CN107469855B - Preparation method of nitrogen-doped graphene-loaded metal monatomic catalyst - Google Patents
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Abstract
A preparation method of a nitrogen-doped graphene-supported metal monatomic catalyst comprises the steps of taking ethylene diamine tetraacetic acid disodium salt as a complexing agent, forming a stable complex with metal ions through an ion exchange reaction in a liquid phase, fully and uniformly mixing the complex with alkali metal salt after evaporation to dryness, and obtaining the nitrogen-doped graphene-supported metal monatomic catalyst through synchronous pyrolysis conversion. The prepared catalyst has the appearance characteristics of an ultrathin large-area two-dimensional microstructure, the thickness is 0.5-2 nm, the number of graphene layers is 1-8, and the metal loading is 0.01-10 wt%, and the catalyst can be applied to the catalytic synthesis fields of energy, catalysis, medicines, biology and the like. The method can be generally suitable for synthesis of various metal monatomic catalysts, and the obtained metal monatomic can be firmly riveted on the surface of the graphene, so that the load is high, and the thermal stability is good. The method has the advantages of simple and safe operation process, low cost, controllable preparation, large-scale synthesis and the like, and is suitable for industrial production and large-scale application.
Description
Technical Field
The invention belongs to the technical field of preparation of monatomic catalysts, and particularly relates to a catalyst prepared by usingNitrogen-containing organic complexesA method for preparing a nitrogen-doped graphene-loaded metal monatomic catalyst by synchronous pyrolysis and conversion.
Background
The dimension and size of the material are reduced to synthesize the catalyst with nanoclusters or monoatomic dispersion, so that the catalytic activity of the material can be remarkably improved, and further, the ideal catalytic efficiency is obtained. With the continuous development of the nano material synthesis technology, mankind has made great progress on the multi-scale of material, but still faces significant challenges in realizing the structural synthesis, regulation and control and application of the catalytic material with single atom dispersion. Because the monoatomic substance is unstable and is easy to aggregate and agglomerate in the synthesis and application processes, the simple, high-efficiency and large-scale synthesis of the thermally stable monoatomic dispersion catalyst material is not really realized so far. The monoatomic dispersion catalyst is the minimum limit of the material size, can reach the maximum limit of the atom utilization rate in the catalytic reaction, is a catalyst material with the most application prospect, is also a bridge for connecting heterogeneous catalysis and homogeneous catalysis, and is a reliable way for realizing heterogeneous catalysis of homogeneous catalysis. Although more and more methods for preparing the monatomic dispersion catalyst are reported successively, the methods generally need precise regulation and control synthesis, have various operation steps and small yield, are only suitable for synthesis under laboratory conditions, the types of the synthesized monatomic catalysts are limited to common elements, and the carriers used are still limited to metal or metal oxide, so that the wide application of the monatomic dispersion catalysts is limited by synthesis technology of suitable materials.
The graphene is a single-layer two-dimensional crystal structure in which carbon atoms are arranged in a hexagonal honeycomb shape, and due to the atomic-level thickness, the graphene has a unique electronic structure and can show novel macroscopic physicochemical characteristics. Due to its high specific surface area, good electronic conductivity and unique graphitized two-dimensional planar structure, graphene is considered as an ideal carrier of a monoatomic dispersion catalyst, and has recently attracted great interest to researchers. However, graphene synthesized by the existing method is a chemically stable material and is difficult to coordinate with a single metal atom, and even though researchers report that the atomic layer deposition method realizes the synthesis of graphene-supported Pt and Pd single atom dispersion catalysts, the metal loading is very low, the metal atom dispersibility is poor, and the single atom types are limited.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the current technical situation that the graphene loaded metal monatomic catalyst cannot be simply and massively prepared at present, the general method for simply and efficiently preparing the nitrogen-doped graphene loaded metal monatomic catalyst in a large quantity is provided, and meanwhile, the prepared catalyst has the advantages of high metal loading capacity, wide metal type coverage, high atom dispersibility and the like.
