A palladium-tin-gallium ternary alloy nanomaterial, a preparation method and application thereof

Abstract

The application provides a preparation method of a palladium-tin-gallium ternary alloy nanomaterial, which comprises the following steps: A) under the protection of inert gas, mixing a metal palladium precursor, a metal tin precursor, a metal gallium precursor, methylamine hydrochloride, tri-octyl phosphine and oleylamine, and performing a warming reaction to obtain a preliminary reaction solution; and B) further performing a warming reaction on the reaction solution, washing and drying the reaction solution to obtain the palladium-tin-gallium ternary alloy nanomaterial. The preparation method is simple in operation and controllable in reaction conditions, and the obtained nanomaterial is spherical in shape, uniform in size and good in dispersity. The component of the nanomaterial can be accurately controlled by adjusting the feeding ratio of the metal precursors. The carbon-loaded nanomaterial catalyst prepared by loading the nanomaterial on a carbon carrier has excellent catalytic activity and stability for the electrocatalytic oxidation reaction of various alcohols, and has important application prospects in the field of new energy technologies such as direct alcohol fuel cells.

Description

Technical Field

[0001] This invention relates to the fields of functionalized nanomaterials and electrocatalysis, and in particular to a palladium-tin-gallium ternary alloy nanomaterial, its preparation method, and its electrocatalytic application in alcohol oxidation. Background Technology

[0002] With the continued growth of global energy demand and the increasingly severe environmental problems caused by the overuse of fossil fuels, the development of efficient, clean, and sustainable energy conversion technologies has become an important direction for scientific research. Direct alcohol fuel cells, due to their advantages such as high energy density, wide availability of fuel sources, convenient storage and transportation, and environmental friendliness, are considered to be a next-generation portable power source and power source with great development potential. Among them, small-molecule alcohol fuels such as methanol, ethylene glycol, and glycerol have characteristics such as liquid properties, good stability, and relatively low toxicity. Their electrocatalytic oxidation reaction, as the anode reaction of direct alcohol fuel cells, has advantages such as high energy density and a large number of electron transfers, and has important application value in the field of new energy.

[0003] In the research of electrocatalytic oxidation catalysts for alcohols, palladium (Pd)-based materials have become an important alternative to platinum-based catalysts due to their excellent catalytic activity in alkaline media and relatively low cost. However, pure Pd catalysts suffer from rapid activity decay and poor stability during long-term operation, which severely restricts their application in practical fuel cells. To address these issues, researchers have widely adopted alloying strategies. By introducing a second metal to form a binary alloy with Pd, and utilizing electronic structure modulation and lattice strain effects, the d-band center position of Pd is optimized, and the adsorption energy of reactants and intermediates on the catalyst surface is adjusted, thereby improving catalytic activity and stability.

[0004] Among numerous Pd-based binary alloy systems, the Pd-Sn system has attracted considerable attention due to Sn's excellent oxygen affinity. Sn can significantly enhance the performance of Pd electrocatalytic oxidation reactions by modulating the electronic structure of Pd active sites. However, the ability of binary alloys to modulate Pd active sites remains relatively limited, making it difficult to overcome the inherent constraint between catalytic activity and stability.

[0005] In recent years, researchers have further introduced a third element to construct ternary alloy systems. This not only breaks the performance limitations of binary systems but also achieves dual optimization at the levels of electronic structure and lattice distortion through the synergistic effect between multiple elements, thereby greatly enhancing the intrinsic activity of the catalyst. Therefore, the development of novel Pd-based ternary alloys has become an important breakthrough in the field of electrocatalysis.

[0006] In the selection of the third element, p-block main group elements (such as Ga and In) have unique advantages over traditional transition metals. These elements possess unsaturated p orbitals, which can undergo strong orbital hybridization with the d orbitals of Pd, resulting in a more thorough reshaping of the electronic structure and thus more effective control over catalytic performance. Among them, gallium (Ga), as a typical p-block main group element, can effectively adjust the d-band center position of Pd and optimize the adsorption free energy of alcohol molecules and their oxidation intermediates on the catalyst surface. However, due to the significant differences in the standard reduction potentials and atomic radii among Ga, Sn, and Pd, how to uniformly and stably dope Ga into the Pd-Sn lattice to construct ternary alloy nanomaterials with well-defined structures and controllable compositions remains a core technical challenge in current research.

[0007] On the other hand, most methods for synthesizing Pd-Sn-Ga ternary alloys employ high-temperature solid-state reaction routes, such as arc melting combined with prolonged high-temperature annealing. These methods not only require extremely sophisticated equipment and consume enormous amounts of energy, but also have long production cycles, making large-scale production difficult. More importantly, existing research often struggles to ensure the uniformity of material morphology when introducing Ga, resulting in products that are mostly irregular blocky metals or aggregates with a wide particle size distribution. Complex external substrates are necessary for physical confinement to prevent particle agglomeration, leading to a smaller electrochemically active surface area and failing to fully realize the potential advantages of ternary alloys in catalytic performance.

[0008] Therefore, in view of the technical bottlenecks in the existing Pd-Sn-Ga ternary alloy synthesis methods, such as harsh conditions, high energy consumption, long cycle, difficulty in controlling morphology, and small specific surface area, it is very necessary to propose a mild liquid-phase synthesis strategy. Summary of the Invention

[0009] In view of this, the technical problem to be solved by the present invention is to provide a palladium-tin-gallium ternary alloy nanomaterial. The prepared nano-alloy has uniform element distribution, controllable morphology, clear structure, and high stability, which significantly improves its electrocatalytic oxidation performance for various alcohols (including methanol, ethylene glycol, and glycerol).

[0010] This invention provides a method for preparing palladium-tin-gallium ternary alloy nanomaterials, comprising the following steps:

[0011] A) Under inert gas protection, palladium precursor, tin precursor, gallium precursor, methylamine hydrochloride, trioctylphosphine and oleylamine are mixed and heated to obtain a preliminary reaction solution.

[0012] B) The reaction solution is further heated and reacted, and after washing and drying, palladium-tin-gallium ternary alloy nanomaterials are obtained.

[0013] In some specific embodiments, the palladium precursor is palladium acetylacetonate; the tin precursor is tin acetate; the gallium precursor is gallium acetylacetonate; and the mass ratio of palladium acetylacetonate, gallium acetylacetonate, and tin acetate is 1:(0.12~0.6):(0.39~0.7).

[0014] In some specific embodiments, the mass ratio of the palladium precursor to methylamine hydrochloride is 1:(0.3~0.7); the mass ratio of the palladium precursor to the volume ratio of trioctylphosphine is 1 mg:(0.006~0.01) mL.

