DE102013017826A1 - Process for the preparation of a hydrotalcite - like surface material, products produced by the process and their uses - Google Patents

Abstract

The invention relates to the production of an innovative, non-naturally occurring layer-hydrotalcite-like surface material (INNO-LDH-LSM). On the carrier layer (T) is a solid metal (M1) which after a halide coating (A) is capable of reacting with a second metal ion (M2) to form a hydrotalcite-like layer. For preparation, a metal halide solution for M2 layer formation may be used or a halide treatment of the solid metal surface (M1) may be performed. The addition of a halide salt to the metal ion solution is also possible.

Description

The present invention relates to the production of an innovative, non-naturally occurring layer-hydrotalcite-like surface material (INNO-LDH-LSM). The support layer consists of a solid metal (M1) which after a halide coating (A) is capable of reacting with a second metal ion (M2) to form a hydrotalcite-like layer. For preparation, a metal halide solution for M2 layer formation may be used or a halide treatment of the solid metal surface (M1) may be performed. The addition of a halide salt to the metal ion solution is also possible.

Background and state of the art

Naturally occurring layer hydrotalcites

The naturally occurring layered hydrotalcites (LDH, layered double hydroxides) usually have the following chemical composition: [Me2 _1-x Me3 _x (OH) ₂ ] ^{x +} (A ^n- ) _{x / n} * _m H ₂ O. where Me2 and Me3 for different divalent cations z. As Ca ²⁺ , Mg ²⁺ , Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ or Zn ²⁺ or trivalent cations such as Al ³⁺ , Fe ³⁺ , Cr ³⁺ , Mn ³⁺ , Co ³⁺ and Ni ³⁺ . A ⁿ stands for anions such as Cl ^- , Br ^- , NO ₃ ^- , CO ₃ ^2- , SO ₄ ^2- and SeO ₄ ^2- .

• – Die in der Fougèrit-Gruppe natürlich vorkommenden ”grünen Ruß Minerale” sind sehr starke Reduktionsmittel, mit M²⁺ = Fe²⁺, M³⁺ = Fe³⁺ unterschiedlicher Verhältnisse und einigen O^2– Substitutionen für OH^– im Brucit.
• – Die zu der Hydrotalkit-Gruppe zählenden Minerale haben das Verhältnis M²⁺:M³⁺ = 3:1.
• – Die Minerale in der Cualstibit-Gruppe kennzeichnet eine Zwischenschicht von [Sb(OH)₆]^–.
• – Die zu der Quintinit-Gruppe zählenden Minerale haben das Verhältnis M²⁺:M³⁺ = 2:1.
• – Die Minerale in der Woodwardit-Gruppe haben unterschiedliche M²⁺:M³⁺ Verhältnisse und sind durch eine Zwischenschicht mit Sulfationen gekennzeichnet.
• – Die Minerale der Hydrocalumit-Gruppe haben M²⁺ = Ca²⁺ und M³⁺ = Al³⁺, mit Brucit-ähnlichen Schichten in denen das Ca:Al Verhältnis 2:1 beträgt und das Ca²⁺ koordiniert ist mit einer Zwischenschicht aus Wasser.
• – Die Glaucocerinit-Gruppe ist sowohl gekennzeichnet durch eine Zwischenschicht aus Sulfationen, wie auch einer Zwischenschicht aus Wassermolekülen.
• – Die Minerale in der Wermlandit-Gruppe besitzen Brucit-ähnliche Schichten mit Vorkommen kationischer Komplexe mit Anionen.

