Nitrogen atom doped intermetallic compound catalyst and preparation method and application thereof

Abstract

The invention aims to provide a nitrogen atom-doped intermetallic compound catalyst as well as a preparation method and application thereof, the molecular formula of the nitrogen atom-doped intermetallic compound catalyst is NixMyNn / Al2O3, and NixMyNn is an active component doped with nitrogen atoms. The nitrogen atom doped intermetallic compound catalyst is in the shape of an irregular block. The catalyst shows excellent naphthalene hydrogenation catalytic performance: under the conditions that the temperature is 230 DEG C, the pressure is 4 MPa, the hydrogen-oil ratio is 300 and the liquid phase volume space velocity is 94.5 h <-1 >, the naphthalene conversion rate in a 24-hour stability test can reach 100%, and the decahydronaphthalene selectivity reaches up to 97.7% or above. The invention also provides a preparation method and application of the nitrogen atom doped intermetallic compound catalyst.

Description

Technical Field

[0001] The present invention belongs to the technical field of catalysts, and in particular relates to a nitrogen atom-doped intermetallic compound catalyst, a preparation method and an application thereof. Background Art

[0002] As a renewable energy source with zero carbon emissions and high energy storage density, hydrogen's large-scale application can reduce the energy mix's reliance on fossil fuels while also reducing carbon emissions and alleviating environmental issues. In recent years, the development of hydrogen energy has led to a mismatch between regional supply and demand, making hydrogen storage and transportation a major bottleneck restricting its development. The development of economical, safe, and efficient storage and transportation technologies is an effective solution to these challenges and a key link in the hydrogen energy industry chain. Currently, hydrogen storage and transportation are categorized into high-pressure gaseous hydrogen storage, low-temperature liquid hydrogen storage, solid-state hydrogen storage, and liquid organic hydrogen storage (LOHCs). LOHCs combine hydrogen with aromatic hydrocarbons via unsaturated bonds to form stable covalently bonded compounds, enabling hydrogen storage and transportation at ambient temperature and pressure in the form of liquid saturated bonds. They have attracted widespread attention due to their high hydrogen storage density, superior safety, and economical and convenient operation. The development of LOHC systems primarily involves the construction of hydrogen storage systems and the design and preparation of hydrogenation / dehydrogenation catalysts.

[0003] The choice of hydrogen storage medium determines the hydrogen storage capacity of the hydrogen storage system. Currently, the commonly used media for LOHCs are: N-ethylcarbazole, toluene and dibenzyltoluene, with hydrogen storage densities of 5.8 wt.%, 6.12 wt.%, and 6.23 wt.%, respectively; compared with the above media, decalin has a hydrogen storage density of up to 7.29 wt.%, which has greater hydrogen storage advantages.

[0004] Traditionally, catalysts based on precious metals (Pt and Pd) have been used in naphthalene hydrogenation. However, the high cost of precious metals significantly increases storage and transportation costs. Research has shown that Ni-based catalysts, due to their outer electron structure similar to precious metals, have the potential to serve as active catalytic components in hydrogenation reactions. However, due to the challenges of resonance energy, steric hindrance, and competitive adsorption during the hydrogenation process, enhancing the catalyst's adsorption of reactants and key intermediates, as well as its ability to dissociate hydrogen, is crucial for improving catalytic performance. Summary of the Invention

[0005] In view of the above problems, the present invention aims to provide a nitrogen atom-doped intermetallic compound catalyst and its preparation method and application.

[0006] The present invention adopts the following technical solutions: A nitrogen-doped intermetallic compound catalyst with the molecular formula Ni x M y N n / Al2O3, with Al2O3 as the carrier, and Nix M y N n It is the active component of the catalyst, x represents the number of metal Ni atoms in the intermetallic compound; M represents the added metal additive, y represents the number of additive atoms in the compound, and n is the number of nitrogen atoms in the compound, and the range of n is 0.5~0.1.

[0007] Furthermore, the Ni content is 20 wt.%~80 wt.%.

