CN118122323A - Noble metal monoatomic doped metal oxide catalyst and preparation method and application thereof - Google Patents

Noble metal monoatomic doped metal oxide catalyst and preparation method and application thereof Download PDF

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CN118122323A
CN118122323A CN202410420131.9A CN202410420131A CN118122323A CN 118122323 A CN118122323 A CN 118122323A CN 202410420131 A CN202410420131 A CN 202410420131A CN 118122323 A CN118122323 A CN 118122323A
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oxide catalyst
nitrate
catalyst
metal oxide
noble metal
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刘淮
陈佩雅
彭林才
张俊华
贾文龙
张蕊
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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Abstract

The invention discloses a noble metal monoatomic doped metal oxide catalyst, a preparation method and application thereof, wherein the noble metal monoatomic doped metal oxide catalyst is prepared by taking a precursor a, an active metal b and an auxiliary agent c as raw materials, and the precursor is at least one of manganese nitrate, cobalt nitrate, ferric nitrate, nickel nitrate, chromium nitrate and copper nitrate; the active metal is at least one of ruthenium trichloride, iridium trichloride, rhodium trichloride, silver nitrate, chloroauric acid, palladium chloride and platinum tetrachloride; the auxiliary agent c is polyol or organic acid. The catalyst of the method can react at 100-150 ℃ by taking oxygen as an oxidant, and can effectively oxidize 5-hydroxymethylfurfural to prepare 2, 5-furandicarboxylic acid.

Description

Noble metal monoatomic doped metal oxide catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of natural perfume, and particularly relates to a noble metal monoatomic doped metal oxide catalyst, and a preparation method and application thereof.
Background
The exhaustion of fossil fuels and the changing problem of global climate make the search for new renewable resources urgent. Biomass energy is considered a potential alternative to fossil fuels because of its wide range of sources and renewable. Currently, many studies indicate that biomass resources can be converted into biofuels and value added chemicals. Among them, 2, 5-furandicarboxylic acid is widely used because of its unique furan ring-attached functional diacid group. In the field of bio-based polymers, 2, 5-furandicarboxylic acid has the potential to replace fossil terephthalic acid due to its structure similar to terephthalic acid, and can be used as a monomer for producing polyvinyl fluoride (PEF) plastics. PEF has significant advantages in terms of oxygen content and oxygen separation rate and is considered a very promising feedstock in polyester chemicals. At present, the preparation of 2, 5-furandicarboxylic acid by catalytic oxidation of biomass-based platform molecules 5-hydroxymethylfurfural is a main way for synthesizing 2, 5-furandicarboxylic acid. Most of the reactions are carried out under the condition of a supported nano catalyst, and the single-atom catalyst is used as a novel catalyst, has the action mechanism similar to that of the traditional supported nano catalyst, has the characteristics of higher catalytic activity, selectivity, atom utilization rate and adjustable active center, and becomes a popular direction for the research of the catalytic field in recent years.
When the oxidation of the lower 5-hydroxymethylfurfural is realized mainly by a supported bimetallic oxide catalyst. Liao et al conducted a study on catalyst performance comparing the reaction effect of Pd nanoparticle supported MnO 2 catalyst (PdNP-MnO 2) with Pd atom supported MnO 2(Pd-MnO2) catalyst in the oxidation of 5-hydroxymethylfurfural. The experimental results show that 2-fold yields of 2, 5-furandicarboxylic acid can be obtained using the Pd-MnO 2 catalyst compared to the PdNP-MnO 2 catalyst. This means that the latter catalysts are twice as efficient as the former under the same conditions. The results of this study show that by changing the distribution and morphology of the active components in the catalyst, the performance of the catalyst can be significantly affected. More active sites can be provided in the Pd-MnO 2 catalyst, thereby improving the yield of 2, 5-furandicarboxylic acid. Therefore, the development of the monoatomic catalyst is beneficial to solving the problems of low catalytic efficiency, low metal utilization rate and the like of the catalyst.
Disclosure of Invention
A first object of the present invention is to provide a noble metal monoatomically doped metal oxide catalyst; a second object is to provide a method for preparing the noble metal monoatomic doped metal oxide catalyst; a third object is to provide the use of the noble metal monoatomic doped metal oxide catalyst.