Depending on the composition - not just the metal combination but also their relationship to each other - and the nature of the anion, the naturally occurring LDHs have different names depending on which of the following eight groups they are assigned:

• - The naturally occurring in the Fougèrit group "green carbon black minerals" are very strong reducing agents, with M ²⁺ = Fe ²⁺ , M ³⁺ = Fe ³⁺ different ratios and some O ^2- substitutions for OH ^- in brucite.
• - The minerals belonging to the hydrotalcite group have the ratio M ²⁺ : M ³⁺ = 3: 1.
• - The minerals in the Cualstibit group indicate an intermediate layer of [Sb (OH) ₆ ] ^- .
• - The minerals belonging to the quintinite group have the ratio M ²⁺ : M ³⁺ = 2: 1.
• - The minerals in the woodwardite group have different M ²⁺ : M ³⁺ ratios and are characterized by an intermediate layer with sulfate ions.
• - The minerals of the hydrocalumite group have M ²⁺ = Ca ²⁺ and M ³⁺ = Al ³⁺ , with brucite-like layers in which the Ca: Al ratio is 2: 1 and Ca ^{2+ is} coordinated with an intermediate layer of water.
• - The glaucocerinite group is characterized by an intermediate layer of sulfate ions as well as an intermediate layer of water molecules.
• - The minerals in the Wermlandite group have brucite-like layers with cationic complexes with anions.

Application of layered hydrotalcites (LDH)

Currently, there is a lot of interest in LDH and LDH-like materials ^[1] , because of the broad field of application and enormous application potential in various important areas such as electrochemistry, catalysis, polymerization, photochemistry, the environmental sector and biomedicine.

• [1] Cavani et al., Catal. Today, 1991, 11, 173; Newman et. al., New J. Chem., 1998, 22 (2), 105; Rives, Layered Double Hydroxides: Presentand Future, Nova Science Publishers Inc., 2001, New York; Li et. al., Struct. Bond., 2005, 119 (1), 193; Evans et. al., Chem. Commun., 2006, 5, 485
• [2] Liao et al., Electrochim. Acta, 2004, 49 (27), 4993
• [3] Roelofs et al., J. Catal., 2001, 203 (1), 184
• [4] Nishimura et al., Chem. Commun., 2000, 14, 1245
• [5] Tsyganok et al., J. Catal., 2003, 213 (2), 191
• [6] Lin et al., Polym. Degrad. Stabil., 2005, 88 (2), 286
• [7] Evans et. al., Chem. Commun., 2006, 5, 485
• [8] Shimizu et al., Inorg. Chem., 2006, 45 (25), 10240
• [9] Gardner, Biomaterials, 1985, 6 (3), 153; Rahman et al., Catal. Today, 2004, 95 (1), 405

In electrochemistry, LDHs are used as nanocomposite polymer electrolyte ^[2] . LDHs have shown interesting applications for catalysis in acid-base processes ^[3] , redox processes, ^[4] as well as in the preparation of small source chemicals ^[5] . In the field of polymerization, the LDH and LDH-like materials were used as a stabilizer in the polymer ^[6] and for the heat resistance of polymers ^[7] . The object of LDH research is to increase the photosensitivity of materials for photochemical processes ^[8] . LDHs have also been used in the formulation of pharmaceutical products and controlled release drug delivery systems ^[9] .

• [1] Cavani et al., Catal. Today, 1991, 11, 173; Newman et. al., New J. Chem., 1998, 22 (2), 105; Rives, Layered Double Hydroxides: Present and Future, Nova Science Publishers Inc., 2001, New York; Li et. al., Struct. Bond., 2005, 119 (1), 193; Evans et. al., Chem. Commun., 2006, 5, 485
• [2] Liao et al., Electrochim. Acta, 2004, 49 (27), 4993
• [3] Roelofs et al., J. Catal., 2001, 203 (1), 184
• [4] Nishimura et al., Chem. Commun., 2000, 14, 1245
• [5] Tsyganok et al., J. Catal., 2003, 213 (2), 191
• [6] Lin et al., Polym. Degrad. Stable, 2005, 88 (2), 286
• [7] Evans et. al., Chem. Commun., 2006, 5, 485
• [8th] Shimizu et al., Inorg. Chem., 2006, 45 (25), 10240
• [9] Gardner, Biomaterials, 1985, 6 (3), 153; Rahman et al., Catal. Today, 2004, 95 (1), 405

Synthesis of LDHs

Apart from the natural occurrence of LDHs, they can also be artificially produced relatively easily with ordinary laboratory equipment.

