Supported platinum-nickel alloy catalyst as well as preparation method and application thereof

Abstract

The invention discloses a supported platinum-nickel alloy catalyst and a preparation method and application thereof, and belongs to the technical field of catalysis. The preparation method of the supported platinum-nickel alloy catalyst comprises the following steps: mixing a platinum source, a nickel source and an organic ligand in an organic solvent, stirring, filtering, washing and drying to obtain a platinum-nickel complex; dispersing the platinum-nickel complex and the nitrogen-doped porous carbon in an organic solvent, and performing ultrasonic treatment, centrifugation and drying to obtain a supported platinum-nickel catalyst precursor; and carrying out reduction annealing treatment on the supported platinum-nickel catalyst precursor in an argon atmosphere, and cooling to obtain the platinum-nickel alloy catalyst. The supported platinum-nickel alloy catalyst provided by the invention can be applied to deuteration reaction of polycyclic aromatic hydrocarbon compounds, is high in catalytic activity and few in side reaction, and has a good industrial application prospect.

Description

Technical Field

[0001] The invention belongs to the technical field of catalysis and relates to a supported platinum-nickel alloy catalyst and a preparation method and application thereof. Background Art

[0002] Deuterium-substituted OLED materials can significantly improve the overall performance of OLED devices, including improving the luminous efficiency, stability, color purity and device life of OLED materials. Studies have shown that after the CH bond in the blue light material molecule is changed to a CD bond, the service life of the OLED device can be increased by more than 2.4 times. Therefore, deuterium-substituted OLED materials are widely used in high-end display devices, including large-size TVs and high-end smartphones.

[0003] The hydrogen-deuterium exchange reaction technology using Pt / C as a catalyst is the mainstream method for the industrial preparation of deuterated materials for OLEDs. When commercial Pt / C catalysts are currently used for the deuteration reaction of condensed-ring aromatic compounds, it is usually accompanied by the formation of reaction byproducts such as dearomatization (deuterated dihydroanthracene, deuterated tetrahydroanthracene), aromatic ring cracking, and aromatic ring coupling (deuterated bianthracene). These byproducts are difficult to remove, making it difficult to achieve a purity requirement of >99.9% during the product purification process, resulting in a low product yield and increased production costs. Summary of the invention

[0004] The present invention aims to solve the problems and defects in the above-mentioned prior art. The present invention provides a supported platinum-nickel alloy catalyst and a preparation method and application thereof, which improves the activity and reaction selectivity of the supported platinum-nickel alloy catalyst by regulating the platinum-nickel ratio in the preparation process of the supported platinum-nickel alloy catalyst, and reduces the generation of reaction by-products that are difficult to purify and remove.

[0005] In the first aspect, the present invention provides a method for preparing a supported platinum-nickel alloy catalyst, comprising: mixing a platinum source, a nickel source, and an organic ligand in an organic solvent for reaction, filtering, washing, and drying to obtain a platinum-nickel complex; dispersing the platinum-nickel complex and nitrogen-doped porous carbon in an organic solvent, ultrasonicating, centrifuging, and drying to obtain a platinum-nickel catalyst precursor; and reducing and annealing the platinum-nickel catalyst precursor in an argon atmosphere, cooling, and obtaining a platinum-nickel alloy catalyst.

[0006] Furthermore, in the method for preparing the supported platinum-nickel alloy catalyst provided by the present invention, the platinum source is selected from any one of chloroplatinic acid hexahydrate, potassium chloroplatinate, and sodium tetrachloroplatinate dihydrate;

[0007] The nickel source is selected from any one of nickel nitrate hexahydrate, nickel sulfate heptahydrate, and nickel chloride hexahydrate;

[0008] The organic ligand is selected from any one of 2,2'-bipyridine, 2,2'-biquinoline, and 1,10-phenanthroline;

[0009] The organic solvent is selected from any one of methanol, ethanol, ethylene glycol and N,N-dimethylformamide.

[0010] Furthermore, in the preparation method of the supported platinum-nickel alloy catalyst provided by the present invention, the preparation method of the nitrogen-doped porous carbon comprises: coconut shell, urea and nicotinamide are prepared by impregnation-pyrolysis method.

