PdPtCu ternary metal alkene catalyst as well as preparation method and application thereof

Abstract

The invention discloses a PdPtCu ternary metal alkene catalyst, the surface of the catalyst has crystal, amorphous, line defects, point defects and holes, the PdPtCu ternary metal alkene is formed by alloying three elements of Pd, Pt and Cu, and the PdPtCu ternary metal alkene catalyst has the characteristics of high activity and stability. The invention further discloses a preparation method and application of the PdPtCu ternary metal alkene catalyst.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electrocatalysis, in particular to a PdPtCu ternary metal olefin catalyst and a preparation method and application thereof. BACKGROUND

[0002] Hydrogen energy has attracted people's attention due to its high energy, zero emission and renewable characteristics, and is expected to become an ideal substitute for fossil fuels. Electrocatalytic water splitting for hydrogen production has the characteristics of clean and environmental protection, sustainability and high purity. However, the high reaction energy barrier of anode OER limits its efficiency. The theoretical oxidation potential of small molecules such as formic acid or formate is much lower than that of OER (1.23 V vs. RHE), which can more efficiently realize electrolytic water splitting for hydrogen production, and is widely used to replace anode OER for auxiliary hydrogen evolution. However, during the oxidation process of formate, the intermediate is easily adsorbed on the surface of the catalyst, which leads to catalyst poisoning, reduces the activity and stability of the catalyst. Therefore, how to develop a catalyst with high activity and stability for hydrogen evolution and formate oxidation reaction (FOR) is a technical problem. SUMMARY

[0003] In order to solve the above problems, the present application provides a PdPtCu ternary metal olefin catalyst.

[0004] A PdPtCu ternary metal olefin catalyst, the surface of the catalyst has crystals, amorphous, line defects, point defects and pores, and the crystal / amorphous interface, pores, point and line defects expose a large number of active sites, increasing the number of sites accessible to the solution; the PdPtCu ternary metal olefin is composed of Pd, Pt and Cu three elements, the introduced Cu and Pt elements regulate the electronic structure of Pd, reduce the d-band center of Pd, which is conducive to reducing the adsorption energy of the intermediate, thereby improving the performance of Pd in catalyzing FOR; in addition, Cu has strong adsorption capacity for oxygen-containing substances, after Cu adsorbs oxygen-containing substances, the adsorption strength of Pd to the intermediate is reduced, thereby improving the performance of the catalyst in catalyzing FOR; at the same time, Cu has strong adsorption capacity for hydroxyl ions, which is conducive to the dissociation of water in alkaline solution (KOH), thereby improving the performance of the catalyst in catalyzing HER.

[0005] The present application also provides a preparation method of a PdPtCu ternary metal olefin catalyst, the preparation method comprising: Step one: mixing N,N-dimethylformamide (DMF) and ethylene glycol (EG) to obtain a mixed solution, adding potassium hydroxide (KOH) to dissolve in the mixed solution to obtain solution A; Step two: dissolve sodium tetrachloropalladate (Na2PdCl4) in DMF solvent to prepare a 0.1 M (0.1 mol / L) solution B, and dissolve platinum acetylacetonate (Pt(acac)2) in DMF solvent to prepare a 0.05 M solution C; after adding solution B, solution C, copper acetylacetonate (Cu(acac)2) and diethylenetriamine (DETA) to solution A, ultrasonic treatment is performed to obtain solution D; Step three: pour solution D into a stainless steel reaction kettle lined with polytetrafluoroethylene, seal it and place it in an oven at 200 ℃ for 8 h, and then clean the product with ethanol and water after cooling.

[0006] The following also provides several optional modes, but not as an additional limitation to the above general scheme, just a further supplement or preferred, without technical or logical contradiction, each optional mode can be combined with the above general scheme alone, and can also be combined between multiple optional modes.

[0007] Optionally, the volume of N,N-dimethylformamide is 5.7 mL, the volume of ethylene glycol is 4 mL, and the mass of potassium hydroxide is 1.2 g.

