ones, wherein the donor / acceptor portion of one or more adjacent layers may be different. The efficiency of the charge transfer is improved with the addition of a charge generating layer located between the adjacent donor layers and the acceptor layers. The complexes are useful for the production of photocurrents, conversion and storage of solar energy, and as catalysis for reduction reactions, for example, the production of hydrogen peroxide from oxygen gases and hydrogens, the production of H2 gas from water, and the reduction of ketones to form alcohols.

BRIEF DESCRIPTION OF THE DRAWINGS FIGURE 1 is a schematic view of the highly ordered structure of a substrate and film according to the present invention. FIGURE 2 is a schematic view of a solid composition incorporating "stalactite" and "staglamite" ligands according to the present invention. FIGURE 3 is a schematic view of a solid of the present invention incorporating metal particles and "stalactite" and "stalagmite" ligands according to the present invention. FIGURE 4 is a schematic view for the production of multilayer films. FIGURE 5 is a graph of the photochemical measurements of the films of Example 45. FIGURE 6 is a graph of the photochemical measurements of the films of Example 46. FIGURE 7 is a graph of the photochemical measurements of the films of Example 48 FIGURE 8 is a graph of the photochemical measurements of the films of Example 50. FIGURE 9 is a graph of the photochemical measurements of the films of Example 52. FIGURE 10 is a graph of the photochemical measurements of the films of Example 54 FIGURE 11 is a graph of the photochemical measurements of the films of Example 56. FIGURE 12 is a graph of the photochemical measurements of the films of Example 58. FIGURE 13 is a graph of the photochemical measurements of the films of Example 58 FIGURE 14 is a schematic view of a multilayer, thin film with a charge generating layer. FIGURE 15 is a schematic view of possible load transfer systems. FIGURE 16 is a schematic view for the production of a substrate with a joining means. FIGURE 17 is a schematic view of an alternative chemical method. FIGURE 18 is a schematic view of the preparation of a charge generating layer.

DETAILED DESCRIPTION In general, the invention relates to multilayer compositions comprising two or more layers of adjacent metal, independently of one another, comprised of atoms of a divalent, trivalent or tetravalent metal of the Groups III, IV A, IV B that have an atomic number of at least 21 or atoms of a lanthanide, which forms a cohesive layer. The metal layers are spaced apart and in the reaction substantially parallel to each other and to the substrate. Arranged between, and in substantially perpendicular relationship to, the metal layers, are the organic columns that are independently of one another, covalently attached to two of the adjacent metal layers and thus form interstices between the columns and the two layers of adjacent metal . This layered composition may take the form of, for example, a thin film or a microcrystalline solid. The organic columns are polished by the formula: /. - (Y103-Z-Y203) - each of Y1 and Y2, independently of one another, is phosphorus or arsenic; Z is an electron that accepts a divalent donor group that contains a conjugated network that is capable of alternating between a reduced stable form and a stable oxidized form; A sufficient number of anions are attached to the metal ions that make the metal layers, so that the metal ions have an effective valence of +1 to +6, preferably +3 or +4. A separate group of anions is present within the lattice formed by the columns and metal atoms to counterbalance any residual charge in the composition. Additionally, the composition may comprise particles of at least one Group VIII metal in the zero valence trapped in the gap between the columns and the adjacent metal layers. These particles can increase the function of the composition, for example, acting as a catalysis for reduction actions. The compositions may also comprise organic ligands disposed between the metal layers and between the columns that are independently, one from the other, covalently bound to the metal layers. The ligands are illustrated by the formula: //. Y3O3-R3 Y3 is phosphorus or arsenic and R3 is a non-reducible corked group. In a first embodiment, the invention relates to a composition of compound in which a film is disposed on a supported substrate. In this form, the layer closest to the substrate is flanged to the substrate by a joining means. The substrate may be, for example, metals, glasses, silicas, polymers, semiconductors (e.g. silicone, gallium arsenide), combinations thereof such as a gold layer or an aluminum base, and the like. The substrate can be in any form, for example, sheets, foil, plates, films, electrodes, colloidal particles in suspension, polymer templates, high area surface supports, and the like. The surface of the substrate can be uniform (soft) or non-uniform (rough). The film is composed of a plurality of metal complexes in columns, each of the formula: ///. [(Y1 O3-Z-Y2O3) l k * p (X q- > where: L is a means of attachment; each of Y1 and Y2, independently of one another, is phosphorus or arsenic; Z is a divalent group that reversibly forms a reduced stable form and an oxidized stable form; X is anion; Me? is Me1nWm, wherein Me1 is a divalent, trivalent, or tetravalent metal of Group III, IV A, or IV B having an atomic number of at least 21 or a lanthanide; W is an anion, such as, but not limited to, halides or pseudohalides, or -OH; n is 1, 2 or 3; m is 0, 1, 2, 3 0 4; k has a value from 1 to about 250; p has a value of 0, 1, 2 or 3; and q is the charge of the anion, where for each additional k value, the other layer is added to the film. Me1 may be, for example, a metal of group IV A having an atomic number of at least 21 such as germanium, tin or lead, a metal of group IV B such as titanium, zirconium, or hafnium, a metal of group IIIA having an atomic number of at least 21 such as gallium, indium or thallium, a metal of group IIIB such as Scandium, trio, or a lanthanide such as, for example, lanthanum, cerium, praseodium, etc. of them, titanium, zirconium, hafnium, germanium, tin and lead are preferred with zirconium being particularly useful. Each of Y1 or Y2 is phosphorus or arsenic, preferably phosphorus, each of Y1Ü3 and Y2Ü3 in this way being a phosphonate or arsonate group. The group Z is divalent, being attached to a phosphorus or arsenic atom of the phosphonate or arsonate group defined by Y103 and Y2O3. In practice, the precise structure of the Z group is of less importance than its electronic properties; Z must be able to exist both in a reduced stable form and reversibly in a stable oxidized form. In one embodiment, Z may contain two conjugated cationic centers that together have an E ° network value; that is, a reduction potential below hydrogen. The two conjugated cationic centers can be for example tetravalent nitrogen atoms which are conjugated ring members in an aromatic ring system. In one embodiment, each tetravalent nitrogen atom is a ring member in a separate aromatic ring system and two ring systems, which may be of the same or different structure, are attached to one another directly through a covalent bond. Each aromatic ring system can be a monocycle such as pyridine, pyrazine or pyrimidine. Alternatively, each aromatic ring system can be a combined polycycle in which a pyridine, pyrazine or pyrimidine ring is combined with one or more benzo or naphtho ring systems, such as quinolinium, isoquinolinium, phenanthridine, acridine, benz [/? ] isoquinoline, and the like. The two aromatic ring systems, which may be of the same or different structure, may alternatively be linked through a conjugated divalent system such as diazo (-N = N-), imino (-CH = N-), vinylene , buta-1, 3-diene-1,4-diyl, phenylene, biphenylene and the like. In a further embodiment, the two conjugated cation centers can be in a simple aromatic system such as phenanthroline, 1, 10-diazantrene, and phenazine. Typical dicationic structures suitable as Z of this form include 2,2-bipyridinium, 3,3-bipyridinium, 4,4-bipyridinium, 2,2-bip ?? azinium, 4,4-biquinolinium, 4,4-biisoquininolinium, 4- [2- (4-pyridinium) vinyl] pyridinium, 4,4'-bis (4-pyridinium) bi phenyl, and 4- [4- (4 pyridinium) phenyl] pyridinium. The aromatic systems in which the two conjugated cationic centers are located can be substituted or unsubstituted, for example as alkyl of 1 to 6 carbon atoms or alkoxy of 1 to 6 carbon atoms. Such substitution may be inert or may have an effect on the reduction potentials of the cationic centers spherically or through induction. While the two cationic centers must be united through conjugation, the complete system comprised by Z does not need to be conjugated. In this way, Z can be linked to each of Y '? 3 and Y2? 3 through a conjugated or unconjugated bridge. Therefore, a highly desirable structure for Z is characterized by the structure: IV. (R1) n-Z '- (R2), wherein Z 'is a divalent aromatic group containing at least two conjugated tetravalent nitrogen atoms; each of n and m, independently of one another, has a value of 0 or 1; and each of R1 and R2, independently of one another, is a divalent aromatic aliphatic hydrocarbon group. Typically each of n and m will be 1 and each of R1 and R2, independently of each other, will be a linear or branched divalent alkane chain of six or fewer carbon atoms, such as, for example, methylene, ethane, trimethylene, propane-1. , 2-diyl, 2-methylpropane-1,2-diyl, butane-1,2-diyl, butane-1,3-diyl, tetramethylene, and the like or divalent aryl, substituted or unsubstituted, such as benzyl. Other forms of Z include 1,4-Bis (4-phosphonobutylamino) benzene (PAPD); porphyrin derivatives and phthalocyanine derivatives. Using circled Z portions should result in columns illustrated by the formula: where X is O or (CH2) y, where y is 1 to 6. The group X is an anionic group, one or more of which (depending on the value of k and the charge of X) will balance the cationic charges of Z and results in a net positive valence of Me? being equal to (4-p * q). The precise nature of X is relatively unimportant and X may be for example a halogen anion such as chloride, bromide, and iodide, a pseudohului, sulfate, sulfonate, nitrate, carbonate, carboxylate, etc.

The group W is an anonic group, one or more of which (depending on the metal ion, Me1, used) will result in a net ositive valence of Me? being equal to (4 - (p * q)). The precise nature of W is relatively unimportant and W can be for example a halide, a pseudohalide, hydroxy, etc. Each complex represented by Formula III is surrounded to the substrate by means of the joining means represented; the plurality of units -L-Y103-Z-Y203Me? in the substrate, therefore produces a stacked structure. Each complex can contain a unit containing Z ("pillars") in which case k has a value of 1, but preferably k has a value in excess of 2 such that the unit - (Y103-ZY 03) Me? - converts the monomer of the stacked polymer complex at which k averages from 2 to about 250, typically from about 5 to about 100. This multilayer structure can be used by the formula: Such films can be prepared through the sequential absorption reactions analogously to those described by Rong et al., Coordination Chemistry Reviews, 97, 237 (1990). The synthetic and stoichiometric method used can affect and determine the resulting configuration and the morphology of the compositions. Figure 16 illustrates a method for producing a substrate with attachment means. An example of the preparation method starting with a substrate, which is typically hydroxy-terminated, such as metals (the surfaces of which invariably includes the metal oxide), glass, silicas, gallium arsenide, and the like, which is first derivative with a reactive hydroxy reagent that introduces the joining means L or the components of those joining means. Typically the distal orifice of L will end in, and thus eventually be bound to Y1Oβ through, a Me3 metal atom that is similar to Me1, ie, a divalent, trivalent, or tetravalent metal of Group III, IV A or IV B that has an atomic number of at least 21, or a lanthanide. In this way, for example, the substrate can be treated with a compound of the formula: SAW. X "-R1-Z-Y303H2-2X 'in which R1 and Z are as defined herein, Y3 is phosphorus or arsenic, X' is an anion analog to X (X 'may be, but not necessarily needs be, the same anion as it will appear in the final complex) and X "is a reactive halogen such as chlorine or bromine. Consequently, it is the intermediate produced: Vile. substrate-0-R1-Z-Y3O3H2-2X 'The above reactions can be conducted in two stages, first treating the substrate with a component of the formula X "-R1-Z" 2X 'and then treating the product with a phosphoryl halide such as phosphoryl chloride or phosphoryl bromide or a corresponding arsonyl halide. In this embodiment, the bonding means produced is similar to the repeating unit to such a degree as its content -Z-Y303. Alternatively, the joining means may be unequal to the repeating unit.Thus the substrate may be treated with such a silane. as an aminoalkyltrialkoxysilane such as for example 3-aminopropyltriethoxysilane and this substrate derived then treated with a phosphoryl halide such as phosphoryl chloride or phosphoryl bromide or a corresponding arsonyl halide to produce: VIII. [substrate] -alkyl-NH-Y3O3H2 Other examples of binding media include: IX. [substrate] -O-alkyl-Y3O3H2.

