CN109718822B - Method for preparing metal-carbon composite catalytic material and application thereof - Google Patents

Method for preparing metal-carbon composite catalytic material and application thereof Download PDF

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CN109718822B
CN109718822B CN201811483981.4A CN201811483981A CN109718822B CN 109718822 B CN109718822 B CN 109718822B CN 201811483981 A CN201811483981 A CN 201811483981A CN 109718822 B CN109718822 B CN 109718822B
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carbon composite
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CN109718822A (en
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邱介山
谭新义
于畅
倪林
姚秀超
洪家富
崔崧
黄红菱
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Dalian University of Technology
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Abstract

The invention belongs to the technical field of preparation of carbon-based materials, and relates to a method for preparing a metal-carbon composite catalytic material and application thereof, wherein the preparation method comprises the following steps: (1) mixing 0.5-5g of carbon source and 0.02-1g of metal salt, placing the mixture in a ball milling tank made of 50mL of zirconia, carrying out ball milling for 30-60min, then adding 1-20g of nitrogen source, and carrying out ball milling for 30-60min to obtain ball-milled powder; (2) and (3) placing the powder subjected to ball milling in the step (1) into a tubular furnace, and roasting at high temperature for 1-2 hours under the protection of argon to obtain the metal-carbon composite catalytic material. The metal-carbon composite material prepared by the method has the advantages of small size of metal nanoparticles, less impurities, high catalytic activity, stable active substances and the like, has great application potential in the field of catalysis, and researches the catalytic activity of the composite material in water decomposition and carbon dioxide reduction reactions. The method has the advantages of simple process, short production period, low cost and environmental protection.

