TW505617B - Electron acceptor compositions on polymer templates and the catalytic production of hydrogen peroxide - 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. 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 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

^ 5617. Description of the Invention (Technical Field / The present invention relates to a stable electron acceptor composition that is effective and maintains a charge-separated state of photoluminescence. BACKGROUND OF THE INVENTION ^ Solar energy can efficiently produce long-term photoluminescence. The charge separation (by forming long-lived free pairs (a state achieved in photo-synthetic systems) is utilized and stored. Several artificial systems that can effectively undergo photon-electron transfer are reported, unfortunately Often, thermal back electron transfer is performed at a sensible rate, which limits the availability of these systems. Therefore, a system is needed that can transfer light and charge effectively and form it in the air. The long-term surviving state of charge separation is that charge separation in the system generally includes photo-excited donors and suitable

Departures: (la) D + hv ― &gt; D * (lb) D * + A- UD (2) D ten + A '― D + A (Please read the precautions on the back before filling this page) ^ ^ 1 -1 I — .....!-, -Kou m Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs The cations and anions produced in this method are better oxidants and reducing agents than neutral ground state molecules, respectively. In order to collect the light and put it into this system, before the pen f is transferred back (Equation 2) to generate the starting material, the oxidizing and reducing power of the species produced by the light is needed. It is desirable to control the rapid reheating electron transfer reaction which is not produced by this photochemistry. One method is to incorporate the donor and recipient into a solid matrix. Individual components in the state of charge separation have appropriate ground potentials for carrying out water -4- melon paper, so the standard is Chinese National Standard (CNS) A4 (210X297 mm) 010 A7 _____B7______ 5. Description of the invention (2) Reduction reaction and Oxidation reaction. Unfortunately, these direct reactions are limited in kinetics, requiring catalysts to overcome this dynamic barrier. Colloidal ‘particles are an ideal catalyst for reducing water to hydrazone :. In the system for reducing water and light, the electron transfer from the reduced redox (viologen) to the pt particles needs to be efficiently completed by electron transfer, so it is more likely to occur in the compounds and Pt particles. The high potential free electrons are in close contact. The platinum particles may be present in the reaction solution, or incorporated into the composition structure or both. Compounds that can perform reduction reactions using tritium gas as their reducing equivalents can be used as catalysts that convert a mixture of hydrogen and oxygen into hydrogen peroxide. Hydrogen peroxide is a very large amount of chemicals, with annual production in the United States exceeding 500 million hours. Several methods have been patented for the production of hydrogen peroxide, all of which rely on the following two reactions. The goals are to promote response (3) and prevent response (4). 〇2 Η 2 〇 2 (4) Η20 2 + Η 2 2 Η 2 〇 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs This reaction has been reported by several catalysts, including homogeneous and heterogeneous catalysts. The composition of the present invention can be prepared to maintain a charge-separated state of light emission, which enables the composition to be used for solar energy conversion and storage. In addition, the composition can reduce various metal ions to produce a zero-valent metal trapped in the matrix of the composition in a colloidal state. These zero-valent metal-containing latter substrates have various uses, such as being used for water decomposition to generate hydrogen and oxygen. In addition, the zero-valent metal matrix can be used, for example, in the production of hydrogen peroxide and methane oligomerization to form higher hydrocarbons for catalysis. SUMMARY OF THE INVENTION The present invention provides a multi-layered combination of parallel "pillars" and multi-layered paper. The paper size is reversed to the Chinese National Standard (CNS) 505617 Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 5. Description of the invention ( 3) The object 'which includes a bivalent electron acceptor moiety containing a phosphonate or kunate at each end' of each layer of parallel pillars is borrowed by () [VA), (IVB), (ΙΠ A) or (Π IB ) Group metal layer or lanthanum layer. The composite may further include at least one group V111 metal particle trapped in each layer of the composite at zero valence, and the composite may also be incorporated to provide about one of each electron accepting group. "Stalactites" or "stalagmites", which are end-capped arsenate or phosphonate ligands scattered by a series of cracked pillars. The composite can be used to convert and store solar energy and act as a catalyst for reduction reactions such as producing hydrogen peroxide from oxygen and hydrogen, producing tritium 2 gas from water, and reducing ketones to form alcohols. Brief Description of the Drawings Fig. 1 is a schematic diagram of a high-level structure of a substrate and a film of the present invention. Figure 2 is a schematic diagram of a solid composition incorporating the "stalactite" and "stalagmite" ligands of the present invention. FIG. 3 is a schematic diagram of a ligand solid incorporating the metal particles and “stalactites” and “stalagmites” of the present invention. A description of a preferred embodiment The present invention relates to a layering composition that includes two or more adjacent The metal layers' are each composed of a divalent, trivalent, or tetravalent metal atom or a lanthanum atom of 111, I ν A, IVB group having an atomic order of at least 21, which can form a bonding layer. The metal layer system Adjacently spaced and substantially parallel to each other and the substrate system, organic pillars are disposed therebetween and substantially perpendicular to the metal layer, and each of them is covalently connected to two adjacent metal layers. A gap is formed between the pillars and two adjacent metal layers. This layering composition can be -6-this paper size is applicable to the national standard (CNS) A4 specification (2iOX 297 g) (Please read the precautions on the back before filling this page ) Order printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs) 吣 617 A7 __ B7 V. Description of the invention (4) It is, for example, a thin film or a microcrystalline solid. The organic pillar is described by the following formula: I.-(Υ1〇 3-Z-Υ203)-Y1 and Y2 are separated from each other Don't be phosphorus or arsenic; z is an electron acceptor &lt; divalent group containing two negative ㈤ 値 J conjugated cation centers, where Z can alternate between a stable reduced state and a stable oxidation state; a sufficient number The anion is bound to the metal ions constituting the metal layer, so that the metal ions have an effective valence of +1 to +6, preferably +3 or +4. The anion spacer is formed by the pillar and the metal atom. In the crystal lattice to balance any free charge in the composition. In addition, the composition may include at least one kind of v J π metal particles trapped in the gap between the pillar and the adjacent metal layer with zero valence. Particles can function as two strong compositions, for example, as catalysts for reduction reactions. The group of mouthpieces can also include organic ligands placed between metal layers and between pillars that are covalently connected to each other to the metal layer. The ligand is described by the following formula: n. -Y3〇3-R3, which is scale or broken; and a non-reducible end-capping group. In a specific embodiment, the present invention relates to a film in which a thin film is placed on a supporting substrate. Above <composite composition. In this type, the most The layers of the substrate are bonded to the substrate by means of bonding. The substrate may be, for example, metal, glass, silicon oxide, polymer, semiconductor (such as silicon, gallium arsenide), and a composition thereof, such as a metal on an aluminum-based substrate. The substrate can be of any type, such as sheet, foil, paper ruler ~ Chinese national standard :, A4 specifications (210χϋ [] —, ih—nr-# — 丨 (Please read the precautions on the back before (Fill in this page) ---- ^ Order

J 505617 V. Description of the invention (Consumer cooperation of employees of the Central Bureau of Standards of the Ministry of Economic Affairs to print ancient shapes, films, electrodes, colloidal particles in suspension, polymer stencils, supports with the same surface area, etc. This film can be made of multiple columnar metals The composite is composed of each having the following formula: ΙΠ · &quot; L-[(Y103 ^ Z-Y203) MeY] k * k * p (Xq-) where L is a bonding method; Y1 and Y2 are each phosphorus or Arsenic; Z is a divalent radical that reversibly forms a stable reduced state and contains two co-dried cation centers with a common E ° red value; X is an anion; wherein M e 1 is an atom having an atomic number of at least 2 1 n I, I va, or I v B divalent, trivalent or tetravalent metal or lanthanum: W is an anion such as (but not limited to) a halide or pseudo-halide, or -oh; η is 1, 2 or 3; m is 0, 1, 2, 3, or 4; k has a 値 · of 1 to about 1,000; ρ has a 値 of 0, 1, 2, or 3; and q is a charge on the anion, for each additional In terms of k 値, an additional layer may be added to the film. Me 1 may be, for example, a Group A metal such as germanium, tin, or lead with an atomic order of at least 21, and a Group IVB metal such as titanium, zirconium, or hafnium, having Group III A metals with an atomic order of at least 21 such as 'indium' or inscriptions 'Group 111B metals such as sharp, period, or system such as lanthanum, cerium, spectrum, etc. Among them,', junction, donor, germanium, tin, and erroneous Better, JT—h • 丨 丨 nr surname 丨 — (Please read the notes on the back before filling this page)

、 1T paper rule (CNS) A4 size (210X 297 printed by the Central Consumers Bureau of the Ministry of Economic Affairs, printed by the Consumer Cooperatives 505617 A7 ___ _ B7 V. Description of the invention (6) and the knot is particularly good. Each of Y1 and Y2 is Phosphorus or arsenic, preferably phosphorus, so γ103 and γ203 are phosphonate or arsenate groups. Ζ is ... s phosphonate or phosphonate phosphate defined by \ 1 〇3 and γ2 Q 3 Divalent radical of a broken atom. In fact, the exact structure of the ζ group is less important than its electronic properties. First, it must contain two conjugated cation centers with a negative ^ ㈣ 値, that is, the reduction potential is lower than hydrogen; Z needs to exist in both a stable reduced state and a reversibly oxidized state. The two conjugated cation centers may be, for example, a tetravalent nitrogen atom that is a conjugated% component in an aromatic ring system. In a specific example Each tetravalent nitrogen atom is a ring component in an individual aromatic ring system, and two such ring systems, which may be the same or different structures, are directly bonded to one another through a covalent bond. Or 'each aromatic ring system May be one in which a pyridine, pyridine, or pyrimidine ring system is networked to one or more benzenes Or condensed polycyclic rings of the fluorene ring system, such as quinoids, isoquinones, acridines, phenylhydrazone [h] isoquinolines, etc. The two aromatic ring systems may be the same or different structures or may be Via a divalent conjugate system such as diazo (_N = N-), imino (-CH = N-), vinylidene, -1,3-diene-1,4-diyl, phenylene , Phenylene, etc. In another specific example, the two conjugated cation centers can be in a single-aromatic system such as ph enanthroline, 1,10-diazoanthracene and phen ,. Suitable as a typical dication structure of Z and thus containing 2,2-bipyridine, 3,3-bipyridine, 4,4-bipyridine, 2,2-bipyridine, 4,4-bipyridine Squat '4' 4 -Lian Yi 4 City j 4-[2-(4-ί 比 键)-乙 晞 基] p 比 键, and 4 * · [4, -9- This paper is again suitable for financial purposes House logo CNS) Λ4 »(210x797 ^ 11 &quot; '丨: |-:: 7 _——_ 蜷 丨 丨 (Please read the precautions on the back before filling this page) Order 505617 A7

(4-Ebony) phenyl]! 7 than the key. (Please read the notes on the back before filling out this page) / The aromatic system containing two common ions centers can be replaced without delay, such as with An environmental group of up to 6 carbon atoms or a group containing 6 carbon atoms is substituted by an alkoxy group. This substituent may be an influential influence on the cation center or an influence on the cation center by a steric or inducing effect. % 、 Although the two cation centers need to be connected by I, they are composed of z (the entire system does not need to be conjugated, so z can be connected to each core 3 and Y% through co-consumption or non-co-constituent bridge bonds. Therefore, a structure having a high demand for Z is a structure characterized by: iv-(R1) nZ ^ (R ^) m. Let Z 'be a divalent aromatic group containing at least 2 conjugated tetravalent nitrogen atoms; each η And m each have a 値 of 0 or 1; and each of ... and ... are each a divalent aliphatic or aromatic hydrocarbon group. Typically each of 11 and 0 is 1 and each of R1 & R2 each contains 6 or less Straight or branched divalent alkane chains of carbon atoms, for example, methylene 'ethylene, dimethylene, propyl_i, 2_diyl, 2_methylpropyl_i, 2_yl, Ding-1,2-diyl, jui, diyl, tetraphenylene, etc. The X group printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs is an anionic group, one or more of which (depending on k 値 and X charge) ) Can balance the cationic charge of Z and result in a net negative valence equal to (4-p * q). The intrinsic properties of X are relatively unimportant, and X can be, for example, a halogen anion such as a halide chloride, bromide, or iodide , Halides, sulfates, sulfonates, nitrates, osmium carbonate, citric acid, etc. The W group is an anionic group, and one or more of them (depending on the μe used, depending on the metal ion) will result in a MeYt net positive valence equal to (4- (p * q)). The actual nature of w is not important. W can be, for example, a halide, a pseudo-halide, a hydroxyl group, etc. -10- This paper size applies to China National Standard (CNS 210X 297 mm) 505617 A7 _____ B7 V. Description of the invention (8) Each compound shown in Formula 111 is bonded to the substrate via the described bonding method; therefore, a plurality of -L-YiC ^ -ZY ^ sMeY units on the substrate generate columns Each compound may contain a Z-containing unit ("pillar"), in this example, k 値 is 1, but preferably k 値 is greater than 1, so that Y2〇3) Me 'units become columnar polymer composites Monomers, where k is 2 to about 100, typically about 5 to about 50. This multilayer structure can be described by:

