A platinum-palladium-silver bifunctional nanalloy electrocatalyst and a preparation method thereof

Abstract

The application belongs to the technical field of electrocatalysis, and discloses a platinum-palladium-silver bifunctional nano-alloy electrocatalyst and a preparation method thereof. The method comprises the following steps: 1) mixing a chloropalladic acid solution and a cetyltrimethylammonium bromide solution, adding sodium borohydride to obtain a palladium seed solution; 2) mixing cetyltrimethylammonium bromide, chloroplatinic acid, chloropalladic acid and silver nitrate in water to obtain a growth solution; mixing the growth solution and the seed solution, adding an ascorbic acid solution, and performing a reaction at 80-90 DEG C, centrifugation, washing and drying to obtain the platinum-palladium-silver bifunctional nano-alloy electrocatalyst. The method has the advantages of simplicity, rapid synthesis, green environmental protection and the like, and the prepared catalyst can be used as an anode catalyst for catalyzing glycerol oxidation at an anode and as a cathode catalyst for catalyzing hydrogen evolution reaction at a cathode, and can simultaneously achieve the following effects: obtaining high-value-added glycerol oxidation products, reducing overpotential, improving hydrogen production efficiency and reducing hydrogen production energy consumption.

Description

Technical Field

[0001] This invention belongs to the field of electrocatalysis, specifically relating to a multimetallic Pt x Pd y Ag z Bifunctional nanoalloy electrocatalysts and their preparation methods. Background Technology

[0002] Currently, to achieve carbon peaking and carbon neutrality as soon as possible, and to actively develop non-fossil energy sources such as biomass energy and hydrogen energy, it is essential to develop a bifunctional catalyst that can catalyze both biomass conversion and hydrogen evolution reactions. Glycerin, a byproduct of the biodiesel industry, is a commonly used raw material for producing high-value-added chemicals. Glycerin (GLY) can be converted into various important C3 products, including glyceric acid, glyceraldehyde, dihydroxyacetone, and tartaric acid. These high-value-added oxidation products have wide applications in the chemical, pharmaceutical, and cosmetic industries, and producing high-value-added chemicals through electrolytic oxidation of glycerin is currently the greenest and most efficient way to reuse glycerin.

[0003] Hydrogen is widely considered one of the most promising energy carriers due to its high energy density, cleanliness, and sustainability. Currently, the most common method for hydrogen production is steam methane reforming. However, this process heavily relies on fossil fuels. Electrocatalytic water splitting to produce high-purity hydrogen is a green alternative. However, in actual industrial production, the electrolysis of water for hydrogen production is limited by the excessively high overpotential in the oxygen evolution reaction (OER), significantly reducing energy conversion efficiency. Therefore, replacing the OER with the low-potential glycerol oxidation reaction to reduce energy consumption in the electrolysis process, improve hydrogen production efficiency, and simultaneously produce valuable glycerol conversion products represents a win-win energy development path.

[0004] Traditional Pt-based alloys are susceptible to poisoning effects from CO intermediates during glycerol oxidation, resulting in reduced catalytic activity and stability. While traditional Pd-based alloys exhibit stronger resistance to CO poisoning than Pt-based alloys, their activity remains limited. Although multi-element alloys can improve catalytic performance in a balanced way, the incompatibility between different elements makes it difficult to achieve ideal morphologies at the nanoscale. Furthermore, many existing synthetic methods involve demanding conditions, complex processes, and unsustainable raw materials, thus presenting significant limitations. Summary of the Invention

[0005] In view of the shortcomings and deficiencies of the existing technology, the primary objective of this invention is to provide a method for preparing a multi-metal PtPdAg bifunctional nanoalloy electrocatalyst.

[0006] Another objective of this invention is to provide a multi-metallic PtPdAg bifunctional nanoalloy electrocatalyst prepared by the above method.

[0007] The objective of this invention is achieved through the following technical solution:

[0008] A method for preparing a platinum-palladium-silver bifunctional nanoalloy electrocatalyst includes the following steps:

[0009] 1) Mix chloropalladic acid solution with hexadecyltrimethylammonium bromide solution, add sodium borohydride and react to obtain palladium seed solution;

[0010] 2) Mix hexadecyltrimethylammonium bromide, chloroplatinic acid, chloropalladic acid and silver nitrate in water to obtain a growth solution; mix the growth solution with the seed solution, add ascorbic acid solution, react at 80~90℃, centrifuge, wash and dry to obtain a platinum-palladium-silver bifunctional nano-alloy electrocatalyst.