The first object of the invention is realized in that the noble metal single-atom doped metal oxide catalyst is prepared by taking a precursor a, an active metal b and an auxiliary agent c as raw materials, wherein the precursor is at least one of manganese nitrate, cobalt nitrate, ferric nitrate, nickel nitrate, chromium nitrate and copper nitrate; the active metal is at least one of ruthenium trichloride, iridium trichloride, rhodium trichloride, silver nitrate, chloroauric acid, palladium chloride and platinum tetrachloride; the auxiliary agent c is polyol or organic acid.
The second object of the present invention is achieved by comprising a pretreatment and calcination step, comprising in particular:
A. Pretreatment: weighing a precursor a, an active metal b and an auxiliary agent c according to the formula proportion, fully mixing and grinding uniformly to obtain a material a;
B. Calcining: and calcining the material a to obtain the target noble metal monoatomic doped metal oxide catalyst.
The specific operation is as follows:
Placing at least one of precursor manganese nitrate, cobalt nitrate, ferric nitrate, nickel nitrate, chromium nitrate or copper nitrate, namely, one of ruthenium trichloride, iridium trichloride, rhodium trichloride, silver nitrate, chloroauric acid, palladium chloride and platinum tetrachloride, namely, b, and polyalcohol or organic acid auxiliary agent, namely c, in an agate mortar, fully grinding to obtain a uniform mixture, and calcining the obtained mixture at 200-400 ℃ for 1-3 h ℃ to obtain a noble metal monoatomic doped metal oxide catalyst, wherein the molar ratio of a to b is (95-99.9): (0.1-5), and the molar ratio of the sum of c and a+b is 0.1-0.3:1; the polyalcohol or the organic acid auxiliary agent C comprises at least one of citric acid, ethylenediamine tetraacetic acid, malic acid, tartaric acid, sorbitol, vitamin C or xylitol.
In a preferred embodiment of the invention, the resulting mixture is calcined at 200-400℃for 1-3 h.
In a preferred embodiment of the present invention, the polyol or organic acid adjunct includes, but is not limited to, at least one of citric acid, ethylenediamine tetraacetic acid, malic acid, tartaric acid, sorbitol, vitamin C, or xylitol.
In a preferred embodiment of the invention, the calcination is carried out under an air atmosphere.
The third object of the invention is realized in that the noble metal single-atom doped metal oxide catalyst is applied to the preparation of 2, 5-furandicarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural.
The preparation method comprises the following specific steps:
Mixing 5-hydroxymethylfurfural, alkali and a solvent, then placing the mixture in a reaction vessel, adding the noble metal monoatomic doped metal oxide catalyst, taking oxygen as an oxygen source for reaction, and regulating the pH of a reaction solution to be acidic by using concentrated hydrochloric acid after the reaction is finished to obtain 2, 5-furandicarboxylic acid, wherein the reaction temperature is 100-150 ℃, the time is 0.5-3 h, the pressure is 1-20 bar, the concentration of 5-hydroxymethylfurfural in the solvent is 0.5-20 wt%, the mass ratio of the catalyst to the 5-hydroxymethylfurfural is 0.2-3:1, and the molar ratio of the alkali to the 5-hydroxymethylfurfural is 0.1-3:1.
In a preferred embodiment of the invention, the above reaction is carried out at a temperature of 100-150 ℃ for a time of 1-3 h, at a pressure of 1-20 bar, at a concentration of 0.5-20 wt% of 5-hydroxymethylfurfural in the solvent, at a mass ratio of catalyst to 5-2:1, and at a molar ratio of base to 5-hydroxymethylfurfural of 0.5-2:1.
In a preferred embodiment of the present invention, the base used is one of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate or potassium bicarbonate.
Compared with the background technology, the technical proposal has the following advantages:
1. The catalyst prepared by the invention utilizes noble metal with low doping amount to prepare a single-atom catalyst, and effectively oxidizes 5-hydroxymethylfurfural to prepare 2, 5-furandicarboxylic acid.