Such films can be prepared via a review of coordination chemistry similar to R011g et al., A sequential adsorption reaction of 9 7, 23 7 (1 990). The synthetic method and chemical measurement used can influence and determine the configuration and morphology of the resulting composition. One preparation method starts with a substrate, which is generally one with a hydroxyl end, such as metal (the surface of which contains metal oxides invariably), glass, silicon oxide, gallium arsenide, etc., which first starts with a hydroxyl reactant (introduced linkage) Component of method L or linkage method) derivatization. Typically, the last part of L will terminate and thus finally be incorporated into Y 1 〇3 via a metal atom M e 3 similar to Me 1, which is Me 1, 111, IVA or Group IVB bivalent, trivalent or tetravalent metal or lanthanum. Therefore, the substrate can be treated with a compound of the following formula, for example: -11- This paper 'long scale applies Chinese National Standard (CMS) A4 specification (210X297 public love) _ 疃! (Please read the precautions on the back before filling out this page) A-style square-square-square-square-square-square-square-square-square-square-square-edge-to-square .. 111 Substrate ... V. Consumption by employees of the Central Standards Bureau of the Ministry of Economic Affairs Cooperative cooperative printing 505617 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Α7 Β7 V. Description of invention (9) V 1 X &quot; R 1-Z-Y 3 〇3 Η 2 · 2 X, where R1 and Z are as defined above Γ3 is phosphorus or arsenic; χ is an anion similar to χ (X may but need not be the same anion appearing in the final complex), and X "is a reactive autogen such as gas or bromine. Thus the following intermediates are produced Substance: VII substrate-. 2 ×, the aforementioned reaction can be carried out in two stages. The substrate is first treated with a compound of the formula X ”_ r 1 _ Z-2 X, and then treated with phosphorus phosphonium such as phosphonium chloride or phosphonium bromide or the corresponding This product was treated with quinone. In one of the objectives of this specific example, the resulting linkage is similar to a repeating unit containing _Z-y3O3. Alternatively, 'the way of bonding may be different from the repeating unit. Therefore, the substrate can be crushed and burned, such as ammonium trialkyloxy, such as 3-aminopropyltriethoxy, and then the biochemical substrate is treated with phosphorous halogen such as phosphorium hafnium or thallium bromide or corresponding The arsenic hafnium halide treatment yields the following formula: VIII substrate-alkyl N Η-Y3 Ο 3 Η 2 Other examples of the bonding method include: IX substrate-〇-alkyl-υ3ο3η2 X substrate · alkyl- ο- υ3ο3η2 Another specific example uses an organic polymer stencil as a square bonding method for bonding the composition / film to the surface of a hydrophobic substrate (such as quartz, quartz, or metal). These polymer stencils are derivatized with phosphonates or phosphonates, such as by scaling; the hydroxyl side chains on the polymer backbone are treated with acid to produce side chain phosphates. The hydrophobic polymer template is adsorbed on the surface of the hydrophobic substrate, leaving free hydrophilic phosphonic acid / orthophosphate for cross-linking. The paper size of these side-bonded phosphonic acid or broken acid is applicable to Chinese National Standard (CNS) A4 specification (2.0 × 297 mm) I- I— n I I-- clothing-(Please read the precautions on the back before Fill in this page) Order 505617 A7 B7 V. Description of the invention (10 Cross-linking with ions of group III, IVA, I vB divalent, trivalent or tetravalent metal or lanthanum metal with atomic number of at least 2 1 to form the first Metal layer. These polymer stencils show good adhesion to the substrate surface and produce a highly porous structure (especially on metal substrates). The polymer can be any polymer with side chains that can be derivatized with phosphonate or arsenate Preferred polymers are those in which a portion (less than half of the pyrene) of the pyridyl group has been alkylated with X (CH2) nP03H2 (where X is an anion and η is 1 to 16 and 2 to 4). Polyethylene pyridine (abbreviated as pvp-CnP). For enhanced binding to Au, Ag and pt substrates, a polymer backbone with a side chain mercapto group is preferred. In another specific example, the substrate may be a polymer Model body. Films grown on polymer templates can grow in solution. Polymer bone The hydrophobic nature of the framework causes the polymer to condense into a sheet in the solution, while the side chain hydrophilic phosphonate or arsenate extends into the solution, similar to a lipid bilayer. This structure can be explained by the following formula:

XL 丨 「丨 丨 丨 ——_ 蜷 — 丨 (Please read the notes on the back before filling out this page), 11 Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

Colloidal particles of a Group VIII metal (preferably platinum) may be present in the solution. The hydrophobic nature of the aggregate agglomerates attracts the particles. The particles are then arrested: -13. Common Chinese National Standard for Paper Size (cns) μ size 505617 A7

V. Description of the invention (U B7: in the water competition environment between polymer backbones. This structure can be described by the formula II-I · XII.

Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. In this example, the substrate with a rich phosphonate or ^ surface &lt; substrate is then treated with a 2e reagent such as zirconium hafnium chloride. Metal ions are bound to and effectively cross-linked with phosphines, roots or phases to produce metal-rich surfaces and are characterized by "substrate. L, _Me3" (where L, _Me3 is equivalent to the bond of formula ⑴). The intermediate provides a way that its _ end is bonded to the substrate and the other end has a metal Me3 for further compounding. The substrate-L- is then separated from the reagent that provides Me3 ions, washed with water, and treated with a bisphosphonic acid or bisarsenic acid solution of the following formula: XIII h2y1o3-z-y2o3h2 * 2X1 where Y i, γ 2, Z, and χ 'As defined above. This reaction is completed within several hours, such as about 4 to 5 hours, and can be accelerated by using suitable heat, such as at about 80 to about 100 ° C. Layer deposition can be tracked spectrometer by wavelengths from about 260 to about 285 nm. For consistency, a range of 2s0-285 nm is usually used. One of the bases is combined with rich --------- (Please read the precautions on the back before filling this page) nn mm »1 j1 ·· VV τ · 1 · -14- Quick use of this paper scale China National Standard (CNS) A4 specification (210X297 mm) Printed by the Consumers 'Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 505617 5. Description of the invention (12 $? "Table:' while the other remains uncoordinated, resulting in a rich phosphine Gen or Kun acid (Intermediate on the surface, the intermediate can be described as follows: XIV substrate Qi Yang 2X, = substrate-L -MP-γΐ〇3 | γ2〇3Η2 · 2χ, since bisphosphonic acid or bisarsenic again ' Remove the 'sufficient wash I from the fenestrin, followed by

The Iu complex of formula 1 is prepared. LA repeats the foregoing sequence of the last two synthetic steps, that is, treatment with bisphosphonic acid or bisarsenic acid, followed by treatment with a reagent that can provide Mel ions, to produce a complex with tritium &quot; As measured, the number increases linearly with the number, and provides a convenient method for the formation of the tracking layer composition. The anterior suffix sequence is easily and better modified to capture zero-valent to Vin group metal atoms in the compound, such as indium,.! Bar, iron, junction, nickel, poor iron, or iridium. It was then treated with bisphosphonic acid or bisphosphonic acid, but the sample was immersed in a solution of the vm group metal, an ionic salt solution before being treated with a reagent for coke and Mel ions. After a short period of time, the metal ions in the sample were replaced with 2-chloroanion. The stoichiometry of this exchange will depend on the respective valence of the two anions. For example, the four gasification pin and the hexachloride surface each have a valence of · 2 and the right emulsion is the starting anion, the -anion of these metal anions will be exchangeable with two gas ions. After that, the reaction is repeated as described above, and the reaction can be repeated with a reagent capable of providing an M ion, as described above, and the reaction can be repeated until the desired k 値 is reached. Then it is repeated to simply expose the main, τ reduces the metal ions in the hydrogen to produce a zero μ-shaped heart (Umbra and colloidal state in the matrix of the composite. As mentioned earlier, this paper is suitable for money_ 丨「丨 丨 丨 (Please read the notes on the back before filling this page)

1T 15- 505617 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (13) The materials used in the production of hydrogen peroxide, methane oligomerization to form advanced hydrocarbons, and water decomposition to produce hydrogen and oxygen are: Highly effective catalyst. This composition can also be used to reduce various organic substrates. When a layer of compound is grown on a polymer template as a substrate, the above process is generally followed, but the sequential processing steps are separated by a dialysis step to remove unused reactants instead of cleaning. More than one Group VIII metal can be used in any sample, soluble salts of Group VIII metals that are different from one or more exchangers or one or more exchanges with Group VIII metals and then different Group νιπ metals X for. Therefore, the final reduction is a homogeneous composition in which two kinds of metal colloidal particles of group V111 having different chemical and electronic properties are captured in a single matrix. Preferred specific examples of these layered metal phosphonate compounding wheels (where Z is a redox) are found to be very effective in collecting solar radiation and converting it into stored chemical energy. The activation wavelength of this process is in the ultraviolet part of the spectrum. The energy storage reaction can be confirmed by the deep blue color displayed in the solid, which lasts for a long time in the air. This blue color is derived from a reduced redox compound. The reduced redox will react quickly when reduced in ##: However, it does not react in the solid because it is trapped inside the dense solid. Milk and other foreign reagents cannot approach the reactive inner layer of solids. 0 In order to make use of the chemical energy stored in these compounds — specific examples include multiple open pore structures. The opening 2: the incoming reagent is easy to access the chemical energy generated by the light. These ::::::: 16-

Applicable standards for this paper size (CNS,:! —— 蝌 · —I (Please read the precautions on the back before filling this page)

