Metal monatomic alloy catalyst as well as preparation method and application thereof
The preparation of metal single-atom alloy catalysts through grinding-reduction method solves the problem of low catalytic efficiency of hydrodeoxygenation of biomass-based alcohol/aldehyde compounds, and realizes simple, green and efficient catalyst preparation and application.
Patent Information
- Application Number
- CN202510428034.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-07
- Publication Date
- 2025-07-11
AI Technical Summary
In the prior art, the hydrodeoxygenation catalyst of biomass-based alcohol/aldehyde compounds has problems of low catalytic efficiency and insufficient utilization of precious metal atoms, and the traditional preparation method is complex and not environmentally friendly.
The metal single-atom alloy catalyst was prepared by grinding-reduction strategy. By mixing the single-atom noble metal precursor and the support metal precursor, reducing and calcining by hydrogen, a metal single-atom alloy catalyst was obtained, which was applied to the hydrodeoxygenation reaction of biomass-based alcohols/aldehyde compounds.
It realizes the simple, green and easy-to-scale preparation of high-efficiency metal single-atom alloy catalysts, improves catalytic performance, and is suitable for the hydrodeoxygenation reaction of biomass-based alcohols/aldehyde compounds.
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Figure CN120286024A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the field of chemical engineering, and particularly relates to a multi-metal single-atom alloy catalyst, a preparation method thereof, and an application thereof. Background Art
[0002] Biomass-based alcohol / aldehyde compounds (such as 5-hydroxymethylfurfural, furfural, levulinic acid, vanillin, benzaldehyde, p-anisyl alcohol, p-hydroxybenzyl alcohol, etc.) are important platform molecules of renewable resources, and the catalytic hydrodeoxygenation technology thereof is one of the core paths for realizing the high-value utilization of biomass. This technology selectively removes oxygen-containing functional groups and hydrogenates unsaturated bonds to generate hydrocarbon compounds or fine chemicals with high energy density and strong stability. It should be noted that for biomass platform molecules represented by 5-hydroxymethylfurfural, selective catalytic hydrodeoxygenation can produce high-value biofuels (2,5-dimethylfuran). Because of its excellent properties such as high octane number (119), moderate boiling range (92-94 °C), and low miscibility with water, it becomes an ideal component of liquid transportation biofuels. In addition, vanillin can be hydrodeoxygenated to obtain promising liquid biofuel 2-methoxy-4-methylphenol, and levulinic acid can be hydrogenated to prepare γ-valerolactone, which can be used as a green solvent and a pharmaceutical intermediate, etc. Generally, the hydrodeoxygenation of biomass-based alcohol / aldehyde compounds is carried out on noble metal nanoparticle catalysts, however, there are problems of low catalytic efficiency and insufficient utilization rate of noble metal atoms. Single-atom catalysts have far higher catalytic performance than nanoparticle catalysts due to their high atomic utilization rate and controllable coordination structure, and have become an important research direction in the field of biomass conversion.
[0003] However, there are some limitations in traditional preparation methods of single-atom catalysts: Although atomic layer deposition can achieve high dispersion of single atoms, there are problems of complex preparation process and high cost; the impregnation method has a simple process but is limited by disadvantages such as low loading, easy agglomeration, and heavy metal waste liquid pollution. Therefore, developing a synthesis method of single-atom catalysts with universality, economy, and "environmental friendliness" is still the key to be urgently broken through in this field.
[0004] Compared with traditional preparation methods of single-atom catalysts based on wet chemical methods, the method for preparing single-atom alloy catalysts based on the grinding-reduction strategy in the present invention not only has a simpler synthesis process and lower equipment requirements, but also does not require the use of solvents. Therefore, it can be considered as a green, convenient, and industrially applicable synthesis method of single-atom catalysts. Summary of the Invention
[0005] The first object of the present invention is to provide a metal single-atom alloy catalyst; the second object is to provide a preparation method of the metal single-atom alloy catalyst; the third object is to provide an application of the metal single-atom alloy catalyst.
[0006] The first object of the present invention is achieved in that the metal single-atom alloy catalyst is prepared by pre-treatment and calcination of a single-atom noble metal precursor a and a carrier metal precursor b, wherein the single-atom noble metal precursor a is one or more of ruthenium trichloride, iridium trichloride, rhodium trichloride, silver nitrate, chloroauric acid, palladium chloride and platinum tetrachloride; and the carrier metal precursor is one or more of cobalt nitrate, manganese nitrate, iron nitrate, nickel nitrate, chromium nitrate, copper nitrate, zinc nitrate and aluminum nitrate.