[0011] The reaction time in step 1) is 1.5 to 2.5 hours. The reaction is a static reaction at room temperature.

[0012] The reaction time described in step 2) is 1 to 3 hours.

[0013] The concentration of the chloropalladium acid solution in step 1) is 0.01~0.03 mol / L; the concentration of the hexadecyltrimethylammonium bromide solution is 0.1~0.3 mol / L.

[0014] The volume ratio of the chloropalladic acid solution to the hexadecyltrimethylammonium bromide solution is (0.3~0.8):(18~20).

[0015] The sodium borohydride is used in solution form with a concentration of 0.01~0.03 mol / L and a volume ratio of sodium borate solution to chloropalladium solution of (0.8~1.5):(0.3~0.8).

[0016] The substances in the growth medium are used in solution form. The concentration of hexadecyltrimethylammonium bromide solution is 3~6 mmol / L, the concentration of chloroplatinic acid solution is 0.01~0.03 mol / L, the concentration of chloropalladium acid solution is 0.01~0.03 mol / L, and the concentration of silver nitrate solution is 0.01~0.03 mol / L. The volume ratio is 350~450:4~15:4~15:3~8, preferably 350~450:8~15:8~15:3~8.

[0017] The molar ratio of hexadecyltrimethylammonium bromide, chloroplatinic acid, chloropalladic acid and silver nitrate in the growth solution of step 2) is (0.9~2.7):(0.04~0.45):(0.04~0.45):(0.03~0.24), preferably (0.9~2.7):(0.08~0.45):(0.08~0.45):(0.03~0.24).

[0018] The concentration of the ascorbic acid solution is 0.1~0.3 mol / L. The molar ratio of ascorbic acid to chloroplatinic acid is (0.8~4.5):(0.04~0.45).

[0019] In step 2), the molar ratio of chloroplatinic acid in the growth solution to that in the seed solution is (0.08~0.45):(0.003~0.024).

[0020] The centrifugation mentioned in step 2) refers to centrifugation at a speed of 11000~13000 rpm for 10~15 min, washing refers to washing with ethanol, and drying refers to vacuum drying at 60~80℃ for 12~18 h.

[0021] A multi-metallic PtPdAg bifunctional nanoalloy electrocatalyst was prepared by the above method.

[0022] The principle of this invention is as follows: A simple seed-mediated method is employed, using a palladium seed solution obtained by reducing chloropalladium acid solution with sodium borohydride as a precursor, and a mixture of hexadecyltrimethylammonium bromide solution, chloroplatinic acid solution, chloropalladium acid solution, and silver nitrate solution as a growth medium. Through the reduction reaction with ascorbic acid, a multi-metallic Pt with uniform size and morphology and high catalytic activity is synthesized. x Pd y Ag z Nanoalloys.

[0023] The preparation method and the product obtained by the present invention have the following advantages and beneficial effects:

[0024] (1) This invention uses a seed-mediated method to prepare polymetallic Pt x Pd y Ag z This bifunctional nanoalloy electrocatalyst has a simple preparation process using green raw materials and boasts advantages such as simple operation, low cost, and environmental friendliness. It can provide some guidance for the synthesis of high-performance catalysts for the electrocatalytic oxidation of glycerol and the cathodic hydrogen evolution reaction in the electrolysis of water to produce hydrogen.

[0025] (2) The polymetallic Pt prepared by the present invention x Pd y Ag zThe bifunctional nanoalloy electrocatalysts are all uniform porous spheres with consistent size at the nanoscale, with individual alloy particles measuring 30±2 nm.