1T 505617 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. The description of the invention (14) includes a mixture of the first specific example of dispersed smaller ligands. These smaller components leave open space in this new solid, and a wide range of different smaller components with different properties and sizes can be used to prepare these solids' leading to very diverse solids. The general formula of the material of this second specific example is: XV. K * P (xm (Y3〇3R3) 2nMeY: 1 wherein each Y1, Y2, Z, X, MeY, p, and q are as defined above; Y 3 is phosphorus or Arsenic; η has a plutonium of 0.1 to 0.8; and R3 is a non-reducible end-capping group. Compared with the first specific example material, which is made of a thin film on a substrate, the second specific example material is better Manufactured from crystalline or amorphous solids. But similar to the film of the first specific example, a zero-valent Group VIIi metal can be incorporated into these substrates./ As seen in formula XV, two different ligands make the metal Mei & Me2 complex 'its first-similar to those used in Formula 111, that is, Y 1 〇 Guang z _ γ 2' and each such ligand can be complexed with two metal atoms. The second ligand \ Ο3 R can be recombined with the sole metal atom. Therefore, the entire structure can be regarded as a series of parallel layers of the metal M e 1 and M e 2 and Υ 1 Ο 3-Zn-Υ 2 〇3 as a pillar. By The metal extensions between these pillars are y3o3r3 bases, which are between the pillars, stalactites and stalagmites. Therefore, the resulting structure has a gap of about each base. Series. The size of these gaps and the hydrophobicity of the α-defining surface are controlled by selecting R3. Therefore, one is to choose a relatively small R3 group such as methyl 'to produce a larger gap, or to choose a relatively large R 3 bases such as benzene • 17- ---- -.---------- (Please read the precautions on the back before filling out this page) Order 505617 Consumption Cooperation with Employees of the Central Standards Bureau of the Ministry of Economic Affairs Du printed Α7 Β7 V. Description of the invention (15) group or benzyl group, which results in relatively small gaps. Similarly, the nicotinic group of R3, such as propyl, can be used to impart the hydrophobic nature of j and the defined surface of the gap or can be used to make it hydrophilic Groups such as carboxyl-substituted R 3 groups to reduce hydrophobicity. Examples of suitable R 3 groups include (but are not limited to): Η, C Η 3, CH 2 C 1 2, CH 2CH 3, CH 2 CH 2 CH 3, OH, 0- and 0 CH 3 〇 Due to these gaps, it is possible to introduce the Vln group metal after forming the composite, instead of reducing it to zero valence as described above after the etching step. Therefore, the compound of formula XV is a water-soluble anion of a V Π I metal Treatment of an aqueous solution of a salt and treatment of the resulting composition with hydrogen to produce a colloidal group VIII Metals. These compositions can be used as catalysts as described above. Furthermore, the gaps allow various molecules to pass into the composite, for example oxygen can enter the matrix and then oxidize the _ζ-group. Since -Z- The reduced state of the base is white and yellow, so the performance can be used to detect a very small amount of oxygen. In addition, the ability to control the size of the gap allows the material to be used for selective reactions. For example, if The size of the gap is selected to allow the former molecule to pass through rather than the larger molecule, and the benzophenone can be selectively reduced in a mixture of benzophenone and 3,5 · di-tert-butylbenzophenone. . This complex can be easily prepared by treating a mixture of R3Y3O3H2 and Η2γΐ〇3_ζ_ Υ203〇2 with a desired molar ratio with a metal ion source. This reaction can be carried out under reflux or hot liquid and the product can be easily separated and purified. These porous solids do not show photochemical activity in the air because oxygen easily diffuses into the interior of the solid. If porous solids are irradiated with ultraviolet light under anaerobic conditions, the same activated species will be formed, that is, the reduction observed for dense solids. 18- This paper size applies to China K family standard (CNS) A4 size (210 X 297) Quot) 蜷 — 丨 (Please read the notes on the back before filling in this page) Order 505617 Employee Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs printed A7 B7 5. Description of the invention (16) Electron receptor. Interestingly, the photochemical efficiency of children's open-celled solids is much greater than that of dense materials. Porous solids that are irradiated under anaerobic conditions are rapidly bleached if they are treated with air. Oxygen can diffuse freely into the solid and react with the reduced electron acceptor produced by light. The reaction product between the reduced electron acceptor and oxygen is hydrogen peroxide, so these materials can be used as photochemically produced hydrogen peroxide. The catalyst. It is desirable to extract photochemically stored energy by generating mobile high-energy chemical species that can diffuse out of solids. The goal is to incorporate colloidal metal particles into a preferred redox-containing solid ft. This | metal is known and can be used as a catalyst for the reaction between reduced redox and water to generate hydrogen. Experiments have successfully shown that the material of the second embodiment can be used to convert solar energy into chemical energy in a hydrogen state. The system = includes: 1) light produces reduced redox products, 2) transfers electrons from reduced oxygen ions to colloidal metal particles, 3) protonates metal particles, and 4) eliminates hydrogen. As a real catalyst, these materials will also accelerate the forward and reverse reactions, so if the "metallized" material is treated with hydrogen, it will produce some =: redox. Under this standard, these materials can be used as the reducing agent f2 chemical energy without the need to produce reduced redox products; hydrogen can be used to achieve the social effect. Therefore, this chemistry produces a system of reduced redox products. X «Clothing: 1) Add i to the metal particles, 2) Transfer electrons from the metal particles to μ sheep L 彳 Ci reduced molecules to form reduced Redox, and 3) Degradation of metal colloids "Quantitative reduction. The diagram of porous solids such as argon under a crane is shown in Figures 2 and 3. The following examples will further illustrate the nature of the present invention, but I + To limit its -19- This paper size applies Chinese National Standard (CNS) A4 specification (210X29? Mm) --------- ^ 衣 __ (Please read the precautions on the back before filling in this Page}-Ordered by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs to print 505617 Α7-------B7 V. Scope of the invention (17), the scope of the invention is only defined by the scope of the patent application with green attached. Example 1 2_ / Diethyl ethylphosphonate (2 5 g) and 4,4, -bipyridine (7.3 5 g) were refluxed in 1 2 5 m 1 of water for 3 days, and the same amount of concentrated hydrochloric acid was added and refluxed for several hours. The Luo solution was concentrated to 200ml by distillation under normal pressure, and was added dropwise with stirring 3 :) 0ml isopropanol while freezing in an ice bath The mixture. The formed solid was collected by vacuum filtration and washed with cold isopropanol to give dichloride, bis, bisphosphonium ethyl-4, bipyridine. NMR (D20) 9.1 (d), 8-5 (d ), 4.2 (m), 2.0 (m) ppm; NMR (D2〇) i5i, 147,128,% ppm; 31? NMR (D20) 17.8 (s) ppm; IR (Kbr) 31 12, 3014, 1640, 1555, 1) 06, 1443, 1358, 1281, 1175, 1112, 1020, 936, 816, 485 cm · 1 〇) In a similar manner, use 2,2-bipyridine, 3,3-bipyridine, 2,2 -synthesis 鉼 '4,4_biquine-like, 4, renylisoquine-like, 4] 2_ (4-pyridine) ethenyl] E bond, and 4_ [4- (4-pyridine ) Phenyl] pyridine to obtain 1 'bis-bisphosphinoethyl-2,2-bipyridine dichloride, 1,1,1-bisphosphinoethylethyl-3,3_bipyridine dichloride, respectively 1, diphosphinofluorenyl ethyl a, 2-bipyridoxine 'dichloride 1, 1, bisphosphinofluorenyl ethyl-4, 4-biquinol, digasified 1, bisphosphinofluorenyl ethyl -4,4-biisoquine-like, digassed 1 · phosphinophosphoranylethyl_4_ [2 azimuthron ethylpyridine) ethenyl] pyridine, and 1-phosphinophosphoniumethyl dichloride- 4 _ [4-(1 -Phosphinoethylethyl 4-pyridine) phenyl] pyridine. Corresponding by substitution For example, the acid is replaced by concentrated hydrobromic acid or sulfuric acid in the procedure of this example to obtain other cationic species such as the corresponding dibromide or disulfate. -20- This paper uses China 5155771 ^ 7 ^ I— 11 —— (Please read the notes on the back before filling in this page) Order 505617 Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (18) Example 2 Fusion silicon oxide flat substrate (9 χ2 5 cm) was washed with 30% hydrogen peroxide and concentrated sulfuric acid in a 1: 1 solution, dried at 2000 t for 1 hour, and then with 2% (v / v) 3-aminopropyl triethoxysilane at 5 It was treated in a refluxing solution of omi octane for 20 minutes. The substrate was washed with octane and acetonitrile and treated at room temperature with a solution of 10 μM of each phosphonium chloride and 2'6-dimethylpyridine in acetonitrile for 12 hours. After cleaning in water, the substrate was washed at room temperature with 6 5 mM zirconium hafnium chloride solution for 3 hours. The foregoing procedure is used to prepare a multilayer film on a different substrate such as a silicon wafer or a gold film of a vaporizer. Then the substrate sequentially performs the following two steps. A) After removing the condensed chloride, the sample was thoroughly washed with deionized water and gasified with 1,1 bisphosphonium ethyl, 4,4'-bipyridine at 6 m 2 for 4 hours and treated with Wash thoroughly with deionized water. (The absorbance was measured at 28.4 nm after the treatment, and the absorbance coefficient measured for bisphosphonic acid 4,4'-synthetic hinge at 26.5 nm was 24.0 MUcnr1). B) The sample was then treated with a 65 mM zirconium hafnium chloride solution at room temperature for 1 hour, and then washed thoroughly with deionized water. After completing steps A and B—cycles, a plurality of formulas I in which k 値 is 1 are obtained on a planar silicon oxide supporting substrate; [I metal complex. Each repetition of steps A and B cycles increases k 値 by 1, the number of layers and thus the number of cycles is related to the absorbance at 2 8 4 nm, which can be seen from the following: -21- This paper uses the Chinese national standard ( CNS) A4 specifications (2i〇X297 ^ Fl one by one (Please read the precautions on the back before filling this page)

1T 505617 A7 B7 V. Description of the invention (19) Number of layers absorption 0 0.057 I 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 II 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 --------- Clothing-(Please read the precautions on the back before filling out this page) «lm_ · mu ULr ^ V, \ 呑 Ministry of Economic Affairs Printed by the Consumer Standards Cooperative of the Central Bureau of Standards

123456789012 1X 1 1X Example 3 By replacing the 1,1'-bisphosphinophosphoranylethyl-4,4'-bipyridine dibromide in the procedure of Example 2, a series of multilayer composites with the following absorbances were obtained: Number of layers Absorptivity 0.083 0.098 0.113 0.157 0.182 0.239 0.286 0.350 0.353 0.391 0.465 0.557 -22- This paper rule applies to China National Standards (CNS) Λ4 specifications (2 i 0 X 297 mm) 505617 Employees' Cooperatives of China Standards Bureau, Ministry of Economic Affairs Print A7 _____B7 ________ 5. Description of the invention (2) Example 4 By using other metals instead of the knots in step B, such as G, Qin, tin, gallium, etc., you can also obtain high-quality films, as shown in the following procedures. The flat fused silica substrate (9x2 5 cm) was cleaned as in Example 2 and used Haller in j. Am. Chem. Soc. 100, 8050 (1978) deposits a layer of 3-aminopropyltriethoxysilane from the gas phase. The substrate was annealed as in Example 2, cleaned and treated with 10 ml of a 6 5 mM aqueous solution of chlorine for 3 hours at room temperature. (A) treated at 80 ° C with an aqueous solution containing 6 m Μ 1,1, -bisphosphinophosphoranylethyl-4,4, bipyridine and 20 m Μ sodium gaseous solution for 4 hours and ( (B) Alternating treatment with a 65 mM radon aqueous solution at room temperature for 1 hour. After each treatment, they were thoroughly washed with deionization, and then a series of multi-layer compositions characterized by a spectrum of 2 8 4 nm were produced. Layer number absorbance 1 0.052 2 0.086 4 0.175 6 0.250 8 0.304 1 0 0.3 84 12 0.5 18 Example 5 After performing one or more steps A but before performing the corresponding step b, let kw 'text in 6 m μ4 The procedure in Example 2 was modified by exchanging two trianionized platinum anions for two hours in an aqueous chlorodi-platinum solution for 0.5 hours, followed by step β as in Example 2. -23- X. Shizhang ~ 1 Applicable to Zhongshang State 豕 檩 standard (八) Eight materials threat (2⑴ 乂 2.97mm) — '^ &quot; &quot; —-1 ^ --- II ----- ( Please read the precautions on the back before filling this page) Order 505617 A7 B7 V. Description of the invention (21% after the last cycle of steps A and B 'The compound is circulated in water and hydrogen is passed into the mixture for 2 hours, so that the pin It was reduced to a zero-valent colloidal state and captured in the entire matrix. Example 6 The oxidized stone particles (1 §) were heated in a dried cypress for 1 hour, and then 150 ml of a zirconium hafnium aqueous solution (60 mM) was oxidized with Silicon (1 g) was disturbed at 60 ° C for 2 days. The solid was separated by filtration or centrifugation, washed 3 times with 150 ml of deionization, and washed with 150 ml of 1, 1, bisphosphonium ethyl-4, bipyridine. The 20 μM solution of the ingot was treated with agitation at 65 ° C. for 6 hours. The solid was separated from the aqueous solution and washed with deionized water 3 times. Then the solid was treated at room temperature with 150 m 1 hexachloride_platinum 2. The m μ solution was treated for 3 hours, so that one platinum hexachloride anion was substituted for two chloride anions. A solid solution of 150 m rn 1 and a 60 m solution was added to the solid and the slurry was at room temperature. Run for 3 hours and wash the rattan three times with deionization. Repeat the previous steps 4 times to prepare a five-layer composition containing platinum cations. Then treat the aqueous slurry of the platinum-plated material with hydrogen to convert the platinum ions into colloidal zero-valent metal Example 7 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Miscellaneous gas octahydrate (1.444 g, 4. · 8 mmol) was dissolved in 50 m 1 of water and added. 50% hydrofluoric acid (0.756 g, 19 mmol). To this was added 1 g of 1,1'-bisphosphinophosphoranylethyl-4,4, -bipyridine dichloride (2.2 mmol) and 0.5 16 g of 50% aqueous solution of 85% phosphoric acid (4.5 mmol), the reaction was refluxed for 7 days and the white crystalline product was filtered, washed with water, methanol and acetone and dried in air to obtain a mixed complex:- 24- This paper size applies to the China National Standard (CNS) 8-4 specification (2! 〇 &gt; &lt; 297 Ghost Magic 505617 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (22