[0007] The second object of the present invention is achieved by comprising pre-treatment and reduction treatment steps, specifically comprising: A. Pretreatment: Weigh the single-atom noble metal precursor a and the carrier metal precursor b according to the formula ratio, mix and grind them evenly to obtain material c; B. Reduction treatment: calcining material c in a hydrogen reducing atmosphere to obtain the target metal single atom alloy catalyst.
[0008] The atmosphere of the tubular furnace described in step B is a 10% H2 / N2 mixed gas, the reduction temperature is 200-500°C, and the time is 1-5h.
[0009] The specific operations are: A single-atom noble metal precursor a (one or more of ruthenium trichloride, iridium trichloride, rhodium trichloride, silver nitrate, chloroauric acid, palladium chloride and platinum tetrachloride) and a carrier metal precursor b (one or more of cobalt nitrate, manganese nitrate, iron nitrate, nickel nitrate, chromium nitrate, copper nitrate, zinc nitrate and aluminum nitrate) are placed in an agate mortar and ground thoroughly to obtain a uniform mixture. The obtained material c is then calcined in a tubular furnace with a H2 / N2 mixed gas at 200-500°C for 1-5h to obtain a metal single-atom alloy catalyst, wherein the molar ratio of a to b is (0.1-3):100.
[0010] In a preferred embodiment of the present invention, the obtained material c is calcined at 200-500° C. in a 10% H 2 / N 2 mixed gas atmosphere for 2 h.
[0011] The third object of the present invention is achieved by using the metal single-atom alloy catalyst in catalyzing the hydrodeoxygenation reaction of biomass-based alcohol / aldehyde compounds.
[0012] The specific steps are as follows: The hydrogenation and deoxygenation of 5-hydroxymethylfurfural to prepare 2,5-dimethylfuran is used as a model reaction for the hydrogenation and deoxygenation of biomass-based alcohol / aldehyde compounds to study the application performance of the metal single-atom alloy catalyst, specifically including: loading 5-hydroxymethylfurfural, the metal single-atom alloy catalyst and a solvent into a high-pressure reactor, sealing it after mixing evenly, and carrying out a closed reaction at a stirring rate of 600 rpm under the conditions of 100 - 160 °C and a hydrogen pressure of 10 bar for 1 - 3 h, then cooling to room temperature to obtain 2,5-dimethylfuran, and detecting the cooled solution by a gas chromatograph (Agilent 7820).
[0013] In a preferred embodiment of the present invention, the temperature of the above reaction is 100 - 160 °C, the time is 1 - 3 h, the hydrogen pressure is 10 bar, the concentration of 5-hydroxymethylfurfural in the solvent is 1 - 10 wt%, and the mass ratio of the catalyst to 5-hydroxymethylfurfural is (0.3 - 1.6):1.
[0014] In a preferred embodiment of the present invention, the solvent used is ethanol.
[0015] Compared with the background technology, the present technical solution has the following advantages: 1. The metal single-atom alloy catalyst prepared in the present invention effectively catalyzes the hydrogenation and deoxygenation of biomass-based alcohol / aldehyde compounds to prepare downstream derivatives.
[0016] 2. The present invention provides a solvent-free, simple and easily scalable method for preparing the metal single-atom alloy catalyst. The preparation process is solvent-free, simple, environmentally friendly and easy to prepare on a large scale. In this method, the required metal single-atom alloy can be obtained through simple grinding and reduction treatments.
[0017] The method for preparing the metal single-atom alloy catalyst of the present invention has the advantages of being solvent-free and simple in operation, and at the same time, the prepared metal single-atom alloy has excellent catalytic hydrogenation and deoxygenation reaction activity. Brief Description of the Drawings
[0018] Figure 1 is the aberration-corrected transmission electron microscopy image of the catalyst; Figure 2 is the X-ray energy spectrum analysis Co element map of the catalyst; Figure 3 is the X-ray energy spectrum analysis Ru element map of the catalyst. Detailed Embodiments
[0019] The following further illustrates the present invention with reference to embodiments, but the present invention is not limited in any way. Any transformation or replacement based on the teachings of the present invention falls within the protection scope of the present invention.