[0011] Furthermore, in the preparation method of the supported platinum-nickel alloy catalyst provided by the present invention, the mixing reaction time for preparing the platinum-nickel complex is 5h to 8h;

[0012] The ultrasonic time for preparing the platinum nickel catalyst precursor is 4h to 6h.

[0013] Furthermore, in the method for preparing the supported platinum-nickel alloy catalyst provided by the present invention, the molar ratio of the platinum source to the nickel source is 1:0.3-1.5;

[0014] The mass ratio of the platinum nickel complex to the nitrogen-doped porous carbon is 1:1-5.

[0015] Furthermore, in the method for preparing the supported platinum-nickel alloy catalyst provided by the present invention, the reduction annealing temperature is 600-700° C., and the reduction annealing time is 2-6 hours.

[0016] In a second aspect, the present invention provides a supported platinum-nickel alloy catalyst prepared by the above preparation method.

[0017] In a third aspect, the present invention provides the use of a supported platinum-nickel alloy catalyst in the deuteration reaction of condensed-ring aromatic hydrocarbon compounds.

[0018] Furthermore, the use of the supported platinum-nickel catalyst provided by the present invention in the deuteration reaction of condensed-ring aromatic hydrocarbon compounds comprises: heating the condensed-ring aromatic hydrocarbon compounds, a deuterium source and a supported platinum-nickel alloy catalyst for reaction, and separating and purifying after the reaction to obtain a fully deuterated product of the condensed-ring aromatic hydrocarbons.

[0019] Furthermore, in the application of the supported platinum-nickel catalyst provided by the present invention in the deuteration reaction of condensed-ring aromatic hydrocarbon compounds, the deuterium source is selected from any one of deuterated water, deuterated benzene, and deuterated ethanol;

[0020] The temperature of the heating reaction is 150-280° C., and the time of the heating reaction is 4-24 hours.

[0021] Compared with the prior art, the technical solution provided by the present invention has at least the following beneficial effects or advantages:

[0022] (1) The present invention uses relatively cheap transition metal nickel and platinum to form a platinum-nickel alloy, which can not only effectively reduce the amount of platinum used, but also improve the utilization rate of platinum. Through the compressive strain and coordination of nickel, the d-band center of platinum is negatively shifted, the original electronic structure of platinum is adjusted, and the adsorption capacity of platinum to intermediate products is reduced, thereby regulating the catalytic activity of the platinum-based catalyst.

[0023] (2) The nitrogen-doped porous carbon used in the present invention helps to strengthen the interaction between the metal and the carrier, thereby reducing the agglomeration of platinum-nickel nanoparticles during the pyrolysis preparation process of the catalyst.

[0024] (3) The present invention uses nitrogen-containing bidentate ligands such as organic small molecules 2,2'-bipyridine as ligands to couple nickel ions and platinum ions, and combines the thermal annealing process to synthesize a size-controllable platinum-nickel alloy catalyst.

[0025] (4) The present invention provides a supported platinum-nickel alloy catalyst, which does not involve processes such as hydrothermal reaction and freeze-drying, and can be used to prepare an industrial-grade supported platinum-nickel alloy catalyst, and has strong practicality.

[0026] (4) The supported platinum-nickel alloy catalyst provided by the present invention is applied to the deuteration reaction of condensed-ring aromatic hydrocarbon compounds, which can greatly reduce or avoid the formation of reaction by-products such as dearomatization (deuterated dihydroanthracene, deuterated tetrahydroanthracene), aromatic ring cracking, and aromatic ring coupling (deuterated dianthracene), shorten the purification process, and improve the product yield, thus having good prospects for industrial application. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is a scanning electron microscope image of the supported platinum-nickel alloy catalyst. DETAILED DESCRIPTION

[0028] The technical scheme of the present invention is described below in conjunction with the embodiments, but the present invention is not limited to the following embodiments. The experimental methods and detection methods described in each embodiment are conventional methods unless otherwise specified; the reagents and materials described are all commercially available unless otherwise specified.

[0029] Example 1

[0030] This embodiment provides a method for preparing a supported platinum-nickel alloy catalyst.