Description

Method for preparing metal-carbon composite catalytic material and application thereof
Technical Field
The invention relates to a method for preparing a metal-carbon composite catalytic material and application thereof, belonging to the technical field of preparation of carbon-based materials.
Background
Carbon-based nano materials have attracted extensive attention in the aspects of energy storage, heterogeneous catalysis, environmental protection and the like in recent years due to the advantages of excellent electrical conductivity and thermal conductivity, good mechanical properties, high specific surface area, easily-regulated structure, abundant active sites, relatively low price and the like. More importantly, the carbon nano material with unique physicochemical properties and easy regulation can easily adjust the surface properties by introducing intrinsic defects, doping atoms and functional groups, which provides a chance for further reasonably designing advanced carbon-based nano materials and is helpful for better understanding the relationship between structure and performance. Recent studies have shown that the emphasis of doped carbon materials is mainly on nitrogen-doped carbon (N-C material) and metal nitrogen-doped carbon (M-N-C). In particular, such metal-carbon composites (M-N-C), which combine the advantages of metal and nitrogen-doped carbon materials and contain a catalytically active "MNXThe 'sites' have porphyrin-like structures, single metal sites in the 'sites' can also be directly used as active sites, the materials have the advantages of maximum atom utilization rate, uniform catalytic active sites, low metal coordination number, easily-regulated electronic structure and the like, show catalytic properties which are obviously different from those of corresponding bulk materials, and have great application prospects in the fields of water cracking, metal-air batteries and traditional heterogeneous catalysis. However, the preparation of such metal-carbon composite nano-materials usually requires taking a metal organic framework compound or an organic small molecule compound and an organic polymer as precursors, and preparing the metal-carbon composite nano-materials by high-temperature roasting; or by wet chemical impregnation reduction. Therefore, in the preparation process, a considerable amount of solvent (such as organic agents such as alcohol or auxiliary agents such as acid-base agents and surfactants) is inevitably required, and whether the organic solvent/auxiliary agent or the acid-base agent is used, a large amount of waste liquid is necessarily generated, the environmental burden and the manufacturing cost are increased, the green chemical concept is seriously violated, and the scale-up of the green chemical concept is greatly limitedPreparation and industrial application prospect. Therefore, there is a need to develop a green, low-cost, convenient and large-scale production method for preparing high-quality metal-carbon composite materials with good morphology to meet the future application requirements.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a method for preparing a metal-carbon composite catalytic material and application thereof. The method has the advantages of simple process, short production period, low cost, environmental protection and large-scale preparation of the metal-carbon composite material. The metal-carbon composite material prepared by the method has the advantages of small size of metal nanoparticles, less impurities, high catalytic activity, stable active substances and the like, has great application potential in the field of catalysis, and researches the catalytic activity of the composite material in water decomposition and carbon dioxide reduction reactions.
In order to achieve the above purpose and solve the problems existing in the prior art, the invention adopts the technical scheme that: a method of making a metal-carbon composite catalytic material comprising the steps of:
step 1, mixing 0.5-5g of carbon source and 0.02-1g of metal salt, placing the mixture in a ball milling tank made of 50mL of zirconia, carrying out ball milling for 30-60min, then adding 1-20g of nitrogen source, and carrying out ball milling for 30-60min to obtain ball-milled powder; the carbon source is selected from one of tannic acid, ellagic acid, gallnut tannin, quercetin or digallic acid tannin, the metal salt is selected from one of nickel acetate, copper sulfate, cobalt acetate, ferric nitrate, zinc chloride, manganese nitrate, silver acetate, gold acetate or palladium acetate, and the nitrogen source is selected from one of dicyandiamide, urea or melamine;
and 2, placing the powder obtained in the step 1 after ball milling into a tubular furnace, and roasting for 1-2h at the temperature of 600 ℃ and 1000 ℃ under the protection of argon to obtain the metal-carbon composite catalytic material.
The metal-carbon composite catalytic material prepared by the method is applied to water decomposition catalytic reaction and carbon dioxide electrochemical reduction catalytic reaction.