Zr (〇3PCH2CH ^ l ^ -CH2CH2PO3 (cn2) 05. (〇3P〇H) X-ray diffraction analysis shows d = l44, infrared analysis is as follows: (IR (cm-i), 3126, 3056, 1633, 1562 , 1499, 1450, 1217, 105, 816, 738, 647, 612, 520, 471). The 31P NMR (ppm) is: 3 · 〇, -18 · 6, _24 5 〇 Example 8 -a Germanium chloride Octahydrate (0.21 g, 0.7 mm) was dissolved in 10 ml of water and 50% hydrofluoric acid (0.11 g, 2.8 mmol) was added. To this was added 0.5 g of dichloride 1, 1. Bisphosphonium ethyl 4,4, bipyridine (0.35 mm) and Q. 06 86 g of 85% osmic acid (0.6 mmol) in 10 ml aqueous solution, the solution was placed in a 4 5 ml Teflon bottle Adjust the total volume to 2 7, seal the bottle and heat it at 150 C for 6 days to obtain a mixed compound:

Zr (〇3PCH2CH2- 联 talking drum-Cl-I2C1I2P03 (C1-) 2) 0 5 · (〇3p〇H) X-ray diffraction analysis showed d = 144, infrared and 31P NMR (ppm) were the same as in Example 7. Example 9 Zirconium hafnium chloride octahydrate (0.36 g, 1.12 mmol) was dissolved in 10 ml of water and 50% hydrofluoric acid (0.179 g, 4.5 mmol) was added, and 0.25 g of an emulsified 1,1 'was added thereto. -Bisphosphonium ethyl-4,4'-Lian'e hinge (0.56 mmol) and 0.1 29 g 85% squat acid (0.11 mmol) in 50 ml 3N hydrochloric acid solution, the reaction was refluxed for 7 days and the white crystalline product was filtered , Washed with water, methanol and acetone, and dried in air to obtain a mixed compound:

Beta 1 ′ (〇3? (^ 20: 112-bipyridine-(: 112 (: 112? 03 (&31;) 2) 0.5. (〇3? 〇11) X-ray diffraction analysis shows d 2 1 8 · 5θ, infrared latitude and 31P NMR -25- Each paper size applies Chinese national standard ^ (CNS) 8 4 specifications (210X 297 mm) 11 (Please read the precautions on the back before filling this page }

505617 A7 ________B7_ __ 5. The description of the invention (23) (ppm) is the same as that shown in Example 7. Example 1 0 Tritium gas (octahydrate) (.361 g, 1.12 1 Ώ 109) was dissolved in 10 ml of water and 0.189 g of 50% hydrofluoric acid (4.8 mmol) was added; 1. Bisphosphonium ethyl bipyridine (0.25 g, 0.56 mmol) and phosphorous acid (0.092 g, 1.12 mmol) were dissolved in 10 μx 1 water and this solution was added to the aqueous solution. · The reaction is applied for 7 days' and the white crystalline product is washed, washed with water, methanol and acetone, and dried in the air to obtain a mixed compound:

Zr (03PCH2CH2-bipyridine-CH2CH2PO3 (cr) 2) 05 · ΗΡ03 X-ray diffraction analysis shows d == l 8 · 44, infrared analysis is as follows: 3 126, 3056, 2436, 2358, 2330, 1633, 1 555, 1499, 1443, 1386, 1210, 1161, 1048, 830, 731, 548. 31P NMR (ppm) is: 5 · 5-9 · 5 ο Example 11 Following the procedure of Example 10, but using 0.1 67 g (〇 .3 8 mmol) of digasified 1,1, -bisphosphinoethylbipyridine and 0.123 g (1.5 mmol) of phosphorous acid to obtain a mixed complex:

Zr (03PCH2CH2-bipyridine-CH2C.H2PO3 (Cr) 2) 0 34 · (HPOA 32 This material is amorphous, infrared and 31 PNMR (ppm) are the same as in Example 1 〇 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Example 1 2 Following the procedure of Example 10, but using 0.125 g (0.28 mmol) of 1,1'-bisphosphine, ethyl dichloride and 0-138 g (1.68 mmol) of arsenic acid to obtain a mixture Compound: -26- ϋ &amp; ΐmonth Chinese National Standard (CNS) A4 Regulation I (210 X 297 mm) 505617 Employees' Cooperatives of China Standards Bureau of the Ministry of Economic Affairs printed A7 B7 V. Description of Invention (24)

Zr (03PCH2CH2-bipyridine-CH2CH2P03 (Cn2) 〇.25 · (HPOJuo This material is amorphous, infrared and 31 PNMR (ρ pm) are the same as those described in Example 1 〇. Example 1 3 Wrong gas (octahydrate) ) (0.151 g, 0.47 mmol) was dissolved in 10 ml of water and 50% hydrofluoric acid (0.79 g, 1.9 mmol) was added. 1,1, -Bisphosphonium ethyl dichloride dichloride Pyridine (0.105 g, 0.24 mmol) and methylphosphoric acid (0.045 g, 0.47 mmol) were dissolved in 10 ml of water and this solution was added to the aqueous hammer solution. The reaction was refluxed for 7 days and the white crystalline product was filtered to Washed with water, methanol and acetone 'and dried in air to obtain a mixed compound: This material is amorphous, and infrared analysis is as follows: (IR (em-i), 3450, 3133, 3056, 2922, 1633, 1 555, 1499, 1450, 1309, 1168, 1027, 823, 781, 527) 〇 Example 14 In a manner similar to that described in Example 8, 0.993 111111〇1 zirconium hafnium chloride, 0.34 mm 0 dichloride 1 , I'-bispyridine ethyl bipyridine and 0.90 mmol 3-aminoethylphosphonic acid are heated in a bottle at 150 ° C, and after separation as described herein, the amorphous mixed composite exhibits the following I R spectrum: (IR (enrl), 3500, 3126, 3055, 1646, 1548, 1499, 1443, 1379, 1154, 1041, 865, 823, 760, 731, 541, 499). Example 15k The method similar to that described in Example 7 or 8 'makes the wrong gas as described in the following table, a chlorine "b 1,1-bisphosphine ethyl ethyl p ratio bond and scale-containing: co-ligand reaction -27- The paper's k-scale avoids the national standard of country F (cNs) A4 (210X297 mm) ~-—, ^ — n --- 1 ------- (Please read the precautions on the back first Refill this page) Order 505617 A7 B7 V. Description of the invention (25) Table 1 Co-ligand reagents mol BPBP1 (, mol) ZrOCl2 (mmol conditions CH3PO (OH) 2 0.47 0.23 0.47 Example 8: 150 ° C CH3CH2PO (OH) 2 1.12 0.56 1.12 Example, 7 CH3CH2CH2PO (OH) 2 0.94 0.47 0.94, Example 8: 200oC CH3CH2CH2PO (OH) 2 0.83 0.41 0.80 Example 8: 140 ° C HOCOCH2CH2PO (OH) 2 0.30 0.19 0.15 Example &amp; 110 ° C 1 Phenyl po (oh) 2 1.12 0.56 1.12 Example 7 C1CH2PO (OCH2CH3) 2 1.12 0.56 1.12 Example 7 Benzyl po (och2ch3) 2 0.70 0.33 0.65 Example 7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

Rule | Sheet Paper I Standard Bid Country Country i Used | Li 1 BPBP = Dichloride 1, Γ-bisphosphine and ethyl-biamine? Than the drum, so a mixed compound of the following formula is produced ...

Zr (03PC.H2CH2-bipyridine-CH2CH2P03 (Cr) 2V5 · R3P〇3 The data of these products are as follows: 505617 A7

V. Description of the invention (26)

Table 2 R3 X-ray IR data -ch3 * 10.9λ * See examples. 13 -ch2ch3 d = spectrum I -ch2ch2ch3 d = 11.8λ *: spectrum Π -ch2ch2ch3 d-13.6A * spectrum π -ch2ch2cooh d = 15.4 Spectrum 1III-Phenyl d = 19.7A * Spectrum IV-CH2C1 d = 11in * Spectrum V-Benzyl d = 14.5 Human spectrum VI = Peak due to pure metal bisphosphonate 'Spectrum i: (IR (cm -l), 3507, 3126, 3056, 2978, 2943, 2887, 1640, 1563, 1506, 1450, 1393, 1281, 1168, 1048, 872, 830, 738, 541. Spectrum //: (IR (cm-l ), 3500, 3126, 3049, 2950, 2866, 1633, 1555, 1499, 1450, 1393, 1246, 1041, 872, 823, 795, 731, 541. Spectrum //: (IR (cm-1), 3500 , 2915, 1717, 1633, 1415, 1260, 1027, 816, 752, 534Spectrum / V: (IR (cm-1), 3500, 3126, 3049, 1 (333, 1555, 1499, 1443, 1386, 1161 , 1055, 865, 823, 749, 731, 710, 541. Spectrum K (IR (cm-1), 3500, 3119, 3049, 1633, 1555, 1499, 1443, 1386, 1161, 1055, 865, 823, 759 , 731, 710, 541. Spectra V7: (IR (cm-1), 3500, 3126, 3056, 1633, 1598, 1492, 1450, 1386, 1253, 1161, 1034, 830, 781, 738, 696, 626, 541, 499. Examples 16 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. The compound Zr (〇3PCH2CHr-linked ratio-CH2CH2P03 (Cn2) 0.5. (〇3PO〇H) and 10ml 10 as prepared in Example 7 mM dipotassium tetrachloride platinum aqueous solution was stirred at room temperature for 2 days. During the reaction, the solid was changed from white to yellow. Then the solid was separated by filtration, washed extensively with deionized water and dried in the air; the solid was suspended in deionized The hydrogen was allowed to pass into the mixture for 10 hours in water, and the solid changed from yellow to dark purple. The solid was separated by filtration, washed with deionized water and dried in the air to obtain a brown solid. -29- This paper size applies to China's Family Standards Rate (CNS) 8 4 corpses (BGX297 mm)

505617 Employees of the Central Bureau of Standards of the Ministry of Economic Affairs print and print A7 B7. V. Description of the invention (27) Example 17 7 The substrate deposited on the metal film and then deposited on the glass is first 3 -aminopropyl Ethoxysilane was then treated with phosphonium chloride, and then the procedure of Example 2 was performed three times to prepare a composition of formula 111 where k was 3. This composition exhibited a reversible reduction wave at -0.74 V to a saturated calomel electrode. In water, it shows irreversible reduction under the same standard electrode below 4 V. Example 1 8 5111 containing 25 11 ^ of the composition prepared as in the previous Example 6] [(311 ^ ethylenediamine tetraacetic acid disodium (as a sacrificial reducing agent) in a 1 cm 2 box with 200 watts of Hg / Xe lamp irradiation. The amount of hydrogen was measured by gas chromatography. The rate of hydrogen production was 0.07 ml / hr within 18 hours of photolysis. Passing light through a 330 nm cut-off filter (G &gt; 330 nm) enables hydrogen production. The rate is reduced by more than equal proportions. If the oscillator is removed, the sample lightly generates hydrogen as described above. The hydrogen formed in this system: T 'Yield (2 X H2 Molars / G & 330 rim The mole number of projected photons is 0.00 8. One of the preferred compositions of the second embodiment is composed of Pt and Pd colloidal particles in a porous redox metal phosphonate matrix. These materials are very different from others Pt + Pd catalyst · The redox group makes the chemical properties significantly different. The oxygen reduction reaction is carried out by the reduced redox and it is not on the colloidal surface (such as in the material of the DuPont patent), because of borrowing The oxygen reduction rate of the reduced redox is much higher than that of colloidal metal particles. Because of the solid nature of the preparation, ”Or bromide” accelerators, can not be incorporated inevitably. Test different materials of Guangfanyuan. A highly active compound contains bisphosphine-30-this paper is suitable for the Chinese National Standard (CNS) 槻 47 ^ [ ^ 7mm) 丨 「|; |! _ 镬 -I (Please read the notes on the back before filling this page)

