Supported metal catalysts, methods for their synthesis and use

Abstract

The application provides a supported metal catalyst, application and synthesis method thereof, and the method comprises the following steps: dispersing chloromethyl resin in a first solvent, adding a modifier, i.e., a nitrogen and / or sulfur and / or phosphine containing organic compound, after first heating and stirring, drying the obtained solid to obtain a modified resin; dispersing the modified resin in a second solvent, adding a metal precursor, after second heating and stirring, drying the obtained solid to obtain a supported metal catalyst. The monodisperse supported metal catalyst has the advantages of simple preparation method, good metal versatility, high loading capacity, high activity and adjustable structure.

Description

Technical Field

[0001] This invention relates to a supported metal catalyst, its synthesis method, and its application. Background Technology

[0002] Single-atom catalysts are supported metal catalysts in which the active metal component exists in a single-atom dispersed form on a support. The concept of "single-atom catalysis" was first proposed in 2011 by Academician Zhang Tao of the Dalian Institute of Chemical Physics and Professor Li Jun of Tsinghua University (Nat. Chem., 2011, 3, 634). In recent years, with the continuous in-depth research on single-atom catalysts, single-atom catalysis has become a cutting-edge research area in catalysis. Compared with traditional nanocatalysts, single-atom catalysts exhibit significantly different activities, selectivity, and stability in many redox reactions.

[0003] Currently, the main methods for preparing single-atom catalysts include co-precipitation, atomic layer deposition, impregnation, stepwise reduction, and solid-phase melting. Co-precipitation is a traditional method for preparing nano-metal catalysts. The components can be precipitated by adjusting the pH of the solution with a precipitant to obtain a supported catalyst. Zhang Tao et al. prepared a 0.17% Pt / FeOx single-atom catalyst by co-precipitation in an alkaline solution of sodium carbonate using chloroplatinic acid and ferric nitrate as raw materials. The catalyst showed good catalytic performance in the catalytic oxidation of carbon monoxide [Qiao B.T. et al., Nature Chemistry 3(8), 634-641]. Wu Yu'en et al. obtained zinc- and cobalt-containing MOF-based precursors using cobalt nitrate, zinc nitrate, and dimethylimidazole as raw materials. These precursors were then further pyrolyzed at 800℃ in a nitrogen atmosphere to obtain cobalt-based single-atom materials with a loading of 4% [Yin PQ, et al., Angew. Chem. Int. Ed., 2006, 55(36), 10800-10805]. Ji Hongbing et al. employed a precursor atomization method to prepare single-atom catalysts. By atomizing and dispersing metal salts on a support surface, they underwent high-temperature calcination to obtain different single-atom supported catalysts [CN110479249].

[0004] These preparation methods suffer from drawbacks such as complex processes, high costs, and difficulties in industrial-scale production. For the active metal component, these methods exhibit certain limitations, including specific requirements for the metal composition, low process versatility, and low catalyst loading. Therefore, developing a supported catalyst preparation method with good versatility, low cost, and high active component content holds great promise for practical application. Summary of the Invention

[0005] The purpose of this invention is to provide a method for preparing single-atom metal materials using chloromethyl resin. This invention involves functionalizing the chloromethyl resin and then reducing and loading a metal precursor to obtain a monodisperse supported metal catalyst. The method of this invention is simple and rapid throughout the synthesis process and can be applied to the synthesis of various single-atom dispersed metal catalyst systems.

[0006] According to a first aspect of the present invention, a supported metal catalyst is provided, the catalyst comprising: a modified chloromethyl resin support and an elemental metal component supported on the support, wherein the modified chloromethyl resin support and the elemental metal component supported on the support are a crosslinked composition of an organic compound containing nitrogen and / or sulfur and / or phosphine and a chloromethyl resin.

[0007] According to a second aspect of the present invention, the present invention provides the application of the catalyst described herein in a hydrogenation reaction.

[0008] According to a third aspect of the present invention, the present invention provides a method for synthesizing the supported metal catalyst of the present invention, the method comprising:

[0009] 1) Disperse chloromethyl resin in a first solvent, add a modifier containing nitrogen and / or sulfur and / or phosphine organic compounds, heat and stir for the first time, and then dry the resulting solid to obtain the modified resin;

[0010] 2) The modified resin is dispersed in a second solvent, a metal precursor is added, and after heating and stirring, the resulting solid is dried to obtain a supported metal catalyst.

