Hydrogen-mediated d-p-f orbital hybridization metal nanomaterials, methods of making, and electrocatalysts

Abstract

Hydrogen-mediated d-p-f orbital hybridization metal nanomaterial, preparation method and electrocatalyst belong to the field of electrocatalyst, the metal nanomaterial contains d-region metal, p-region metal, f-region metal and carbon carrier, and the molar ratio of the three d-region metal, p-region metal and f-region metal is any ratio, and the molar ratio of any one of the three metals to the carbon carrier is 1:0.1-10.The present application realizes the orbital hybridization of d-p-f by taking carbon as the carrier under the hydrogen reduction condition, prepares the nano metal as the electrocatalyst, solves the problems of poor dispersibility and easy clustering of metal nanoparticles, and further improves the catalytic activity.

Description

Technical Field

[0001] This invention relates to the field of electrocatalysts for electrocatalytic pollution treatment, specifically to hydrogen-mediated dpf orbital hybrid metal nanomaterials, their preparation methods, and electrocatalysts. Background Technology

[0002] With the development of science and technology and the continuous growth of the economy, human society is increasingly concerned about global issues such as environmental pollution and energy shortages. Against this backdrop, how to efficiently convert pollutants, waste, and low-value-added compounds generated in industrial production into high-value-added products has become an important direction for research on resource recycling and sustainable development. Traditional treatment methods typically rely on harsh conditions such as high temperature and high pressure, which not only consumes a lot of energy but also easily generates toxic byproducts during the reaction process, causing secondary pollution. In contrast, electrocatalysis technology, with its mild reaction conditions, excellent energy consumption control, and environmentally friendly characteristics, can achieve efficient conversion and resource utilization of pollutants at room temperature and pressure, while significantly reducing the emission of harmful substances, demonstrating broad application prospects.

[0003] Extensive research has been conducted on the synthesis of electrocatalysts. Liu et al. introduced 3d metals such as Fe, Co, Ni, and Cu into WO2 to regulate the hybridization between the 3d and 5d orbitals of the metals, thereby optimizing the coordination strength of *H and improving catalytic activity during the hydrogen evolution reaction. Han et al. prepared electrocatalysts by doping Ga and Cu and conducted electrocatalytic tests on carbon dioxide reduction, confirming that the pd orbital hybridization between Ga and Cu promotes the adsorption of *CO intermediates, thereby promoting the coupling of CC.

[0004] Despite significant research findings on the coupling of dd, dp, and df orbitals in regulating electrocatalytic activity, several key bottlenecks remain in the underlying mechanisms. For dp orbital hybridization, the energy level distribution of the hybrid orbitals is relatively simple, and the electron delocalization range is limited, making it difficult to effectively adapt to the complex electronic structure regulation requirements in multi-metal synergistic catalysis scenarios. Meanwhile, fd orbital hybridization is limited by the weak diffusion of the f orbital electron cloud, the extremely low matching degree with the d orbital energy level, and the insufficient orbital overlap, making it difficult for it to form an efficient and stable hybrid configuration with the d orbital. Summary of the Invention

[0005] The purpose of this invention is to provide a hydrogen-mediated dpf orbital hybrid metal nanomaterial, its preparation method, and an electrocatalyst. Using carbon as a support, dpf orbital hybridization is achieved under special conditions to prepare nano-metals as electrocatalysts, solving the problems of poor dispersion and easy clustering of metal nanoparticles, and further improving catalytic activity.

[0006] The technical solution adopted by the present invention to achieve the above-mentioned technical objective is as follows: hydrogen-mediated dpf orbital hybrid metal nanomaterial, which contains d-block metal, p-block metal, f-block metal and carbon support, and the molar ratio of the three metals is arbitrary, and the molar ratio of any one of the three metals to the carbon support is 1:0.1-10.

[0007] As an optimized scheme for the aforementioned hydrogen-mediated dpf orbital hybrid metal nanomaterials, the d-region metal is cobalt, iron, manganese, copper, palladium, platinum, rhodium, nickel, or ruthenium.

[0008] As another optimized option for the aforementioned hydrogen-mediated dpf orbital hybrid metal nanomaterials, the p-region metal is gallium, indium, bismuth, tin, or lead.

