CN113198463A - Method for loading metal monoatomic atoms on surface of carbon material - Google Patents
Method for loading metal monoatomic atoms on surface of carbon material Download PDFInfo
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/75—Cobalt
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Abstract
The invention discloses a method for loading metal monoatomic atoms on the surface of a carbon material, which comprises the steps of carrying out pre-oxidation treatment on the carbon material in a mixed solution of sulfuric acid and nitric acid, drying an oxidation product after centrifugal washing to obtain the carbon material with oxidized surface, and mixing a water-soluble metal precursor molecular solution and the carbon material with oxidized surface in ultrapure water; then transferring the mixture into a tube furnace after freeze-drying; obtaining a nano material with metal single atoms loaded on the surface of carbon after heat treatment; the method has the advantages of simple process, low requirement on equipment and low cost, and is suitable for industrial production and market popularization and application.
Description
Technical Field
The invention relates to a method for loading metal monoatomic atoms on the surface of a carbon material, belonging to the field of nano materials.
Background
A catalyst, or catalyst, refers to a substance that affects the rate of chemical reaction of other substances in a chemical reaction without changing before or after the chemical reaction. The catalyst plays a very important role in social development, and according to incomplete statistics, the chemical raw materials and intermediates synthesized directly and indirectly by the catalyst are about 3 thousands of the total. The materials are necessary products directly related to basic life of people, and also relate to the modern high-tech fields, such as aerospace, new energy conversion devices, biomedical engineering and the like. The chemical industry catalysts are mainly homogeneous catalysts and heterogeneous catalysts. Wherein, the catalyst is a homogeneous catalyst consistent with the state of the catalytic reactant; different from the state of the reactants is a heterogeneous catalyst.
In recent years, monatomic catalysts (SACs) have become an important branch in the field of catalyst research due to the extremely high metal atom utilization rate (-100%), controllable metal atom chemical environment, unique electronic structure and strong interaction between metal and a carrier. The homogeneous dispersed metal monoatomic as a catalytic active center is similar to homogeneous catalysis, provides a good research platform for the research of various catalytic reaction mechanisms, and simultaneously has the characteristics of stability and easy separation of a heterogeneous catalyst, so that the realization of high activity, high selectivity and high stability of catalytic reaction is possible. Thus, SACs are considered as a bridge between traditional homogeneous and heterogeneous catalysis (Accounts of Chemical Research, 2013, 46, 1740-.
SACs support materials significantly affect their catalytic properties, such as activity, selectivity and stability, and different support materials can lead to different metal monoatomic dispersivity and electronic structural characteristics. In the preparation and reaction processes of the monatomic catalyst, due to the fact that metal monatomic active valence electrons are easy to sinter and agglomerate to cause catalyst deactivation, and therefore, the selection of a proper metal monatomic carrier is the basis for synthesizing the high-performance SACs. Among many carriers of SACs, carbon materials have unique advantages such as low price, various structures, good stability, high conductivity, adjustable crystal structure and electronic structure, etc., and are widely used as carrier materials of SACs. Therefore, the method has important significance for preparing SACs with high activity, high selectivity and high stability by loading metal monoatomic atoms on the surface of the carbon material.