[0026] (3) Pt prepared in this invention x Pd y Ag z Nanoalloys can be used as anodic catalysts for glycerol oxidation at the anode and as cathode catalysts for hydrogen evolution reaction at the cathode. This allows for the simultaneous achievement of obtaining high-value-added glycerol oxidation products while reducing overpotential, improving hydrogen production efficiency, and reducing hydrogen production energy consumption. Attached Figure Description

[0027] Figure 1 , Figure 2 , Figure 3 The polymetallic Pt obtained in Example 3 x Pd y Ag z Transmission electron microscopy (TEM) images of bifunctional nano-alloy electrocatalysts at different magnifications;

[0028] Figure 4 The polymetallic Pt obtained in Example 3 x Pd y Ag z High-angle annular dark-field image of a bifunctional nano-alloy electrocatalyst—HAADF-STEM image;

[0029] Figure 5 The polymetallic Pt obtained in Example 3 x Pd y Ag z Electron energy loss spectrum (EELS) of bifunctional nanoalloy electrocatalysts;

[0030] Figure 6 The polymetallic Pt obtained in Example 3 x Pd y Ag z X-ray diffraction (XRD) pattern of bifunctional nanoalloy electrocatalyst;

[0031] Figure 7 The polymetallic Pt obtained in Example 3 x Pd y Ag z Linear scan voltammetry (LSV) plot of bifunctional nanoalloy electrocatalysts oxidizing glycerol at a scan rate of 2 mV / s in 0.1 M KOH + 1 MGLY electrolyte, where Pt / C is the standard comparison sample;

[0032] Figure 8 The polymetallic Pt obtained in Examples 2 and 1 xPd y Ag z Linear scan voltammetry (LSV) plot of bifunctional nanoalloy electrocatalysts oxidizing glycerol at a scan rate of 2 mV / s in 0.1 MKOH + 1 M GLY electrolyte, where Pt / C is the standard comparison sample;

[0033] Figure 9 The polymetallic Pt obtained using platinum seeds and silver seeds were used in Comparative Examples 1 and 2, respectively. x Pd y Ag z Linear scan voltammetry (LSV) plot of alloy electrocatalyst oxidizing glycerol at a scan rate of 2 mV / s in 0.1 M KOH + 1 M GLY electrolyte, where Pt / C is the standard comparison sample;

[0034] Figure 10 The polymetallic Pt obtained in Example 3 x Pd y Ag z Distribution of high-value-added products obtained by continuous electrolysis of glycerol oxidation for 2 h in 0.1 M KOH + 1 M GLY solution under different applied voltages from bifunctional nano-alloy electrocatalysts;

[0035] Figure 11 The polymetallic Pt obtained in Example 3 x Pd y Ag z A schematic diagram illustrating the simultaneous catalysis of glycerol oxidation and hydrogen evolution reactions by a bifunctional nano-alloy electrocatalyst acting as both anode and cathode in a 0.1 M KOH + 0.1 M GLY solution;

[0036] Figure 12 The polymetallic Pt obtained in Example 3 x Pd y Ag z LSV curves of bifunctional nano-alloy electrocatalysts used as both anode and cathode in 0.1 M KOH solution and 0.1 M KOH + 0.1 M GLY solution at a scan rate of 2 mV / s;

[0037] Figure 13 The polymetallic Pt obtained in Example 3 x Pd y Ag z Distribution of glycerol oxidation products after 2 hours of simultaneous catalysis of glycerol oxidation and hydrogen evolution reaction by a bifunctional nano-alloy electrocatalyst acting as both anode and cathode in a 0.1 M KOH + 0.1 M GLY solution powered by a 1.5 V solar panel. Detailed Implementation

[0038] The present invention will be further described in detail below with reference to embodiments, but the implementation of the present invention is not limited thereto.

[0039] Example 1 Pt x Pd y Ag z Nano-alloy preparation

[0040] (1) Weigh 0.5 ml of chloropalladium acid solution (0.03 mol / L) and 19.5 ml of cetyltrimethylammonium bromide solution (0.1 mol / L) to obtain a mixed solution, then add 1.2 ml of sodium borohydride solution (0.01 mol / L) and let it stand for 2 h to obtain a palladium seed precursor solution.

[0041] (2) Weigh 400 ml of cetyltrimethylammonium bromide solution (4.5 mmol / L), 10 ml of chloroplatinic acid solution (0.03 mol / L), 4 ml of chloropalladic acid solution (0.02 mol / L), and 4 ml of silver nitrate solution (0.01 mol / L) to form the growth solution.

[0042] (3) Take the palladium seed solution obtained in step (1) and add it to the growth solution obtained in (2), and then add 10 ml of ascorbic acid solution (0.1 mol / L) to form a reaction solution.

[0043] (4) Transfer the reaction solution obtained in (3) to an oil bath and react at 85°C for 2 hours, then cool to room temperature;

[0044] (5) After centrifugation and washing with ethanol three times, the product obtained after the reaction was dried under vacuum at 60°C for 15 hours to obtain polymetallic Pt. x Pd y Ag z Bifunctional nanoalloy electrocatalyst.