X. [substrate] -alkyl-O-Y3O3H2. The substrate can also be treated with a thiol to form the binding means. Such a linked thiol is particularly useful on gold substrates. Examples of such thiols include thiophosphonic acids having the formula: HS- (CH2) n-P03H2 or thioalkylsilanes having the formula: HS- (CH2) n-Si (O-alkyl) 3, wherein n is 1 to 16 and alkyl is linear or branched alkyl of 1 to 16 carbon atoms. Using such resulting thioacylisilanes in an intermediate binding medium have hydroxy groups for the attachment of the metal layer. Another embodiment uses a template of an organic polymer as a joining means to join the compositions / films to the surface of the hydrophobic substrates (eg, quartz, silicon and metals). These polymer templates are derivatized with phosphonate or arsonate groups, for example, by treating epoxy groups pendent to the polymer backbone with phosphoric acid to produce pendant phosphonates. The hydrophobic polymer template is absorbed on the surface of the hydrophobic substrate leaving the free hydrophilic phosphonate / arsonate groups reticular. These pendant phosphonate or arsonate groups are cross-linked with divalent, trivalent, or tetravalent metal groups of Group III, IV A, IV B having atomic numbers of at least 21 or of a lanthanide forming a first metal layer. These polymer templates show good adhesion to the substrate surface, and performance to a highly porous structure, (especially on metal substrates). The polymer can be any polymer having side chains that are capable of being derived with phosphonate or arsonate groups. A preferred polymer is polyvinylpyridine in which a fraction, preferably less than one half, of the pyridyl groups is being alkylated with X (CH2) nP03H2, wherein X is an anion and where n can be 1 to 16, preferably 2 to 4 , (PVP-CnP) abbreviated). A polymer backbone having pendant thiol groups is preferred for improved bonds to Au, Ag, and Pt substrates. In another embodiment, the substrate may be the tempered polymer by itself. The films grown in the polymer template are grown in solution. The hydrophobic properties of the polymer backbone cause the polymer in the solution to aggregate in the sheet form, with the hydrophobic pending phosphonate or arsonate groups existing outside the solution, similar to two layers of lipid. This structure can be illustrated by the formula: The colloidal particles of a Group VIII metal, preferably platinum, may be present in the solution. The hydrophobic properties of the aggregate of the polymer backbone attract the particles. The particles are then plugged into the hydrophobic environment between the polymer backbones. This structure can be illustrated by the formula: In any case, the substrate has a rich surface in phosphonate or arsonate groups, then it is treated with a reagent that provides Me3, for example, zirconyl chloride. The metal atoms attached to, and effectively cross-linked, the phosphonate or arso-ato groups, in turn produce an intermediate that has a metal-rich surface and that is characterized as "substrate-L'-Me3" where L ' -Me3 corresponds to link means, L, of Formula III, provides means in which (/ ') in a manual connection to the substrate and (/' / ') in the other presents a Me3 metal for additional build.

Layer Formation The individual layers of the donor, acceptor and charge generator are applied to the prepared substrate, following the scheme illustrated in Figure 4. Continuing the process of the foregoing, the substrate L is then separated from the reagent providing Me3 ions, washed with Water, and treated with a solution of a bisphosphonic acid or bisarsonic acid of the formula: XIII. H2Y1O3-Z-Y203H2 * 2X 'in which Y1, Y2, Z and X' are as defined in the above. This reaction is completed within a few hours, such as for example about 4 to 5 hours, and can be accelerated through the use of moderate heat, such as from about 80 to about 100 ° C. The deposition of this layer can be monitored instantaneously spectrophotometrically at wavelengths from about 260 to about 285 nm. For consistency, generally the range of 280-285 nm is employed. One of the groups -YO3H2 and - Y2O3H2 attached to the rich surface of metal, while the other peimanece uncoordinated, so now produces an intermediate that has a surface rich in phosphonate and arsonate groups. This intermediate can be represented as: XIV. substrate-L'-Me3-Y1? 3-Z-Y2? 3H2-2X 'The substrate -L'-Me3-Y1O3-Z-Y2O3H2'2X' is removed from the solution of bisphosphonic acid or bisarsonic acid, rinsed thoroughly, and then treated with a reagent that provides Me1 ions to produce a complex of Formula III in which r1 is 1. The above sequence of the last two synthetic steps, which is treated with a bisphosphonic acid or bisarsonic acid followed by treatment with a Reagent that provides ions Me1 is repeated to produce complexes that have higher k values. The absorbance, as for example, at 280-285 nm, appears to increase linearly with the number of layers and provide a convenient method of monitoring the formation of multilamellar compositions. The above process is easily and preferably modified to trap atoms of at least one Group VIII metal, such as for example platinum, palladium, iron, cobalt, nickel, ruthenium, rhodium, osmium, or iridium, at zero valency within the complexes . In this way the treatment with a bisphosphonic acid or bisarsonic acid follows but before the treatment with a regent provides Me1 ions, the sample is immersed in an aqueous solution of a soluble anionic salt of the Guipo VIII metal. The stoichiometries of this exchange will depend on the respective valences of the two anions. The anions of platinum tetrachloride and platinum hexachloride, for example, each have a valence of -2 and if the chloride is the initial anion, an anion of any of these metal anions must be exchanged for two chloride anions. Following this exchange, treated with an agent provides Me1 ions then it is performed as described in the following. As in the above, these reactions are repeated until the desired k value is reached. The mixture is then simply exposed to hydrogen gas which reduces the metal anion to produce the metal in a state of zero valence and a colloidal form within the matrix of the mixture. As previously observed, such materials are highly effective as catalysts in the production of hydrogen peroxide, the oligomerization of methane to form high hydrocarbons, the decomposition of water produces hydrogen gas and the detection of oxygen. The compositions can also be used to reduce various organic substrates. When the compounds grow in layers in a tempered polymer as the substrate, the above processes are generally followed, however, the sequential treatment steps are separated by dialysis steps to remove unused reaction, not by increase. It is possible to use more than one HIV group metal in any sample, either using soluble salts of Group VIII metals other than one or more exchanges or conducting one or more exchanges with a first metal of Group VIII and subsequent metals with a metal of Group VIII differently. Thus created in the eventual reduction are unique compositions in which the colloidal particles of the two metals of Group VIII have different chemical and electronic properties are trapped in a simple matrix. The process shown in Figure 4 involves the increase of arsonate tin / metal phosphonate film layers; however, other chemicals can be used to make the thin film layers. For example, thiols can be used in place of phosphonate / arsonate groups. The result should be a thin film [M (S-R-S) n] of metal sulfide. The same type of chemical must be used with the load generator to ensure good alignment of the load generators. An example of this alternative chemical is illustrated in Figure 17. This approach can be used to increase the donor, acceptor, and load-generating thin film layers. The advantages of these novel increase chemicals (for example, metal thiolates) are producing materials with conductivity, highly significant conduction for the operation of the improved device. A preferred embodiment of these compounds in layers, where Z is a viologen, was found to be very efficient in collecting solar radiation and converting that into a stored chemical energy. The active wavelengths for this process are in an ultraviolet portion of the spectrum. The reaction that stores energy is evidenced by a development of deep blue color in the solid, which persists for long periods of time in the air. This blue color is due to a reduced viologen compound. The reduced viologen reacts rapidly with oxygen when prepared in solution, but does not react in the solid due to its clogging within the dense solid. Oxygen and other external agents are inadequate to gain access to the reactive inner layers of the solid. Another preferred embodiment of these layered compounds has a heterolaminar structure. By varying the composition of the pillars, firstly by varying Z for each layer, compositions capable of producing a photocurrent are produced. The basic structure is having a layer of an electron donor composition and a second layer of an electron acceptor composition; the order, that is, the substrate-donor-acceptor or substrate-acceptor-donor, determines the direction of current flow. A variation in the basic structure is to have several layers of donadoi (or acceptor) and then the different layers of acceptor (or donor) essentially producing layers of donor and thick acceptor. This variation of photovol properties is improved by increasing the amount of light absorbed. Another variation has alternate repeat layers of one or more donor layers and one or more layers of acceptor (or the opposite order), for example, substrate-donor-acceptor-donor-acceptor-etc. (or substrate-acceptor-donor-acceptor-donor-etc). In these compositions the electron donor / acceptor property of each layer is relative and not absolute. In this way, the composition may have layers which are all generally considered to have accepting properties when viewed independently; however, if the layers are formed in, for example, a gradient order of acceptor resistance, the first layer must act as a donor in relation to the second layer; the second layer must behave as a donor in relation to the third layer; etc. The compositions using this gradient variation should be illustrated, for example, by the formula: substrate-donor-donor-donor "-ceptor-acceptor-acceptor" -etc.

The layers of g will prevent transfer of back-up electron and increase the flow of current through, and eventually left the film. In a preferred embodiment, the efficiency of the charge transfer between donor or donor and acceptor or acceptor is improved by incorporating a charge generator layer between the donor and the acceptor layers. The incorporation of a charge generator increases the quantum efficiency by the separation of charge in thin film materials. A preferred thin film is comprised of a region of one or more donor layers connected to a region of one or more acceptor layers with a charge generating layer. This thin film structure is illustrated in Figure 14. A charge generating layer is similar in structure to a donor / acceptor layer comprised of substituted pillar metal phosphonate / arsonate, wherein the "pillar" has the characteristic in that It is in excited state, it has a great dipole moment, which creates a large local field that facilitates electron transfer. The charge generator can be excited by direct absorption of light or this can have the excitation transferred to it from an excited donor or acceptor (Figure 15). Examples of materials used as charge generators in thin multilamellar films include, but are not limited to, stybazolium compounds, asymmetric diazo compounds and other materials. Some preferred compounds that are useful as charge generators are Mustiados by the following formulas: Estilbazol Diazo asymmetric wherein Ri and R2 are suitably reactive such as: -P03H2, -AsO3H2, -SH, -NH2, etc. Examples of the synthetic methods for preferred asymmetric diazo charge generating materials follow the process: * HOAc / 30% HOOH Phenylene diamine in HOAc N -NH3 O ™ (1 Week) R2 or ( 8 hours ) Examples of the synthetic methods for preferred stybazole charge generating materials follow the do n Amine? process: These materials have two forms of resonance; the no-load form is expected to be the dominant form in the state of increase, while a switerionic form must be of the form in the excited state. For example, the direction and magnitude of the dipole moments of the phenoxide analogues of a preferred stilbazolium compound are illustrated in the following: The dipole moment of the charged resonance form is preferably greater and in the opposite direction of that of the resonance form without loading When a charge-generating material is placed at the interface between the donor and acceptor region of a multilamellar structure, the high-dipole field form (ie, high electric field) will introduce charge transfer from the region of donor to acceptor, as illustrated in Figure 15. Preferred charge generating materials are prepared as asymmetric compounds that will facilitate the increase of highly oriented thin films; The layers of this "pillars" charge generator are formed in sequence with donor layers and acceptor layers in thin multilamellar films. In order to increase a film layer of the charge generator (for example a stilbazolium compound) it is preferable that the "pillars" are deposited in a well-aligned manner. This can be achieved by the use of charge generating compounds that have chemically distinct ends. For example, a phosphonate group at one end of the "pillar" charge generator is used to attach one end of the molecule to the exposed metal surface of the last layer of donor / acceptor film formed. An amine group used at the other end of the "pillar" charge generator is then returned in a f? Síonato / ai sonat? by treatment with POCI3 or AsOCI3 and lutidine. The surface can then be treated with a metal complex, such as ZrX4 to give a metal-rich surface. This process is illustrated in Figure 18. Therefore,, the method for forming a charge generating layer is the same as illustrated in Figure 4, except that an extra step is added to convert the amine group to a phosphonate / arsonate. This method can be used to prepare donor / charge-generator / acceptor films as shown in Figure 14. The excited state of the charge generator will inject holes and electrons into the donor and acceptor films, respectively. While Figure 14 shows only one orientation of the charge generator, if the films grow with the first acceptor layer, the charge generator may increase in the opposite orientation by preparing the charge generating compound with the phosphonate / arsonate at the end of the charge. imine and the free amine group at the end of divinyl amino.