[0011] The monodisperse supported metal catalyst of the present invention has the advantages of simple preparation method, good metal versatility, high loading, high activity and tunable structure.

[0012] This invention provides a synthetic method for preparing highly loaded single-atom dispersed supported metal catalysts. The reaction conditions are mild and the method has good versatility. It can be used to synthesize single-atom highly loaded catalysts of different single-component and two-component types.

[0013] The catalyst prepared by the method of the present invention can be used in hydrogenation reactions, specifically in the hydrogenolysis of glycerol to produce 1,2-propanediol. Attached Figure Description

[0014] Figure 1 These are the XRD patterns of the catalysts prepared in Example 1 and Comparative Example 1;

[0015] Figure 2 These are TEM images of the catalyst prepared in Example 1;

[0016] Figure 3Here is a SEM image of the catalyst prepared in Example 1;

[0017] Figure 4 These are TEM images of the catalyst prepared in Comparative Example 1;

[0018] Figure 5 This is a SEM image of the catalyst prepared in Comparative Example 1. Detailed Implementation

[0019] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0020] This invention provides a supported metal catalyst comprising: a modified chloromethyl resin support and a elemental metal component supported on the support. The modified chloromethyl resin support is a crosslinked composition of an organic compound containing nitrogen and / or sulfur and / or phosphine and a chloromethyl resin. The monodisperse supported metal catalyst of this invention has the advantages of simple preparation method, good metal versatility, high loading capacity, and tunable structure.

[0021] According to a preferred embodiment of the present invention, the mass ratio of the nitrogen- and / or sulfur- and / or phosphine-containing organic compound to the chloromethyl resin is 0.05-0.4:1, preferably 0.1-0.3:1. Using the aforementioned ratio can improve the activity of the catalyst.

[0022] According to a preferred embodiment of the present invention, the mass ratio of metal to support is 0.1-30:100, preferably 0.5-20:100, and more preferably 1-10:100. Using the aforementioned ratio can improve the dispersion of the catalyst.

[0023] In this invention, the range of types of metal components is relatively wide. Any metal active component that can be used in hydrogenation reaction can be used in this invention. According to a preferred embodiment of this invention, the metal component is a hydrogenation active metal. Preferably, the metal element is selected from one or more of Group VIII, Group IB and Group IIB, more preferably from one or more of gold, silver, copper, palladium, ruthenium and platinum, and more preferably from one or more of palladium, silver, ruthenium and platinum.

[0024] In this invention, the range of nitrogen- and / or sulfur- and / or phosphine-containing organic compounds is relatively wide. For this invention, preferably, the nitrogen- and / or sulfur- and / or phosphine-containing organic compounds are selected from one or more of amines, pyridine, imidazoles, quinolines, pyrroles, indoles, carbazoles, thiazoles, thiophenes, phosphononitriles, thiols, thioethers, piperazines, and phosphine trichloride; more preferably, they are one or more of imidazoles, pyridines, thiophenes, thiazoles, piperazines, and phosphine trichloride; more preferably, they are one or more of imidazoles, pyridines, piperazines, and thiophenes; more preferably, they are a mixture of imidazoles and pyridines; and more preferably, the ratio of imidazoles to pyridines is 0.1-10:1. Using the aforementioned preferred nitrogen- and / or sulfur- and / or phosphine-containing organic compounds can improve the activity of the catalyst.

[0025] In this invention, the range of types of chloromethyl resin is relatively wide. Preferably, the chloromethyl resin is one or more of chloromethyl-modified polystyrene, chloromethyl-modified polyethylene, chloromethyl-modified carboxylic acid resin, and chloromethyl-modified phenolic resin; more preferably, it is selected from chloromethyl-modified polystyrene. Using the aforementioned preferred chloromethyl resin can improve the strength and activity of the catalyst.

[0026] In this invention, the morphology of the chloromethyl resin can be various, such as spherical. Using the aforementioned preferred morphology can improve the uniformity and activity of the catalyst.

[0027] According to a preferred embodiment of the present invention, the chloromethyl resin contains more than 5% by weight, preferably 10-18% by weight.

[0028] In this invention, the chloromethyl resin has a particle size of 0.1-3 mm, preferably 0.1-0.8 mm. Using the aforementioned preferred particle size can improve the uniformity and activity of the catalyst.

