CN111266118B - Preparation method of AuPt @ PtCoAu double-alloy nested-structure nanoparticles - Google Patents
Preparation method of AuPt @ PtCoAu double-alloy nested-structure nanoparticles Download PDFInfo
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- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention relates to a preparation method of an AuPt @ PtCoAu double-alloy nested structure nano particle, which belongs to the technical field of inorganic compound semiconductor material preparation and comprises the following steps: the method comprises the following steps: dissolving a surfactant in an inert organic solvent and heating to above 210 ℃; step two: adding an inert organic solvent for dissolving cobalt salt into the solution obtained in the step one to obtain Co nanoparticles; step three: dissolving cobalt salt, chloroplatinic acid and chloroauric acid in an inert organic solvent containing a surfactant, and mixing with the Co nanoparticles in the second step; heating to obtain the AuPt @ PtCoAu double-alloy nested-structure nano particle. The prepared product is a double-alloy nested structure taking AuPt binary alloy as a core and PtCoAu ternary alloy as a shell layer. The invention is characterized in that Au is continuously distributed from the core to the shell in a concentration decreasing mode, the surface enrichment and component loss of Au are inhibited, and a new thought is provided for the preparation of the high-performance Pt-based catalytic material. The obtained product has larger performance adjusting space, and the production is easy to enlarge.
Description
Technical Field
The invention relates to a preparation method of an AuPt @ PtCoAu double-alloy nested structure nano particle, belonging to the technical field of preparation of inorganic compound catalytic materials.
Background
The Pt-M (M ═ Fe, Co, Ni and the like) alloy nanoparticles can not only reduce the use amount of the noble metal Pt, but also effectively reduce the overpotential, and show great application potential. However, the non-noble metal component of the Pt-M alloy nanoparticles may be lost during a long-term electrochemical catalysis process, resulting in an unstable performance. Experimental results show that the catalytic stability of the Pt-M nano particles can be remarkably improved by introducing the metal Au into the Pt-M nano particles. Therefore, the synthesis and performance research of Pt-Au-M ternary metal nanoparticles becomes a leading research edge in recent years.
At present, the method used for preparing the Pt-Au-M ternary metal nano particles is mainly an electrochemical displacement method or a co-reduction method. For example, Zhangli task group of Beijing university of Industrial science and energy engineering institute takes Cu nanoparticles as core, and HAuCl is added gradually in different proportions4And K2PtCl4By Au3+With Pt2+And the PtAuCu/C nano particles with different Pt/Au/Cu ratios are prepared by electrochemical replacement reaction with Cu. Research results show that the d-band center of the surface Pt is reduced due to the synergistic effect of Cu and Au, and meanwhile, the surface of the PtAuCu nano particle is gradually dealloyed in the activation process of Oxygen Reduction Reaction (ORR), so that more catalytic active sites are exposed, and the catalytic performance of the PtAuCu nano particle is superior to that of commercial Pt/C. During the course of the ORR cycle,with the loss of surface Cu, Pt-Au skin is gradually formed, wherein Au increases the oxidation-reduction potential of Pt to make it not easy to lose, therefore Pt-Au skin protects the Cu substrate in the sub-layer to increase the stability of the nano-particle (volume of Electrochemical Acta 212, page 277-285, 2016). The Xuebieqing project group of the chemistry system of Qinghua university takes Au nano particles as cores and adopts acetylacetone platinum [ Pt (acac)2]With acetylacetonatonickel [ Ni (acac) ]2]The Au @ Pt is synthesized by heteroepitaxial growth on an Au substrate through coreduction2NimCore-shell structured nanoparticles and further investigated the influence of product composition and treatment conditions on the ORR reaction (ACS Catalysis 6 Vol., 1680-. Although the two methods described above have shown some successful examples in synthesizing Pt-Au-M ternary metal nanoparticles, on the one hand, the low surface energy of Au makes it prone to surface enrichment, thereby sacrificing the catalytic activity of the catalyst; on the other hand, since Au is not continuously distributed in the whole nanoparticle, Au on the surface layer gradually runs off along with the progress of the catalytic reaction, which is not favorable for maintaining the stability of the catalyst.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of the AuPt @ PtCoAu double-alloy nested-structure nano particles, which has the advantages of simple equipment, easiness in realization and control, good process repeatability, stable product performance and the like.
