CN108212155B - Clay mineral loaded uniformly-dispersed metal ion/atom catalyst and preparation method thereof - Google Patents
Clay mineral loaded uniformly-dispersed metal ion/atom catalyst and preparation method thereof Download PDFInfo
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- CN108212155B CN108212155B CN201810139781.0A CN201810139781A CN108212155B CN 108212155 B CN108212155 B CN 108212155B CN 201810139781 A CN201810139781 A CN 201810139781A CN 108212155 B CN108212155 B CN 108212155B
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
Abstract
The invention provides a clay mineral loaded uniformly dispersed metal ion/atom catalyst and a preparation method thereof, and relates to the technical field of catalysts. A clay mineral supported uniformly dispersed metal ion/atom catalyst comprising the steps of: mixing clay minerals and metal salts, sequentially heating, washing and drying to obtain a product, and preferably, reducing the product in situ; or mixing the clay mineral and the aqueous solution of the metal salt, stirring or immersing, washing, drying, crushing and heating in sequence to obtain the product, preferably, reducing the product in situ. The invention takes clay mineral and metal salt as raw materials, and utilizes the compound hexagonal holes of the silica tetrahedron of the clay mineral to fix metal ions/atoms, thereby obtaining the catalyst with the clay mineral loaded with uniformly dispersed metal ions/atoms.
Description
Technical Field
The invention relates to the technical field of catalysts, and in particular relates to a clay mineral loaded uniformly-dispersed metal ion/atom catalyst and a preparation method thereof.
Background
For traditional supported metal catalysts, the active centers are usually limited to surface atoms, which on the one hand results in a low utilization of the active sites of the catalyst and on the other hand results in a waste of active components (e.g. noble metals). In order to improve the catalytic efficiency of the catalyst and reduce the use cost of the catalyst, it is an important direction of current research to disperse the active components of the catalyst on the carrier (alumina, silica, activated carbon, etc.) with high specific surface area as much as possible by a certain process. A Pt monatomic catalyst with high catalytic activity is prepared by a professor team of great works in Chinese academy of sciences through an immersion method, and the concept of the monatomic catalyst is put forward for the first time (Qiao et al, Nature Chemistry 3.2011,634-641). The monoatomic dispersion realizes the maximum utilization of catalytic active atoms, and greatly improves the catalytic efficiency of catalytic reaction; but because of the instability of the single atom, the single atom is easy to agglomerate and inactivate in the preparation and reaction processes. Although some methods for preparing monatomic catalysts are reported successively, the methods are often limited by the disadvantages of complicated operation, low yield, low active component loading and the like, and are difficult to realize industrial preparation and application.
The clay mineral has the advantages of natural micro-nano structure, high specific surface area, abundant reserves and the like, and is commonly used as a carrier of various catalysts. A large number of researches show that the clay mineral can effectively improve the dispersibility of active components, prevent agglomeration, increase the specific surface area and active sites of the catalytic material, prevent the loss of a catalyst in the catalytic reaction process and improve the utilization rate of the catalytic material. However, in the current studies on clay minerals as catalyst carriers, the catalytically active components are still distributed in particulate form on the carrier, and their effective utilization is still very limited (Llabre's i Xamena et al, J.Phys. chem.B.2003, 7036-7044); or ionically dispersed in the interlaminar domain, which is easily desorbed and has poor stability (R.Swarnakar et al, Applied Catalysis A: general.1996, 61-71).
Disclosure of Invention
The invention aims to provide a clay mineral loaded uniformly dispersed metal ion/atom catalyst which has good stability, high catalytic efficiency and high catalytic activity and can be used for various catalytic reactions.
The invention also aims to provide a preparation method of the clay mineral loaded uniformly-dispersed metal ion/atom catalyst, which is simple, strong in controllability, environment-friendly, cheap and easily available in raw materials, low in cost and capable of being prepared in a large scale.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
a clay mineral supported catalyst with uniformly dispersed metal ions/atoms is prepared from clay mineral and metal salt, wherein the clay mineral has silicon-oxygen tetrahedron hexagonal pores, and at least a part of metal ions/atoms are fixed in the silicon-oxygen tetrahedron hexagonal pores.