[0031] 1. Preparation of supported platinum-nickel alloy catalyst precursor: Hexahydrate chloroplatinic acid (8.20 g), nickel sulfate heptahydrate (5.56 g) and 2,2'-bipyridine (9.37 g) were mixed in 200 mL of ethanol and stirred for 5 h to produce a bright red precipitate, which was then filtered, the filter cake was washed with ethanol, and dried in a constant temperature oven at 60 ° C to obtain a platinum-nickel complex; the obtained platinum-nickel complex (4.20 g) and nitrogen-doped porous carbon (4.20 g) were dispersed in 150 mL of ethanol, ultrasonically treated for 4 h, and after being fully mixed, centrifuged, the solid was dried in a constant temperature oven at 70 ° C overnight to obtain a black-red supported platinum-nickel alloy catalyst precursor. Among them, the nitrogen-doped porous carbon was prepared by impregnation-pyrolysis method using coconut shell as the carbon source, urea and nicotinamide as the nitrogen source, and the molar ratio of the platinum source to the nickel source was 1:0.8.

[0032] 2. Preparation of nitrogen-doped porous carbon:

[0033] (1) Pretreatment of coconut shell: First, the coconut shell is crushed and sifted to obtain shredded coconut shells, which are then washed, dried, and placed in a tubular furnace. The temperature is raised to 400° C. at a rate of 5° C. / min under inert gas protection and maintained for 2 hours. The pre-carbonized material a is then cooled to room temperature.

[0034] (2) Alkali washing and acid washing: The pre-carbonized material a is alkaline washed with a potassium hydroxide solution at 60°C for 8 hours, filtered and washed with water until the filtrate is neutral; then acid washed with a dilute hydrochloric acid solution at 60°C for 1 hour, filtered and washed with water until the filtrate is neutral, and dried to obtain material b.

[0035] (3) Activation treatment: potassium hydroxide and potassium bicarbonate were weighed in a mass ratio of 1:3 to prepare a mixed solution, material b was dispersed in the mixed solution, stirred at 60° C. for 1 hour, and then melamine solution was added. Stirring was continued for 2 hours, and then the mixture was transferred to a culture dish and freeze-dried in a freeze dryer to obtain material c.

[0036] (4) High temperature carbonization: Material c was placed in a tubular furnace, heated to 800 °C at a rate of 2 °C / min under inert gas protection and maintained for 2 h, then cooled to 400 °C at a rate of 5 °C / min, and then naturally cooled to room temperature to obtain material d.

[0037] (5) Acid washing and drying: Material d was acid washed with a dilute hydrochloric acid solution for 1 hour, filtered and washed with water until the filtrate was neutral, and then dried to obtain a nitrogen-doped porous carbon material.

[0038] 3. Preparation of supported platinum-nickel alloy catalyst: The supported platinum-nickel alloy catalyst precursor was subjected to reduction annealing in an argon atmosphere with an argon flow rate of 200 mL / min, a reduction annealing temperature of 700°C, and a reduction annealing time of 4 h. The supported platinum-nickel alloy catalyst was obtained by naturally cooling to room temperature under an argon atmosphere. Figure 1The following is a scanning electron microscope image of the supported platinum-nickel alloy catalyst prepared in this example. Characterization and analysis by high-resolution transmission electron microscopy and ICP-AES showed that the particle size of the supported platinum-nickel alloy catalyst particles was 3.92 nm, and the platinum loading was 2.8%.

[0039] Example 2

[0040] This embodiment provides a method for preparing a supported platinum-nickel alloy catalyst.

[0041] 1. Preparation of supported platinum-nickel alloy catalyst precursor: Potassium chloroplatinate (8.90 g), nickel nitrate hexahydrate (8.10 g) and 2,2′-biquinoline (15.36 g) were mixed in 200 mL of ethanol and stirred for 5 h to produce a bright red precipitate, which was then filtered, the filter cake was washed with ethanol, and dried in a constant temperature oven at 60 ° C to obtain a platinum-nickel complex; the obtained platinum-nickel complex (5.50 g) and nitrogen-doped porous carbon (13.75 g) were dispersed in 180 mL of ethanol, ultrasonically treated for 4 h, and after being fully mixed, centrifuged, the solid was dried in a constant temperature oven at 70 ° C overnight to obtain a black-red supported platinum-nickel alloy catalyst precursor. Among them, the nitrogen-doped porous carbon was prepared by impregnation-pyrolysis method using coconut shell as the carbon source, urea and nicotinamide as the nitrogen source, and the molar ratio of the platinum source to the nickel source was 1:0.65.