[0009] As another optimized scheme for the above-mentioned hydrogen-mediated dpf orbital hybrid metal nanomaterials, the f-block metal is cerium, praseodymium, lanthanum, neodymium, dysprosium, samarium, terbium, europium, erbium, lutetium, or gadolinium.

[0010] As another optimized option for the aforementioned hydrogen-mediated dpf orbital hybrid metal nanomaterials, the carbon support is carbon black, carbon nanotubes, or graphene.

[0011] The above-mentioned method for preparing hydrogen-mediated dpf orbital hybrid metal nanomaterials involves uniformly mixing a precursor of d-block metal, a precursor of p-block metal, a precursor of f-block metal, and a carbon support, and then heating and reducing them at a temperature of 300-800℃ for 1-24 hours in a hydrogen atmosphere to obtain the product.

[0012] As an optimized scheme for the preparation method of the above-mentioned hydrogen-mediated dpf orbital hybrid metal nanomaterials, the precursor of the d-region metal is cobalt chloride, ferric chloride, manganese chloride, ferrous chloride, copper oxide, sodium tetrachloropalladate, potassium chloroplatinate, rhodium acetylacetonate, nickel acetylacetonate, or ruthenium acetylacetonate; the precursor of the p-region metal is gallium acetylacetonate, indium chloride, bismuth oxide, tin tetrachloride, or lead acetylacetonate; and the precursor of the f-region metal is cerium acetylacetonate, cerium oxide, praseodymium acetylacetonate, lanthanum acetylacetonate, neodymium acetylacetonate, dysprosium acetylacetonate, samarium acetylacetonate, terbium acetylacetonate, europium acetylacetonate, erbium acetylacetonate, lutetium acetylacetonate, or gadolinium acetylacetonate.

[0013] As another optimized method for preparing hydrogen-mediated dpf orbital hybrid metal nanomaterials, the "uniform mixing" refers to dispersing the precursors of d-region metal, p-region metal, and f-region metal and the carbon support in a solvent, ultrasonically treating them to form a uniform and stable solution, and then magnetically stirring them until homogeneous before vacuum drying.

[0014] As another optimized method for preparing the above-mentioned hydrogen-mediated dpf orbital hybrid metal nanomaterials, the solvent is deionized water, ethanol, benzyl alcohol, formic acid, or acetic acid.

[0015] An electrocatalyst made from the aforementioned hydrogen-mediated dpf orbital hybrid metal nanomaterial.

[0016] Compared with the prior art, the present invention has the following beneficial effects: 1) This invention utilizes carbon as a support to achieve orbital hybridization of dpf under hydrogen reduction conditions, preparing nano-metals as electrocatalysts. This solves the problems of poor dispersion and easy clustering of metal nanoparticles, further enhancing catalytic activity. During the hydrogen thermal reduction process, the oxygen-containing functional groups on the carbon support surface undergo a reduction reaction with hydrogen, generating water and carbon-hydrogen bonds (-C-OH+H2→-C-H+H2O). This removes impurity functional groups from the carbon support surface, increases the active sites on the carbon support surface, and simultaneously improves the conductivity of the carbon support, providing a stable support environment for the dispersion and orbital hybridization of the three metals. The d-block metal is reduced to elemental metal (MX). n +n / 2H₂→M+nHX), the d orbitals are in an incompletely filled state, possessing the electronic basis for hybridization with f and p orbitals; the p-block metal is also reduced to a metallic element, the p orbital electron cloud remains active, and can interact electronically with the d orbitals of the transition metal, laying the foundation for subsequent dp orbital hybridization; the f-block metal is first reduced to a lanthanide element, then the lanthanide element reacts with hydrogen to form lanthanide hydrides (LnX). n +n / 2H2→M+nHX、Ln+n / 2H2→LnH n The formation of lanthanide hydrides provides core support for reducing the energy level difference between f and d orbitals and enhancing orbital hybridization. 2) The hydrogen-mediated dpf orbital hybridization network established in this invention overcomes the limitations of traditional dd, dp, and df hybridization in the following two aspects: Firstly, the introduced lanthanide hydride (LnH) can significantly modulate the band position of the f orbital of the Ln element, effectively reducing the energy level difference between it and the metal d orbital, creating thermodynamic conditions for strong orbital coupling; secondly, the p orbital of the p-block element has suitable energy levels and spatial expansion, which can act as an electron bridge between the metal d orbital and the Ln f orbital, enhancing orbital overlap and electronic synergy among the three, promoting the formation of the hybridization network. The synergistic effect of the two enables hydrogen-mediated dpf orbital hybridization to overcome the technical problem of excessive energy level difference between f and p orbitals, which prevents direct hybridization, and achieves wide-range tunability of hybrid orbital energy levels; at the same time, the synergistic hybridization of the three greatly expands the electron delocalization range, increases the number of electron transport paths, and significantly improves electron transport efficiency. Attached Figure Description