The technical scheme of the invention is as follows:
a preparation method of a nitrogen-doped graphene-loaded metal monatomic catalyst is characterized by comprising the following steps:
1) adding a nitrogenous organic compound, namely ethylene diamine tetraacetic acid disodium salt and a metal salt into deionized water, wherein the mass ratio of the two is 1000: 1-100: 1, and uniformly mixing to obtain an aqueous solution with the molar concentration of the metal salt being 0.001-0.5 mol/L; then carrying out ion exchange reaction for 0.5-6 h at 40-120 ℃ to obtain a stable complex, and drying by distillation to obtain complex solid powder;
2) fully and uniformly mixing the complex solid powder obtained in the step 1) with an alkali metal salt, wherein the mass ratio of the complex solid powder to the alkali metal salt is 1: 5-1: 20, putting the mixture into a tubular furnace, performing heat treatment at 800-1200 ℃ for 0.5-3 h in an inert atmosphere, and then naturally cooling to room temperature to obtain a mixture of a nitrogen-doped graphene-supported metal monatomic catalyst and the alkali metal salt;
3) washing and drying the mixture obtained in the step 2) by using an acidic aqueous solution, pure water and absolute ethyl alcohol in sequence to obtain the nitrogen-doped graphene-loaded metal monatomic catalyst.
In the technical scheme, the metal single atom in the catalyst is Ru, Rh, Pd, Re, Ir, Pt, Fe, Co, Ni, Mn or Cu. The metal salt is one of chlorides, sulfates, nitrates and acetylacetone salts of Ru, Rh, Pd, Re, Ir, Pt, Fe, Co, Ni, Mn or Cu. The alkali metal salt is one or more of sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sulfate, potassium sulfate, sodium chloride, potassium chloride, sodium nitrate and potassium nitrate. The inert gas is nitrogen or argon.
The invention is also characterized in that: the nitrogen-doped graphene loaded metal monatomic catalyst has the two-dimensional microstructure morphology characteristic, the thickness of the nitrogen-doped graphene loaded metal monatomic catalyst is 0.5-2 nm, the number of graphene layers is 1-8, and the metal loading amount is 0.01-10 wt%.
Compared with the prior art, the invention has the following advantages and prominent technical effects:
the preparation method of the graphene-supported metal monatomic catalyst provided by the invention is characterized in that ethylene diamine tetraacetic acid disodium salt is used as a complexing agent, the complexing agent and metal ions form a stable complex through an ion exchange reaction in a liquid phase, and then the nitrogen-doped graphene-supported metal monatomic catalyst can be obtained through synchronous pyrolysis conversion. Ru, Rh, Pd, Re, Ir, Pt, Fe, Co, Ni, Mn and Cu in the material are loaded on the surface of graphene in a single atom form, the variety of metals is multiple, the preparation method is simple and practical, different metal single atom dispersion catalysts can be obtained only by changing the variety of metal precursor salt, and the synthesis method has universal applicability.
The Ru, Rh, Pd, Re, Ir, Pt, Fe, Co, Ni, Mn and Cu elements in the invention are stabilized by nitrogen atoms on the graphene carrier, so that the graphene carrier has good thermal stability and high metal atom loading concentration.
The method has the advantages of simple and safe operation process, low cost, controllable preparation, large-scale synthesis and the like, and is suitable for industrial production and large-scale application.
Drawings
Fig. 1 is an image of the graphene-supported Pd monatomic catalyst prepared in example 1 under a high-angle annular dark-field scanning transmission electron microscope.
Fig. 2 is an image of the graphene-supported Pt monatomic catalyst prepared in example 2 under a transmission electron microscope.
FIG. 3 shows an embodiment2Prepared graphene loadingPtImages of monatomic catalysts under high angle annular dark field scanning transmission electron microscopy.
FIG. 4 shows graphene prepared in example 3Load(s)CoImages of monatomic catalysts under high angle annular dark field scanning transmission electron microscopy.
Fig. 5 is an image of the graphene-supported Ni monatomic catalyst prepared in example 4 under a high-angle annular dark-field scanning transmission electron microscope.
Fig. 6 is an image of the graphene-supported Fe monatomic catalyst prepared in example 5 under a high-angle annular dark-field scanning transmission electron microscope.