The invention has the beneficial effects that: a method for preparing a metal-carbon composite catalytic material and application thereof are provided, wherein the preparation method comprises the following steps: (1) mixing 0.5-5g of carbon source and 0.02-1g of metal salt, placing the mixture in a ball milling tank made of 50mL of zirconia, carrying out ball milling for 30-60min, then adding 1-20g of nitrogen source, and carrying out ball milling for 30-60min to obtain ball-milled powder; (2) and (3) placing the powder subjected to ball milling in the step (1) into a tube furnace, and roasting for 1-2h at the temperature of 600-1000 ℃ under the protection of argon to obtain the metal-carbon composite catalytic material. The metal-carbon composite material prepared by the method has the advantages of small size of metal nanoparticles, less impurities, high catalytic activity, stable active substances and the like, has great application potential in the field of catalysis, and researches the catalytic activity of the composite material in water decomposition and carbon dioxide reduction reactions. The method has the advantages of simple process, short production period, low cost, environmental protection and capability of preparing the metal-carbon composite catalytic material on a large scale.
Drawings
FIG. 1 is an X-ray diffraction analysis chart of the Ni-N-C catalyst prepared in example 1.
FIG. 2 is a transmission electron micrograph of the Ni-N-C catalyst prepared in example 2.
In the figure: (a) a high-power transmission electron microscope image with the dimension of 50nm, and (b) a high-power transmission electron microscope image with the dimension of 20 nm.
FIG. 3 is an X-ray diffraction analysis chart of the Pd-N-C catalyst prepared in example 10.
FIG. 4 is a graph of the performance of the electrochemical reduction of carbon dioxide described in example 11.
FIG. 5 is a graph of the results of example 12 under acidic conditions (0.5M H)2SO4) Hydrogen evolution polarization diagram of (a).
FIG. 6 is a graph of the results of example 13 under acidic conditions (0.5M H)2SO4) Oxygen evolution polarization diagram of (a).
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Respectively weighing 0.5g of tannic acid and 0.1g of nickel acetate, mixing, placing in a ball milling tank made of 50mL of zirconia, carrying out ball milling for 30min, then adding 1g of melamine, and carrying out ball milling for 30 min. And then placing the powder obtained after ball milling into a tubular furnace, and roasting for 1h at 700 ℃ under the protection of argon gas to obtain the Ni-N-C carbon-based nano material catalyst. From the XRD pattern (fig. 1) of the sample, it can be clearly seen that the (002) characteristic diffraction peak of carbon does not appear, and the characteristic diffraction peak of elemental nickel is not obvious.
Example 2
Respectively weighing 1g of ellagic acid and 0.5g of nickel acetate, mixing, placing in a ball milling tank made of 50mL of zirconia material, ball milling for 30min, then adding 3g of dicyandiamide, and ball milling for 30 min. And then, putting the powder obtained after ball milling into a tubular furnace, and roasting for 2 hours at 800 ℃ under the protection of argon gas to obtain the Ni-N-C carbon-based nano material catalyst. From the transmission electron micrograph (fig. 2) of the sample, it can be seen that the material has a rich pore structure, and the material shows excellent catalytic activity when applied to electrochemical reduction of carbon dioxide.
Example 3
Respectively weighing 5g of tannic acid and 1g of copper sulfate, mixing, placing in a ball milling tank made of 50mL of zirconia, carrying out ball milling for 60min, then adding 20g of dicyandiamide, and carrying out ball milling for 60 min. And then, putting the powder obtained after ball milling into a tube furnace, and roasting for 2 hours at 800 ℃ under the protection of argon gas to obtain the Cu-N-C carbon-based nano material catalyst.
Example 4
2g of gallnut tannin and 0.3g of cobalt acetate are respectively weighed, mixed and placed in a ball milling tank made of 50mL of zirconia, ball milling is carried out for 30min, then 5g of urea is added, and ball milling is carried out for 30 min. And then placing the powder obtained after ball milling into a tube furnace, and roasting for 1h at 600 ℃ under the protection of argon gas to obtain the Co-N-C carbon-based nano material catalyst. The catalyst is applied to electrolyzing water to generate hydrogen under an acidic condition, and shows relatively excellent catalytic activity.
Example 5
Respectively weighing 1g of tannic acid and 0.1g of ferric nitrate, mixing, placing in a 50mL ball milling tank made of zirconia, ball milling for 30min, then adding 10g of melamine, and ball milling for 40 min. And then, putting the powder obtained after ball milling into a tubular furnace, and roasting for 1h at 900 ℃ under the protection of argon gas to obtain the Fe-N-C carbon-based nano material catalyst. When the catalyst is applied to electrolysis of water under an acidic condition for oxygen evolution, relatively excellent catalytic activity is shown.
Example 6
3g of quercetin and 1g of zinc chloride are respectively weighed, mixed and placed in a ball milling tank made of 50mL of zirconia, ball milled for 45min, then 6g of melamine is added, and ball milled for 45 min. And then, putting the powder obtained after ball milling into a tube furnace, and roasting for 1.5h at 1000 ℃ under the protection of argon gas to obtain the Zn-N-C carbon-based nano material catalyst.
Example 7
2g of tannic acid and 0.5g of manganese nitrate are respectively weighed, mixed and placed in a 50mL ball milling tank made of zirconia, ball milled for 45min, then 6g of melamine is added, and ball milled for 45 min. And then, putting the powder obtained after ball milling into a tubular furnace, and roasting for 2 hours at 850 ℃ under the protection of argon gas to obtain the Mn-N-C carbon-based nano material catalyst.