[0008] Furthermore, the M includes any one of Mo, W, Zn, Fe, Co, In, and Ga.

[0009] A method for preparing a nitrogen atom-doped intermetallic compound catalyst comprises the following steps: S1. Prepare alkaline solution: fully dissolve soluble carbonate in deionized water to obtain solution I, and fully dissolve strong base in deionized water to obtain solution II; S2, synthesis of metal oxide precursor: 2+ Soluble salts containing metal elements M and soluble salts containing Al 3+ The soluble salt of the catalyst is fully dissolved in deionized water to obtain solution III; solution III is added dropwise to solution I, and solution II is added to adjust the pH to 8-13 to obtain an emulsion; the emulsion is then subjected to a hydrothermal reaction to obtain a precipitate, which is centrifuged, washed to neutrality, and then dried and calcined to obtain a fresh catalyst; S3. Nitrogen atom doping: The fresh catalyst is first reduced with H2, then NH3 gas is introduced, and finally O2 is introduced to passivate the sample to obtain the desired nitrogen atom-doped intermetallic compound catalyst.

[0010] Furthermore, the soluble carbonate includes any one of sodium carbonate, potassium carbonate, and ammonium carbonate, preferably sodium carbonate, and the concentration of solution I is 0.5-0.75 mol / L.

[0011] Furthermore, the strong base includes any one of sodium hydroxide and potassium hydroxide, preferably sodium hydroxide, and the concentration of solution II is 2 mol / L to 5 mol / L.

[0012] Furthermore, the Ni-containing 2+ The soluble salt includes any one of nickel nitrate, nickel acetate and nickel sulfate.

[0013] Furthermore, the metal element M includes any one of Mo, W, Zn, Fe, Co, In, and Ga, preferably Zn, and the soluble salt containing the metal element M includes any one of nitrate, carbonate, and sulfate.

[0014] Furthermore, the Al-containing 3+ The soluble salts include one or more of aluminum nitrate, aluminum sulfate, and aluminum chloride; the solution III contains Al 3+ The solution concentration of soluble salt is 0.0001 mol / L~0.0005 mol / L.

[0015] Furthermore, the Ni-containing 2+ Soluble salts containing metal elements M contain Al 3+ The molar ratio between the soluble salts is 3: (1~3): 1.

[0016] Furthermore, the temperature of the hydrothermal reaction is 100-150° C., and the hydrothermal time is 12-30 hours.

[0017] Furthermore, the calcination temperature is 400-550° C., the heating rate is 1-5° C. / min, and the calcination time is 2-6 h.

[0018] Furthermore, the reduction temperature is 500-600° C., and the time is 1-3 hours.

[0019] Furthermore, after the NH3 gas is introduced, the nitrogen atom doping process temperature is 400-600°C and the time is 0.5-5h.

[0020] Furthermore, the concentration of O2 used in the passivation is 0.5-3%, and the passivation time is 5-10 hours; the inert gas is balanced during the passivation process, and the inert gas includes Ar or He.

[0021] A nitrogen atom-doped intermetallic compound catalyst is applied to the naphthalene hydrogenation reaction.

[0022] Furthermore, the naphthalene hydrogenation reaction is carried out in a fixed bed reactor, and the naphthalene is dissolved in a solvent before the reaction; the product analysis uses an internal standard method, and an internal standard substance needs to be added to the reactant solution; The prepared nitrogen atom-doped intermetallic compound catalyst was loaded into a fixed-bed reactor for naphthalene saturation hydrogenation reaction at a reaction temperature of 100-270°C, a reaction pressure of 3-6 MPa, a hydrogen-to-oil ratio of 150-1800, and a liquid phase volume space velocity of 2-300 h -1 .

[0023] Furthermore, the solvent includes any one of n-hexane, n-heptane, n-octane, and n-decane.

[0024] Furthermore, the internal standard substance includes any one of n-dodecane, n-tetradecane, and n-hexadecane.