Solid Complexes To make it possible to use the chemical energy stored in these compounds, a second modality comprises a more open structure. The advantage of the open structure is that it will allow the external tegente to have quick access to photogenic chemical energy. These solids are composed of a mixture of pillars of the first additional embodiment comprising another intermixed amount of small ligands of pillars. These small components leave open space in this new solid. A wide range of different small components have different properties and sizes that can be used to prepare these solids, leading to a very diverse family of solids. The general formula for the materials of this second modality is: XV (YO3-Z-Y2O3) • k * p (X < t). "(I,!. 3) *, Mc? where each of Y1, Y2, Z, X, Me ?, p, and q are as defined: Y is phosphorus or arsenic; n has a value of 0.1 to 0.8; and R3 is a non-reducible corked group. In contrast to the materials of the first embodiment which are preferably produced as a film in a substrate, the materials of the second embodiment are preferably produced as crystalline or amorphous solids. Analogously to the films of the first modality, however, the metals of Group VIII of zero valence can be incorporated in these matrices.

As apparent from formula XV, two complex ligands other than metal Me1 and Me2. The first of these is analogous to that used in Figure III, mainly Y103-Z-Y203, and each such ligand is capable of binding with two metal atoms. The second ligand, Y3OaR3, is capable of complexing with only one metal atom. In this way the entire structure can be seen as a series of parallel layers of metals Me1 and Me2 with groups Y103-Z-Y203 which serve as pillars. Extending from the metal layers these pillars are groups Y30 R3, formed as these were a series of "stalactites" and "stalagmites" between the pillars. The resulting structure in this way has a series of interstices around each group Z. The dimensions of these interstices and the hydrophobicity thereof define surfaces that can be controlled through the section R3. In this way one can select relatively small R3 groups such as methyl, create large interstices, or relatively large R3 groups such as phenyl or benzyl, thereby producing relatively small interstices. Similarly, one can impart hydrophobic properties to the defined surfaces of the interstices using a hydrocarbon group such as propyl for R3 or alternatively decrease the hydrophobicity by using a group R3 which is substituted with a hydrophilic group such as carboxy. Examples of suitable R3 groups include, but are not limited to: H, CH3, CH2Cl, CH2CH3, CH2CH2CH3, OH, O ", and OCH3 Due to these interstices, it is possible to introduce Group VIII metals after complex formation , greater than after each stage, and when they reduce these valencies to zero as described above, therefore a Formula XV complex is treated with an aqueous solution of a soluble anionic salt of a Group VIII metal and the resulting composition treated with hydrogen to produce the group VIII metal in colloidal form.These compositions can be used as catalysts as previously described.In addition, these interstices allow the passage of several molecules in the complexes.For example, oxygen can enter the matrices and then oxidize the Z groups. Then the reduced form of the Z group is colored while the oxidized form is white or yellow, this phenomenon can be used to detect oxygen at extremely low levels. In addition, the ability to control the dimensions of the interstices allows the use of these materials in effectively selective reactions. For exampleit is possible to selectively reduce acetophenone in a mixture of acetophenone and 3,4-di-er, butylacetophenone if the dimensions of the interstices are selected to allow the passage of the forming molecule but not the last, more bulky molecule. The complexes are easily prepared by treating a mixture of R3Y303H2 and H2Y103 Z Y203H in the desired molar ratio with a source of metal ions. The reaction can be conducted either by reflux or hydrothermally and the products are isolated and purified easily. These pure solids do not show photochemical activity in the air due to the rapid diffusion of oxygen inside the solid. If the porous solids are irradiated with ultraviolet light under anaerobic conditions the same active species, that is, the reduced electron acceptor is formed, observed by the dense solids. Interestingly, the photochemical efficiency of these open solids is much greater than dense materials. If the porous solids that are irradiated under anaerobic conditions with air treat, they are quickly bleached. Oxygen can freely propagate in the solids and react with the photogenerated reduced electron acceptor. The reaction product between the electron acceptor produced and the oxygen is hydrogen peroxide. One can thus use these materials as catalysts for photochemical production of hydrogen peroxide. It will be possible to extract the photochemically stored energy by generating mobile high energy chemical species that can propagate out of the solid. The objective is to incorporate colloidal metal particles in the solids that contain preferred viologen. These metals are well known to act as catalysts for the reaction of reduced viologen with water to produce hydrogen gas. The experiments successfully showed that the materials of the second modality could be used to convert solar energy into chemical energy in the form of hydrogen gas. The process will involve: 1) photogeneration of reduced viologen, 2) transfer of electron from the reduced viologen to colloidal metal particles, 3) protonation of the metal particle and 4) elimination of hydrogen gas. Being a true catalysis these materials will also accelerate the forward and reverse reactions, in this way, if the "metallized" material is treated with hydrogen some amount of reduced viologen is generated. In these bases these materials can be used as reducing agents. Photochemical energy is not necessary to produce reduced viologen: hydrogen can be reduced to achieve the same result. The process for this chemical generation of reduced viologen is then: 1) hydrogen addition to the metal particle, 2) transfer electron from the metal particle to the viologen molecule forming reduced viologen, and 3) deprotonation of the metal colloid. Experiments have shown that the viologen molecules of these materials can be quantitatively reduced with hydrogen gas at atmospheric pressure. The schematic drawings of these porous solids are "shown in Figures 2 and 3. The following examples will further serve to particularize the nature of the invention but will not be construed as a limitation on the scope thereof which is defined only by the appended claims .

EXAMPLE 1 Diethyl 2-bromoethylphosphonate (25 g) and 4,4 'bipyridine (7.35 g) in 125 mLs of water is refluxed for three days. An equal volume of concentrated hydrochloric acid is added and maintained at continuous reflux for several hours. The solution is concentrated to 120 mLs by atmospheric distillation and 550 mL of isopropanol are added dropwise with stirring while the mixture is cooled in an ice bath. The solid that forms is collected by vacuum filtration and washed with cold isopropanol to produce 1,1'-bisphosphonoethyl-4,4'-bipyridinium dichloride. (1H NMR (D20) 9.1 (d), 8.5 (d), 4. 2 (m), 2.0 (m) ppm; 13 C NMR (D 20) 151, 147, 128, 58, 30 ppm; 31 P NMR (D 2 O) 17.8 (s) ppm; IR (KBr) 3112, 3014, 1640, 1555, 1506, 1443, 1358, 1281, 1175, 1112, 1020, 936, 816, 485 cm "1) In a similar manner, using 2,2-bipyridinium, 3,3-bipyridinium, 2,2-bipyrazin, 4, 4-biquinolino, 4,4-biisoquinolinium, 4- [2- (4-pyridinium) vinyl] pyridinium, and 4- [4- (4-pyridinium) phenyl] pyridinium, respectively, is obtained 1, 1 '- bisphosphonoethyl-2,2-bipyridinium dichloride, 1,1 '-bisphosphonoethyl-3,3-bipyridinium dichloride, 1,1'-biphosphonoethyl-2,2-bipyrazinium dichloride, 1,1' -biphosphonoethyl-4,4 bi-quinolinium dichloride, 1, 1'-biphosphonoethyl-4,4-biisoquninium dichloride, 1-phosphonoethyl-4- [2- (1-phosphonoethyl-4-pyridinium) vinyl] -pyridinium dichloride, and 1-phosphonoethyl- 4 [4- (1-phosphonoethyl-4-pyridinium) phenyl] pyridinium dichloride Other cationic species, such as the corresponding dibromides or disulfides, are obtained by substitution of the corresponding acids such as concentrated hydrobromic acid or sulfuric acid, by hydrochloric acid in the procedure of this example.

EXAMPLE 2 Planked substrates of combined silica (9x25mm) are rinsed in a 1: 3 solution of 30% hydrogen peroxide and concentrated sulfuric acid, dried at 200 ° C for one hour, and then treated with a refluxing solution of 2% (v / v) 3-aminopropyltriethoxysilane in 50 mL of octane for 20 minutes. The substrates are rinsed with octane and acetonitrile and treated for 12 hours at room temperature with a solution of 10 mM each of phosphoryl chloride and 2,6-Iutinino in acetonitrile. After rinsing in water, the substrates are treated with a 65 mM solution of zirconyl chloride for three hours at room temperature. The above procedure can be used to prepare multilayer films on other substrates such as silicon microplates and vapor deposited on gold films. The following substrate is sequentially subjected to the following two steps. TO). After the removal of the zirconyl chloride solution, the samples are thoroughly rinsed with deionized water and treated with 6 mM 1,1'-bisphosphonoethyl-4,4'-bipyridinium dichloride at 80 ° C during 4 hours and then thoroughly rinsed with deionized water. (Absorption is measured at 284 nm after treating the measured extinction coefficient for 4,4'-bipyridine biphosphonate being 24,000 M "1 cm" 1 at 265 nm). H.H). The following samples are treated with a solution of 65 mM zirconium chloride at room temperature for one hour and again thoroughly rinsed with deionized water. At the completion of a cycle of steps A and f, a plurality of a metal complex of Formula III in which k is 1 is obtained on the planar silica substrate. Each repetition of stages A and ß increases the value of k by one. The number of layers, and thus the number of cycles, correlates to absorbance at 284 nm, as can be seen from the following: No. of layers Absorbance 0 0.057 1 0.083 2 0.091 3 0.109 4 0.130 5 0.152 6 0.177 7 0.201 8 0.217 9 0.242 10 0.263 11 0.281 12 0.299 13 0.327 14 0.341 15 0.357 16 0.367 17 0.373 18 0.383 19 0.407 20 0.423 21 0.452 22 0.458 EXAMPLE 3 By replacing 1-1'-bisphosphonoethyl-4,4'-bipyridinium dibromide in the procedure of Example 2, a series of multilamellar compositions are obtained having the following absorbances. No. of Layers Absorbance 1 0.083 2 0.098 3 0.113 4 0.157 5 0.182 6 0.239 7 0.286 8 0.350 9 0.353 10 0.391 11 0.465 12 0.557 EXAMPLE 4 High quality films are also obtained by the use of other metals instead of zirconium in stage B, by example, hafnium, titanium, tin, gallium, etc., as shown in the following procedure. Planar fused silica substrates (9x25mm) are cleaned as described in Example 2 and a layer of 3-aminopropyltriethoxysilane is deposited therein from the gas phase using the method of Haller, J. Am. Chem. Soc, 100 , 8050 (1978). The substrates are phosphorylated as described in Example 2, rinsed, and treated with 10 mL of a 65 mM aqueous solution of hafnil chloride for three hours at room temperature. Alternating treatments with (A) an aqueous solution containing 6 mM of 1, 1 '-bisphosphonoethyl-4, 4'-b ip i ridinyl dibromide and 20 mM of sodium chloride at 80 ° C for 4 hours and (B) an aqueous solution of 65 mM hafnil chloride for one hour, with vigorous rinsing with deionized water after each, then produces a series of multilamellar compositions which can be characterized spectrophotometrically at 284 nm. No. of layers Absorbance 1 0.052 2 0.086 4 0.175 6 0.250 8 0.304 10 0.384 12 0.518 EXAMPLE 5 The procedure of Example 2 is modified after one or more executions of stage A but before the execution of the corresponding stage B by immersing the samples of the aqueous solution of 6 mM dipotassium platinum tetrachloride for 0.5 hours by the exchange of an anion of platinum tetrachloride for two chloride anions. Step B is then improved as described in Example 2. After completing the final cycle of steps A and B, the composition is suspended in water and the hydrogen gas is bubbled through the mixture for two hours. Platinum is reduced to a colloidal state of zero valence trapped in the complete matrix.

EXAMPLE 6 The silica particles (1 g) are heated in a drying oven for one hour and then stirred with 150 mL of an aqueous solution (60 mM) of zirconyl chloride with the silica (1 g) at 60 ° C for two days. . The solid is isolated by filtration or centrifugation, washed three times with 150 mL of deionized water and treated with 150 mL of a 20 mM solution of 1, 1'-bisphosphonoethyl-4,4'-bipyridinium for six hours at 65 ° C. with agitation. The solid is separated from the aqueous solution and washed three times with deionized water. The solid is then washed three times with 150 mL of a 20 mM solution of potassium platinum hexachloride for three hours at room temperature, whereby an anion of platinum hexachloride is exchanged for two chloride anions. One hundred fifty milliliters of a 60 mM solution of zirconium chloride are added to the solid and the stirred solution for three hours at room temperature is elevated three times with deionized water. The above steps are repeated four times to produce a pentalaminar composition containing platinum cations. An aqueous solution of the materials platinized with hydrogen then converts the platinum ions into platinum metal of zero colloidal valence.