[0029] The catalyst of this invention is particularly suitable for use in hydrogenation reactions.

[0030] This invention provides the application of the catalyst described herein in hydrogenation reactions.

[0031] Catalysts possessing the aforementioned characteristics of this invention can achieve the objectives of this invention, and their preparation methods are not particularly required. According to a preferred embodiment of this invention, this invention provides a method for synthesizing the supported metal catalyst described herein, the method comprising:

[0032] 1) Disperse chloromethyl resin in a first solvent, and under first heating and stirring conditions, add a modifier containing nitrogen and / or sulfur and / or phosphine organic compounds, and dry the resulting solid to obtain modified resin;

[0033] 2) The modified resin is dispersed in a second solvent, and under a second heating and stirring condition, a metal precursor is added. The resulting solid is dried to obtain a supported metal catalyst. The catalyst prepared by the aforementioned method can improve catalyst activity.

[0034] According to a preferred embodiment of the present invention, the chloromethyl resin is one or more selected from chloromethyl-modified polystyrene, chloromethyl-modified polyethylene, chloromethyl-modified carboxylic acid resin, and chloromethyl-modified phenolic resin; preferably selected from chloromethyl-modified polystyrene. Using the aforementioned preferred chloromethyl resin enables the prepared catalyst to possess uniformity and activity.

[0035] According to a preferred embodiment of the present invention, the chloromethyl resin is spherical.

[0036] According to a preferred embodiment of the present invention, the chloromethyl resin has a particle size of 0.1-3 mm.

[0037] According to a preferred embodiment of the present invention, the chloromethyl resin contains more than 5% by weight, preferably 10-18% by weight.

[0038] In this invention, the range of types of the first solvent is relatively wide. Preferably, the first solvent has reducing properties. According to a preferred embodiment of this invention, the first solvent is one or more of toluene, methanol, ethanol, ethylene glycol, n-propanol, n-butanol, isobutanol, tert-butanol, tetrahydrofuran, dichloromethane, trichloromethane, amide, and ether, preferably N,N-dimethylformamide.

[0039] In this invention, the range of types of nitrogen- and / or sulfur- and / or phosphine-containing organic compounds is relatively wide. For this invention, it is preferred that the nitrogen- and / or sulfur- and / or phosphine-containing organic compounds are selected from one or more of piperazine, amine, pyridine, imidazole, quinoline, pyrrole, indole, carbazole, thiazole, thiophene, phosphononitrile, thiol, thioether, and phosphine trichloride. More preferably, it is selected from one or more of piperazine, imidazole, pyridine, thiophene, thiazole, and phosphine trichloride. More preferably, it is selected from one or more of piperazine, imidazole, pyridine, and thiophene. More preferably, it is a mixture of imidazole and pyridine, and more preferably, the ratio of the two is 0.1-10:1.

[0040] In this invention, the mass ratio of the nitrogen- and / or sulfur- and / or phosphine-containing organic compound to the chloromethyl resin is 0.5-5, preferably 0.8-2.

[0041] In this invention, the conditions for the first heating and stirring can be selected from a wide range. For this invention, the preferred conditions for the first heating and stirring include: a heating temperature of 50-150℃; preferably 70-90℃.

[0042] In this invention, the conditions for the first heating and stirring can be selected from a wide range. For this invention, the preferred conditions for the first heating and stirring include: a stirring rate of 50-1000 rpm, preferably 400-600 rpm.

[0043] In this invention, the conditions for the first heating and stirring can be selected from a wide range. For this invention, the preferred conditions for the first heating and stirring include: a stirring time of 1-24 hours, preferably 10-14 hours.

[0044] According to a preferred embodiment of the present invention, the conditions for the first heating and stirring include: a heating temperature of 50-150°C, a stirring rate of 50-1000 rpm, and a stirring time of 1-24 h.

[0045] According to a preferred embodiment of the present invention, the range of possible second solvent types is relatively wide. For the present invention, alcohols are preferred, and more preferably one or more of methanol, ethanol, ethylene glycol, propanol, propylene glycol, glycerol, butanol, pentanol, and glucose, with ethylene glycol and / or glycerol being more preferred. Using the aforementioned preferred second solvent types can increase the catalyst loading.