2. The invention provides a solvent-free, simple and easy-to-scale method for preparing metal oxide doped with a small amount of noble metal single atoms. The preparation method is a solvent-free preparation process, and the preparation process is simple, environment-friendly and easy for large-scale preparation. In the method, the required metal oxide can be obtained through simple grinding and calcining, and the content of noble metal monoatoms in the catalyst can be effectively changed by selecting different metal mole ratios in the grinding process, so that the catalytic oxidation activity of the catalyst is greatly improved.
The method uses a solvent-free, simple and easy-to-scale method to prepare the noble metal single-atom doped metal oxide as the catalyst, does not need solvents, acid and alkali and other expensive and pollution chemical reagents in the preparation process, and is an economic and environment-friendly catalyst preparation process. The prepared monoatomic doped oxide catalyst has high catalytic efficiency, and can be used for efficiently catalyzing and oxidizing 5-hydroxymethylfurfural to synthesize 2, 5-furandicarboxylic acid under mild reaction conditions.
Drawings
FIG. 1 is a spherical aberration correcting transmission electron microscope map of a catalyst;
Wherein, the a-catalyst aberration corrects the high angle annular dark field scanning transmission electron microscope map; b-correcting a high-angle annular dark field scanning transmission electron microscope map by using the catalyst aberration; c-analyzing an Mn element map by using an X-ray energy spectrum of the catalyst; d-analyzing Ru element patterns by using an X-ray energy spectrum of the catalyst;
FIG. 2 is a synchrotron radiation spectrum of a catalyst;
Wherein, the X-ray absorption near side structure of the a-catalyst Ru K side; b-X-ray absorption fine structure spectrum of the catalytic Ru K side.
Detailed Description
The invention is further illustrated, but is not limited in any way, by the following examples, and any alterations or substitutions based on the teachings of the invention are within the scope of the invention.
The noble metal monoatomic doped metal oxide catalyst is prepared from a precursor a, an active metal b and an auxiliary agent c serving as raw materials, wherein the precursor is at least one of manganese nitrate, cobalt nitrate, ferric nitrate, nickel nitrate, chromium nitrate and copper nitrate; the active metal is at least one of ruthenium trichloride, iridium trichloride, rhodium trichloride, silver nitrate, chloroauric acid, palladium chloride and platinum tetrachloride; the auxiliary agent c is polyol or organic acid.
The polyalcohol is sorbitol or xylitol.
The organic acid is citric acid, ethylenediamine tetraacetic acid, malic acid, tartaric acid or vitamin C.
The mol ratio of the precursor a to the active metal b is (95-99.9): (0.1 to 5); the mole ratio of the sum of the auxiliary agent c and a+b is (0.1-0.3): 1.
The preparation method of the noble metal monoatomic doped metal oxide catalyst comprises the steps of pretreatment and calcination, and specifically comprises the following steps:
A. Pretreatment: weighing a precursor a, an active metal b and an auxiliary agent c according to the formula proportion, fully mixing and grinding uniformly to obtain a material a;
B. Calcining: and calcining the material a to obtain the target noble metal monoatomic doped metal oxide catalyst.
And B, calcining at the temperature of 200-400 ℃ for 1-3 hours.
The calcination in the step B is carried out under an air atmosphere.
The application of the noble metal monoatomic doped metal oxide catalyst disclosed by the invention is the application of the noble metal monoatomic doped metal oxide catalyst in preparing 2, 5-furandicarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural.
The preparation of 2, 5-furandicarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural comprises the steps of pretreatment and main reaction, and specifically comprises the following steps:
A. Pretreatment: mixing 5-hydroxymethylfurfural, alkali and deionized water, then placing the mixture in a reaction container, and adding the noble metal monoatomic doped metal oxide catalyst; the alkali is sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate or potassium bicarbonate;
B. The main reaction: and (3) taking oxygen as an oxygen source to react for 0.5-3 hours at the temperature of 100-150 ℃ and the pressure of 1-20 bar to obtain the 2, 5-furandicarboxylic acid.
The concentration of the 5-hydroxymethylfurfural in the solvent in the step A is 0.5-20wt%; the mass ratio of the noble metal monoatomic doped metal oxide catalyst to the 5-hydroxymethylfurfural is (0.2-3): 1, a step of; the molar ratio of the alkali to the 5-hydroxymethylfurfural is (0.1-3): 1.