[0017] Figure 1 This is a transmission electron microscope (TEM) image from Example 1; Figure 2 This is a mapping diagram of each element in Example 1; Figure 3 The X-ray photoelectron spectrum of Pt in Example 1; Figure 4 The X-ray photoelectron spectrum of Ga in Example 1; Figure 5 The X-ray photoelectron spectrum of La in Example 1; Figure 6 This is the density of states diagram of Pt atoms obtained through simulation calculation in Example 1; Figure 7 This is the density of states diagram of Ga atoms obtained through simulation calculation in Example 1; Figure 8 This is the density of states diagram of the La atom obtained through simulation calculation in Example 1. Detailed Implementation

[0018] To better understand the present invention, the technical solution of the present invention will be clearly and completely described below. However, the described embodiments are only some embodiments of the present invention, and the content of the present invention is not limited to the following embodiments.

[0019] Hydrogen-mediated dpf orbital hybrid metal nanomaterials were synthesized in a one-step process using p-block, d-block, and f-block elements. The hydrogen-mediated dpf orbital hybridization influences electron transfer, thereby improving catalyst performance. The addition of a carbon support addresses the issues of easy agglomeration and poor dispersibility of nanoparticles, exposing more active sites and further enhancing catalytic activity. The synthesized metallic nanomaterials contain d-block metals, p-block metals, f-block metals and carbon support, and the molar ratio of the three metals is arbitrary, with the molar ratio of any one of these three metals to the carbon support being 1:0.1-10. The d-region metal is cobalt, iron, manganese, copper, palladium, platinum, rhodium, nickel, or ruthenium; the p-region metal is gallium, indium, bismuth, tin, or lead; the f-region metal is cerium, praseodymium, lanthanum, neodymium, dysprosium, samarium, terbium, europium, erbium, lutetium, or gadolinium; and the carbon carrier is carbon black, carbon nanotubes, or graphene.

[0020] The above-mentioned method for preparing hydrogen-mediated dpf orbital hybrid metal nanomaterials involves uniformly mixing a precursor of d-block metal, a precursor of p-block metal, a precursor of f-block metal, and a carbon support, and then heating and reducing them at a temperature of 300-800℃ for 1-24 hours in a hydrogen atmosphere to obtain the product. The precursors of the d-region metals are cobalt chloride, ferric chloride, manganese chloride, ferrous chloride, copper oxide, sodium tetrachloropalladate, potassium chloroplatinate, rhodium acetylacetonate, nickel acetylacetonate, or ruthenium acetylacetonate; the precursors of the p-region metals are gallium acetylacetonate, indium chloride, bismuth oxide, tin tetrachloride, or lead acetylacetonate; and the precursors of the f-region metals are cerium acetylacetonate, cerium oxide, praseodymium acetylacetonate, lanthanum acetylacetonate, neodymium acetylacetonate, dysprosium acetylacetonate, samarium acetylacetonate, terbium acetylacetonate, europium acetylacetonate, erbium acetylacetonate, lutetium acetylacetonate, or gadolinium acetylacetonate. The term "uniform mixing" refers to dispersing the precursors of the d-region metal, p-region metal, and f-region metal, along with the carbon support, in a solvent, ultrasonically treating them to form a homogeneous and stable solution, then magnetically stirring until homogeneous, followed by vacuum drying. The magnetic stirring speed is 100-1000 rpm, and the stirring time is 1-24 hours; the vacuum drying temperature is 40-80℃, and the drying time is 12-48 hours. The solvent is deionized water, ethanol, benzyl alcohol, formic acid, or acetic acid; An electrocatalyst made from the aforementioned hydrogen-mediated dpf orbital hybrid metal nanomaterial.

