CN114308025A - Preparation method of atomic-level dispersed precious metal/carbon composite material - Google Patents
Preparation method of atomic-level dispersed precious metal/carbon composite material Download PDFInfo
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- CN114308025A CN114308025A CN202210016265.5A CN202210016265A CN114308025A CN 114308025 A CN114308025 A CN 114308025A CN 202210016265 A CN202210016265 A CN 202210016265A CN 114308025 A CN114308025 A CN 114308025A
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Abstract
The invention discloses a preparation method of an atomic-level dispersed noble metal/carbon composite material. Mixing the purified paper with a compound solution, drying in a drying oven to obtain a precursor, placing the precursor in a porcelain boat, placing in an atmosphere furnace, heating to a certain temperature under the protection of inert atmosphere for pyrolysis treatment, cooling the furnace body to room temperature, mixing the sample with water or hydrochloric acid, filtering, washing, drying, grinding to obtain a powdered carbon material, dispersing the powdered carbon material in water to obtain a dispersion liquid, slowly dripping a noble metal compound solution into the dispersion liquid, stirring, filtering, washing, and drying to obtain the noble metal/carbon composite material with atomic-level dispersion. The preparation method is simple to operate, has low requirements on instruments and equipment, strong controllability and easy amplification preparation, can be used for preparing various atomically decomposed precious metal/carbon composite materials, and the prepared composite materials can be applied to the fields of various chemical catalysis and electrochemical energy conversion and have wide application prospects.
Description
Technical Field
The invention belongs to the technical field of material synthesis, and particularly relates to a preparation method of an atomic-scale dispersed precious metal/carbon composite material.
Background
With the worldwide economic trend toward a rapid increase, there is an increasing demand for various chemicals and energy sources. Conventionally, various fossil fuels, such as petroleum, coal, natural gas, and other resources, are converted to obtain chemicals and energy, and the process usually requires various catalysts, such as noble metal-based catalysts. For the economic development at the present stage, in order to pursue sustainability, development and utilization of various renewable new energy sources such as wind energy, water energy and solar energy are required. These new energy sources are further converted into electric energy, and the electric energy is stored and released through the storage of the electric energy or directly used for electrocatalytic synthesis and conversion reaction, such as the synthesis of various organic and inorganic chemicals (carbon monoxide, hydrogen, methane, formic acid, ammonia and the like) or the oxidation reduction of various organic matters. These processes also require various catalyst adjustments to reduce energy losses in the process. Among the various transition metal, noble metal and non-metal catalysts currently studied, the noble metal-based catalyst has the best activity stability and is most widely used. However, noble metal-based catalysts are extremely costly and have limited use on a large scale. The development of the noble metal catalyst with atomic-level dispersion is beneficial to maximizing the utilization rate of noble metal atoms and reducing the use cost, and is a feasible technical scheme for solving the effective application of the noble metal catalyst.
In the above-mentioned various chemical and electrochemical conversion reactions, various noble metal-based catalysts have been reported, such as single-metal and multi-metal alloy materials based on Au, Ir, Rh, Pt, Ru, Pd, Ag, etc. In order to prevent the atomically dispersed noble metal components from diffusing and aggregating during use, various carriers such as metal oxides, carbon, polymers, etc. are required. The interaction between the noble metal and the carrier is beneficial to synthesizing the noble metal-based composite material with atomic-level dispersion. How to realize the composition of the two through a proper chemical method is the key of the synthesis of the atomic-level dispersed noble metal-based material at present. At present, the synthesis of the noble metal-based material is carried out by the following common methods: (1) the wet chemical synthesis method is that noble metal salt is dissolved and the carrier is dispersed into solution, and then the steps of drying, heat treatment, activation or reduction and the like are carried out to realize the load of atomic-level metal. (2) The metal etching method is that metal salt and organic matter are compounded, dried and pyrolyzed, and the metal nano particles are removed through acid treatment to prepare the metal material with carbon carrying atomic level dispersion. (3) Electrodeposition, i.e., the deposition of atomic scale metals onto the substrate surface by potential control. (4) The metal-organic framework method is that metal ions and organic ligands are firstly compounded to form a metal-organic framework compound, and then the metal-organic framework compound is heated and hydrolyzed to obtain the monatomic material. The methods have respective advantages and disadvantages, and particularly, most methods are complicated in process, low in controllability, expensive in raw materials and not beneficial to expanded application.
