CN111644168A - Method for preparing atomic-scale catalyst by slowly raising temperature to greatly improve yield of hydrogen peroxide - Google Patents

Abstract

The invention relates to a method for slowly heating up an atomic-level catalyst to greatly increase the yield of hydrogen peroxide, and belongs to the fields of material science and engineering technology and chemistry. The catalyst raw materials prepared by the invention are metal phthalocyanine and carbon nanomaterials, and the involved metals include non-precious metal elements such as Fe, Co, Ni, Mn, Cu, and Zn. First, configure the mixed solution A of metal phthalocyanine and precursor fluorinated carbon nanotubes containing a certain loading ratio, ultrasonically and stir at room temperature to make it fully react and load evenly. After the loading is completed, remove the dispersing solvent, and put the prepared intermediate Product B was placed in a tube furnace and heated under inert gas conditions for several hours to obtain product C. The method has the advantages of simple operation, high efficiency and wide application range. Compared with the traditional method for preparing hydrogen peroxide, it has the advantages of easy operation, high yield, safety and reliability.

Description

A kind of slow heating to prepare atomic-scale catalyst to greatly increase the production of hydrogen peroxide method

technical field

The invention relates to a method for slowly heating up an atomic-level catalyst to greatly increase the yield of hydrogen peroxide, and belongs to the fields of material science and engineering technology and chemistry.

Background technique

Hydrogen peroxide is not only a versatile and environmentally friendly chemical oxidant widely used in water treatment, pulp bleaching and chemical synthesis, but also a potential energy storage substance. Today, the high demand for hydrogen peroxide makes this chemical one of the most important products in the world. However, the industrial production of hydrogen peroxide is mainly based on the Riedl-Pfleidererpro process developed nearly 70 years ago, involving the sequential hydrogenation and oxidation of anthraquinones. The inherent complexity and high energy consumption of this process has prompted researchers to explore alternative processes for hydrogen peroxide production. _In this context, it would be an attractive strategy to develop an electrochemical process for the partial reduction of _O2 to H2O2 in an alkaline medium, however, we still lack the ability to produce _hydrogen peroxide in an alkaline medium. , exhibit high activity and selectivity, practical and cost-effective electrocatalysts. Considering that temperature is an important parameter affecting the kinetics and thermodynamics of chemical reactions, this method adopts a widely used catalyst preparation method, slow heating method, increasing the temperature under controlled gas environment, changing the bonding method between material elements, and activating the catalysis of metals. At a suitable thermal activation temperature, the metal atoms are combined with NFC to form an efficient active center, and a catalyst with strong ORR performance is obtained. The catalyst has stronger adsorption capacity of HOO* in the two-electron and four-electron O ₂ reduction pathways, achieves high hydrogen peroxide catalytic activity, and greatly improves the yield of hydrogen peroxide in electrochemical catalysis.

SUMMARY OF THE INVENTION

1. Object of the present invention

The purpose of the present invention is to obtain a kind of method that greatly improves the hydrogen peroxide production. The ORR performance and extremely high hydrogen peroxide selectivity of the metal catalyst can be improved by the slow heating method.

2. The main points of the invention of this technology

The main points of the present invention are as follows:

(1) A reactant solution A with a mass-volume concentration of 2-4 mg/ml is prepared with metal phthalocyanine, inorganic materials and a solvent, and the metal salt elements are Fe, Co, Ni, Mn, Cu, and Zn, so The inorganic material is fluorinated carbon nanotubes, and the solvent is anhydrous ethanol.

(2) After sonicating the solution until no particles exist, stirring for 12 hours, suction filtration, and obtaining the reactant on qualitative filter paper. After the reactants are completely dried, the obtained reactants are calcined in a vacuum tube furnace, generally using nitrogen or argon as the protective gas, the annealing temperature is 500℃～800℃, the annealing time is 9-14h, and the holding time is 1h. The heating rate is 1°C/min

The slow heating-up preparation catalyst proposed by the present invention improves the high hydrogen peroxide yield, and the advantages are: this method has a wide range of applications, and can synthesize various metal catalysts, such as Fe, Co, Ni, Mn, Cu, Zn, etc., and the chemical The performance is stable, the raw materials are easily obtained, the synthesis process is simple, and it can be mass-produced.