[0045] Example 2 Pt x Pd y Ag z Nano-alloy preparation

[0046] (1) Weigh 0.5 ml of chloropalladium acid solution (0.02 mol / L) and 19.5 ml of cetyltrimethylammonium bromide solution (0.2 mol / L) to obtain a mixed solution, then add 1.2 ml of sodium borohydride solution (0.02 mol / L) and let stand for 2 h to obtain palladium seed precursor solution.

[0047] (2) Weigh 400 ml of cetyltrimethylammonium bromide solution (4.5 mmol / L), 4 ml of chloroplatinic acid solution (0.02 mol / L), 10 ml of chloropalladic acid solution (0.02 mol / L), and 4 ml of silver nitrate solution (0.02 mol / L) to form the growth solution.

[0048] (3) Take the palladium seed solution obtained in step (1) and add it to the growth solution obtained in (2), and then add 10 ml of ascorbic acid solution (0.2 mol / L) to form a reaction solution.

[0049] (4) Transfer the reaction solution obtained in (3) to an oil bath and react at 90°C for 2 hours, then cool to room temperature;

[0050] (5) After centrifugation and washing with ethanol three times, the product obtained after the reaction was dried under vacuum at 65°C for 12 hours to obtain polymetallic Pt. x Pd y Ag z Bifunctional nanoalloy electrocatalyst.

[0051] Example 3 Pt x Pd y Ag z Nano-alloy preparation

[0052] (1) Weigh 0.5 ml of chloropalladium acid solution (0.01 mol / L) and 19.5 ml of cetyltrimethylammonium bromide solution (0.1 mol / L) to obtain a mixed solution, then add 1.2 ml of sodium borohydride solution (0.01 mol / L) and let stand for 2 h to obtain palladium seed precursor solution.

[0053] (2) Weigh 400 ml of cetyltrimethylammonium bromide solution (4.5 mmol / L), 10 ml of chloroplatinic acid solution (0.01 mol / L), 10 ml of chloropalladic acid solution (0.01 mol / L), and 4 ml of silver nitrate solution (0.01 mol / L) to form the growth solution.

[0054] (3) Take the palladium seed solution obtained in step (1) and add it to the growth solution obtained in (2), and then add 10 ml of ascorbic acid solution (0.1 mol / L) to form a reaction solution.

[0055] (4) Transfer the reaction solution obtained in (3) to an oil bath and react at 85°C for 2 hours, then cool to room temperature;

[0056] (5) After centrifugation and washing with ethanol three times, the product obtained after the reaction was dried under vacuum at 60°C for 12 hours to obtain polymetallic Pt. x Pd y Ag z Bifunctional nanoalloy electrocatalyst.

[0057] Figure 1 , Figure 2 , Figure 3 The polymetallic Pt obtained in Example 3 x Pd y Agz Transmission electron microscopy (TEM) images of bifunctional nanoalloy electrocatalysts at different magnifications. From Figures 1-3 As can be seen, the alloy nanoparticles have a uniform porous spherical structure with an average size of 35±2 nm. The small particle size and numerous pore channels provide more active catalytic sites for the alloy nanoparticles.

[0058] Figure 4 The polymetallic Pt obtained in Example 3 x Pd y Ag z High-angle annular dark-field image of a bifunctional nanoalloy electrocatalyst—HAADF-STEM image.

[0059] Figure 5 The polymetallic Pt obtained in Example 3 x Pd y Ag z Electron energy loss spectroscopy (EELS) of bifunctional nanoalloy electrocatalysts, from Figure 5 It can be seen that the three metals Pt, Pd and Ag are evenly dispersed, which is completely different from the general core-shell structure, and therefore helps to enhance the synergistic effect between different metals.

[0060] Figure 6 The polymetallic Pt obtained in Example 3 x Pd y Ag z X-ray diffraction (XRD) pattern of the bifunctional nanoalloy electrocatalyst. The image shows that all crystal planes exhibit sharp, symmetrical peaks, indicating the formation of a highly crystalline alloy structure.