[0025] The present invention modulates the electronic structure of the active metal Ni by introducing a second metal promoter and heteroatom doping, creating an electron-deficient state on the Ni surface. The key to the naphthalene hydrogenation reaction lies in the adsorption of the reactants and the intermediate species they produce. The adsorption of these species on the surface of the supported Ni-based catalyst follows a π-complexation adsorption mechanism. The electron-deficient active metal Ni enhances the adsorption of the reactants and inhibits the desorption of key reaction intermediates, thereby improving the catalyst's hydrogenation and dehydrogenation capabilities.

[0026] The beneficial effects of the present invention are as follows: The nitrogen-doped intermetallic compound catalyst prepared by the preparation method of the present invention exhibits excellent naphthalene hydrogenation catalytic performance, achieves rapid hydrogen storage under relatively mild conditions, and has good stability. 230 ° C, 4 MPa, hydrogen-to-oil ratio of 300, liquid phase volume space velocity of 94.5 h -1 Under the conditions of 100%, the naphthalene conversion rate can reach 100% in the 24h stability test, and the decalin selectivity is as high as over 97.7%. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is the XRD pattern of fresh catalyst I in experimental group 1.

[0028] Figure 2 This is the SEM image of fresh catalyst I in experimental group 1.

[0029] Figure 3 This is the XRD pattern of catalyst I after nitrogen atom doping in experimental group 2.

[0030] Figure 4 This is the SEM image of catalyst I after nitrogen atom doping in experimental group 2.

[0031] Figure 5 This is the pore size distribution diagram of catalyst I after nitrogen atom doping in experimental group 2.

[0032] Figure 6 This is the N2 adsorption-desorption isotherm diagram of catalyst I after nitrogen atom doping in experimental group 2.

[0033] Figure 7 This is the TEM image of catalyst I after nitrogen atom doping in experimental group 2.

[0034] Figure 8 This is the HR-TEM image of catalyst I after nitrogen atom doping in experimental group 2.

[0035] Figure 9 This is the performance diagram of naphthalene hydrogenation reaction of catalyst I in experimental group 3.

[0036] Figure 10 This is the XRD pattern of fresh catalyst II in experimental group 4.

[0037] Figure 11 This is the SEM image of fresh catalyst II in experimental group 4.

[0038] Figure 12 This is the XRD pattern of catalyst II after nitrogen atom doping in experimental group 5.

[0039] Figure 13 This is the SEM image of catalyst II after nitrogen atom doping in experimental group 5.

[0040] Figure 14 This is the performance diagram of naphthalene hydrogenation reaction of catalyst II in experimental group 6.

[0041] Figure 15 This is the SEM image of catalyst II after reaction in experimental group 6. DETAILED DESCRIPTION

[0042] The following embodiments are merely preferred technical solutions of the present invention and are not intended to limit the present invention in any way. It will be apparent to those skilled in the art that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, improvements, and the like made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

[0043] Example 1 A method for preparing a nitrogen atom-doped intermetallic compound catalyst comprises the following steps: S1. Prepare alkaline solution: fully dissolve soluble carbonate in deionized water to obtain solution I, and fully dissolve strong base in deionized water to obtain solution II; S2, synthesis of metal oxide precursor: 2+ Soluble salts containing metal elements M and soluble salts containing Al 3+ The soluble salt of the catalyst is fully dissolved in deionized water to obtain solution III; solution III is added to solution I, and solution II is added to adjust the pH to 8-13 to obtain an emulsion; the emulsion is then subjected to a hydrothermal reaction to obtain a precipitate, which is centrifuged, washed to neutrality, and then dried and calcined to obtain a fresh catalyst; S3. Nitrogen atom doping: The fresh catalyst is first reduced with H2, then NH3 gas is introduced, and finally O2 is introduced to passivate the sample to obtain the desired nitrogen atom-doped intermetallic compound catalyst.

[0044] In step S1, the soluble carbonate may be sodium carbonate, potassium carbonate, or ammonium carbonate, preferably sodium carbonate; the strong base may be sodium hydroxide or potassium hydroxide, preferably sodium hydroxide, and further, the concentration of solution II is 2 mol / L to 5 mol / L.