[0020] The metal single-atom alloy catalyst described in the present invention is prepared by pretreatment and calcination of a single-atom noble metal precursor a and a support metal precursor b. The single-atom noble metal precursor a is one or more of ruthenium trichloride, iridium trichloride, rhodium trichloride, silver nitrate, chloroauric acid, palladium chloride, and platinum tetrachloride; the support metal precursor is one or more of cobalt nitrate, manganese nitrate, iron nitrate, nickel nitrate, chromium nitrate, copper nitrate, zinc nitrate, and aluminum nitrate.
[0021] The molar ratio of the single-atom noble metal precursor a to the support metal precursor b is (0.1~3):100.
[0022] The preparation method of the metal single-atom alloy catalyst described in the present invention includes pretreatment and reduction treatment steps, specifically including: A. Pretreatment: Weigh the single-atom noble metal precursor a and the support metal precursor b according to the formula ratio, mix and grind them evenly to obtain material c; B. Reduction treatment: The material c is calcined in a hydrogen reduction atmosphere to obtain the target metal single-atom alloy catalyst.
[0023] The hydrogen reduction atmosphere in step B is a hydrogen-nitrogen mixture.
[0024] The volume ratio of hydrogen to nitrogen is (5~15):(85~95).
[0025] The volume ratio of hydrogen to nitrogen is 10:90.
[0026] The calcination temperature in step B is 200 - 500 °C.
[0027] The calcination time in step B is 1~5 h.
[0028] The application described in the present invention is the application of the metal single-atom alloy catalyst in the hydrodeoxygenation reaction of biomass-based alcohol / aldehyde compounds.
[0029] The hydrodeoxygenation reaction of the biomass-based alcohol / aldehyde compounds described includes pretreatment and main reaction steps, specifically including: A. Pretreatment: Mix the reaction substrate and ethanol, place them in a reaction vessel, and add the metal single-atom alloy catalyst; B. Main reaction: Using hydrogen as the hydrogen source, react at a temperature of 100~160 °C for 1 - 3 h.
[0030] In step A, the concentration of 5-hydroxymethylfurfural in the solvent is 1 - 10 wt%; the mass ratio of the metal single-atom alloy catalyst to 5-hydroxymethylfurfural is (0.3 - 1.6):1.
[0031] The present invention will be further described below with specific implementation cases: Example 1
[0032] Preparation of ruthenium-cobalt single-atom alloy catalyst: The single-atom noble metal precursor a (ruthenium trichloride, 0.01 mmol) and the support metal precursor b (cobalt nitrate, 10 mmol) were mixed and ground evenly, and the molar ratio of b to a was 100 / 0.1. The obtained mixture was calcined in a tubular furnace with a 10% H2 / N2 mixed gas at 300 °C for 2 h to obtain the ruthenium-cobalt single-atom alloy catalyst.
[0033] Hydrodeoxygenation reaction process of 5-hydroxymethylfurfural: 0.06 g of 5-hydroxymethylfurfural and 5 mL of ethanol were added to a 10 mL high-temperature and high-pressure autoclave, and then 0.06 g of the above ruthenium-cobalt single-atom alloy catalyst was added; after sealing the reaction kettle, 10 bar of hydrogen was introduced, and then it was heated to 140 °C under vigorous stirring (600 rpm) and maintained for 1 h to end the reaction. The cooled solution was qualitatively and quantitatively detected using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 1, with the serial number being 1.
[0034] Example 2
[0035] Preparation of ruthenium-cobalt single-atom alloy catalyst: The single-atom noble metal precursor a (ruthenium trichloride, 0.05 mmol) and the support metal precursor b (cobalt nitrate, 10 mmol) were mixed and ground evenly, and the molar ratio of b to a was 100 / 0.5. The obtained mixture was calcined in a tubular furnace with a 10% H2 / N2 mixed gas at 300 °C for 2 h to obtain the ruthenium-cobalt single-atom alloy catalyst.
[0036] The hydrodeoxygenation reaction process of 5-hydroxymethylfurfural was the same as that in Example 1, only replacing the catalyst in Example 1 with this catalyst. Qualitative and quantitative detection was carried out using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 1, with the serial number being 2.