EXAMPLE 7 Zirconyl chloride octahydrate (1444 g, 4.8 mmol) is dissolved in 50 mLs of water and 50% hydrofluoric acid (0.756 g, 19 mmol) is added. To this is added a solution of 1 g of 1,1 '-bisphosphonoethyl-4,4'-bipyridinium dichloride (2.2 mmoles) and 0.516 g of 85% phosphoric acid (4.5 mmoles) in 50 mLs of water. The reaction is refluxed for seven days and the white crystalline product is filtered and washed with water, methanol and acetone and air dried to yield the mixed complex: Zr (03PCH2CH2-bipyridinium-CH2CH2P03 (Cr) 2) o.5. (03POH) X-ray diffraction analysis shows d = 14Á. The infrared analysis is as follows: (IR (cm-l), 3126, 3056, 1633, 1562, 1499, 1450, 1217, 1055, 816, 738, 647, 612, 520, 471). 31P NMR (ppm) are: 3.0, -18.6, -24.5.

EXAMPLE 8 Zirconyl chloride octahydrate (0.21 g, 0.7 mmol) is dissolved in 10 mLs of water and 50% hydrofluoric acid (0.11 g, 2.8 mmol) is added. It is thus added to a solution of 0.15 g of 1,1'-bisphosphonoethyl-4,4'-bipyridinium dichloride (.35 mmoles) and 0.686 g of 85% phosphoric acid (0.6 mmoles) in 10 mLs of water. The solution is placed in a Teflon pump of 45 mL and the total volume adjusted to 27 mLs. The pump is sealed and heated at 150 ° C for six days to produce the mixed complex: Zr (? 3PCH2CH2-bipyridinium-CH2CH2P? 3 (Cr) 2) o.5. (03POH) X-ray diffraction analysis shows d = 14A. The infrared and 31P NMR (ppm) are identical to those given in Example 7.

EXAMPLE 9 Zirconyl chloride octahydrate (0.36 g, 1.12 mmol) is dissolved in 10 mLs of water and 50% hydrofluoric acid (4.5 mmol) is added. To this is added a solution of 0.25 g of 1,1'-bisphosphonoethyl-4,4'-bipyridinium dichloride (0.56 mmol) and 0.129 g of 85% phosphoric acid (0.11 mmol) in 50 mLs of 3N hydrochloric acid. The reaction is refluxed for seven days and the white crystalline product is filtered and washed with water, methanol and acetone and air dried to produce the mixed complex: Zr (03PCH2CH2-bipyridin-CH2CH2P03 (Cr) 2) or 5- (03POH) X-ray diffraction analysis shows d = 18.5Á. The infrared and 31P NMR (ppm) analysis are identical to those given in Example 7.

EXAMPLE 10 Circonal chloride (octahydrate) (0.361g, 1.12 mmol) is dissolved in 10 mLs of water and 0.189 g of 50% or hydrofluoric acid (4.8 mmol) is added. Dissolve 1, 1'-bisphosphonoethyl-bipyridinium dichloride (0.25 g, 0.56 mmole) and phosphoric acid (0.092 g, 1.12 mmole) in 10 mLs of water and this solution is added to the aqueous zirconium solution. The reaction is brought to reflux for seven days and the white crystalline product is filtered and washed with water, methanol and acetone and air dried to yield the mixed complex: Zr (03PCH2CH2-bipyridine-CH2CH2P? 3 ( Cr) 2) or 5'HP03 X-ray diffraction analysis shows d = 18.4Á. The infrared analysis is as follows: 3126, 3056, 2436, 2358, 2330, 1633, 1555, 1499, 1443, 1386, 1210, 1161, 1048, 830, 731, 548. 31P NMR (ppm) are: 5.5, -9.5 .

EXAMPLE 11 By the procedure of Example 10 but using 0.167 (0.38 mmol) of 1,1'-bisphosphonoethyl-bipyridinium dichloride and 0.123 g (1.5 mmol) of phosphoric acid, the mixture of the complex is obtained: Zr (03PCH2CH2-bipyridinium- CH2CH2P? 3 (Cr) 2) or 34 • (HP03)? 32 The material is amorphous. Infrared and 31P NMR (ppm) are identical to those given in Example 10.

EXAMPLE 12 By the procedure of Example 10 but using 0.125 (0.28 mmoles) of 1, 1'-bisphosphonoethyl-bipyridinium dichloride and 0.138 g (1.68 mmoles) of phosphoric acid, the mixture of the complex is obtained: Zr (? 3PCH2CH2-bipyridinium-CH2CH2P03 (CI ") 2) o.25 • (HPO3)? 50 The material is amorphous, Infrared and 31P NMR (ppm) are identical to those given in Example 10.

EXAMPLE 13 Zirconium chloride (octahydrate) (0.151 g, 0.47 mmol) is dissolved in 10 mLs of water and 50% hydrofluoric acid (0.079 g, 1.9 mmol) is added. Dissolve 1,1'-bisphosphonoethyl-bipyridinium dichloride (0.105 g, 0.24 mmol) and methyl phosphoric acid (0.045 g, 0.47 mmol) in 10 mLs of water and this solution is added to the aqueous zirconium solution. The reaction is refluxed for seven days and the white crystalline product is filtered and washed with water, methanol and acetone and air dried to yield the mixed complex: Zr (03PCH2CH2-bipyridinium-CH2CH2P03 (Cr) 2) o.5. (CH3P03) ?.

The material is amorphous. The infrared analysis is as follows: (IR (cm-1), 3450, 3133, 3056, 2922, 1633, 1555, 1499, 1450, 1309, 1168, 1027, 823, 781, 527).

EXAMPLE 14 They are heated in a manner similar to that described in Example 8, 0.93 mmoies of zirconyl chloride, 0.34 mmoles of 1,1'-bisphosphonoethyl-bipyridinium dichloride, and 0.90 mmoles of 3-aminoethylphosphonic acid is heated in a bomb at 150 ° C. In isolation as described herein the amorphous mixed complex shows the following IR spectrum. (IR (cm-1), 3500, 3126, 3055, 1646, 1548, 1499, 1443, 1379, 1154, 1041, 865, 823, 760, 731, 541, 499.

EXAMPLE 15 In a manner similar to that described in any of Example 7 and Example 8, zirconyl chloride, 1,1'-bisphosphonoethyl-bipyridinium dichloride, and a phosphorus containing oligomer as shown in the following table is approved for react.

TABLE 1 * BPBP = Dichloride 1, 1'-bisphosphonoethyl-bipyridinium or what produced are complex mixtures of the formula: Zr (? 3PCH2CH2-bipyridinium-CH2CH2P? 3 (Cr) 2) or 5 • R3P03.

I Data of these products are as follows: TABLE 2 R3 X-Rays IR-CH3 Data * See Eiem.13 -CH2C__3 d = 10.9Á * Spectrum I -CI.2CH2CII3 d = 1I.8Á * Spectrum II -C__2C __, CH3 ti = 13.6 Á * Spectrum II -CH2CH2COOH = 15.4Á Spectrum III -phenium d = 19.7Á * Spectrum IV -CH2C1 d = 11A * Spectrum V -benzyl d = 14.5Á Spectrum VI * = Peaks present that are attributable to pure metal bisphosphonate.

Spectrum I: (IR (c? N-1), 3507, 3126, 3056, 2978, 2943, 2887, 1640, 1563, 1506, 1450, 1393, 1281, 1168, 1048, 872, 830, 738, 541. Spectrum II: (IR (cm-1), 3500, 3126, 3049, 2950, 2866, 1633, 1555, 1499, 1450, 1393, 1246, 1041, 872, 823, 795, 731, 541. Spectrum III: (IR ( cm-1), 3500, 2915, 1717, 1633, 1415, 1260, 1027,816, 752, Spectrum IV: (IR (cm-1), 3500, 3126, 3049, 1633, 1555, 1499, 1443, 1386, 1161, 1055, 865, 823, 749, 731, 710, 541.

Spectrum V: (IR (cm-1), 3500, 3119, 3049, 1633, 1555, 1499, 1443, 1386, 1161, 1055, 865, 823, 759, 731, 710, 54. Spectrum VI: (IR ( cm-1), 3500, 3126, 3056, 1633, 1598, 1492, 1450, 1386, 1253, 1161, 1034, 830, 781, 738, 696, 626, 541, 499.

EXAMPLE 16 Zr (? 3PCH2CH2-bipyridinium-CH2CH2P? 3 (CI ") 2) o.5 (03POH) The complex prepared as in Example 7 (0.05 g) is stirred with 10 mLs of a 10 mM aqueous solution of dipotassium platinum tetrachloride at room temperature for two days. Over the course of the reaction, the solid changes from white to yellow. The solid is then isolated by filtration, washed extensively with deionized water and air dried. The solid is suspended in deionized water and hydrogen gas bubbled through the mixture for ten hours. The solid changes from yellow to dark purple. The solid is isolated by filtration, washed with deionized water and dried in air to give a brown solid.

EXAMPLE 17 A gold substrate deposited on a chromium metal film in turn deposited on glass is treated with 3-aminopropyltriethoxysilane and then the phosphoryl chloride that was previously described and then subjected to the procedure of Example 2 three times to prepare a composition of Formula III in which k is 3. This composition shows a reversible reduction wave at -0.74 V against a saturated calomel electrode. In water, an irreversible reduction is shown below -1.4 V against the same standard electrode.

EXAMPLE 18 Twenty-five milligrams of a composition prepared as set forth in Example 6 in 5 mL of ethylene diamine tetraacetic acid of 0.1 M disodium as a reducing agent sacrificed in a cell of 1 cm 2 is irradiated with a lamp of 200 Watt Hg / Xe. Hydrogen levels are measured with gas chromatography. The ratio of hydrogen production over 18 hours of photolysis is 0.07 mL / hr. Passing light through a 330 nm short-circuit filter (G> 330 nm) decreases the ratio of hydrogen production by more than one order of magnitude. If the filter is removed, the sample will generate hydrogen as before. The yield of quantum by the formation of hydrogen (2 x moles of H2 moles of photons impinge with G < 330 nm) in this system is 0.008. A preferred class of compositions of the second embodiment consists of colloidal particles of Pt and Pd in a phosphonated matrix of porous viologen metal. These materials are very different from other Pt + Pd catalysis; viologen groups make a significant difference in the chemistry involved. The reduction of oxygen is carried out by the reduced viologen and not (as is the case in the DuPont patent materials) on the colloidal surface, since the reduction ratio of oxygen by reduced viologen is much higher than by colloidal metal particles. By the nature of the way that solids are prepared, the "promoters" chloride or bromide are inevitably incorporated. A wide range of different materials were tested. A broadly active compound contains a mixture of bisphosphonic acid and phosphonate (ie, Me (03P-0rl)? (03P-Z-P0j) u. • nH20 • Pt / Pd). Compounds with the phosphonate-ligand wherein R3 is OH was found to be between 10 and 100 times more active than the compounds wherein R3 was H, CH3, CH1CI, CH2CH3, or CH2CH2CH3. A wide range of relationships different from Pd: Pt was also tested. The catalysis has been examined to determine its uniformity and composition. The samples were dissolved in HF and the resulting solutions analyzed by ICP achieved the total metal compositions (weight% of Zr, Pt and Pd, see Table 3). The simple particles were analyzed by electron microprobeta and were found to have a uniformity of Zr: Pt: Pd ratio through the particles.

A wide range of different electrons accepted groups that can be associated in that structure that must be feasible for reduction by hydrogen (via colloidal metal particles) and subsequent use as a catalyst for the formation of hydrogen peroxide and other reduced species. . The following are results of the side-by-side comparisons of the novel catalysts of this invention with other Pt + Pd catalysts which are conducted under identical conditions (See Table 3). The amount of novel metal (Pt + Pd) in both of the materials of this invention and the other materials was analyzed, and then those analyzes were used to grade the amount of catalysis in the experiments to have the same amount of noble metal in each case. The comparisons were improved with mixtures of hydrogen and oxygen at atmospheric pressure. At increased pressures the concentration of hydrogen peroxide in steady state (ratios of equations 1 and 2 above are identical so that the concentration of H202 is constant with time) will increase.

TAIS LA 3.