[0008] Optionally, in step two, 300 μL of solution B, 20 μL of solution C, 5 mL of diethylenetriamine and 2 mg of copper acetylacetonate are added to solution A in the step two.

[0009] The application provides an application of the PdPtCu ternary metal olefin catalyst or the PdPtCu ternary metal olefin catalyst prepared by the preparation method to formate oxidation reaction (FOR) or cathode hydrogen evolution reaction. The FOR is a two-electron reaction process, the oxidation reaction path is more direct, and the oxidation can be realized at a lower potential, and the hydrogen production by electrolysis of water can be more efficiently realized by using formic acid assisted hydrogen evolution, so that the PdPtCu ternary metal olefin catalyst is used in the FOR, and the efficiency of the hydrogen production by electrolysis of water is improved. BRIEF DESCRIPTION OF DRAWINGS

[0010] Figure 1 XRD spectrum of the PdPtCu metal olefin obtained in Example 1; Figure 2 X-ray energy dispersive spectrum (EDS) of the PdPtCu metal olefin obtained in Example 1; Figure 3 TEM diagram of the PdPtCu metal olefin obtained in Example 1; Figure 4 CV curve of the PdPtCu metal olefin obtained in Example 1, the PdPt metal olefin obtained in Comparative Example 1 and the PdCu metal olefin obtained in Comparative Example 2 recorded in 1 M KOH; Figure 5 CV curves of PdPtCu metal ene obtained in Example 1, PdPt metal ene obtained in Comparative Example 1 and PdCu metal ene obtained in Comparative Example 2 were recorded in 0.5 M HCOOK and 1.0 M KOH solutions and CV curves were obtained after mass normalization treatment; Figure 6 CV curves of PdPtCu metal ene obtained in Example 1, PdPt metal ene obtained in Comparative Example 1 and PdCu metal ene obtained in Comparative Example 2 were recorded in 0.5 M HCOOK and 1.0 M KOH solutions and CV curves were obtained after active area normalization treatment; Figure 7 Mass activity and specific activity comparison chart of PdPtCu metal ene obtained in Example 1, PdPt metal ene obtained in Comparative Example 1 and PdCu metal ene obtained in Comparative Example 2 were recorded in 0.5 M HCOOK and 1.0 M KOH solutions; Figure 8 Chronoamperometry (CA) test curve of PdPtCu metal ene obtained in Example 1, PdPt metal ene obtained in Comparative Example 1 and PdCu metal ene obtained in Comparative Example 2; Figure 9 Linear sweep voltammetry (LSV) curve of PdPtCu metal ene obtained in Example 1, PdPt metal ene obtained in Comparative Example 1 and PdCu metal ene obtained in Comparative Example 2; Figure 10 Tafel curve of PdPtCu metal ene obtained in Example 1, PdPt metal ene obtained in Comparative Example 1 and PdCu metal ene obtained in Comparative Example 2; Figure 11 EIS spectrum of PdPtCu metal ene obtained in Example 1, PdPt metal ene obtained in Comparative Example 1 and PdCu metal ene obtained in Comparative Example 2; Figure 12 Cyclic voltammetry (CV) curve of PdPtCu metal ene obtained in Example 1, PdPt metal ene obtained in Comparative Example 1 and PdCu metal ene obtained in Comparative Example 2; dl ; Figure 13 LSV curve of PdPtCu metal ene obtained in Example 1 before and after 1000 CV cycles; Figure 14 Chronopotentiometry curve of Pd 1.5 Pt1 metal ene obtained in Example 3 at 10 mA cm −2 ; Figure 15 LSV curve comparison of FOR || HER and OER || HER electrolytic cell; Figure 16A comparison chart of cell voltage of PdPtCu || PdPtCu, RuO2|| Pd / C two-electrode system in HCOOK-assisted water electrolysis; Figure 17 A chronoamperogram of PdPtCu / CP || PdPtCu / CP in HCOOK-assisted water electrolysis system at 10 mA cm −2 DETAILED DESCRIPTION

[0011] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the scope of protection of the present application.