[0037] Example 3
[0038] Preparation of ruthenium-cobalt single-atom alloy catalyst: The single-atom noble metal precursor a (ruthenium trichloride, 0.1 mmol) and the support metal precursor b (cobalt nitrate, 10 mmol) were mixed and ground evenly, and the molar ratio of b to a was 100 / 1. The obtained mixture was calcined in a tubular furnace with a 10% H2 / N2 mixed gas at 300 °C for 2 h to obtain the ruthenium-cobalt single-atom alloy catalyst.
[0039] The hydrodeoxygenation reaction process of 5-hydroxymethylfurfural was the same as that in Example 1, only replacing the catalyst in Example 1 with this catalyst. Qualitative and quantitative detection was carried out using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 1, with the serial number being 3.
[0040] Example 4
[0041] Preparation of ruthenium-manganese single-atom alloy catalyst: Mix and grind evenly the single-atom noble metal precursor a (ruthenium trichloride, 0.05 mmol) and the support metal precursor b (manganese nitrate, 10 mmol), where the molar ratio of b to a is 100 / 0.5. The obtained mixture is calcined in a tubular furnace with a 10% H2 / N2 mixed gas at 300 °C for 2 h to obtain the ruthenium-manganese single-atom alloy catalyst.
[0042] The process of hydrodeoxygenation reaction of 5-hydroxymethylfurfural is the same as that in Example 1, only replacing the catalyst in Example 1 with this catalyst. Qualitative and quantitative detections are carried out using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 1, with the serial number being 4.
[0043] Example 5
[0044] Preparation of ruthenium-iron single-atom alloy catalyst: Mix and grind evenly the single-atom noble metal precursor a (ruthenium trichloride, 0.05 mmol) and the support metal precursor b (iron nitrate, 10 mmol), where the molar ratio of b to a is 100 / 0.5. The obtained mixture is calcined in a tubular furnace with a 10% H2 / N2 mixed gas at 300 °C for 2 h to obtain the ruthenium-iron single-atom alloy catalyst.
[0045] The process of hydrodeoxygenation reaction of 5-hydroxymethylfurfural is the same as that in Example 1, only replacing the catalyst in Example 1 with this catalyst. Qualitative and quantitative detections are carried out using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 1, with the serial number being 5.
[0046] Example 6
[0047] Preparation of ruthenium-nickel single-atom alloy catalyst: Mix and grind evenly the single-atom noble metal precursor a (ruthenium trichloride, 0.05 mmol) and the support metal precursor b (nickel nitrate, 10 mmol), where the molar ratio of b to a is 100 / 0.5. The obtained mixture is calcined in a tubular furnace with a 10% H2 / N2 mixed gas at 300 °C for 2 h to obtain the ruthenium-nickel single-atom alloy catalyst.
[0048] The process of hydrodeoxygenation reaction of 5-hydroxymethylfurfural is the same as that in Example 1, only replacing the catalyst in Example 1 with this catalyst. Qualitative and quantitative detections are carried out using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 1, with the serial number being 6.
[0049] Example 7
[0050] Preparation of ruthenium-chromium single-atom alloy catalyst: The single-atom noble metal precursor a (ruthenium trichloride, 0.05 mmol) and the support metal precursor b (chromium nitrate, 10 mmol) were mixed and ground evenly, and the molar ratio of b to a was 100 / 0.5. The obtained mixture was calcined in a tubular furnace with 10% H2 / N2 mixed gas at 300 °C for 2 h to obtain the ruthenium-chromium single-atom alloy catalyst.
[0051] The process of hydrodeoxygenation reaction of 5-hydroxymethylfurfural was the same as that in Example 1, only replacing the catalyst in Example 1 with this catalyst. Qualitative and quantitative detections were carried out using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 1, with the serial number being 7.
[0052] Example 8
[0053] Preparation of ruthenium-copper single-atom alloy catalyst: The single-atom noble metal precursor a (ruthenium trichloride, 0.05 mmol) and the support metal precursor b (copper nitrate, 10 mmol) were mixed and ground evenly, and the molar ratio of b to a was 100 / 0.5. The obtained mixture was calcined in a tubular furnace with 10% H2 / N2 mixed gas at 300 °C for 2 h to obtain the ruthenium-copper single-atom alloy catalyst.
[0054] The process of hydrodeoxygenation reaction of 5-hydroxymethylfurfural was the same as that in Example 1, only replacing the catalyst in Example 1 with this catalyst. Qualitative and quantitative detections were carried out using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 1, with the serial number being 8.