Disclosure of Invention
The invention aims to provide a preparation method of an atomically dispersed precious metal/carbon composite material, which adopts low-cost raw materials and a simple mixing synthesis process to prepare the atomically dispersed precious metal/carbon composite material and realize the application of the atomically dispersed precious metal/carbon composite material.
The typical raw material characteristic of the invention is to adopt various paper materials, the typical synthesis characteristic is a compound carbon etching process and a mixed surface reduction deposition process, the typical structure characteristic is that noble metals dispersed in atomic level are on the carbon surface, and the typical performance characteristic is to realize higher activity under the same noble metal loading. In the synthesized composite material, the size of the noble metal component dispersed on the surface of the carbon is less than 1 nm, and the substrate carbon has different nano or micro structures.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
(1) mixing a commercially purchased paper material with a solvent I according to a mass ratio of 1: 0.1-100, soaking for a period of time, airing, and removing soluble impurities.
The paper material can be roll paper, tissue paper, printing paper, filter paper, kraft paper and the like.
The solvent I refers to water, ethanol, acetone, DMF, glacial acetic acid or chloroform.
The soaking time is 0.1 hour to 10 days.
(2) And adding 0.01-100 g of chemical forming compound solution into each milliliter of solvent II, mixing the dried paper material with the compound solution, uniformly mixing, and drying in an oven to obtain the precursor.
The solvent II refers to water, ethanol or acetone.
The chemicals are NaOH, KOH, Ca (OH)2、Mg(OH)2A basic compound such as LiOH, or ZnCl2、ZnSO4Or zinc acetate.
(3) And (2) placing the precursor in an atmosphere furnace, heating to a specific temperature under a specified atmosphere, preserving heat for a period of time, cooling, mixing the obtained material with water or hydrochloric acid, filtering, drying, and grinding into powder to obtain the powdered carbon material.
The atmosphere in the atmosphere furnace is one of air, argon-hydrogen mixed gas and nitrogen.
The specific temperature is 300-1500 ℃, and the heat preservation time is 0.01-48 hours.
(4) And dissolving a noble metal-based compound in the solvent III to obtain a noble metal-based compound solution, dispersing the powdery carbon material in water to obtain a dispersion liquid, then adding the noble metal-based compound solution into the dispersion liquid, stirring for a period of time, filtering, washing and drying to obtain the noble metal/carbon composite material with atomic-scale dispersion.
The noble metal compound comprises one or more of chlorides, hydrochlorides, acetylacetonates and nitrates of Au, Ir, Rh, Pt, Ru, Pd, Ag and the like.
The solvent III is water, ethanol, acetone, DMF or chloroform.
The stirring time is 0.1 hour to 5 days.
The method utilizes paper materials and compounds to etch and synthesize carbon, and synthesizes the noble metal/carbon composite material with atomic-level dispersion by simple mixing and stirring reaction through in-situ reduction deposition on the surface of the carbon, thereby realizing lower cost and wider application. The synthesis method adopted by the invention has strong universality, is suitable for synthesizing various noble metals to be deposited on carbon in an atomic dispersion manner, has low requirements on equipment and is suitable for large-scale production.
Compared with the existing synthetic method and the synthetic atomic-scale dispersed material, the method has the following advantages:
(1) the preparation process of the general atomic-level dispersed noble metal-based catalytic material is complex and various, and the equipment requirement is high. The synthesis method is simple, the synthesis is completed through pyrolysis carbonization treatment and simple stirring reduction processes, the requirements on equipment conditions are low, the efficiency is high, and the large-scale production is facilitated.
(2) The raw materials used in the synthesis are expensive, for example, the synthesis by a metal-organic framework method and a metal etching method requires expensive organic ligands or organic substances to prepare the carbon carrier. The synthetic materials used in the invention are paper materials and precious metal compounds, the paper materials are low in price, the use amount of the precious metal compounds can be controlled, and the actual synthesis cost is greatly reduced.
(3) In the general process of synthesizing the atomic-level dispersed noble metal material, the control conditions of the synthesis are strict and strict, and the controllability is poor. Such as electrodeposition, require strict control of potential and solution state. The preparation method has simple and reliable control process, and easily realizes the dispersion of the atomic-level noble metal on the carbon surface (the size is less than 1 nm) through the in-situ reduction and deposition of the carbon surface defects.