[0046] According to a preferred embodiment of the present invention, the conditions for the second heating and stirring include: a heating temperature of 60-250°C, preferably 160-190°C.

[0047] According to a preferred embodiment of the present invention, the conditions for the second heating and stirring include: a stirring rate of 50-1000 rpm, preferably 400-600 rpm.

[0048] According to a preferred embodiment of the present invention, the conditions for the second heating and stirring include: a stirring time of 1-24 hours, preferably 3-6 hours.

[0049] According to a preferred embodiment of the present invention, the conditions for the second heating and stirring include: a heating temperature of 60-250°C, a stirring rate of 50-1000 rpm, and a stirring time of 1-24 h. Using the aforementioned preferred conditions can increase the catalyst loading.

[0050] According to a preferred embodiment of the present invention, the metal precursor is selected from metal nitrates and / or metal chlorides.

[0051] According to a preferred embodiment of the present invention, the mass ratio of the metal precursor to the modified resin is 0.001-0.5, preferably 0.05-0.2. Using the aforementioned ratio can increase the catalyst loading.

[0052] According to a preferred embodiment of the present invention, the drying conditions in steps (1) and (2) include a temperature of 70-150°C and a time of 2-48 hours.

[0053] According to a preferred embodiment of the present invention, in steps (1) and (2), the obtained reactants are separated into solid and liquid phases and washed to obtain solids.

[0054] The technical solution of the present invention will be further illustrated below through embodiments, but the scope of protection of the present invention is not limited to the embodiments. In the present invention, wt% is a mass fraction.

[0055] In this invention, XRD was measured on a Bruker D8 AdvanceSS X-ray diffractometer with CuKα radiation, 40 kV, 300 mA, and a scan rate of 2° / min.

[0056] In this invention, the chlorine content is measured by collecting the combustion components after the resin is burned, collecting the combustion components with sodium hydroxide solution, and then measuring them by ion chromatography.

[0057] Example 1

[0058] In a 500ml three-necked flask, add 50g of chloromethyl polystyrene resin (spherical, particle size 0.4-0.6mm, chlorine content 17% by weight), add 200ml of N,N-dimethylformamide, stir at 500 rpm, heat to 70℃, add 50g of imidazole, react for 12h, cool and separate, wash with deionized water, and dry overnight at 100℃ to obtain the modified resin.

[0059] In a 500ml three-necked flask, 5g of modified resin and 200ml of ethylene glycol solvent were added. The mixture was stirred at 500 rpm, and 0.7g of sodium chloropalladium was added. The mixture was heated to 160℃ and reacted for 4 hours. After cooling, the mixture was separated, washed with deionized water, and dried overnight at 100℃ to obtain catalyst C1. ICP testing showed that the palladium loading was 4.82% by weight.

[0060] Figure 1 The XRD pattern of the catalyst in Example 1 shows that sample C1 has only one diffuse peak belonging to the resin, and no characteristic peak of palladium was observed, indicating that the palladium particles in the sample are small and highly dispersed. Figure 2 The image shows a TEM image of the catalyst prepared in Example 1. As can be seen from the image, no obvious palladium particles can be observed in sample C1, indicating that the palladium particles in the sample are small in size and highly dispersed, and cannot be directly observed under electron microscopy resolution. Figure 3 The image shows a SEM image of the catalyst prepared in Example 1. As can be seen from the image, the C1 surface is relatively smooth, retaining the smooth morphology of the chloromethyl resin itself, and the palladium particles are uniformly dispersed.

[0061] Example 2

[0062] In a 500ml three-necked flask, 50g of chloromethyl polystyrene resin (spherical, particle size 0.3-0.5mm, chlorine content 18% by weight) was added, followed by 200ml of N,N-dimethylformamide. The mixture was stirred at 500 rpm and heated to 80℃. Then, 50g of piperazine was added. After reacting for 12 hours, the mixture was cooled and separated. After washing with deionized water, the resin was dried overnight at 100℃ to obtain the modified resin.

[0063] In a 500 ml three-necked flask, 5 g of modified resin and 200 ml of ethylene glycol solvent were added. The mixture was stirred at 500 rpm, and 0.54 g of palladium nitrate was added. The mixture was heated to 160 °C and reacted for 4 h. After cooling, the mixture was separated, washed with deionized water, and dried overnight at 100 °C to obtain catalyst C2. ICP testing showed that the palladium loading was 4.61% by weight. The XRD, TEM, and SEM spectra were consistent with those of C1.