All known production methods of LDHs were from He et. al. (in Struct Bond, 2006, 119, 89) described in detail. Some examples from the publication, which can roughly be divided into the following groups, are presented here:
Simultaneous precipitation, ion-exchange method, structural memory-utilizing dehydration, hydrothermal method, intercalation with dissolution and renewed simultaneous precipitation, salt oxide / hydroxide method, aging method, surface method and template method.

Of all these methods, simultaneous precipitation is the most commonly used. It takes place in a reaction vessel in which both the two metals as well as the anions or organic anions have been mixed in their desired ratio to a supersaturated solution. The supersaturation is pH-controlled at a level where most of the soluble hydroxides precipitate. The precipitated product is thermally treated for hours or days in aqueous solution between 273 and 373 K. In a second step, the product is autoclaved at 10 to 150 MPa. Simultaneous precipitation sets either a slight supersaturation or a high supersaturation. The slightly supersaturated method results in a more pure product as one of the metal salts is added slowly. The method is much slower.

The ion-exchange method is used when the divalent or trivalent metal is not stable in alkaline solution and therefore does not precipitate simultaneously. For this reason, the LDH must be produced in two steps. In the first step, monovalent anions such as chloride, nitrate or bromide are used, which are exchanged after the platelets have been formed by hydroxides or other "guests" (for example in drug delivery).

During dehydration, LDHs are calcined to completely remove intercalated water, hydroxides and anions and to obtain a mixed oxide layer. When this material comes in contact with water and anions dissolved in it, the typical hydroxide layers with their specific anions are formed.

With the hydrothermal method, it is even possible to store organic anions, which actually have a low affinity to deposit as guests in LDHs. In this case, insoluble metal hydroxides of magnesium or aluminum are used to occupy the space between two layers, so that the organic molecules can penetrate.

In the case of intercalation with dissolution and renewed simultaneous precipitation, it is possible to form carboxylate layers from carbonate acid LDHs. This is made possible by feeding an aqueous solution with the carboxylate of the precursors and then precipitating with a base.

The salt oxide / hydroxide method allows for example by means of a mixture of magnesium hydroxide and sodium aluminate to produce an LDH.

In the three ways aging, surface and Matrizen method, it is possible to influence the crystal growth by means of, for example, sound or microwaves. In the case of surface-assisted LDHs, one not only finds the LDH-typical property advantages, but also that of the supporting material. One of the few examples is an α-Al ₂ O ₃ in which either Co ⁺² , Ni ²⁺ or Zn ^{2+ were} added to obtain an M ²⁺ LDH. The aluminum then becomes the donor of the M ^{3+ of} the LDH.

In the matrix method one uses the self-assembly of aggregates which often leads to inorganic-organic combinations where the organic part is subsequently removed (ex. Calcination) to obtain the LDH.

Restructuring of layered hydrotalcites

• 1. Dehydratisierung (100–250°C): [Me2_1-xMe3_x(OH)₂]^x+(A^n–)_x/nmH₂O → [Me2_1-xMe3_x(OH)₂]^x+(A^n–)_x/n
• 2. Dehydroxylierung (350–450°C): [Me2_1-xMe3_x(OH)₂]^x+(A^n–)_x/n → [Me2_1-xMe3_xO]^x+(A^n–)_x/n
• 3. Abspaltung der Anionen (420–470°C): [Me2_1-xMe3_xO]^x+(A^n–)_x/n → Me2_1-xMe3_xO₁ + _x/2(BO_y)
• 4. Oxidrückbildung (450–700°C): Me2_1-xMe3_xO₁ + _x/2(BO_y) → Me2O + Me2Me3₂O₄ + BO_y