A preparation method of a clay mineral loaded uniformly dispersed metal ion catalyst comprises the following steps: the clay mineral and the metal salt are mixed and the solid phase mixture is heat treated.
A preparation method of a clay mineral loaded uniformly dispersed metal ion catalyst comprises the following steps: mixing the clay mineral and the metal salt water solution, stirring or standing, centrifuging and drying, and carrying out heat treatment on the obtained metal ion-loaded clay mineral.
A preparation method of a clay mineral loaded catalyst with uniformly dispersed metal atoms comprises the following steps: the clay mineral load uniformly dispersed metal ion catalyst is prepared by the preparation method of the clay mineral load uniformly dispersed metal ion catalyst, and the clay mineral load uniformly dispersed metal ion catalyst is subjected to in-situ reduction to obtain the product, namely the clay mineral load uniformly dispersed metal atom catalyst.
The clay mineral loaded uniformly dispersed metal ion/atom catalyst and the preparation method thereof have the beneficial effects that:
according to the invention, cheap natural clay mineral is used as a carrier, and active metal ions are efficiently locked by utilizing the specific sub-nanometer-scale silicon-oxygen tetrahedron complex hexagonal holes of the clay mineral, so that a stable and uniformly dispersed metal ion catalyst is obtained; further, metal ions with complex hexagonal holes are reduced into metal atoms in situ, and the uniformly dispersed metal atom catalyst can be obtained. The catalyst has good stability, high catalytic efficiency and high catalytic activity, and can be used for various catalytic reactions, such as selective hydrogenation reaction, carbon dioxide reduction and the like. The preparation method is efficient and simple, the preparation process is environment-friendly, the cost is low, the metal element loading capacity is controllable, large-scale preparation can be realized, and the industrial application prospect is wide.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the embodiments will be briefly described below. It is appreciated that the following drawings depict only certain embodiments of the invention and are therefore not to be considered limiting of its scope. For a person skilled in the art, it is possible to derive other relevant figures from these figures without inventive effort.
FIG. 1 is an X-ray diffraction pattern of the product prepared in example 1 of the present invention;
FIG. 2 is a high resolution X-ray fluorescence spectrum of the product prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following is a detailed description of the clay mineral supported uniformly dispersed metal ion/atom catalyst and the preparation method thereof according to the embodiment of the present invention.
According to the clay mineral supported catalyst with uniformly dispersed metal ions/atoms, natural clay minerals are used as carriers, active metal ions or atoms are efficiently locked by using silicon-oxygen tetrahedron compound hexagonal holes of the clay minerals, and the metal ions or atoms are fixed in holes. The obtained metal ion or atom catalyst has good stability and high catalytic efficiency.
Further, in a preferred embodiment of the invention, the clay mineral comprises at least one of montmorillonite, vermiculite, halloysite, sepiolite or palygorskite. The clay mineral has a lamellar structure with hexagonal pores compounded by silica tetrahedron.
Further, in preferred embodiments of the present invention, the metal salt comprises any one or at least two of chlorides, sulfates, or nitrates of Fe, Co, Ni, Cu, Ag, Au, Ru, Rh, Pd, Re, Ir, or Pt.
In order to ensure that metal ions or atoms in the metal salt can fully and uniformly enter the silicon-oxygen tetrahedron hexagonal pores of the clay mineral, in a preferred embodiment of the invention, the dosage ratio of the clay mineral to the metal salt is 1g (0.05-10) mol. Preferably, the clay mineral and the metal salt may be used in a ratio of 1g:0.09mol, 1g:1.3mol, 1g:2.5mol, 1g:3.4mol, 1g:4.7mol, 1g:5.6mol, 1g:7.1mol, 1g:8.3mol, 1g:9.8 mol. Preferably, when the loading amount of the metal element in the clay mineral loaded uniformly dispersed metal ion/atom catalyst is 1-6%, the clay mineral loaded uniformly dispersed metal ion/atom catalyst has good stability and good catalytic performance.