[0064] Example 3

[0065] In a 500ml three-necked flask, add 50g of chloromethyl polystyrene resin (spherical, particle size 0.15-0.25mm, chlorine content 15% by weight), add 200ml of N,N-dimethylformamide, stir at 500 rpm, heat to 90℃, add 50g of pyridine, react for 12h, cool and separate, wash with deionized water, and dry overnight at 100℃ to obtain the modified resin.

[0066] In a 500 ml three-necked flask, 10 g of modified resin and 200 ml of glycerol solvent were added. The mixture was stirred at 500 rpm, and 0.51 g of sodium chloroplatinate was added. The mixture was heated to 190 °C and reacted for 4 h. After cooling, the mixture was separated, washed with deionized water, and dried overnight at 100 °C to obtain catalyst C3. ICP testing showed a platinum loading of 4.48% by weight. The XRD, TEM, and SEM spectra were consistent with those of C1.

[0067] Example 4

[0068] In a 500ml three-necked flask, add 50g of chloromethyl polystyrene resin (spherical, particle size 0.2-0.45mm, chlorine content 12% by weight), add 200ml of N,N-dimethylformamide, stir at 500 rpm, heat to 90℃, add 50g of imidazole, react for 12h, cool and separate, wash with deionized water, and dry overnight at 100℃ to obtain the modified resin.

[0069] In a 500 ml three-necked flask, 10 g of modified resin and 200 ml of ethylene glycol solvent were added. The mixture was stirred at 500 rpm, and 0.51 g of ruthenium chloride was added. The mixture was heated to 160 °C and reacted for 4 h. After cooling, the mixture was separated, washed with deionized water, and dried overnight at 100 °C to obtain catalyst C4. ICP testing showed that the ruthenium loading was 4.72% by weight. The XRD, TEM, and SEM spectra were consistent with those of C1.

[0070] Example 5

[0071] In a 500ml three-necked flask, add 50g of chloromethyl polystyrene resin (spherical, particle size 0.5-0.8mm, chlorine content 10% by weight), add 200ml of N,N-dimethylformamide, stir at 500 rpm, heat to 90℃, add 100g of imidazole, react for 12h, cool and separate, wash with deionized water, and dry overnight at 100℃ to obtain the modified resin.

[0072] In a 500ml three-necked flask, 10g of modified resin and 200ml of ethylene glycol solvent were added. The mixture was stirred at 500 rpm, and 0.47g of silver nitrate was added. The mixture was heated to 160℃ and reacted for 4 hours. After cooling, the mixture was separated, washed with deionized water, and dried overnight at 100℃ to obtain catalyst C5. ICP testing showed a ruthenium loading of 4.56% by weight. The XRD, TEM, and SEM spectra were consistent with those of C1.

[0073] Example 6

[0074] In a 500ml three-necked flask, 50g of chloromethyl polystyrene resin (spherical, particle size 0.3-0.6mm, chlorine content 17% by weight) was added, followed by 200ml of N,N-dimethylformamide. The mixture was stirred at 500 rpm and heated to 90℃. Then, 40g of imidazole was added. After reacting for 12 hours, the mixture was cooled and separated. After washing with deionized water, the resin was dried overnight at 100℃ to obtain the modified resin.

[0075] In a 500ml three-necked flask, 10g of modified resin and 200ml of ethylene glycol solvent were added. The mixture was stirred at 500 rpm, and 1g of palladium nitrate was added. The mixture was heated to 160℃ and reacted for 4 hours. After cooling, the mixture was separated, washed with deionized water, and dried overnight at 100℃ to obtain catalyst C6. ICP testing showed that the palladium loading was 8.7% by weight. The XRD, TEM, and SEM spectra were consistent with those of C1.

[0076] Example 7

[0077] Following the method of Example 2, except that piperazine was replaced with the same amount of imidazole, catalyst C7 was obtained. The XRD, TEM, and SEM spectra were consistent with those of C1.

[0078] Example 8

[0079] Following the method of Example 2, except that piperazine was replaced with a mixture of imidazole and pyridine in the same amount (weight ratio 1:1), catalyst C8 was obtained. The XRD, TEM, and SEM spectra were consistent with those of C1.