[0012] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0013] A PdPtCu ternary metal olefin catalyst, the surface of the catalyst has crystals, amorphous, linear defects, point defects and pores, the crystal / amorphous interface, pores, point and linear defects expose a large number of active sites, and the number of solution accessible sites is increased; the PdPtCu ternary metal olefin is composed of Pd, Pt and Cu three elements, the introduced Cu and Pt elements regulate the electronic structure of Pd, reduce the d-band center of Pd, and are beneficial to enhancing the adsorption energy of intermediates, thereby being beneficial to improving the electrocatalytic performance of FOR; in addition, Cu has a strong adsorption capacity for oxygen-containing substances, after Cu adsorbs oxygen-containing substances, the adsorption strength of Pd to intermediates is reduced, thereby improving the performance of the catalyst in catalyzing FOR; at the same time, Cu has a strong adsorption capacity for hydroxyl ions, which is beneficial to the dissociation of water in the alkaline solution (KOH), thereby improving the performance of the catalyst in catalyzing HER.

[0014] The present application also provides a preparation method of the PdPtCu ternary metal olefin catalyst, and the preparation method comprises the following steps: Step one: N,N-dimethylformamide (DMF) and ethylene glycol (EG) are ultrasonically treated and mixed to obtain a mixed solution, potassium hydroxide (KOH) is added and dissolved in the mixed solution to obtain solution A; ​Step two: 0.1 M solution B was prepared by dissolving sodium tetrachloropalladate (Na2PdCl4) in DMF solvent, and 0.05 M solution C was prepared by dissolving platinum acetylacetonate (Pt(acac)2) in DMF solvent; solution B, solution C, copper acetylacetonate (Cu(acac)2) and diethylenetriamine (DETA) were added to solution A and then ultrasonically treated to obtain solution D; Step three: solution D was poured into a stainless steel reaction kettle lined with polytetrafluoroethylene, sealed and placed in an oven at 200 °C for 8 h, and then cooled and washed with ethanol and water.

[0015] The volume of N,N-dimethylformamide was 5.7 mL, the volume of ethylene glycol was 4 mL, and the mass of potassium hydroxide was 1.2 g.

[0016] In step two, 300 μL of solution B, 20 μL of solution C, 5 mL of diethylenetriamine and 2 mg of copper acetylacetonate were added to solution A.

[0017] Example 1 5.6 mL of N,N-dimethylformamide and 4 mL of ethylene glycol were mixed and ultrasonically treated, and then 1.2 g of KOH was dissolved in the solution to obtain solution A. Na2PdCl4 and Pd(acac)2 were dissolved in DMF to prepare solutions B and C with concentrations of 0.1 M and 0.05 M, respectively. Then, 300 μL of solution B and 20 μL of solution C were added to solution A, and 2 mg of Cu(acac)2 and 5 mL of diethylenetriamine were added to the above mixed solution, and the resulting mixture was ultrasonically treated to form a uniform solution. Then, the resulting uniform solution was poured into a stainless steel reaction kettle lined with polytetrafluoroethylene, sealed and placed in an oven at 200 °C for 8 h. After the reaction was completed, the product was cooled to room temperature, washed with ethanol and water, and dried in a vacuum drying box to obtain a catalyst, which was labeled as PdPtCu metal olefin.

[0018] Comparative Example 1 5.6 mL of N,N-dimethylformamide and 4 mL of ethylene glycol were ultrasonically mixed, and then 1.2 g of KOH was added to dissolve the mixture, yielding solution A. Na₂PdCl₄ and Pt(acac)₂ were dissolved in N,N-dimethylformamide to prepare solutions B and C with concentrations of 0.1 M and 0.05 M, respectively. Then, 300 μL of solution B and 20 μL of solution C were added to solution A, along with 5 mL of diethylenetriamine. The resulting mixture was ultrasonicated to form a homogeneous solution. The homogeneous solution was then poured into a stainless steel reactor lined with polytetrafluoroethylene, sealed, and heated in an oven at 200 °C for 8 h. After the reaction was complete, the mixture was cooled to room temperature, thoroughly washed with ethanol and water, and dried in a vacuum drying oven to obtain the catalyst, which was labeled as PdPt metal olefin.