1T 505617 A7 B7 V. Description of the invention (28) Mixture of acid and phosphate (ie, 5.iiH2O • Pt / Pd). Compounds containing phosphate co-ligands in which R3 is 0H were found to be between 10 and 100 times more active than compounds in which R3 is fluorene, CH3, CH2C12, CH2CH3 or CH2CH2CH3. A wide range of Pd: pt is also tested. View this catalyst to determine its uniformity and composition. The sample was dissolved in HF and the resulting solution was analyzed by IPC to obtain the total metal composition (zr, Pt and Pd by weight, see Table 3). An electronic microprobe was used to analyze a single particle, and it was found that the entire particle had a uniform Z Γ ·· p t: p d ratio. Guangfanyuan's different electron accepting groups can be combined in this structure, which can be obediently reduced by hydrogen (via colloidal metal particles) and subsequently used as a catalyst in the formation of peroxide wind and other reducing species. The following are the results of item-by-item comparisons between the novel catalyst of the present invention and other Pt + Pd catalysts under the same conditions (see Table 3). The amount of noble metal (Pt + pd) in the material of the present invention and the other materials was analyzed, and then these analyses were used to determine the amount of catalyst in the experiment so that the same amount of noble metal was used in each case. This comparison was made with a mixture of hydrogen and oxygen foot at atmospheric pressure. When the pressure is increased, the hydrogen peroxide concentration in the steady state (the same equations 1 and 2 are used at the same rate so that the η 2 02 concentration remains constant over time) increases.丨 ί; | 丨 丨, sample clothing 丨 丨 (Please read the precautions on the back before filling out this page) Order by the Central Standards Bureau of the Ministry of Economic Affairs and printed by Consumer Cooperatives -------- Table 3 ------ ---- The compound of Example 24 (see below) + other catalysts + wt% Pt [ie, Pt / (Pt + Pd)] 0.1 0.05-0.16 [Η202] (Μ) in a stable state at atmospheric pressure ~~ —-'―— 0.14 * One—— -—------- 0.07 Initial flip (hour-1) — ~~ ^ 30 ------ ------------- This paper size applies Chinese National Standard (CNS) A4 specification (21〇χ 297 ^^ ~~~~~-'~ 一一 --------- 505617 A7 B7 V. Description of the invention (29) * Indeed 〇 2 2 Μ: In this procedure, the solution is reversed to 10 ml before taking an integer to supplement the vaporizer. The steady-state concentration of peroxide (reaction 1 rate = reaction 2 rate) needs to be constant, and the sample volume Nothing. Therefore, when the sample is diluted, the measured amount of peroxide decreases. If the reaction conditions are the same to obtain 014 M peroxide, but the reaction mixture is not 10 m 1 before removing an integer part, the concentration just obtained is 0. · 2 2 M, so the steady state concentration of peroxide is roughly estimated as 50% + Zr (03P0H) (03PCH2CH2 · Pyridine CH2CH2P03) Cn. Pt 〇Pd-093 Ten best catalysts disclosed in DuPont patent (U.S. Patent No. 4,83 2,93 8) 〇Number of preparation and research of the present invention Different materials, porous giant solids and thin films grown on a high surface support. By first preparing a layered porous solid of formula XV; then halide ions exchange polyhalide metal anions (such as Ptcu2-); and then polyhalides The metal ions are reduced with hydrogen to obtain porous solids containing infiltrated metal particles, and giant solids are prepared. In the ion exchange reaction, it was found that the temperature needs to be increased. At room temperature, Ptci? Is more dominant than PdClj2-, resulting in a larger ratio than the solution. The preparation is richer? 1: solids. If ion exchange is performed at high temperature, the exchange is uniform and the composition of the solids is indeed in solution. Prepare the following examples as in Examples 7, 8, and 9 above

Zr (03P0H) (03PCH2CH2 bipyridine CH2CH2P03) a. Then incorporate the beginning and the various proportions as follows: Example 1 9

Zr (03POH) (〇3PCH2CH2, pyridinium CH2CH2P03), Ct Pt. Pd-58: -32- This paper size is applicable to a country's national dimension (CNS) A4 specification (210X297 mm) f Please read the precautions on the back before filling-fill in this page) Staff Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs Printing 505617 Α7 Β7 V. Description of the invention (30) 170 mg of Zr (03P〇H) (〇3pCH2CtM ^ pyridine CH2CH2PC) 3) C1 and 4.6 ml PdCl2 (7.3 x 1〇 * 3 M) ^ 2.8 ml K2PtCl4 ( 6.1 x 10 ^ M) ^, the mixture was heated to 60 ° C for 1 hour with continuous stirring, the yellow powder was filtered and washed with water 3 to 4 times, the yellow solid was suspended in water and aerated gas was passed at 6 (rc 1 / For 2 hours, the grey / black solid was filtered and washed with water followed by ethanol. This solid was then dried in air. 0.0007 g of the above solid was dissolved in concentrated 11 (: 1, a few drops of concentrated Η Ν Ο 3 and several In 59% HF drops, the solution was diluted to 1000 m 1 and Zr, Pt, and Pd were analyzed by ICP. The solution analysis (ppm) was Zr = 14.05; Pt = 1.01; Pd = 0.73. Example 20

Zr (03P0H) (03PCH2CIU Pyridium CH2CH2P03) C Pt. Pd-32: 260 mg Zr (03P0H) (03PCH2CHj) E3 CH2CH2P03) C1 and 3 ml of 0 · 11 M K2PdCl4 solution and δ · 4 x ι ·· 3Μ K2PtCl4 * solution is heated to 60 ° C for 3 minutes and continued Stir, filter the resulting yellow solid and wash the IF strips several times with water. This solid was resuspended in water and treated with Krypton gas as described in the first synthesis. 0.0136 g of dry solid was dissolved and analyzed as described above. The ppm 値 was: Zr = 24.72; Pt = 0.69; Pd = 1. 5 〇 Example 2 1 Produced by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs

Zr (03P0H) (03PCH2CH2: #pyridine CH2CH2P03) C and Pt. Pd-OG 2 00 mgZr (O3POH) (〇3PCH2CH2 .; ^ itCH2CH2PO3) Cl &amp; 1 ml of 0.11 M K2PdCi4 and 0.18 mi of 1.6 × 10 · 3 Μ 〖; ^ (: 14 treatment and as in the previous example Hydrogenation. 0_0117 g of the finally obtained black solid was dissolved in concentrated HC1, a few drops of concentrated Ν Ο 3 and a few drops of 50% HF, the solution was diluted to 2 5 m 1, the solution was analyzed as follows: Zr (ppm) = 48.92; pt 二Not detected; Pd -33- This paper is again suitable for China National Standards (CNS) A4 (210X297 ^ 505617 Ministry of Economic Affairs t Central Standards Bureau staff consumption F7 printed by the cooperative Fifth, the description of the invention (31 (ppm) = 6_75. Example 2 2

Zr (03P0H) (03PCH2CH2 bipyridine CH2CH2P03) Cl. Pt. Pd-30: 200 mgZr (03P0H) (03PCH2CH2_pyridine CH2CH2P〇3) C1,! Ml of 4.8 x 1〇-2 M K2PdCl4, and 0.275 ml of 4.7 x 1 (T2 M K2PtCl4 stirred at 60 ° C for 20 minutes The yellow solid obtained was filtered, washed with water, and hydrogenated as described above. 0.0125 g of the solid was dissolved as described above and diluted to 25 ml for analysis. Zr = 49.91 ppm, Pt = 2.15 ppm, and Pd = 4-9 2 ppm. Example 2 3

Zr (03P0H) (03PCH2CH2 bipyridine CH2CH2P03) C Pt. Pd-ll: 500 mg Zr (03P0H) (03PCH2CH2 bipyridine CH2CH2P03) C1 and 15 ml of 7.4 x 1 (T3 M Pd. 12 and 0.99 ml 5.1 · 1 x 1 (T3 K2PtCl4 reflux for 6 hours, filter solids, such as Wash as before, and proceed with the solid hydrogenation reaction as before, but for 1 hour. 0.0172 g of this solid was dissolved as described above and diluted to 25 ml for analysis to obtain Zr = 70.29 ppm; Pt = 1.18 ppm; Pd = 9.10 ppm 0 Example twenty four

Zr (03P0H) (03PCH2CH2J ^ said bond CH2CH2P03) C Pt. Pd-093: 500 mg Zr (03P0H) (03PCH2CH2 bipyridine CH2CH2P03) C1, 15 ml of 7.4 x 1 (T3 M PdCl2 and 0.99 ml of 5.1 xl0_3 M K2PtCl4 reflux for 65 hours, filter as in the previous example, After washing and hydrogenation, 0.018 g of the solid was dissolved and diluted to 25 m 1 as described above for analysis, and Z r = 1 2 7 9 8 ρ P m; Pt = 0.78 ppm; Pd = 7.72 ppm. Example 2 5 -34- This paper size i «uses Chinese national standard (CNS :, A4 size (210X297 mm) (Please read the precautions on the back before filling in this page)

505617 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of Invention (32)

Zr (〇3p〇H) (03PCH2CH2 bipyridine CH2CH2P03) C R 200 mg Zr (03P0H) (03PCH2CH2 bipyridine CH2CH2P03) C1 treated with 2 ml of 5.1 X 1 (T3M K2PtCl4) solution at 60 ° C for 1 hour The solid was filtered, washed, and hydrogenated as in the previous example, and 25 ml of cereal was prepared for analysis using 0.0162 g of solid to obtain Z r = 1 1 7.9 ρ pm; P t = 2 0 0 1 ppm. Example 2 6

Zr (03POH) (03PCH2CH2 bipyridine CH2CH2P03) CJ. Pd: 100 mg Zr (03P0H) (03PCH2CH2_ pyridinium CH2CH2P03) C1 and 1 ml of 6.3 x 10 · 2 M PdCl2 * 60 ×: heated for 4 hours, filtered orange solid, washed rattan and hydrogenated as before, 0.0131 g This solid was dissolved in 25 ml for analysis as described above to obtain Zr = 92.96 ppm; Pd = 8.54 ppm 0 The substance was grown on a high surface area support in a multi-step process as described below. Ion exchange is performed during or after film growth. Example 2 7

Si02. Synthesis of Zr (03P0H) (03PCH2CH2 bipyridine CH2CH2P〇3) C: 1 g of silicone (Selecto Industries, Cat # 162544, batch # 2 16073) was heated at 200 ° C for 1 hour, and 150 ml at 60 ° C. 65 mM ZrOC.l2 was treated for 2 days, and then treated with 150 ml of a solution containing 20 mM (03PCH2CHd ^ pyridine CH2CH2P03) C1, 20 ml of osmic acid and 60 m M NaCl at 60 ° C for 18 hours. These treatments were repeated several times. At the end, the pale yellow solid was washed with water and dried. Example 2 8

Si02. Zr (03P0H) (03PCH2CH2 bipyridine CH2CH2P03) C]. Pt. Pd-21: 270 mg Si02. Zr (03P0H) (03PCH2CH2.Pyridine CH2CH2P03) C1 with 3mLt ^ * 0.12MK2PdCl ^? L6.4xl03MK2PtCl4t. -35, this paper's policy standards apply the Chinese National Standard (CNS) A4 specification (210X297 mm) 丨 ————! _! # II (Please read the notes on the back before filling this page)

1T 505617 A7 B7 V. Description of the invention (33) The liquid was treated at 60 ° C for 1 hour, filtered and washed. The solid was hydrogenated as before. 0.0494 g of this solid was dissolved in HC1, HNO3 and 50% HF, and diluted to 25 ml. Analysis showed ζΓ = 166 · 8 ppm; Pt = 2.97 ppm; Pd == 1089 ppm ° Example 29 As the above example 19- 28 Samples were prepared synthetically for each compound, and the metal content of the solution was measured at lcp. The weight percentage of the redox was estimated from Zr 値 ', assuming that there are 2 ζ Γ atoms per redox molecule in this solid. The redox unit was taken as C1GH8N2, and the data obtained are shown in Table 4 below.丨: | ΓΓ-I 丨 (Please read the precautions on the back before filling this page) Order printed by the Central Bureau of Standards of the Ministry of Economic Affairs and Consumer Cooperatives to print 6 3! Quasi-f standard I &gt; country-country t: use a suitable iaogong 97 505617 A7 B7 V. Description of the invention (34) Table 4 Elemental analysis of all compounds listed in this disclosure (ICP of dissolved sample) (% is wt%) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Compound R (Observation 値) R (Theoretical 値)% Pt% Pd% Zr Du-D ，; sample 1 0.02 0.08 0.01 0.38 0 DU-D, sample 2 0.08 0.093 0.02 0.23 0 DU-F 0.2 0.3 0.05 0.2 0 DU- H 0.65 0.7 0.15 0.08 0 Zr * PV (POH) * Pd 0 0 0 1.63 17.74 Zr * PV (POH) * Pt * Pd-005 0 0.005 Not detected. 1.44 17.24 Zr * PV (POH) * Pt * Pd- 093 0.092 0.093 0.11 1.07 17.78 Zr * PV (POH) * Pt * Pd-ll 0.16 0.093 0.32 1.65 16.37 Zr * PV (POH) * Pt * Pd-14 r 0.14 0.09 2.42 1.48 18.29 Zr * PV (POH) * Pt * Pd-30 0.29 0.14 0.43 1.17 18.71 Zr * PV (POH) * Pt * Pd-32 0.32 0.093 0.51 1.1 18.18 Zr * PV (POH) * Pt * Pd-58 0.58 0.49 1.4 1.01 19.51 Zr * PV (POH) * Pt 1 1 3.09 0 18.19 Zr * PV (POH) * Pd-fPtCl4 0.85 Unknown t 3.86 0.66 4 6.56 Zr * PV * Pt 1 1 4.3 0 12.35 Zr * PV (PH) * Pt 1 1 7.96 0 14.87 Zr * PV (POH) * Pt + PdCl4 0.6 Unknown 2.35 1.57 16,55 Si02 * Zr * PV (POH) * Pt * Pd-l 1 .11 0.093 0.1 0.78 8.06 Si02 * Zr * PV (P0H) * Pt * Pd-21 .21 0.093 0.15 0.55 8.7 Si02 * Zr * PV (P0H) * Pt * Pd-27 .27 0.093 0.35 0.9 2.67 Please read back A and winter items before filling in page-37- This paper size is in accordance with the Chinese National Standard (CNS) Λ4 specification (210X297 mm) 505617 Employees of the Central Standards Bureau of the Ministry of Economic Affairs printed by the cooperative A7 B7 V. Invention Explanation (35) Definitions in Table 1: 011-0: DuPont's Wu Guo Patent 4,832,983 Table 1 Eight Preparation 1 :); 〇1; 4: DuPont's US Patent 4,832,938 Table 1 A Preparation F; DU-H: DuPont's U.S. Patent 4,83 2,9 3 8 Table 1 A Preparation of rhenium.