[0021] To make the disclosure of this invention more complete, more specific embodiments will be used to explain and illustrate it below.

[0022] Example 1 like Figure 1 As shown, this embodiment provides a method for synthesizing hydrogen-mediated dpf orbital hybrid metal nanomaterials, the specific steps of which are as follows: Accurately weigh 83.3 mmol of carbon black, 8.33 mmol of platinum acetylacetone, 8.33 mmol of gallium acetylacetone, and 8.33 mmol of lanthanum acetylacetone into a clean beaker. Add 200 mL of phenylethanol, add a magnetic stir bar, and stir on a magnetic stirrer for 3 hours to obtain a uniformly dispersed mixed solution. Place the solution in a vacuum drying oven and dry under vacuum at 80°C for 48 hours to obtain a solid powder. Transfer the solid powder to a clean porcelain boat and place it in a tube furnace. Heat at 800°C for 1 hour under a hydrogen atmosphere to finally obtain Pt-Ga-LaH nanomaterials. The preparation process is as follows: Figure 1 As shown.

[0023] Figure 1 This is a projection electron microscope (TEM) image of the nanomaterial in this embodiment. The alloy nanoparticles are uniformly distributed on the carrier and have a uniform morphology. Figure 2 This is a mapping diagram of each element in the nanomaterial in this embodiment, showing that each element is evenly distributed.

[0024] Figures 3-5The image shown is the X-ray photoelectron spectrum (XPS) of the nanomaterial in this embodiment. The XPS shows the valence states of each element. Pt is mainly in the 0 valence state, Ga is in the 0 valence state, and La is in the +3 valence state.

[0025] Figures 6-8 The density of states (DOS) diagram of each atom in the nanomaterial of this embodiment, obtained through simulation calculation, reveals that after the formation of lanthanide hydrides, the Laf orbitals shift towards the Fermi level, reducing the energy difference with the Ptd orbitals and further enhancing the overlap between the Laf and Ptd orbitals, thus promoting their direct hybridization. Furthermore, the broadened Gap orbitals exhibit strong orbital overlap with both the Ptd and Cef orbitals, becoming highly efficient electron transfer bridging sites, further strengthening the gradient hybridization of the dpf orbitals, ultimately constructing a unique hydrogen-mediated dpf orbital hybridization network.

[0026] Example 2 Accurately weigh 66.7 mmol of carbon nanotubes, 13.34 mmol of ferric chloride, 13.34 mmol of tin tetrachloride, and 13.34 mmol of cerium acetylacetonate into a clean beaker. Add 100 mL of deionized water, add a magnetic stir bar, and stir on a magnetic stirrer for 2 hours to obtain a uniformly dispersed mixed solution. Place the solution in a vacuum drying oven and dry under vacuum at 60°C for 24 hours to obtain a solid powder. Transfer the solid powder to a clean ceramic boat and place it in a tube furnace. Heat at 600°C for 8 hours under a hydrogen atmosphere to finally obtain Fe-Sn-CeH nanomaterials.

[0027] Example 3 Accurately weigh 54.2 mmol of carbon nanotubes, 32.52 mmol of cobalt acetate, 5.42 mmol of lead acetylacetone, and 542 mmol of dysprosium acetylacetone into a clean beaker. Add 80 mL of phenylethanol, add a magnetic stir bar, and stir on a magnetic stirrer for 2 hours to obtain a uniformly dispersed mixed solution. Place the solution in a vacuum drying oven and dry under vacuum at 45°C for 24 hours to obtain a solid powder. Transfer the solid powder to a clean ceramic boat and place it in a tube furnace. Heat at 450°C for 16 hours under a hydrogen atmosphere to finally obtain Co-Pb-DyH nanomaterials.

[0028] Example 4 Accurately weigh 41.7 mmol of carbon nanotubes, 4.17 mmol of copper chloride, 13.9 mmol of gallium chloride, and 125.1 mmol of neodymium acetylacetone into a clean beaker. Add 80 mL of phenylethanol, add a magnetic stir bar, and stir on a magnetic stirrer for 1 h to obtain a uniformly dispersed mixed solution. Place the solution in a vacuum drying oven and dry under vacuum at 50 °C for 24 h to obtain a solid powder. Transfer the solid powder to a clean ceramic boat and place it in a tube furnace. Heat at 400 °C for 12 h under a hydrogen atmosphere to finally obtain Cu-Ga-NdH nanomaterials.