[0015] In some specific embodiments, the flow rate of the inert gas is 80~120 mL / min.

[0016] In some specific embodiments, the rate of heating reaction in step A) is 5–15 °C / min; the reaction temperature is 80–120 °C; and the reaction time is 20–60 min.

[0017] In some specific embodiments, the rate of heating reaction in step B) is 5–15 °C / min; the reaction temperature is 250–320 °C; and the reaction time is 30–120 min.

[0018] This invention provides a palladium-tin-gallium ternary alloy nanomaterial, which is prepared by any one of the preparation methods described in the above technical solutions.

[0019] This invention provides an electrocatalytic alcohol oxidation catalyst, comprising a palladium-tin-gallium ternary alloy nanomaterial and a palladium-tin-gallium ternary alloy nanomaterial supported on a support. The palladium-tin-gallium ternary alloy nanomaterial is the palladium-tin-gallium ternary alloy nanomaterial prepared by any of the preparation methods described in the above technical solutions or the palladium-tin-gallium ternary alloy nanomaterial in the above technical solutions.

[0020] This invention provides an application of electrocatalytic alcohol oxidation at the anode of an alcohol fuel cell, comprising the electrocatalytic alcohol oxidation catalyst described in the above technical solution.

[0021] In some specific embodiments, the alcohol in the anode electrocatalytic alcohol oxidation reaction of the alcohol fuel cell includes one or more of methanol, ethylene glycol, and glycerol.

[0022] Compared with existing technologies, this invention provides a method for preparing palladium-tin-gallium ternary alloy nanomaterials, comprising the following steps: A) Under inert gas protection, palladium precursor, tin precursor, gallium precursor, methylamine hydrochloride, trioctylphosphine, and oleylamine are mixed and heated to obtain a preliminary reaction solution; B) The reaction solution is further heated and reacted, then washed and dried to obtain the palladium-tin-gallium ternary alloy nanomaterials. This invention employs a solvothermal method and successfully achieves the controllable preparation of palladium-tin-gallium ternary alloys through a dual-ligand synergistic regulation strategy of methylamine hydrochloride and the surface ligand trioctylphosphine. Furthermore, by controlling the proportion of metal precursors added, precise control of the ternary alloy composition can be achieved. By adjusting the atomic ratio of Ga and Sn, the electronic structure of the Pd sites is synergistically optimized, maximizing electrocatalytic performance and significantly enhancing the electrocatalytic oxidation activity for various alcohols (including methanol, ethylene glycol, and glycerol). This effectively overcomes the problems of slow kinetics and insufficient stability in the anode alcohol oxidation reaction of direct alcohol fuel cells, providing a new strategy for reducing fuel cell catalyst costs and promoting the development of clean energy technologies.

[0023] The method for preparing palladium-tin-gallium ternary alloy nanomaterials described in this invention is simple, and the resulting nanoparticles have regular morphology, uniform particle size distribution, and adjustable atomic ratios. The prepared carbon-supported palladium-tin-gallium catalyst is suitable for the electrocatalytic oxidation of various alcohols, with the optimal doping ratio being Pd₂(Ga₂)₂. 0.13 Sn 0.87 The nanocatalyst exhibits a mass activity of up to 3.21 A / mg for the oxidation of glycerol, ethylene glycol, and methanol in alkaline media. Pd 4.38 A / mg Pd and 1.41 A / mg Pd The specific activity for the oxidation of glycerol, ethylene glycol, and methanol is as high as 20.94 mA / cm. 2 22.29 mA / cm 2 and 7.14 mA / cm 2 Meanwhile, the catalyst exhibits excellent durability and has broad application prospects in new energy technologies such as direct liquid alcohol fuel cells and high-value conversion of biomass. Attached Figure Description

[0024] Figure 1 The Pd2(Ga) prepared in Example 1 of this invention 0.13 Sn 0.87 (a) Transmission electron microscopy, (b) XRD diffraction pattern, (c) elemental composition diagram obtained by energy-dispersive X-ray spectroscopy, and (d) elemental distribution diagram obtained by electron energy loss spectroscopy analysis of nanomaterials;

[0025] Figure 2 The Pd2(Ga) prepared in Example 2 of this invention0.2 Sn 0.8 (a) Transmission electron microscopy, (b) XRD diffraction pattern and (c) elemental composition diagram of nanomaterials obtained by energy-dispersive X-ray spectroscopy;

[0026] Figure 3 The Pd2(Ga) prepared in Example 3 of this invention 0.09 Sn 0.91 (a) Transmission electron microscopy, (b) XRD diffraction pattern and (c) elemental composition diagram of nanomaterials obtained by energy-dispersive X-ray spectroscopy;

[0027] Figure 4 The following are the transmission electron microscope (TEM) and XRD diffraction (XRD) patterns of the Pd2Sn nanomaterials prepared in Comparative Example 1 of this invention, and the elemental composition diagram measured by energy-dispersive X-ray spectroscopy (EDS).

[0028] Figure 5 The following are the transmission electron microscope (TEM) and XRD diffraction (XRD) patterns of the Pd2Ga nanomaterials prepared in Comparative Example 2 of this invention, and the elemental composition diagram measured by energy-dispersive X-ray spectroscopy (EDS).

[0029] Figure 6 In Application Example 1 of this invention, the following data are presented: (a) mass activity, (b) specific activity, (c) activity comparison, and (d) time-current curves of chronopotential method for the electrocatalytic oxidation of glycerol in a 1 M KOH + 1 M glycerol mixture, comparing ternary alloy nanosphere catalysts with different Ga doping amounts, comparative binary samples, and commercial carbon-supported Pd catalysts.

[0030] Figure 7 In Example 2 of this invention, the following are the (a) mass activity, (b) specific activity, (c) activity comparison, and (d) time-current curves of chronopotential method for the electrocatalytic oxidation of ethylene glycol in a 1 M KOH + 1 M ethylene glycol mixture, comparing ternary alloy nanosphere catalysts with different Ga doping amounts, comparative binary samples, and commercial carbon-supported Pd catalysts.

[0031] Figure 8 In Example 3 of this invention, the following data are presented: (a) mass activity, (b) specific activity, (c) activity comparison, and (d) time-current curves of chronopotential method for the electrocatalytic methanol oxidation reaction of ternary alloy nanosphere catalysts with different Ga doping amounts, comparative binary samples, and commercial carbon-supported Pd catalysts in a 1 M KOH + 1 M methanol mixture. Detailed Implementation

[0032] This invention provides a palladium-tin-gallium ternary alloy nanomaterial, its preparation method, and its application in electrocatalytic alcohol oxidation. Those skilled in the art can refer to the content of this document and appropriately modify the process parameters to achieve the desired result. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art and fall within the scope of this invention. The method and application of this invention have been described through preferred embodiments. Those skilled in the art can clearly modify or appropriately change and combine the method and application described herein without departing from the content, spirit, and scope of this invention to realize and apply the technology of this invention.

