CN108187693B - Method for synthesizing PtCu hollow nano cage material by one-pot template-free solvothermal method - Google Patents
Method for synthesizing PtCu hollow nano cage material by one-pot template-free solvothermal method Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J23/8926—Copper and noble metals
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- B01J35/40—
Abstract
The invention discloses a method for synthesizing a PtCu hollow nano cage material by a one-pot template-free solvothermal method, belonging to the technical field of synthesis of cage-like nano materials. The technical scheme provided by the invention has the key points that: placing a morphology directing agent of hexadecyl trimethyl ammonium chloride, a metal precursor of platinum acetylacetonate, copper chloride, a reducing agent of arginine and a solvent of oleylamine into a reaction vessel, uniformly mixing, placing the obtained mixed material into an oil bath kettle, heating to 160 ℃, reacting for 8 hours, cooling to room temperature after the reaction is finished, centrifuging, washing and drying to obtain the PtCu hollow nano cage material. The preparation process is simple and convenient and easy to control, and the catalytic activity and stability of the prepared PtCu hollow nano cage material for oxygen reduction reaction, ethylene glycol oxidation reaction and glycerol oxidation reaction are obviously improved.
Description
Technical Field
The invention belongs to the technical field of synthesis of cage-shaped nano materials, and particularly relates to a method for synthesizing PtCu hollow nano cage (PtCu NCs) materials by a one-pot template-free solvothermal method.
Background
With the proliferation of the population and the large consumption of fossil energy, the fuel cell is receiving increasing attention as a clean energy alternative technology due to the dual pressures of energy crisis and environmental pollution all over the world. Platinum (Pt) catalysts are the most efficient single metal catalysts in fuel cell cathode catalytic applications. However, the high price, low cathodic oxygen reduction activity and low resistance to CO toxicity of Pt limit its large-scale commercial application. Therefore, how to reduce the amount of Pt and improve the catalytic activity and stability of cathode oxygen becomes one of the key scientific problems in the basic scientific research of catalysis.
To date, most research has focused primarily on the modification and direction of modification of pure Pt catalysts. On one hand, the quality specific activity of the catalyst is improved, a Pt-M (M = Cu, Ni, Co and the like) bimetallic alloy catalyst is formed mainly by doping non-noble metal elements, the electronic structure of Pt is regulated while the content of Pt in the catalyst is reduced so as to improve the catalytic effect of the catalyst, and the performance of the catalyst can be improved by regulating the distribution of each element component in nanoparticles. On the other hand, the active specific surface area is increased, and the utilization rate of Pt is effectively improved by means of constructing a three-dimensional structure, regulating the shape and size of the nano catalyst and the like. So far, controllable synthesis of nano materials with specific morphological components has been advanced, and various advantages such as small Pt dosage and good performance are shown. However, such catalysts often experience problems with sintering, agglomeration and dissolution of transition metals during use, resulting in an evolution of material morphology and a reduction in durability. Therefore, it remains a great challenge to find a balance between the activity and stability of the nanocatalyst.
In response to this problem, researchers have been mainly dedicated to develop various synthetic strategies to prepare highly active and stable polycrystalline Pt-M nanocages, and these synthetic methods mainly include seed growth method, electrochemical displacement method, sacrificial template method, etc. However, most of the traditional synthetic methods are constructed in multiple steps, the synthetic process is complex, and the time consumption is long, so that the construction of the nano cage by a one-pot method is always a difficult point for researchers to research.
Disclosure of Invention
The invention provides a method for synthesizing a PtCu hollow nano cage material by a one-pot template-free solvothermal method, which is simple and controllable in preparation process, for overcoming the problems existing in the synthesis of metal nano cage materials in multiple steps in the prior art.
The invention adopts the following technical scheme for solving the technical problems, and the method for synthesizing the PtCu hollow nano cage material by the one-pot template-free solvothermal method is characterized by comprising the following specific steps of: the morphology directing agent Cetyl Trimethyl Ammonium Chloride (CTAC), the metal precursor platinum acetylacetonate (Pt (acac)2) With copper chloride (CuCl)2·2H2O), a reducing agent arginine and a solvent oleylamine are placed in a reaction container and uniformly mixed, wherein the molar concentration of hexadecyl trimethyl ammonium chloride is 20mM, the molar concentration of acetylacetone platinum is 5mM, the molar concentration of copper chloride is 5mM, and the molar concentration of arginine is 60mM, the obtained mixed material is placed in an oil bath pot and heated to 160 ℃ for reaction for 8 hours, and after the reaction is finished, the mixed material is cooled to room temperature, centrifuged, washed and dried to obtain the PtCu hollow nano cage material.