[0029] Example 5 Accurately weigh 25.0 mmol of graphene, 200.0 mmol of sodium tetrachloropalladium, 50.0 mmol of indium chloride, and 5.0 mmol of praseodymium acetylacetonate into a clean beaker. Add 150 mL of ethanol, add a magnetic stir bar, and stir on a magnetic stirrer for 1 h to obtain a uniformly dispersed mixed solution. Place the solution in a vacuum drying oven and dry under vacuum at 40 °C for 24 h to obtain a solid powder. Transfer the solid powder to a clean ceramic boat and place it in a tube furnace. Heat at 300 °C for 24 h under a hydrogen atmosphere to finally obtain Pd-In-PrH nanomaterials.

[0030] Example 6 Accurately weigh 12.5 mmol of graphene, 37.5 mmol of manganese chloride, 12.5 mmol of bismuth oxide, and 2.5 mmol of samarium acetylacetonate into a clean beaker. Add 100 mL of formic acid, add a magnetic stir bar, and stir on a magnetic stirrer for 1.5 h to obtain a uniformly dispersed mixed solution. Place the solution in a vacuum drying oven and dry under vacuum at 60 °C for 30 h to obtain a solid powder. Transfer the solid powder to a clean ceramic boat and place it in a tube furnace. Heat at 550 °C for 8 h under a hydrogen atmosphere to finally obtain Mn-Bi-SmH nanomaterials.

[0031] Example 7 Accurately weigh 8.33 mmol of graphene, 33.33 mmol of platinum acetylacetone, 58.31 mmol of bismuth chloride, and 8.33 mmol of terbium acetylacetone into a clean beaker. Add 150 mL of phenylethanol, add a magnetic stir bar, and stir on a magnetic stirrer for 2 hours to obtain a uniformly dispersed mixed solution. Place the solution in a vacuum drying oven and dry under vacuum at 55°C for 18 hours to obtain a solid powder. Transfer the solid powder to a clean ceramic boat and place it in a tube furnace. Heat at 750°C for 5 hours under a hydrogen atmosphere to finally obtain Pt-Bi-TbH nanomaterials.

[0032] Example 8 Accurately weigh 6.67 mmol of carbon black, 33.33 mmol of rhodium acetylacetone, 3.33 mmol of lead acetylacetone, and 66.7 mmol of europium acetylacetone into a clean beaker. Add 100 mL of acetic acid, add a magnetic stir bar, and stir on a magnetic stirrer for 3 hours to obtain a uniformly dispersed mixed solution. Place the solution in a vacuum drying oven and dry under vacuum at 40°C for 30 hours to obtain a solid powder. Transfer the solid powder to a clean porcelain boat and place it in a tube furnace. Heat at 650°C for 7 hours under a hydrogen atmosphere to finally obtain Rh-Pb-EuH nanomaterials.

[0033] Example 9 Accurately weigh 69.9 mmol of carbon black, 209.7 mmol of Ni acetylacetone, 23.33 mmol of gallium chloride, and 116.5 mmol of erbium acetylacetone into a clean beaker. Add 160 mL of phenylethanol, add a magnetic stir bar, and stir on a magnetic stirrer for 3 h to obtain a uniformly dispersed mixed solution. Place the solution in a vacuum drying oven and dry under vacuum at 65 °C for 14 h to obtain a solid powder. Transfer the solid powder to a clean ceramic boat and place it in a tube furnace. Heat at 350 °C for 18 h under a hydrogen atmosphere to finally obtain Ni-Ga-ErH nanomaterials.

[0034] Example 10 Accurately weigh 93.31 mmol of graphene, 13.33 mmol of palladium acetylacetonate, 66.65 mmol of indium chloride, and 466.55 mmol of lutetium acetylacetonate into a clean beaker. Add 120 mL of ethanol, add a magnetic stir bar, and stir on a magnetic stirrer for 1.5 h to obtain a uniformly dispersed solution. Place the solution in a vacuum drying oven and dry under vacuum at 75 °C for 12 h to obtain a solid powder. Transfer the solid powder to a clean ceramic boat and place it in a tube furnace. Heat at 600 °C for 10 h under a hydrogen atmosphere to finally obtain Pd-In-LuH nanomaterials.