* Currently 0.22: In this procedure the solution is returned to 10 mL before an aliquot is taken, compensated by evaporation. The state of stable peroxide concentration (reaction ratio 1 = reaction ratio 2) must be constant, regardless of the volume of the sample. Thus when the sample is diluted the amount of peroxide measured is lower. If the reaction conditions are the same, it gives 0.14 M peroxide, but the reaction mixture is not attracted to 10 mL before the aliquot removal of the measured concentration is 0.22 M. Thus the steady state concentration of peroxide was underestimated further or less 50%. fZ? - (? 3POH) (? 3PCH2CH2bipyridiniumCH2CH2P? 3) CloPfPd-093t The best catalyst described in the DuPont patent (US Pat. No. 4,832,938). A number of different materials according to the present invention, porous thick solids in thin films grow on thin surface area supports, were prepared and studied. The coarse solids were prepared by the first preparation of the porous solid in layers of Formula XV; then the halide ions are ions exchanged for polyhalomtal anions (such as PtCl 2), and then the polyhalomtal ions are reduced with hydrogen to give a porous solid with impregnated metal particles to carry out the exchange reaction of ion it was found that high temperatures are necessary.At room temperature PtCI42"preferably occupy about PdCI42", leaving a solid that is richer in Pt than the solution from which it was prepared. performed at elevated temperatures, the exchange is uniform and the composition in the solid equivalents of the solution exactly Zr (03POH) (03PCH2CH2bipyridiniumCH2CH2P? 3) CI was prepared for the following examples in Examples 7, 8 and 9 Several platinum and palladium relationships were then incorporated as follows: EXAMPLE 19 Zr (03POH) (03PCH2CH2bipyridinylCH2CH2P3) Cl0Pt0Pd-58: 170 mg of Zr (03P0H) (03PCH2CH2 bipyridiniumCH2CH2P3) Cl0Pt0Pd-58 was mixed with 4.6 ml of PdCI2 (7.3X10 3M) and 2.8 ml of K2PtCI4 (6.1 X10'3M). This mixture was heated to 60 ° C with constant stirring for 1 hour. The white powder was filtered and washed three or four times with water. The white solid was suspended in water and the hydrogen gas was bubbled for 1 / hour at 60 ° C. The gray / black solid was filtered and washed first with water and then with ethanol. This solid was then air dried. 0.0072 g of the above solid were dissolved in concentrated HCl, a few drops of concentrated HNO3, and a few drops of 59% HF. The solution was diluted to 100 mL and analyzed for Zr, Pt and Pd by ICP. The analysis (ppm) of the solution is Zr = 14.05, Pt = 1.01; Pd = 0.73 EXAMPLE 20 Zr (? 3POH) (? 3PCH2CH2bipyridiniumCH2CH2P? 3) Cl0Pt0Pd-32: 260 mg of Zr (03POH) (03PCH2CH2 bipyridinoCH2CH2PO3) CI and 3 ml of 0.11M K2PdCI4 solution and 6.4 X 10"3M K2PtCI4 were heated to 60 ° C for 30 minutes with constant stirring The yellow solid thus obtained was filtered and washed several times with water.This solid was resuspended with water and treated with H2 gas as mentioned in the first synthesis. dry solid and analyzed as in the above, values in ppm: Zr = 24.72; Pt = 0.69; Pd = 1.5.

EXAMPLE 21 Zr (? 3POH) (? 3PCH2CH2bipyridiniumCH2CH2P? 3) CloPtoPd-00: 200 mg of Zr (03 <POH) (03PCH2CH2 bpyridine CH2CH2P? 3) CI were treated with 1 ml of 0.11 M K2PdCI4 and 0.18 ml of 1.6X10"3M K2PtCI and hydrogenated (as mentioned in the previous example.) 0.0117 g of the final black solid was dissolved in concentrated HCl, a few drops of concentrated HN03, and a little 50% drops HF This solution was diluted to 25 ml The analysis of the solution is as follows: Zr (ppm) =: 48.92, Pt = not detected, Pd (ppm) = 6.75.

EXAMPLE 22 (Zr (O3POH) (O3PCH2CH2bipyridin¡oCH2CH2PO3) CrPtoPd-30: 200 mg of Zr (03POH) (03PCH2CH2 bipyridine or CH2CH2P03) CI, 1 ml of 4.8X10"2M K2PdCl4, and 0.275 ml of 4.7X10 were stirred. "2M K2PtCI4 at 60 ° C for 20 minutes The yellow solid thus obtained was filtered, washed with water, and hydrogenated as above, 0.0125g of the solid was dissolved as above and diluted to 25 ml by analysis for give Zr = 49.91 ppm, Pt = 2.15ppm, Pd = 4.92ppm.

EXAMPLE 23 Zr (03POH) (? 3PCH2CH2bipyridiniumCH2CH2P? 3) CrPt0Pd-11: 500 mg of Zr (03POH) (03PCH2CH2 bipyridiniumCH2CH2P03) CI was refluxed for 6 hours with 15 ml of 7.4X10"3M PdCI2, and 0.99 ml of 5.1X10"3M K2PtCI4. The solid was filtered, washed and as in the above. Hydrogenation of the solid was carried out as above except for one hour 0.0172g of the solid was dissolved as above and diluted to 25 ml by analysis to give Zr = 70.29 ppm, Pt = 1.18ppm, Pd = 9.10ppm .

EXAMPLE 24 Zr (? 3POH) (O 3 PCH 2 CH 2 bipyridinium CH 2 CH 2 PO 3) CloPtoPd-093: 500 mg of Zr (O 3 POH) (O 3 PCH 2 CH 2 bipyridine) HC2CH 2 P0 3) CI, 15 ml was refluxed. of 7.4X10"3M PdCI2, and 0.99 ml of 5.1X10" 3MK2PtCI4 for 65 hours. Filtering, washing and hydrogenated as mentioned in the previous example. 0.018 g of the solid was dissolved as above and diluted to 25 ml by analysis to give Zr = 127.98 ppm, Pt = 0.78ppm; Pd = 7.72ppm.

EXAMPLE 25 Zr (03POH) (? 3PCH2CH2bip¡r¡din¡oCH2CH2P? 3) Ci0Pt0: 200 mg of Zr (03POH) (03PCH2CH2 bipyridiniumCH2CH2PO3) CI were treated with 2 ml of 5.1X10"3M solution of K2PtCI4 a 60 ° C for 1 hour The solid was filtered, washed and hydrogenated as mentioned in the previous example 0.0162g of solid was used to prepare a 25 ml solution by analysis to give Zr = 117.9 ppm, Pt = 20.01ppm .

EXAMPLE 26 Zr (03POH) (03PCH2CH2bipyridiniumCH2CH2P? 3) CrPd: 100 mg of Zr (03POH) (03PCH2CH2bipyridinium CH2CH2P03) CI and 1 ml of 6.3X10"2M PdCI2 at 60 ° C for 4 hours The orange solid was filtered, washed and hydrogenated as above 0.0131g of the solid was dissolved in 25 ml as it was mentioned in the above by analysis to give Zr = 92.96 ppm, Pd- = 8.54ppm Materials were increased in supports of high surface area in a multistage process, as described in the following. carried out either as the film is grown or later prepared.

EXAMPLE 27 Synthesis of S020Zr (? 3POH) (? 3PCH2CH2bipyridiniumCH2CH2P? 3) CIO: One gram of silica gel (Selecto, Inc. Cat # 162544, It # 216073) was heated at 200 ° C for 1 hour. This was treated with 150 ml of 65 mM Zr03OCI2 at 60 ° C for two days. This was followed by a treatment with 150 ml of solution, which consists of 20 mM of (03PCH2CH2b, pyridin, or CH2CH2P03) CI, 20 mM of phosphoric acid, and 60 mM of NaCl at 60 ° C for 18 hours. These treatments were repeated four times. At the end of the pale yellow solid it was washed with water and dried.

EXAMPLE 28 Si? 20Zr (O3POH) (? 3PCH2CH2bipyridiniumCH2CH2P? 3) Cl0Pt0Pd-21: 270 mg of Si020Zr (03POH) (? 3PCH2CH2 bipyridiniumCH2CH2P? 3) CI, were treated with 3 ml of solution, which was .12 M in K2PtCI4 and 6.4X10"3 M in K2PtCI4 at 60 ° C for one hour The solid was hydrogenated as mentioned above.0494 g of this solid was dissolved in HCl, HNO3, and 50 HF and diluted to 25 ml. Analysis: Zr = 166.8 ppm, Pt = 2.97 ppm, Pd = 10.89 ppm.

EXAMPLE 29 The samples were prepared as described above in the synthesis of each compound in Examples 19-28. The metal content of these solutions was determined by ICP. The weight percentage of viologen was calculated from the Zr value, assuming that there are 2 Zr atoms per viologen molecule in the solid. The viologen unit was taken to be C? OHaN_. The resulting data were presented in Table 4 below.TABLE 4 Elemental analysis of all the compounds listed in this description (ICP in dissolved samples), (the percentage is% by weight).

TABLE 4 Definitions for Table 1: DU-D: North American Patent No. 4,832,938 from DuPont Table I A prep D; DU-F: Notte American Patent No. 4,832,938 of D Pont Table I A prep.F; DU-H: North American Patent No. 4,832,938 of DuPont Table 1 A piep.H. Z? PV (POH) = Zn? 3POH) (? 3PCl CH2bipyridiniumCH2CH2P? 3) CI ZrW = Zr (O0PCI LC. IJjipiidininioCI LCH PO3) CI R = Pt / (Pt + Pd) (pVp.) 6-1 R (obs.) = The calculated ratio of Pty Pd analysis by ICP. R (teo) = The calculated ratio of the initial concentrations of Ry Pd in the reaction solution.

FORMATION OF HYDROGEN PEROXIDE: The materials of the present invention can be used as catalysts for the production of hydrogen peroxide. The process comprises treating an aqueous suspension of the catalyst with an oxygen source and a source of hydrogen. Sources for oxygen include pure oxygen, air, ozone or any nitrogen oxide. The suspension may also contain acids or bases to control the pH of the system.

EXAMPLE 30 An amount of each of the catalysts is placed in a 50 mL plastic tube. 10 mL of 0.15 mM acetanilide solution in 0.1 M HCl is added to each tube, and sealed with a plastic barrier. A mixture of oxygen and hydrogen is bubbled through the suspension. In some cases the air is used better than 02. In the sequential time intervals, starting at one hour (above about 28 hours) the loss of the volume of solution due to evaporation was made adopted by the addition of 0.15 mM of solution of acetanilide in 0.1 M HCl and an amount of the reaction mixture was extracted and diluted to 5 mL with previously prepared titanium sulfate solution in sulfuric acid. The absorbance of the solutions was recorded at 410 nm. The calorimetric tests have been verified by grinding the same solutions with KMn04 and they are very suitable. Table 4 shows the elemental analysis of the sintered and / or used compounds. The data shows the catalytic properties of the compounds in the production of hydrogen peroxide in various stages and under various conditions including different ratios of Pt to Pd and in a number of pHs. The data listed in Table 5 represent the H202 production for two preferred materials according to the present invention and some other catalysts. Table 6 shows similar test data for other compounds according to the present invention and other compounds. Table 7 shows data collected by several catalysts having different ratios from Pt to Pd. Table 8 shows data in a number of different pHs.

TABLE 5. Formation of hydrogen peroxide, pH = 1 atm. The amount of catalysts used in each experiment was adjusted to give a constant number of moles of Pt + Pd in each experiment.

DU-D: U.S. Patent No. 4,832,938 to DuPont Table I A prep D. DU-F: U.S. Patent No. 4,832,938 to DuPont Table 1 A prep.F.

DU-H: North American Patent No. 4,832,938 of DuPont Table I A prep.H. Zr * PV (POH) = Zr (O3POH) (O3PCH2CH2bipyridinium-CH2CH2PO3) CI Zr * PV (PH) = Zr (O3PH) (O3PCH2CH2bipyridinium- CH2CH2PO3) CI Zr * PV = Zr (O3PCH2CH2bipyridiniumCH2CH2PO3) CI Pd-Pt- # refers a Pt / (Pt + Pd) (p / p) Table 6. Comparison of the DuPont catalyst and novel catalysts according to the present invention using a H2: 02 ratio of 2: 1 (air 02) at pH = 1. The amount of the catalyst used in each experiment was adjusted to give a constant number of moles of Pd + Pt in each experiment.

