阅读说明：本技术 电催化氧化甘油制甲酸盐用Cu-CuS/BM电极材料及制备方法 (Cu-CuS/BM electrode material for preparing formate by electrocatalytic oxidation of glycerol and preparation method thereof ) 是由 雷晓东 杜嘉玮 秦洋 窦彤 王一平 于 2021-09-07 设计创作，主要内容包括：本发明提供了一种电催化氧化甘油制甲酸盐用Cu-CuS/BM电极材料及制备方法,本发明以黄铜网为基底,在黄铜网上化学沉积原位生长硫化铜纳米片阵列,并采用化学歧化的方法将铜纳米颗粒均匀附着在硫化铜/黄铜网上形成的电极材料,所述的黄铜网是化学式为Cu-(0.64)Zn-(0.36)的黄铜丝编织的网。该材料的特点是铜纳米颗粒均匀分散在硫化铜纳米片上,铜纳米颗粒的平均直径约50-70nm。该电极材料用于电催化甘油氧化制备甲酸盐具有良好的催化性能,在过电位为1.37V时,电流密度可达到10mA·cm～(2),初始电位可低至1.10V。在1.45V电位下,甲酸盐的选择性达到73.0-87.6％,生成甲酸盐的法拉第效率为86.0-97.0％。(The invention provides a Cu-CuS/BM electrode material for preparing formate by electrocatalytic oxidation of glycerol and a preparation method thereof 0.64 Zn 0.36 A mesh woven from brass wires. The material is characterized in that copper nanoparticles are uniformly dispersed on a copper sulfide nanosheet, and the average diameter of the copper nanoparticles is about 50-70 nm. The electricityThe electrode material has good catalytic performance when being used for preparing formate by electrocatalysis glycerol oxidation, and the current density can reach 10 mA-cm when the overpotential is 1.37V 2 The initial potential can be as low as 1.10V. Under the potential of 1.45V, the selectivity of the formate reaches 73.0-87.6%, and the faradaic efficiency of the generated formate is 86.0-97.0%.)

1. A preparation method of a Cu-CuS/BM electrode material for preparing formate by electrocatalytic oxidation of glycerol is characterized by comprising the following steps:

A. preparing CuS/BM according to the method of patent CN 111974415A; BM stands for brass mesh substrate, is made of Cu_0.64Zn_0.36The brass wire braided net of (1), CuS is a hexagonal nanosheet array structure;

B. dissolving CuBr in acetonitrile to prepare the solution with the concentration of 0.005-0.03 mol.L^-1A CuBr solution, CuS/BM is placed in the solution and is taken out after being placed for 0.5-30min, and CuBr is attached to the surface of the CuS/BM to form CuBr-CuS/BM;

C. c is to be₁₀H₁₄N₂Na₂O₈·2H₂Dissolving O in deionized water to obtain a solution with a concentration of 0.005-0.03 mol.L^-1The solution of (1); placing the CuBr-CuS/BM obtained in the step B in the solution, standing for 0.5-30min, taking out, washing with deionized water, and drying in a drying oven at 40-80 ℃ to obtain the Cu-CuS/BM electrode material, wherein copper nanoparticles are uniformly dispersed on copper sulfide nanosheets, and the average diameter of the copper nanoparticles is 50-70 nm;

cu in step C⁺At C₁₀H₁₄N₂Na₂O₈·2H₂Generated under the action of an aqueous solution of OAnd (4) carrying out disproportionation reaction to form copper nanoparticles attached to the surface of the copper sulfide nanosheet, so as to obtain the Cu-CuS/BM electrode material.

2. The Cu-CuS/BM electrode material for formate preparation by electrocatalytic oxidation as set forth in claim 1, wherein copper nanoparticles are uniformly attached to the CuS/BM nanosheets to form the Cu-CuS/BM electrode material, and wherein the copper nanoparticles have an average particle size of 50 to 70 nm.

Technical Field

The invention relates to an electrode material for generating formate by electrocatalytic oxidation of Glycerol (GLY), in particular to Cu-CuS/BM with a nano-particle structure, a preparation method thereof and application of the electrode material in generating formate by electrocatalytic oxidation of glycerol.