Disclosure of Invention
The invention provides a method for loading metal monoatomic atoms on the surface of a carbon material, which comprises the steps of firstly carrying out surface pre-oxidation treatment on the carbon material in a mixed solution of sulfuric acid and nitric acid; then, stirring the metal precursor and the carbon material subjected to surface oxidation treatment in an aqueous solution at constant temperature to obtain a mixture; freeze-drying the mixture and transferring the mixture to a tube furnace; successfully loading metal single atoms on the surface of the carbon material after heat treatment, and specifically comprises the following steps:
(1) mixing a sulfuric acid solution with the concentration of 0.1-18 mol/L and a nitric acid solution with the concentration of 0.1-14 mol/L according to the volume ratio of 1: 0.01-1: 100 to prepare a mixed acid solution, placing a carbon material in the mixed acid solution, oxidizing in a water bath at the temperature of 30-35 ℃ for 1-30 h, then, centrifugally washing with water, and drying to prepare a carbon material with oxidized surface;
the carbon material is graphite, single-layer or multi-layer graphene, carbon nano-tube, conductive carbon black, conductive diamond, carbon nano-horn, graphite alkyne, activated carbon, biomass carbonized material, polymer carbonized material, cyanamide carbonized material, metal organic framework carbonized material, covalent organic framework carbonized material, nano porous carbon, carbon nano sphere, carbon nitride, g-C3N4The carbon fiber is one or more of phthalocyanine derived carbon, carbon fiber and graphite fiber, wherein the carbon nanotube is a single-walled or multi-walled carbon nanotube with the pipe diameter of 5-100 nm, and the polymer carbonized material is prepared by polymerizing and carbonizing one or more of aniline polymer, polyethylene, polypyrrole, polypyridine, polyporphyrin and poly phthalocyanine;
(2) placing the carbon material with the oxidized surface into ultrapure water, stirring and ultrasonically preparing a suspension with the concentration of 0.5-10 mg/mL, mixing the water-soluble metal precursor molecular solution and the carbon material suspension with the oxidized surface according to the volume ratio of the water-soluble metal precursor molecular solution to the carbon material suspension with the oxidized surface of 1: 0.1-1: 2000, and stirring for 3-24 hours at the temperature of 20-50 ℃, wherein the concentration of metal ions in the water-soluble metal precursor molecular solution is 0.01-1000 g/L;
the water-soluble metal precursor molecules are water-soluble metal coordination compounds and metal salt compounds, which are conventional commercial products or compounds prepared by a conventional method; specifically, the metal complex can be a water-soluble coordination compound and a salt compound of platinum, palladium, rhodium, iridium, gold, silver, iron, cobalt, nickel, copper, zinc, manganese or chromium;
(3) freeze-drying the mixture obtained in the step (2), and placing the mixture in a tube furnace in N2And (3) preserving the heat for 0.5-10 h at 120-1000 ℃ in the atmosphere, and cooling to room temperature to obtain the material with the metal monoatomic load on the surface of the carbon material.
The main principle of the invention is that the carbon material is oxidized on the surface in the mixed acid water solution, the oxygen group of the oxidized carbon material is deprotonated in the water solution to form colloid particles with negative charges, and metal ions or coordination compounds with positive charges are mixed with the colloid particles; due to electrostatic interactions, metal precursor molecules are adsorbed to the surface of the oxidized carbon material; and then carrying out heat treatment on the carbon oxide material adsorbed with the metal precursor molecules, and capturing metal single atoms by remaining carbon dangling bonds after removing oxygen groups on the surface of the carbon material in the treatment so as to obtain a new material loaded with the metal single atoms on the surface of the carbon material.
The invention has the following beneficial effects:
(1) the invention loads metal single atoms on the surface of the carbon material to realize the atomic-scale nano-engineering processing of the carbon material, and the material can be used for: energy conversion device catalysts, such as fuel cells, metal air cells, photoelectrocatalytic systems; degrading environmental pollutants; the biomedical fields of tumor treatment, antibiosis, antioxidation, biosensing and the like;
(2) the method has the advantages of simple process, low requirement on equipment, easy amplification, low cost and good industrial application prospect.
Drawings
FIG. 1 is a diagram of a spherical aberration scanning transmission electron microscope (AC-STEM) in which a Pt monoatomic atom is supported on conductive carbon black in example 1 of the present invention;
FIG. 2 is an AC-STEM diagram of Pt monoatomic supported conductive carbon black prepared in example 2 of the present invention;
FIG. 3 is an AC-STEM diagram of Pt monoatomic supported conductive carbon black prepared in example 3 of the present invention;
FIG. 4 is an AC-STEM diagram of Pt monoatomic supported conductive carbon black prepared in example 4 of the present invention;
FIG. 5 is an AC-STEM diagram of multi-layer graphene loaded with a single atom of Cu prepared in example 5 of the present invention;
FIG. 6 is an AC-STEM diagram of multi-layer graphene loaded with a single Co atom prepared in example 6 of the present invention.