[0019] Comparative Example 2 5.6 mL of N,N-dimethylformamide and 4 mL of ethylene glycol were ultrasonically mixed, and then 1.2 g of KOH was added to dissolve the mixture, yielding solution A. Na₂PdCl₄ was dissolved in N,N-dimethylformamide to prepare solution B with a concentration of 0.1 M. Then, 300 μL of solution B was added to solution A, along with 2 mg of Cu(acac)₂ and 5 mL of diethylenetriamine. The resulting mixture was ultrasonicated to form a homogeneous solution. The homogeneous solution was then poured into a stainless steel reactor lined with polytetrafluoroethylene (PTFE), sealed, and heated in an oven at 200 °C for 8 h. After the reaction was complete, the mixture was cooled to room temperature, thoroughly washed with ethanol and water, and dried in a vacuum drying oven to obtain the catalyst, which was labeled as PdCu metal olefin.

[0020] The specifications and manufacturers of the reagents used above are as follows: Transmission electron microscopy (TEM) analysis was performed on a JEM 2100 Plus TEM with an accelerating voltage of 120 kV. X-ray diffraction (XRD) data were collected on a D8 Advance instrument using Cu Kα radiation (λ = 0.15406 nm) at a voltage of 40 kV and a current of 30 mA.

[0021] The electrocatalytic performance of FOR and HER was tested using a three-electrode system (CHI760E). This system consisted of a Hg / HgO reference electrode, a Pt sheet as the counter electrode, and a glassy carbon electrode (GC electrode, 3 mm in diameter) with the catalyst as the working electrode. Catalyst ink was prepared by ultrasonically dispersing 2 mg of catalyst in a mixed solution containing 50 μL (5 wt%) Nafion, 750 μL of water, and 200 μL of isopropanol. Subsequently, 5 μL of the ink was dropped onto a polished GC electrode and allowed to dry naturally. Furthermore, a bifunctional electrode for formate-assisted hydrolysis was a carbon paper with a catalyst loading of 1 mg cm⁻¹. −2 .

[0022] When measuring FOR performance, firstly, in a 1 M KOH solution (saturated with N2), at 50 mV s... −1 The catalyst was activated by cyclic voltammetry (CV) at a scan rate of 50 mV s. Subsequently, it was activated in a 1 M KOH + 1 M HCOOK mixture at a scan rate of 50 mV s. −1 The CV curve for FOR was recorded at the scan rate. Chronocurrent curves were measured in the same electrolyte at −0.5 V vs. Hg / HgO. The electrochemical active surface area (ECSA) was calculated using equation (1): ECSA = Q (m × 420) (1) Where Q is the integral area of ​​the oxidation peak in the CV curve of Pd obtained in 1 M KOH solution, m represents the mass of Pd, and 420 is the charge associated with the reduction of Pd oxide monolayer (in μC cm⁻¹). -2 ).

[0023] When measuring HER performance, it was performed in a 1 M KOH solution saturated with N2 at a concentration of 50 mV s. −1 Surface activation was achieved by performing CV scanning at a rate of 5 mV / s. The linear sweep voltammetry (LSV) curve was obtained at 5 mV / s. −1 The rate data was recorded. All potentials were converted to potentials relative to the reversible hydrogen electrode (RHE) using the following formula: E (RHE) = E (Hg / HgO) + 0.0592 × pH + 0.098 - iRs (2) Electrochemical impedance spectroscopy (EIS) was performed at a test potential of -0.004 V vs. RHE, with a frequency range of 100,000 to 0.1 Hz. The non-Radidatic potential range was 5 to 25 mV s-1 within the range of 0.046 to 0.146 V vs. RHE. −1CV curves were recorded at different scanning rates. A linear simulation plot of the current difference (ΔJ) at 0.096 V versus the scan rate was plotted; half of the slope represents the double-layer capacitance (C). dl The value of ). Finally, at 10 mA cm ⁻2 The timing potential curve of HER was measured.