Zr * PV (P0H) = Zr * (03P0H) (03PCH2CH2 bipyridine CH2CH2P03) Cl Zr * P \ (PH) = Zr (03PH) (03PCH2CH2 ^ rf: ingot CH2CH2P03) C1 Zr * PV = Zr (03PCH2CHJ pyridinium CH2CH2P〇3) Cl R = Pt / (Pt + Pd) (weight / weight) R (observation 値) = the ratio calculated by ICP analysis of Pt and PddR (theoretical 値 by the initial concentration of Pt and Pd in the reaction solution Calculated ratio 値. Hydrogen peroxide formation: The material of the present invention can be used as a catalyst in the production of hydrogen peroxide. This process includes treating the aqueous suspension of the catalyst with an oxygen source and a hydrogen source. The oxygen source contains pure oxygen and 2 gases. , Ozone or any nitrogen oxides. The suspension may also contain acid or p H of the control system. Example 30 Put a certain amount of each catalyst in a 50 m 1 plastic tube, and add i to each tube. A solution of acetanilide in 〇m 1 in 0.1 M H c 1 and 15 m MH, and sealed with a rubber diaphragm. A mixed gas of oxygen and hydrogen is passed into the suspension. In some cases, air is used. Not 〇 2. At sequential time intervals, starting from 1 hour (up to about 28 hours), add acetanilide to 0 1 MH H c 1 0 · 15 m Μ solution to supplement the loss due to evaporation Solution volume A sample of the reaction mixture was taken and diluted to 5 m 1 with ammonium sulfate solution (prepared in sulfuric acid as described above). Record the absorbance of the green solution at 4 10 nm. Titrate the same solution with KMη04 and check Paper size applies to China National Standard (CNS) A4 specification (210X297 mm) I — i; i- 丨 丨 *-丨 _ # clothing! (Please read the precautions on the back before filling in this page j Erding A7 B7 V. Description of the invention (36) The colorimetric analysis is very accurate. Table 4 shows the elemental analysis of the compound synthesized and / or used. The data shows that the compound is in various stages and under various conditions (including the difference between Pt and Pd). Ratio and properties of catalysts in the production of hydrogen peroxide at several pH). The data listed in Table 5 represent the production of two preferred materials for the two preferred materials of the present invention and some other catalysts. Table 6 shows other properties of the present invention. Similar test data for compounds and other compounds. Table 7 shows data collected for several catalysts with different Pt to pd ratios. Table 8 shows data at several different pHs. N ^ iai emMmta— Him -ϋ_ι ϋϋ mammmmem / n · (Please read the back first Please pay attention to this page and fill in this page again.) Consumers' cooperation of the Ministry of Economic Affairs of the China Bureau of Economic Cooperation, the printing of standards by the society | 505617 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (37) Table 5 Hydrogen peroxide formation, pH = l atou The amount of catalyst used in each experiment was adjusted to obtain a constant Pt + P & lt 3 Molars

-40- (Please read the precautions on the back before filling this page) This paper size applies to China National Standards (CNS) A4 (ZWX297 mm) · 505617 Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 5. Description of the invention (38) Table 5 Continued Gas Specific Catalyst Amount · Time | H202 | (mM) Compound 112: 02 (mg) (hours) Initial inversion # Zr.PV (POH) .Pt.Pd-093 1:40 23 1 2.4 2.4 (Continued) 3.5 28 5.5 45 7.5 54 23 88 26 79 28 76 Si02.Zr.PV (P0H) .Pt.Pd-21 1: 5 44 1 10 10 2.5 22 4 31 6.5 33 8.3 33 9 33 DU -D, sample 2 1: 5 118 1 16 16 2.9 31 3.9 38 5.9 49 7.9 58 23 77 DU-H 1: 5 128 1.1 16 16 2.5 24 4 32 f Continued on the next page, ... 7.3 36 —ΤΙΤΓ &quot; 丨 丨^: (Please read the notes on the back before filling this page)

、 1T -4i-l paper size applies Chinese National Standard (CNS) A4 regulations; ^ (2 丨 OX 297 mm) 505617 A7 B7 V. Description of the invention (39) Table 5 Continuing compound gas ratio 112: 02 Catalyst amount ^ (mg) Time (hours) | H202 | (mM) First turn over forest table 5 Continuation compound (DU-Η (continued ..) Gas ratio 1 112: 02 Catalyst amount (mg) Time (hours) | H202 | (mM ) Initial turnover 23 50 26 50 28 50 DU-F 1: 5 122 1 10 10 2.3 19 4 30 6 44 9 58 24 46 DU-D ·· DuPont USP 4,832,938 Table 1A Preparation D. DU-F: DuPont USP 4,832,938 Table 1A Preparation F ◊ DU-H: DuPont USP 4,832,938 Table 1A Preparation Η (Please read the precautions on the back before filling this page)

, Order-.! * I Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs

Zr * PV (P0H) = Zr (〇3P〇H) (03PCH2CH2 bipyridine CH2CH2P〇3) C1 ethyl 1 '* 1) ¥ (? ^; Canton 21, (〇3? 11) (〇3? (: 112〇1 Twelve bipyridine (: 1120112? 03) (: 1 Zr * PV two Z r (03PCH2CH2 joint ratio bond CH2CH2P〇3) Cl Pd-Pt # represents Pt / (Pt + Pd) (weight / Weight) -42- Chinese paper standard (CNS) A4 size; ^ (2 丨 0X297 mm) 505617 A7 B7 V. Description of the invention (40) Table 6 uses the ratio of h2: o2 to 2: ι (obtained from 〇2) In the air, the DuPont catalyst and the novel catalyst of the present invention are compared at ph = 1. The amount of catalyst used in each experiment is adjusted to Pd + Pt in each experiment to obtain a constant mole number DU-D: DuPont USP 4,832,938 Table 1A Preparation D. DU-F: DuPont USP 4,832,938 Table 1A Preparation F. 01 &gt; 1 Seven DuPont USP 4,832,938 Table 1A Preparation Η. The amount of compound printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs l. (mg) H2O2 (mM) at 18 hours 202 (πιΜ) Moore% at 45 hours? (1 DU-D si ----- 152 4.6 1.0 _ 0.545 DU-F 246 2.2 0.5 〆 0.464 DU-H 262 4.6 4 · 5 〆0.200 Zr.PV (P〇H) Pt.Pd-58 25 12.5 2 · 6 〆0.238 Zr.PV (P〇H) Pt.P d-32 38 22.5 15.1 __ 0.394 Zr.PV (P〇H) Pt.Pd-30 42 18.3 9.0-0.386 Zr.PV (P〇H) Pt.Pd-00 43 13.7 10.1 0.584 Si02.Zr.PV (P0H ) Pt.Pd-27 49 3.5 2.6 * ^ 0.416 Zr.PV.Pt 25 0.5 Zr.PV (PH) .Pt 40 0.6 Zr.PV (POH) .Pt 30 5.5 (Please read the precautions on the back before filling in this page)

Zr * PV (POH) 2 Zr (03P0H) (03PCH2CH2 bipyridine CH2CH2P〇3) Cl redundant 1, 叩 ¥ (? 1 ^ two 21, (03? 1 ^) (03? € 112 (3112 bipyridine ( ： 112 (： 1 ^ 2? 03) 〔1 Zr * PV two Zr (03PCH2CHJ ^ pyridine CH2CH2P03) C1 Pd-Pt # means Pt / (Pt + Pd) (weight / weight) -43- National National Standard (CNS ) Α4 specifications (210 × 29 ^ 1Ύ 505617 A7 B7 V. Description of the invention (41) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. Table 7 is produced by different quantities (different R 値) 'h2: o2 is a mixture of 2: 1 ( Use air as the oxygen source) to produce H202 compounds at 1 atm, pH = l • Amount (mg) Time (hours) h2o2 (mM) Zr.PV (POH) .Pt.Pd-005 28 "2.2-23 2.5 JT. 5 2.5 30 2.7 Zr.PV (POH) .Pt.Pd-ll 29 1 2.8 23 ^ 4.5 27.5 5.8 30 8.9 Zr.PV (P〇H) .Pt.Pd-093 56 1 4.2 7 7.7 Zr.PV (POH ) .Pt.Pd-32 31 J_ 2.5 23 4.9 27.5 5.1 30 5.2 Zr.PV (P〇H) .Pt.Pd-58 30 1 2.2 23 3 27.5 2.9 30 2.9

Zr * PV (P0H) = Zi, (03P0H) (03PCH2CH2, and ingot CH2CH2P03) C1 Pd-Pt # means Pt / (Pt + Pd) (weight / weight) -44- | _ _____ This paper is applicable to China (210X297) (Centi) 1 ^ .11,1144 (Please read the notes on the back before filling in this I) ------ 505617 A7 B7 V. Description of the invention (42) Table 8 Use Zr (03P0H) (03PCH2CU_ Pyridine CH2CH2P03) Cb Pt * Pd-093 at Η2: 02 = 1 · 5 and 1 atm, the pH is changed with HC1. The amount of the compound is one (clear time (small 皡) η2ο2 (mM) flip # (total) 1 23 1.3 --- ----- 33 29 2.3 ----- 5i 4.6 71 6.3 79 8.3 ----------- 80 24 140 125 2 • 22 1.3 18 17 3.3 68 4.8 78 5.8 80 6.8 89 85 3 23 1.0 17 16 2.8 23 4, 0_ 23 21 6.3 19 (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Central Standards Bureau, Ministry of Economic Affairs The above examples all include atmospheric pressure reactions. There are two in this regard. Important parameters are the initial rate of hydrogen peroxide formation and the steady state concentration of hydrogen peroxide. The steady state concentration indicates that the system is produced from peroxide at the same rate as the peroxide is formed. The concentration in water, and the initial rate is an indication of the rate of peroxide formation. The best stable state observed is 140 mM (Table 5). In the steady state, the oxygen reduction rate (Equation 3) and hydrogen peroxide reduction The rates (Table 4) are equal, so the hydrogen peroxide concentration is constant. In these experiments, the initial reaction rate was 30 turnovers per hour (based on the redox moles present in the system). These -45-This paper Standards apply to Chinese National Standards (CNS) Α4ϋ— (21〇1Γ297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 505617 A7 ---------- B7 V. Description of the Invention (4 · 3) Experiment It was carried out with a catalyst having R = 0.03 and a mixture of i: 5 with H 2: 〇2. DuPont's best catalyst (DU_D) treated in the same way produced only 77 mM hydrogen peroxide in a stable state. When the mixture of &amp; and ο: is adjusted to be richer in oxygen (ie, H2: 〇2 = 1: 10), the amount of hydrogen peroxide produced is reduced. Other catalysts loosen the good areas of their activity very quickly. To test this phenomenon, I took a catalyst sample and used it in several sequential experiments. The results are shown in the table. 9. In order to minimize the danger, the mixture of hydrogen and air was used in these experiments to make the stable state of hydrogen peroxide concentration 値 lower than the above-mentioned number 値. The first three experiments showed very similar amounts of peroxide production, and the fourth experiment showed lower activity than the first three. This amount of activity is still much higher than that observed by DuPont's catalyst under the same conditions. Elemental analysis showed that after the fourth cycle, the weight% of Pt and p d increased slightly, while the amount of Zr decreased. This observation shows that the activity decreases with the partial dissolution of the metal phosphonate. Table 9 Use of ZrPV (POH) · Pt · Pd-093, pH 2, 1, H2: 02, 2: 1 (using air as 〇2 source), pressure = 1 atm of hydrogen peroxide to form a cycle # time (hours) [ H202] _). Total turnover. First time 1 4.2 1.5 2.5 4.3 5 6.1 7 7.7 2.8 25 4.6 Second time 1 4.5 2.6 2.8 9.8 5.6 5.1 7.9 6.8 8 -45- ^ Paper rule ^ suitable; ii Chinese national standard ( CNS) A4 size (210X297mm) (Please read the precautions on the back before filling this page)