[0033] To address the technical bottlenecks of existing Pd-Sn-Ga ternary alloy synthesis methods, such as stringent conditions, high energy consumption, long cycles, difficulty in morphological control, and small specific surface area, this invention proposes a mild liquid-phase synthesis strategy. By designing palladium-tin-gallium ternary alloy nanomaterials, Ga was successfully introduced into the Pd₂Sn lattice, resulting in nanospheres with tunable composition and uniform morphology. The obtained nanomaterials exhibit high specific surface area and excellent mass transfer efficiency. Combined with the strong electronic synergistic effect among Pd, Sn, and Ga, the local electronic environment and coordination structure of the catalyst are effectively optimized, significantly reducing the reaction energy barrier of the electrocatalytic alcohol oxidation reaction and greatly improving the catalyst's activity and long-term operational stability. This invention provides a new technical route for the development of high-performance anode catalysts for direct alcohol fuel cells, with promising application prospects and industrialization potential.

[0034] This invention provides a method for preparing palladium-tin-gallium ternary alloy nanomaterials, comprising the following steps:

[0035] A) Under inert gas protection, palladium precursor, tin precursor, gallium precursor, methylamine hydrochloride, trioctylphosphine and oleylamine are mixed and heated to obtain a preliminary reaction solution.

[0036] B) The reaction solution is further heated and reacted, and after washing and drying, palladium-tin-gallium ternary alloy nanomaterials are obtained.

[0037] This invention provides a method for preparing palladium-tin-gallium ternary alloy nanomaterials. Under inert gas protection, a palladium precursor, a tin precursor, a gallium precursor, methylamine hydrochloride, trioctylphosphine, and oleylamine are mixed. Preferably, the palladium precursor, gallium precursor, tin precursor, methylamine hydrochloride, trioctylphosphine, and oleylamine are mixed under ultrasonic conditions to form a homogeneous solution. The mixed solution is then placed in a heating device, and an inert gas is continuously introduced into the mixed solution to carry out the reaction. The inert gas mentioned in this invention includes, but is not limited to, argon and nitrogen; nitrogen is preferred. In this invention, the flow rate of the N2 gas is preferably 80-120 mL / min, preferably within the range of any of the above values ​​as the upper or lower limit, and more preferably 90-110 mL / min. Specifically, it can be 90 mL / min, 95 mL / min, 100 mL / min, 105 mL / min, or 110 mL / min.

[0038] Wherein, the palladium precursor is palladium acetylacetonate; the tin precursor is tin acetate; and the gallium precursor is gallium acetylacetonate.

[0039] According to the present invention, the mass ratio of palladium acetylacetonate, gallium acetylacetonate, and tin acetate is 1:(0.12~0.6):(0.39~0.7). More preferably, it is 1:(0.3~0.4):(0.5~0.6), specifically, it can be:

[0040] 1:0.3:0.5, 1:0.35:0.55, 1:0.36:0.54, 1:0.4:0.6; preferably, the range of values ​​with any of the above values ​​as the upper or lower limit.

[0041] In some specific embodiments, the heating rate in step A) is 5–15 °C / min; specifically, it can be 5 °C / min, 8 °C / min, 10 °C / min, 12 °C / min, or 15 °C / min; the reaction temperature is 80–120 °C; specifically, it can be 80 °C, 90 °C, 100 °C, 110 °C, or 120 °C; the reaction time is 20–60 min; specifically, it can be 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, or 60 min; preferably, any of the above values ​​are within the upper or lower limit range.

[0042] In this invention, the mass ratio of the palladium precursor to methylamine hydrochloride is preferably 1:(0.3~0.7), more preferably 1:(0.35~0.65), specifically 1:0.35, 1:0.4, 1:0.45, 1:0.5, 1:0.55, 1:0.6, 1:0.65, and preferably within the range of any of the above values ​​as the upper or lower limit. During the reaction, methylamine hydrochloride acts as a morphology control agent, capable of regulating the morphology and structure of the ternary alloy nanomaterial.

[0043] In this invention, the mass-to-volume ratio of the palladium precursor to trioctylphosphine is preferably 1 mg:(0.006~0.01) mL, more preferably 1 mg:(0.007~0.01) mL, specifically 1 mg:0.007 mL, 1 mg:0.008 mL, 1 mg:0.009 mL, or 1 mg:0.01 mL, preferably within the range of any of the above values ​​as the upper or lower limit. Trioctylphosphine, as a surface ligand, can promote the nucleation and growth of alloy nanocrystals and help regulate the uniform morphology of the material.

[0044] The reaction solution is further heated to obtain palladium-tin-gallium ternary alloy nanomaterials.

[0045] In some specific embodiments, the heating rate in step B) is 5–15 °C / min; specifically, it can be 5 °C / min, 8 °C / min, 10 °C / min, 12 °C / min, or 15 °C / min, preferably within the range of any of the above values ​​as the upper or lower limit. The reaction temperature is 250–320 °C; specifically, it can be 250 °C, 260 °C, 280 °C, 300 °C, 310 °C, or 320 °C, preferably within the range of any of the above values ​​as the upper or lower limit; the reaction time is 30–120 min, specifically, it can be 30 min, 40 min, 50 min, 60 min, 80 min, 100 min, or 120 min, again preferably within the range of any of the above values ​​as the upper or lower limit.

[0046] After the reaction is completed, the present invention centrifuges and washes the mixture cooled to room temperature. The centrifugation and washing specifically includes: centrifuging the mixture cooled to room temperature, discarding the supernatant, mixing the obtained precipitate with chloroform and ethanol under ultrasonic conditions, centrifuging again, repeating the above centrifugation and washing operation multiple times, and finally washing the nanomaterials with a mixed solution of acetone and ammonium thiocyanate. After washing, the bottom product is collected and dried at room temperature to obtain the nanomaterials.

[0047] In this invention, the volume ratio of chloroform to ethanol is preferably 1:(3~5), more preferably 1:(4~4.5). Specifically, it can be 1:3, 1:3.5, 1:4, 1:4.2, 1:4.5, or 1:5, preferably within the range of any of the above values ​​as the upper or lower limit. During centrifugation and washing, chloroform can dissolve unreacted residual organic ligands in the system, and ethanol can adjust the polarity of the dispersion, promoting the removal of impurities from the surface of the nanomaterials. The combination of the two can effectively remove unreacted raw materials and byproducts while preserving the product's composition and structure, thereby improving the purity of the final product.