wobei Me2O für gewöhnlich ein Oxid in Natriumchlorid-Struktur ist, das Me2Me3₂O₄ für gewöhnlich ein Mischoxid der Spinell-Gruppe ist und BO_y für die Spezies von abgespalteten Anionen steht. Nach der Abspaltung der Anionen erhält man Oxide und oxidstützende Katalysatoren denen eine besondere Bedeutung zugemessen wird. Bei LDHs die oxidierbare zweiwertige Kationen enthalten wie beispielsweise Co²⁺, Fe²⁺, Ni²⁺ und Mn²⁺ tritt eine spontane Oxidation während Erhitzung in Luft auf. In diesem Fall wird Dehydroxylierung ermöglicht und das bereits bei Temperaturen unterhalb 250–300°C oder überlappt sogar mit der Dehydratisierung, d. h. kann bereits unterhalb 100°C auftreten.In addition to the production of LDHs with different M ²⁺ , M ³⁺ and anions, it is also possible to modify the structure after production. It will be at Xu et. al. (in Applied Clay Science, 2011, 53, 139) describes very precisely how four different states of LDHs can be achieved. The first is called dehydration, the second dehydroxylation, the third anion cleavage and the fourth oxide reformation described below. The process of producing these mixed oxides is primarily heating to a certain temperature. By way of illustration, the temperature ranges of transformation from magnesium / aluminum containing hydrotalcite to mixed sodium chloride structure MgO + MgAl ₂ O _{4 are given} in parentheses:

• 1. Dehydration (100-250 ° C): [Me2 _1-x Me3 _x (OH) ₂ ] ^{x +} (A ^n- ) _{x / nm} H ₂ O → [Me 2 _1-x Me 3 _x (OH) ₂ ] ^{x +} (A ^n- ) _{x / n}
• 2. Dehydroxylation (350-450 ° C): [Me2 _1-x Me3 _x (OH) ₂ ] ^{x +} (A ^n- ) _{x / n} → [Me 2 _1-x Me 3 _x O] ^{x +} (A ^n- ) _{x / n}
• 3. Cleavage of the anions (420-470 ° C): [Me2 _1-x Me3 _x O] ^{x +} (A ^n- ) _{x / n} → Me 2 _1-x Me 3 _x O ₁ + _{x / 2} (BO _y )
• 4. Oxide Recovery (450-700 ° C): Me2 _1-x O ₁ + _x Me3 _{x / 2} (BO _y) → Me2O + Me2Me3 ₂ O ₄ + BO _y

wherein Me2O is usually an oxide in sodium chloride structure, the Me2Me3 ₂ O ₄ is typically a mixed oxide of the spinel group and _y BO stands for the species of cleaved anions. After the cleavage of the anions, oxides and oxide-supporting catalysts which are of particular importance are obtained. For LDHs containing oxidizable divalent cations such as Co ²⁺ , Fe ²⁺ , Ni ^2+, and Mn ²⁺ , spontaneous oxidation occurs during heating in air. In this case, dehydroxylation is possible even at temperatures below 250-300 ° C or even overlaps with dehydration, ie may already below 100 ° C occur.

Fenton reagent - iron catalysis

The Fenton reagent is a solution that contains hydrogen peroxide and an iron catalyst, and is commonly used to oxidize organic substrates in wastewater. Some examples of organic substances that are destroyed are trichloroethene (TCE) and tetrachloroethene (PCE). The Fenton reagent was developed in 1890 by Henry Fenton for analysis.

The effect of the Fenton reagent is based on the process that iron (II) is oxidized by hydrogen peroxide to iron (III). In this step (1), a hydroxyl radical and a hydroxyl anion are formed. In the second step, the iron (III) is reduced again to iron (II) on which then a peroxide radical and a proton are formed. The radicals formed, and especially hydroxyl radicals, are very strong non-selective oxidants, resulting in the oxidation of organic substrates being very fast and exothermic. Fe ²⁺ + H ₂ O ₂ → Fe ³⁺ + ∘OH ∙ + OH ^- (1) Fe ³⁺ + H ₂ O ₂ → Fe ²⁺ + ∘OOH + + H ⁺ (2)

