CN112391652A - Self-adsorption preparation method of atomic-level dispersion transition metal/precious metal composite material - Google Patents
Self-adsorption preparation method of atomic-level dispersion transition metal/precious metal composite material Download PDFInfo
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Abstract
The invention provides a self-adsorption preparation method of an atomic-level dispersed transition metal/precious metal composite material. The method comprises the following steps: adding a noble metal catalyst into the solvent I, and stirring for 1h to obtain a noble metal catalyst mixed solution; adding salts of transition metals Sn, Bi, Pb and Sb into a solvent II to form a transition metal salt solution; slowly dripping a transition metal salt solution into the catalyst mixed solution for adsorption reaction; and filtering the solution subjected to the adsorption reaction, washing with deionized water, and drying the filtered filter residue to obtain the atomic-scale dispersed transition metal/noble metal composite material. The related synthesis method is simple, is completed through a one-step self-adsorption process, has low requirements on instrument conditions, can be realized through a stirring device under conventional conditions, has short period of the whole process and high efficiency, and is beneficial to large-scale production. The composite material prepared by the invention not only can be applied to inorganic substances and organic micromolecules, but also can be applied to inorganic substance electrochemical reduction and the like.
Description
Technical Field
The invention relates to a self-adsorption preparation method of an atomic-level dispersed transition metal/precious metal composite material, belonging to the technical field of electrochemistry and material synthesis.
Background
With the rapid development of domestic and foreign economy, people increasingly demand organic chemicals and energy. The preparation of organic chemicals and energy supply have been traditionally accomplished mainly by the conversion or utilization of fossil fuels, such as coal, oil, natural gas, and other resources. However, these fossil fuels have a very limited reserve on the earth's crust, and their utilization is not sustainable for economic development, while also presenting serious environmental pollution problems. Therefore, the technology for realizing inorganic-organic, organic-organic and organic-inorganic electrochemical conversion is developed by utilizing the electric energy further converted from renewable energy sources such as wind energy, water energy and solar energy, and the problems of unsustainability, environmental pollution and the like can be effectively solved. Among the electrochemical conversion techniques, inorganic substances (e.g. CO, H)2O、H2Etc.) and organic small molecules (such as methanol, methane, formic acid, ethanol, ethylene glycol, isopropanol, glycerol, phenyl compounds, etc.), inorganic substances (such as H2O、CO2、N2And the like) electrochemical reduction, becomes an electrochemical conversion technology which is researched more currently, has higher application potential, and is an effective technical scheme for solving the current energy crisis and environmental problems.
In the above-mentioned electrochemical conversion technology, the electrocatalyst is the core, and the high-efficiency electrocatalyst can promote the reactions, improve the conversion efficiency of the electrochemical technology, and promote the practical application. Currently, the most active materials for these electrochemical conversion reactions are still concentrated in noble metal catalysts, including Pt, Pd, Ru, Ir, Au, Rh, etc. The surfaces of the noble metals are further modified with Sn, Bi, Pb and Sb, so that the activity and the electrocatalytic efficiency of the noble metals can be further improved, and meanwhile, the use amount of the noble metals can be reduced on the basis of the same activity, so that the use cost of the noble metals is reduced, and the large-scale application of the noble metals is realized. Based on the characteristics of the solid surface of the noble metal on the specific adsorption property of the transition metal ions, the invention synthesizes the atomic-level dispersed transition metal/noble metal composite material by simple mixing and stirring reaction and assisted heating and the like to promote the reaction rate, develops the self-adsorption synthesis technology, and realizes lower cost and higher electrocatalytic reaction performance.
Disclosure of Invention
The invention aims to overcome the problems of high consumption and low activity of a noble metal electrocatalyst in an electrocatalytic reaction, prepare a high-activity atomic-level dispersed transition metal/noble metal composite material through a simple self-adsorption process, an auxiliary heating process and the like, and realize the application of the composite material in an electrochemical reaction. The invention provides a preparation method and application field of an atomic-level dispersed transition metal/noble metal composite material, which is characterized in that the typical synthesis characteristic is that transition metal ions are self-adsorbed to the surface of a noble metal solid for deposition, the typical structure characteristic is that the atomic-level dispersed transition metal is adsorbed and deposited on the surface of the noble metal in a high dispersion state, and the typical performance characteristic is that the transition metal in the high dispersion state on the surface can assist the active site of the noble metal to carry out more effective electrocatalytic reaction, thereby realizing high activity or lower noble metal dosage and cost under the same activity. The size of the transition metal component dispersed on the surface of the noble metal is less than 1 nm, and the base noble metal can have different nano or micro structures.