Further preferably, the average particle size of the prepared PtCu hollow nanocage material is 11.2nm, the average thickness of the hollow framework is 2.09nm, and the specific process for forming the hollow nanocage structure is as follows: the method comprises the steps that a metal precursor platinum acetylacetonate and copper chloride form Pt atoms and Cu atoms under the co-reduction action of a reducing agent arginine and solvent oleylamine, PtCu nuclei are finally formed through overpotential reduction deposition, the PtCu nuclei selectively stretch outwards along edge {110} special crystal surfaces under the action of a morphology directing agent hexadecyl trimethyl ammonium chloride, after 4 hours of reaction time, the PtCu nuclei form an inwards concave solid structure, and with the prolonging of the reaction time, under an oxidizing corrosive agent Cl-/O2Under the action of the chemical mechanical polishing solution, the concave solid structure is gradually oxidized and etched into a hollow porous structure, and finally a hollow nano cage structure is generated.
Compared with the prior art, the invention has the following advantages: the PtCu hollow nano cage material is prepared by a one-pot template-free solvothermal method, a template does not need to be synthesized in advance, a hollow structure is prepared in one step, the process is simple and convenient, and the control is easy.
Drawings
FIG. 1 is a transmission electron microscope image and a high-angle annular dark-field scanning transmission electron microscope image of a PtCu NCs material, wherein an inset in B is a structural model thereof, a circle in C represents an atomic step, and an arrow indicates a high-index crystal plane;
FIG. 2 is an energy spectrum (EDX), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) of the PtCu NCs material;
FIG. 3 is a transmission electron microscope image of PtCu NCs under different reaction time conditions, wherein A is 2h, B is 4h, C is 6h, D is 8h, and E is a schematic diagram of the PtCu NCs forming process;
FIG. 4 shows the Cyclic Voltammetry (CV) curves for PtCu NCs, Pt/C and Pt black in 0.5M KOH, B the ORR polarization curves for PtCuNCs, Pt/C and Pt black in 0.5M KOH saturated with oxygen, and C and D at 0.90V ((V))vs.RHE) potential, mass activity (C) and area activity (D) around 1000 cycles of cyclic scan;
in FIG. 5, A and C are CV diagrams of PtCu NCs, Pt/C and Pt black in 0.5M KOH solution (containing 0.5M ethylene glycol and glycerol, respectively), and B and D are corresponding If/Ib（IfAnd IbRepresenting the forward and reverse peak current densities, respectively), where a and B correspond to EGOR, and C and D correspond to GOR;
in FIG. 6, A and C are the mass activity and area activity of PtCu NCs, Pt/C and Pt black on EGOR and GOR, and B and D are the corresponding chronoamperometric curves, wherein A and B correspond to EGOR and C and D correspond to GOR.
Concrete real-time mode
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
Reagent and instrument
Cetyl trimethyl ammonium chloride, platinum acetylacetonate, copper chloride (CuCl)2·2H2O), arginine, oleylamine, simethicone, ethanol, cyclohexane were purchased from the Shanghai chemical plant, and all reagents were analytically pure. Scanning electron microscope (SEM, JSM-6390LV, JEOL, Japan), transmission electron microscope (TEM, JEM-2100, JEOL, Japan), acceleration voltage was 200 kV. The chemical composition of PtCu NCs is determined by energy dispersive spectroscopy (EDX, Oxford), X-ray diffraction (XRD), and the chemical valence states of Pt and Cu are determined byX-ray photoelectron spectroscopy (XPS).
The morphology directing agent of hexadecyl trimethyl ammonium chloride, the metal precursor of platinum acetylacetonate and copper chloride (CuCl)2·2H2O) and a reducing agent arginine are placed in a reaction vessel containing 5mL solvent oleylamine and are mixed uniformly by ultrasound, wherein the molar concentration of hexadecyl trimethyl ammonium chloride is 20mM, the molar concentration of acetylacetone platinum is 5mM, the molar concentration of copper chloride is 5mM, and the molar concentration of arginine is 60mM, the obtained mixed solution is placed in an oil bath pot (dimethyl silicone oil) to be heated to 160 ℃ for reaction for 8 hours, after the reaction is finished, the mixed solution is cooled to room temperature, centrifuged, washed and dried to obtain the PtCu NCs material, and the used washing agent is the mixed solution of ethanol and cyclohexane with the volume ratio of 9: 1.