The invention is further illustrated by the following examples:
Example 1
Preparation of ruthenium monoatomically doped manganese oxide catalyst: manganese nitrate a (9.99 mmol), ruthenium trichloride b (0.01 mmol) and an auxiliary agent C (2 mmol) vitamin C are mixed and ground uniformly, wherein the molar ratio of a to b is 99.9/0.1, and the molar ratio of C to the sum of a and b is 0.2. The obtained mixture is calcined at 350 ℃ for 2 hours in an air atmosphere to obtain the ruthenium monoatomic doped manganese oxide catalyst.
The oxidation reaction process of the 5-hydroxymethylfurfural comprises the following steps: 0.03 g of 5-hydroxymethylfurfural, 0.04 g of sodium bicarbonate and 3 g of water are added into an autoclave of 10 mL, and 0.03 g of the ruthenium monoatomic doped manganese oxide is added as a catalyst; after sealing the reactor, oxygen was introduced to raise the pressure to 10bar, and the reaction was then terminated after heating to 130℃with vigorous stirring (600 rpm) and holding for 1.5 hours. Qualitative and quantitative measurements were performed using HPLC (Water 2487), the results of which are shown in Table 1 under the number 1.
Example 2
Preparation of ruthenium monoatomically doped manganese oxide catalyst: manganese nitrate a (9.95 mmol), ruthenium trichloride b (0.05 mmol) and an auxiliary agent C (2 mmol) vitamin C are mixed and ground uniformly, wherein the molar ratio of a to b is 99.5/0.5, and the molar ratio of C to the sum of a and b is 0.2. The obtained mixture is calcined at 350 ℃ for 2 hours in an air atmosphere to obtain the ruthenium monoatomic doped manganese oxide catalyst.
The oxidation process of 5-hydroxymethylfurfural was the same as in example 1, except that the catalyst of example 1 was replaced with the present catalyst. Qualitative and quantitative measurements were performed using HPLC (Water 2487), the results of which are shown in Table 1 under the number 2.
Example 3
Preparation of ruthenium monoatomically doped manganese oxide catalyst: manganese nitrate a (9.9 mmol), ruthenium trichloride b (0.1 mmol) and an auxiliary agent C (2 mmol) vitamin C are mixed and ground uniformly, wherein the molar ratio of a to b is 99/1, and the molar ratio of C to the sum of a and b is 0.2. The obtained mixture is calcined at 350 ℃ for 2 hours in an air atmosphere to obtain the ruthenium monoatomic doped manganese oxide catalyst.
The oxidation process of 5-hydroxymethylfurfural was the same as in example 1, except that the catalyst of example 1 was replaced with the present catalyst. Qualitative and quantitative measurements were performed using HPLC (Water 2487), the results of which are shown in Table 1 under the number 3.
Example 4
Preparation of ruthenium monoatomically doped cobalt oxide catalyst: cobalt nitrate a (9.95 mmol), ruthenium trichloride b (0.05 mmol) and an auxiliary agent C (2 mmol) vitamin C are mixed and ground uniformly, wherein the molar ratio of a to b is 99.5/0.5, and the molar ratio of C to the sum of a and b is 0.2. The obtained mixture is calcined at 350 ℃ for 2 hours in an air atmosphere to obtain the ruthenium monoatomic doped cobalt oxide catalyst.
The oxidation process of 5-hydroxymethylfurfural was the same as in example 1, except that the catalyst of example 1 was replaced with the present catalyst. Qualitative and quantitative measurements were performed using HPLC (Water 2487), the results of which are shown in Table 1 under the number 4.
Example 5
Preparation of ruthenium monatomic doped iron oxide catalyst: iron nitrate a (9.95 mmol), ruthenium trichloride b (0.05 mmol) and an auxiliary agent C (2 mmol) vitamin C are mixed and ground uniformly, wherein the molar ratio of a to b is 99.5/0.5, and the molar ratio of C to the sum of a and b is 0.2. The resulting mixture was calcined at 350 ℃ for 2 hours under an air atmosphere to obtain a ruthenium monoatomic doped iron oxide catalyst.