[0045] In step S2, preferably, the element M may be one of Mo, W, Zn, Fe, Co, In, and Ga, preferably Zn.

[0046] Metal Al 3+ The soluble salt may be one or a mixture of aluminum nitrate, aluminum sulfate, and aluminum chloride; the concentration of the soluble salt is preferably 0.0001 mol / L to 0.0005 mol / L.

[0047] Preferably, the Ni 2+ Soluble salts containing metal elements M contain Al 3+ The molar ratio of the soluble salts is 3: (1-3): 1. By determining the dosage ratio, the structure and performance of the synthesized catalyst can be better guaranteed.

[0048] The step of adding solution III to solution I is preferably done dropwise, that is, adding solution III dropwise to solution I. Furthermore, solution II is added to adjust the pH to 11.

[0049] Preferably, the temperature of the hydrothermal reaction is 100-150° C., and the time is 12 h-30 h. In some preferred embodiments, the temperature of the hydrothermal reaction is 120° C., and the time is 24 h.

[0050] Preferably, the calcination temperature is 400-550°C, the heating rate is 1-5°C / min, and the calcination time is 2 h-6 h. In some preferred embodiments, the calcination temperature is 500°C, the heating rate is 2°C / min, and the calcination time is 3 h.

[0051] Specifically, step S2 can be as follows: nickel nitrate, aluminum nitrate, and zinc nitrate are dissolved together to form solution III, solution III is added dropwise to solution I, and solution II is combined to stabilize the pH at 11 to obtain solution IV, solution IV is placed in a hydrothermal kettle, and hydrothermally reacted at 120°C for 24 hours to obtain a hydrothermal product, the hydrothermal product is centrifuged and washed to neutrality, dried at 100°C for 12 hours, and then heated to 500°C at a heating rate of 2°C / min, and calcined for 3 hours to obtain a fresh catalyst.

[0052] In step S3, the reduction temperature is preferably 500-600°C, and the reduction time is preferably 1-3 hours. Furthermore, the reduction temperature is 550°C, the reduction time is 2 hours, and the hydrogen concentration in the reducing environment is preferably 60%-100%. After hydrogen reduction, a nitrogen atom doping process is performed, switching the hydrogen gas to NH3, with a purity of 1%-100%. The NH3 concentration is preferably 5%, and the treatment time is 1 hour. An appropriate amount of O2 is introduced to passivate the nitrogen-doped catalyst, with the O2 content being 0.5%-3% (balanced with an inert gas, Ar or He), to obtain the nitrogen-doped intermetallic compound catalyst of the present invention.

[0053] Example 2 The prepared catalyst was used for naphthalene hydrogenation. The naphthalene hydrogenation reaction was carried out in a fixed-bed reactor. Since the reactants were in a solid phase, naphthalene needed to be dissolved, and the solvent was n-octane. The product analysis used the internal standard method, with n-tetradecane as the internal standard. The prepared nitrogen atom-doped intermetallic compound catalyst was loaded into a fixed-bed reactor for naphthalene saturation hydrogenation. The reaction temperature was 230°C, the reaction pressure was 4 MPa, the hydrogen-to-oil ratio was 300, and the liquid phase volume space velocity was 94.5 h-1 / 2. -1 The catalyst was tested to have good saturated hydrogenation ability. In the 24-h stability test, the naphthalene conversion rate could reach 100%, and the decahydronaphthalene selectivity was as high as over 97.7%.

[0054] Some specific experimental groups and test / characterization results are provided below Experimental Group 1 Take 3.98 g of anhydrous Na2CO3 and dissolve it in deionized water to obtain the required solution I. Then take 6.00 g of NaOH and dissolve it in deionized water to obtain 1.5 mol / L strong alkaline solution II.