[0024] like Figure 1 As shown, significant diffraction peaks are observed at 40.10°, 46.66°, 68.11°, and 86.62°, corresponding to the (111), (200), (220), and (311) crystal planes of Pd (JCPDS 46-1043), respectively. The addition of Cu and Pt elements did not cause significant shifts in the diffraction peaks of the Pd metal olefins. This is mainly because the atomic radii of Cu and Pt are close to those of Pd, and they do not cause significant changes in the crystal lattice, thus preventing any shift in the XRD diffraction peaks.

[0025] like Figure 2 As shown, Pd, Pt, and Cu are uniformly distributed on the surface of the PdPtCu trimetallic olefin, with atomic contents of 75.33%, 2.42%, and 22.25%, respectively. Figure 3 As shown, the surface of metal olefins contains crystals, amorphous materials, pores, point defects, and line defects. The crystal / amorphous interface, pores, point defects, and line defects expose a large number of active sites, increasing the number of sites that the electrolyte can access, which is beneficial to improving the catalytic activity of the catalyst.

[0026] The electrocatalytic performance of FOR was measured in a 1 M KOH + 0.5 M HCOOK solution. First, in N2-saturated 1 M KOH, the electrocatalytic performance was measured at 50 mV s⁻¹. −1 The CV curve of the sample was measured at a scan rate to identify its electrochemically active area (ECSA). For example... Figure 4 As shown, the peaks around −0.2 V vs. Hg / HgO are attributed to the reduction peaks of PdO. The ECSA of each Pd-based metal alkene can be calculated by integrating the corresponding areas of the reduction peaks. The ECSA values ​​of PdPtCu metal alkene, PdCu metal alkene, and PdPt metal alkene are 54.2, 52.1, and 48.3 m, respectively. 2 g −1 It is evident that the ternary PdPtCu metalene, after incorporation of Cu and Pt, possesses the largest active surface area. This is mainly attributed to the abundant active sites exposed at crystal / amorphous interfaces, pores, and point and line defects within the PdPtCu metalene. CV curves for PdPtCu, PdCu, and PdPt metalenes were further recorded in 1 M KOH containing 0.5 M HCOOK, and mass and specific surface area were normalized. The corresponding curves are shown below. Figure 5 andFigure 6 As shown. From Figure 7 Further analysis reveals that PdPtCu trimetallenes exhibit the highest mass activity (MA), reaching 1.5 mA μg. −1 cat This is a PdPt metalene (1.32 mA μg) −1 cat 1.14 times that of PdCu metalloene (1.01 mA μg) −1 cat It is 1.49 times that of ECSA. Specific surface area activity (SA) is defined as the ratio of mass activity to ECSA. The SA of Pd metalloenes is 1.31 mA cm⁻¹. cat -2 Lower than 1.93 mAcm for PdCu metalloenes cat -2 2.73 mA cm⁻¹ for PdPt metalenes cat -2 It is even lower than the 2.77 mA cm⁻¹ of PdPtCu metalloalkenes. cat -2 The reason lies in the abundant active sites exposed by the crystal / amorphous interfaces, pores, point and line defects in the PdPtCu metalloalkene. In addition, the introduced Cu and Pt elements regulate the electronic structure of Pd, reduce the d-band center of Pd, which is beneficial to weaken the adsorption energy of intermediates such as CO, thereby improving the performance of Pd catalytic FOR. At the same time, Cu has a strong ability to adsorb oxygen-containing substances. After Cu adsorbs oxygen-containing substances, it reduces the adsorption strength of Pd for intermediates, thereby improving the mass activity of the catalyst.