1. A preparation method of AuPt @ PtCoAu double-alloy nested nanoparticles is characterized by comprising the following steps:
(1) dissolving a surfactant I in an inert organic solvent, and uniformly mixing to obtain a mixed solution I; and dissolving cobalt salt in an inert organic solvent, and uniformly mixing to obtain a mixed solution II.
(2) Stirring the mixed solution I at room temperature for 30min, and then raising the temperature to 220-230 ℃ under the protection of inert gas and maintaining for 30 min; then adding the mixed solution II into the mixed solution I and reacting for 30 min; and removing a heat source after the reaction, cooling the reaction liquid, performing centrifugal separation, collecting precipitate, cleaning twice with ethanol with the purity of more than 98%, and putting into n-hexane to obtain the Co nano particle sol.
(3) Dissolving cobalt salt, chloroplatinic acid and chloroauric acid in an inert organic solvent containing a surfactant II, uniformly mixing, and adding Co nano particle sol to obtain a mixed solution III.
(4) Stirring the mixed solution III at room temperature for 60min, and then raising the temperature to 210-230 ℃ under the protection of inert gas and maintaining for 60-90 min; and after the reaction, removing a heat source, cooling the reaction liquid, performing centrifugal separation, collecting precipitate, alternately cleaning for six times by using ethanol with the purity of more than 98% and n-hexane with the purity of more than 95%, and drying in an oven to obtain the AuPt @ PtCoAu double-alloy nested-structure nano particle.
2. The preparation method of the AuPt @ PtCoAu double-alloy nested structure nano particle according to 1 is characterized by comprising the following steps: in the steps (1) and (3), the cobalt salt is any one of acetylacetone salt and carbonyl salt; the inert organic solvent comprises any one of diphenyl ether and dichlorobenzene; in the step (1), the surfactant I is a mixture of oleic acid and tetrabutylammonium borohydride (TBAB), or a mixture of oleic acid and tetraethylammonium borohydride (TEAB); in the step (3), the surfactant II is a mixture of 1, 2 dodecanediol, oleylamine and oleic acid.
3. The preparation method of the AuPt @ PtCoAu double-alloy nested structure nano particle according to 1 is characterized by comprising the following steps: in the step (1), in the mixed solution I, the molar concentration of the surfactant I meeting TBAB or TEAB is 0.01-0.04 mol/L, and the molar ratio of TBAB or TEAB to oleic acid is 0.5: 1-1: 1; the molar concentration of the cobalt ions in the mixed solution II is 0.10-0.30 mol/L.
4. The preparation method of the AuPt @ PtCoAu double-alloy nested structure nano particle according to 1 is characterized by comprising the following steps: in the step (2), the heating rate is 10-15 ℃/min; the mass concentration of Co in the Co nanoparticle sol is 1-20 mg/mL.
5. The preparation method of the AuPt @ PtCoAu double-alloy nested structure nano particle according to 1 is characterized by comprising the following steps: in the step (3), the Co nanoparticle sol, the cobalt salt, the chloroplatinic acid and the chloroauric acid in the mixed solution III are added in a proportion range which satisfies the molar ratio of Co to Pt to Au (60-120): (4-16): (0.5 to 2); in the mixed solution III, the surfactant II meets the requirement that the molar concentration of 1, 2 dodecanediol is 0.02-0.10 mol/L; the mol ratio of 1, 2 dodecanediol, oleic acid and oleylamine is 1: (4-15): (4-15).
6. The preparation method of the AuPt @ PtCoAu double-alloy nested structure nano particle according to 1 is characterized by comprising the following steps: in the step (4), the heating rate is 10-15 ℃/min.
7. The preparation method of the AuPt @ PtCoAu double-alloy nested structure nano particle according to 1 is characterized by comprising the following steps: the prepared product has a double-alloy nested structure with AuPt alloy as a core and PtCoAu alloy as a shell layer.
The invention has the advantages that:
1. the invention provides a preparation method of AuPt @ PtCoAu double-alloy nested nanoparticles, which combines an electrochemical replacement sacrificial template method with continuous redox epitaxial growth and effectively adjusts the component distribution of each component in a catalyst by utilizing the dynamic change characteristic of ion concentration in the reaction process. The continuous distribution of Au inside the particles, the synergistic effect of each component and the surface reconstruction of the catalyst in the catalytic circulation process are utilized to achieve the aim of improving the stability and maintaining high activity, and a new thought is provided for the preparation of a high-stability and high-activity catalytic material.