[0048] In this invention, the preferred ratio of acetone to ammonium thiocyanate is 1 mL:(5~20) mg, more preferably 1 mL:(10~15) mg. Specifically, it can be 1 mL:10 mg, 1 mL:12 mg, or 1 mL:15 mg, preferably within the range of any of the above values ​​as the upper or lower limit. During centrifugation and washing, ammonium thiocyanate can effectively remove organic ligands adsorbed on the surface of nanomaterials, further improving the surface cleanliness of the final product.

[0049] This invention achieves precise control over the nucleation and growth process of ternary alloys by synergistically regulating the proportions of the aforementioned palladium, tin, and gallium precursors, combined with the joint regulation of methylamine hydrochloride and trioctylphosphine ligands, and the dispersing and protective effect of oleylamine. This results in palladium-tin-gallium ternary alloy nanomaterials with uniform composition, uniform particle size, and excellent catalytic activity.

[0050] This invention provides a palladium-tin-gallium ternary alloy nanomaterial, which is prepared by any one of the preparation methods described in the above technical solutions.

[0051] The preparation method described above has been clearly described in this invention, and will not be repeated here.

[0052] This invention provides an electrocatalytic alcohol oxidation catalyst, comprising a palladium-tin-gallium ternary alloy nanomaterial and a palladium-tin-gallium ternary alloy nanomaterial supported on a support. The palladium-tin-gallium ternary alloy nanomaterial is the palladium-tin-gallium ternary alloy nanomaterial prepared by any of the preparation methods described in the above technical solutions or the palladium-tin-gallium ternary alloy nanomaterial in the above technical solutions.

[0053] In this invention, the support is preferably a carbon support, and the carbon support is preferably carbon black. In the electrocatalytic alcohol oxidation catalyst, the mass ratio of palladium-tin-gallium nanomaterials to the support is preferably 1:(0.5~4), more preferably 1:(2~3), and preferably within the range of any of the above values ​​as the upper or lower limit.

[0054] The present invention preferably prepares the above-mentioned electrocatalyst for alcohol oxidation according to the following steps:

[0055] (1) Palladium-tin-gallium nanomaterials, ethanol and chloroform were mixed, and the mixture was then centrifuged and washed. The nanoparticles were then washed with a mixture of acetone and ammonium thiocyanate. The precipitate was dried to obtain the processed sample.

[0056] (2) The treated sample is mixed with carbon support, Nafion, anhydrous ethanol and deionized water to obtain a carbon-supported palladium-tin-gallium nanomaterial catalyst dispersion.

[0057] (3) The carbon-supported palladium-tin-gallium nanocatalyst dispersion is coated onto the electrode surface and allowed to stand and dry to obtain a working electrode supported on an electrocatalytic alcohol oxidation catalyst.

[0058] This invention involves removing surface ligands from nanomaterials using ammonium thiocyanate and then combining it with carbon materials to prepare carbon-supported palladium-tin-gallium catalysts. In this invention, the preferred ratio of palladium-tin-gallium nanomaterials to ammonium thiocyanate is 1 mg:(2-5) mg, more preferably 1 mg:(3-4) mg.

[0059] In this invention, the centrifugal washing is preferably performed using a mixed solvent of chloroform and ethanol, and the volume ratio of chloroform to ethanol is preferably 1:(3~5), more preferably 1:(4~4.5).

[0060] In this invention, the drying temperature in step (1) is preferably room temperature (e.g., 20~25 ℃), and the drying time is preferably 3~8 hours, more preferably 5~6 hours.

[0061] In this invention, the treated sample is preferably mixed with a carbon support, Nafion, ethanol, and water under ultrasonic conditions. The preferred ratio of the treated sample to the carbon support, Nafion, ethanol, and water is 1 mg:(0.1~5) mg:(5~15) μL:(0.05~0.5) mL:(0.05~0.5) mL, more preferably 1 mg:(1~3) mg:(8~10) μL:(0.1~0.3) mL:(0.1~0.3) mL. Specifically, in some embodiments of this invention, it can be 1 mg:4 mg:10 μL:0.5 mL:0.5 mL. The carbon support is preferably carbon black, more preferably SuperP, and the mass concentration of Nafion is preferably 5~20%, more preferably 10~15%.

[0062] In this invention, the electrode is preferably a platinum-carbon electrode, the drying temperature is preferably room temperature (e.g., 20-25°C), and the drying time is preferably 15-30 min, more preferably 20-25 min.

[0063] This invention provides an application of electrocatalytic alcohol oxidation reaction at the anode of an alcohol fuel cell, including the electrocatalytic alcohol oxidation catalyst described in the above technical solution.

[0064] In some specific embodiments, the alcohol in the electrocatalytic alcohol oxidation reaction includes one or more of methanol, ethylene glycol, and glycerol. The concentration of the alcohol in the alcohol solution is preferably 0.5–2 mol / L, more preferably 1–1.5 mol / L; the alcohol solution also includes an alkaline reagent, preferably KOH or NaOH, and the concentration of the alkaline reagent is preferably 0.5–2 mol / L, more preferably 1–1.5 mol / L.

[0065] The present invention also provides an application of the electrocatalytic alcohol oxidation catalyst described above in the electrocatalytic alcohol oxidation reaction, using a glassy carbon electrode coated with a carbon-supported palladium-tin-gallium catalyst as the working electrode, an Hg / HgO electrode as the reference electrode and a platinum mesh as the counter electrode, and an alcohol solution as the electrolyte, and employing a three-electrode system to carry out the electrocatalytic alcohol oxidation reaction.

[0066] This invention provides a method for preparing palladium-tin-gallium ternary alloy nanomaterials, comprising the following steps: A) Under inert gas protection, palladium precursor, tin precursor, gallium precursor, methylamine hydrochloride, trioctylphosphine, and oleylamine are mixed and reacted at elevated temperature to obtain a preliminary reaction solution; B) The reaction solution is further reacted at elevated temperature, washed, and dried to obtain the palladium-tin-gallium ternary alloy nanomaterials. This invention employs a solvothermal method and successfully achieves the controllable preparation of palladium-tin-gallium ternary alloys through a dual-ligand synergistic regulation strategy of methylamine hydrochloride and the surface ligand trioctylphosphine. Furthermore, by adjusting the proportion of metal precursors added, precise control of the ternary alloy composition can be achieved. By adjusting the atomic ratio of Ga and Sn, the electronic structure of the Pd sites is synergistically optimized, maximizing electrocatalytic performance and significantly enhancing the electrocatalytic oxidation activity for various alcohols (including methanol, ethylene glycol, and glycerol). This effectively overcomes the problems of slow kinetics and insufficient stability in the anode alcohol oxidation reaction of direct alcohol fuel cells, providing a new strategy for reducing fuel cell catalyst costs and promoting the development of clean energy technologies.