Recently, interesting discoveries have been made with iron oxides in nanomaterials. For example, describes Cui et. al. (in Chem. Commun., 2013, 49, 2332) that Fe ₂ O ₃ which has been coated with silicate in the presence of H ₂ O _{2 is} capable of degrading a dye to water and CO ₂ similar to the described Fenton reaction. Another example comes from Behera et. al. (in World Journal of Nanoscience Science and Engineering, 2012, 2, 196) which produce nano Fe ₃ O ₄ between 10-120 nm. These nanoparticles were tested for pathogenic bacteria, four of which were gram positive and six gram negative. Staphylococcus aureus, Shigella flexneri, Bacillus licheniformis, Bacillus brevis, Vibrio cholerae, Pseudomonas aeruginosa, Streptococcus aureus, Staphylococcus epidermidis, Bacillus subtilis, Escherichia coli.

The authors suggest that the key mechanism responsible for the antibacterial activity of the particles is believed to be due to oxidative stress due to the formation of reactive oxygen species (ROS). ROS includes superoxide radicals (∘O ₂ ^- ), hydroxyl radicals (∘OH), hydrogen peroxide (H ₂ O ₂ ) and singlet oxygen ( ¹ O ₂ ) and can destroy proteins and bacterial DNA. In the study in question, metal oxides (FeO) could be the source of ROS, which eventually led to the inhibition of most pathogenic bacteria. Also, the publication suggests that the small size of iron oxide is toxic to bacteria. In any case, it is interesting that no hydrogen peroxide was required for the formation of ROS in the Fe ₃ O ₄ nanoparticles, in contrast to Fe ₂ O ₃ nanoparticles. Neither Cui nor Behera, however, were finally able to fully explain the catalytic mechanism that occurs in their iron oxide and leads to the formation of ROS in a Fenton-like manner, and Behera could not clearly say whether it was not due to the size alone Nanoparticles lay.

Further state of the art

Nocchetti et. al. (in J. Mater Chem. B, 2013, 1, 2383) describe in their publication some Ag / AgCl nanoparticles which had as growth nuclei a ZnAlM1 layer, which were then reduced with NaBH ₄ to produce silver nanoparticles. These Ag / AgCl nanoparticles have been shown to have good antimicrobial activity against both Gram positive (Staphylococcus epidermidis and S. aureus) and Gram negative (Pseudomonas aeruginosa) bacteria and against yeasts (Candida albicans). An examination of their three versions of the product for silver discharge was also made and it was found that the product with the lowest silver output was also the one with the worst activity, which means that the antibacterial effect of the Ag / AgCl nanoparticles on the discharge of silver ions based.

Bouariu et. al. (in J. Therm Anal Calorim, 2013, 111, 1263) showed some interesting results after giving silver ions to MgAl-LDH and ZnAl-LDH. With the "adhesive" silver ions between the cavities of MgAl and ZnAl, they were able to organize themselves into structures that were different in thermal decomposition compared to the starting LDHs.

Chen et. al., (in Adv. Funct. Mater., 2012, 22, 780) describe how they produce silver nanoparticles on an LDH surface. These nanoparticles sitting on the surface of LDH were tested for their antibacterial properties against gram positive (B. subtilis and S. aureus) and gram negative (E. coli and P. aeruginosa) bacteria. Also in this case, the antibacterial property is due to leaking silver ions whose concentration is enormous because of the large surface area.

Fan et. al. (in Chem. Eur. J., 2013, 19, 2523) describe in their publication how to prepare homogeneously distributed Ag / AgBr nanoparticles on Co-Ni-NO ₃ LDH to which an AgNO ₃ solution has been added. In the absence of light, organic soil particles were adsorbed and after irradiation with light, these particles were decomposed.

Marcato et. al. (in Braz. Chem. Soc., 2013, 24 (2), 266) showed how they combined a Mg-Al LDH with what they call biogenic silver nanoparticles to produce an antibacterial material. Their material was tested against Staphylococcus aureus and Escherichia coli and showed very good activity, due to the strong release of silver ions as the active substance.