Example 8
0.5g of tannic acid and 0.03g of silver acetate are respectively weighed, mixed and placed in a 50mL ball milling tank made of zirconia, ball milled for 50min, then added with 8g of melamine, and ball milled for 30 min. And then, putting the powder obtained after ball milling into a tubular furnace, and roasting for 1h at 800 ℃ under the protection of argon gas to obtain the Ag-N-C carbon-based nano material catalyst.
Example 9
0.5g of tannic acid and 0.02g of gold acetate are respectively weighed, mixed and placed in a ball milling tank made of 50mL of zirconia, ball milling is carried out for 40min, then 8g of melamine is added, and ball milling is carried out for 50 min. And then, placing the powder obtained after ball milling in a tubular furnace, and roasting for 1h at 950 ℃ under the protection of argon gas to obtain the Au-N-C carbon-based nano material catalyst.
Example 10
Respectively weighing 0.5g of gallic acid tannin and 0.03g of palladium acetate, mixing, placing in a ball milling tank made of 50mL of zirconium oxide, performing ball milling for 35min, then adding 5g of melamine, and performing ball milling for 55 min. And then, putting the powder obtained after ball milling into a tubular furnace, and roasting for 2 hours at 800 ℃ under the protection of argon gas to obtain the Pd-N-C carbon-based nano material catalyst. From the XRD pattern (fig. 3) of the sample, it can be clearly seen that the (002) characteristic diffraction peak of carbon does not appear, and the characteristic diffraction peak of elemental palladium is not obvious.
Example 11
The prepared metal-carbon composite catalyst was subjected to an electrochemical reduction carbon dioxide performance test using an electrochemical workstation of shanghai chen hua CHI 660E. The electrolytic cell is H-shaped, nafion 117 is used as a proton exchange membrane, and 0.1M NaHCO is used3And as an electrolyte, a silver/silver chloride electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, and conductive carbon paper loaded by a catalyst is used as a working electrode to form a three-electrode system. The catalyst prepared in the example 2 is used for carrying out electrochemical reduction carbon dioxide performance test, 5mg of the prepared catalyst is taken and dissolved in 1mL of ethanol, then 30 mu L of nafion adhesive is added, and 100 mu L of nafion adhesive is taken and coated on 1cm of catalyst after ultrasonic treatment for 30min-2On carbon paper, the carbon dioxide-reducing agent shows excellent carbon dioxide reducing performance as a working electrode after being dried at room temperature, the faradaic efficiency of carbon monoxide is as high as 94.8% under the voltage of-0.86V, the excellent performance is shown in figure 4, and the current density is as high as 18.2mA cm-2And has excellent stability, and can be stably tested for 25 hours.
Example 12
The prepared metal-carbon composite catalyst is subjected to an electrolytic water evolution hydrogen energy test, and an electrochemical workstation used is Shanghai Chenghua CHI 660E. The electrolytic cell is in the shape of a three-necked bottle, 0.5M H2SO4And as an electrolyte, a silver/silver chloride electrode is used as a reference electrode, a carbon rod is used as a counter electrode, and conductive carbon paper loaded by a catalyst is used as a working electrode to form a three-electrode system. The catalyst prepared in the example 4 is used for carrying out the electrolytic water evolution hydrogen energy test, 2mg of the prepared catalyst is taken and dissolved in 1mL of ethanol, then 30 mu L of nafion adhesive is added, and 20 mu L of nafion adhesive is taken and coated on 0.2cm after ultrasonic treatment for 30min-2The carbon paper is dried at room temperature and then used as a working electrode to perform hydrogen evolution performance test, shows relatively excellent performance, and can be obtained from a hydrogen evolution polarization curve (LSV, figure 5) of the carbon paper, and the hydrogen evolution performance reaches 10mA cm-2The current density was only 34mV over-potential.
Example 13
The prepared metal-carbon composite catalyst is subjected to an electrolytic water oxygen evolution performance test, and an electrochemical workstation used is Shanghai Chenghua CHI 660E. The electrolytic cell is in the shape of a three-necked bottle, 0.5M H2SO4And as an electrolyte, a silver/silver chloride electrode is used as a reference electrode, a carbon rod is used as a counter electrode, and conductive carbon paper loaded by a catalyst is used as a working electrode to form a three-electrode system. The catalyst prepared in the example 5 is used for carrying out the test of electrolytic water oxygen evolution energy, 2mg of the prepared catalyst is taken and dissolved in 1mL of ethanol, then 30 mu L of nafion adhesive is added, and 20 mu L of nafion adhesive is taken and coated on 0.2cm after ultrasonic treatment for 30min-2The oxygen evolution performance test is carried out on the carbon paper as a working electrode after being dried at room temperature, relatively excellent performance is shown, and the oxygen evolution polarization curve (LSV, figure 6) can be obtained and reaches 10mA cm-2The current density was 480mV over-potential.