(4) Generally, the synthesis is only suitable for obtaining the atomic-level dispersion state of a single noble metal or transition metal. The synthesis method is suitable for obtaining various noble metals and composite metals in an atomic-level dispersion state, and has wide applicability.
(5) The atomic-level dispersed noble metal/carbon composite material obtained by the invention can effectively improve the atom utilization rate of various existing noble metal-based materials, and is an improvement approach of noble metal materials with very wide application prospects.
Drawings
Fig. 1 is (a) low power and (b) high power Transmission Electron Microscope (TEM) images of the atomic-scale dispersed Pt/carbon composite in example 1.
FIG. 2 is the hydrogen evolution performance from electrolyzed water of the atomic-scale dispersed Pt/carbon composite material in example 1.
Detailed Description
The technical solution of the present invention is further explained by way of embodiments with reference to the accompanying drawings.
Example 1
Preparation of atomic-level dispersed Pt/carbon composite material and physical and electrochemical characterization
(1) 10g of roll paper is taken out and soaked in 500ml of water, taken out and dried.
(2) And 2g of the purified and air-dried roll paper is soaked in 10ml of 1M KOH solution, and after complete adsorption, the roll paper is dried in a drying oven at 100 ℃ overnight to obtain a precursor.
(3) Placing the precursor in a porcelain boat in the middle of an alumina tube, and under the protection of argon atmosphere, using a tube furnace at 10 ℃ for min-1Heating to 900 ℃ at the heating rate, keeping for 2 hours, cooling to room temperature, mixing the obtained material with 100ml of water, stirring for 1 hour, filtering, washing, drying, grinding into powder to obtain powder defective carbon, and naming the powder defective carbon as DC;
(4) dispersing 100mg of defect state carbon (DC) in 5ml of water, and performing ultrasonic treatment for 20 min to obtain a dispersion liquid; 0.5ml of 18.9 mmol L-1Slowly dripping a chloroplatinic acid solution into the dispersion, standing for 24 h after ultrasonic homogenization, filtering, washing for 3 times by using water, and drying overnight at 60 ℃ to obtain a sample, namely the atomic-scale dispersed platinum/carbon composite material, which is named as Pt-C.
As shown in FIG. 1, the carbon in the composite material is in a nano-sheet structure, and single atoms Pt are loaded on the surface of the carbon. As shown in figure 2, the hydrogen evolution performance of the composite material in acid electrolysis water is better than that of commercial Pt/C (JM) under the same noble metal loading, and the hydrogen evolution performance is 100 mA cm-2At a current of (2), the overpotential thereof is only 54mV。
Example 2
Preparation and physical characterization of atomic-level dispersed Pd/carbon composite material
(1) 20g of filter paper is taken out and soaked in 1000ml of water for 1 day, and then taken out and dried.
(2) 1g of the purified and dried filter paper was taken to absorb 5ml of 0.5M ZnCl2And (3) after the solution is completely adsorbed, drying the solution in a drying oven at 80 ℃ overnight to obtain a precursor.
(3) Placing the precursor in a porcelain boat in the middle of a tube furnace, and under the protection of argon atmosphere, the tube furnace is heated at 5 ℃ for min-1Heating to 800 deg.C, holding for 2 hr, and naturally cooling to room temperature. Mixing the obtained material with 100ml of 1M hydrochloric acid solution, ultrasonically stirring for 1 hour, filtering, washing with water for 3 times, drying, and grinding into powder to obtain a powdery carbon material;
(4) 200mg of powdered carbon material was dispersed in 10ml of water, and subjected to ultrasonic treatment for 30 min to obtain a dispersion. 1ml of 36 mmol L-1Slowly dripping a palladium chloride solution into the dispersion liquid, standing for 48 h after ultrasonic homogenization, filtering, washing for 3 times by using water, and drying overnight at 60 ℃ to obtain a sample, namely the atomic-scale dispersed palladium/carbon composite material.
It should be understood that the above-described embodiments of the present invention are illustrative and not restrictive, and the scope of the invention is not to be restricted by the appended claims.