2. The invention provides a preparation method of an AuPt @ PtCoAu double-alloy nested structure nano particle, an obtained product has a larger performance adjustment space, and the catalytic performance of the product can be adjusted by adjusting the concentration of a precursor and the subsequent feeding ratio to adjust the proportion among Pt, Au and Co among inner and outer nested alloys.
3. The invention provides a preparation method of the AuPt @ PtCoAu double-alloy nested structure nano particle, which has the advantages of simple equipment, good process repeatability and stable product quality and is expected to be produced and applied in a large scale.
Drawings
FIG. 1: the invention provides a flow chart of a preparation method of AuPt @ PtCoAu double-alloy nested nanoparticles;
FIG. 2: the transmission electron microscope photo and the element distribution diagram of the AuPt @ PtCoAu double-alloy nested-structure nano particle obtained in the embodiment 1 of the invention;
FIG. 3: an XRD spectrogram of the AuPt @ PtCoAu double-alloy nested-structure nano particle obtained in the embodiment 1 of the invention.
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples, but the scope of the present invention is not limited to the following examples.
Example 1：
Mixing TBAB 64.3mg with oleic acid 100 μ L and diphenyl ether 10ml (TBAB molar concentration is 0.025mol/L, TBAB to oleic acid molar ratio is 0.8: 1), stirring at room temperature for 30min, and stirring at 15 deg.C for 15 min under inert gas protection-1The rate of (2) was increased to 230 ℃ and maintained for 30 min. Then, 3ml of diphenyl ether (molar concentration of cobalt ion: 0.17mol/L) mixed with 128.6mg of cobalt acetylacetonate was rapidly injected into the system, followed by maintaining at 230 ℃ and reacting for 30 min. And after the reaction, removing a heat source, cooling the reaction solution, performing centrifugal separation, collecting precipitate, cleaning twice by using ethanol (the purity is more than 98 percent), and putting into normal hexane to obtain the Co nano particle sol (the mass concentration of Co is 10 mg/mL).
96.5mg of cobalt acetylacetonate, 151.8mg of 1, 2 dodecanediol, 42mg of chloroplatinic acid, 5.5mg of chloroauric acid and 2mL of the synthesized Co nanoparticles are uniformly mixed with 10mL of diphenyl ether, 2mL of oleylamine and 2mL of oleic acid (Co: Pt: Au ═ 71: 8: 1.3; molar concentration of 1, 2 dodecanediol is 0.047 mol/L; molar ratio of diol, oleic acid and oleylamine in the mixed solution III is 1: 8: 8), stirred at room temperature for 30min, and then stirred under the protection of inert gas for 15 min-1The rate of (2) was increased to 230 ℃ and maintained for 90 min. And after the reaction, centrifuging the product, and circularly cleaning the product with ethanol and n-hexane for three times to obtain a black sample, namely the AuPt @ PtCoAu nano particle. The prepared AuPt @ PtCoAu double-alloy nested nanoparticles are observed by a transmission electron microscope, as shown in figure 2, the particle size of the prepared nanoparticles is about 11.1nm, and the typical polycrystalline structure is shown by staggered lattice stripes. In the single-particle EDX line scan curve spectrogram (figure 2), Co element presents a remarkable valley shapeIt is mainly present in the shell layer; the Pt element showed a plateau-like shape, indicating a more uniform distribution throughout the particle; the Au element shows a shape of a central peak, indicating that the content is continuously distributed from the inside to the outside. Through the analysis, the particle is a binuclear gold nested nanoparticle which takes AuPt as a core and PtCoAu as a shell and Au is continuously distributed in the whole particle. The diffraction pattern of the AuPt @ PtCoAu dual-alloy nested nano-particles is shown in figure 3 by powder X-ray diffraction analysis, and the diffraction pattern comprises obvious Pt-Co base alloy (111) peak and Au3The diffraction peak for Pt (111), but not the independent diffraction peaks for Au or Co, indicates that it contains two alloy structures.
Example 2：
Mixing 46.4mg TEAB with 100 μ L oleic acid and 10ml diphenyl ether uniformly (molar concentration of TEAB is 0.032mol/L, molar ratio of TEAB to oleic acid is 1: 1), stirring at room temperature for 30min, and then stirring at 10 deg.C for min under protection of inert gas-1The rate of (2) was increased to 230 ℃ and maintained for 30 min. Then, 3ml of diphenyl ether (molar concentration of cobalt ion: 0.21mol/L) mixed with 106.9mg of cobalt carbonyl was rapidly injected into the system, followed by maintaining at 230 ℃ and reacting for 30 min. And after the reaction, removing a heat source, cooling the reaction liquid, performing centrifugal separation, collecting precipitate, cleaning twice by using ethanol (the purity is more than 98 percent), and putting into normal hexane to obtain the Co nano particle sol (the mass concentration of Co is 12.5 mg/mL).