[0042] 2. Preparation of supported platinum-nickel alloy catalyst: The supported platinum-nickel alloy catalyst precursor was subjected to reduction annealing in an argon atmosphere, with an argon flow rate of 200 mL / min, a reduction annealing temperature of 600°C, and a reduction annealing time of 6 h. The supported platinum-nickel alloy catalyst was obtained by naturally cooling to room temperature in an argon atmosphere. Characterization and analysis by high-resolution projection electron microscopy and ICP-AES showed that the particle size of the supported platinum-nickel alloy nanoparticles was 4.56 nm, and the platinum loading was 4.5%.

[0043] Example 3

[0044] This embodiment provides a method for preparing a supported platinum-nickel alloy catalyst.

[0045] 1. Preparation of supported platinum-nickel alloy catalyst precursor: Sodium tetrachloroplatinate dihydrate (8.90 g), nickel chloride hexahydrate (8.10 g) and 1,10-phenanthroline (14.28 g) were mixed in 200 mL of methanol and stirred for 6 h to produce a bright red precipitate, which was then filtered, the filter cake was washed with methanol, and dried in a constant temperature oven at 60 ° C to obtain a platinum-nickel complex; the obtained platinum-nickel complex (5.50 g) and nitrogen-doped porous carbon (5.50 g) were dispersed in 180 mL of methanol, ultrasonically treated for 4 h, and after being fully mixed, centrifuged, the solid was dried in a constant temperature oven at 70 ° C overnight to obtain a black-red supported platinum-nickel alloy catalyst precursor. Among them, the nitrogen-doped porous carbon was prepared by impregnation-pyrolysis method using coconut shell as the carbon source, urea and nicotinamide as the nitrogen source, and the molar ratio of the platinum source to the nickel source was 1:0.3.

[0046] 2. Preparation of supported platinum-nickel alloy catalyst: The supported platinum-nickel alloy catalyst precursor was subjected to reduction annealing in an argon atmosphere with an argon flow rate of 200 mL / min, a reduction annealing temperature of 600°C, and a reduction annealing time of 2 h. The supported platinum-nickel alloy catalyst was obtained by naturally cooling to room temperature under an argon atmosphere.

[0047] Example 4

[0048] 1. Preparation of supported platinum-nickel alloy catalyst precursor: Hexahydrated chloroplatinic acid (8.20 g), heptahydrated nickel sulfate (6.67 g) and 2,2'-bipyridine (9.37 g) were mixed in 200 mL of ethylene glycol and stirred for 8 h to produce a bright red precipitate, which was then filtered, the filter cake was washed with ethylene glycol, and dried in a constant temperature oven at 60 ° C to obtain a platinum-nickel complex; the obtained platinum-nickel complex (4.20 g) and nitrogen-doped porous carbon (21.00 g) were dispersed in 150 mL of ethylene glycol, ultrasonically treated for 6 h, and after being fully mixed, centrifuged, the solid was dried in a constant temperature oven at 70 ° C overnight to obtain a black-red supported platinum-nickel alloy catalyst precursor. Among them, the nitrogen-doped porous carbon was prepared by impregnation-pyrolysis method using coconut shell as the carbon source, urea and nicotinamide as the nitrogen source, and the molar ratio of the platinum source to the nickel source was 1:1.5.

[0049] 2. Preparation of supported platinum-nickel alloy catalyst: The supported platinum-nickel alloy catalyst precursor was subjected to reduction annealing in an argon atmosphere with an argon flow rate of 200 mL / min, a reduction annealing temperature of 700°C, and a reduction annealing time of 4 h. The supported platinum-nickel alloy catalyst was obtained by naturally cooling to room temperature under an argon atmosphere.

[0050] Example 5

[0051] This embodiment provides a method for preparing a supported platinum-nickel alloy catalyst.

[0052] This example is the same as Example 1, except that the organic solvent ethanol used in preparing the supported platinum nickel catalyst in Example 1 is replaced by N,N-dimethylformamide.