[0067] The method for preparing palladium-tin-gallium ternary alloy nanomaterials described in this invention is simple, and the resulting nanoparticles have regular morphology, uniform particle size distribution, and adjustable atomic ratios. The prepared carbon-supported palladium-tin-gallium catalyst is suitable for the electrocatalytic oxidation of various alcohols, with the optimal doping ratio being Pd₂(Ga₂)₂. 0.13 Sn 0.87 The nanocatalyst exhibits a mass activity of up to 3.21 A / mg for the oxidation of glycerol, ethylene glycol, and methanol in alkaline media. Pd 4.38 A / mg Pd and 1.41 A / mgPd The specific activity for the oxidation of glycerol, ethylene glycol, and methanol is as high as 20.94 mA / cm. 2 22.29 mA / cm 2 and 7.14 mA / cm 2 Meanwhile, the catalyst exhibits excellent durability and has broad application prospects in new energy technologies such as direct liquid alcohol fuel cells and high-value conversion of biomass.

[0068] It should be understood that the expression “one or more of…” individually includes each of the objects described after the expression, as well as various different combinations of two or more of the described objects, unless otherwise understood from the context and usage. The expression “and / or” combined with three or more described objects should be understood to have the same meaning, unless otherwise understood from the context.

[0069] The terms “including,” “having,” or “containing,” including the use of their grammatical synonyms, should generally be understood as open-ended and non-restrictive, for example, not excluding other unstated elements or steps, unless otherwise specifically stated or understood from the context.

[0070] In this application, the term "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural.

[0071] In this application, "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items.

[0072] It should be understood that the order of the steps or the order in which certain actions are performed is not important as long as the invention remains operational. Furthermore, two or more steps or actions can be performed simultaneously.

[0073] The use of any and all instances or exemplary language such as “e.g.” or “including” in this document is merely intended to better illustrate the invention and is not intended to limit the scope of the invention unless the claims are made. No language in this specification should be construed as indicating that any unclaimed element is essential to the practice of the invention.

[0074] Furthermore, the numerical ranges and parameters used to define the present invention are approximate values, and the relevant values ​​in the specific embodiments have been presented as precisely as possible. However, any value inevitably contains standard deviations due to individual test methods. Therefore, unless explicitly stated otherwise, it should be understood that all ranges, quantities, values, and percentages used in this disclosure are modified with the word "approximately". Here, "approximately" generally means that the actual value is within plus or minus 10%, 5%, 1%, or 0.5% of a specific value or range.

[0075] It should be understood that in the various embodiments of this application, the order of the above processes does not imply the order of execution. Some or all steps may be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of this application.

[0076] The embodiments and comparative examples of this invention describe some examples, in which the embodiments illustrate certain implementations of the invention. However, this does not mean that the effects of the invention can only be achieved in these examples.

[0077] To further illustrate the present invention, the following describes in detail, with reference to embodiments, a palladium-tin-gallium ternary alloy nanomaterial, its preparation method, and its application in electrocatalytic alcohol oxidation.

[0078] Example 1

[0079] 30.5 mg of palladium acetylacetonate, 11 mg of gallium acetylacetonate, 16.6 mg of tin acetate, 10 mg of methylamine hydrochloride, 0.3 mL of trioctylphosphine, and 10 mL of oleylamine were placed in a three-necked flask. N2 gas was continuously bubbled into the reaction system. After 7 min, the temperature was raised to 100 °C and maintained for 30 min. Then, after 25 min, the reaction solution was heated from 100 °C to 300 °C and maintained at this temperature for 60 min. After the reaction system cooled to room temperature, the reaction solution was transferred to centrifuge tubes and washed by centrifugation at 6000 r / min. The washing was repeated three times with a mixture of chloroform and ethanol, followed by washing with a solution of ammonium thiocyanate in acetone. The resulting precipitate was dried at room temperature and named Pd2(Ga) 0.13 Sn 0.87 ).

[0080] Figure 1 The Pd2(Ga) prepared in Example 1 is shown below. 0.13 Sn 0.87Transmission electron microscopy (TEM), XRD diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), and electron energy loss spectroscopy (EES) analysis of the elemental distribution of the nanomaterials were performed. TEM showed that the prepared material exhibited good dispersion and a uniform morphology of nanospheres. The elemental composition was determined to be Pd, Ga, and Sn, with a uniform elemental distribution. The atomic ratio of Ga to Sn was approximately 5:33, indicating the successful preparation of palladium-tin-gallium (PaTiGa) nanomaterials. XRD analysis showed that the main peaks corresponded to Pd₂Sn, with a certain degree of shift, indicating that Ga was successfully introduced into the Pd₂Sn lattice, synthesizing a ternary nanoalloy.

[0081] Example 2

[0082] 30.5 mg of palladium acetylacetonate, 18.4 mg of gallium acetylacetonate, 11.8 mg of tin acetate, 20 mg of methylamine hydrochloride, 0.3 mL of trioctylphosphine, and 10 mL of oleylamine were placed in a three-necked flask. N2 gas was continuously bubbled into the reaction system. After 7 min, the temperature was raised to 100 °C and maintained for 30 min. Then, after 25 min, the reaction solution was heated from 100 °C to 300 °C and maintained at this temperature for 60 min. After the reaction system cooled to room temperature, the reaction solution was transferred to a centrifuge tube and washed by centrifugation at 6000 r / min. The washing was repeated three times with a mixture of chloroform and ethanol, followed by washing with a solution of ammonium thiocyanate in acetone. The resulting precipitate was dried at room temperature and named Pd2(Ga) 0.2 Sn 0.8 ).

[0083] Figure 2 The Pd2(Ga) prepared in Example 2 is shown below. 0.2 Sn 0.8 Transmission electron microscopy (TEM), XRD diffraction (XRD), and energy-dispersive X-ray spectroscopy (EDS) analysis of the nanomaterials were performed. TEM showed that the prepared material exhibited good dispersion and a uniform morphology of nanospheres. The elemental composition was determined to be Pd, Ga, and Sn, with a Ga to Sn atomic ratio of 8:32, indicating successful preparation of palladium-tin-gallium nanomaterials. XRD analysis revealed that the main peaks corresponded to Pd₂Sn, with a certain degree of shift, indicating that Ga was successfully introduced into the Pd₂Sn lattice, synthesizing a ternary nanoalloy.