The oxidation process of 5-hydroxymethylfurfural was the same as in example 1, except that the catalyst of example 1 was replaced with the present catalyst. Qualitative and quantitative measurements were performed using HPLC (Water 2487), the results of which are shown in Table 1 under the number 5.
Example 6
Preparation of ruthenium monoatomically doped nickel oxide catalyst: nickel nitrate a (9.95 mmol), ruthenium trichloride b (0.05 mmol) and an auxiliary agent C (2 mmol) vitamin C are mixed and ground uniformly, wherein the molar ratio of a to b is 99.5/0.5, and the molar ratio of C to the sum of a and b is 0.2. The obtained mixture is calcined at 350 ℃ for 2 hours in an air atmosphere to obtain the ruthenium monoatomic doped nickel oxide catalyst.
The oxidation process of 5-hydroxymethylfurfural was the same as in example 1, except that the catalyst of example 1 was replaced with the present catalyst. Qualitative and quantitative measurements were performed using HPLC (Water 2487), the results of which are shown in Table 1 under the number 6.
Example 7
Preparation of ruthenium monoatomically doped chromium oxide catalyst: chromium nitrate a (9.95 mmol), ruthenium trichloride b (0.05 mmol) and an auxiliary agent C (2 mmol) vitamin C are mixed and ground uniformly, wherein the molar ratio of a to b is 99.5/0.5, and the molar ratio of C to the sum of a and b is 0.2. The obtained mixture is calcined at 350 ℃ for 2 hours in an air atmosphere to obtain the ruthenium monoatomic doped chromium oxide catalyst.
The oxidation process of 5-hydroxymethylfurfural was the same as in example 1, except that the catalyst of example 1 was replaced with the present catalyst. Qualitative and quantitative measurements were performed using HPLC (Water 2487), the results of which are shown in Table 1 under the number 7.
Example 8
Preparation of ruthenium monatomic doped copper oxide catalyst: copper nitrate a (9.95 mmol), ruthenium trichloride b (0.05 mmol) and an auxiliary agent C (2 mmol) vitamin C are mixed and ground uniformly, wherein the molar ratio of a to b is 99.5/0.5, and the molar ratio of C to the sum of a and b is 0.2. The resulting mixture was calcined at 350 ℃ for 2 hours under an air atmosphere to obtain a ruthenium monoatomically doped copper oxide catalyst.
The oxidation process of 5-hydroxymethylfurfural was the same as in example 1, except that the catalyst of example 1 was replaced with the present catalyst. Qualitative and quantitative measurements were performed using HPLC (Water 2487), the results of which are shown in Table 1 under the number 8.
Example 9
Preparation of iridium monoatomically doped manganese oxide catalyst: manganese nitrate a (9.95 mmol), iridium trichloride b (0.05 mmol) and an auxiliary agent C (2 mmol) vitamin C are mixed and ground uniformly, wherein the molar ratio of a to b is 99.5/0.5, and the molar ratio of C to the sum of a and b is 0.2. Calcining the obtained mixture for 2 hours at 350 ℃ in an air atmosphere to obtain the iridium monoatomic doped manganese oxide catalyst.
The oxidation process of 5-hydroxymethylfurfural was the same as in example 1, except that the catalyst of example 1 was replaced with the present catalyst. Qualitative and quantitative measurements were performed using HPLC (Water 2487), the results of which are shown in Table 1 under the number 9.
Example 10
Preparation of rhodium monatomic doped manganese oxide catalyst: manganese nitrate a (9.95 mmol), rhodium chloride b (0.05 mmol) and an auxiliary agent C (2 mmol) vitamin C are mixed and ground uniformly, wherein the molar ratio of a to b is 99.5/0.5, and the molar ratio of C to the sum of a and b is 0.2. Calcining the obtained mixture for 2 hours at 350 ℃ in an air atmosphere to obtain the rhodium monatomic doped manganese oxide catalyst.
The oxidation process of 5-hydroxymethylfurfural was the same as in example 1, except that the catalyst of example 1 was replaced with the present catalyst. Qualitative and quantitative measurements were performed using HPLC (Water 2487), the results of which are shown in Table 1 under the number 10.