Background

With the continuous consumption of fossil fuels such as petroleum and natural gas, biodiesel as a renewable biomass energy source becomes a good substitute for fossil fuels. However, the production of biodiesel is currently accompanied by the production of glycerol as a by-product. In recent years, the production of glycerol has been excessive due to the increase in demand for biodiesel, and the value thereof has been greatly reduced. Glycerol, as a biomass-derived platform molecule, has great development value and can be converted into various high-value-added chemicals, such as glyceraldehyde, glyceric acid, dihydroxyacetone, glycolic acid, formic acid and the like. Over the past several decades, there have been many researchers working on finding catalytic pathways for the conversion of glycerol to value added products. Compared with photocatalysis and traditional thermal catalysis, the condition of electrocatalytic glycerol oxidation reaction is milder, the reaction can be carried out at normal temperature and normal pressure, and the cathode hydrogen evolution reaction and the anode glycerol oxidation reaction can be combined by applying proper potential, so that the method is a more economic way for producing high value-added chemicals and is more and more attracted by people. However, because the glycerol oxidation process is complex, electrocatalytic glycerol oxidation still presents some challenges. On the one hand, in the past electrocatalytic oxidation reaction of glycerin, more researchers choose to use noble metals for preparing active catalysts, however, noble metals have the characteristics of scarcity and high price, and do not have high economic benefits for producing value-added chemicals. On the other hand, electrocatalytic glycerol oxidation is a multiple electron transfer process, and the reaction process involves the breaking of C-C bonds and the effective removal of various intermediate products on the catalyst surface, easily resulting in low product selectivity. Therefore, designing a catalyst for effectively electrocatalytic oxidation of glycerol, which has economic benefits and simultaneously has high selectivity for generating value-added chemicals, becomes a key point and a difficult point in the research of electrocatalytic oxidation reaction of glycerol.

Copper as groundA transition metal element with rich source and low price on the ball not only has good conductivity, but also is found to have the capability of adjusting electrochemical performance, and a copper-based material as a catalyst can be used for electrocatalysis glycerin oxidation reaction. In document 1, ACS cat, 2020,10,6741-6752, a series of cobalt-based spinel oxides rich in earth resources are prepared for electrocatalytic glycerol oxidation reaction, wherein copper-cobalt spinel has higher electrocatalytic glycerol activity and selectivity to formic acid reaches 80.6% at 1.3V (vs. reversible hydrogen electrode). In document 2, appl.cat.b, 2020,265,118543, copper oxide was synthesized by a two-step simple precipitation method for electrocatalytic oxidation of glycerin, and when the pH of the electrolyte solution was 9, the selectivity of dihydroxyacetone reached 60% at 2.06V (vs.rhe), but at this voltage, the current density reached only 3mA · cm^-2. Document 3, in chem electrochem, 2020,7,951-958, a Cu/Cu with dendritic structure is prepared by electrodeposition on a smooth copper electrode₂O-foam, used as an effective electrocatalyst for the electrooxidation of glycerol, with initial voltages as low as 0.12V (vs. saturated calomel electrode, SCE; 1.13V vs. RHE). The copper sulfide series nanocrystals are special inorganic functional materials, have good metal conductivity, have a large number of holes in the structure as a typical p-type semiconductor material, and are widely applied to solar photovoltaic panels, chemical sensors, photoelectric catalysts and the like. The unique mesh shape of the brass mesh facilitates the internal diffusion of glycerol.

The invention content is as follows:

the invention aims to provide a Cu-CuS/BM electrode material for preparing formate by electrocatalytic oxidation of glycerol and a preparation method thereof.

The Cu-CuS/BM electrode material provided by the invention takes a brass net as a substrate, copper sulfide grows in situ on the brass net substrate (BM) through a chemical deposition method to form the CuS/BM material, and copper nanoparticles are uniformly attached on copper sulfide nanosheets through a chemical disproportionation method to form the Cu-CuS/BM electrode material, wherein the average particle size of the copper nanoparticles is 50-70 nm. The electrode material has good catalytic performance, can realize high-selectivity conversion of glycerol into formic acid when being used for electrocatalysis of glycerol oxidation reaction, and has good stability.