[0084] Example 3

[0085] 30.5 mg of palladium acetylacetonate, 3.7 mg of gallium acetylacetonate, 21.3 mg of tin acetate, 10 mg of methylamine hydrochloride, 0.3 mL of trioctylphosphine, and 10 mL of oleylamine were placed in a three-necked flask. N2 gas was continuously bubbled into the reaction system. After 7 min, the temperature was raised to 100 °C and maintained for 30 min. Then, after 25 min, the reaction solution was heated from 100 °C to 300 °C and maintained at this temperature for 60 min. After the reaction system cooled to room temperature, the reaction solution was transferred to a centrifuge tube and washed by centrifugation at 6000 r / min. The washing was repeated three times with a mixture of chloroform and ethanol, followed by washing with a solution of ammonium thiocyanate in acetone. The resulting precipitate was dried at room temperature and named Pd2(Ga) 0.09 Sn 0.91 ).

[0086] Figure 3 The Pd2(Ga) prepared in Example 3 of this paper is shown. 0.09 Sn 0.91 Transmission electron microscopy (TEM), XRD diffraction (XRD), and energy-dispersive X-ray spectroscopy (EDS) analysis of the nanomaterials were performed. TEM showed that the prepared material exhibited good dispersion and a uniform morphology of nanospheres. The elemental composition was determined to be Pd, Ga, and Sn, with a Ga to Sn atomic ratio of 4:38, indicating successful preparation of palladium-tin-gallium nanomaterials. XRD analysis revealed that the main peaks corresponded to Pd₂Sn, with a certain degree of shift, indicating that Ga was successfully introduced into the Pd₂Sn lattice, synthesizing a ternary nanoalloy.

[0087] Comparative Example 1

[0088] 30.5 mg of palladium acetylacetone, 23.7 mg of tin acetate, 10 mg of methylamine hydrochloride, 0.3 mL of trioctylphosphine, and 10 mL of oleylamine were placed in a three-necked flask. N2 gas was continuously bubbled into the reaction system. After 7 min, the temperature was raised to 100 °C and maintained for 30 min. Then, after 25 min, the reaction solution was heated from 100 °C to 300 °C and maintained at this temperature for 60 min. After the reaction system cooled to room temperature, the reaction solution was transferred to a centrifuge tube and washed by centrifugation at 6000 r / min. The washing was repeated three times with a mixture of chloroform and ethanol, followed by washing with a solution of ammonium thiocyanate in acetone. The resulting precipitate was dried at room temperature and named Pd₂Sn.

[0089] Figure 4The images show the transmission electron microscope (TEM) and XRD diffraction (XRD) patterns of the Pd₂Sn nanomaterials prepared in Example 4, as well as the elemental composition determined by energy-dispersive X-ray spectroscopy (EDS). TEM indicates that the prepared material exhibits good dispersion and a uniform morphology of nanospheres. The elemental composition is Pd and Sn, with an atomic ratio of Pd to Sn of 63:37, indicating successful preparation of Pd₂Sn nanospheres. XRD results are consistent with the standard Pd₂Sn card, demonstrating the successful preparation of the binary alloy.

[0090] Comparative Example 2

[0091] 30.5 mg of palladium acetylacetonate, 36.7 mg of gallium acetylacetonate, 20 mg of methylamine hydrochloride, 0.03 mL of trioctylphosphine, and 10 mL of oleylamine were placed in a three-necked flask. N2 gas was continuously bubbled into the reaction system. After 7 min, the temperature was raised to 100 °C and maintained for 30 min. Then, after 15 min, the reaction solution was heated from 100 °C to 220 °C and maintained at this temperature for 60 min. After the reaction system cooled to room temperature, the reaction solution was transferred to a centrifuge tube and washed by centrifugation at 6000 r / min. The washing was repeated three times with a mixture of chloroform and ethanol, followed by washing with an ammonium thiocyanate solution in acetone. The resulting precipitate was dried at room temperature and named Pd₂Ga.

[0092] Figure 5 The images show the transmission electron microscope (TEM) and XRD diffraction (XRD) patterns of the Pd₂Ga nanomaterials prepared in Example 5, as well as the elemental composition determined by energy-dispersive X-ray spectroscopy (EDS). TEM indicates that the prepared material exhibits good dispersion and a uniform morphology of nanospheres. The measured elemental composition is Pd and Ga, with an atomic ratio of Pd to Ga of 61:39, indicating successful preparation of the alloy nanomaterial. The XRD results are consistent with the standard Pd₂Ga card, demonstrating the successful preparation of the binary alloy.

[0093] Application Example 1

[0094] The steps for testing the performance of the electrocatalytic glycerol oxidation reaction are as follows:

[0095] The carbon-supported palladium-tin-gallium catalysts prepared in Examples 1-3, the carbon-supported Pd₂Sn and Pd₂Ga catalysts prepared in the comparative examples, and a commercially available carbon-supported Pd catalyst were respectively loaded onto electrodes as working electrodes. A Hg / HgO electrode was used as the reference electrode, a platinum mesh as the counter electrode, and a 1 M KOH + 1 M glycerol solution as the electrolyte. Cyclic voltammetry and chronopotentiometric methods were performed on an electrochemical workbench. The scan rate for cyclic voltammetry was 50 mV / s, and the test potential for chronopotentiometric method was -0.1 V.

[0096] Figure 6Figure a shows a comparison of cyclic voltammetry curves for different catalysts used in the glycerol oxidation reaction in this application example. The results indicate that the carbon-supported Pd2(Ga) catalyst in Example 1... 0.13 Sn 0.87 The catalyst electrode exhibits optimal mass activity at 3.21 A / mg. Pd It is significantly higher than that of carbon-supported Pd2(Ga) in Example 2. 0.2 Sn 0.8 Catalyst electrode (1.55 A / mg) Pd Carbon-supported Pd2(Ga) in Example 3 0.09 Sn 0.91 Catalyst electrode (1.06 A / mg) Pd The carbon-supported Pd₂Sn catalyst electrode in the comparative example (0.58 A / mg) Pd Carbon-supported Pd₂Ga catalyst electrode (0.54 A / mg) Pd ) and commercial carbon-supported Pd catalyst electrode (0.68 A / mg Pd Therefore, the palladium-tin-gallium ternary alloy nanomaterial catalyst described in this invention can effectively improve the quality activity of the electrocatalytic oxidation reaction of glycerol.