505617 A7 B7 V. Description of the invention (44) Cycle # Time (hours) [η2〇2] (_ Total flip third time 1 7.1 4.0 5 10.7 6.1 One -----… -... 7 3.6 Fourth time 1.2 4.2 2.4 3 4.1 6 4.5 2.6 ——Π! ——— (Please read the precautions on the back before filling this page) Example 3 1 High pressure hydrogen peroxide formation: In a 70 m 1 pressure bottle with a gas pressure of various compositions ( (2, 02, N 2) for several experiments. Add 5 m 1 0.1 M H c 1 and 25 mg Zr (03P0H) (03PCH2CH2 bipyridine CH2CH2P03) Cl * Pt * Pd-14 to the reaction flask, Add a mixture of oxygen, hydrogen, and nitrogen at a specified pressure to the bottle to allow the reaction to proceed for various times (Table 10). The h2o2 concentration is similar to that obtained in experiments at atmospheric pressure (see above). The data shows the reactor bottle volume Increasing or increasing the I force will result in a higher concentration of Η202, that is, if pH 2 and P〇2 increase with a factor of 5, the result is 1 mole Η2 〇2 (see, for example, the examples in Table 1 〇 2). -47- Chinese National Standard () 8 wire (210X297 mm) Ordered by the Consumers Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs to print A7 B7 five tables f〇 明Ming (45

0.143 0.214 0.410 0.084 0.062 Final 丨 H202 | (Mole / L) Total Pressure (psi) P〇2 (psi)

Pm (psi)

Pn2 (psi) H2 Mor in the system 175 175 175 150 150 100 100 100 100 120 120 15 15 15 24 24 0.0029 0.0029 0.0011 0.0011 25% 37% 38% 28% Printed by the China National Association of Prospective Consumers Cooperative F 2 4 After hours, the system was emptied and fresh feed of the same gas mixture was added, followed by a reaction for another 24 hours. Example 3 Synthesis of a phosphonate-derived polymer template: Diethyl bromide was prepared by the Michaelis-Arbuzor rearrangement reaction of Br (CH2) 4Br and triethyl phosphite Phosphonate. 1,4-Dibromobutane (2 1.5 g, 100 mm) and triethyl phosphite (6.65 g, 40 mmol) were heated to 1 50 ° C for 6 hours. Reaction of 1,4-dibromobutane. Poly (4-ethylamidine π specific bite) (p v p) was tiger-formed with 4-ethyl butylphosphonic acid diethyl acetate to obtain a polymer (PVP-C4P). PVP (1 g, 9.5 mmol) and 148 g (5.4 mmol) of diethyl-4-bromobutylphosphonate were dissolved in 60 ml of v, dimethylformamide (DMF). The mixture was stirred at 60 ° C for 2 hours, and the DiMF was removed under vacuum. The remaining solid was 1: 4 (V: V) in methanol and ether; the compound was first washed, and then refluxed in ether for 2 hours. The solid sample was filtered and dried. Then dry the sample and dissolve it in 30 ml of dichloromethane, add 12 g of bromotrimethyl stone and mix in argon and stir for 6 hours. Add Ηβ (80 ml) and the solution is disturbed again. -48- This paper is for Chinese country ^ Standard (CNS) A4 size (2ί〇 [297 公 ji relative to the h2o2 yield of h2 in the silk 1 (Please read the precautions on the back before filling this page}

505617 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Invention Description (46) Mix for 1 hour. The aqueous phase was separated and removed in vacuo to give a yellow-brown solid (p v p _ C4P). The CHN analysis of PVP-C4P was C: 5 5 76, h: 6.67, N: 8.20. This analysis is consistent with 25% of pyridyl oxidized. [C 7 Η 7 N] 3 [C i i H i 7 Ν Ο 3 P B r] * 3 Η 2 〇 to obtain c Η N analysis as C: 5 5.57, Η: 6. · 4, Ν: 8-10. The PVP-c4PtNMR spectrum is composed of a relatively broad green 'because of the polymeric nature of the material. The three broad bands appearing in the 1H NMR spectrum in d 6 _ DMS0 / D20 are 8.2, 6.6, and 1.6 ppm, and the integrated intensities are 1, 1, and 24. If the two low magnetic field peaks are identified as Pathway / 17 ratio end resonance and the peak at 1 _ 6 ρ pm is identified as all c η 2 groups except those bound to nitrogen (based on model compounds, the latter peak is expected to fall Under HDO), since this yields a ratio of ι: 1: 2 · 3, this ratio corresponds to a 25% derivative. Example 33 A platinum colloid was prepared by reducing a hexachloroplatinate solution from sodium citrate. This reduction reaction is similar to the method described by Brugger et al., But the temperature is maintained at 90 ° C to obtain a uniform particle size (P. Brugger, P. Cuendet, M. Gatzel, J. Am. Chem. Soc., (1981), 103, p. 2923). K2PtCl6 (40 mg) was dissolved in 300 ml (distilled water and the solution was heated to 90 ° C. Aqueous sodium citrate solution (30 ml, 1% by weight sodium citrate) was added and the solution was stirred for 3 hours. The colloidal suspension was cooled After reaching room temperature 'Amberlite-MB-1 exchange resin was added and the mixture was stirred to remove excess citrate until the solution conductivity was below 5 mS / cm 0 Example 3 4 Zirconium Redox Bisphosphonic Acid The growth of salt (Z r VP) on PVP-C 4 P: -49- The paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) ~ &quot; &quot; · ::! &Quot; 丨 II · &quot; 丨 — 锄 衣 C Please read the precautions on the back before filling out this page} mu · ϋ_ϋ— mmtti — &gt; 1ιϋ —ml, ι Li ^ 11 ^ 1 «ϋ« ι 505617 Central Bureau of Standards, Ministry of Economic Affairs Printed by employee consumer cooperative A 7 -----_____ B7 _ V. Description of the invention (47) Polymer P \ P-C4P (5 mg) dissolved in 50 mi of the above pt colloidal suspension ° Pt: polymer The weight ratio is 1: 2.5. The mixture is shaken for 1 hour to reach equilibrium. Dissolve 0.3 g of Zr〇Cl2 · 8h2〇 in PVP-C4P / Pt suspension ° W and shake at room temperature. Zr4 + ions are fully reacted with the phosphonate core of the polymer. The mixture is then dialyzed against distilled water to remove free ions. The molecular weight cut off by the dialysis tube used herein is 12,000-15,000. Dialysis is performed until the water conductivity is below 5 m S / cm. The suspension was poured back into the bottle, '0,04 g of redox bisphosphonic acid was added and the mixture was shaken overnight at 60 ° C, and a similar dialysis process was performed to a conductivity of less than 5 m S / cm. Hammer and bisphosphonate The treatment was repeated up to 5 times to grow multiple layers of ζ Γ V p material. Example 3 5 Photochemically Generated Hydrogen: Performed by irradiating a polymer template Zr VP sample on a Pt colloid in a TD solution (Example 3 4) Photochemically generated hydrogen. The suspension was maintained at 2 0 throughout the photochemical experiment. (: 1 cm square hole. Before photolysis, pass n 2 into the liquid to make 4 ml of sample suspension and 1 ml The mixture of 0.1 M NaEDTA (sacrifice reducing agent) was fully degassed. Then the sample was irradiated with a 2000 watt Hg / Xe arc lamp. The hydrogen was measured by gc. Suspended with 0.05 M NaEDTA containing 11 mg ZrPV (Cl) Liquid sample was illuminated with 2 QQ Watt H g / X e lamp Causing the first hour square. 2 5 ml / hr of the hydrogen generation rate. EDTA is used as a sacrificial reducing agent to turn the system over. The longer the irradiation time, the lower the hydrogen generation rate. This is similar to multilayer films grown on the surface of oxidized oxidants. Light cuts through 2 60 ri m; the wave filter reduces the hydrogen generation rate by about 50%, but -50- this paper size applies the Chinese Standard 1 CNS) ΛϋΤ ^ 5297 mm) — ^ —-(please first Read the notes on the back and fill in this page) i --- ^ Order ml · —mu β · ϋ-ϋ I mu— ϋι ^ ϋ .ί. 505617 A7 _________B7 V. Description of the invention (48) produced in a longer time About 20% more hydrogen. In this system, the dependent wavelength of light to generate hydrogen is closely related to the observers who form the state of charge separation in the semiconductor and Z r P V (C 1) thin film samples. Example 3 6 Preparation of samples and substrates Using the method described in Example 3 2 to synthesize polymers from poly (4 · ethylfluorene? Specific bite) and diethyl 4-bromobutylphosphonate? \ ^-(24? (Molecular weight = 10,000,000). Prepared as in Example 1 Η 2 〇3 p CH 2 C Η 2 (bipyridine) CH2 CH 2P03H2C12 (V2P). Each polishing using a single crystal Silicon wafer and micro-fused silicon oxide (quartz) wave plate (~ 1x3 cm2) and 0.05-0.1 mm thick gold foil, platinum foil and palladium foil (~ 1x0.5 cm2) are used as substrates. Before use Wash with a mixture of concentrated h2s04 &amp; 30% H202 (v / v 3: 1), wash thoroughly with distilled water and heat at 500 ° C overnight to obtain a dehydroxylated surface. Surface removal procedure Silicon wafer, quartz glass The sheet or metal foil strip was immersed in a 0.5% (w / w) aqueous solution of p V p-c 4 P. After 5 minutes, the glass slide was taken out of the solution and dried by blowing a pure atmosphere and dried. 'Coated on the surface of the glass slide A thin layer of cloth 2; rCl2 80 mM solution to achieve cross-linking of polymer phosphonic acid residues and allow the membrane to dry in air. To ensure that the polymer has been completely cross-linked with Z r 4-ions, repeat the process The slide was washed green twice with distilled water to remove excess ions from the surface. The film was grown by repeatedly immersing the substrate in 8 ° C such as a clear I substrate in a 10 μM V 2 P aqueous solution 4 Hours (step 1), followed by immersion in 60 m Μ Z r Ο C 12 aqueous solution for 2 hours (step 2) at room temperature to produce a multilayer zr PV (C 1) compound -51- winter on the surface rich in zirconium Paper size applies to China National Standard (CNS) A4 (210X? 97 mm) (Jing Xian 闳 read the notes on the back before filling in this page) A7 B7 printed by the Consumer Standards Cooperative of the Central Bureau of Standards 5. Description of the invention (49). The surface was thoroughly washed with distilled water between two immersions (step 3), and steps 1 to 3 constitute a cycle treatment.丨 Five films were prepared in five cycles. The step-by-step step 2 can be omitted after taking the sample. Example 3 7 Atomic Intensity Microscopy (AFM) was obtained using a super-frequency oscilloscope 111 and tracing probe microscope (Lianjido Instruments). ) Image. The surface is imaged in a drilling mode with a silicon cantilever (typically 32-36 kHz). The sample &lt; AFM image (〇5 χ 0.5 &quot; m2) shows its finest features and proves that The structure and thickness of the thin film made by the same method are related to the nature of the substrate; Some samples show a significant increase in RMS roughness on film growth. Examining AFMW images shows that in all cases, the material growing on the surface is composed of microcrystals. This is related to the smooth surface roughness of tZn &amp; Cu alkane bisphosphonates. W membrane is opposite (Yang, H. C., K. Aoki, H.-G. Hong, DD Sacked MF Arendt, S.-L. Yau, CM Bell, TE Mallouk J.