The preparation method of the Cu-CuS/BM electrode material with the nano-particle structure comprises the following specific steps:

A. preparing CuS/BM according to the method of patent CN 111974415A; BM stands for brass mesh substrate, is made of Cu_0.64Zn_0.36The brass wire braided net of (1), CuS is a hexagonal nanosheet array structure.

B. Cuprous bromide (CuBr) is dissolved in acetonitrile to prepare the solution with the concentration of 0.005-0.03 mol.L^-1The CuBr solution is prepared by placing CuS/BM in the solution, standing for 0.5-30min, and taking out, wherein CuBr is attached to the surface of CuS/BM to form CuBr-CuS/BM.

C. Mixing disodium ethylene diamine tetraacetate dihydrate (C)₁₀H₁₄N₂Na₂O₈·2H₂O) is dissolved in deionized water to prepare the solution with the concentration of 0.005-0.03 mol.L^-1The solution of (1); and B, placing the CuBr-CuS/BM obtained in the step B in the solution for 0.5-30min, taking out, washing with deionized water, and drying in a drying oven at 40-80 ℃ to obtain the Cu-CuS/BM electrode material, wherein copper nanoparticles are uniformly dispersed on the copper sulfide nanosheets, and the average diameter of the copper nanoparticles is 50-70 nm.

Cu in step C⁺At C₁₀H₁₄N₂Na₂O₈·2H₂Carrying out disproportionation reaction under the action of the aqueous solution of O to form copper nanoparticles attached to the surface of the copper sulfide nanosheet, and obtaining the Cu-CuS/BM electrode material.

The Cu-CuS/BM electrode material has good conductivity, can be used for electrically catalyzing and oxidizing glycerol to generate formate, and has a current density of 10 mA-cm at an over-potential of 1.37V (vs. RHE)^-2The initial potential is as low as 1.10V (vs. RHE), the selectivity to formate is as high as 73.0-87.6%, the Faraday efficiency of formate is 86.0-97.0%, and the electric double layer capacitance of electrode reaches 2.46mF cm^-1Indicating a larger electrochemically active surface area.

Characterization and application experiments

FIG. 1 is a Scanning Electron Microscope (SEM) characterization of the Cu-CuS/BM of example 1, from which it can be seen that copper nanoparticles are uniformly grown on the surface of copper sulfide nanoplatelets having an average diameter of about 50-70 nm.

FIG. 2 is a High Resolution Transmission Electron Microscopy (HRTEM) characterization of Cu-CuS/BM from example 1, from which it can be seen that copper nanoparticles are uniformly grown on copper sulfide nanoplatelets and a lattice spacing of 0.209nm is detected, corresponding to the (111) plane of Cu (JCPDS No. 04-0836).

FIG. 3 is an X-ray photoelectron spectroscopy (XPS) chart of Cu-CuS/BM (FIG. b) and CuS/BM (FIG. a) in example 1. The comparison shows that the Cu of the Cu-CuS/BM⁰The content is obviously increased.

FIG. 4 shows the Cu-CuS/BM electrode of example 1 at 0.1 mol. L^-1KOH and a catalyst containing 0.1 mol. L^-1Linear voltammetric scan curves in a mixed electrolyte of GLY. RHE at 1.37V (vs. cm), the current density was 10mA cm^-2The material can effectively catalyze the glycerol oxidation reaction, and the initial potential of the Cu-CuS/BM electrode electrocatalytic glycerol oxidation reaction is 1.10V (vs. RHE), which shows that the material has good kinetics of the glycerol oxidation reaction.

FIG. 5 is a cyclic voltammetry curve of 0.51-0.55V for the Cu-CuS/BM electrode of example 1 at different scanning speeds, with the inset being the relationship between the scanning speed and the current density. Calculating to obtain the electric double layer capacitance value C of the Cu-CuS/BM electrode_dIIs 2.46mF cm^-1The result shows that the electrochemical active surface area of Cu-CuS/BM is larger, which is beneficial to the electrocatalytic oxidation reaction of glycerol.

FIG. 6 shows the selectivity of formate and the Faraday efficiency of formate formation measured at different potentials for the Cu-CuS/BM electrode of example 1. As can be seen from the figure, the selectivity of the product formate of the method can reach 85.6 percent under 1.45V (vs. RHE), and the faradaic efficiency of the generated formate can reach 88.9 percent. The Cu-CuS/BM has good selectivity for generating formate by electrocatalytic oxidation of glycerol.

