CN115770620A - Heterogeneous single-site preparation method of noble metal substrate - Google Patents
Heterogeneous single-site preparation method of noble metal substrate Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 9
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- 239000002184 metal Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003446 ligand Substances 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 22
- 229910052737 gold Inorganic materials 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 229910052709 silver Inorganic materials 0.000 claims description 11
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- -1 tungsten-molybdenum metal oxide Chemical class 0.000 claims description 4
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- 239000002904 solvent Substances 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
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- 125000000524 functional group Chemical group 0.000 abstract description 2
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- 239000003054 catalyst Substances 0.000 description 2
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- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
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- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
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- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
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- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
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- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
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- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
The invention provides a heterogeneous single-site preparation method of a noble metal substrate. Adding a single site of homogeneous tungsten and molybdenum metal complex with functional group modification, namely a metal single atom or a metal single cluster into water or a solvent, wherein a ligand is a compound molecule containing oxygen/sulfur/nitrogen and capable of being coordinated with metal, namely metal oxygen/sulfur/nitride uniformly dispersed in the solvent, and preparing a homogeneous complex solution. After the substrate material with surface defects is added into the solution, homogeneous sites are loaded at the defects or gaps on the surface of the substrate material by standing freezing/heating or pH or voltage adding modes to form heterogeneous preparation.
Description
Technical Field
The invention relates to the field of material synthesis and catalyst preparation, in particular to a preparation method of a homogeneous atomic-scale site and a process of a heterogeneous catalyst loaded on different precious metal material substrates, wherein the process is suitable for large-scale mass production.
Background
The fields of catalysts, catalytic materials, and the like have been rapidly developed in recent ten years. Such materials are used in the fields of petrochemical, biopharmaceutical, instrumentation, and the like. In practical applications, the realization of a heterogeneous catalytic material with high activity, durability and low cost is an important direction.
Metal complexes are a class of compounds having a metal active center coordinated to surrounding molecules. The metal center is the active center of catalytic reaction due to the unique electron orbital distribution. The coordinating molecule stabilizes the valence and position of the metal. It is also possible to use molecules with end-functionalization for the organocatalytic reaction. Such catalytic reactions are often used as heterogeneous catalysts in organic catalysis and industrial catalysis. The metal complex with catalytic activity is adsorbed or fixed on the surface of the material by using a conventional substrate material such as silicon oxide, titanium dioxide, zinc oxide, graphene, gold, silver, copper, carbon material and the like as a carrier.
The heterogeneous metal complex sites still maintain the active center structure and properties in the homogeneous phase. Thus, an organocatalytic reaction in heterogeneous phase can be achieved. The presence of the molecule is confirmed and quantitatively detected by detecting the resistivity, raman or refraction of the reactants and reaction products before and after the reaction by an electric signal, a scattered signal, a refractive index or the like.
Disclosure of Invention
In view of the above, the main objective of the present invention is to provide a heterogeneous preparation method for supporting homogeneous metal complex sites and a method for monitoring catalytic target molecules by using the same, so as to solve at least one of the above technical problems.
In order to achieve the above object, as one aspect of the present invention, there is provided a method for preparing silicon oxide supporting an oxide of monatomic tungsten.
(1) The invention forms a homogeneous solution system by stably coordinating and combining tungsten or molybdenum-containing metal oxide and/or tungstate or heteropoly acid and organic chain molecules with O, S and N in water.
(2) The invention is a solution chemical synthesis, has small instrument investment and simple preparation of the precursor solution, and is beneficial to large-scale production;
(3) The deposition of the sites on the surface defects of the noble metal utilizes the principle of lowest energy, on one hand, the metal surface defects are in atomic scale, and the invention utilizes the solution environment to distribute atomic-level sites in a homogeneous system on the defects on the surface of the substrate. On the other hand, the electrostatic force is controlled by utilizing environmental factors such as temperature, voltage, pH and the like, so that effective combination of the single atom and the substrate is facilitated. The method is effective and low in cost, so that the substrate material of the method is not only suitable for Ag and Au. A great extension can be obtained, for example substrates comprising: pure metals, oxides, MOFs, graphene, carbon nitride, metal atoms including: transition group metals, main group metals;
(4) The invention utilizes a heterogeneous loading process, and the key is that the surface of the metal substrate has defects or gaps or periodic defects. The substrate is constructed in the processes of magnetron sputtering and thermal evaporation. Secondly, surface isomerism by heat treatment or light irradiation. Such construction methods the present invention will be referred to in the examples;
(5) The substrate material includes: noble metals Au or Ag;
(6) The heterogeneous loading process is controlled by using voltage or temperature or pH value parameters, and the homogeneous metal complex is loaded on the substrate material. Wherein, the regulation and control of pH are as follows: hydrochloric acid, sulfuric acid, nitric acid, ammonia water, sodium hydroxide;
drawings
FIG. 1 shows the loading of monoatomic W/Ag, the first column for different Ag concentrations, the second column for the first column after light irradiation, and the third column for the film forming effect by coating.