The invention provides a preparation method of the clay mineral loaded uniformly dispersed metal ion/atom catalyst, which comprises the following steps:
mixing clay mineral and metal salt in proportion, carrying out heat treatment on the solid phase mixture to enable the metal salt to be molten, enabling active metal ions to enter interlayer of the clay mineral, then enabling the metal ions to further migrate to silicon-oxygen tetrahedron complex hexagonal holes of the clay mineral, and locking the metal ions by utilizing sub-nanometer scale holes peculiar to the clay mineral to enable the metal ions to be fixed in the holes. In an embodiment of the present invention, the heat treatment comprises: preserving the heat for 0.5-24 h at the temperature of 80-500 ℃, and cooling. And washing the mixture after the heat treatment by using ultrapure water, removing redundant metal salt, centrifuging and drying to obtain the product, namely the clay mineral loaded uniformly dispersed metal ion catalyst. The preparation method enables the metal ions to be uniformly dispersed in the pores of the clay mineral, and the obtained clay mineral loaded uniformly dispersed metal ion catalyst has good stability.
The invention provides another preparation method of the clay mineral loaded uniformly dispersed metal ion/atom catalyst, which comprises the following steps:
dissolving metal salt in water to obtain aqueous solution, mixing the aqueous solution of metal salt with clay mineral, stirring or standing for a period of time to make metal ions enter the interlayer of clay mineral. Centrifuging and drying to remove the excess metal salt. Subsequently, the clay loaded with metal ions is subjected to a heat treatment, and the metal ions migrate to the complex hexagonal pores of silica tetrahedrons of the clay mineral. The heat treatment comprises the following steps: and (3) preserving the heat for 0.5-24 h at the temperature of 80-300 ℃, and cooling to obtain the clay mineral loaded uniformly dispersed metal ion catalyst.
Further, in a preferred embodiment of the present invention, the obtained clay mineral supported uniformly dispersed metal ion catalyst is subjected to in-situ reduction to obtain a clay mineral supported uniformly dispersed metal atom catalyst. The in-situ reduction method comprises light irradiation, heat treatment or reducing agent reduction. The reducing agent comprises at least one of sodium borohydride, potassium borohydride, lithium aluminum hydride or hydrazine hydrate.
The preparation method adopts the clay mineral complex hexagonal holes to lock the metal ions/atoms, so that the stability of the fixed metal ions/atoms is enhanced, the dispersion of the metal ions/atoms is facilitated, and the element utilization rate is improved. The preparation method has the advantages of high efficiency, simplicity, environmental protection in the preparation process, low cost, controllable metal element loading, large-scale preparation and wide industrial application prospect.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
This example provides a method for preparing a clay mineral supported uniformly dispersed metal ion/atom catalyst, comprising:
uniformly mixing 1g of montmorillonite and 0.05mol of cobalt nitrate hexahydrate, placing the mixture in a beaker, keeping the temperature at 90 ℃ for 3 hours, naturally cooling, washing the mixture after heat treatment by using ultrapure water, removing redundant cobalt nitrate, centrifuging and drying;
and (3) preserving the temperature of the product at 200 ℃ for 4h, naturally cooling and collecting a sample to obtain the clay mineral loaded uniformly dispersed Co ion catalyst.