[0053] Example 6

[0054] This embodiment provides a method for preparing deuterated anthracene.

[0055]

[0056] Add 50.00g anthracene and 56.50g (99.9atom%D) heavy water (the molar ratio of heavy water to anthracene is 10:1) to the autoclave, add 8.10g of a supported platinum-nickel alloy catalyst with a platinum loading of 2.8%, and then replace the remaining air in the autoclave with nitrogen. Heat the autoclave to 230°C and react for 6h under stirring. After the reaction is completed, separate the water phase and perform the deuteration reaction again in the same reaction mode. Each reaction is to add 56g of heavy water to the system, stir and heat to 230°C for 6h, and after the reaction is completed, separate the water phase and perform the next deuteration reaction.

[0057] After the five deuteration reactions were completed, the aqueous phase was separated, dichloroethane was added to dissolve the crude product, and the product was filtered after stirring to obtain a filtrate; the filtrate was distilled to remove dichloroethane to obtain 45.29 g of deuterated anthracene with a deuteration rate of 98.48%, a yield of 85.76%, and a purity of 99.8%. The by-products mainly included deuterated dihydroanthracene, deuterated tetrahydroanthracene and deuterated bianthracene.

[0058] The characterization data of deuterated anthracene are as follows: 1H NMR (600 MHz, DMSO-d6) δ8.58 (s, 0.01H), 8.09 (s, 0.02H), 7.51 (s, 0.03H). MS (EI) 188.2.

[0059] Example 7

[0060] This embodiment provides a method for preparing deuterated carbazole.

[0061]

[0062] 80.10g of carbazole and 95.80g (99.9atom%D) of heavy water (the molar ratio of heavy water to anthracene is 10:1), 12.00g of a supported platinum-nickel alloy catalyst with a platinum loading of 2.8% were added to the autoclave, and then the remaining air in the autoclave was replaced with nitrogen. The autoclave was heated to 240°C and reacted for 8h under stirring. After the reaction was completed, the water phase was separated and the deuteration reaction was carried out again in the same reaction mode. Each reaction was carried out by adding 95.80g of heavy water to the system, stirring and heating to 240°C for 8h. After the reaction was completed, the water phase was separated and the next deuteration reaction was carried out.

[0063] After the four deuteration reactions were completed, the aqueous phase was separated, dichloroethane was added to dissolve the crude product, and the product was filtered after stirring to obtain a filtrate; the filtrate was distilled to remove dichloroethane to obtain 72.96 g of deuterated carbazole with a deuteration rate of 98.89%, a yield of 88.56%, and a purity of 99.9%. The by-products mainly included deuterated bicarbazole.

[0064] The characterization data of deuterated carbazole are as follows: 1H NMR (600 MHz, DMSO-d6) δ8.10 (s, 0.01H), 7.48 (s, 0.02H), 7.38 (s, 0.01H), 7.15 (s, 0.04H). MS (EI) 173.9.

[0065] Example 8

[0066] This embodiment provides a method for preparing deuterated 9-phenylanthracene.

[0067]

[0068] Add 60.00g 9-phenylanthracene and 47.20g (99.9atom%D) heavy water (the molar ratio of heavy water to anthracene is 10:1) to the autoclave, and 10.80g of a supported platinum-nickel alloy catalyst with a platinum loading of 4.5%, and then replace the remaining air in the autoclave with nitrogen. Heat to 225°C, react for 8h under stirring, and after the reaction is completed, separate the water phase, and perform the deuteration reaction again in the same reaction mode. Each reaction is to add 47.20g heavy water to the system, stir and heat to 225°C for 8h, and after the reaction is completed, separate the water phase, and then perform the next deuteration reaction.

[0069] After the four deuteration reactions were completed, the aqueous phase was separated, dichloroethane was added to dissolve the crude product, and the product was filtered after stirring to obtain a filtrate; the filtrate was distilled to remove dichloroethane to obtain 55.37 g of deuterated 9-phenylanthracene with a deuteration rate of 96.65%, a yield of 87.50%, and a purity of 99.80%. The by-products mainly included deuterated dihydro-9-phenylanthracene, deuterated tetrahydro-9-phenylanthracene and deuterated bi-9-phenylanthracene.