Example 11
Preparation of silver monoatomically doped manganese oxide catalyst: manganese nitrate a (9.95 mmol), silver nitrate b (0.05 mmol) and an auxiliary agent C (2 mmol) vitamin C are mixed and ground uniformly, wherein the molar ratio of a to b is 99.5/0.5, and the molar ratio of C to the sum of a and b is 0.2. The obtained mixture is calcined at 350 ℃ for 2 hours in an air atmosphere to obtain the silver monoatomic doped manganese oxide catalyst.
The oxidation process of 5-hydroxymethylfurfural was the same as in example 1, except that the catalyst of example 1 was replaced with the present catalyst. Qualitative and quantitative measurements were performed using HPLC (Water 2487), the results of which are shown in Table 1 under the number 11.
Example 12
Preparation of Jin Shan atom doped manganese oxide catalyst: manganese nitrate a (9.95 mmol), chloroauric acid b (0.05 mmol) and an auxiliary agent C (2 mmol) vitamin C are mixed and ground uniformly, wherein the molar ratio of a to b is 99.5/0.5, and the molar ratio of C to the sum of a and b is 0.2. The obtained mixture is calcined for 2 hours at 350 ℃ in air atmosphere to obtain the gold monoatomic doped manganese oxide catalyst.
The oxidation process of 5-hydroxymethylfurfural was the same as in example 1, except that the catalyst of example 1 was replaced with the present catalyst. Qualitative and quantitative measurements were performed using HPLC (Water 2487), the results of which are shown in Table 1 under the number 12.
Example 13
Preparation of palladium monoatomically doped manganese oxide catalyst: manganese nitrate a (9.95 mmol), palladium chloride b (0.05 mmol) and an auxiliary agent C (2 mmol) vitamin C are mixed and ground uniformly, wherein the molar ratio of a to b is 99.5/0.5, and the molar ratio of C to the sum of a and b is 0.2. Calcining the obtained mixture for 2 hours at 350 ℃ in an air atmosphere to obtain the palladium monoatomic doped manganese oxide catalyst.
The oxidation process of 5-hydroxymethylfurfural was the same as in example 1, except that the catalyst of example 1 was replaced with the present catalyst. Qualitative and quantitative measurements were performed using HPLC (Water 2487) and the results are shown in Table 1 under the number 13.
Example 14
Preparation of platinum monoatomically doped manganese oxide catalyst: manganese nitrate a (9.95 mmol), platinum tetrachloride b (0.05 mmol) and an auxiliary agent C (2 mmol) vitamin C are mixed and ground uniformly, wherein the molar ratio of a to b is 99.5/0.5, and the molar ratio of C to the sum of a and b is 0.2. The obtained mixture is calcined at 350 ℃ for 2 hours in an air atmosphere to obtain the platinum monoatomic doped manganese oxide catalyst.
The oxidation process of 5-hydroxymethylfurfural was the same as in example 1, except that the catalyst of example 1 was replaced with the present catalyst. Qualitative and quantitative measurements were performed using HPLC (Water 2487) and the results are shown in Table 1 under the number 14.
Example 15
Preparation of ruthenium monoatomically doped manganese oxide catalyst: manganese nitrate a (9.95 mmol), ruthenium trichloride b (0.05 mmol) and an auxiliary agent c (2 mmol) citric acid are mixed and ground uniformly, wherein the molar ratio of a to b is 99.5/0.5, and the molar ratio of c to the sum of a and b is 0.2. The obtained mixture is calcined at 350 ℃ for 2 hours in an air atmosphere to obtain the ruthenium monoatomic doped manganese oxide catalyst.
The oxidation process of 5-hydroxymethylfurfural was the same as in example 1, except that the catalyst of example 1 was replaced with the present catalyst. Qualitative and quantitative measurements were performed using HPLC (Water 2487) and the results are shown in Table 1 under the number 15.
Example 16
Preparation of ruthenium monoatomically doped manganese oxide catalyst: manganese nitrate a (9.95 mmol), ruthenium trichloride b (0.05 mmol) and an auxiliary agent c (2 mmol) are mixed and ground uniformly, wherein the molar ratio of a to b is 99.5/0.5, and the molar ratio of c to the sum of a and b is 0.2. The obtained mixture is calcined at 350 ℃ for 2 hours in an air atmosphere to obtain the ruthenium monoatomic doped manganese oxide catalyst.