[0055] 4.36 g Ni(NO₃)₂·6H₂O, 1.88 g Al(NO₃)₃·9H₂O, and 2.97 g Zn(NO₃)₂·6H₂O were dissolved in deionized water and stirred until the nitrates were fully dissolved to obtain Solution III. Solution III was slowly added dropwise to Solution I, and the pH was adjusted to 11 with the prepared Solution II. The mixture was stirred thoroughly for 0.5 h to obtain an emulsion. The emulsion was then placed in a stainless steel reactor and hydrothermally reacted at 120°C for 24 h to obtain a precipitate. The precipitate was centrifuged, washed to neutrality, and dried in an 80°C oven for 10 h. Fresh catalyst I was then calcined at 550°C for 3 h at a heating rate of 2°C / min.

[0056] Experimental Group 2 The fresh catalyst obtained from experimental group 1 was reduced at 550 °C in H2 atmosphere for 2 h, and then NH3 was introduced for 1 h to obtain catalyst I doped with nitrogen atoms.

[0057] Experimental Group 3 0.10 g of the prepared nitrogen-doped intermetallic compound catalyst I was used for the hydrogenation of naphthalene. The reactant was a naphthalene-octane solution (with n-tetradecane as the internal standard), the reaction temperature was 230°C, the reaction pressure was 4 MPa, the hydrogen-to-oil ratio was 300, and the liquid phase volumetric space velocity was 94.5 h-1 / h. –1 .

[0058] Experimental Group 4 The 2.97 g Zn(NO3)2·6H2O in experimental group 1 was replaced with 1.96 g (NH4)2MoO4 to obtain fresh catalyst II.

[0059] Experimental Group 5 The fresh catalyst obtained from experimental group 1 was reduced at 550 °C in H2 atmosphere for 1 h, and then NH3 was introduced for 2 h to obtain catalyst II doped with nitrogen atoms.

[0060] Experimental Group 6 0.10 g of the prepared nitrogen-doped intermetallic compound catalyst II was used for the hydrogenation of naphthalene. The reactant was a naphthalene-octane solution (with n-tetradecane as the internal standard), the reaction temperature was 230°C, the reaction pressure was 4 MPa, the hydrogen-to-oil ratio was 300, and the liquid phase volumetric space velocity was 94.5 h-1 / h. –1 .

[0061] The following tests / characterizations are performed on the above experimental groups 1. Characterization of the fresh catalyst obtained from experimental group 1 Figure 1 is the XRD pattern of the fresh catalyst in experimental group 1. Figure 1 It can be seen that in 2 θ = 37.2° and 43.3°, which are respectively attributed to the NiO (101) and (012) crystal planes; the rest are at 2 θ = 31.8°, 34.4°, 36.3°, 47.5°, 56.6°, 62.9°, 67.9°, and 69.1° are all attributed to ZnO.

[0062] Figure 2 This is the SEM image of the precursor before calcination in experimental group 1. The fresh catalyst has an irregular blocky appearance.

[0063] 2. Characterization of the nitrogen-doped intermetallic compound catalyst obtained in Experimental Group 2 Figure 3is the XRD pattern of the nitrogen-doped intermetallic compound catalyst in experimental group 2. Figure 3 It can be seen that 2 θ =42.7°, 49.8° and 73.2°, which are characteristic diffraction peaks belonging to Ni3ZnN. Compared with undoped Ni3Zn, the addition of nitrogen atoms causes the diffraction peaks to shift to lower angles.

[0064] Figure 4 This is the SEM image of the nitrogen-doped intermetallic compound catalyst in Experimental Group 2. It can be seen that the catalyst still maintains an irregular blocky morphology after nitrogen atom doping.

[0065] Figure 5 and Figure 6 The pore size distribution diagram and N2 adsorption-desorption isotherm of the catalyst are shown respectively. The specific surface area of the catalyst is 81 m 2 / g, compared with the pre-doping (78 m 2 / g), no obvious change was found, indicating that the doping of nitrogen atoms had no significant effect on the specific surface area and pore structure of the catalyst.

[0066] Figure 7 and Figure 8 TEM and HR-TEM images of the catalyst. As can be seen from the figure, the catalyst particles are evenly distributed. HR-TEM images show clear lattice fringes attributable to the Ni3ZnN (111) and (200) crystal planes. Compared with Ni3Zn (0.212 nm and 0.183 nm), the lattice spacing is increased, further proving that nitrogen atoms have been successfully incorporated into the lattice of the Ni3Zn alloy.