DU-D: U.S. Patent No. 4,832,938 of DuPont Table I A prep D. DU-F: U.S. Patent No. 4,832,938 of DuPont Table I A prep.F. DU-HI: U.S. Patent No. 4,832,938 to DuPont Table I A prep.H. Zr * PV (POH) = Zr (O3POH) (O3PCH2CH2bipyridinium-CH2CH2PO3) CI Zr * PV (PH) = Zr (O3PH) (O3PCH2CH2b¡p¡r¡dinio- CH2CH2PO3) CI Zr * PV = Zr (O3PCH2CH2bpyridiniumCH2CH2P? 3) CI Pd-Pt- # refers to Pt (Pt + Pd) (p / p) Table 7. H202 production for catalysts with different amounts of Pt (different R-values) mixture 2: 1 to H2: 02 (air was used as an oxygen source) 1 atm, pH = 1.

Zr * PV (POH) Zr (O3POH) (O3PCH2CH2bipiri dinioCH2CH2PO3) CI Pd-Pt- # refers to Pt / (Pt + Pd) (w / w) Table 8. Alternating pH with HCl, H2: 02 = 1: 5, 1 atm. use Zr (? 3POII) (? 3PCH2'CH2bipyridiniumCH2CH2PO3) CI.Pt.Pd-093.

The above examples involve reactions of atmospheric pressure. Two parameters are important in this regard, those are the initial ratio of hydrogen peroxide formation and the steady state concentration of hydrogen peroxide. The steady state concentration indicates the concentration at which the system is making peroxide water in the same ratio that the peroxide is being formed, while the initial ratio is an indication of the hydrogen peroxide formation ratio. The best stable state value observed was 140 mM (Table 5). In the steady state the ratio of the reduction of oxygen (equation 3) and the reduction of hydrogen peroxide (equation 4) were equal, so the concentration of hydrogen peroxide is constant. The initial reaction ratio in these experiments is 30 productions per hour (based on the moles of the vioiogen present in the system). These experiments were carried out with a catalyst having an R of 0.093 and a mixture of 1: 5 of H2: 02- The best DuPont catalyst (DU-D) treated in an identical manner produces only 77 mM of hydrogen peroxide in stable state. As the mixture of H2 and 02 becomes more oxygen rich (ie H2: 02 = 1:10) the amount of hydrogen peroxide produced decreases. Other catalysts lose a good fraction of their activity very quickly. To this test a sample of the catalyst was taken and used in several experiments successively. The results are shown in Table 9. At minimum risk, a mixture of hydrogen and air was used in these experiments, so the steady-state values for the peroxide concentration were less relative to the numbers cited above. The first three experiments show very similar levels of peroxide production. The fourth experiment shows a lower level of activity than the first three. This level of activity is still much higher than that observed by the DuPont catalyst under identical conditions. Elemental analysis shows that after the fourth weight percent cycle of Pt and Pd has slight loss, while the amount of Zr has low loss. These observations suggest that the decrease in activity tends to be with partial dissolution of the metal phosphonate. TABLE 9. Formation of hydrogen peroxide using Zr.PV (POH) .Pt.Pd-093, pH = 1, \\ 2: 2 = 2: 1 (air used as source 02), pressure = 1 atm.

EXAMPLE 31 Formation of High Pressure Hydrogen Peroxide: A number of experiments were performed with various combinations of gas pressure (H2, 02, N2) in a 70 ml basal pressure vessel. Five mis of 0.1 M HCl and 25 milligrams of Zr (03POH) (03PCH2CH2bipyridiniumCH2CH2P03) CI * Pt * Pd-14 are added to the basal vessel. A mixture of oxygen, hydrogen and nitrogen at the prescribed pressures are added to the container. The reactions are approved to continue for several times. (TABLE 10) The H202 concentrations are similar to those obtained in the experiments (see above). The data show that an increase in any volume of reaction vessel or an increase in pressure will produce higher H202 concentrations, that is, if PH2 and P02 are increased by a factor of 5 the result should be a molar \\ 02 (see for example, Example 2 in Table 10). t After 24 hours the system was vented and a fresh charge of the same gas mixture was added then allowed to react for another 24 hours.

EXAMPLE 32 Synthesis of Tetrated Phosphonated Derivatized Polymer: Diethyl-4-bromobutylphosphonate was made by the Bridging of Michealis-Arbuzov Br (CH2) 4Br with triethyl phosphite. It heated up 1, 4-dibromobutane (21.5 g, 100 mmol) and triethylphosphite (6.65 g, 40 mmol) at 150 ° C for 6 hours. Unreacted 1,4-dibromobutane was removed by vacuum distillation. Poly (4-vinylpyridine) (PVP) was alkylated with diethyl 4.bromobutyl phosphonate to give polymers (PVP-C4P). PVP (1 g 9.5 mmol) was dissolved in 60 mL of N, N-dimethylformamide (DMF) with 1.48 g (5.4 mmol) of diethyl-4-bromobutylphosphonate. The mixture was stirred at 60 ° C for 2 hours and DMF was removed under vacuum. The remaining solid was washed with a mixture of 1: 4 (v: v) methanol and diethyl ether, and then refluxed in ether for 2 hours. The solid sample was filtered and dried. The dry sample was then dissolved in 30 ml of methylene chloride, 12 g of bromotrimethylsilane were added and the mixture was stirred for 6 hours under an atmosphere of Ar. H20 (80 mL) was added and the solution was stirred an additional hour. The water phase was separated, and removed under vacuum to give the yellow-brown solid (PVP-C4P). The CHN analysis of PVP-C4P gave C: 55.76 H: 6.67, N: 8.20. This analysis is consistent with 25% of the pyridyl groups being alkylated [C7H7N] 3 [C1 H17N03PBr] * 3H20 should give a CHN analysis of C: 55.57, H: 6.41, N: 8.10. The NMR spectrum of PVP-C4P consists of relatively broad lines, due to the nature of the polymer of the material. Three enlargements appear in the 1H NMR spectrum in DMSO / D20 at 8.2, 6.6 and 1.6 ppm, with integrated intensities of 1, 1, and 2.4. This relationship is consistent with the 25% derivation if the two peaks of the non-active areas are assigned to the pyridyl / pyridinium resonates and the peak at 1.6 ppm is assigned to all of the CH2 groups except the nitrogen bound (based on the compound models the last peak is expected to fall under HDO), since this should give a ratio of 1: 1: 2.3.

EXAMPLE 33 1 Platinum colloids were prepared by reducing the hexachloroplatinate solution by sodium citrate. The reduction was similar to that described by Brugger, et al., Except that the temperature was maintained at 90 ° C to give the uniform particle size (P. Brugger, P. Cuendet, M. Gatzel, J. Am. Chem. Soc, (1981), 103 page 2923). K2PtCI6 (40 mg) was dissolved in 300 mL of distilled water and the solution was heated to 90 ° C. An aqueous solution of sodium citrate (30 mL, 1% weight percent sodium citrate) was added and the solution was stirred for 3 hours. After the colloidal suspension was cooled to room temperature, Amberlite-MB-1 was added changing to resin and the mixture was stirred to remove the excess citrate until the conductivity of the solution was less than 5 μS / cm.

EXAMPLE 34 Increase in zirconium bisphosphonate-viologen (ZrVP) in PVP-C4P PVP-CP polymer (5 mg) was dissolved in 50 ml of colloidal suspension Pt described above. The weight ratio of Pt: polymer is 1: 2.5. After the mixture was stirred for 1 hour to reach equilibrium, 0.3 gm of ZrOCI2 »8H2? was dissolved in the PVP-C4P / Pt suspension. The mixture was stirred at room temperature overnight to complete the reaction of Zr4 + ions with the phosphonate groups of the polymer. The mixture was then dialyzed against distilled water to remove the free ions. The short molecular weight of the dialysis tube used in the present was 12,000-15,000. The dialysis was carried out until the water conductivity was less than 5 mS / cm. The suspension was again poured into a flask, 0.04 g of viologen bisphosphonic acid was added and the mixture was stirred at 60 ° C overnight, a similar dialysis process was carried out at a conductivity of less than 5 mS / cm. The zirconium and bisphosphonate treatments were performed five times to increase the multiple layers of the materials.

EXAMPLE 35 Generation of Photochemical Hydrogen The generation of photochemical hydrogen was carried out by irradiation samples of the tempered ZrVP polymer in Pt colloids (Example 34) in EDTA solutions. The solutions were maintained in a 1 cm square cell maintained at 20 ° C through the photochemical experiment. A mixture of 4 ml of the sample suspension and 1 ml of 0.1 M NaEDTA (sacrifice reduction agent) was vigorously degassed by bubbling N2 through the suspension prior to photosynthesis. The sample was then irradiated with an arc lamp 200 Watts Hg / Xe. Hydrogen levels were measured by GC. Photolysis of a suspension sample with 11 mg ZrPV (CI) in NaEDTA 0.05 M by a lamp of 200 w Hg / Xe leads to a hydrogen production ratio 0.25 mL / hr for the first hour. EDTA was used as a sacrificial reducing agent to return the system on top. The ratio of hydrogen production gradually decreased over the longer irradiation time. This is similar to that increase of thin multilayer films on the silica surface. Passing the light through a short circuit filter of 260 nm decreased the ratio of hydrogen production by approximately 50%, but produced approximately 20% more hydrogen in a longer period of time. The dependence of the wavelength by photoproduction of hydrogen in this system well correlated with that observed in the formation of the state of charge separated in both samples of thin film and microcrystalline ZrPV (Cl).

EXAMPLE 36 Sample and substrate preparation .. PVP-C4P polymer was synthesized (molecular weight = 100,000) of the poly (4-vinylpyridine) and diethyl, 4-bromobutyl phosphonate by the method described in Example 32. • H 2 O 3 PCH 2 CH 2 (bipyridinium) CH 2 CH 2 P 0 3 H 2 Cl 2 (V 2 P) was prepared as described in Example 1. The microplates Silicone polished single crystal and silica combined microscopic (quartz) sliding (-1x3 cm2) and palladium and platinum sheet, gold 0.05 -0.1mm thick (-1x0.5 cm2) was used as substrate. They were cleaned before use with a mixture of concentrated H2SO4 and 30% H202 (v / v 3: 1), rinsed vigorously with distilled water and heated at 500 ° C overnight to provide a dehydroxylated surface.

Surface initiation procedure. A silicone chip, quartz transparency or metal sheet band were immersed in a 0.5% aqueous solution (w / w) of PVP-C4P. After 5 minutes, the transparency of the solution was removed and dried by pure blowing N2. The thin layer of the 80 mM solution of ZrOCI2 was applied to the surface of the transparency to achieve crosslinking of the polymer phosphonic acid residues, and the film was air dried. To ensure that the polymer was completely cross-linked with Zr4 + ions, the process was repeated twice. The transparency was then washed with distilled water to remove extra surfaces.

Film increase _ Multilayers of compound ZrPV (CI) were produced on the zirconium-rich surfaces by repeatedly submerging the initialized substrate in the 10 mM V2P aqueous solution at 80 ° C for 4 hours (step 1), then the aqueous solution ZrOC. 60 mM at room temperature for 2 hours (step 2). The surface was rinsed thoroughly with distilled water between dives (stage 3). Steps 1-3 constitute a treatment cycle. Several films were made by repetition at 15 cycles. In the last stage 2 cycle was usually omitted.

EXAMPLE 37 The microscopic atomic force (AFM) images were obtained with NanoScope III Scanning Probe Microscope (Digital Instruments). The surface is reflected in a branching mode with corbels (typical 320-360 kHzF0). The AFM images (0.5x0.5μm2) of the samples reveal their suitable characteristics and demonstrate that the structure and thickness of the films prepared in the manner shown depends on the nature of the substrate. All the samples showed a significant increase in RMS roughness in the film increment. The examination of the AFM images shows that in all cases the materials increase in the surface consisting of microcrystallites. It is in contrast to the increase of multilayer films of Zn and Cu alkanebisphosphonate (Yang, H. C, K. Aoki, H.-G. Hong, DD Sackett, MF Arendt, S. -L. Yau, CM Bell, TE Mallouk J. Am. Chem. Soc. 1993, 115, 11855-11862.) Which results in smoothing of the rough surface. The crystals are smaller in the case of quartz and silicone substrates and larger in the case of metals. This seems to be uncorrelated directly between the total rugosity of the film and the crystal size, as well as between the roughness of the sparse substrate and the film in it. Quartz films consist of small crystals evenly distributed on the surface. The gold and platinum films are made of crystals a little longer than those in quartz, but there is still uniformity distributed in gold and tend to be added in longer agglomerates in platinum. The increase of films in Pd leads to long crystals that appear agglomerated in even longer islands. No difference was observed in the untreated AFM images and PVP-C4P treated substrates.