Detailed Description
The invention will be described in more detail with reference to the following figures and specific examples, but the scope of the invention is not limited thereto;
example 1
(1) Mixing a sulfuric acid solution with the concentration of 5mol/L and a nitric acid solution with the concentration of 5mol/L according to the volume ratio of 1:1 to prepare 80mL of mixed acid solution, placing 500mg of conductive carbon black (Kabot BP2000) carbon material in a beaker containing the mixed acid solution, carrying out water bath constant temperature of 30 ℃, carrying out magnetic stirring for 24 hours, then carrying out centrifugal washing for 3 times by using water, and transferring the material to a vacuum drying oven for drying for 6 hours at the constant temperature of 30 ℃ to obtain conductive carbon black with oxidized surface;
(2) 100mg of conductive carbon black with oxidized surface is put into 25mL of ultrapure water, suspension with the concentration of 4mg/mL is prepared by stirring and ultrasonic, 0.15mL of dihydroxytetraammineplatinum ([ Pt (NH) is taken3)4](OH)2) Mixing the aqueous solution (Pt ion concentration of 900g/L, purchased from New noble metal materials of Yunnan province, China, Ltd.) with the conductive carbon black suspension with oxidized surface, and stirring the mixture at 30 ℃ for 24 h;
(3) freeze-drying the mixture obtained in the step (2), placing the mixture into a tube furnace, introducing nitrogen for 30min, heating the tube furnace to 900 ℃ at the heating rate of 20 ℃/min, and then heating the tube furnace to N2Keeping the temperature for 1h at 900 ℃ in the atmosphere, cooling the tubular furnace to room temperature, and taking out the reaction product to obtain the material of the conductive carbon black with the surface loaded with the Pt monoatomic atoms.
The material of the conductive carbon black prepared in this example, which carries Pt monoatomic atoms on the surface, is characterized by AC-STEM, and it can be seen from fig. 1 that Pt monoatomic atoms are successfully carried on the conductive carbon black, but some Pt nanoparticles are also present.
Example 2
(1) Preparing 80mL of mixed acid solution by using 5mol/L sulfuric acid solution and 14mol/L nitric acid solution according to the volume ratio of 5:1, placing 500mg of conductive carbon black (Kabot BP2000) carbon material in a beaker containing the mixed acid solution, carrying out water bath constant temperature of 30 ℃, carrying out magnetic stirring for 20h, then carrying out centrifugal washing for 3 times by using water, and transferring the material to a vacuum drying oven for drying at the constant temperature of 30 ℃ for 10h to obtain conductive carbon black with oxidized surface;
(2) 200mg of conductive carbon black with oxidized surface is put into 25mL of ultrapure water, suspension with the concentration of 8mg/mL is prepared by stirring and ultrasonic, 0.25mL of dihydroxytetraammineplatinum ([ Pt (NH) is taken3)4](OH)2) Mixing the aqueous solution (Pt ion concentration of 500g/L, purchased from New noble metal materials of Yunnan province, China, Inc.) with the conductive carbon black suspension with oxidized surface, and stirring the mixture at 40 ℃ for 15 h;
(3) freeze-drying the mixture obtained in the step (2), placing the mixture into a tube furnace, introducing nitrogen for 30min, heating the tube furnace to 800 ℃ at the heating rate of 20 ℃/min, and then heating the tube furnace to N2Keeping the temperature at 800 ℃ for 1h in the atmosphere, cooling the tubular furnace to room temperature, and taking out the reaction product to obtain the material with the surface of the conductive carbon black loaded with the Pt monoatomic atoms.
The material of the conductive carbon black prepared in this example, which carries Pt monoatomic atoms on the surface, is characterized by AC-STEM, and it can be seen from fig. 2 that Pt monoatomic atoms are successfully carried on the conductive carbon black, and Pt nanoparticles also appear.
Example 3
(1) Preparing 80mL of mixed acid solution by using 10mol/L sulfuric acid solution and 14mol/L nitric acid solution according to the volume ratio of 1:0.5, placing 500mg of conductive carbon black (Kabot BP2000) carbon material in a beaker containing the mixed acid solution, carrying out water bath constant temperature of 35 ℃, carrying out magnetic stirring for 10 hours, then carrying out centrifugal washing for 3 times by using water, transferring the material into a vacuum drying oven, and drying for 6 hours at the constant temperature of 30 ℃ to obtain conductive carbon black with oxidized surface;
(2) 50mg of conductive carbon black with oxidized surface is put into 25mL of ultrapure water, the suspension with the concentration of 2mg/mL is prepared by stirring and ultrasonic, and 0.5mL of dihydroxytetraammineplatinum ([ Pt (NH) is taken3)4](OH)2) Mixing the aqueous solution (Pt ion concentration is 900 g/L) with the conductive carbon black suspension with oxidized surface, and stirring the mixture for 24 hours at 25 ℃;
(3) freeze-drying the mixture obtained in the step (2), placing the mixture into a tube furnace, introducing nitrogen for 30min, heating the tube furnace to 700 ℃ at the heating rate of 20 ℃/min, and then heating the tube furnace to N2Keeping the temperature of the atmosphere at 700 ℃ for 1h, cooling the tubular furnace to room temperature, and taking out the reaction product to obtain the material of the conductive carbon black with the surface loaded with the Pt monoatomic atoms;
the material of the conductive carbon black prepared in this example, which carries Pt monoatomic atoms on the surface, is characterized by AC-STEM, and it can be seen from fig. 3 that Pt monoatomic atoms are successfully carried on the conductive carbon black, but some Pt nanoparticles are also present.