FIG. 1 is a transmission electron microscope image and a high-angle annular dark-field scanning transmission electron microscope image of a PtCu NCs material. The PtCu NCs material is a hollow porous three-dimensional cage-shaped structure, the average grain diameter is 11.2nm, the edge thickness is about 2.09nm, and a large number of lattice defects and high-index crystal faces exist on the surface of the structure, so that rich active sites can be provided for catalytic reaction. As can be seen from D in fig. 1, the Pt element and the Cu element are uniformly distributed, demonstrating that the PtCu NCs material forms an alloy structure. The inset electron diffraction pattern of C in fig. 1 illustrates the polycrystalline nature thereof.
FIG. 2 is an energy spectrum (EDX), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) chart of the PtCu NCs material. The EDS results in FIG. 2A show that the Pt/Cu atomic ratio in the PtCu NCs material is 49/51, the XRD results in FIG. 2B further show that the PtCu NCs material has an alloy structure, and the XPS results in FIG. 2C-D show that the metal precursor Pt (acac)2And CuCl2·2H2O is effectively reduced to Pt atoms and Cu atoms.
Fig. 3 is an intermediate product obtained by different reaction times to explain the growth mechanism of the PtCu NCs material, which can be explained by three steps of nucleation, selective growth and oxide etching. Metal precursor Pt (acac)2And CuCl2·2H2O forms Pt atoms and Cu atoms under the co-reduction of arginine and oleylamine, and PtCu nuclei are formed through overpotential reduction deposition and are shaped and guided in the shapeUnder the action of a catalyst CTAC, the PtCu nucleus is selectively and epitaxially stretched along the {110} special crystal face at the edge, after 4 hours of reaction time, the PtCu nucleus forms a concave solid structure, and the PtCu nucleus is subjected to oxidation corrosion agent Cl along with the prolonging of the reaction time-/O2Under the action of the chemical mechanical polishing solution, the concave solid structure is gradually oxidized and etched into a hollow porous structure, and finally a hollow nano cage structure is generated.
FIGS. 4-6 are catalytic applications of PtCu NCs materials to ORR, EGOR and GOR under alkaline conditions.
In FIG. 4, A is a CV diagram of PtCu NCs, Pt/C and Pt black in a 0.5M KOH solution, and the electrochemically active area (EASA) of the PtCu NCs was 19.8M, calculated from the hydrogen evolution dehydrogenation section (0.1-0.4) V2g–1 PtAlthough smaller than commercial Pt/C, it is larger than Pt black (particle size about 8 nm), which is attributed to the hollow porous intrinsic structure of PtCu NCs materials. The larger EASA of PtCu NCs material demonstrates the presence of abundant electrochemically active sites on its surface, which promote gas diffusion and electron transfer, thereby improving the catalytic performance of the material. FIG. 4, B is the ORR polarization plot of PtCu NCs, Pt/C and Pt black in oxygen saturated 0.5M KOH solution at 1600rpm with sweep rate of 10mVs–1. The onset potential (1.02V) of the PtCu NCs material is more positive than commercial Pt/C (0.97V) and Pt black (0.93V), reflecting the highly efficient catalytic activity of the PtCu NCs material. In addition, fig. 3, C and D show the mass activity and area activity (normalized to Pt loading and EASA, respectively) of PtCu NCs material at 0.90V before and after 1000 cycles of cyclic scan (1.28 Amg) (1.90V)–1 Pt) And area activity (6.46 mAcm–2 EASA) Greater than Pt/C (0.43 Amg)–1 Pt，0.88mAcm–2 EASA) And Pt black (0.074 Amg)–1 Pt，0.48mAcm–2 EASA) This result further indicates that the PtCu NCs material has high electrocatalytic performance. Furthermore, combining the mass activity and area activity of the above materials at 1000 th round, the mass activity and area activity of the PtCu NCs material at 0.90V decreased by 15.4% after accelerated stability testing (ADT), less than Pt/C (69.0%) and Pt black (65.1%), which demonstrates PtCThe u NCs material has good stability to ORR.