The technical scheme adopted for realizing the purpose of the invention is as follows:
(1) adding 0.01-1000 mg of powdery or flaky noble metal catalyst into each milliliter of solvent I, and carrying out ultrasonic or common stirring for 1 hour to obtain noble metal catalyst mixed liquor. When the noble metal catalyst is powdery, the noble metal catalyst is in a suspension state;
the noble metal catalyst is composed of one or more than two alloys of Pt, Pd, Ru, Ir, Au and Rh in any proportion, or a noble metal-loaded catalyst, and can be purchased commercially or synthesized;
the solvent I refers to glycol, acetone, deionized water, DMF, glacial acetic acid, glycerol, ethanol or acetone.
(2) Adding 0.001-100 mg of transition metal Sn, Bi, Pb and Sb salts into each ml of solvent II to form a transition metal salt solution;
the salts refer to chlorides, sulfates, acetates and nitrates of transition metals Sn, Bi, Pb and Sb;
the solvent II refers to glycol, acetone, deionized water, DMF, glacial acetic acid, glycerol, ethanol or acetone.
(3) Keeping the catalyst mixed solution in a stirring state, and slowly dripping a transition metal salt solution into the catalyst mixed solution for adsorption reaction;
the molar ratio of the transition metal to the noble metal is 0.001-0.5: 1;
the adsorption reaction lasts for 0.001-10 hours.
(4) After the reaction, the solution of the adsorption reaction was filtered and washed with deionized water 3 times. And drying the filtered filter residue in a drying oven to obtain the atomic-scale dispersed transition metal/noble metal composite material.
Compared with the existing noble metal material synthesis method and the synthesized noble metal material, the preparation and the material of the transition metal/noble metal composite material have the following obvious synthesis and structure characteristics:
(1) in the general preparation process of the noble metal-based catalytic material, a multi-step synthesis process such as carbon pretreatment is required, and the substrate treatment and the synthesis process are complicated in electrodeposition. The synthesis method related in the patent is simple, is completed through a one-step self-adsorption process, has low requirements on instrument conditions, can be realized through a stirring device under conventional conditions, has short period of the whole process and high efficiency, and is beneficial to large-scale production.
(2) Generally, the conditions for controlling the atom and the nano structure in the synthesis are strict. In the patent, the preparation method realizes the dispersion of the atomic-scale transition metal on the surface of the noble metal (the size is less than 1 nm) through the processes of ion self-absorption and deposition, accurately controls the dispersion form of the transition metal and provides a foundation for the preparation of the high-activity composite material.
(3) The electronic structure and the geometric structure of the surface of the noble metal are adjusted through the modification effect of the transition metal on the surface of the noble metal, the activity of the noble composite material is improved, and the using amount of the noble metal can be reduced under the condition of the same activity, so that the cost of the catalyst is reduced. If the activity is doubled, the consumption of the noble metal is correspondingly doubled, and the cost is reduced to 50 percent, thereby greatly promoting the practical application cost of the composite material in the electrochemical reaction.
(4) The composite material prepared by the invention is not only applied to inorganic substances (such as CO and H)2O、H2Etc.) and organic small molecules (such as methanol, methane, formic acid, ethanol, ethylene glycol, isopropanol, glycerol, phenyl compounds, etc.), and can be used in inorganic substances (such as H)2O、CO2、N2Etc.) in electrochemical reduction.
(5) The atomic-level dispersed transition metal/noble metal composite material can effectively improve the activity of various existing noble metal-based materials, has the advantages of simple synthesis, wide application types and the like, and is a noble metal material improvement way with a very good application prospect.
Drawings
FIG. 1 is an EDS analysis of the Bi-Pt/CNTs composite prepared in example 1;
FIG. 2 is an XRD characterization of the Bi-Pt/CNTs composite prepared in example 1;
FIG. 3 is a comparison of the performance of Bi-Pt/CNTs composites prepared in example 1 with commercial Pt/CNTs for ethanol oxidation;
FIG. 4 EDS analysis of PtRuBi/C and PtRu/C.