The obtained material was analyzed by X-ray diffraction spectroscopy (XRD) (see FIG. 1), and the result showed that the obtained product exhibited a characteristic diffraction peak of montmorillonite, indicating that the layered structure of montmorillonite was not changed. The Cation Exchange Capacity (CEC) of the heat-treated montmorillonite was reduced to 32% of that of the non-heat-treated montmorillonite, indicating that Co was present after heat treatment2+Migrating to a montmorillonite lamellar structure, and neutralizing part of lamellar charges of montmorillonite; co2p high resolution X-ray fluorescence Spectroscopy (XPS) (see FIG. 2) shows that peaks with binding energies of 780.4eV, 782.2eV and 786.0eV are assigned to Co2+This isShowing that the cobalt ions migrated into the hexagonal pores of the montmorillonite are Co2+Exist in the form of (1).
Example 2
This example provides a method for preparing a clay mineral supported uniformly dispersed metal ion/atom catalyst, comprising:
uniformly mixing 1g of montmorillonite and 0.05mol of cobalt nitrate hexahydrate, placing the mixture in a beaker, keeping the temperature at 90 ℃ for 3 hours, naturally cooling, washing the mixture after heat treatment by using ultrapure water, removing redundant cobalt nitrate, centrifuging and drying;
preserving the temperature of the product at 200 ℃ for 4h, and naturally cooling;
and mixing a 2% hydrazine hydrate solution with the obtained product, stirring for a certain time, centrifuging, washing with ultrapure water, centrifuging, drying, and collecting a sample to obtain the clay mineral loaded uniformly-dispersed Co atomic catalyst.
The characterization result of X-ray diffraction spectrum (XRD) shows that the product after reduction is montmorillonite, and no simple substance Co appears. The Cation Exchange Capacity (CEC) of the heat-treated montmorillonite was reduced to 32% of that of the non-heat-treated montmorillonite, indicating that Co was present after heat treatment2+Migrating to a montmorillonite lamellar structure, and neutralizing part of lamellar charges of montmorillonite; co2p high resolution X-ray fluorescence (XPS) shows that Co migrating into montmorillonite complex hexagonal pores2+Is reduced to elemental Co.
Example 3
This example provides a method for preparing a clay mineral supported uniformly dispersed metal ion/atom catalyst, comprising:
1) uniformly mixing 1g of sepiolite and 0.05mol of copper nitrate trihydrate, placing the mixture in a beaker, keeping the temperature at 120 ℃ for 3 hours, naturally cooling, washing the mixture subjected to heat treatment by using ultrapure water, removing redundant copper nitrate, centrifuging and drying;
2) preserving the temperature of the product at 200 ℃ for 3h, and naturally cooling;
3) mixing a 10% potassium borohydride solution with the product obtained in the step 2), stirring for a certain time, centrifuging, washing with ultrapure water, centrifuging, drying, and collecting a sample to obtain the clay mineral loaded Cu atomic catalyst with uniform dispersion.
The characterization result of X-ray diffraction spectrum (XRD) shows that the product after reduction is montmorillonite, and the diffraction peak of simple substance Cu does not appear; the Cation Exchange Capacity (CEC) of the montmorillonite after heat treatment is reduced to 32 percent of that of the sepiolite without heat treatment; the Cu2p high-resolution X-ray fluorescence spectrogram (XPS) shows that Cu transferred into the montmorillonite complex hexagonal holes2+Is reduced to elemental Cu.
Example 4
This example provides a method for preparing a clay mineral supported uniformly dispersed metal ion/atom catalyst, comprising:
1) 1g of vermiculite and 0.05mol of ferric chloride are uniformly mixed, placed in a muffle furnace by a glass ampoule, kept at 350 ℃ for 5 hours, cooled in liquid nitrogen, washed by ultrapure water to remove redundant ferric chloride, centrifuged and dried;
2) mixing the polyalcohol solution with the product obtained in the step 1), stirring for a certain time, washing with ultrapure water, centrifugally drying, and collecting a sample to obtain the clay mineral supported uniformly dispersed Fe atomic catalyst.