FIG. 5 is a CV diagram of PtCu NCs against EGOR and GOR under alkaline conditions (0.5M KOH solution). Under the condition of the same catalyst amount, compared with a control material, the PtCu NCs material has the highest current density, and the current density reaches 111.43mAcm for EGOR and GOR respectively–2And 134.54mAcm–2And it If/IbAt the maximum, the PtCu NCs material has stronger CO poisoning resistance.
Fig. 6 visually reveals the catalytic activity and stability of PtCu NCs materials in EGOR and GOR tests. Mass Activity of PtCuNCs materials (EGOR and GOR are 2.65Amg, respectively)–1 PtAnd 3.19Amg–1 Pt) And area activity (EGOR and GOR are 13.40mAcm, respectively–2 EASAAnd 16.08mAcm–2 EASA) Much larger than the control materials Pt/C and Pt black, which also demonstrates the high catalytic ability of the PtCu NCs material for ethylene glycol and glycerol. In FIG. 6, C and D are the stability tests of PtCu NCs in 0.5M KOH solution for EGOR and GOR, and the current density of the PtCu NCs was maintained at 4.0mA cm for 10000s by chronoamperometry at a potential of 0.70V–2And 7.8mA cm–2Greater than Pt/C (0.6 mAcm)–2And 1.36mA cm–2) And Pt black (0.5 mAcm)–2And 0.3mAcm–2) This again demonstrates the superior catalytic performance and long-lasting stability of the PtCu NCs material.
Example 2
In this example, the concentration of arginine as a reducing agent was changed (30 mM, 80 mM), and other experimental conditions were maintained as in example 1, and the prepared PtCu NPs material exhibited in the support material, and the hollow porous structure disappeared, the uniformity of the particles became poor, the aggregation among the particles became severe, and the particle size became large.
Example 3
In the present example, arginine was replaced with histidine and glutamic acid, respectively, and other experimental conditions were the same as in example 1, and the prepared PtCu NPs material was shown in the support material, and the hollow porous morphology disappeared and became solid irregular particles.
From examples 1-3, it can be seen that the concentration of the reducing agent, the type of reducing agent, and the reaction time are all critical in the formation of the hollow nanocage structure.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (2)
1. A method for synthesizing a PtCu hollow nano cage material by a one-pot template-free solvothermal method is characterized by comprising the following specific steps: the morphology directing agent of hexadecyl trimethyl ammonium chloride, the metal precursor of platinum acetylacetonate and copper chloride CuCl2·2H2And O, a reducing agent arginine and a solvent oleylamine are placed in a reaction container and uniformly mixed, wherein the molar concentration of hexadecyl trimethyl ammonium chloride is 20mM, the molar concentration of acetylacetone platinum is 5mM, the molar concentration of copper chloride is 5mM, and the molar concentration of arginine is 60mM, the obtained mixed material is placed in an oil bath pot and heated to 160 ℃ for reaction for 8 hours, and after the reaction is finished, the mixed material is cooled to room temperature, centrifuged, washed and dried to obtain the PtCu hollow nano cage material.
2. The method for synthesizing the PtCu hollow nanocage material by the one-pot template-free solvothermal method according to claim 1, wherein the method comprises the following steps: the average particle size of the prepared PtCu hollow nano cage material is 11.2nm, the average thickness of the hollow framework is 2.09nm, and the specific process of forming the hollow nano cage structure is as follows: the method comprises the steps that a metal precursor platinum acetylacetonate and copper chloride form Pt atoms and Cu atoms under the co-reduction action of a reducing agent arginine and solvent oleylamine, PtCu nuclei are finally formed through overpotential reduction deposition, the PtCu nuclei selectively stretch outwards along edge {110} special crystal surfaces under the action of a morphology directing agent cetyl trimethyl ammonium chloride, and after 4 hours of reaction time, the PtCu nuclei form an inwards concave solid structure along with the formation of the inwards concave solid structureProlonged reaction time in oxidizing corrosive agent Cl-/O2Under the action of the chemical mechanical polishing solution, the concave solid structure is gradually oxidized and etched into a hollow porous structure, and finally a hollow nano cage structure is generated.
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