Detailed Description
The present invention will be described in further detail below by way of examples with reference to the accompanying drawings.
Example 1
Preparation of Bi-Pt/CNTs composite material by using Pt/CNTs catalyst with Bi self-adsorbing platinum
(1) Preparation of Pt/CNTs:
dispersing 5g CNTs into HNO3/H2SO4100ml of the mixed solution was heated to 120 ℃ for 1 hour. And (3) dropwise adding KOH to neutralize the acid in the solution to neutrality, filtering, washing with water and ethanol for 3 times respectively, and freeze-drying for 48 hours to obtain the acid-treated CNTs. 147mg of the treated CNTs were taken and 10 ml of chlorine were addedAdding 500 ml of ethylene glycol into a platinic acid solution (18.9 mM), carrying out ultrasonic treatment for 1 hour, then treating for 10 min under microwave treatment (800W), cooling, filtering, washing for 3 times, and drying to prepare the Pt/CNTs catalyst.
(2) Preparation of Bi-Pt/CNTs composite material
And dispersing 500 mg of Pt/CNTs catalyst into 100ml of deionized water, performing ultrasonic stirring for 1 hour to obtain a Pt/CNTs catalyst mixed solution, and then keeping magnetic stirring for 500 revolutions per minute.
(3) 0.5 ml of Bi (NO) is taken3）3The ethylene glycol solution (18.9 mM) was slowly added dropwise to the Pt/CNTs mixture, and self-adsorbed for 2 hours with stirring. After filtration, washed three times with water. And drying in a vacuum drying oven overnight to prepare the Bi-Pt/CNTs composite material.
Characterization of the Bi-Pt/CNTs composite material: fig. 1 is EDS analysis of the composite material, showing that Pt and Bi coexist in the composite material. Fig. 2 is an XRD diffractogram of the composite material, which shows that the composite material Pt has a crystalline structure, and Bi may be atomically dispersed on the Pt surface. FIG. 3 is a graph showing the electrooxidation performance of the composite material in 1M KOH solution to 1M ethanol, and shows that the performance of the Bi-Pt/CNTs composite material is improved to 2.5 times that of the Pt/CNTs material.
Example 2
PtRuBi/C composite material prepared by PtRu/C catalyst with Bi self-adsorbing Pt
(1) 92.2 mg of PtRu/C catalyst is dispersed in 50 ml of deionized water, and the mixture is stirred by ultrasonic for 60 minutes to obtain PtRu/C catalyst mixed solution, and the continuous magnetic stirring is kept.
This example, PtRuBi/C catalyst, purchased directly from Johnson Matthey Inc., was prepared by mixing Pt: the Ru ratio is 1: 1, mass fraction of Pt 20 wt.%.
(2) Mixing the components in a ratio of 0.1: 1 Bi: according to the Pt atomic proportion, dropwise adding an acetone solution of bismuth nitrate into the PtRu/C catalyst mixed solution, and keeping stirring for self-adsorption reaction for 4 hours; and after the adsorption reaction is finished, filtering the system, washing the system for a plurality of times by using deionized water, and drying the system in a freeze drying box for 24 hours to prepare the PtRuBi/C composite material.
EDS analysis characterized co-presence of Pt, Ru and Bi elements in the composite as shown in figure 4. The electric oxidation performance of the PtRuBi/C composite material to methanol is improved by 2.4 times compared with that of the PtRu/C material.
Example 3
Sb-Pd composite material electrode synthesized from Pd dendrites formed by self-adsorption of antimony to electrodeposition
(1) Pd dendrite electrodeposition: cutting commercially available hydrophilic carbon paper into a shape with an area of 1 × 1 cm for electrochemical deposition2Size. Carbon paper was dipped into 0.3M PdCl2+ 0.3M HCl solution as the working electrode. The reference electrode is a silver/silver chloride electrode of saturated KCl solution, and the counter electrode is a carbon rod electrode. Controlling the potential of a working electrode to be-1.0V through an electrochemical workstation, electrolyzing for 2 minutes, washing the electrode by deionized water after the electrodeposition reaction is completed, and drying in the air to prepare the Pd dendritic crystal electrode.