[0080] Example 9

[0081] Following the method of Example 2, except that piperazine was replaced with the same amount of thiophene (weight ratio 1:1), catalyst C9 was obtained. The XRD, TEM, and SEM spectra were consistent with those of C1.

[0082] Example 10

[0083] Following the method of Example 2, except that piperazine was replaced with the same amount of phosphorus trichloride (weight ratio 1:1), catalyst C10 was obtained. The XRD, TEM, and SEM spectra were consistent with C1.

[0084] Comparative Example 1

[0085] In a 500 ml three-necked flask, 5 g of chloromethylstyrene resin was added, followed by 200 ml of ethylene glycol solution. The mixture was stirred at 500 rpm, and then 0.54 g of palladium nitrate was added. The mixture was heated to 160 °C and reacted for 4 h. After cooling, the mixture was separated, washed with deionized water, and dried overnight at 100 °C to obtain catalyst D1. ICP testing showed that the palladium loading was 4.76% by weight.

[0086] Figure 1 The XRD pattern of catalyst D1 in Comparative Example 1 is shown in the figure. It can be seen from the figure that a sharp peak appears at the characteristic peak of palladium, indicating particle agglomeration and the presence of large metal particle size defects in the catalyst. Figure 4 The image shows a TEM image of catalyst D1 prepared in Comparative Example 1. As can be seen from the image, there are obvious palladium particles with large particle size and uneven particle size distribution. Figure 5 The image shows a SEM image of catalyst D1 prepared in Comparative Example 1. As can be seen from the image, the surface of D1 is relatively rough with many protrusions. This is because the chloromethyl resin itself has a small specific surface area, and the generated palladium particles accumulate in large quantities on the resin surface, forming a rough surface morphology.

[0087] Catalyst evaluation

[0088] Catalysts C1-C10 and D1 obtained in Examples 1-10 and Comparative Example 1 were evaluated according to the following method. 0.2 g of catalyst and 30 ml of 1 wt% glycerol aqueous solution were weighed and sealed into a 100 ml reactor. The reactor was purged five times with 5 MPa high-purity hydrogen gas to remove air. The reactor pressure was maintained at 5 MPa. The mixture was stirred at 200 rpm and heated to 150 °C, then the stirring speed was increased to 600 rpm. Timing was started, and after 24 h of reaction, heating and stirring were turned off. The reactor was placed in a water bath for rapid cooling to end the reaction. After opening the reactor lid, the liquid product was analyzed by gas chromatography. The glycerol conversion rate was calculated using the following formula: Glycerol conversion rate C (wt%) = (number of carbon moles of converted glycerol / number of moles of added glycerol) * 100%; 1,2-propanediol selectivity S (wt%) = (number of carbon moles in the product / number of moles of added glycerol) * 100%. The results are shown in Table 1.

[0089] Table 1. Evaluation results of catalytic performance of different catalysts

[0090]

[0091] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A supported metal catalyst characterized in that, The catalyst contains: The modified chloromethyl resin carrier is a cross-linked composition of nitrogen and / or sulfur-containing organic compounds and chloromethyl resin; the metal component is a hydrogenation active metal; The nitrogen and / or sulfur-containing organic compound is one or more of imidazole, pyridine, piperazine and thiophene; The mass ratio of the nitrogen and / or sulfur-containing organic compound to chloromethyl resin is 0.05-0.4:1; The mass ratio of metal to carrier is 0.1-30:

100.

2. The catalyst of claim 1, wherein, The mass ratio of the nitrogen and / or sulfur-containing organic compound to chloromethyl resin is 0.1-0.3:

1.

3. The catalyst of claim 1, wherein, The mass ratio of metal to carrier is 0.5-20:

100.

4. The catalyst of claim 3, wherein, The mass ratio of metal to carrier is 1-10:

100.

5. The catalyst of claim 1, wherein, The nitrogen and / or sulfur-containing organic compound is selected from a mixture of imidazole and pyridine; and / or The chloromethyl resin is one or more of chloromethyl-modified polystyrene, chloromethyl-modified polyethylene, chloromethyl-modified carboxyl-based resin and chloromethyl-modified phenolic-based resin; and / or The chloromethyl resin is spherical; and / or The chlorine content in the chloromethyl resin is greater than 5% by weight; and / or The particle size of the chloromethyl resin is 0.1-3 mm.