FIG. 2 is an HAADF-STEM image of a W complex-supporting carbon material
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
The invention discloses a preparation method of a heterogeneous material loaded with tungsten and molybdenum metal complexes. The site was prepared as follows: in water and/or ethanol solvent, adding organic chain polymer with-CH CH OH functional group into dissolved tungstate and/or suspended tungsten-containing metal oxide to form metal precursor liquid; the noble metal Au nano-particles are uniformly mixed with the metal precursor liquid in a solvent of water and/or ethanol by stirring, and then the sulfuric acid is gradually dropped. W is bonded at the noble metal surface defects by electrostatic force.
Specifically, the tungsten-molybdenum-loaded homogeneous material system comprises:
metal tungsten molybdenum oxoates and/or metal oxides, metal chlorides, heteropoly acid compounds;
water and/or an organic solvent as a solvent;
wherein the organic solvent comprises: ethanol, isopropanol, acetone, DMF, DMSO, CCl 4 。
Organic/inorganic of ligand groups; among these, acids or organic compounds containing acid groups include, for example, but are not limited to: weak acids such as tartaric acid, EDTA; medium strong acids, such as oxalic acid, citric acid, benzenesulfonic acid; strong acids, such as sulfuric acid, hydrochloric acid, nitric acid; polymers with acid functionality, such as acrylic acid, polyacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, poly (2-acrylamido-2-methylpropanesulfonic acid), aminobenzylamine, porphyrins, imidazoles, aminothiophenol, organic nitrogen.
Example 1:
the heterogeneous preparation method of the gold Au substrate surface loaded with tungsten-thiophenol coordination comprises the following steps:
to 100ml of deionized water, 0.3g of sodium tungstate was added, and the mixture was stirred until it was clarified. 0.1g of hydroxythiophenol ligand molecule was added thereto, and 1wt% diluted hydrochloric acid was added thereto to adjust pH 2. Stirring for 1 hour at the temperature of 50 ℃, and forming a bond with a metal central atom through an SH bond to generate a coordination reaction of the hydroxythiophenol and the metal tungsten and molybdenum. Then, in the above clear solution after cooling, a substrate of gold Au particles arranged in a thickness of 100nm prepared by chemical synthesis was left standing at 4 degrees for 1 hour to deposit a load. And (4) taking out the substrate, and washing the substrate for 2 times by using clear water to obtain the gold substrate with the metal tungsten complex single sites.
Example 2:
the preparation method of the heterogeneous coordination of the carboxyl of the heteropoly acid of tungsten loaded on the surface of the silver Ag substrate comprises the following steps:
to 100ml of deionized water, 0.3g of paratungstic acid was added, the pH was adjusted to 3 with 5wt% dilute sulfuric acid, and the mixture was stirred for 1 hour until it was clear. 0.2g of citric acid molecules containing carboxyl is added, and the mixture is stirred for 1 hour at the temperature of 70 ℃, and the coordination reaction is carried out through the weak action of hydrogen bonds formed between-COOH bonds and W atoms in the metal center. Then, in the above clear solution after cooling, an Ag substrate (periodic defects were obtained by heat treatment at 300 degrees after 1 hour) of 200nm by magnetron sputtering was placed therein, and left to stand at 40 degrees for 1 hour to deposit a load. After being taken out, the mixture is washed for 2 times by clean water. A silver substrate with single sites of the metal tungsten complex was obtained.
Example 3:
the preparation method of the hetero-phase of the amino coordination of the heteropoly acid with molybdenum loaded on the surface of the silver Ag substrate comprises the following steps:
0.4g of heteropolyammonium molybdate is added into 100ml of deionized water, the pH value is adjusted to 3 by using 10wt% of dilute sulfuric acid, and the mixture is stirred for 1 hour until the mixture is clear. 0.1g of aminobenzylamine was dissolved in 30ml of dimethyl sulfoxide. After the two solutions are clarified, they are mixed into a solution. Stirring for 1 hour at the temperature of 80 ℃, and carrying out coordination reaction by bonding-NH bond with Mo atom at the metal center. Then, in the above clear solution after cooling, a 200nm Ag substrate by magnetron sputtering (periodic defects were obtained by heat treatment at 300 ℃ for 1 hour) was placed therein, and an electrode was applied with a deposition load of 0.6V voltage for a period of 1 hour. After being taken out, the mixture is washed for 2 times by clean water. Obtaining the silver substrate with the metal molybdenum complex sites.