[0061] Comparative Example 1: Preparation of Pt using platinum seeds x Pd y Ag z Nano alloys

[0062] (1) Weigh 0.5 ml of chloroplatinic acid solution (0.01 mol / L) and 19.5 ml of cetyltrimethylammonium bromide solution (0.1 mol / L) to obtain a mixed solution, then add 1.2 ml of sodium borohydride solution (0.01 mol / L) and let it stand for 2 h to obtain a platinum seed precursor solution.

[0063] (2) Weigh 400 ml of cetyltrimethylammonium bromide solution (4.5 mmol / L), 10 ml of chloroplatinic acid solution (0.01 mol / L), 10 ml of chloropalladic acid solution (0.01 mol / L), and 4 ml of silver nitrate solution (0.01 mol / L) to form the growth solution.

[0064] (3) Take the platinum seed solution obtained in step (1) and add it to the growth solution obtained in (2), and then add 10 ml of ascorbic acid solution (0.1 mol / L) to form a reaction solution.

[0065] (4) Transfer the reaction solution obtained in (3) to an oil bath and react at 85°C for 2 hours, then cool to room temperature;

[0066] (5) After centrifugation and washing with ethanol three times, the product obtained after the reaction was dried under vacuum at 60°C for 12 hours to obtain polymetallic Pt. x Pd y Ag z Bifunctional nanoalloy electrocatalyst.

[0067] Comparative Example 2: Using silver seeds Pt x Pd y Ag z Nano-alloy preparation

[0068] (1) Weigh 0.5 ml of silver nitrate solution (0.01 mol / L) and 19.5 ml of cetyltrimethylammonium bromide solution (0.1 mol / L) to obtain a mixed solution, then add 1.2 ml of sodium borohydride solution (0.01 mol / L) and let stand for 2 h to obtain silver seed precursor solution.

[0069] (2) Weigh 400 ml of cetyltrimethylammonium bromide solution (4.5 mmol / L), 10 ml of chloroplatinic acid solution (0.01 mol / L), 10 ml of chloropalladic acid solution (0.01 mol / L), and 4 ml of silver nitrate solution (0.01 mol / L) to form the growth solution.

[0070] (3) Take the silver seed solution obtained in step (1) and add it to the growth solution obtained in (2), and then add 10 ml of ascorbic acid solution (0.1 mol / L) to form a reaction solution.

[0071] (4) Transfer the reaction solution obtained in (3) to an oil bath and react at 85°C for 2 hours, then cool to room temperature;

[0072] (5) After centrifugation and washing with ethanol three times, the product obtained after the reaction was dried under vacuum at 60°C for 12 hours to obtain polymetallic Pt. x Pd y Ag z Bifunctional nanoalloy electrocatalyst.

[0073] Example 4 Pt x Pd y Ag z Electrocatalytic oxidation of glycerol by nano-alloys under alkaline conditions

[0074] The Pt obtained in the examplex Pd y Ag z The nano-alloy catalyst was dispersed in ethanol and prepared into a 1 mg mL solution. -1 A dispersion of the catalyst was prepared. The catalyst dispersion was then drop-coated onto a 2×2 cm piece of carbon paper to create the anode for the electrocatalytic oxidation of glycerol. A blank 2×2 cm piece of carbon paper served as the cathode. The electrolyte was a 0.1 M KOH + 0.1 M GLY solution. The applied potential was controlled between 0.4 and 1.3 V vs RHE, thus achieving the electrocatalytic oxidation of glycerol under alkaline conditions. The catalytic activity was as follows: Figures 7-9 As shown, the types and distribution of glycerol oxidation products obtained after continuous electrolysis for 2 hours at different applied potentials are as follows: Figure 10 As shown.

[0075] Figure 7 The polymetallic Pt obtained in Example 3 x Pd y Ag z Linear scan voltammetry (LSV) plot of bifunctional nanoalloy electrocatalysts oxidizing glycerol at a scan rate of 2 mV / s in 0.1 M KOH + 1 MGLY electrolyte, where Pt / C is the standard comparison sample. The results indicate that Pt in alkaline solution... x Pd y Ag z The catalyst's activity is 11.5 times that of commercial Pt / C catalysts;

[0076] Figure 8 The polymetallic Pt obtained in Examples 2 and 1 x Pd y Ag z Linear scan voltammetry (LSV) plot of bifunctional nanoalloy electrocatalysts oxidizing glycerol at a scan rate of 2 mV / s in 0.1 MKOH + 1 M GLY electrolyte, where Pt / C is the standard comparison sample.