[0055] Example 9
[0056] Preparation of ruthenium-zinc single-atom alloy catalyst: The single-atom noble metal precursor a (ruthenium trichloride, 0.05 mmol) and the support metal precursor b (zinc nitrate, 10 mmol) were mixed and ground evenly, and the molar ratio of b to a was 100 / 0.5. The obtained mixture was calcined in a tubular furnace with 10% H2 / N2 mixed gas at 300 °C for 2 h to obtain the ruthenium-zinc single-atom alloy catalyst.
[0057] The process of hydrodeoxygenation reaction of 5-hydroxymethylfurfural was the same as that in Example 1, only replacing the catalyst in Example 1 with this catalyst. Qualitative and quantitative detections were carried out using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 1, with the serial number being 9.
[0058] Example 10
[0059] Preparation of ruthenium-aluminum single-atom alloy catalyst: The single-atom noble metal precursor a (ruthenium trichloride, 0.05 mmol) and the support metal precursor b (aluminum nitrate, 10 mmol) were mixed and ground evenly, with the molar ratio of b to a being 100 / 0.5. The resulting mixture was calcined in a tubular furnace with a 10% H2 / N2 mixture at 300 °C for 2 h to obtain the ruthenium-aluminum single-atom alloy catalyst.
[0060] The process of hydrodeoxygenation reaction of 5-hydroxymethylfurfural was the same as that in Example 1, except that this catalyst was used to replace the catalyst in Example 1. Qualitative and quantitative detections were carried out using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 1, with the serial number being 10.
[0061] Example 11
[0062] Preparation of iridium-cobalt single-atom alloy catalyst: The single-atom noble metal precursor a (iridium trichloride, 0.05 mmol) and the support metal precursor b (cobalt nitrate, 10 mmol) were mixed and ground evenly, with the molar ratio of b to a being 100 / 0.5. The resulting mixture was calcined in a tubular furnace with a 10% H2 / N2 mixture at 300 °C for 2 h to obtain the iridium-cobalt single-atom alloy catalyst.
[0063] The process of hydrodeoxygenation reaction of 5-hydroxymethylfurfural was the same as that in Example 1, except that this catalyst was used to replace the catalyst in Example 1. Qualitative and quantitative detections were carried out using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 1, with the serial number being 11.
[0064] Example 12
[0065] Preparation of rhodium-cobalt single-atom alloy catalyst: The single-atom noble metal precursor a (rhodium trichloride, 0.05 mmol) and the support metal precursor b (cobalt nitrate, 10 mmol) were mixed and ground evenly, with the molar ratio of b to a being 100 / 0.5. The resulting mixture was calcined in a tubular furnace with a 10% H2 / N2 mixture at 300 °C for 2 h to obtain the rhodium-cobalt single-atom alloy catalyst.
[0066] The process of hydrodeoxygenation reaction of 5-hydroxymethylfurfural was the same as that in Example 1, except that this catalyst was used to replace the catalyst in Example 1. Qualitative and quantitative detections were carried out using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 1, with the serial number being 12.
[0067] Example 13
[0068] Preparation of silver-cobalt single-atom alloy catalyst: The single-atom noble metal precursor a (silver nitrate, 0.05 mmol) and the support metal precursor b (cobalt nitrate, 10 mmol) were mixed and ground evenly, where the molar ratio of b to a was 100 / 0.5. The obtained mixture was calcined in a tube furnace with a 10% H2 / N2 mixture at 300 °C for 2 h to obtain the silver-cobalt single-atom alloy catalyst.
[0069] The process of hydrodeoxygenation reaction of 5-hydroxymethylfurfural was the same as that in Example 1, only replacing the catalyst in Example 1 with this catalyst. Qualitative and quantitative detections were carried out using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 1, with the serial number being 13.
[0070] Example 14
[0071] Preparation of gold-cobalt single-atom alloy catalyst: The single-atom noble metal precursor a (chloroauric acid, 0.05 mmol) and the support metal precursor b (cobalt nitrate, 10 mmol) were mixed and ground evenly, where the molar ratio of b to a was 100 / 0.5. The obtained mixture was calcined in a tube furnace with a 10% H2 / N2 mixture at 300 °C for 2 h to obtain the gold-cobalt single-atom alloy catalyst.
[0072] The process of hydrodeoxygenation reaction of 5-hydroxymethylfurfural was the same as that in Example 1, only replacing the catalyst in Example 1 with this catalyst. Qualitative and quantitative detections were carried out using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 1, with the serial number being 14.