EXAMPLE 38 Cyclic voltammograms (CV) were recorded on Au, Pt and Pd electrodes (the working surface area -0.3 cm2) covered with ZrPV (CI) films as described above in Examples 36-37. PAR Potentiostat / Galvanostst Model 283 was used. An electrode counter (Pt wire) was separated from the worked aqueous 0.1M KCI solution by a porous glass agglomeration. The reference was a saturated calomel electrode (SCE). Oxygen was removed from the worked solution by bubbling with argon gas of high purity. Cyclic voltammograms of films ZrPV (CI) on Au electrodes, Pt and Pd show large peaks with reduction potentials (E ° surf = (EP? C + Ep, a) / 2, where Ep c and Ep a are potential cathode and anodic peaks, respectively) close to -0.77 V, with peak-to-peak separations (_E) of 120-200 mV. _E is slightly affected by the number of treatments in gold and platinum but shows no change for palladium. This _E increased as the experimental time scale is shortened (at high potential screening rates) indicate the kinetic limitations for transfer change that are more serious for anodic processes and for Pt and Pd electrodes. The integration of the reduction peaks in cyclic voltammograms confirms that the amount of ZrPV (CI) accumulated on the surface after the same number of treatment is different for different substrates. Much more material is being accumulated in Pt and Pd than Au. These results are consistent with the AFM data which indicates that the films in Pt and Pd are rougher than Au. Valuations based on integrals obtained from cyclic voltammograms indicate that each treatment cycle does not result in a single layer that covers but adds 3-6 layers that depend on substrate. The values E ° bU, f are 100 mV more negative than E ° for the reduction of an electron of V2P in the aqueous solution that are found to be -0.67 V (__E = 70 mVKJos which close to the redox potential reported by the coupling radical redox of dication / methylviologen cation (-0.69 V) .100 mV changes from E ° SUrf to the most negative values in the films as compared to V2P in the solution is not significantly affected by the number of times the substrate it is treated with Zr 4 + and the bisphosphonate viologen.

EXAMPLE 39 The blue color should be observed for the separation of photochemical charge in ZrPV (CI) in layers with poly-carbon templates, if the sample is photolized with a lamp of 200 w Hg / Xe under vacuum or under N2. Five minutes of photolysis leads to the formation of reduced viologen monomer and dimer in the irradiated sample. The electron spectrum shows the decrease band of 270 nm, and the appearance of the bands at 405, 605 nm and 380, 540 nm, corresponding to the monomer and dimer respectively. The electronic spectrum of the ZrPV (CI) is copied with several tempered soaps, as well as the air sensitivity of the sample. Photoreducide suggests that this multilayer compound is not packed tightly like the microcrystalline samples of ZrPV (CI). The treatment of a photoreducted suspension sample of ZrPV (Ci) in layers with air template directs to whiten completely within a matter of seconds, while microcrystalline samples require hours to days. Oxygen appears to spread freely through more open framework of the compounds. This is probably related to the template type characteristic of the template materials. EXAMPLE 40 Synthesis of 1,4-bis (4-phosphonobutylaminojbenzene (PAPD) (H203P- (CH2) 4-NHC6H4NH- (CH2) 4-P03H2) 5.0 g (0.046 mole) of p-phenylenediamine are brought to reflux. 15.6 g (0.114) of diethyl 4-bromobutyl phosphonate in 50 ml of THF in the presence of 1.56 g of NaH for 2 days After cooling, 50 ml of H20 is slowly added to the reaction mixture. times with 100 ml portions of CHCl3, the TLC showed the desired product in the CHCI3 layer, decolorized carbon was added to the CHCl3 solution and stirred for 1 h, then filtered, the CHCl3 solution was taken to dryness to an oil coffee 1H NMR (D2), 6.9 (4H, s), 3.1 (4H, t), 1.5 (12H, m) ppm Mass Spectrum: EI, measured M 1 = 492, theoretical M + 1 = 492; Main: 446, 354, 193, 137, 125. The ester was acid hydrolyzed by reflux in 6M HCl for two days.The acid was precipitated from this solution by the addition of acetone.

EXAMPLE 41 Synthesis of bisphosphonic acid salts of viologen [N, N'-bis (2-phosphonoethyl) 4,4'-bipyridine dihalide] (PV (X)): (H2? 3P- (CH2) 2-4,4 '-bipyridinium- (CH2) 2-P03H2). The viologen dichloride salt was prepared by reaction of 1.2 g (6.0 mmoles) of diethyl (2-chloroethyl) phosphonate with 0.47 g (3.0 mmoles) of 4, 4'-bipyridine in 120 ml of H 0 at 110 ° C for 40 hours. The ester was converted to the acid by refluxing in 6M HCl. The viologen dibromide salt was prepared as above except that diethyl-2-bromoethylphosphonate was used. The ester was dried under vacuum then converted to the acid by stirring overnight with three fold excesses of bromotrimethyl silane in dry acetonitrile followed by the addition of water. The viologen diiodide salt was prepared by the addition of AgPF6 to a solution of the viologen dichloride salt to precipitate AgCl. When the dihexafluorophosphate salt of biologen was isolated, an excess of Kl was added to the solution. The resulting reddish-brown solid was isolated by filtration. All the viologen salts were purified by dissolving in a minimum volume of water and precipitated by the slow addition of isopropyl alcohol. 1H NMR of all salts, (D20), 9.1 (4H, d), 8.5 (4H, d), 4.2 (4H, m), 2.0 (4H, m) ppm.

EXAMPLE 42 Synthesis of 4,4'-bis (2-phosphonoethyl) biphenyl (EPB): (H203P- (CH2) - (4,4'-biphenyl) - (CH2) 2-P03H2). 3.8 g (9.4 mmoles) diiodobiphenyl, 3.23 g, are added in a dry glass pressure tube. (20 mmoles) of d-ethyl vinylphosphonate, 0.05 g (0.2 mmoles) of palladium acetate and 0.23 g (0.7 min) of t ritol i Ifosf ina dissolved in 20 ml of dry triethylamine and 30 ml of dry toluene. The mixture is purged with Ar for 10 minutes then closed. The reaction was heated at 110 ° C with stirring for 24 hours. The approximate biphenyl yield of 4,4'-bis (diethylvinylphosphonate) was 30% - __ 1 H NMR (DMSO), 7. 8 (8H, rn), 7.4 (2H, d), 6.5 (2H, t), 4.0 (8H, m), 1.2 (12H, t) ppm. Mass spectrum: E.l. + 1 measured = 478, theoretical M + = 478; Main fragments: 369, 341, 313, 231, 202. This intermediate was hydrogenated with Pd / C in methanol. To the ester was added 20 ml of dry CH 2 Cl 2 and 1 ml of bromotrimethyl silane. After addition of water and separation with ether, the acid was isolated. 1 H NMR (CDCl 3) 7.4 (8H, d), 2.9 (4H, m), 2.1 (4H, m) ppm.

EXAMPLE 43 Synthesis of N, N'-bis (2-phosphonoethyl) -4,4'-bis (4-vinylpyridine) biphenyl dichloride (VPB): (H2O_P- (CH _) _- NC_H4-CH = CH- (4 , 4, -biphenyl) -CH = CH-C5H4N- (CH2) 2-P03H2). 1.04g was added in a dry glass pressure tube. (2.6 mmoles) of diiodobiphenyl, 3.0 mL (27 mmoles) of vinylpyridine, 0.09 g. (0.36 mmoles) of palladium acetate and 0.2 g (0.6 mmoles) t rito I i os if dissolved in 8 mL of dry triethylamine and 20 mL of dry acetonitrile. The mixture was purged with Ar for 15 minutes then closed. The reaction was heated to 110 ° C with stirring for 48 hours. The approximate yield of 4,4'-bis (4-vinylpyridine) biphenyl was 30%. 1HMR (CDCl 3), 8.9 (4H, d), 8.2 (4H, d), 8.1 (4H, d), 7.9 (4H, d), 7.6 (4H, d) ppm. Mass Spectrum: E.I., M + 1 measured = 360, M + 1 theoretical = 360; Main fragments: 266, 180, 91. 0.3 g (0.83 mmoles) of these were combined with 0.5 g (2.0 mmoles) of diethyl-2-bromoethylphosphonate in a round bottom flask and dissolved in 10 mL of DMF. The mixture was heated at 90 ° C for 16 hours until a yellow precipitate was observed. DMF was distilled under vacuum and the yellow ester was obtained. 10 mL of dry CH2Cl2 and 1 mL of bromotrimethyl silane were added to the ester. The mixture was stirred for 12 hours, then H20 was added causing an orange precipitate. The solid was isolated and crystallized from H20 by the slow addition of cold metal. NMR showed the disappearance of the ester peaks indicating that the acid was formed. 1 H NMR (DMSO), 8.42 (2H, d), 8.22 (4H, d), 7.55 (8H, m), 7.04 (4H, d), 4.26 (4H, t), 1.41 (4H, t) ppm.

EXAMPLE 44 Au / 4 photoelectrode preparation (ZrAV2P) The gold leaf (0.1 mm thickness) was cut into 2x50 mm2 pieces and cleaned in a concentrated HN03 for 10 minutes. Then it was rinsed thoroughly with distilled water and 100% ethanol. Self-assembled (3-mercaptopropyl) trimethoxysilane (3-MPT) films were formed by immersing the Au sheet in the 20 mM 3-MPT solution in 100% ethanol for 2 hours at room temperature. (See, for example, W.R. Thompson, J.E. Pemberton, Thin Sol-Gel Silica Films on (3-Mercaptopropyl) trimetoxysilane modified Ag and Au electrodes, Chem. Mater. 7, 130-136 (1995)). Then Au was rinsed with 100% ethanol and allowed to air dry. The hydrolysis of 3-MPT surface modified then was achieved by immersion in an aqueous 0.1 M HCl solution for 12 hours at room temperature. The surface was zirconated by immersing the leaf in ZrOCI2 60 mM aqueous solution for 2 hours at room temperature. AV2P (H2? 3P- (CH2) -C6H4-NC5H4-C5H4N-C6H4- (CH2) -P03H2) was synthesized using standard literature procedures. The ZrAV2P film was increased by the alternating treatment in 10 mM AV2P solution at 80 ° C for 4 hours and then in the 60 mM ZrOCI2 aqueous solution at room temperature for 2 hours. Then the two stages were repeated 4 times each (4 cycles of deposition.).

EXAMPLE 45 Photochemistry of the Film of Example 44 Photoelectrochemical measurements were made in a quartz cell containing 0.1 M NaCI04 (supporting electrolyte) and 10-2 M Eu (N03) 3 (electron acceptor). The dark currents and photocurrents were measured PAR M283 Potentiostat / Galvanostat using M270 chronoamometer software. An Au / 4 electrode (ZrAV2P) prepared in Example 44 was used as a working electrode, with Pt serving as a counter electrode (2 electrode circuits) and, to a separate extent, with SCE as a reference electrode and Pt as a counter electrode (3 electrode circuits). The Au / 4 electrode (ZrAV2P) was illuminated with a 200 W Hg / Xe lamp with a UV light cut filter below 360 nm. The illuminated area of the electrode was -0.5 cm2. The results of these tests were shown in the graph of figure 5. 9 EXAMPLE 46 Photochemistry of the film of Example 44 The photoelectrochemical measurements were made in a quartz cell containing 0.1 M NaCl04 (supporting electrolyte) and Eu (N03) 3 10-2 M (electron acceptor). The dark and photocurrent currents were measured with PAR M283 Potentiostat / Galvanostat using M270 chronoamometer software. An Au / 4 electrode (ZrAV2P) prepared in Example '44 was used as a working electrode, with Pt serving as a counter electrode (2 electrode circuits), and, in a separation measure with SCE as a reference electrode I and Pt as a counter electrode (3 electrode circuits). The Au / 4 electrode (ZrAV2P) was illuminated with 200 W Hg / Xe lamp. The illuminated area of the electrode was -0.5 cm2. The results of these tests are shown in the graph of Figure 6.