Description of drawings

FIG. 1 is a scanning transmission electron microscope image of the nanotubes loaded with cobalt phthalocyanine according to the method of the present invention. Figure 2 is a comparison diagram of hydrogen peroxide yield and electron transfer number under the catalysis of cobalt-doped catalyst;

Detailed ways

Embodiments of the inventive method are introduced below:

Example 1

Preparation of 3%-800℃-Co-NFC catalyst

First, mix cobalt phthalocyanine, fluorinated carbon nanotubes and anhydrous ethanol thoroughly. The loading ratio of cobalt phthalocyanine to the precursor is 3%, and configure a mixed solution A of 2 mg/ml. The solution is sonicated until no particles exist. After that, it was stirred for 12 hours, filtered with suction, and the reactant was obtained on qualitative filter paper. After the reactants are completely dried, the obtained reactants are calcined in a vacuum tube furnace. Generally, nitrogen or argon is used as a protective gas. The annealing temperature is 800°C, the holding time is 1h, and the heating rate is 1°C/min. After completion, cooling to room temperature yielded the final product.

Example 2

Preparation of 3%-800℃-Fe-NFC catalyst

First, fully mix iron phthalocyanine, fluorinated carbon nanotubes and anhydrous ethanol, the loading ratio of iron phthalocyanine to precursor is 3%, configure a mixed solution A of 2 mg/ml, and sonicate the solution until no particles exist. After that, it was stirred for 12 hours, filtered with suction, and the reactant was obtained on qualitative filter paper. After the reactants are completely dried, the obtained reactants are calcined in a vacuum tube furnace. Generally, nitrogen or argon is used as a protective gas. The annealing temperature is 800°C, the holding time is 1h, and the heating rate is 1°C/min. After completion, cooling to room temperature yielded the final product.

Example 3

Preparation of 3%-800℃-Cu-NFC catalyst

First, fully mix copper phthalocyanine, carbon fluoride nanotubes and absolute ethanol, the loading ratio of copper phthalocyanine to precursor is 3%, configure a mixed solution A of 2 mg/ml, and sonicate the solution until no particles exist After that, it was stirred for 12 hours, filtered with suction, and the reactant was obtained on qualitative filter paper. After the reactants are completely dried, the obtained reactants are calcined in a vacuum tube furnace. Generally, nitrogen or argon is used as a protective gas. The annealing temperature is 800°C, the holding time is 1h, and the heating rate is 1°C/min. After completion, cooling to room temperature yielded the final product.

Example 4

Preparation of 3%-800℃-Ni-NFC catalyst

First, fully mix nickel phthalocyanine, carbon nanotubes and anhydrous ethanol, the loading ratio of nickel phthalocyanine to precursor is 3%, and configure a mixed solution A of 2 mg/ml, and ultrasonicate the solution until no particles exist. After that, it was stirred for 12 hours, filtered with suction, and the reactant was obtained on qualitative filter paper. After the reactants are completely dried, the obtained reactants are calcined in a vacuum tube furnace. Generally, nitrogen or argon is used as a protective gas. The annealing temperature is 800°C, the holding time is 1h, and the heating rate is 1°C/min. After completion, cooling to room temperature yielded the final product.

Example 5

Preparation of 3%-800℃-Zn-NFC catalyst

First, fully mix zinc phthalocyanine, carbon nanotubes and anhydrous ethanol, the loading ratio of zinc phthalocyanine to precursor is 3%, configure a mixed solution A of 2 mg/ml, and sonicate the solution until no particles exist. After that, it was stirred for 12 hours, filtered with suction, and the reactant was obtained on qualitative filter paper. After the reactants are completely dried, the obtained reactants are calcined in a vacuum tube furnace. Generally, nitrogen or argon is used as a protective gas. The annealing temperature is 800°C, the holding time is 1h, and the heating rate is 1°C/min. After completion, cooling to room temperature yielded the final product.

Example 6

Preparation of 3%-800℃-Mn-NFC catalyst

First, fully mix manganese phthalocyanine, fluorinated carbon nanotubes and anhydrous ethanol, the loading ratio of manganese phthalocyanine to precursor is 3%, configure a mixed solution A of 2 mg/ml, and sonicate the solution until no particles exist. After that, it was stirred for 12 hours, filtered with suction, and the reactant was obtained on qualitative filter paper. After the reactants are completely dried, the obtained reactants are calcined in a vacuum tube furnace. Generally, nitrogen or argon is used as a protective gas. The annealing temperature is 800°C, the holding time is 1h, and the heating rate is 1°C/min. After completion, cooling to room temperature yielded the final product.