FIG. 7 is a graph of the selectivity of the product formate and the Faraday efficiency of formate formation in the electrocatalytic oxidation glycerol cycling experiment at 1.45V (vs. RHE) for the Cu-CuS/BM electrode of example 1. As can be seen from the figure, after 20 times of cycle tests, the selectivity of the formate product is kept stable at 86.4%, and the Faraday efficiency of generating formic acid is kept stable at 90.3%, which indicates that the Cu-CuS/BM material has good stability when being used for high-selectivity generation of formate by electrocatalytic oxidation of glycerol.

The invention has the beneficial effects that:

the invention adopts a chemical bath deposition method to grow copper sulfide hexagonal nanosheets on the brass net in situ, the copper sulfide is relatively cheap, and the unique characteristic of the p-type semiconductor is favorable for the oxidation reaction. Then the CuBr is adsorbed on the surface of the copper sulfide by a chemical disproportionation method, and C is utilized₁₀H₁₄N₂Na₂O₈·2H₂O to Cu²⁺Coordination of (2) promoting Cu⁺And (3) disproportionating the surface of the copper sulfide nanosheet, and attaching copper nanoparticles on the premise of keeping the nanosheet structure of CuS to obtain the Cu-CuS/BM with a unique structure. The material has the advantages of simple preparation method, low cost and easy operation at low temperature, the initial potential of the material used in the electrocatalytic oxidation reaction of glycerol is as low as 1.10V (vs. RHE), and the current density can reach 10 mA-cm at 1.37V (vs. RHE)^-2And the selectivity of the material on formate generated by electrocatalytic oxidation of glycerol can reach 85.6%, and the selectivity after 20-cycle test is still well maintained at 86.4%, which shows that the material has excellent performance on electrocatalytic oxidation reaction of glycerol and has good stability.

Drawings

FIG. 1 is a Scanning Electron Microscope (SEM) characterization of the Cu-CuS/BM of example 1.

FIG. 2 is a High Resolution Transmission Electron Microscopy (HRTEM) characterization of Cu-CuS/BM in example 1.

FIG. 3 is an X-ray photoelectron spectroscopy (XPS) chart of Cu-CuS/BM and CuS/BM in example 1.

FIG. 4 is a linear voltammogram scan of the Cu-CuS/BM electrode of example 1.

FIG. 5 shows the Cu-CuS/BM electrode of example 1 at 20-100 mV s^-1Cyclic voltammogram at the scan rate of (a).

FIG. 6 is the formate selectivity and the faradaic efficiency for formate formation at potentials of 1.2-1.6V for the Cu-CuS/BM electrode of example 1.

Figure 7 is a graph of the formic acid selectivity and faradaic efficiency of formate formation after cycling experiments with electrocatalytic oxidation of glycerol at 1.45V (vs. rhe) for the Cu-CuS/BM electrode of example 1.

Detailed Description

Example 1

A. Preparing CuS/BM according to the method of patent CN 111974415A, weighing 12.009g of sodium sulfide, 2g of sodium hydroxide and 1.6g of sulfur powder, dissolving in 50mL of deionized water continuously filled with nitrogen to prepare a mixed solution, wherein the molar concentrations of the sodium sulfide, the sulfur and the sodium hydroxide are respectively 0.1 mol.L^-1，0.1mol·L^-1And 0.1 mol. L^-1. Cutting a brass net into pieces with the size of 4.0cm multiplied by 3.0cm, placing the pieces in the mixed solution, keeping the temperature at 30 ℃ for 24h, taking out the pieces, washing the pieces with deionized water, and placing the pieces in a 60 ℃ drying oven for drying to obtain the CuS/BM.

B. Weighing 0.072g of cuprous bromide, dissolving the cuprous bromide in 50mL of acetonitrile, and performing ultrasonic treatment to completely dissolve the cuprous bromide to obtain an acetonitrile solution of the cuprous bromide with the concentration of 0.01 mol.L^-1. Soaking CuS/BM with a size of 4.0cm × 3.0cm in the solution for 1min, taking out, and drying in an oven at 60 deg.C.