Example 4:
the heterogeneous preparation method of the polymer hydroxyl with molybdenum single sites loaded on the surface of the silver Ag substrate comprises the following steps:
adding MoCl 6 (0.2 g) and PEO (0.01 mmol) were dissolved in 40ml of iced ethanol and nitrogen was bubbled for 1h to prepare a single molybdenum atom oxide on a PEO carrier. Stirring for 1 hour at the temperature of 90 ℃, and carrying out coordination reaction by bonding the-OH bond with the Mo atom at the metal center. Then, in the above clear solution after cooling, an Ag substrate thermally evaporated at 100nm (periodic defects were obtained by heat treatment at 200 degrees for 1 hour thereafter) was placed therein, the pH was adjusted to 10 with a 20wt% aqueous ammonia solution, a 50-degree deposition load was heated, and the load was allowed to stand still for 2 hours. After being taken out, the mixture is washed for 2 times by clean water. Obtaining a single site with a metal molybdenum complexA silver substrate of (1).
Example 5:
the heterogeneous preparation method of the gold Au substrate surface loaded with tungsten thiophenol coordination comprises the following steps:
to 100ml of deionized water, 0.3g of sodium tungstate was added, and the mixture was stirred until it was clarified. 0.1g of thiophenol ligand molecule was added thereto, and pH 2 was adjusted by adding 10wt% dilute hydrochloric acid. Stirring for 1 hour at the temperature of 50 ℃, and generating coordination reaction of thiophenol and metal tungsten through SH bond and metal central atom. Then, in the above clear solution after cooling, a gold Au substrate with a thickness of 100nm prepared by magnetron sputtering was left, the pH was adjusted to 10 with a 1wt% solution of sodium hydroxide, left to stand at 4 ℃ for 1 hour, and a load was deposited. After removal, it was washed with ethanol and dried in a vacuum oven at 80 ℃ for 6h. Then, under the protection of Ar, the mixture is heated for 1h by microwave and repeated for 5 times. And obtaining the surface of the gold Au substrate with a clean surface.
Example 6
The preparation method of the silver-doped wire silicon dioxide loaded with the monoatomic W coordinated citric acid comprises the following steps:
adding 50ml of deionized water and 25ml of ethanol clear mixed solvent into a reaction flask, dispersing 12.5ml of ethyl orthosilicate into 25ml of ethanol, dropwise adding the mixture into the reaction flask, magnetically stirring the colorless mixed solution of water and ethanol at 1000 revolutions per minute, adding 0.3g of sodium tungstate into the 100ml of solution, stirring the mixture until the mixture is clear, dropwise adding 8ml of a prepared 5wt% polyacrylic acid aqueous solution, stirring the mixture for half an hour, and changing the liquid from primary turbidity to complete transparency, which represents uniform dispersion. Then, 10g of aqueous conductive silver wire slurry is added, and the mixture is stirred for 12 hours at 800 revolutions per minute. The powder is added to a reactor, addition 10 -4 Reacting ethanol in mol per liter at 120 ℃ for 1 hour, and drying the liquid coating at 60 ℃ to obtain white silver wire-carried silicon oxide with monoatomic W, wherein the material is uniformly coated on a conductive electrode.
Example 7
A preparation method of Ag quantum dot modified load monatomic W silicon dioxide.
100ml of 2wt% silver nitrate aqueous solution is prepared, sealed and protected by Ar gas, 50ml of deionized water and 25ml of ethanol are added into a reaction flask to clarify a mixed solvent, 12.5ml of tetraethoxysilane is dispersed in 25ml of ethanol, the tetraethoxysilane and the ethanol are magnetically stirred to be colorless, 0.6g of sodium molybdate is added into the solution which is close to 100ml, and 10ml of 20wt% dilute sulfuric acid is gradually added. And (3) dripping 2wt% of silver nitrate solution into 10ml of liquid, stirring for 2 hours, fully and uniformly mixing, converting the liquid from primary turbidity to complete transparency, and drying a liquid coating film at the temperature of 60-80 ℃ to obtain the light brown to pure white Ag quantum dot modified load monatomic W silicon dioxide. Reversible color change can be achieved under UV light irradiation by applying a voltage of 1V or illuminating the sample characteristics as shown in FIG. 1.