The oxidation process of 5-hydroxymethylfurfural was the same as in example 1, except that the catalyst of example 1 was replaced with the present catalyst. Qualitative and quantitative measurements were performed using HPLC (Water 2487) and the results are shown in Table 1 under the number 16.
Example 17
Preparation of ruthenium monoatomically doped manganese oxide catalyst: manganese nitrate a (9.95 mmol), ruthenium trichloride b (0.05 mmol) and an auxiliary agent c (2 mmol) malic acid are mixed and ground uniformly, wherein the molar ratio of a to b is 99.5/0.5, and the molar ratio of c to the sum of a and b is 0.2. The obtained mixture is calcined at 350 ℃ for 2 hours in an air atmosphere to obtain the ruthenium monoatomic doped manganese oxide catalyst.
The oxidation process of 5-hydroxymethylfurfural was the same as in example 1, except that the catalyst of example 1 was replaced with the present catalyst. Qualitative and quantitative measurements were performed using HPLC (Water 2487) and the results are shown in Table 1 under the number 17.
Example 18
Preparation of ruthenium monoatomically doped manganese oxide catalyst: manganese nitrate a (9.95 mmol), ruthenium trichloride b (0.05 mmol) and an auxiliary agent c (2 mmol) tartaric acid are mixed and ground uniformly, wherein the molar ratio of a to b is 99.5/0.5, and the molar ratio of c to the sum of a and b is 0.2. The obtained mixture is calcined at 350 ℃ for 2 hours in an air atmosphere to obtain the ruthenium monoatomic doped manganese oxide catalyst.
The oxidation process of 5-hydroxymethylfurfural was the same as in example 1, except that the catalyst of example 1 was replaced with the present catalyst. Qualitative and quantitative measurements were performed using HPLC (Water 2487) and the results are shown in Table 1 under the number 18.
Example 19
Preparation of ruthenium monoatomically doped manganese oxide catalyst: manganese nitrate a (9.95 mmol), ruthenium trichloride b (0.05 mmol) and an auxiliary agent c (2 mmol) sorbitol are mixed and ground uniformly, wherein the molar ratio of a to b is 99.5/0.5, and the molar ratio of c to the sum of a and b is 0.2. The obtained mixture is calcined at 350 ℃ for 2 hours in an air atmosphere to obtain the ruthenium monoatomic doped manganese oxide catalyst.
The oxidation process of 5-hydroxymethylfurfural was the same as in example 1, except that the catalyst of example 1 was replaced with the present catalyst. Qualitative and quantitative measurements were performed using HPLC (Water 2487) and the results are shown in Table 1 under the number 19.
Example 20
Preparation of ruthenium monoatomically doped manganese oxide catalyst: manganese nitrate a (9.95 mmol), ruthenium trichloride b (0.05 mmol) and xylitol as an auxiliary agent c (2 mmol) are mixed and ground uniformly, wherein the molar ratio of a to b is 99.5/0.5, and the molar ratio of c to the sum of a and b is 0.2. The obtained mixture is calcined at 350 ℃ for 2 hours in an air atmosphere to obtain the ruthenium monoatomic doped manganese oxide catalyst.
The oxidation process of 5-hydroxymethylfurfural was the same as in example 1, except that the catalyst of example 1 was replaced with the present catalyst. Qualitative and quantitative measurements were performed using HPLC (Water 2487) and the results are shown in Table 1 under the number 20.
Examples 21 to 23
To an autoclave of 10mL, 0.03 g of 5-hydroxymethylfurfural, 3. 3 g of Water and 0.04g of sodium hydrogencarbonate were added, and further the ruthenium monoatomically doped manganese oxide (0.03. 0.03 g) prepared in example 2 was added as a catalyst, the autoclave was sealed, 5. 5 bar, 15. 15 bar or 20. 20 bar of oxygen was introduced, vigorously stirred (600. 600 rpm), heated to 130℃and kept for 1.5 hours, the reaction was cooled to room temperature and sampled, and qualitative and quantitative detection was performed using HPLC (Water 2487), the detection results being listed in Table 1 under numbers 21 to 23.