Claims (2)

1. A method for preparing a metal-carbon composite catalytic material, characterized by comprising the steps of:
step 1, mixing 0.5-5g of carbon source and 0.02-1g of metal salt, placing the mixture in a ball milling tank made of 50mL of zirconia, carrying out ball milling for 30-60min, then adding 1-20g of nitrogen source, and carrying out ball milling for 30-60min to obtain ball-milled powder; the carbon source is selected from one of tannic acid, ellagic acid, gallnut tannin, quercetin or digallic acid tannin, the metal salt is selected from one of nickel acetate, copper sulfate, cobalt acetate, ferric nitrate, zinc chloride, manganese nitrate, silver acetate, gold acetate or palladium acetate, and the nitrogen source is selected from one of dicyandiamide, urea or melamine;
step 2, placing the ball-milled powder obtained in the step 1 in a tube furnace, and under the protection of argon gas, 600-oAnd C, roasting for 1-2h to obtain the metal-carbon composite catalytic material.
2. The use of the metal-carbon composite catalytic material prepared according to the method of claim 1 in catalytic reactions for electrochemical reduction of carbon dioxide to carbon monoxide and in catalytic reactions for water decomposition.
CN201811483981.4A 2018-12-06 2018-12-06 Method for preparing metal-carbon composite catalytic material and application thereof Active CN109718822B (en)

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CN108706566A (en) * 2018-05-18 2018-10-26 辽宁大学 Porous polymer and its derivative Carbon Materials of the template-free method synthesis based on tannic acid under temperate condition
CN112871146B (en) * 2021-01-14 2023-05-23 常州大学 Double-functional metal-organic framework material modified composite membrane and preparation method and application thereof
CN113548700A (en) * 2021-07-26 2021-10-26 河南师范大学 Preparation method of iron-nickel-nitrogen-carbon nano material
CN113789524A (en) * 2021-09-29 2021-12-14 大连理工大学 Preparation method and application of biomass-based nickel-nitrogen-carbon composite catalytic material
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CN114632533B (en) * 2022-03-09 2024-02-13 深圳信息职业技术学院 Sub-nanometer metal catalyst and preparation method and application method thereof
CN114917892A (en) * 2022-06-07 2022-08-19 中国科学技术大学 Preparation method of carbon-based metal monatomic catalyst in carbon dioxide cycloaddition reaction

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CN105944746A (en) * 2016-05-18 2016-09-21 中国科学院理化技术研究所 Carbon supported nickel nitride catalyst and preparation method and application thereof
CN108906109A (en) * 2018-07-23 2018-11-30 江南大学 A kind of mechanical ball mill preparation method of carbonitride encapsulation nitridation metallic catalyst

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Publication number Priority date Publication date Assignee Title
WO2014085563A1 (en) * 2012-11-27 2014-06-05 Stc.Unm Mechanochemical synthesis for preparation of non-pgm electrocatalysts
CN105944746A (en) * 2016-05-18 2016-09-21 中国科学院理化技术研究所 Carbon supported nickel nitride catalyst and preparation method and application thereof
CN108906109A (en) * 2018-07-23 2018-11-30 江南大学 A kind of mechanical ball mill preparation method of carbonitride encapsulation nitridation metallic catalyst

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