EXAMPLE 47 Preparation of photoelectrode Au / 4ZrDABP) / 4 (ZrAV2P): The gold leaf (0.1 mm thickness) was cut into pieces of 2x50 mm2 and cleaned in an HN03 concentrate for 10 minutes, then rinsed thoroughly with distilled water and 100% ethanol.

Self-assembling films of (3-mercaptopropyl) trimethoxysilane (3-MPT) were formed by immersing the Au sheet in 20 mM 3-MPT solution in 100% ethanol for 2 hours at room temperature. See for example W.R. Thompson, J.E. Pemberton, 77? / 77, Sol-Gel Silica Films on (3-Mercaptopropyl) trimetoxysilane modified Ag and Au electrodes, Chem, Mater. 7. 130-136 (1995)). Au was then rinsed with 100% ethanol and allowed to air dry. The hydrolysis of modified 3-MPT surface was then achieved by immersion in an aqueous 0.1 M HCl solution for 12 hours at room temperature. The surface was zirconated by submerging the sheet in 60 mM ZrOCI2 aqueous solution for 2 hours at room temperature. DABP (H203P- (CH2) -C6H4-N = N-C6H4- (CH2) -P03H2) was synthesized using the procedures of the standard literature. The ZrDABP / ZrAV2P film was increased by alternating treatment in 10mM DABP solution at 80 ° C for 4 hours in a 60 mM ZrOCI2 aqueous solution at room temperature during 2 hours (4 cycles of deposition), then by alternating treatment in 10 mM AV2P solution at 80 ° C for 4 hours and in the 60 mM ZrOCI2 aqueous solution at room temperature during 2 hours (after 4 cycles of deposition). 9-1 EXAMPLE 48 Physical Focality of the Film of Example 47 The photoelectrochemical measurements were made in a quartz cell containing NaCl0 0.1M (supporting electrolytes) and Eu (N0 3) 3 10-2M (electron acceptor). The dark and photocurrent currents were measured with PAR M283 Potentiostat / Galvanostat using M270 chronoammeter software. An Au / 4 (ZrDABP) / 4 (ZrAV2P) electrode prepared in Example 47 was used as a working electrode, with Pt serving as a counter electrode (2 electrode circuits), and, in a separate measurement, with SCE as a reference electrode and Pt as a counter electrode (3 electrode circuits). The electrode Au / 4 (ZrDABP) / 4 (ZrAV2P) was illuminated with a lamp 200 W Hg / Xe with a separate UV light filter below 420 nm. The illuminated area of the electrode was -0.5 cm2. The results of these tests are shown in the graph of Figure 7. EXAMPLE 49 Photochemistry of the film of Example 47 The photoelectrochemical measurements were made in a quartz cell containing 0.1 M NaCl04 (supporting electrolyte) and Eu (N03) 3 10-2M (electron acceptor). Dark currents and photocurrents were measured with PAR M283 Potentiostat / Galvanostat using M270 chronoamperometric software. An Au / 4 (ZrDABP) / 4 (ZrAV2P) electrode prepared in Example 47 was used as a working electrode, with Pt serving as a counter electrode (2 electrode circuits) and, in a separate measurement with SCE as a reference electrode and Pt as a counter electrode (3 electrode circuits). The Au / 4 electrode (ZrDABP) / 4 (ZrAV2P) was illuminated with a 200 W Hg / Xe lamp with a separate UV light filter below 360 nm. The illuminated area of the electrode was -0.5 cm2. The results of these tests are shown in the graph of Figure 8.

EXAMPLE 50 Photochemistry of the film of Example 47 The photoelectrochemical measurements were made in a quartz cell containing 0.1 M NaCl0 (supporting electrolyte) and Eu (N03) 3 10-2 M (electron acceptor). The dark and photocurrent currents were measured with PAR M283 Potentiostat / Galvanostat using M270 chronoammeter software. An Au / 4 (ZrDABP) / 4 (ZrAV2P) electrode prepared in Example 47 was used as a working electrode, with Pt serving as a counter electrode (2 electrode circuits) and, in a separate measurement with SCE as an electrode. reference electrode and Pt as a counter electrode (3 electrode circuits). The electrode Au / 4 (ZrDABP) / 4 (ZrAV2P) was illuminated with a lamp of 200 W Hg / Xe. The illuminated area of the electrode was -0.5 cm2. The results of these tests are shown in the graph of Figure 9.

EXAMPLE 51 Preparation of the photoelectrode Au / 4 (ZrPAPD) / 4 (ZrAV2P): The gold leaf (0.1 mm thickness) was cut into pieces of 2x50 mm2 and cleaned in an HN03 concentrate for 10 minutes, then rinsed to conscience with distilled water and 100% ethanol. Self-assembly films of (3-MPT) were formed by immersing the Au sheet in 20 mM 3-MPT solution in 100% ethanol for 2 hours at room temperature. See for example W. R. Thompson, J. E. Pemberton, Thin, Sol-Gel Silica Films on (3-Mercaptopropyl) trimetoxysilane modified Ag and Au electrodes, Chem, Mater. 7. 130-136 (1995)). The Au was then rinsed with 100% ethanol and allowed to air dry. The hydrolysis of modified 3-MPT surface was then achieved by immersion in an aqueous 0.1 M HCl solution for 12 hours at room temperature. The surface was zirconated by submerging the sheet in 60 mM aqueous ZrOCI2 solution for 2 hours at room temperature. The ZrDABP / ZrAV2P film was increased by the alternating treatment in 10mM DABP solution at 80 ° C for 4 hours and in a 60 mM ZrOCI2 aqueous solution at room temperature for 2 hours (4 cycles of deposition), and then by alternating treatment in 10 mM AV2P solution at 80 ° C for 4 hours and in the 60 mM ZrOCI2 aqueous solution at room temperature for 2 hours (then 4 cycles of deposition).

EXAMPLE 52 Film Photo of Example 51 The photoelectrochemical measurements were performed in a quartz cell containing 0.1 M NaCl04 (supporting electrolyte) and Eu (N03) 3 10-2 M (electron acceptor). Dark currents and photocurrents were measured with PAR M283 Potentiostat / Galvanostat using M270 chronoammeter software. An Au / 4 electrode (ZrAV2P) prepared in Example 51 was used as a working electrode, with either Pt serving as a counter electrode (2 electrode circuits) or with SCE as a reference electrode and Pt as a counter electrode (3 electrode circuits). The electrode Au / 4 (ZrPAPD) / 4 (ZrAV2P) was illuminated with a lamp of 200 W Hg / Xe. The illuminated area of the electrode was -0.5 cm2. The results of these tests were shown in the graph of Figure 10.

EXAMPLE 53 Electrode preparation Au / 4 (PAPD) / 4 (PV) A gold substrate was treated with thiophosphonic acid (HS (CH2) 4P03H2). The surface was then zirconate (See for example W. R. Thompson, J. E. Pemberton, Thin Sol-Gel Silica Films on (3-Mercaptopropyl) trimetoxysilane modified Ag and Au electrodes, Chem. Mater. 7, 130-136 (1995)). The ZrPAPD / ZrPV film was increased by alternating treatment in the PAPD solution and in the ZrOCI2 aqueous solution at room temperature (4 cycles of deposition), then by alternate treatment in PV solution and in aqueous solution ZrOCI2 at room temperature (immediately after 4 cycles of deposition ).

EXAMPLE 54 Photochemistry of Example 53 Current density versus time for the Au / 4 (PAPD) / 4 (PV) electrode. The potential was set at 0.0V against SCE. The currents were obtained using two electrode cells in an aqueous 0.1 M NaCl0 solution. The dark current is measured when the sample is irradiated without light. The current against time was verified with zero applied potential in the dark until the stabilized system, usually 3-4 minutes. The Au ° PAPD / PV electrode was then exposed to light for approximately the same length of time and was then cycled back and forth between the dark and exposed light. The photocurrents were recorded using a PAR potientiostat / Galvanostat Model 683 in an aqueous solution of 0.1 M NaCIO from two electrode cells. The worked electrode was the covered film gold Au ° PAPD / PV of Example 53 and the reference electrode (SCE) also served as the counter electrode. The measurements were also repeated using three electrode cells and the results were identical, although the signal-to-noise ratio decreased. The results are shown in the graph of figure 11.

EXAMPLE 55 Au / 4 (PV) / 4 (PAPD) electrode preparation: A gold substrate was treated with thiophosphonic acid (HS (CH2) 4P03H2). The surface was then zirconate. (See, for example, W. R. Thompson, J. E. Pemberton, Thin Sol-Gel Sílíca Films on (3-Mercapt? propyl) trimetoxysilane modified Ag and Au electrodes, Chem. Mater. 7, 130-136 (1995)). ZrPV / ZrPAPD was increased by alternating treatment in the PV solution and in aqueous solution ZrOCI2 at room temperature (4 cycles of deposition), then by alternating treatment in PAPD solution and in aqueous solution ZrOCI2 at room temperature (immediately after 4 cycles of deposition ).

EXAMPLE 56 Photochemistry of Example 55 Current density versus time for the Au / 4 (PV) / 4 electrode (PAPD) The potential at 0.0V against SCE was established. The currents were obtained using two electrode cells in an aqueous solution of 0.1 M EDTA under anaerobic conditions. The dark current is measured when no light is irradiating the sample. Photocorrients are obtained using a lamp of 200 W Hg / Xe- without filtering. Positive currents indicate the flow of electrons to the gold electrode. The results are shown in the graph of figure 12.

EXAMPLE 57 Preparation of Au / 4 (PAPD) / 4 electrode (VBP): A gold substrate was treated with thiophosphonic acid (HS (CU _), tPOjHj). The surface was then zirconated (See, for example, W. R. Thompson, J. E. Pemberton, Thin Sol-Gel Silica Films on (3-Mercaptopropyl) trimetoxysilane modified Ag and Au electrodes, Chem. Mater. 7, 130-136 (1995)). ZrPAPD / ZrPV was increased by alternating treatment in PAPD solution and in aqueous solution ZrOCI2 at room temperature (4 cycles of deposition), then by alternate treatment in VBP solution and in aqueous solution ZrOCI2 at room temperature (after 4 cycles of deposition).

EXAMPLE 58 Photochemistry of Example 57 Current density versus time for the Au / 4 (PAPD) / 4 electrode (VBP). The potential at 0.0V against SCE was established. The currents were obtained using two electrode cells in an aqueous 0.1 M NaCl0 solution. The dark current was measured when no light is irradiating the sample. The photocurrents were obtained using a 200 W Hg / Xe-lamp with a UV filter (> 330 nm). The negative current indicates the flow of electrons from the gold electrode.

The results are shown in the graph of the figure 13.

Claims (3)

1. A photovoltaic device comprising a support substrate having on its surface a heterolaminar film having one or two charge donor layers and one or more charge acceptor layers, each characterized in that it comprises: (i) a plurality of complexes of the formula: [(Y103-Z-Y203) Me?] / (- / í * p (Xq-) where each of Y1 and Y2, independently of one another, is phosphorus or arsenic; Z is a divalent group that reversibly forms a reduced stable form and an oxidized stable form X is an anion; Me? is Me1pWm, where Me1 is a divalent, trivalent or tetravalent metal of Group III, IVA, or IVB having an atomic number of at least 21 or a lanthanide, W is an anion, n is 1, 2 or 3, m is 0, 1, 2, 3, 0 4, k has a value of 1 to about 250 p has a value of 0, 1, 2, or 3, and q is the charge in X, where each of Y1, Y2, Z and Me1 can be different for each layer, i) one or more load-generating layers between a or more charge donor layers and one or more charge acceptor layers; wherein the film is attached to the substrate through a bonding means.

2. The photovoltaic device according to claim 1, characterized in that the film further comprises colloidal particles of at least one metal of group VIII at zero valency trapped within the complexes by the Me1 atoms.

3. The photovoltaic device according to claim 1, characterized in that the charge generating layer comprises a stybazole or an asymmetric diazole.