[0067] 3. Test the naphthalene hydrogenation performance of the prepared nitrogen atom-doped intermetallic compound catalyst I: Figure 9 The naphthalene hydrogenation performance diagram of the nitrogen-doped intermetallic compound catalyst in experimental group 3 is shown in the figure. It can be seen from the figure that the catalyst has a high hydrogenation performance at 230 °C, 4 MPa, a hydrogen-to-oil ratio of 300, and a liquid phase volume space velocity of 94.5 h –1 Under the conditions of 100%, 100% naphthalene conversion and 97.7% decalin selectivity can be maintained.

[0068] 4. Characterization of the fresh catalyst obtained from Experimental Group 4: Figure 10 This is the XRD pattern of fresh catalyst II in experimental group 4. Figure 10 It can be seen that the catalyst has a characteristic diffraction peak attributed to Ni(MoO4), indicating that the two elements Ni and Mo in the fresh catalyst II exist in an oxidized form.

[0069] Figure 11This is the SEM image of fresh catalyst II. The calcined catalyst exhibits a rod-like morphology of varying lengths.

[0070] 5. Characterization of the nitrogen-doped catalyst II obtained in Experimental Group 5: Figure 12 The XRD pattern of catalyst II after nitrogen atom doping. Characteristic diffraction peaks attributed to metal Ni appeared at 44.4°, 51.8°, and 76.5°. Characteristic diffraction peaks attributed to Ni appeared at 32.2°, 36.5°, 49.4°, 65.7°, and 77.6°. 0.2 Mo 0.8 The characteristic diffraction peak of N indicates that part of Ni exists in the form of metal nitride and the other part exists in the form of metallic Ni.

[0071] Figure 13 This is the SEM image of catalyst II after nitrogen atom doping. As can be seen from the figure, after the reduction and nitridation process, the rod-like structure of the catalyst is partially broken, and the catalyst exhibits an irregular block structure.

[0072] 6. Naphthalene hydrogenation performance test and characterization of the prepared nitrogen atom-doped intermetallic compound catalyst II: Figure 14 The naphthalene hydrogenation performance of catalyst II after nitrogen atom doping is shown in the figure. The catalyst is heated at 230℃, 4MPa, hydrogen-to-oil ratio of 300, and liquid phase volume space velocity of 94.5 h –1 Under the conditions of 10 h stability test, the conversion of naphthalene can still be maintained at 100%, and the selectivity of decalin is still higher than 78%.

[0073] Figure 15 This is the SEM image of the catalyst after naphthalene hydrogenation performance test. Compared with before the reaction, the catalyst morphology has not changed significantly and still shows an irregular blocky appearance, indicating that the catalytic reaction process has affected the micromorphology of catalyst II.

[0074] In summary, the nitrogen-doped intermetallic compound catalyst prepared in the present invention can meet the requirements of the hydrogenation reaction in the naphthalene-decalin hydrogen storage system, effectively solve the problems existing in the hydrogen energy storage and transportation links, and is of great benefit to optimizing the energy structure and solving environmental problems.

[0075] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations that come within the meaning and range of equivalents of the claims be embraced therein.

[0076] In addition, it should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

Claims

1. A nitrogen atom-doped intermetallic compound catalyst, characterized in that: The molecular formula of the catalyst is Ni x M y N n / Al2O3, with Al2O3 as the carrier, and Ni x M y N n It is the active component of the catalyst, x represents the number of metal Ni atoms in the intermetallic compound; M represents the added metal additive, y represents the number of additive atoms in the compound, and n is the number of nitrogen atoms in the compound, and the range of n is 0.5~0.

1.

2. The nitrogen-doped intermetallic compound catalyst according to claim 1, characterized in that: The content of Ni is 20 wt.%~80 wt.%; The M includes any one of Mo, W, Zn, Fe, Co, In, and Ga.