[0027] Given the excellent FOR activity of PdPtCu ternary metal alkenes, the change in current density over time at a potential of -0.4 V vs. Hg / HgO was tested. Figure 8 As shown, in the initial stage, the current density decreases rapidly due to double-layer discharge and the adsorption and accumulation of reaction intermediates on the surface of the active sites. The current density eventually stabilizes. Importantly, the final stable current density of PdPtCu metal ene is higher than that of PdPt and PdCu metal enes. This indicates that PdPtCu metal enes possess better catalytic activity and stability because they have a weaker ability to adsorb CO intermediates, increased resistance to poisoning, and can maintain a higher TOF (time-of-flight) at the active sites, thus resulting in better catalytic activity and stability.

[0028] The HER performance of each sample was tested in 1 M KOH solution. Figure 9 As shown, PdCu metallene and PdPt reach 10 mA cm⁻¹. −2At the same current density, 173 mV and 106 mV are required, respectively, but the overpotential of the defect-rich PdPtCu metal alkene is only 51 mV. This is mainly attributed to the abundant active sites exposed by the crystal / amorphous interfaces, pores, point and line defects in the PdPtCu metal alkene. In addition, the introduction of Cu and Pt elements modulates the electronic structure of Pd, reduces the d-band center of Pd, which is beneficial to weakening the adsorption energy of intermediates such as H, thereby improving the performance of Pd in ​​catalyzing HER. At the same time, Cu has a strong ability to adsorb hydroxide ions, which is beneficial to the dissociation of water in alkaline solution (KOH), thereby improving the performance of the catalyst in catalyzing HER.

[0029] like Figure 10 As shown, PdPtCu trimetallic olefins exhibit the lowest Tafel slope, at 45.59 mV dec. −1 This is lower than that of PdCu bimetallic olefins (98.84 mV dec). −1 ) and PdPt bimetallic olefins (54.37 mV dec) −1 This indicates that the mechanism of Pd-based metal ene-catalyzed basic HER follows the Volmer-Heyrovsky pathway, and that ternary PdPtCu metal enes exhibit faster reaction kinetics compared to binary PdPt and PdCu metal enes. This is attributed to defects such as crystalline / amorphous heterojunction interfaces in PdPtCu and the synergistic effects of various elements on the reaction kinetics. Figure 11 As shown, the PdPtCu ternary metalene exhibits the lowest charge transfer resistance (Rct) at 145.1 Ω, which is much lower than the 224.1 Ω of PtPt bimetallic ene and the 1320.5 Ω of PdCu bimetallic ene. Since Pt and Cu have better conductivity than Pd, the introduction of Pt and Cu gives the PdPtCu ternary metalene a highly efficient electron transfer capability, which helps to improve HER performance.

[0030] C dl The redistribution of interfacial charge when no Faraday reaction occurs on the electrode surface can be used to reflect the number of active sites on the catalyst. For example... Figure 12 As shown, the C of PdPtCu metal alkene, PdPt metal alkene, and PdCu metal alkene are... dl The values ​​were 30.65 mF cm. −2 10.21 mF cm −2 5.08 mFcm −2 The abundant point and line defects in PdPtCu metalloalkenes provide a higher density of active sites. Catalyst stability is also an important indicator of catalyst performance. For example... Figure 13As shown, after 1000 CV cycles, the curve only shifted slightly to the right, indicating that PdPtCu metalloalkenes possess excellent catalytic activity and stability. Furthermore, its long-term stability was tested using a constant current mode. Figure 14 As shown, it is at 10 mA cm −2 It can maintain a stable potential for up to 24 hours under current density, which further confirms its good stability.

[0031] The effect of HCOOK on the pressure of the water electrolyzer was investigated in the constructed two-electrode system, such as... Figure 15 As shown, the introduction of 1 M HCOOK into the alkaline electrolyte significantly reduced the battery voltage required for overall water decomposition. This voltage reached 10 mA cm⁻¹. −2 At a current density of [value missing], the FOR || HER electrolyzer requires only 0.26 V of cell voltage, which is 1.64 V lower than the 1.9 V of the conventional OER || HER electrolyzer. This indicates that HCOOK-assisted water splitting can produce hydrogen more energy-efficiently and effectively than conventional water splitting. Figure 16 As shown, the cell pressure for formate-assisted water splitting using a two-electrode system of PdPtCu metalene||PdPtCu metalene is significantly lower than that of the RuO2||Pd / C system. For example, at 10 mA cm⁻¹ −2 At current density, the cell voltage of PdPtCu metal olefin || PdPtCu metal olefin is 1.44V lower than that of RuO2 || Pd / C system.