[0077] Figure 9 The polymetallic Pt obtained using platinum seeds and silver seeds were used in Comparative Examples 1 and 2, respectively. x Pd y Ag z Linear sweep voltammetry (LSV) plots of the alloy electrocatalyst oxidizing glycerol at a scan rate of 2 mV / s in 0.1 M KOH + 1 M GLY electrolyte are shown, with Pt / C serving as the standard comparative sample. The results indicate that the Pt prepared using platinum and silver seeds... x Pd y Ag z The catalytic activity of the alloys for glycerol oxidation is lower than that of the Pt prepared using palladium seeds in the examples. x Pd yAg z alloy.

[0078] Figure 10 The polymetallic Pt obtained in Embodiment 3 of the present invention x Pd y Ag z Distribution of high-value-added products obtained by continuous electrolysis of glycerol oxidation for 2 h in a bifunctional nano-alloy electrocatalyst under different applied voltages in a 0.1 M KOH + 1 M GLY solution. The results show that Pt under alkaline conditions... x Pd y Ag z The catalyst can continuously electrolyze and oxidize glycerol to obtain high-value-added products such as dihydroxyacetone, glyceraldehyde, glyceric acid, and glycolic acid, and the selectivity for dihydroxyacetone reaches 75% at 0.5V vs RHE.

[0079] Example 5 Pt x Pd y Ag z Electrocatalytic oxidation of glycerol by nano-alloys under acidic conditions

[0080] The Pt obtained in Example 3 x Pd y Ag z The nano-alloy catalyst was dispersed in ethanol and prepared into a 1 mg mL solution. -1 The catalyst dispersion was then drop-coated onto a 2×2 cm carbon paper to form the anode for electrocatalytic glycerol oxidation. A blank carbon paper of the same size (2×2 cm) was used as the cathode. The electrolyte was a 0.1 M HClO4 + 0.1 M GLY solution. The applied potential was controlled between 0.7 and 1.0 V vs RHE, thus achieving electrocatalytic oxidation of glycerol under acidic conditions.

[0081] Example 6 Using Pt x Pd y Ag z Nanoalloys couple catalytic glycerol oxidation and hydrogen evolution reactions

[0082] The Pt obtained in Example 3 x Pd y Ag z The nano-alloy catalyst was dispersed in ethanol and prepared into a 1 mg mL solution. -1 The catalyst dispersion was then drop-coated onto two 2×2 cm sheets of carbon paper to form the anode for catalytic glycerol oxidation and the cathode for catalytic hydrogen evolution. The electrolyte was a 0.1 M KOH + 0.1 M GLY solution. Applying a voltage of 0.5 V was sufficient to couple the catalytic glycerol oxidation and hydrogen evolution reactions. A schematic diagram of the coupling reaction is shown below. Figure 11As shown, the catalytic activity is as follows Figure 12 As shown, the types and distribution of glycerol oxidation products obtained by continuous electrolysis for 2 hours at an applied potential of 1V are as follows. Figure 13 As shown.

[0083] Figure 11 The polymetallic Pt obtained in Example 3 x Pd y Ag z A schematic diagram illustrating the simultaneous catalysis of glycerol oxidation and hydrogen evolution reactions by a bifunctional nanoalloy electrocatalyst acting as both anode and cathode in a 0.1 M KOH + 0.1 M GLY solution. In the diagram, "glycerol" represents glycerol, "anode" represents the anode, "membrane" represents the membrane, "cathode" represents the cathode, and "water" represents water.

[0084] Figure 12 The polymetallic Pt obtained in Example 3 x Pd y Ag z LSV curves of the bifunctional nanoalloy electrocatalyst, used as both anode and cathode, were plotted at a scan rate of 2 mV / s in 0.1 M KOH solution and 0.1 M KOH + 0.1 M GLY solution. The results indicate that replacing the oxygen evolution reaction with glycerol oxidation at the anode reduces the oxidation overpotential from 0.9 V to 0.5 V and doubles the hydrogen production efficiency.

[0085] Figure 13 The polymetallic Pt obtained in Example 3 x Pd y Ag z The distribution of glycerol oxidation products after 2 hours of simultaneous glycerol oxidation and hydrogen evolution reactions catalyzed by a bifunctional nano-alloy electrocatalyst acting as both anode and cathode in a 0.1 M KOH + 0.1 M GLY solution powered by a 1.5 V solar panel is shown in the figure. The results indicate that this invention successfully achieves electrolytic hydrogen production driven by a 1.5 V solar panel, and a large amount of high-value-added glycerol oxidation products such as glyceric acid, glycolic acid, and lactic acid were collected at the anode.