Example 7

Preparation of 5%-800℃-Co-NFC catalyst

First, mix cobalt phthalocyanine, fluorinated carbon nanotubes and anhydrous ethanol thoroughly. The loading ratio of cobalt phthalocyanine to the precursor is 5%, and configure a mixed solution A of 3 mg/ml. The solution is sonicated until no particles exist. After that, it was stirred for 12 hours, filtered with suction, and the reactant was obtained on qualitative filter paper. After the reactants are completely dried, the obtained reactants are calcined in a vacuum tube furnace. Generally, nitrogen or argon is used as a protective gas. The annealing temperature is 800°C, the holding time is 1h, and the heating rate is 1°C/min. After completion, cooling to room temperature yielded the final product.

Example 8

Preparation of 5%-800℃-Fe-NFC catalyst

First, fully mix iron phthalocyanine, fluorinated carbon nanotubes and absolute ethanol, the loading ratio of iron phthalocyanine to the precursor is 5%, configure a mixed solution A of 3 mg/ml, and sonicate the solution until no particles exist. After that, it was stirred for 12 hours, filtered with suction, and the reactant was obtained on qualitative filter paper. After the reactants are completely dried, the obtained reactants are calcined in a vacuum tube furnace. Generally, nitrogen or argon is used as a protective gas. The annealing temperature is 800°C, the holding time is 1h, and the heating rate is 1°C/min. After completion, cooling to room temperature yielded the final product.

Example 9

Preparation of 5%-800℃-Cu-NFC catalyst

First, fully mix copper phthalocyanine, carbon fluoride nanotubes and absolute ethanol, the loading ratio of copper phthalocyanine to precursor is 5%, prepare a mixed solution A of 3 mg/ml, and sonicate the solution until no particles exist. After that, it was stirred for 12 hours, filtered with suction, and the reactant was obtained on qualitative filter paper. After the reactants are completely dried, the obtained reactants are calcined in a vacuum tube furnace. Generally, nitrogen or argon is used as a protective gas. The annealing temperature is 800°C, the holding time is 1h, and the heating rate is 1°C/min. After completion, cooling to room temperature yielded the final product.

Example 10

Preparation of 5%-800℃-Zn-NFC catalyst

First, fully mix zinc phthalocyanine, carbon nanotubes and anhydrous ethanol, the loading ratio of zinc phthalocyanine to precursor is 5%, configure a mixed solution A of 3 mg/ml, and sonicate the solution until no particles exist. After that, it was stirred for 12 hours, filtered with suction, and the reactant was obtained on qualitative filter paper. After the reactants are completely dried, the obtained reactants are calcined in a vacuum tube furnace. Generally, nitrogen or argon is used as a protective gas. The annealing temperature is 800°C, the holding time is 1h, and the heating rate is 1°C/min. After completion, cooling to room temperature yielded the final product.

Example 11

Preparation of 5%-800℃-Ni-NFC catalyst

First, fully mix nickel phthalocyanine, carbon nanotubes and anhydrous ethanol, the loading ratio of nickel phthalocyanine to precursor is 5%, and configure a mixed solution A of 3 mg/ml, and sonicate the solution until no particles exist. After that, it was stirred for 12 hours, filtered with suction, and the reactant was obtained on qualitative filter paper. After the reactants are completely dried, the obtained reactants are calcined in a vacuum tube furnace. Generally, nitrogen or argon is used as a protective gas. The annealing temperature is 800°C, the holding time is 1h, and the heating rate is 1°C/min. After completion, cooling to room temperature yielded the final product.

Example 12

Preparation of 5%-800℃-Mn-NFC catalyst

First, fully mix manganese phthalocyanine, fluorinated carbon nanotubes and absolute ethanol, the loading of manganese phthalocyanine and the carrier is 5%, and prepare a mixed solution A of 3 mg/ml. After the solution is sonicated until no particles exist, Stir for 12 hours, filter with suction, and obtain the reactant on qualitative filter paper. After the reactants are completely dried, the obtained reactants are calcined in a vacuum tube furnace. Generally, nitrogen or argon is used as a protective gas. The annealing temperature is 800°C, the holding time is 1h, and the heating rate is 1°C/min. After completion, cooling to room temperature yielded the final product.

Example 13

Preparation of 3%-500℃-Co-NFC catalyst

First, mix cobalt phthalocyanine, fluorinated carbon nanotubes and anhydrous ethanol thoroughly. The loading ratio of cobalt phthalocyanine to the precursor is 3%, and configure a mixed solution A of 2 mg/ml. The solution is sonicated until no particles exist. After that, it was stirred for 12 hours, filtered with suction, and the reactant was obtained on qualitative filter paper. After the reactants are completely dried, the obtained reactants are calcined in a vacuum tube furnace. Generally, nitrogen or argon is used as a protective gas. The annealing temperature is 800°C, the holding time is 1h, and the heating rate is 1°C/min. After completion, cooling to room temperature yielded the final product.