Li et. al., (in J. of Mat. Sci., 2005, 40, 1917) describe the preparation of magnetic nanoparticles consisting of MgO and MgFe ₂ O ₄ spinel ferrite. The compound was prepared by using hydrotalcite-like LDHs of the type [Mg _1-xy Fe ²⁺ _y Fe ³⁺ _x (OH) ₂ ] _x + (A) _{x / 2} · mH ₂ O (y≥0; A = CO ₂ ^-3 or SO ₂ ^-4 ) as precursor which was subsequently calcined for 2 hours at 900 ° C. The MgFe ₂ O ₄ nanocomposite was tested against Staphylococcus aureus. The conclusion Li et. al. The larger the ratio of MgO to iron, the more antibacterial the compound was.

In all the examples of the literature in which silver is investigated with LDHs, silver nanoparticles were always formed on an LDH prepared in advance. In no case was it shown that an LDH was formed on a silver halide-containing surface. In the only case found, in which iron and LDH are related to antibacterial activity, more appears to depend on the magnesium oxide, especially since no hydrogen peroxide was added to start the Fenton reaction.

The invention

The invention relates to a method for producing a novel material (INNO-LDH-LSM) containing
a carrier material (T) made of any solid material,
a metal layer (M1) deposited on the carrier material, the metal being silver, an anionic layer (A) located on the metal layer (M1),
wherein the anion is a halide ion,
a metal hydroxide / oxide layer (M2) on the anionic layer, wherein the metal can be chosen arbitrarily,
by wetting the M1-coated support material (T) with a solution containing M2 halide at 0-100 ° C., in particular 5-75 ° C., especially 20-50 ° C. to 30 days, in particular up to 10 days
and subsequent drying to 1000 ° C, in particular to 550 ° C with access of air to 50 hours, the product produced by this method and its multiple uses.

The invention describes an antibacterial, fungicidal and antiviral material (INNO-LDH-LSM) which is as efficient as Beheras Fe ₃ O ₄ , which is also capable of producing ROS without addition of hydrogen peroxide and even at temperatures above 0 ° C Fenton-like way to form in water. The material according to the invention consists of a novel, non-naturally occurring, surface-supported LDH on a carrier ( 1 ). The carrier (T) may be of any nature, in particular it may be graphite, glass, PTFE, copper, titanium, aluminum, zinc, magnetic iron or textile. The shape of the carrier is very diverse. Particles, spheres, nets, lattices, plates and powders are particularly suitable as forms. The material according to the invention consists of a solid metal layer (M1), an anionic layer (A) and a metal hydroxide / oxide layer (M2) and becomes INNO-LDH-LSM (innovative, non-naturally occuring layered double-oxide-like surface material). called. The solid metal layer (M1) consists of silver, with little admixtures of other metals are not critical. As metals of the metal hydroxide / oxide layer (M2), in principle all metals are suitable, in particular subgroup metals, in particular platinum metals, in particular platinum, in particular gold, in particular ruthenium. The most preferred metal for layer M2 is iron. Also with regard to the metal hydroxide / oxide layer (M2), it is true that small admixtures of other metals are not critical.

It is novel above all that it is possible to coat very noble metals with base metals by means of halide ions (A), in particular chloride ions, and to produce an LDH-like material. The INNO-LDH-LSM is prepared either by adding a metal halide solution, in particular a metal chloride solution for M2 layer formation or prepared by adding a halide, in particular salt-like halide, in particular chloride salt, in particular sodium chloride to the metal ion solution or by treating the metal (M1) with dilute Hydrochloric acid produced. The preparation of the INNO-LDH-LSM on a carrier (T1) is carried out simply by wetting an M1-coated carrier (T-M1) to an M2 halide-containing Solution. After treatment, the solution is poured off and the resulting LDH-like material undergoes spontaneous dehydroxylation below 100 ° C resulting in a hydroxide / oxide species. This is washed several times with water to give the highly efficient INNO-LDH-LSM which forms ROS in a Fenton-like manner without hydrogen peroxide. It only takes a small activation energy to keep the catalysis running and, like all ROS catalytic reactions, it is the more efficient the more oxygen is available. The advantage of this method is that any type of surface, no matter what size or shape can be coated, as long as the carrier (T) can be dipped or sprayed. After the INNO-LDH-LSM has been prepared, it is possible to use either the ion exchange method, the dehydration using the structural memory or the hydrothermal method to exchange the anions, even against organic anions.