(2) Preparing an Sb-Pd composite material electrode: dissolving a certain amount of antimony trichloride in an ethanol solution, putting the certain amount of antimony trichloride solution into 100ml of water solution, immersing the prepared Pd dendrite electrode into the solution, keeping the solution stirred for 200 r/m, reacting for 1 hour, taking out the Sb-Pd composite material electrode, washing with deionized water for several times, and drying in a drying box to prepare the Sb-Pd composite material electrode. The composite electrode can be used for the isoelectric oxidation reaction of formate, methanol and ethanol, and CO2The field of reduction reaction.
It should be understood that the above description is illustrative of the preferred embodiment of the present invention and is not to be construed as limiting the scope of the invention, which is defined by the appended claims.
Claims (7)
1. A self-adsorption preparation method of an atomic-level dispersed transition metal/precious metal composite material is characterized by comprising the following steps:
(1) adding 0.01-1000 mg of powdery or flaky noble metal catalyst into each ml of the solvent I, and carrying out ultrasonic or common stirring for 1 hour to obtain noble metal catalyst mixed liquor;
(2) adding 0.001-100 mg of transition metal Sn, Bi, Pb and Sb salts into each ml of solvent II to form a transition metal salt solution;
(3) keeping the catalyst mixed solution in a stirring state, and slowly dripping a transition metal salt solution into the catalyst mixed solution for adsorption reaction;
(4) and after the reaction is finished, filtering the solution subjected to the adsorption reaction, washing the solution for 3 times by using deionized water, and drying the filtered filter residue in a drying oven to obtain the atomic-scale dispersed transition metal/noble metal composite material.
2. The self-adsorption preparation method of atomic-scale dispersion transition metal/noble metal composite material according to claim 1, characterized in that the noble metal catalyst is composed of one or more than two of Pt, Pd, Ru, Ir, Au, Rh in any proportion or noble metal supported catalyst.
3. The self-adsorption preparation method of atomic-scale dispersion transition metal/noble metal composite material according to claim 1, wherein the solvent I is ethylene glycol, acetone, deionized water, DMF, glacial acetic acid, glycerol, ethanol or acetone.
4. The self-adsorption preparation method of atomic-scale dispersion transition metal/noble metal composite material according to claim 1, characterized in that the salts are chlorides, sulfates, acetates, nitrates of transition metals Sn, Bi, Pb, Sb.
5. The self-adsorption preparation method of atomic-scale dispersion transition metal/noble metal composite material according to claim 1, wherein the solvent II is ethylene glycol, acetone, deionized water, DMF, glacial acetic acid, glycerol, ethanol or acetone.
6. The self-adsorption preparation method of atomic-scale dispersion transition metal/noble metal composite material according to claim 1, wherein the molar ratio of the transition metal to the noble metal is 0.001-0.5: 1.
7. The self-adsorption preparation method of atomic-scale dispersion transition metal/noble metal composite material according to claim 1, wherein the adsorption reaction is carried out for 0.001-10 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114308025A (en) * | 2022-01-07 | 2022-04-12 | 福建师范大学 | Preparation method of atomic-level dispersed precious metal/carbon composite material |
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| US20080241642A1 (en) * | 2006-12-29 | 2008-10-02 | Coca Iordache | Electrochemical oxidation of formic acid using a noble metal based catalyst with admetals |
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| CN111659387A (en) * | 2020-05-21 | 2020-09-15 | 中国原子能科学研究院 | Platinum-based catalyst containing thorium or compound thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080241642A1 (en) * | 2006-12-29 | 2008-10-02 | Coca Iordache | Electrochemical oxidation of formic acid using a noble metal based catalyst with admetals |
| CN109148905A (en) * | 2018-09-30 | 2019-01-04 | 北京海得利兹新技术有限公司 | A kind of polymer dielectric film fuel cell high activity elctro-catalyst and preparation method thereof |
| CN111659387A (en) * | 2020-05-21 | 2020-09-15 | 中国原子能科学研究院 | Platinum-based catalyst containing thorium or compound thereof |
Non-Patent Citations (1)
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| YIYIN HUANG,ET AL.: "A high-efficiency microwave approach to synthesis of Bi-modified Pt nanoparticle catalysts for ethanol electro-oxidation in alkaline medium", 《APPLIED CATALYSIS B:ENVIRONMENTAL》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114308025A (en) * | 2022-01-07 | 2022-04-12 | 福建师范大学 | Preparation method of atomic-level dispersed precious metal/carbon composite material |
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Application publication date: 20210223 |