[0070] The characterization data of deuterated 9-phenylanthracene are as follows: 1H NMR (600 MHz, CDCl3) δ8.52 (s, 0.02H), 8.07 (s, 0.02H), 7.69 (s, 0.03H), 7.58 (s, 0.02H), 7.56 (s, 0.01H), 7.48 (s, 0.03H), 7.46 (s, 0.02H), 7.36 (s, 0.02H). MS (EI) 268.1.

[0071] Example 9

[0072] This embodiment provides a method for preparing perdeuterated deuterated N-phenylcarbazole.

[0073]

[0074] 70.10 g N-phenylcarbazole and 57.67 g (99.9 atom% D) heavy water (the molar ratio of heavy water to anthracene is 10:1), 13.50 g of a supported platinum-nickel alloy catalyst with a platinum loading of 4.5% were added to the autoclave, and then the remaining air in the autoclave was replaced with nitrogen. The autoclave was heated to 230° C. and reacted for 6 h under stirring. After the reaction was completed, the water phase was separated and the deuterated reaction was carried out again in the same reaction mode. Each reaction was performed by adding 57.67 g heavy water to the system, stirring and heating to 230° C. for 6 h. After the reaction was completed, the water phase was separated and the next deuterated reaction was carried out.

[0075] After the five deuteration reactions were completed, the aqueous phase was separated, dichloroethane was added to dissolve the crude product, and the product was filtered after stirring to obtain a filtrate; the filtrate was distilled to remove dichloroethane to obtain 63.85 g of deuterated carbazole with a deuteration rate of 98.52%, a yield of 86.50%, and a purity of 99.70%. The by-products mainly included deuterated biphenylcarbazole.

[0076] The characterization data of deuterated N-phenylcarbazole are as follows: 1H NMR (600 MHz, DMSO-d6) δ8.55 (s, 0.02H), 7.94 (s, 0.01H), 7.62 (s, 0.03H), 7.58 (s, 0.02H), 7.50 (s, 0.01H), 7.35 (s, 0.03H), 7.20 (s, 0.01H). MS (EI) 256.2.

[0077] Example 10

[0078] This embodiment provides a method for preparing deuterated anthracene.

[0079] This embodiment is the same as embodiment 6, except that the deuterium source in this embodiment is deuterated benzene, the reaction temperature is 280° C., and the reaction time is 24 h.

[0080] Embodiment 11

[0081] This embodiment provides a method for preparing deuterated anthracene.

[0082] This embodiment is the same as embodiment 6, except that the deuterium source in this embodiment is deuterated ethanol, the reaction temperature is 150° C., and the reaction time is 4 hours.

[0083] Comparative Example 1

[0084] This comparative example provides a method for preparing deuterated anthracene.

[0085]

[0086] Add 50.00g anthracene and 56.50g (99.9atom%D) heavy water (the molar ratio of heavy water to anthracene is 10:1) to the autoclave, add 8.10g of 5wt% commercial Pt / C catalyst (purchased from Xi'an Kaili New Materials Co., Ltd.), and then replace the remaining air in the autoclave with nitrogen. Heat the autoclave to 230℃ and react for 6h under stirring. After the reaction is completed, separate the water phase and perform the deuteration reaction again in the same reaction mode. Each reaction is to add 56g of heavy water to the system, stir and heat to 230℃ for 6h, and then separate the water phase before the next deuteration reaction.

[0087] After the five deuteration reactions were completed, the aqueous phase was separated, dichloroethane was added to dissolve the crude product, and the product was filtered after stirring to obtain a filtrate; the filtrate was distilled to remove dichloroethane to obtain 44.65 g of deuterated anthracene with a deuteration rate of 97.62%, a yield of 82.38%, and a purity of 98.8%. The by-products mainly included deuterated dihydroanthracene, deuterated tetrahydroanthracene and deuterated bianthracene.

[0088] Comparative Example 2

[0089] This comparative example provides a method for preparing deuterated carbazole.