[0097] Figure 6 In Figure b, the specific activity is calculated after normalizing the current to the corresponding electrochemical active area. In Example 1, the carbon-supported Pd2(Ga) 0.13 Sn 0.87 The catalyst electrode exhibits optimal specific activity of 20.94 mA / cm². 2 The value is significantly higher than that of carbon-supported Pd2(Ga) in Example 2. 0.2 Sn 0.8 The specific activity of the catalyst electrode is 8.99 mA / cm². 2 In Example 3, carbon-supported Pd2(Ga) 0.09 Sn 0.91 The specific activity of the catalyst electrode is 7.68 mA / cm². 2 The specific activity of carbon-supported Pd₂Sn in the comparative example was 4.29 mA / cm². 2 The specific activity of the Pd₂Ga catalyst electrode is 2.66 mA / cm². 2 The specific activity of the commercial carbon-supported Pd catalyst electrode is 6.51 mA / cm². 2 This indicates that palladium-tin-gallium ternary alloy nanomaterial catalysts can effectively improve the specific activity of the electrocatalytic oxidation of glycerol.

[0098] Figure 6In the figure, c represents a comparison of the electrocatalytic performance of different palladium-tin-gallium alloys, binary alloys, and commercial Pd / C catalysts in the electrocatalysis of glycerol. It can be seen that the prepared palladium-tin-gallium catalyst has excellent mass activity and specific activity.

[0099] Figure 6 Figure d shows a comparison of the chronopotential testing curves of different catalysts used in the glycerol oxidation reaction in this application example. During the 10000 s test period, the carbon-supported palladium-tin-gallium catalysts prepared in Examples 1-3 all exhibited higher mass activity compared to the carbon-supported Pd₂Sn, Pd₂Ga in the comparative examples and the commercially available carbon-supported Pd catalyst, indicating that the palladium-tin-gallium ternary alloy nanomaterial catalyst of a certain proportion described in this invention can effectively improve the stability of electrocatalytic glycerol oxidation. In addition, the carbon-supported Pd₂(Ga) catalyst in Example 1... 0.13 Sn 0.87 The catalyst electrode also exhibits higher mass activity compared to the catalyst electrodes of Examples 2 and 3, indicating that the catalyst with a Ga / Sn atomic ratio of 0.13:0.87 has the best electrocatalytic stability for glycerol oxidation in the palladium-tin-gallium nanoalloy system.

[0100] Application Example 2

[0101] The steps for testing the performance of the electrocatalytic ethylene glycol oxidation reaction are as follows:

[0102] The carbon-supported palladium-tin-gallium catalysts prepared in Examples 1-3, the carbon-supported Pd₂Sn and Pd₂Ga catalysts prepared in the comparative examples, and a commercially available carbon-supported Pd catalyst were respectively loaded onto electrodes as working electrodes. A Hg / HgO electrode was used as the reference electrode, a platinum mesh as the counter electrode, and a 1 M KOH + 1 M ethylene glycol solution was used as the electrolyte. Cyclic voltammetry and chronopotentiometric methods were performed on an electrochemical workbench. The scan rate for cyclic voltammetry was 50 mV / s, and the test potential for chronopotentiometric method was -0.1 V.

[0103] Figure 7 Figure a shows a comparison of cyclic voltammetry curves for different catalysts used in the ethylene glycol oxidation reaction in this application example. The results indicate that the carbon-supported Pd2(Ga) catalyst in Example 1... 0.13 Sn 0.87 The catalyst electrode exhibits optimal mass activity at 4.38 A / mg. Pd It is significantly higher than that of carbon-supported Pd2(Ga) in Example 2. 0.2 Sn 0.8 Catalyst electrode (3.23 A / mg) Pd Carbon-supported Pd2(Ga) in Example 3 0.09 Sn 0.91 Catalyst electrode (1.71 A / mg) PdThe carbon-supported Pd₂Sn catalyst electrode in the comparative example (1.59 A / mg) Pd Carbon-supported Pd₂Ga catalyst electrode (1.20 A / mg) Pd ) and commercial carbon-supported Pd catalyst electrode (1.02 A / mg Pd Therefore, the palladium-tin-gallium ternary alloy nanomaterial catalyst described in this invention can effectively improve the mass activity of the electrocatalytic ethylene glycol oxidation reaction.

[0104] Figure 7 The specific activity result is calculated by normalizing the current to the corresponding electrochemical active area in section b. In Example 1, the carbon-supported Pd2(Ga) 0.13 Sn 0.87 The catalyst electrode exhibits optimal specific activity of 22.29 mA / cm². 2 The value is significantly higher than that of carbon-supported Pd2(Ga) in Example 2. 0.2 Sn 0.8 The specific activity of the catalyst electrode is 18.67 mA / cm². 2 In Example 3, carbon-supported Pd2(Ga) 0.09 Sn 0.91 The specific activity of the catalyst electrode is 12.28 mA / cm². 2 The specific activity of carbon-supported Pd₂Sn in the comparative example was 11.72 mA / cm². 2 The specific activity of the Pd₂Ga catalyst electrode is 7.68 mA / cm². 2 The specific activity of the commercial carbon-supported Pd catalyst electrode is 9.85 mA / cm². 2 This indicates that palladium-tin-gallium ternary alloy nanomaterial catalysts can effectively improve the specific activity of the electrocatalytic ethylene glycol oxidation reaction.

[0105] Figure 7 In the figure, c represents a comparison of the electrocatalytic performance of different palladium-tin-gallium alloys, binary alloys, and commercial Pd / C catalysts in ethylene glycol electrocatalysis. It can be seen that the prepared palladium-tin-gallium catalyst has excellent mass activity and specific activity.

[0106] Figure 7 Figure d shows a comparison of the chronopotential test curves of different catalysts used in the ethylene glycol oxidation reaction in this application example. During the 10000 s test period, the carbon-supported palladium-tin-gallium catalysts prepared in Examples 1-3 all exhibited higher mass activity compared to the carbon-supported Pd₂Sn, Pd₂Ga in the comparative examples and the commercially available carbon-supported Pd catalyst, indicating that the palladium-tin-gallium ternary alloy nanomaterial catalyst of a certain proportion described in this invention can effectively improve the stability of electrocatalytic ethylene glycol oxidation. In addition, the carbon-supported Pd₂(Ga) catalyst in Example 1... 0.13 Sn 0.87The catalyst electrode also exhibits higher mass activity compared to the catalyst electrodes of Examples 2 and 3, indicating that the catalyst with a Ga / Sn atomic ratio of 0.13:0.87 has the best electrocatalytic stability for ethylene glycol oxidation in the palladium-tin-gallium nanoalloy system.