6. The catalyst of claim 1, wherein, The metal element is selected from one or more of Group VIII, Group IB and Group IIB; and / or In the mixture of imidazole and pyridine, the ratio of the two is 0.1-10:1; and / or The chloromethyl resin is selected from chloromethyl-modified polystyrene; and / or The chlorine content in the chloromethyl resin is 10-18% by weight; and / or The particle size of the chloromethyl resin is 0.1-0.8 mm.

7. The catalyst of claim 6, wherein, The metal element is selected from one or more of gold, silver, copper, palladium, ruthenium and platinum.

8. The catalyst of claim 7, wherein, The metal element is selected from one or more of palladium, silver, ruthenium and platinum.

9. Use of the catalyst of any one of claims 1-8 in a hydrogenation reaction.

10. A method for synthesizing the supported metal catalyst according to any one of claims 1 to 8, characterized by, The method comprises: 1) dispersing chloromethyl resin in a first solvent, adding a modifier, a nitrogen and / or sulfur-containing organic compound, under first heating and stirring conditions, drying the obtained solid to obtain a modified resin; 2) dispersing the modified resin in a second solvent, adding a metal precursor under second heating and stirring conditions, drying the obtained solid to obtain a supported metal catalyst; The second solvent is ethylene glycol and / or glycerol; The heating temperature of the second heating and stirring is 160-190°C.

11. The synthesis method of claim 10, wherein, The chloromethyl resin is one or more of chloromethyl-modified polystyrene, chloromethyl-modified polyethylene, chloromethyl-modified carboxyl-based resin and chloromethyl-modified phenolic-based resin; and / or The chloromethyl resin is spherical; and / or The chlorine content in the chloromethyl resin is greater than 5% by weight; and / or The particle size of the chloromethyl resin is 0.1-3 mm.

12. The synthetic method of claim 11, wherein, the chloromethyl resin is selected from chloromethyl-modified polystyrene; and / or the chloromethyl resin has a chlorine content of 10-18% by weight; and / or the chloromethyl resin has a particle size of 0.1-0.8 mm.

13. The synthetic method of claim 10, wherein, the first solvent is one or more of toluene, methanol, ethanol, ethylene glycol, n-propanol, n-butanol, isobutanol, tert-butanol, tetrahydrofuran, dichloromethane, trichloromethane, amide, and ether; and / or the nitrogen- and / or sulfur-containing organic compound is selected from one or more of piperazine, imidazole, pyridine, and thiophene; and / or the mass ratio of the nitrogen- and / or sulfur-containing organic compound to the chloromethyl resin is 0.5-5; and / or the first heating and stirring condition comprises a heating temperature of 50-150 °C, a stirring rate of 50-1000 rpm, and a stirring time of 1-24 h.

14. The synthetic method of claim 13, wherein, the first solvent is N,N-dimethylformamide; and / or the nitrogen- and / or sulfur-containing organic compound is a mixture of imidazole and pyridine; and / or the mass ratio of the nitrogen- and / or sulfur-containing organic compound to the chloromethyl resin is 0.8-2; and / or the first heating and stirring condition comprises a heating temperature of 70-90 °C, a stirring rate of 400-600 rpm, and a stirring time of 10-14 h.

15. The synthetic method of claim 14, wherein, the mixture of imidazole and pyridine has a ratio of 0.1-10:

1.

16. The synthetic method of claim 10, wherein, the second heating and stirring condition comprises a stirring rate of 50-1000 rpm and a stirring time of 1-24 h.

17. The synthetic method of claim 16, wherein, the second heating and stirring condition comprises a stirring rate of 400-600 rpm and a stirring time of 3-6 h.

18. The synthetic method of claim 10, wherein, the metal precursor is selected from a nitrate salt and / or a chloride salt of a metal; and / or the mass ratio of the metal precursor to the modified resin is 0.001-0.5; and / or the drying condition in step 1) and step 2) comprises a temperature of 70-150 °C and a time of 2-48 h; and / or each of step 1) and step 2) comprises solid-liquid separation and washing of the obtained reaction mass to obtain a solid.

19. The synthetic method of claim 18, wherein, the mass ratio of the metal precursor to the modified resin is 0.05-0.

2. ​ ​

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