Examples 24 to 26
To an autoclave of 10 mL, 0.15 g, 0.3 g or 0.6g of 5-hydroxymethylfurfural, 3g of Water and 0.04 g, 0.19g, 0.4g or 0.8g of sodium hydrogencarbonate were added, and further the ruthenium monoatomic doped manganese oxide (0.15 g, 0.3 g or 0.6 g) prepared in example 2 was added as a catalyst, the autoclave was sealed, 10 bar of oxygen was introduced, vigorously stirred (600 rpm), heated to 130℃and kept for 1.5 hours, the reaction was cooled to room temperature and sampled, and qualitative and quantitative detection was performed using HPLC (Water 2487), the detection results being listed in Table 1 under numbers 27 to 29.
Table 1 results of the tests in the examples
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Claims (10)

1. The noble metal monoatomic doped metal oxide catalyst is characterized in that the noble metal monoatomic doped metal oxide catalyst is prepared by taking a precursor a, an active metal b and an auxiliary agent c as raw materials, wherein the precursor is at least one of manganese nitrate, cobalt nitrate, ferric nitrate, nickel nitrate, chromium nitrate and copper nitrate; the active metal is at least one of ruthenium trichloride, iridium trichloride, rhodium trichloride, silver nitrate, chloroauric acid, palladium chloride and platinum tetrachloride; the auxiliary agent c is polyol or organic acid.
2. The noble metal single atom doped metal oxide catalyst of claim 1, wherein the polyol is sorbitol or xylitol.
3. The noble metal monoatomic doped metal oxide catalyst of claim 1, wherein the organic acid is citric acid, ethylenediamine tetraacetic acid, malic acid, tartaric acid, or vitamin C.
4. The noble metal monoatomic doped metal oxide catalyst according to claim 1, wherein the molar ratio of precursor a to active metal b is (95-99.9): (0.1 to 5); the mole ratio of the sum of the auxiliary agent c and a+b is (0.1-0.3): 1.
5. A method for preparing the noble metal monoatomic doped metal oxide catalyst according to any one of claims 1 to 4, comprising the steps of pretreatment and calcination, specifically comprising:
A. Pretreatment: weighing a precursor a, an active metal b and an auxiliary agent c according to the formula proportion, fully mixing and grinding uniformly to obtain a material a;
B. Calcining: and calcining the material a to obtain the target noble metal monoatomic doped metal oxide catalyst.
6. The method according to claim 5, wherein the calcination in the step B is performed at 200-400 ℃ for 1-3 hours.
7. The process according to claim 5, wherein the calcination in the step B is performed under an air atmosphere.
8. The application of the noble metal monoatomic doped metal oxide catalyst according to any one of claims 1 to 4, which is characterized in that the noble metal monoatomic doped metal oxide catalyst is applied to the preparation of 2, 5-furandicarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural.
9. The use according to claim 8, wherein the preparation of 2, 5-furandicarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural comprises pretreatment and main reaction steps, and specifically comprises:
A. Pretreatment: mixing 5-hydroxymethylfurfural, alkali and deionized water, then placing the mixture in a reaction container, and adding the noble metal monoatomic doped metal oxide catalyst; the alkali is sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate or potassium bicarbonate;
B. The main reaction: and (3) taking oxygen as an oxygen source to react for 0.5-3 hours at the temperature of 100-150 ℃ and the pressure of 1-20 bar to obtain the 2, 5-furandicarboxylic acid.
10. The use according to claim 9, wherein in step a the concentration of 5-hydroxymethylfurfural in the solvent is 0.5-20 wt%; the mass ratio of the noble metal monoatomic doped metal oxide catalyst to the 5-hydroxymethylfurfural is (0.2-3): 1, a step of; the molar ratio of the alkali to the 5-hydroxymethylfurfural is (0.1-3): 1.
CN202410420131.9A 2024-04-09 2024-04-09 Noble metal monoatomic doped metal oxide catalyst and preparation method and application thereof Pending CN118122323A (en)

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