[0107] Application Example 3

[0108] The steps for testing the performance of the electrocatalytic methanol oxidation reaction are as follows:

[0109] The carbon-supported palladium-tin-gallium catalysts prepared in Examples 1-3, the carbon-supported Pd₂Sn and Pd₂Ga catalysts prepared in the comparative examples, and the commercially available carbon-supported Pd catalyst were respectively loaded onto electrodes as working electrodes. A Hg / HgO electrode was used as the reference electrode, a platinum mesh as the counter electrode, and a 1 M KOH + 1 M methanol solution as the electrolyte. Cyclic voltammetry and chronopotentiometric methods were performed on an electrochemical workbench. The scan rate for cyclic voltammetry was 50 mV / s, and the test potential for chronopotentiometric method was -0.1 V.

[0110] Figure 8 Figure a shows a comparison of cyclic voltammetry curves for different catalysts used in the methanol oxidation reaction in this application example. The results indicate that the carbon-supported Pd2(Ga) catalyst in Example 1... 0.13 Sn 0.87 The catalyst electrode exhibits optimal mass activity of 1.41 A / mg. Pd It is significantly higher than that of carbon-supported Pd2(Ga) in Example 2. 0.2 Sn 0.8 Catalyst electrode (0.67 A / mg) Pd Carbon-supported Pd2(Ga) in Example 3 0.09 Sn 0.91 Catalyst electrode (0.36 A / mg) Pd The carbon-supported Pd₂Sn catalyst electrode in the comparative example (0.47 A / mg) Pd Carbon-supported Pd₂Ga catalyst electrode (0.26 A / mg) Pd ) and commercial carbon-supported Pd catalyst electrode (0.28 A / mg Pd Therefore, the palladium-tin-gallium ternary alloy nanomaterial catalyst described in this invention can effectively improve the quality activity of the electrocatalytic methanol oxidation reaction.

[0111] Figure 8 The specific activity result is calculated by normalizing the current to the corresponding electrochemical active area in section b. In Example 1, the carbon-supported Pd2(Ga) 0.13 Sn 0.87 The catalyst electrode exhibits optimal specific activity of 7.14 mA / cm². 2The value is significantly higher than that of carbon-supported Pd2(Ga) in Example 2. 0.2 Sn 0.8 The specific activity of the catalyst electrode is 3.86 mA / cm². 2 In Example 3, carbon-supported Pd2(Ga) 0.09 Sn 0.91 The specific activity of the catalyst electrode is 2.79 mA / cm². 2 The specific activity of carbon-supported Pd₂Sn in the comparative example was 3.42 mA / cm². 2 The specific activity of the Pd₂Ga catalyst electrode is 1.82 mA / cm². 2 The specific activity of the commercial carbon-supported Pd catalyst electrode is 2.72 mA / cm². 2 This indicates that palladium-tin-gallium ternary alloy nanomaterial catalysts can effectively improve the specific activity of the electrocatalytic methanol oxidation reaction.

[0112] Figure 8 In the figure, c represents a comparison of the electrocatalytic methanol performance of different palladium-tin-gallium alloys, binary alloys, and commercial Pd / C catalysts. It can be seen that the prepared palladium-tin-gallium catalyst has excellent mass activity and specific activity.

[0113] Figure 8 Figure d shows a comparison of chronopotential testing curves for different catalysts used in the methanol oxidation reaction in this application example. During the 10000 s test period, the carbon-supported palladium-tin-gallium catalysts prepared in Examples 1-3 all exhibited higher mass activity compared to the carbon-supported Pd₂Sn, Pd₂Ga, and commercially available carbon-supported Pd catalysts in the comparative examples, indicating that the palladium-tin-gallium ternary alloy nanomaterial catalyst of a certain proportion described in this invention can effectively improve the stability of electrocatalytic methanol oxidation. In addition, the carbon-supported Pd₂(Ga) catalyst in Example 1... 0.13 Sn 0.87 The catalyst electrode also exhibits higher mass activity compared to the catalyst electrodes of Examples 2 and 3, indicating that the catalyst with a Ga / Sn atomic ratio of 0.13:0.87 has the best electrocatalytic methanol oxidation stability in the palladium-tin-gallium nanoalloy system.

[0114] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing palladium-tin-gallium ternary alloy nanomaterials, comprising the following steps: A) Under inert gas protection, palladium precursor, tin precursor, gallium precursor, methylamine hydrochloride, trioctylphosphine and oleylamine are mixed and heated to obtain a preliminary reaction solution. B) The reaction solution is further heated and reacted, and after washing and drying, palladium-tin-gallium ternary alloy nanomaterials are obtained.

2. The preparation method according to claim 1, characterized in that, The palladium precursor is palladium acetylacetonate; the tin precursor is tin acetate; the gallium precursor is gallium acetylacetonate; the mass ratio of palladium acetylacetonate, gallium acetylacetonate, and tin acetate is 1:(0.12~0.6):(0.39~0.7).

3. The preparation method according to claim 1, characterized in that, The mass ratio of the palladium precursor to methylamine hydrochloride is 1:(0.3~0.7); the mass ratio of the palladium precursor to the volume ratio of trioctylphosphine is 1 mg:(0.006~0.01) mL.

4. The preparation method according to claim 1, characterized in that, The flow rate of the inert gas is 80~120 mL / min.

5. The preparation method according to claim 1, characterized in that, In step A), the rate of heating the reaction is 5–15 °C / min; the reaction temperature is 80–120 °C; and the reaction time is 20–60 min.

6. The preparation method according to claim 1, characterized in that, In step B), the rate of heating the reaction is 5–15 °C / min; the reaction temperature is 250–320 °C; and the reaction time is 30–120 min.

7. A palladium-tin-gallium ternary alloy nanomaterial, characterized in that, It is prepared by the preparation method according to any one of claims 1 to 6.

8. An electrocatalytic alcohol oxidation catalyst, comprising palladium-tin-gallium ternary alloy nanomaterials and palladium-tin-gallium ternary alloy nanomaterials supported on a support, wherein the palladium-tin-gallium ternary alloy nanomaterials are palladium-tin-gallium ternary alloy nanomaterials prepared by the preparation method according to any one of claims 1 to 6 or palladium-tin-gallium ternary alloy nanomaterials according to claim 7.

9. An application of an alcohol oxidation reaction at the anode of an alcohol fuel cell, characterized in that, Including the electrocatalytic alcohol oxidation catalyst as described in claim 8.

10. The application according to claim 9, characterized in that, The alcohol in the alcohol fuel cell includes one or more of methanol, ethylene glycol, and glycerol.

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