42.8mg of cobalt carbonyl, 101.2mg of 1, 2 dodecanediol, 31.1mg of chloroplatinic acid, 4.1mg of chloroauric acid and 2mL of the synthesized Co nanoparticles are uniformly mixed with 10mL of diphenyl ether, 2mL of oleylamine and 2mL of oleic acid (Co: Pt: Au: 88: 6: 1; the molar concentration of 1, 2 dodecanediol is 0.031 mol/L; the molar ratio of diol, oleic acid and oleylamine in the mixed solution III is 1: 12: 12), stirred at room temperature for 30min, and then stirred under the protection of inert gas for 10 min-1The rate of (2) was increased to 230 ℃ and maintained for 90 min. And after the reaction, centrifuging the product, and circularly cleaning the product with ethanol and n-hexane for three times to obtain a black sample, namely the AuPt @ PtCoAu nano particle.
Example 3：
Mixing 46.4mg TEAB with 100 μ L oleic acid and 10ml dichlorobenzene (molar concentration of TEAB is 0.032mol/L, molar ratio of TEAB and oleic acid is 1: 1), stirring at room temperature for 30min, and stirring at 10 deg.C for 10 min under inert gas protection-1The rate of (2) was increased to 230 ℃ and maintained for 30 min. Then 3ml of dichlorobenzene (molar concentration of cobalt ion: 0.21mol/L) mixed with 106.9mg of cobalt carbonyl was rapidly injected into the system, followed by maintaining at 230 ℃ and reacting for 30 min. And after the reaction, removing a heat source, cooling the reaction liquid, performing centrifugal separation, collecting precipitate, cleaning twice by using ethanol (the purity is more than 98 percent), and putting into normal hexane to obtain the Co nano particle sol (the mass concentration of Co is 12.5 mg/mL).
Uniformly mixing 85.5mg of cobalt carbonyl, 202.4mg of 1, 2 dodecanediol, 57.0mg of chloroplatinic acid, 7.0mg of chloroauric acid and 2mL of the synthesized Co nanoparticles with 10mL of dichlorobenzene, 2mL of oleylamine and 2mL of oleic acid (Co: Pt: Au ═ 93: 11: 1.7; molar concentration of 1, 2 dodecanediol is 0.063 mol/L; molar ratio of diol, oleic acid and oleylamine in the mixed solution III is 1: 6: 6), stirring at room temperature for 30min, and then stirring under the protection of inert gas at 10 ℃ for min-1The rate of (2) was increased to 210 ℃ and maintained for 90 min. And after the reaction, centrifuging the product, and circularly cleaning the product with ethanol and n-hexane for three times to obtain a black sample, namely the AuPt @ PtCoAu nano particle.
Example 4：
Mixing TBAB 48.9mg, oleic acid 100 μ L and dichlorobenzene 10ml (TBAB molar concentration 0.019mol/L, TBAB to oleic acid molar ratio 0.63: 1), stirring at room temperature for 30min, and stirring at 15 deg.C for 15 min under inert gas protection-1The rate of (2) was increased to 230 ℃ and maintained for 30 min. Then, 3ml of dichlorobenzene (molar concentration of cobalt ion: 0.125mol/L) mixed with 96.4mg of cobalt acetylacetonate was rapidly injected into the system, followed by maintaining at 230 ℃ and reacting for 30 min. And after the reaction, removing a heat source, cooling the reaction liquid, performing centrifugal separation, collecting precipitate, cleaning twice by using ethanol (the purity is more than 98 percent), and putting into normal hexane to obtain the Co nano particle sol (the mass concentration of Co is 7.5 mg/mL).