[0073] Example 15
[0074] Preparation of palladium-cobalt single-atom alloy catalyst: The single-atom noble metal precursor a (palladium chloride, 0.05 mmol) and the support metal precursor b (cobalt nitrate, 10 mmol) were mixed and ground evenly, where the molar ratio of b to a was 100 / 0.5. The obtained mixture was calcined in a tube furnace with a 10% H2 / N2 mixture at 300 °C for 2 h to obtain the palladium-cobalt single-atom alloy catalyst.
[0075] The process of hydrodeoxygenation reaction of 5-hydroxymethylfurfural was the same as that in Example 1, only replacing the catalyst in Example 1 with this catalyst. Qualitative and quantitative detections were carried out using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 1, with the serial number being 15.
[0076] Example 16
[0077] Preparation of platinum-cobalt single-atom alloy catalyst: Mix and grind evenly the single-atom noble metal precursor a (platinum tetrachloride, 0.05 mmol) and the support metal precursor b (cobalt nitrate, 10 mmol), where the molar ratio of b to a is 100 / 0.5. Calcinate the obtained mixture in a tube furnace with 10% H2 / N2 mixed gas at 300 °C for 2 h to obtain the platinum-cobalt single-atom alloy catalyst.
[0078] The hydrodeoxygenation reaction process of 5-hydroxymethylfurfural is the same as that in Example 1, only replacing the catalyst in Example 1 with this catalyst. Qualitative and quantitative detections were carried out using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 1, with the serial number being 16.
[0079] Example 17
[0080] Preparation of ruthenium-cobalt single-atom alloy catalyst: Mix and grind evenly the single-atom noble metal precursor a (ruthenium trichloride, 0.05 mmol) and the support metal precursor b (cobalt nitrate, 10 mmol), where the molar ratio of b to a is 100 / 0.5. Calcinate the obtained mixture in a tube furnace with 10% H2 / N2 mixed gas at 200 °C for 2 h to obtain the ruthenium-cobalt single-atom alloy catalyst.
[0081] The hydrodeoxygenation reaction process of 5-hydroxymethylfurfural is the same as that in Example 1, only replacing the catalyst in Example 1 with this catalyst. Qualitative and quantitative detections were carried out using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 1, with the serial number being 17.
[0082] Example 18
[0083] Preparation of ruthenium-cobalt single-atom alloy catalyst: Mix and grind evenly the single-atom noble metal precursor a (ruthenium trichloride, 0.05 mmol) and the support metal precursor b (cobalt nitrate, 10 mmol), where the molar ratio of b to a is 100 / 0.5. Calcinate the obtained mixture in a tube furnace with 10% H2 / N2 mixed gas at 400 °C for 2 h to obtain the ruthenium-cobalt single-atom alloy catalyst.
[0084] The hydrodeoxygenation reaction process of 5-hydroxymethylfurfural is the same as that in Example 1, only replacing the catalyst in Example 1 with this catalyst. Qualitative and quantitative detections were carried out using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 1, with the serial number being 18.
[0085] Example 19
[0086] Preparation of ruthenium-cobalt single-atom alloy catalyst: The single-atom noble metal precursor a (ruthenium trichloride, 0.05 mmol) and the support metal precursor b (cobalt nitrate, 10 mmol) were mixed and ground evenly, and the molar ratio of b to a was 100 / 0.5. The obtained mixture was calcined in a tubular furnace at 500 °C for 2 h under a 10% H2 / N2 mixed gas to obtain the ruthenium-cobalt single-atom alloy catalyst.
[0087] The hydrodeoxygenation reaction process of 5-hydroxymethylfurfural was the same as that in Example 1, except that this catalyst was used to replace the catalyst in Example 1. Qualitative and quantitative detections were carried out using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 1, with the serial number being 19.
[0088] Examples 20 - 22 Add (0.1 g, 0.25 g, 0.5 g) 5-hydroxymethylfurfural and 5 mL of ethanol to a 10 mL high-temperature and high-pressure autoclave, and then add 0.06 g of the ruthenium-cobalt single-atom alloy catalyst prepared in Example 2; after sealing the reaction kettle, introduce 10 bar of hydrogen, and then heat to 140 °C under vigorous stirring (600 rpm) and hold for (2 h, 2.5 h, 3 h) before ending the reaction. The cooled solution was subjected to qualitative and quantitative detections using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 1, with the serial numbers being 20 - 22.