[0032] like Figure 17 As shown, the stability of the PdPtCu metalloene || PdPtCu metalloene electrolytic cell was tested. At 10 mA cm⁻¹ −2 Under the given current density, the cell pressure of the electrolyzer for HCOOK-assisted water electrolysis remained stable within 24 hours, indicating that it has good catalytic stability.

[0033] The technical features of the above embodiments can be combined arbitrarily. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as the combination of these technical features does not contradict each other, it should be considered to be within the scope of this specification. When technical features of different embodiments are embodied in the same drawing, it can be regarded as the drawing also disclosing examples of combinations of the various embodiments involved.

[0034] The above embodiments merely illustrate several implementation methods of the present invention, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of the patent application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention.

Claims

1. A PdPtCu ternary metal olefin catalyst, characterized in that, The surface of the catalyst has crystalline, amorphous, line defects, point defects, and pores, and the PdPtCu ternary metal olefin is composed of alloys of Pd, Pt, and Cu.

2. A method for preparing a PdPtCu ternary metal olefin catalyst, characterized in that, The preparation method includes: Step 1: Mix N,N-dimethylformamide with ethylene glycol to obtain a mixture, then add potassium hydroxide to dissolve in the mixture to obtain solution A; Step 2: Dissolve sodium tetrachloropalladium in N,N-dimethylformamide to prepare a 0.1 M solution B; dissolve platinum acetylacetonate in N,N-dimethylformamide to prepare a 0.05 M solution C; add solutions B, C, copper acetylacetonate, and diethylenetriamine to solution A and then sonicate to obtain solution D; Step 3: Pour solution D into a stainless steel reactor lined with polytetrafluoroethylene, seal it, and heat it in an oven at 200 °C for 8 h. After cooling, wash the product with ethanol and water.

3. The PdPtCu ternary metal olefin catalyst according to claim 2, characterized in that, The volume of N,N-dimethylformamide is 5.7 mL, the volume of ethylene glycol is 4 mL, and the mass of potassium hydroxide is 1.2 g.

4. The PdPtCu ternary metal olefin catalyst according to claim 2, characterized in that, In step two, 300 μL of solution B, 20 μL of solution C, 5 mL of diethylenetriamine, and 2 mg of copper acetylacetonate are added to solution A.

5. An application of a PdPtCu ternary metal olefin catalyst, characterized in that, The PdPtCu ternary metal olefin catalyst is applied to the formate oxidation reaction or the cathodic hydrogen evolution reaction. The surface of the catalyst has crystals, amorphous materials, line defects, point defects and pores. The PdPtCu ternary metal olefin is composed of alloys of Pd, Pt and Cu.

6. The application of the PdPtCu ternary metal olefin catalyst according to claim 5, characterized in that, The preparation method of the PdPtCu ternary metal olefin catalyst includes: Step 1: Mix N,N-dimethylformamide with ethylene glycol to obtain a mixture, then add potassium hydroxide to dissolve in the mixture to obtain solution A; Step 2: Dissolve sodium tetrachloropalladium in N,N-dimethylformamide to prepare a 0.1 M solution B; dissolve platinum acetylacetonate in N,N-dimethylformamide to prepare a 0.05 M solution C; add solutions B, C, copper acetylacetonate, and diethylenetriamine to solution A and then sonicate to obtain solution D; Step 3: Pour solution D into a stainless steel reactor lined with polytetrafluoroethylene, seal it, and heat it in an oven at 200 °C for 8 h. After cooling, wash the product with ethanol and water.

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