Am, Chem. Soc. 1993, 1 15, 1 1855-11862). Crystals are smaller in the case of quartz and silicon substrates and larger in the case of metals. This seems to indicate that there is no direct relationship between the overall roughness of the film and the crystal size, and the rough thickness of the bare substrate and the film on it. The thin film on quartz is composed of small crystals evenly distributed on the surface, while the thin film on gold and platinum is composed of slightly larger crystals than those on quartz, but it is still evenly distributed on gold and tends to be on platinum. Yu condensed into larger pieces. Films grown on Pd cause large crystals which appear to aggregate into larger islands. In contrast, thin films on silicon are composed of very small particles that also aggregate into large islands. No difference was found in the afm images of the untreated and PVP-C ^ P treated substrates. -52-

The size of this paper is suitable for Chinese storehouse standard (CNS) a4 specifications (210X 297mm J --I n I ------ (Please read the precautions on the back before filling this page). Order &quot;- Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 505617 A7 ______B7_ V. Description of the invention (50) Example 3 8 The above example 3 6-3 7 of 21 ^ ¥ (01) ash covered with film 11,? 1 and? (1 The electrode (operating surface area ~ 0.3 cm2) is marked with cyclic voltammetry (Cyclic ¥ 〇—111111 is called 1 ^) (&^;). Use 1 ^ ruler / stabilizer type 2 83 〇 with porous glass The raw material allows the counter electrode (pt coil) to be separated from the 〇1 Μ KC · 1 aqueous solution. The reference is a saturated calomel electrode (s C ε). Oxygen is self-operated from the operation solution by passing high-purity argon gas. Removed. The cyclic voltammetry of the &lt; ZrPV (cl) film on the Au 'Pt and Pd electrodes showed a reduction potential with a broad peak (E. m ^ Ep ^. + Ep.a ·) /], where Ep. c and Ep.a · the peak potentials of the cathode and anode, respectively) are close to V, and have a peak-to-peak separation (ζΛΕ) of 120-200mV. zXE is slightly affected by the number of treatments on gold and Ming but not on palladium The large ΔE (scanning rate at higher potential) which increases with the shortening of the experimental time ratio indicates the dynamic limitation on the charge transfer, which is more important for the anode process and for the pt & pd electrode. The reduction peak integration confirms that the amount of ZrPV (Cl) accumulated on the surface after the same number of treatments also has different D pt and pd accumulation for more substrates than Au. These results show that the film on pt & pd is far more than Au The rough AFM data of the former is consistent. The estimation based on the ring-shaped Anker's points shows that each cycle of processing will not result in a single layer coating, but the addition of 3-6 'depends on the substrate. The E値 is more negative than 电子 (one found to be -0.6 7 V) which is electronically reduced by one of V2P in aqueous solution. MV100mV (△ £ =? 〇mV), which is close to the p-methyl redox dication. / Redox potential (_ 0 · 6 9 V) reported by the cationic radical redox coupling. Compared with v 2 P in solution, in the film • -53- This paper ruler; ^ Shicai Guanjia County ( CNS) A4 ^ m- (210X297 ^^ &quot; &quot; '--- 1: 1 --- ~ clothing (Please read the precautions on the back first Please fill in this page again) ----- ^ Order— &quot;-! 0Jm. 505617 A7 _____ B7 V. Description of the invention (51) E smf is more negative 値 100 mV is not obviously affected by Zr "and redox Of bisphosphonates on substrates. Example 3 9 If the sample is decomposed under 2000 or N 2 under the light of 200 w H g / Xe, the blue due to photochemical charge separation is observed on the layered Z r PV (C 1) with a multi-pack base template. color. The 5-minute photolysis caused the formation of both reduced redox monomers and dimers on the irradiated sample. The electronic spectrum shows a reduction band of 27 nm and appears in the dream regions of 405, 605 m and 380, 5 40 nm, which are equivalent to monomers and dimers, respectively. The electron spectrum of Zrpv (ci) containing a multi-soap-based template and the air sensitivity of the light-reduced sample indicate that this multilayer compound is not as densely packed as the microcrystalline sample of ZrPV (Cl). Samples of light-reduced suspensions of stencil-containing layered ZrP V (C1) with air can cause complete bleaching within seconds, while microcrystalline samples can take hours to days. Oxygen appears to be able to diffuse freely through the larger open-cell lattice of the compound, which may have a flexible felt-like characteristic with regard to stencil-containing materials. Printed by the Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4 5 (Please read the notes on the back before filling out this page; &gt;

Quasi-standard home country j country | Medium-use suitable-foot I sheet, paper '' cm 7 9 2

Claims (1)

^ 617 ^ 617 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs • A composition comprising a supporting substrate having a film on its surface, the film comprising: (i) a plurality of compounds of the following formula: -L-[(Y1〇3 -Z-Y203) MeY] k · k * p (xq-) where L is the bonding mode; each of Y1 and Y2 is phosphorus or arsenic; Z is a reversible stable stable state and contains two negative E. co-peach cation center with a red value; X is an anion; MeY is, wherein Me1 is a bivalent, trivalent, or tetravalent metal or lanthanum of group III, IVA, or IVB having an atomic order of at least 21; W is an anion; η is 1, 2, or 3; m is 0, 1, 2, 3, or 4; k has a value from 1 to about 100; P has a value of 0, 1, 2, or 3; and q is a charge on X, ′ Γ1, γ2, Z, and Me1 in each of the k layers may be different; each of the complexes is bound to the substrate via a bonding method L, and the L system has a side chain derived from a phosphonate or arsenate Organic polymers are characterized by repeating units of the following formula: This paper is scaled to the Chinese National Standard (CNS) Α4 · (21〇χ297 public envy (please read the precautions on the back before filling this page) 5617 A8 B8 C8 D8 6. Scope of patent application p is phosphorus or arsenic; and η is 0 to 10. 2. The composition according to item 1 of the scope of the patent application, wherein the film further comprises colloidal particles of at least one Vi group metal captured by the Me atom in the composite at zero ounces. 3. A composition comprising a supporting substrate having a film on its surface, the film comprising: (i) two or more adjacent metal layers; (11) two covalently connected to two of the adjacent metal layers Organic pillars on top of each other; (Hi) the bonding method of bonding the substrate to the metal layer closest to the substrate; wherein: each metal layer includes each other: a) forming an adhesive layer with an atomic order of at least ^, And a trivalent or tetravalent metal atom or a lanthanum atom of Group IVB; and b) an anion bonded to the metal atom so that the metal ion has an effective valence number from + 1 to + 6; the organic pillar is borrowed by the following formula Explanation:-(Υ1〇3-Z-Υ203)-. Ρ (χ ^) each Υ1 and Υ2 are respectively phosphorus or arsenic; / Ancient; «Eight red values &lt; of the conjugated cation center — (Please read the notes on the back before filling out this page) * 11 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 0ΙΦΙ. -2- 565617 Central Standards of the Ministry of Economic Affairs A8, B8, C8, D8, printed by the Consumer Cooperatives of the Bureau of the People's Republic of China 6. The scope of patent application for electron accepting divalent radicals, in which z is a transition between stable reduced state and stable oxidation state; X is an anion; p has 0, 1, 2 or A value of 3; and q is a charge on X; and the bonding mode is an organic polymer having a side chain derived from a phosphonate or arsenate, which is characterized by repeating units of the following formula ... P is phosphorus or arsenic; and η is 0 to 10. 4. The composition according to item 3 of the scope of patent application, wherein the film further comprises colloidal particles of at least one vn group metal which are trapped in the composite by metal ions at zero valence. 5 · —A composition comprising a supporting substrate having a film on its surface, the film comprising: (i) two or more adjacent metal layers; (ii) covalently connected to the; f mesh adjacent metal layers Organic pillars in two of them: Among them: Each metal layer includes each other: 4 Trivalent or quadrivalent of at least atomic order, IVA and IVB group This paper is applicable in China Standard (CNS) A4 specification (210 × 297) ) &quot; ---- (Please read the notes on the back before filling this page) 505617 A8 B8 C8 D8 VI. Patent application scope metal atom or lanthanum atom; and b) an anion bound to the metal atom, so that the metal ion has an effective valence number of +1 to +6; and a bonding layer is formed; the organic pillar It is explained by the following formula. _ (Γ1〇3-Z · Υ2〇3) ·· ρ (χ) Each of Υ1 and Υ2 is phosphorus or arsenic, respectively; Z is a conjugate cation containing two negative E. red values The center's private sonical bivalent radical, where z can be changed between a stable reduced state and a stable oxidation state; X is an anion; P has a value of 0, 1, 2, or 3; and q is a charge on X ; And the salty substrate is an organic polymer having a side chain derived from phosphonate or pingate, which is characterized by repeating units of the following formula: (Please read the precautions on the back before filling out this page} Set the policy of the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs ## •• 1. Where: P is phosphorus or arsenic; and η is 0 to 10. 6. According to the application The composition of item 5 of the patent also includes colloidal particles of a Group VIII metal, which particles are captured in the hydrophobic environment between the polymer backbones. 4- The paper size is applicable to China National Standard (CNS) A4 specification (210 × 297). (Centimeter) M35617 Inside. 7. The composition according to item 5 of the scope of patent application, wherein the film further comprises colloidal particles of at least one group V111 metal trapped in the gap formed between the pillar and the metal layer at zero valence. 8 · The composition according to item 3, 4, 5, 6, or 7 of the scope of the patent application, and also includes an organic ligand, which is located between the metal layer and the stellate, and each of the ligands is It can be covalently connected to one of the phase Zheng metal layers respectively; wherein the coordination group is described by the following formula: -y3o3-r3 Y is phosphorus or kun; and R3 is a non-reducible end-capping group. 9. A supporting substrate having a thin film on its surface, the thin film including a first layer and one or more sequential layers, each layer including each other: (i) a plurality of compounds described by the formula: &quot; [( Y 1 〇3-Z-Y2 〇3) M e γ] · Among them, each Y 1 and γ2 are respectively phosphorus or arsenic; printed by the staff consumer cooperative of the Central Bureau of Standards, Ministry of Economic Affairs (please read the notes on the back before filling in This page), 1T Z is reversibly formed into a stable reduced state and contains two with negative E in common. The co-consumptive cation center of the fed value lacks a divalent group; X is an anion; MeY4Me1nWm, where Me is a divalent, trivalent, or tetravalent metal or lanthanum of group III, I ^ 8, or Ivb of at least 21; Paper size applies to China National Standard (CNS) A4 (210X297 mm) / Scope of patent application (please read the precautions on the back before filling out this page) W is an anion; η is 1, 2 or 3; m is 0, 1, 2, 3 or 4 · P has 0, 1, 2 or 3 And q is the charge on X, where (γ1〇Z__γ2〇Υβ 3) of the composite is perpendicular to the substrate and the β M e adhesive layer is parallel to the substrate; and the first layer is borrowed by Bonded to the substrate by a bond having the following formula: -L-M ez where L is an organic polymer having a side chain derived from a phosphonate or arsenate, and wherein Me3 is a III having an atomic order of at least 21, Group IVA or IVB trivalent or tetravalent metal or lanthanum, which crosslinks the phosphonate or arsenate of the polymer to form a cohesive layer; W 'is an anion; s is 1, 2 or 3; and t is 0, 1, 2 , 3 or 4; Among them, a plurality of the first layer-covalently bonded to the Mez bonding layer printed by the Employees Consumer Cooperative of the Central Economic and Technical Bureau of the Ministry of Economic Affairs; and a plurality of each of the sequential layers _ (丫 1〇3 -2- ¥ 2〇3) is covalently bonded to the M eY layer of the preamble layer. The composition according to item 1 of the patent application scope, wherein the substrate and the bonding method It is an organic polymer with a side chain derived from phosphonate or arsenate, which is characterized by repeating units of the following formula: -6- This paper size is applicable to China National Standard (CNS) 8-4 (21〇 &gt;) &lt; 297 mm 505617 A8 B8 C8 D8 VI. Application scope Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economics where: P is phosphorus or ping; and η is 0-10. Let a derivatized polymer characterized by a repeating unit of the following formula:-(CH2) n-P03H2 where: P is phosphorus or kun; and η is 0 to 10. 12.-A method of making a composition according to item 5 of the scope of patent application, comprising the following steps: A) dissolving an organic polymer having a side chain derivatized with a phosphonate or arsenate in a solution; B) Adding a solution including ions of the ln, IVA4IVB group trivalent or tetravalent metal or lanthanum metal having an atomic order of at least 21; C) cross-linking phosphonic or arsenate with metal ions; D) dialyzing the mixture against distilled water Removing free ions; E) adding bisphosphonic acid or bisarsenic acid; This paper is suitable for household income (21Qx297h j (Please read the notes on the back before filling out this page) Order 505617 A8 B8 C8 D8 6. Apply for patent scope F) Make the mixture dialysis against water to remove free ions; And G) Repeat steps 骡 B, C, D, E, and F. 13. The method for manufacturing a composition according to item 12 of the scope of patent application, wherein the solution of step) A) is colloidal particles including a group VIII metal Its solution. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs This paper is sized for China National Standards (CNS) A4 (210X297 mm)