[0035] Example 11 Accurately weigh 1.67 mmol of carbon black, 16.7 mmol of ruthenium acetylacetone, 16.7 mmol of indium chloride, and 16.7 mmol of gadolinium acetylacetone into a clean beaker, add 100 mL of ethanol, add a magnetic stir bar, and stir on a magnetic stirrer for 3 h to obtain a uniformly dispersed mixed solution. Place the solution in a vacuum drying oven and dry under vacuum at 70 °C for 16 h to obtain a solid powder. Transfer the solid powder to a clean porcelain boat and place it in a tube furnace. Heat at 700 °C for 4 h under a hydrogen atmosphere to finally obtain Ru-In-GdH nanomaterials.

[0036] The above are merely specific embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any modifications, equivalent substitutions, and improvements made by those skilled in the art within the scope of the technology disclosed in the present invention and within the spirit and principles of the present invention should be covered within the scope of protection of the present invention.

Claims

1. Hydrogen-mediated dpf orbital hybrid metal nanomaterials, characterized in that: The metallic nanomaterial contains d-block metal, p-block metal, f-block metal and carbon support, and the molar ratio of the three metals is arbitrary, with the molar ratio of any one of the three metals to the carbon support being 1:0.1-10.

2. The hydrogen-mediated dpf orbital hybrid metal nanomaterial according to claim 1, characterized in that: The metal in the d-region is cobalt, iron, manganese, copper, palladium, platinum, rhodium, nickel, or ruthenium.

3. The hydrogen-mediated dpf orbital hybrid metal nanomaterial according to claim 1, characterized in that: The p-region metal is gallium, indium, bismuth, tin, or lead.

4. The hydrogen-mediated dpf orbital hybrid metal nanomaterial according to claim 1, characterized in that: The metal in the f-region is cerium, praseodymium, lanthanum, neodymium, dysprosium, samarium, terbium, europium, erbium, lutetium, or gadolinium.

5. The hydrogen-mediated dpf orbital hybrid metal nanomaterial according to claim 1, characterized in that: The carbon support is carbon black, carbon nanotubes, or graphene.

6. The method for preparing hydrogen-mediated dpf orbital hybrid metal nanomaterials according to any one of claims 1-5, characterized in that: The precursors of d-block metal, p-block metal, and f-block metal are mixed evenly with a carbon support and then heated and reduced at 300-800℃ for 1-24 hours in a hydrogen atmosphere to obtain the product.

7. The method for preparing hydrogen-mediated dpf orbital hybrid metal nanomaterials according to claim 6, characterized in that: The precursors of the d-region metals are cobalt chloride, ferric chloride, manganese chloride, ferrous chloride, copper oxide, sodium tetrachloropalladate, potassium chloroplatinate, rhodium acetylacetonate, nickel acetylacetonate, or ruthenium acetylacetonate; the precursors of the p-region metals are gallium acetylacetonate, indium chloride, bismuth oxide, tin tetrachloride, or lead acetylacetonate; and the precursors of the f-region metals are cerium acetylacetonate, cerium oxide, praseodymium acetylacetonate, lanthanum acetylacetonate, neodymium acetylacetonate, dysprosium acetylacetonate, samarium acetylacetonate, terbium acetylacetonate, europium acetylacetonate, erbium acetylacetonate, lutetium acetylacetonate, or gadolinium acetylacetonate.

8. The method for preparing hydrogen-mediated dpf orbital hybrid metal nanomaterials according to claim 6, characterized in that: The term "uniform mixing" refers to dispersing the precursors of the d-region metal, p-region metal, and f-region metal, along with the carbon support, into a solvent, ultrasonically treating them to form a homogeneous and stable solution, then magnetically stirring them until homogeneous, and finally vacuum drying them.

9. The method for preparing hydrogen-mediated dpf orbital hybrid metal nanomaterials according to claim 7, characterized in that: The solvent is deionized water, ethanol, benzyl alcohol, formic acid, or acetic acid.

10. An electrocatalyst, characterized in that: The electrocatalyst is made of hydrogen-mediated dpf orbital hybrid metal nanomaterials as described in any one of claims 1-5.

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