[0086] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A method for preparing a platinum-palladium-silver bifunctional nanoalloy electrocatalyst, characterized in that: Includes the following steps: 1) Mix chloropalladic acid solution with hexadecyltrimethylammonium bromide solution, add sodium borohydride and react to obtain palladium seed solution; 2) Mix hexadecyltrimethylammonium bromide, chloroplatinic acid, chloropalladic acid and silver nitrate in water to obtain a growth solution; mix the growth solution with the seed solution, add ascorbic acid solution, react at 80~90℃, centrifuge, wash and dry to obtain a platinum-palladium-silver bifunctional nano-alloy electrocatalyst. The concentration of the chloropalladic acid solution in step 1) is 0.01~0.03 mol / L; the concentration of the hexadecyltrimethylammonium bromide solution is 0.1~0.3 mol / L; and the volume ratio of the chloropalladic acid solution to the hexadecyltrimethylammonium bromide solution is (0.3~0.8):(18~20). In step 2), the molar ratio of hexadecyltrimethylammonium bromide, chloroplatinic acid, chloropalladic acid, and silver nitrate in the growth solution is (0.9~2.7):(0.04~0.45):(0.04~0.45):(0.03~0.24). In step 2), the molar ratio of chloroplatinic acid in the growth solution to that in the seed solution is (0.04~0.45):(0.003~0.024). The concentration of the ascorbic acid solution mentioned in step 2) is 0.1~0.3 mol / L; the molar ratio of ascorbic acid to chloroplatinic acid is (0.8~4.5):(0.04~0.45).

2. The method for preparing the platinum-palladium-silver bifunctional nanoalloy electrocatalyst according to claim 1, characterized in that: The sodium borohydride mentioned in step 1) is used in the form of a solution with a concentration of 0.01~0.03 mol / L and a volume ratio of sodium borohydride solution to chloropalladium acid solution of (0.8~1.5):(0.3~0.8).

3. The method for preparing the platinum-palladium-silver bifunctional nanoalloy electrocatalyst according to claim 1, characterized in that: In step 2), each substance in the growth solution is used in solution form. The concentration of hexadecyltrimethylammonium bromide solution is 3~6 mmol / L, the concentration of chloroplatinic acid solution is 0.01~0.03 mol / L, the concentration of chloropalladium acid solution is 0.01~0.03 mol / L, and the concentration of silver nitrate solution is 0.01~0.03 mol / L.

4. The method for preparing the platinum-palladium-silver bifunctional nanoalloy electrocatalyst according to claim 1, characterized in that: The reaction time in step 1) is 1.5~2.5 hours; the reaction is a static reaction at room temperature. The reaction time described in step 2) is 1 to 3 hours.

5. The method for preparing the platinum-palladium-silver bifunctional nanoalloy electrocatalyst according to claim 1, characterized in that: The centrifugation mentioned in step 2) refers to centrifugation at a speed of 11000~13000 rpm for 10~15 min, washing refers to washing with ethanol, and drying refers to vacuum drying at 60~80℃ for 12~18 h.

6. A platinum-palladium-silver bifunctional nanoalloy electrocatalyst obtained by the method according to any one of claims 1 to 5.

7. The application of the platinum-palladium-silver bifunctional nanoalloy electrocatalyst according to claim 6, characterized in that: The platinum-palladium-silver bifunctional nanoalloy electrocatalyst is used for the electrocatalytic oxidation of glycerol.

8. The application of the platinum-palladium-silver bifunctional nanoalloy electrocatalyst according to claim 6, characterized in that: The platinum-palladium-silver bifunctional nanoalloy electrocatalyst is used in the cathode hydrogen evolution reaction of the water electrolysis hydrogen production process.

9. The application of the platinum-palladium-silver bifunctional nanoalloy electrocatalyst according to claim 6, characterized in that: The platinum-palladium-silver bifunctional nanoalloy electrocatalyst is used simultaneously for the electrocatalytic oxidation of glycerol and the cathode hydrogen evolution reaction in the electrocatalytic water splitting hydrogen production process.

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