The present invention is therefore the method according to claims 1 to 4 and the material produced by the method of claim 5.

applications

The implementation of INNO-LDH-LSM coated substrates on materials such as glass, ceramics, plastics, paper or wood is possible as well as the coating of materials with INNO-LDH-LSM. A prerequisite for the activity of the layer is the contact with a liquid, in particular water and alcohols, and the substrate. It is possible that a full implementation is made and only over time by abrasion or weathering of the material, the active material is released and only then enters its antibacterial, fungicidal and antiviral property. Since water and alcohols are catalytically activated via ROS, it is also possible to activate water or alcohol-containing liquids first and then to use the activated liquid as an active reagent, eg. As for crop protection, seed treatment and other agricultural applications or for the treatment of surfaces, especially in the medical, life science and cleaning, especially for the treatment of food packaging.

The present invention therefore also relates to the uses of the material produced according to the invention as claimed in claims 6 and 7 and to the use of liquids of claim 8 activated according to the invention according to the invention as claimed in claims 9 and 10.

Examples

The following examples illustrate the subject matter of the invention without wishing to be limiting. The person skilled in the art readily recognizes process variants and other possible uses without having to be inventive.

Example 1:

Coated carrier (T-M1) in the form of spheres between 0.1 and 1 mm, coated glass particles of sizes 2, 14, 40 and 80 μm, coated magnetic iron particles, coated graphite particles / rods and powder.

• a) Fe(II)Cl₂ Lösung (15 g/L)
• b) Ru(III)Cl₃ Lösung (35 g/L, Wasser:Ethanol 1:3)
• c) Ca(II)Cl₂ Lösung (30 g/L)
• d) HAu(III)Cl₄ Lösung (4 g/L)
• e) H₂Pt(IV)Cl₆ Lösung (25 g/L)

In each case 1 g of the coated carrier (T-M1) was placed in glass flasks and exposed to 5 mL of a solution (ae).

• a) Fe (II) Cl ₂ solution (15 g / L)
• b) Ru (III) Cl ₃ solution (35 g / L, water: ethanol 1: 3)
• c) Ca (II) Cl ₂ solution (30 g / L)
• d) HAu (III) Cl ₄ solution (4 g / L)
• e) H ₂ Pt (IV) Cl ₆ solution (25 g / L)

The flasks were shaken for minutes, c) for two days. The product was washed several times with water and ethanol and then dried at different temperatures (15 ° C to 550 ° C).

Example 2:

Coated carrier (T-M1) in the form of coated textile, nets, grids and sheets coated with copper, steel, titanium, aluminum or zinc.

1 cm ² pieces of each sample were each made into a glass bottle and to each was added 5 mL of a Fe (II) Cl ₂ solution (15 g / L). The glass bottles were shaken for minutes. The product was washed several times with water and ethanol and then dried at 80 ° C to 120 ° C.

Example 3:

INNO-LDH-LSM coated spheres, particles, powders or sticks were mixed in paints and varnishes in a concentration of 0.01 to 50 wt%. The modified colors and paints showed after application and drying on different carriers antibacterial and fungicidal properties.

Example 4:

INNO-LDH-LSM coated spheres, particles, powders or rods were in polymers or after its polymerization in concentrations between 0.01 and 50 wt%. The plastic surfaces showed antimicrobial activity on all surfaces where INNO-LDH-LSM had contact to the outside.