Example 4
(1) Mixing a 15mol/L sulfuric acid solution and a 5mol/L nitric acid solution according to a volume ratio of 1:5 to prepare 80mL of mixed acid solution, placing 500mg of conductive carbon black (Kabot BP2000) carbon material in a beaker containing the mixed acid solution, carrying out water bath constant temperature of 32 ℃, carrying out magnetic stirring for 18h, then carrying out centrifugal washing for 3 times by water, and transferring the material to a vacuum drying oven for drying at a constant temperature of 30 ℃ for 6h to obtain conductive carbon black with oxidized surface;
(2) 25mg of conductive carbon black with oxidized surface is put into 25mL of ultrapure water, suspension with the concentration of 1mg/mL is prepared by stirring and ultrasonic, 0.02mL of dihydroxytetraammineplatinum ([ Pt (NH) is taken3)4](OH)2) Mixing the aqueous solution (Pt ion concentration is 900 g/L) with the conductive carbon black suspension with oxidized surface, and stirring the mixture for 5 hours at 50 ℃;
(3) freeze-drying the mixture obtained in the step (2), placing the mixture into a tube furnace, introducing nitrogen for 30min, heating the tube furnace to 600 ℃ at the heating rate of 20 ℃/min, and then heating the tube furnace to N2Keeping the temperature at 600 ℃ for 1h in the atmosphere, cooling the tubular furnace to room temperature, and taking out the reaction product to obtain the material loaded with Pt monoatomic atoms on the surface of the conductive carbon black;
the material of the conductive carbon black prepared in this example, which carries Pt monoatomic atoms on the surface, is characterized by AC-STEM, and it can be seen from fig. 4 that Pt monoatomic atoms are successfully carried on the conductive carbon black.
Example 5
(1) Preparing 80mL of mixed acid solution from 5mol/L sulfuric acid solution and 5mol/L nitric acid solution according to the volume ratio of 1:1, placing 500mg of multilayer graphene material in a beaker containing the mixed acid solution, carrying out water bath at the constant temperature of 30 ℃, carrying out magnetic stirring for 24 hours, then carrying out water centrifugal washing for 3 times, and transferring the material to a vacuum drying oven for drying at the constant temperature of 30 ℃ for 6 hours to obtain graphene with oxidized surface;
(2) 100mg of multilayer graphene with oxidized surface is placed in 25mL of ultrapure water, the suspension with the concentration of 4mg/mL is prepared by stirring and ultrasonic treatment, and 10mL of dihydroxyl tetraammine copper ([ Cu (NH)3)4](OH)2) Mixing an aqueous solution (the concentration of Cu ions is 5g/L, refer to 20161122289.6, and are prepared by the method in the method for synthesizing the Cu-N-C catalyst by a hydrothermal method) with the multilayer graphene suspension with oxidized surfaces, and stirring the mixture at 45 ℃ for 20 hours;
(3) freeze-drying the mixture obtained in the step (2), placing the mixture into a tube furnace, introducing nitrogen for 30min, heating the tube furnace to 600 ℃ at the heating rate of 20 ℃/min, and then heating the tube furnace to N2Keeping the temperature at 600 ℃ for 1h under the atmosphere, cooling the tubular furnace to room temperature, and taking out a reaction product to obtain the material with the surface of the multilayer graphene loaded with the Cu monoatomic atoms;
the material of the multilayer graphene loaded with the Cu monoatomic atom on the surface prepared in this example is characterized by AC-STEM, and it can be seen from fig. 5 that the Cu monoatomic atom is successfully loaded on the multilayer graphene.