An X-ray diffraction spectrum (XRD) characterization result shows that the product after reduction is vermiculite, and no diffraction peak of simple substance Fe appears; the Cation Exchange Capacity (CEC) of the heat-treated vermiculite is reduced to 32 percent of that of the non-heat-treated vermiculite; the Fe2p high-resolution X-ray fluorescence spectrum (XPS) shows that Fe moving to the compound hexagonal holes of vermiculite3+Is reduced to elemental Fe.
Example 5
This example provides a method for preparing a clay mineral supported uniformly dispersed metal ion/atom catalyst, comprising:
1) uniformly mixing 1g of palygorskite and 0.05mol of nickel nitrate hexahydrate, placing the mixture in a beaker, preserving heat for 3 hours at 90 ℃, naturally cooling, washing the mixture after heat treatment by using ultrapure water, removing redundant nickel nitrate, centrifuging and drying;
2) and (3) preserving the temperature of the product at 250 ℃ for 6h, naturally cooling and collecting a sample to obtain the clay mineral loaded uniformly dispersed Ni ion catalyst.
The characterization result of X-ray diffraction spectrum (XRD) shows that the product after reduction is vermiculite; the Cation Exchange Capacity (CEC) of the palygorskite after heat treatment is reduced to 34% of that of the palygorskite without heat treatment; the Ni2p high resolution X-ray fluorescence spectrum (XPS) shows that the nickel ions migrating to the complex hexagonal holes of the palygorskite are Ni2+The form exists.
The results of the embodiments 1 to 5 show that the montmorillonite, vermiculite, halloysite, sepiolite and palygorskite adopted as the precursors have the advantages of large specific surface area, pore structure of the lamella, low cost and the like, and the preparation method is efficient, simple, low in energy consumption, environment-friendly, high in purity of the prepared product, high in yield and easy for large-scale preparation.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (5)
1. The clay mineral loaded uniformly-dispersed metal ion/atom catalyst is characterized in that a clay mineral and metal salt are used as raw materials, the clay mineral is of a lamellar structure with silicon-oxygen tetrahedral hexagonal holes, at least one part of metal ions/atoms are fixed in the silicon-oxygen tetrahedral hexagonal holes, the using amount ratio of the clay mineral to the metal salt is 1g (0.05-10) mol, and the loading amount of metal elements in the clay mineral loaded uniformly-dispersed metal ion/atom catalyst is 1-6%.
2. The clay mineral supported uniformly dispersed metal ion/atom catalyst of claim 1, wherein the clay mineral comprises at least one of montmorillonite, vermiculite, halloysite, sepiolite, or palygorskite.
3. The clay mineral supported uniformly dispersed metal ion/atom catalyst according to claim 1, wherein the metal salt comprises any one or at least two of chloride, sulfate or nitrate of Fe, Co, Ni, Cu, Ag, Au, Ru, Rh, Pd, Re, Ir or Pt.
4. A preparation method of a clay mineral loaded uniformly dispersed metal ion catalyst is characterized by comprising the following steps: mixing a clay mineral having silicon-oxygen tetrahedral hexagonal pores and a metal salt, and heat-treating the solid phase mixture; the heat treatment comprises the following steps: preserving the heat for 0.5-24 h at the temperature of 80-500 ℃, cooling, washing the mixture, and centrifugally drying to obtain a product, namely the clay mineral supported uniformly dispersed metal ion catalyst;
the dosage ratio of the clay mineral to the metal salt is 1g (0.05-10) mol, and the loading amount of the metal element in the clay mineral loading uniformly-dispersed metal ion catalyst is 1-6%.
5. A preparation method of a clay mineral loaded uniformly-dispersed metal atom catalyst is characterized by comprising the following steps: the clay mineral supported uniformly dispersed metal ion catalyst is prepared by the preparation method of the clay mineral supported uniformly dispersed metal ion catalyst according to claim 4, and the clay mineral supported uniformly dispersed metal ion catalyst is subjected to in-situ reduction to obtain the clay mineral supported uniformly dispersed metal atom catalyst.
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