Detailed Description
The invention provides a preparation method of a nitrogen-doped graphene supported metal monatomic catalyst, which is characterized in that ethylene diamine tetraacetic acid disodium salt is used as a complexing agent, the complexing agent and metal ions form a stable complex through ion exchange reaction in a liquid phase, the complex is fully and uniformly mixed with alkali metal salt after being dried by distillation, and the nitrogen-doped graphene supported metal monatomic catalyst is obtained through synchronous pyrolysis conversion, wherein the preparation method mainly comprises the following steps:
1) adding a nitrogenous organic compound, namely ethylene diamine tetraacetic acid disodium salt and a metal salt into deionized water, wherein the mass ratio of the two is 1000: 1-100: 1, and uniformly mixing to obtain an aqueous solution with the molar concentration of the metal salt being 0.001-0.5 mol/L; then carrying out ion exchange reaction for 0.5-6 h at 40-120 ℃ to obtain a stable complex, and drying by distillation to obtain complex solid powder;
2) fully and uniformly mixing the complex solid powder obtained in the step 1) with alkali metal salt, wherein the mass ratio of the complex solid powder to the alkali metal salt is 1: 5-1: 20, putting the mixture into a tube furnace, heat-treating at 800-1200 deg.C for 0.5-3 h under inert atmosphere (generally adopting nitrogen or argon), the complex is pyrolyzed to form carbon nitrogen free radicals and metal ions, the carbon nitrogen free radicals are rearranged in an alkali metal salt reaction medium to form graphene, meanwhile, nitrogen atoms are inserted into the graphene layer in a chemical bond mode to form a coordination bond with metal ions to stabilize metal monoatomic atoms, and metal atoms are uniformly and firmly loaded on the surface of the graphene to finally form the nitrogen-doped graphene-loaded metal monatomic catalyst, then naturally cooling to room temperature to obtain a mixture of the nitrogen-doped graphene-loaded metal monatomic catalyst and the alkali metal salt;
3) washing and drying the mixture obtained in the step 2) by using an acidic aqueous solution, pure water and absolute ethyl alcohol in sequence to obtain the nitrogen-doped graphene-loaded metal monatomic catalyst.
In the above technical scheme, the metal single atom is Ru, Rh, Pd, Re, Ir, Pt, Fe, Co, Ni, Mn, or Cu. The metal salt is one of chlorides, sulfates, nitrates and acetylacetone salts of Ru, Rh, Pd, Re, Ir, Pt, Fe, Co, Ni, Mn or Cu. The alkali metal salt is one or more of sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sulfate, potassium sulfate, sodium chloride, potassium chloride, sodium nitrate and potassium nitrate.
The nitrogen-doped graphene-loaded metal monatomic catalyst prepared by the method has the morphological characteristics of a two-dimensional microstructure, the thickness of the nitrogen-doped graphene-loaded metal monatomic catalyst is 0.5-2 nm, the metal loading amount is 0.01-10 wt%, the graphene carrier is N-doped pyrolytic graphene, and the number of graphene layers is 1-8.
The graphene-supported metal monoatomic dispersion catalytic material provided by the invention is a novel monoatomic dispersion material stabilized by nitrogen atoms on graphene. The doped nitrogen atoms can change the electronic structure of the graphene, improve the conductivity of the graphene, form coordinate bonds with metal atoms to stabilize the metal single atoms, and enable the metal atoms to be uniformly and firmly loaded on the surface of the graphene. The nitrogen-doped graphene-loaded metal monatomic dispersed catalyst provided by the invention can greatly enrich the types of metal monatomic catalysts, provides a brand-new synthesis technology, and also provides possibility for researching the catalytic properties of metal monatomic materials. This patent presents a general method for preparing nitrogen-doped graphene-supported metal monatomic catalysts, the active components of which are stabilized by nitrogen atoms.
The following examples are given to further understand the present invention, but the present invention is not limited to the following examples.
Example 1
Preparing a graphene-loaded Pd monatomic catalyst:
step 1, adding 4g of disodium ethylenediamine tetraacetic acid and 12 mg of sodium tetrachloropalladate into deionized water, magnetically stirring, reacting at 80 ℃ for 2 hours, and then evaporating to dryness and drying;
step 2, fully and uniformly mixing 4g of the product obtained in the step 1 with 30g of sodium carbonate, putting the mixture into a tubular furnace, carrying out heat treatment at 800 ℃ for 3h in an inert atmosphere, and naturally cooling to room temperature to obtain a black mixture;
and 3, washing and drying the black mixture obtained in the step 2 by using a 1M hydrochloric acid solution, pure water and absolute ethyl alcohol in sequence to obtain the nitrogen-doped graphene-loaded metal Pd monatomic catalyst. As shown in fig. 1, which is an image of a graphene-supported Pd monatomic catalyst under a high-angle annular dark-field scanning transmission electron microscope, bright metal Pd monatomics are uniformly dispersed on the surface of graphene, and the metal loading concentration is high.