Example 6
(1) Preparing 80mL of mixed acid solution from 1mol/L sulfuric acid solution and 13mol/L nitric acid solution according to the volume ratio of 10:1, placing 500mg of multilayer graphene in a beaker containing the mixed acid solution, carrying out water bath constant temperature of 35 ℃, carrying out magnetic stirring for 15h, then carrying out water centrifugal washing for 3 times, transferring the material to a vacuum drying oven, and drying for 6h at the constant temperature of 30 ℃ to obtain multilayer graphite with oxidized surfaces;
(2) 150mg of multilayer graphene with oxidized surface is placed in 25mL of ultrapure water, the suspension with the concentration of 6mg/mL is prepared by stirring and ultrasonic treatment, and 10mL of dihydroxy tetra-ammine cobalt ([ Co (NH)3)4](OH)2) Aqueous solution (Co ion)The sub-concentration is 5g/L, refer to 202010963946.3, the preparation method of the cobalt coordination compound molecular intercalation multilayer graphene nano material is prepared), and the mixture is mixed with the multilayer graphene suspension with oxidized surface, and the mixture is stirred for 24 hours at 25 ℃;
(3) freeze-drying the mixture obtained in the step (2), placing the mixture into a tube furnace, introducing nitrogen for 30min, heating the tube furnace to 400 ℃ at the heating rate of 20 ℃/min, and then heating the tube furnace to N2Keeping the temperature of the atmosphere at 400 ℃ for 1h, cooling the tubular furnace to room temperature, and taking out the reaction product to obtain the material with the surface loaded with the Co monoatomic atoms on the multilayer graphene.
The material of the multilayer graphene surface loaded with the Co monoatomic atom prepared in this embodiment is characterized by AC-STEM, and it can be seen from fig. 6 that the Co monoatomic atom is successfully loaded on the multilayer graphene.
Claims (4)
1. A method for loading metal monoatomic atoms on the surface of a carbon material is characterized by comprising the following steps:
(1) mixing a sulfuric acid solution with the concentration of 0.1-18 mol/L and a nitric acid solution with the concentration of 0.1-14 mol/L according to the volume ratio of 1: 0.01-1: 100 to prepare a mixed acid solution, placing a carbon material in the mixed acid solution, oxidizing in a water bath at the temperature of 30-35 ℃ for 1-30 h, then, centrifugally washing with water, and drying to prepare a carbon material with oxidized surface;
(2) placing the carbon material with the oxidized surface into ultrapure water, stirring and ultrasonically preparing a suspension with the concentration of 0.5-10 mg/mL, mixing the water-soluble metal precursor molecular solution and the carbon material suspension with the oxidized surface according to the volume ratio of the water-soluble metal precursor molecular solution to the carbon material suspension with the oxidized surface of 1: 0.1-1: 2000, and stirring for 3-24 hours at the temperature of 20-50 ℃, wherein the concentration of metal ions in the water-soluble metal precursor molecular solution is 0.01-1000 g/L;
(3) freeze-drying the mixture obtained in the step (2), and placing the mixture in a tube furnace in N2And (3) preserving the heat for 0.5-10 h at 120-1000 ℃ in the atmosphere, and cooling to room temperature to obtain the material with the metal monoatomic load on the surface of the carbon material.
2. According to claim 1The method for loading the metal monoatomic atoms on the surface of the carbon material is characterized by comprising the following steps: the carbon material is graphite, single-layer or multi-layer graphene, carbon nanotube, conductive carbon black, conductive diamond, carbon nanohorn, graphyne, activated carbon, biomass carbonized material, polymer carbonized material, cyanamide carbonized material, metal organic framework carbonized material, covalent organic framework carbonized material, nanoporous carbon, carbon nanosphere, carbon nitride, g-C3N4The carbon nano tube is a single-walled or multi-walled carbon nano tube with the tube diameter of 5-100 nm, and the polymer carbonized material is prepared by polymerizing and carbonizing one or more of aniline polymer, polyethylene, polypyrrole, polypyridine, polyporphyrin and poly phthalocyanine.
3. The method for supporting a metal monoatomic atom on a surface of a carbon material according to claim 1, wherein: the water-soluble metal precursor molecules are water-soluble metal coordination compounds and metal salt compounds.
4. The method for supporting a metal monoatomic atom on a surface of a carbon material according to claim 3, wherein: the water-soluble metal coordination compound and the metal salt compound are water-soluble coordination compounds and salt compounds of platinum, palladium, rhodium, iridium, gold, silver, iron, cobalt, nickel, copper, zinc, manganese or chromium.
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