Example 5:

AgNO ₃ was dissolved in 3 mL deionized water. 0.25 g of NaCl, NaBr or NaI was added. With sodium chloride, a fine, white powder was obtained, with sodium bromide and sodium iodide a fine, pale yellow powder. The three powders were each washed several times with water before 5 mL of a Fe (II) Cl ₂ solution (15 g / L) was added. After shaking the solutions for several minutes and then washing the powders several times with water, the powder of the sample containing sodium chloride was found to be yellowish / brownish, and the powders of the other two samples turned deep yellow.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited non-patent literature

• Cavani et al., Catal. Today, 1991, 11, 173; Newman et. al., New J. Chem., 1998, 22 (2), 105; Rives, Layered Double Hydroxides: Present and Future, Nova Science Publishers Inc., 2001, New York; Li et. al., Struct. Bond., 2005, 119 (1), 193; Evans et. al., Chem. Commun., 2006, 5, 485 [0005]
• Liao et al., Electrochim. Acta, 2004, 49 (27), 4993 [0005]
• Roelofs et al., J. Catal., 2001, 203 (1), 184 [0005]
• Nishimura et al., Chem. Commun., 2000, 14, 1245 [0005]
• Tsyganok et al., J. Catal., 2003, 213 (2), 191 [0005]
• Lin et al., Polym. Degrad. Stable., 2005, 88 (2), 286 [0005]
• Evans et. al., Chem. Commun., 2006, 5, 485 [0005]
• Shimizu et al., Inorg. Chem., 2006, 45 (25), 10240 [0005]
• Gardner, Biomaterials, 1985, 6 (3), 153; Rahman et al., Catal. Today, 2004, 95 (1), 405 [0005]
• He et. al. (in Struct Bond, 2006, 119, 89) [0007]
• Xu et. al. (in Applied Clay Science, 2011, 53, 139) [0016]
• Cui et. al. (in Chem. Commun., 2013, 49, 2332) [0019]
• Behera et. al. (in World Journal of Nanoscience Science and Engineering, 2012, 2, 196) [0019]
• Nocchetti et. al. (in J. Mater Chem. B, 2013, 1, 2383) [0021]
• Bouariu et. al. (in J. Therm Anal Calorim, 2013, 111, 1263) [0022]
• Chen et. al., (in Adv. Funct. Mater., 2012, 22, 780). [0023]
• Fan et. al. (in Chem. Eur. J., 2013, 19, 2523) [0024]
• Marcato et. al. (Braz. Chem. Soc., 2013, 24 (2), 266) [0025]
• Li et. al., (in J. of Mat. Sci., 2005, 40, 1917). [0026]
• Li et. al. [0026]

Claims (10)

Process for the preparation of a material (INNO-LDH-LSM) containing a carrier material (T) made of any solid material, a metal layer (M1) deposited on the support material, the metal being silver, an anionic layer (A) on the metal layer (M1), the anion being a halide ion, a metal hydroxide / oxide layer (M2) on the anionic layer, the metal being iron, by wetting the M1-coated support material (T) with an iron halide-containing solution at 0-100 ° C, in particular 5-75 ° C, especially 20-50 ° C to 30 days, especially up to 10 days and subsequent drying to 1000 ° C, in particular up to 550 ° C with access of air to 50 hours. A method according to claim 1, characterized in that the carrier material (T) is selected from graphite, glass, PTFE, copper, titanium, aluminum, zinc, iron or textiles. A method according to claim 1 or 2, characterized in that the carrier material (T) is formed as a particle, ball, mesh, grid, plate or powder. A method according to any one of claims 1 to 3, characterized in that the anionic layer consists essentially of chloride ions. INNO-LDH-LSM material obtainable by a process according to any one of claims 1 to 4. Use of a material according to claim 5 for the antibacterial, fungicidal and / or antiviral coating of surfaces. Use of a material according to claim 5 for medical applications and food packaging. Use of a material according to claim 5 for the activation of liquids, in particular water and alcohols, especially ethanol. Use of a liquid according to claim 8 for the antibacterial, fungicidal and / or antiviral treatment of surfaces. Use of a liquid according to claim 8 for medical applications, for food packaging, for agricultural applications, for life science applications and for cleaning applications.

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