3. A method for preparing the nitrogen-doped intermetallic compound catalyst according to claim 1, characterized in that: The steps include: S1. Prepare alkaline solution: fully dissolve soluble carbonate in deionized water to obtain solution I, and fully dissolve strong base in deionized water to obtain solution II; S2, synthesis of metal oxide precursor: 2+ Soluble salts containing metal elements M and soluble salts containing Al 3+ The soluble salt is fully dissolved in deionized water to obtain solution III; Solution III was added dropwise to solution I, and solution II was added to adjust the pH to 8-13 to obtain an emulsion; Then, the emulsion is subjected to a hydrothermal reaction to obtain a precipitate, which is centrifuged, washed to neutrality, dried, and calcined to obtain a fresh catalyst; S3. Nitrogen atom doping: The fresh catalyst is first reduced with H2, then NH3 gas is introduced, and finally O2 is introduced to passivate the sample to obtain the desired nitrogen atom-doped intermetallic compound catalyst.

4. The method for preparing a nitrogen atom-doped intermetallic compound catalyst according to claim 3, wherein: The soluble carbonate includes any one of sodium carbonate, potassium carbonate, and ammonium carbonate, and the concentration of solution I is 0.5-0.75 mol / L; The strong base includes any one of sodium hydroxide and potassium hydroxide, and the concentration of solution II is 2 mol / L~5 mol / L.

5. The method for preparing a nitrogen atom-doped intermetallic compound catalyst according to claim 3, wherein: The Ni 2+ The soluble salt includes any one of nickel nitrate, nickel acetate, and nickel sulfate; The metal element M includes any one of Mo, W, Zn, Fe, Co, In, and Ga, and the soluble salt containing the metal element M includes any one of nitrate, carbonate, and sulfate; The Al 3+ The soluble salts include one or more of aluminum nitrate, aluminum sulfate, and aluminum chloride; the solution III contains Al 3+ The concentration of soluble salt solution is 0.0001 mol / L~0.0005 mol / L; The Ni 2+ Soluble salts containing metal elements M contain Al 3+ The molar ratio between the soluble salts is 3: (1~3):

1.

6. The method for preparing a nitrogen atom-doped intermetallic compound catalyst according to claim 3, wherein: The temperature of the hydrothermal reaction is 100-150°C, and the hydrothermal time is 12-30h; The calcination temperature is 400-550°C, the heating rate is 1-5°C / min, and the calcination time is 2-6h; The reduction temperature is 500-600°C and the time is 1-3 hours; After the NH3 gas is introduced, the nitrogen atom doping process temperature is 400-600°C and the time is 0.5-5h.

7. The method for preparing a nitrogen atom-doped intermetallic compound catalyst according to claim 3, wherein: The concentration of O2 used in the passivation is 0.5-3%, and the passivation time is 5-10 hours; the inert gas balance during the passivation process includes Ar or He.

8. A nitrogen atom-doped intermetallic compound catalyst as claimed in claim 1 used in naphthalene hydrogenation reaction.

9. The use of a nitrogen atom-doped intermetallic compound catalyst according to claim 8, characterized in that: The naphthalene hydrogenation reaction is carried out in a fixed bed reactor using a nitrogen atom-doped intermetallic compound catalyst, wherein naphthalene is dissolved in a solvent and then reacted; the product is analyzed using an internal standard method, which requires the addition of an internal standard substance to the reactant solution; The prepared nitrogen atom-doped intermetallic compound catalyst was loaded into a fixed-bed reactor for naphthalene saturation hydrogenation reaction at a reaction temperature of 100-270°C, a reaction pressure of 3-6 MPa, a hydrogen-to-oil ratio of 150-1800, and a liquid phase volume space velocity of 2-300 h -1 .

10. The use of a nitrogen atom-doped intermetallic compound catalyst according to claim 9, characterized in that: The solvent includes any one of n-hexane, n-heptane, n-octane, and n-decane; The internal standard substance includes any one of n-dodecane, n-tetradecane and n-hexadecane.

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