C. 0.168g of disodium ethylene diamine tetraacetate is weighed and dissolved in 50mL of deionized water, and the solution is stirred to be completely dissolved to obtain the aqueous solution of disodium ethylene diamine tetraacetate with the concentration of 0.01 mol.L^-1. And C, placing the CuS/BM soaked in the step B in the solution for 1min, taking out, washing with deionized water, and drying in a 60-DEG C oven to obtain the Cu-CuS/BM with the nanoparticle structure.

Example 2

A. The same as in example 1.

B. 0.216g of cuprous bromide is weighed and dissolved in 50mL of acetonitrile, and the solution is completely dissolved by ultrasonic treatment to obtain acetonitrile solution of cuprous bromide with the concentration of 0.03 mol.L^-1. Soaking CuS/BM with a size of 4.0cm × 3.0cm in the solution for 1min, taking out, and drying in an oven at 60 deg.C.

C. The same as in example 1.

Example 3

A. The same as in example 1.

B. 0.144g of bromine was weighedDissolving cuprous bromide in 50mL acetonitrile, and ultrasonically dissolving to obtain acetonitrile solution of cuprous bromide with concentration of 0.02 mol.L^-1. Soaking CuS/BM with a size of 4.0cm × 3.0cm in the solution for 30min, taking out, and drying in an oven at 60 deg.C.

C. 0.336g of disodium ethylene diamine tetraacetate is weighed and dissolved in 50mL of deionized water, and the solution is stirred to be completely dissolved to obtain the aqueous solution of disodium ethylene diamine tetraacetate with the concentration of 0.02 mol.L^-1. And C, placing the CuS/BM soaked in the step B in the solution for 30min, taking out, washing with deionized water, and drying in a 60-DEG C oven to obtain the Cu-CuS/BM with the nanoparticle structure.

Example 4

A. The same as in example 1.

B. Weighing 0.072g of cuprous bromide, dissolving the cuprous bromide in 50mL of acetonitrile, and performing ultrasonic treatment to completely dissolve the cuprous bromide to obtain an acetonitrile solution of the cuprous bromide with the concentration of 0.01 mol.L^-1. Soaking CuS/BM with a size of 4.0cm × 3.0cm in the solution for 15min, taking out, and drying in an oven at 60 deg.C.

C. 0.504g of disodium ethylene diamine tetraacetate is weighed and dissolved in 50mL of deionized water, and the solution is stirred to be completely dissolved to obtain the aqueous solution of the disodium ethylene diamine tetraacetate with the concentration of 0.03 mol.L^-1. And C, placing the CuS/BM soaked in the step B in the solution for 1min, taking out, washing with deionized water, and drying in a 60-DEG C oven to obtain the Cu-CuS/BM with the nanoparticle structure.

Application example 1

Electrochemical performance comparison test:

the Cu-CuS/BM obtained in examples 1 to 4 was cut into 1cm X1 cm pieces of electrode material for the electrocatalytic oxidation of glycerol. Separating the anode chamber and the cathode chamber by a proton exchange membrane through an H-shaped double electrochemical cell reactor; and a three-electrode system is adopted, a Cu-CuS/BM catalyst is used as a working electrode, a platinum electrode is used as an auxiliary electrode, a silver/silver chloride electrode is used as a reference electrode to test a linear volt-ampere scanning curve, and the test condition is that the linear volt-ampere scanning curve is 0.1 mol.L^-1KOH and 0.1 mol. L^-1In the mixed solution of GLY, the sweep rate is 5 mV.s^-1(ii) a Reacting at 1.45V (vs. RHE) for 5h by a chronoamperometric test, and reactingThe product should be analyzed by liquid chromatography after the end. The test results are shown in Table 1.

Table 1.

As can be seen from Table 1, the initial voltage of the Cu-CuS/BM electrode material prepared by the invention during the electrocatalytic glycerol oxidation reaction is as low as 1.10V (vs. RHE), and the current density is 10 mA-cm^-2The corresponding voltage can reach 1.37V (vs. RHE) at the lowest, the selectivity of formic acid can reach 85.6% at the highest, and the Faraday efficiency for generating formic acid can reach 88.9%. The material is shown to have good electrocatalytic oxidation performance of glycerol and high selectivity for converting the glycerol into formic acid.