[0089] Examples 23 - 24 Add 0.06 g of 5-hydroxymethylfurfural and 5 mL of ethanol to a 10 mL high-temperature and high-pressure autoclave, and then add 0.06 g of the ruthenium-cobalt single-atom alloy catalyst prepared in Example 2; after sealing the reaction kettle, introduce 10 bar of hydrogen, and then heat to 140 °C under vigorous stirring (600 rpm) and hold for (2 h, 3 h) before ending the reaction. The cooled solution was subjected to qualitative and quantitative detections using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 1, with the serial numbers being 23 - 24.
[0090] Examples 25 - 28 Add 0.06 g of 5-hydroxymethylfurfural and 5 mL of ethanol to a 10 mL high-temperature and high-pressure autoclave, and then add the ruthenium-cobalt single-atom alloy catalyst prepared in Example 2 (0.02 g, 0.04 g, 0.08 g, 0.1 g); after sealing the reaction kettle, introduce 10 bar of hydrogen, and then heat to 140 °C under vigorous stirring (600 rpm) and hold for 1 h before ending the reaction. The cooled solution was subjected to qualitative and quantitative detections using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 1, with the serial numbers being 25 - 28.
[0091] Examples 29 - 31 Add 0.06 g of 5-hydroxymethylfurfural and 5 mL of ethanol to a 10 mL high-temperature and high-pressure autoclave, and then add 0.06 g of the ruthenium-cobalt single-atom alloy catalyst prepared in Example 2; after sealing the autoclave, introduce 10 bar of hydrogen, and then heat to (100 °C, 120 °C, 160 °C) under vigorous stirring (600 rpm) and hold for 1 h to end the reaction. The cooled solution is subjected to qualitative and quantitative detection using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 1, with serial numbers 29 - 31.
[0092] Example 32
[0093] Add 0.06 g of furfural and 5 mL of ethanol to a 10 mL high-temperature and high-pressure autoclave, and then add 0.06 g of the ruthenium-cobalt single-atom alloy catalyst prepared in Example 2; after sealing the autoclave, introduce 10 bar of hydrogen, and then heat to 140 °C under vigorous stirring (600 rpm) and hold for 1 h to end the reaction. The cooled solution is subjected to qualitative and quantitative detection using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 2, with serial number 32.
[0094] Example 33
[0095] Add 0.06 g of levulinic acid and 5 mL of ethanol to a 10 mL high-temperature and high-pressure autoclave, and then add 0.06 g of the ruthenium-cobalt single-atom alloy catalyst prepared in Example 2; after sealing the autoclave, introduce 10 bar of hydrogen, and then heat to 140 °C under vigorous stirring (600 rpm) and hold for 1.5 h to end the reaction. The cooled solution is subjected to qualitative and quantitative detection using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 2, with serial number 33.
[0096] Example 34
[0097] Add 0.06 g of vanillin and 5 mL of ethanol to a 10 mL high-temperature and high-pressure autoclave, and then add 0.06 g of the ruthenium-cobalt single-atom alloy catalyst prepared in Example 2; after sealing the autoclave, introduce 10 bar of hydrogen, and then heat to 140 °C under vigorous stirring (600 rpm) and hold for 1.5 h to end the reaction. The cooled solution is subjected to qualitative and quantitative detection using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 2, with serial number 34.
[0098] Example 35
[0099] Add 0.06 g of benzaldehyde and 5 mL of ethanol to a 10 mL high-temperature and high-pressure autoclave, and then add 0.06 g of the ruthenium-cobalt single-atom alloy catalyst prepared in Example 2; after sealing the reaction kettle, introduce 10 bar of hydrogen, and then heat to 140 °C under vigorous stirring (600 rpm) and hold for 1.5 h to end the reaction. The cooled solution was subjected to qualitative and quantitative detection using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 2, with the serial number being 35.
[0100] Example 36
[0101] Add 0.06 g of p-methoxyphenol and 5 mL of ethanol to a 10 mL high-temperature and high-pressure autoclave, and then add 0.06 g of the ruthenium-cobalt single-atom alloy catalyst prepared in Example 2; after sealing the reaction kettle, introduce 10 bar of hydrogen, and then heat to 140 °C under vigorous stirring (600 rpm) and hold for 1.5 h to end the reaction. The cooled solution was subjected to qualitative and quantitative detection using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 2, with the serial number being 36.