Example 14

Preparation of 3%-500℃-Fe-NFC catalyst

First, fully mix iron phthalocyanine, fluorinated carbon nanotubes and anhydrous ethanol, the loading ratio of iron phthalocyanine to precursor is 3%, configure a mixed solution A of 2 mg/ml, and sonicate the solution until no particles exist. After that, it was stirred for 12 hours, filtered with suction, and the reactant was obtained on qualitative filter paper. After the reactants are completely dried, the obtained reactants are calcined in a vacuum tube furnace. Generally, nitrogen or argon is used as a protective gas. The annealing temperature is 800°C, the holding time is 1h, and the heating rate is 1°C/min. After completion, cooling to room temperature yielded the final product.

Example 15

Preparation of 3%-500℃-Cu-NFC catalyst

First, fully mix copper phthalocyanine, carbon fluoride nanotubes and absolute ethanol, the loading ratio of copper phthalocyanine to precursor is 3%, configure a mixed solution A of 2 mg/ml, and sonicate the solution until no particles exist After that, it was stirred for 12 hours, filtered with suction, and the reactant was obtained on qualitative filter paper. After the reactants are completely dried, the obtained reactants are calcined in a vacuum tube furnace. Generally, nitrogen or argon is used as a protective gas. The annealing temperature is 800°C, the holding time is 1h, and the heating rate is 1°C/min. After completion, cooling to room temperature yielded the final product.

Example 16

Preparation of 3%-500℃-Zn-NFC catalyst

First, fully mix zinc phthalocyanine, carbon nanotubes and anhydrous ethanol, the loading ratio of zinc phthalocyanine to precursor is 3%, configure a mixed solution A of 2 mg/ml, and sonicate the solution until no particles exist. After that, it was stirred for 12 hours, filtered with suction, and the reactant was obtained on qualitative filter paper. After the reactants are completely dried, the obtained reactants are calcined in a vacuum tube furnace. Generally, nitrogen or argon is used as a protective gas. The annealing temperature is 800°C, the holding time is 1h, and the heating rate is 1°C/min. After completion, cooling to room temperature yielded the final product.

Example 17

Preparation of 3%-500℃-Ni-NFC catalyst

First, fully mix nickel phthalocyanine, carbon nanotubes and anhydrous ethanol, the loading ratio of nickel phthalocyanine to precursor is 3%, and configure a mixed solution A of 2 mg/ml, and ultrasonicate the solution until no particles exist. After that, it was stirred for 12 hours, filtered with suction, and the reactant was obtained on qualitative filter paper. After the reactants are completely dried, the obtained reactants are calcined in a vacuum tube furnace. Generally, nitrogen or argon is used as a protective gas. The annealing temperature is 800°C, the holding time is 1h, and the heating rate is 1°C/min. After completion, cooling to room temperature yielded the final product.

Example 18

Preparation of 3%-500℃-Mn-NFC catalyst

First, fully mix manganese phthalocyanine, fluorinated carbon nanotubes and anhydrous ethanol, the loading ratio of manganese phthalocyanine to precursor is 3%, configure a mixed solution A of 2 mg/ml, and sonicate the solution until no particles exist. After that, it was stirred for 12 hours, filtered with suction, and the reactant was obtained on qualitative filter paper. After the reactants are completely dried, the obtained reactants are calcined in a vacuum tube furnace. Generally, nitrogen or argon is used as a protective gas. The annealing temperature is 800°C, the holding time is 1h, and the heating rate is 1°C/min. After completion, cooling to room temperature yielded the final product.

Claims (1)

1. a kind of slowly warming up prepares the method for atomic-scale catalyst to greatly improve the output of hydrogen peroxide, it is characterized in that this method may further comprise the steps: (1) A reactant solution A of 2-4 mg/ml is prepared with metal phthalocyanine, carbon nanomaterials and a solvent, the metal phthalocyanine elements are Fe, Co, Ni, Mn, Cu, Zn, and the carbon The nanomaterial is fluorinated carbon nanotube, and the solvent is absolute ethanol. (2) After sonicating the solution until no particles exist, stirring for 12 hours, suction filtration, and obtaining the reactant on qualitative filter paper. (3) After the reactants are completely dried, the obtained reactants are annealed in a vacuum tube furnace, generally using nitrogen or argon as the protective gas, the annealing temperature is 500℃～800℃, the annealing time is 9-14h, and the holding time is For 1 h, the heating rate was 1 °C/min, and the reactant was naturally cooled to room temperature after heating. (4) Taking out the reactant, the obtained catalyst can be applied to the reduction reaction of O ₂ to increase the output of hydrogen peroxide.

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