64.3mg of cobalt acetylacetonate, 101.2mg of 1, 2-dodecanediol, 31.1mg of chloroplatinic acid, 4.1mg of chloroauric acid, and 2mL of the above synthesis were introducedThe Co nanoparticles are uniformly mixed with 10ml of dichlorobenzene, 2ml of oleylamine and 2ml of oleic acid (Co: Pt: Au ═ 50: 6: 1; the molar concentration of 1, 2 dodecanediol is 0.031 mol/L; the molar ratio of the diol, the oleic acid and the oleylamine in the mixed solution III is 1: 12: 12), stirred for 30min at room temperature, and then stirred for 15 min under the protection of inert gas-1The rate of (2) was increased to 230 ℃ and maintained for 60 min. And after the reaction, centrifuging the product, and circularly cleaning the product with ethanol and n-hexane for three times to obtain a black sample, namely the AuPt @ PtCoAu nano particle.
Claims (7)
1. A preparation method of AuPt @ PtCoAu double-alloy nested nanoparticles is characterized by comprising the following steps:
(1) dissolving a surfactant I in an inert organic solvent, and uniformly mixing to obtain a mixed solution I; dissolving cobalt salt in an inert organic solvent, and uniformly mixing to obtain a mixed solution II; the surfactant I is a mixture of oleic acid and tetrabutylammonium borohydride (TBAB), or a mixture of oleic acid and tetraethylammonium borohydride (TEAB);
(2) stirring the mixed solution I at room temperature for 30min, and then raising the temperature to 220-230 ℃ under the protection of inert gas and maintaining for 30 min; then adding the mixed solution II into the mixed solution I and reacting for 30 min; removing a heat source after the reaction, cooling the reaction liquid, performing centrifugal separation, collecting precipitate, cleaning twice with ethanol with the purity of more than 98%, and then putting into n-hexane with the purity of more than 95% to obtain Co nano particle sol;
(3) dissolving cobalt salt, chloroplatinic acid and chloroauric acid in an inert organic solvent containing a surfactant II, uniformly mixing, and adding Co nano particle sol to obtain a mixed solution III; the surfactant II is a mixture of 1, 2 dodecanediol, oleylamine and oleic acid;
(4) stirring the mixed solution III at room temperature for 60min, and then raising the temperature to 210-230 ℃ under the protection of inert gas and maintaining for 60-90 min; and after the reaction, removing a heat source, cooling the reaction liquid, performing centrifugal separation, collecting precipitate, alternately cleaning for six times by using ethanol with the purity of more than 98% and n-hexane with the purity of more than 95%, and drying in an oven to obtain the AuPt @ PtCoAu double-alloy nested-structure nano particle.
2. The preparation method of AuPt @ PtCoAu double-alloy nested nanoparticles according to claim 1, which is characterized in that: in the steps (1) and (3), the cobalt salt is any one of acetylacetone salt and carbonyl salt; the inert organic solvent comprises any one of diphenyl ether and dichlorobenzene.
3. The preparation method of AuPt @ PtCoAu double-alloy nested nanoparticles according to claim 1, which is characterized in that: in the step (1), in the mixed solution I, the molar concentration of TBAB or TEAB is 0.01-0.04 mol/L, and the molar ratio of TBAB or TEAB to oleic acid is 0.5: 1-1: 1; the molar concentration of the cobalt ions in the mixed solution II is 0.10-0.30 mol/L.
4. The preparation method of AuPt @ PtCoAu double-alloy nested nanoparticles according to claim 1, which is characterized in that: in the step (2), the heating rate is 10-15 ℃/min; the mass concentration of Co in the Co nanoparticle sol is 1-20 mg/mL.
5. The preparation method of AuPt @ PtCoAu double-alloy nested nanoparticles according to claim 1, which is characterized in that: in the step (3), the Co nanoparticle sol, the cobalt salt, the chloroplatinic acid and the chloroauric acid in the mixed solution III are added in a proportion range which satisfies the molar ratio of Co to Pt to Au (60-120): (4-16): (0.5 to 2); in the mixed solution III, the molar concentration of 1, 2 dodecanediol is 0.02-0.10 mol/L; the molar ratio of 1, 2 dodecanediol, oleic acid and oleylamine in the mixed solution III is 1: (4-15): (4-15).
6. The preparation method of AuPt @ PtCoAu double-alloy nested nanoparticles according to claim 1, which is characterized in that: in the step (4), the heating rate is 10-15 ℃/min.
7. The preparation method of AuPt @ PtCoAu double-alloy nested nanoparticles according to claim 1, which is characterized in that: the prepared product has a double-alloy nested structure with AuPt alloy as a core and PtCoAu alloy as a shell layer, and Au is continuously distributed from the core to the shell in a concentration decreasing mode.
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