[0090]

[0091] Add 80.10g carbazole and 95.80g (99.9atom%D) heavy water (the molar ratio of heavy water to anthracene is 10:1) to the autoclave, add 8.00g of 5wt% commercial Pt / C catalyst, and then replace the remaining air in the autoclave with nitrogen. Heat the autoclave to 240℃ and react for 8h under stirring. After the reaction is completed, separate the water phase and perform the deuteration reaction again in the same reaction mode. Each reaction is to add 95.80g heavy water to the system, stir and heat to 240℃ for 8h, and then separate the water phase before the next deuteration reaction.

[0092] After the five deuteration reactions were completed, the aqueous phase was separated, dichloroethane was added to dissolve the crude product, and the product was filtered after stirring to obtain a filtrate; the filtrate was distilled to remove dichloroethane to obtain 71.25 g of deuterated carbazole with a deuteration rate of 98.74%, a yield of 85.12%, and a purity of 98.40%. The by-products mainly included deuterated bicarbazole.

[0093] The embodiments described above are part of the embodiments of the present invention, but not all of them. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention claimed for protection, but only represents selected embodiments of the present invention. All other embodiments obtained without creative work and related deductions and substitutions made by ordinary technicians in the field under the conditions of the concept of the present invention belong to the scope of protection of the present invention.

Claims

1. A method for preparing a supported platinum-nickel alloy catalyst, characterized in that: include: The platinum source, the nickel source and the organic ligand are mixed and reacted in an organic solvent, filtered, washed and dried to obtain a platinum-nickel complex; the platinum-nickel complex and nitrogen-doped porous carbon are dispersed in an organic solvent, ultrasonicated, centrifuged and dried to obtain a platinum-nickel catalyst precursor; the platinum-nickel catalyst precursor is subjected to reduction annealing treatment in an argon atmosphere, and cooled to obtain a platinum-nickel alloy catalyst.

2. The method for preparing a supported platinum-nickel alloy catalyst according to claim 1, characterized in that: The platinum source is selected from any one of chloroplatinic acid hexahydrate, potassium chloroplatinate, and sodium tetrachloroplatinate dihydrate; The nickel source is selected from any one of nickel nitrate hexahydrate, nickel sulfate heptahydrate, and nickel chloride hexahydrate; The organic ligand is selected from any one of 2,2'-bipyridine, 2,2'-biquinoline, and 1,10-phenanthroline; The organic solvent is selected from any one of methanol, ethanol, ethylene glycol and N,N-dimethylformamide.

3. The method for preparing a supported platinum-nickel alloy catalyst according to claim 1, characterized in that: The preparation method of nitrogen-doped porous carbon comprises: preparing coconut shell, urea and nicotinamide through an impregnation-pyrolysis method.

4. The method for preparing a supported platinum-nickel alloy catalyst according to claim 1, characterized in that: The mixing reaction time for preparing the platinum-nickel complex is 5 h to 8 h; The ultrasonic time for preparing the platinum nickel catalyst precursor is 4h to 6h.

5. The method for preparing a supported platinum-nickel alloy catalyst according to claim 1, characterized in that: The molar ratio of the platinum source to the nickel source is 1:0.3-1.5; The mass ratio of the platinum nickel complex to the nitrogen-doped porous carbon is 1:1 to 1:

5.

6. The method for preparing a supported platinum-nickel alloy catalyst according to claim 1, characterized in that: The reduction annealing temperature is 600-700° C., and the reduction annealing time is 2-6 hours.

7. A supported platinum-nickel alloy catalyst prepared by the method for preparing a supported platinum-nickel alloy catalyst as claimed in any one of claims 1 to 6.

8. Use of the supported platinum-nickel alloy catalyst as claimed in claim 7 in the deuteration reaction of condensed-ring aromatic hydrocarbon compounds.

9. The use according to claim 8, characterized in that: include: The polycyclic aromatic hydrocarbon compounds, a deuterium source and a supported platinum-nickel alloy catalyst are heated to react, and after the reaction is completed, the polycyclic aromatic hydrocarbons are separated and purified to obtain a fully deuterated product.

10. The use according to claim 9, characterized in that: The deuterium source is selected from any one of deuterated water, deuterated benzene, and deuterated ethanol; The temperature of the heating reaction is 150-280° C., and the time of the heating reaction is 4-24 hours.

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