Claims (10)
1. A preparation method of an atomic-scale dispersed precious metal/carbon composite material is characterized by comprising the following steps:
(1) mixing a paper material with a solvent I, soaking for a period of time, and airing to obtain a purified paper material;
(2) uniformly mixing the purified paper material with an alkaline compound or a neutral compound solution, and drying in an oven to obtain a precursor;
(3) placing the precursor in an atmosphere furnace, heating to a specific temperature under a specified atmosphere, preserving heat for a period of time, then cooling, mixing the obtained material with water or hydrochloric acid, filtering, drying, and grinding into powder to obtain a powdered carbon material;
(4) dispersing the powdery carbon material into water to obtain a dispersion liquid, then adding the noble metal-based compound solution into the dispersion liquid, stirring for a period of time, filtering, washing and drying to obtain the noble metal/carbon composite material with atomic-scale dispersion.
2. The method for preparing an atomically dispersed noble metal/carbon composite material according to claim 1, wherein the paper material in step (1) includes roll paper, tissue paper, printing paper, filter paper, kraft paper.
3. The method for preparing the atomically dispersed precious metal/carbon composite material according to claim 1, wherein in the step (1), the solvent I is water, ethanol, acetone, DMF, glacial acetic acid or chloroform, the paper material and the solvent I are mixed according to a mass ratio of 1: 0.1-100, and the soaking time is 0.1 hour-10 days.
4. The method for preparing an atomically dispersed noble metal/carbon composite material according to claim 1, wherein the basic compound or the neutral compound is NaOH, KOH, LiOH, Ca (OH) in the step (2)2、Mg(OH)2、ZnCl2、ZnSO4And zinc acetate.
5. The method of claim 4, wherein the basic compound or the neutral compound is added in an amount of 0.01-100 g/ml solvent II, wherein the solvent II is water, ethanol or acetone.
6. The method for preparing an atomically dispersed noble metal/carbon composite material according to claim 1, wherein in the step (3), the atmosphere in the atmospheric furnace is one of air, argon-hydrogen mixture gas and nitrogen.
7. The method for preparing an atomically dispersed noble metal/carbon composite material according to claim 1, wherein in the step (3), the material is heated to 300 to 1500 ℃ at a rate of 5 to 10 ℃/min, and then the temperature is maintained for 0.01 to 48 hours.
8. The method for preparing an atomically dispersed noble metal/carbon composite material according to claim 1, wherein in the step (4), the noble metal-based compound is one or more of chlorides, hydrochlorides, acetylacetonates, and nitrates of Au, Ir, Rh, Pt, Ru, Pd, and Ag.
9. The method for preparing an atomically dispersed noble metal/carbon composite material according to claim 1, wherein in the step (4), the noble metal-based compound solution is water, ethanol, acetone, DMF, or chloroform as a solvent.
10. The method for preparing an atomically dispersed noble metal/carbon composite material according to claim 1, wherein the stirring time in the step (4) is 0.1 hour to 5 days.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200392054A1 (en) * | 2018-02-20 | 2020-12-17 | The Johns Hopkins University | Method for preparation of nanoceria supported atomic noble metal catalysts and the application of platinum single atom catalysts for direct methane conversion |
| CN112391652A (en) * | 2020-10-23 | 2021-02-23 | 福建师范大学 | Self-adsorption preparation method of atomic-level dispersion transition metal/precious metal composite material |
| CN113368850A (en) * | 2021-06-09 | 2021-09-10 | 中国科学院金属研究所 | Nano carbon loaded atomic-level dispersed rhodium catalyst, preparation method thereof and application thereof in hydrogenation reaction of nitrile compounds |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200392054A1 (en) * | 2018-02-20 | 2020-12-17 | The Johns Hopkins University | Method for preparation of nanoceria supported atomic noble metal catalysts and the application of platinum single atom catalysts for direct methane conversion |
| CN112391652A (en) * | 2020-10-23 | 2021-02-23 | 福建师范大学 | Self-adsorption preparation method of atomic-level dispersion transition metal/precious metal composite material |
| CN113368850A (en) * | 2021-06-09 | 2021-09-10 | 中国科学院金属研究所 | Nano carbon loaded atomic-level dispersed rhodium catalyst, preparation method thereof and application thereof in hydrogenation reaction of nitrile compounds |
Non-Patent Citations (1)
| Title |
|---|
| QUAN WEIWEI等: ""In situ surface reduction for accessing atomically dispersed platinum on carbon sheets for acidic hydrogen evolution"", 《NANOSCALE》 * |
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