Example 2
Preparing a graphene-loaded Pt monatomic catalyst:
step 1, adding 6g of ethylene diamine tetraacetic acid disodium salt and 5.6mg of potassium hexachloroplatinate into deionized water, magnetically stirring, reacting for 6 hours at 80 ℃, and then drying by evaporation;
step 2, fully and uniformly mixing 6g of the product obtained in the step 1 with 30g of sodium sulfate, putting the mixture into a tubular furnace, carrying out heat treatment at 850 ℃ for 2h in an inert atmosphere, and naturally cooling to room temperature to obtain a black mixture;
and 3, washing and drying the black mixture obtained in the step 2 by 0.5M sulfuric acid solution, pure water and absolute ethyl alcohol in sequence to obtain the nitrogen-doped graphene-loaded metal Pt monatomic catalyst. As shown in fig. 2, the image of the graphene-supported Pt monatomic catalyst under a transmission electron microscope shows that the overall morphology of the catalyst is an ultrathin two-dimensional nanostructure and has typical characteristics of graphene. Fig. 3 shows an image of a graphene-supported Pt monatomic catalyst under a high-angle annular dark-field scanning transmission electron microscope, wherein bright metal Pt monatomics are uniformly dispersed on the surface of graphene, and the metal loading concentration is high.
Example 3
Preparing a graphene loaded Co monatomic catalyst:
step 1, adding 2g of ethylene diamine tetraacetic acid disodium salt and 7.6 mg of cobalt nitrate into deionized water, magnetically stirring, reacting at 40 ℃ for 2 hours, and then evaporating to dryness and drying;
step 2, fully and uniformly mixing 2g of the product obtained in the step 1 with 40 g of sodium sulfate, putting the mixture into a tubular furnace, carrying out heat treatment at 900 ℃ for 1h in an inert atmosphere, and naturally cooling to room temperature to obtain a black mixture;
and 3, washing and drying the black mixture obtained in the step 2 by using a 1M hydrochloric acid solution, pure water and absolute ethyl alcohol in sequence to obtain the nitrogen-doped graphene-loaded metal Co monatomic catalyst. As shown in fig. 4, which is an image of the graphene supported Co monatomic catalyst under a high-angle annular dark-field scanning transmission electron microscope, bright metallic Co monatomics are uniformly dispersed on the surface of the graphene.
Example 4
Preparing a graphene-loaded Ni monatomic catalyst:
step 1, adding 8g of ethylene diamine tetraacetic acid disodium salt and 13 mg of nickel chloride into deionized water, magnetically stirring, reacting at 80 ℃ for 0.5h, and then evaporating to dryness and drying;
step 2, fully and uniformly mixing 8g of the product obtained in the step 1 with 48g of potassium carbonate, putting the mixture into a tubular furnace, carrying out heat treatment at 950 ℃ for 0.5h in an inert atmosphere, and naturally cooling the mixture to room temperature to obtain a black mixture;
and 3, washing and drying the black mixture obtained in the step 2 by using a 1M hydrochloric acid solution, pure water and absolute ethyl alcohol in sequence to obtain the nitrogen-doped graphene-loaded metal Ni monatomic catalyst. As shown in fig. 5, which is an image of the graphene-supported Ni monatomic catalyst under a high-angle annular dark-field scanning transmission electron microscope, bright metal Ni monatomics are uniformly dispersed on the surface of graphene, and the metal loading concentration is high.
Example 5
Preparing a graphene-supported Fe monatomic catalyst:
step 1, adding 7g of disodium ethylene diamine tetraacetate and 8.6 mg of ferric chloride into deionized water, magnetically stirring, reacting at 80 ℃ for 2 hours, and then evaporating to dryness and drying;
step 2, fully and uniformly mixing 7g of the product obtained in the step 1 with 35g of sodium nitrate, putting the mixture into a tubular furnace, carrying out heat treatment at 1000 ℃ for 0.5h in an inert atmosphere, and naturally cooling the mixture to room temperature to obtain a black mixture;
and 3, washing and drying the black mixture obtained in the step 2 by using a 1M hydrochloric acid solution, pure water and absolute ethyl alcohol in sequence to obtain the nitrogen-doped graphene-loaded metal Fe monatomic catalyst. As shown in fig. 6, which is an image of the graphene-supported Fe monatomic catalyst under a high-angle annular dark-field scanning transmission electron microscope, bright metallic Fe monatomics are uniformly dispersed on the graphene surface.
Example 6
Preparing a graphene-supported Rh single-atom catalyst:
step 1, adding 9g of ethylene diamine tetraacetic acid disodium salt and 5.6mg of ammonium hexachlororhodate into deionized water, magnetically stirring, reacting at 80 ℃ for 2 hours, and then evaporating to dryness and drying;
step 2, fully and uniformly mixing 9g of the product obtained in the step 1 with 45g of sodium nitrate, putting the mixture into a tubular furnace, carrying out heat treatment at 900 ℃ for 0.5h in an inert atmosphere, and naturally cooling to room temperature to obtain a black mixture;
and 3, washing and drying the black mixture obtained in the step 2 by using a 1M hydrochloric acid solution, pure water and absolute ethyl alcohol in sequence to obtain the nitrogen-doped graphene-loaded metal Rh monatomic catalyst.