Example 8:
the heterogeneous preparation method of the gold Au substrate surface loaded tungsten polymer carboxyl coordination comprises the following steps:
to 100ml of deionized water, 0.3g of sodium tungstate was added, and the mixture was stirred until it was clarified. 0.1g of polyacrylic acid ligand molecule was added thereto, and 10wt% diluted hydrochloric acid was added thereto to adjust pH 2. Stirring for 1 hour at the temperature of 50 ℃, forming a bond with a metal central atom through a-COOH bond, and performing a coordination reaction of carboxyl and metal tungsten and molybdenum. Then, in the cooled clear solution, a gold Au substrate with a thickness of 100nm prepared by magnetron sputtering was placed, left to stand at 4 ℃ for 1 hour, and a load was deposited. After removal, it was washed with ethanol and dried in a vacuum oven at 80 ℃ for 6h. Then, under the protection of Ar, the mixture is heated for 1h by microwave and repeated for 5 times. And obtaining the surface of the gold Au substrate with a clean surface.
Example 9:
the heterogeneous preparation method of the periodic structure Au substrate surface loaded tungsten and hydroxyl coordination comprises the following steps:
1ml of concentrated nitric acid 20wt% and 0.1ml of isopropanol were added to 100ml of deionized water, and after stabilization by magnetic stirring for 3 hours, 10ml of PEG-200 was added, and magnetic stirring was performed at 100 ℃ for 2 hours. Adding 0.5mg of ammonium paratungstate into the solution, sealing, stirring uniformly for 24h, and heating to 50 ℃. After that, the heating was turned off, the stirring was maintained for 24 hours, and the system was cooled to room temperature. The periodic structure Au substrate is a grating structure which is synthesized by utilizing a nano-imprinting technology and has a period of 100nm and an interval of 50 nm. The substrate was placed in the above solution and loaded at 40 degrees for 3 hours. And (3) after taking out the substrate, repeatedly and ultrasonically cleaning the substrate for 3 times by using deionized water and ethanol, placing the substrate in a vacuum drying oven, and drying the substrate at 60 ℃ to obtain a sample.
Example 10:
the invention relates to a heterogeneous preparation method of coordination of tungsten loaded on the surface of gold Au particles and hydroxyl (the invention is suitable for large-scale production):
5000ml of deionized water, 15g of sodium tungstate is added, and the mixture is stirred until the mixture is clear. 5g of PEG200 ligand molecules were added, and pH 2 was adjusted by adding 10wt% dilute sulfuric acid. Stirring for 3 hours at the temperature of 50 ℃ until the solution is clear, forming a bond with a central atom of the metal through an-OH bond, and performing a coordination reaction of hydroxyl and metal tungsten. Then, 1000ml of synthesized wine red 1wt% Au nanoparticles having an average particle diameter of 40nm was added to the above solution, and the mixture was stirred sufficiently and loaded at 80 ℃ for 3 hours. In the above clear solution after cooling, the gold Au substrate supporting tungsten was filtered out, taken out, washed sufficiently with ethanol, deionized water 5 times, and dried in an oven at 80 ℃ for 6 hours. And then, under the protection of Ar, heating for 90-degree 1h by microwave to obtain the gold Au particles with clean surfaces.
Claims (4)
1. The heterogeneous single-site preparation method of the noble metal substrate is characterized by comprising the following raw materials in percentage by mass:
100ml of water or organic solvent, 0.2-0.6g of tungsten-molybdenum metal oxide or salt is added, and the mixture is stirred until the mixture is clear; adding 0.1-1g of ligand molecules containing coordination of O, S or N and metal, and adjusting the pH to 2-3; stirring for more than 1 hour at the temperature of more than 50 ℃; then, in the cooled clear solution, placing a chemically synthesized substrate with Ag or Au arrangement with the thickness of more than 100nm, and depositing and loading; and taking out, washing with clear water for 2 times to obtain the noble metal substrate with the metal tungsten-molybdenum complex single site.
2. The method of claim 1, wherein: the organic solvent is ethanol or acetone or ethylene glycol or dimethylformamide or dimethyl sulfoxide.
3. The production method according to claim 1, characterized in that:
the ligand molecule is: oxalic acid, acrylic acid, polyacrylic acid, citric acid, ethylene diamine tetraacetic acid; ethylene glycol, glycerol, polyethylene glycol; aminobenzylamine; a porphyrin; imidazole; aminothiophenol or organic nitrogen.
4. The method of claim 1, wherein: the pH was adjusted by: hydrochloric acid, sulfuric acid, nitric acid, ammonia water and sodium hydroxide.
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| WO2009066658A1 (en) * | 2007-11-19 | 2009-05-28 | Nihon Parkerizing Co., Ltd. | Base processing agent for metal material and method for processing base for metal material |
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