[0102] Example 37
[0103] Add 0.06 g of p-hydroxybenzyl alcohol and 5 mL of ethanol to a 10 mL high-temperature and high-pressure autoclave, and then add 0.06 g of the ruthenium-cobalt single-atom alloy catalyst prepared in Example 2; after sealing the reaction kettle, introduce 10 bar of hydrogen, and then heat to 140 °C under vigorous stirring (600 rpm) and hold for 1.5 h to end the reaction. The cooled solution was subjected to qualitative and quantitative detection using a gas chromatograph (Agilent 7820), and the detection results are listed in Table 2, with the serial number being 37.
[0104] Table 1 Detection results in each example
[0105] Note: Unless otherwise specified, the reaction conditions are: 0.06 g of catalyst, 5 mL of ethanol, 0.06 g of 5-hydroxymethylfurfural, 10 bar H2, 140 °C, and 1 h.
[0106] a The molar ratio of the support metal precursor b to the single-atom noble metal precursor a is 100 / 0.1; b The molar ratio of the support metal precursor b to the single-atom noble metal precursor a is 100 / 1; c The calcination temperature of the material c in the tubular furnace is 200 °C; d The calcination temperature of the material c in the tubular furnace is 400 °C; e The calcination temperature of material c in the tubular furnace is 500 °C; f 0.1 g of 5-hydroxymethylfurfural is added and the reaction time is 2 h; g 0.25 g of 5-hydroxymethylfurfural is added and the reaction time is 2.5 h; h 0.5 g of 5-hydroxymethylfurfural is added and the reaction time is 3 h; i The reaction time is 2 h; j The reaction time is 3 h; The detection results in each example in Table 2
[0107] Note: The reaction conditions are: 0.06 g of catalyst, 5 mL of ethanol, 0.06 g of reaction substrate, 10 bar H2, 140 °C and 1.5 h.
Claims
1. A metal single-atom alloy catalyst, characterized in that, The described metal single-atom alloy catalyst is prepared by pretreatment and calcination of a single-atom noble metal precursor a and a support metal precursor b. The single-atom noble metal precursor a is one or more of ruthenium trichloride, iridium trichloride, rhodium trichloride, silver nitrate, chloroauric acid, palladium chloride, and platinum tetrachloride; the support metal precursor is one or more of cobalt nitrate, manganese nitrate, iron nitrate, nickel nitrate, chromium nitrate, copper nitrate, zinc nitrate, and aluminum nitrate.
2. The metal single-atom alloy catalyst according to claim 1, characterized in that, The molar ratio of the single-atom noble metal precursor a to the support metal precursor b is (0.1~3):
100.
3. A method for preparing the metal single-atom alloy catalyst according to claim 1 or 2, characterized in that, It includes a pretreatment step and a reduction treatment step, specifically including: A. Pretreatment: Weigh the single-atom noble metal precursor a and the support metal precursor b according to the formula ratio, mix them thoroughly and grind them evenly to obtain material c; B. Reduction treatment: The material c is calcined in a hydrogen reduction atmosphere to obtain the target metal single-atom alloy catalyst.
4. The preparation method according to claim 3, characterized in that, The hydrogen reduction atmosphere in step B is a hydrogen-nitrogen mixed gas.
5. The preparation method according to claim 4, characterized in that The volume ratio of the hydrogen to the nitrogen is (5~15):(85~95).
6. The preparation method according to claim 4, wherein The volume ratio of the hydrogen to the nitrogen is 10:
90.
7. The preparation method according to claim 3, characterized in that, The calcination temperature in step B is 200-500°C.
8. The preparation method according to claim 3, characterized in that, The calcination time in step B is 1~5h.
9. Use of the metal single-atom alloy catalyst according to claim 1 or 2, characterized in that, The application of the described metal single-atom alloy catalyst in the catalytic hydrodeoxygenation reaction of biomass-based alcohol / aldehyde compounds.
10. The application according to claim 9, wherein The catalytic hydrodeoxygenation reaction of the biomass-based alcohol / aldehyde compounds includes a pretreatment step and a main reaction step, specifically including: A. Pretreatment: Mix the reaction substrate and ethanol and place them in a reaction vessel, and add the described metal single-atom alloy catalyst; B. Main reaction: Using hydrogen as the hydrogen source, react at a temperature of 100~160°C for 1-3h.