Example 7
Preparing a graphene-loaded Ru monatomic catalyst:
step 1, adding 5g of ethylene diamine tetraacetic acid disodium salt and 4.3 mg of hydrated sodium chlororuthenate into deionized water, magnetically stirring, reacting for 2 hours at 100 ℃, and then evaporating to dryness and drying;
step 2, fully and uniformly mixing 5g of the product obtained in the step 1 with 45g of sodium nitrate, putting the mixture into a tubular furnace, carrying out heat treatment at 800 ℃ for 2 hours in an inert atmosphere, and naturally cooling the mixture to room temperature to obtain a black mixture;
and 3, washing and drying the black mixture obtained in the step 2 by using a 1M hydrochloric acid solution, pure water and absolute ethyl alcohol in sequence to obtain the nitrogen-doped graphene-loaded metal Ru monatomic catalyst.
Example 8
Preparing a graphene supported Ir monoatomic catalyst:
step 1, adding 7g of ethylene diamine tetraacetic acid disodium salt and 5.7 mg of potassium chloroiridate into deionized water, magnetically stirring, reacting at 80 ℃ for 4 hours, and then evaporating to dryness and drying;
step 2, fully and uniformly mixing 7g of the product obtained in the step 1 with 35g of sodium carbonate, putting the mixture into a tubular furnace, carrying out heat treatment at 1100 ℃ for 0.5h in an inert atmosphere, and naturally cooling the mixture to room temperature to obtain a black mixture;
and 3, washing and drying the black mixture obtained in the step 2 by using a 1M hydrochloric acid solution, pure water and absolute ethyl alcohol in sequence to obtain the nitrogen-doped graphene-loaded metal Ir monatomic catalyst.
Claims (6)
1. A preparation method of a nitrogen-doped graphene-loaded metal monatomic catalyst is characterized by comprising the following steps:
1) adding a nitrogenous organic compound, namely disodium ethylene diamine tetraacetate and a metal salt into deionized water, wherein the mass ratio of the disodium ethylene diamine tetraacetate to the metal salt is 1000: 1-100: 1, and uniformly mixing to obtain an aqueous solution of the metal salt with the molar concentration of 0.001-0.5 mol/L; then carrying out ion exchange reaction for 0.5-6 h at 40-120 ℃ to obtain a stable complex, and drying by distillation to obtain complex solid powder;
2) fully and uniformly mixing the complex solid powder obtained in the step 1) with an alkali metal salt, wherein the mass ratio of the complex solid powder to the alkali metal salt is 1: 5-1: 20, putting the mixture into a tubular furnace, performing heat treatment at 800-1200 ℃ for 0.5-3 h in an inert atmosphere, and then naturally cooling to room temperature to obtain a mixture of a nitrogen-doped graphene-supported metal monatomic catalyst and the alkali metal salt;
3) washing and drying the mixture obtained in the step 2) by using an acidic aqueous solution, pure water and absolute ethyl alcohol in sequence to obtain the nitrogen-doped graphene-loaded metal monatomic catalyst.
2. The preparation method of the nitrogen-doped graphene-supported metal monatomic catalyst according to claim 1, characterized in that: the metal single atom in the catalyst is Ru, Rh, Pd, Re, Ir, Pt, Fe, Co, Ni, Mn or Cu.
3. The preparation method of the nitrogen-doped graphene-supported metal monatomic catalyst according to claim 1, characterized in that: the metal salt is one of chlorides, sulfates, nitrates and acetylacetone salts of Ru, Rh, Pd, Re, Ir, Pt, Fe, Co, Ni, Mn or Cu.
4. The preparation method of the nitrogen-doped graphene-supported metal monatomic catalyst according to claim 1, characterized in that: the alkali metal salt is one or more of mixed salt of sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sulfate, potassium sulfate, sodium chloride, potassium chloride, sodium nitrate and potassium nitrate.
5. The preparation method of the nitrogen-doped graphene-supported metal monatomic catalyst according to claim 1, characterized in that: the inert gas is nitrogen or argon.
6. The method for preparing a nitrogen-doped graphene-supported metal monatomic catalyst according to any one of claims 1 to 5, wherein: the catalyst has the two-dimensional microstructure morphology characteristic that the thickness is 0.5-2 nm, the graphene is pyrolytic graphene, the number of layers of the graphene is 1-8, and the metal loading is 0.01-10 wt%.
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