Nano-catalyst for hydrogen production by hydrolysis of ammonia borane, preparation method thereof and application

Abstract

The present invention belongs to the field of catalyst preparation, and discloses a nanocatalyst for hydrolyzing ammonia borane to produce hydrogen, its preparation method and application. The preparation method is simple, the reagents are safe and non-toxic, and the risk is low. The prepared catalyst uses SBA-15 as a substrate, and its hydrophilic modification is carried out by MoO2 to prepare a MoO2-SBA-15 support, and then nickel nanoparticles are deposited by an impregnation reduction method to obtain a Ni / MoO2-SBA-15 nanocatalyst with a Ni / MoO2 heterostructure. The catalyst prepared by using this preparation method has small particle size and high dispersion of metal particles; it can efficiently catalyze the hydrolysis of ammonia borane to produce hydrogen at room temperature, the hydrogen selectivity reaches 100%, the turnover frequency is high, and it has high hydrophilicity, catalytic activity and stability, and is a catalyst with great development prospects.

Description

Technical Field

[0001] The present invention belongs to the field of catalyst preparation, and particularly relates to a nanocatalyst for hydrolyzing ammonia borane to produce hydrogen, its preparation method and application. Background Art

[0002] Ammonia borane (NH3BH3, AB) is a promising chemical hydrogen storage material, which has the characteristics of high hydrogen content (19.6 wt%), long-term stability and non-toxicity. Under the action of a suitable catalyst, ammonia borane can hydrolyze to produce hydrogen under mild conditions (NH3BH3 + 2H2O → NH4 + + BO2 - + 3H2). In recent years, noble metal catalysts (such as Pt, Rh, and Ru, etc.) that have received much attention have shown excellent catalytic performance in the hydrolysis of ammonia borane to produce hydrogen, but the scarcity of their resources and high cost have greatly limited their practical applications. Therefore, there is an urgent need to develop more economical non-noble metal-based catalysts (such as Fe, Co, Ni, and Cu, etc.) with high efficiency in the hydrolysis of ammonia borane.

[0003] SBA-15 belongs to a kind of mesoporous molecular sieve, which has rich ordered channels and a large specific surface area, and has been proved to be an ideal carrier for stabilizing active metal sites and improving the mass transfer efficiency during the catalytic reaction process. However, the hydrophilicity of SBA-15 has greatly limited its potential performance in the hydrolysis reaction. Therefore, developing catalysts with high activity, high stability and high selectivity is of great significance for ammonia borane as a hydrogen energy carrier. Summary of the Invention

[0004] The purpose of the present invention is to solve the deficiencies of the prior art, and provide a nanocatalyst for hydrolyzing ammonia borane to produce hydrogen, its preparation method and application, and specifically adopt the following technical solutions:

[0005] According to the first aspect of the present invention, a preparation method of a nanocatalyst for hydrolyzing ammonia borane to produce hydrogen includes the following steps:

[0006] First, mix SBA-15, an amination reagent and ethanol evenly, centrifuge and wash, and obtain aminated SBA-15 after drying; then add it and a molybdenum precursor to an ethanol aqueous solution, stir and mix evenly, centrifuge and wash, and dry to obtain an intermediate product; subsequently, under the condition of 600 °C - 900 °C, perform heat treatment on the intermediate product to obtain a MoO2-SBA-15 support; finally, mix the MoO2-SBA-15 support, a nickel precursor and sodium borohydride evenly, and stir until the reaction is complete to obtain a Ni / MoO2-SBA-15 catalyst.

[0007] Based on the principle of hydrophilically modifying a nanocatalyst to improve its activation ability for water molecules, the present invention first proposes to prepare a nanocatalyst by modifying with metal oxide MoO₂ to promote the hydrolysis of ammonia borane. Specifically, SBA-15 is used as a substrate and modified with MoO₂ to obtain a MoO₂-SBA-15 support, and then Ni nanoparticles are deposited by an impregnation reduction method to prepare a Ni / MoO₂-SBA-15 nanocatalyst.

[0008] The Ni / MoO₂-SBA-15 heterojunction nanocatalyst prepared in the present invention has a typical lotus root-like morphology, and Ni and MoO₂ form a nanoheterojunction, which has the characteristics of small particle size (particle size is 1.5 nm) and highly dispersed metal particles. Therefore, the formed nanoheterojunction is confined in the pores of mesoporous silica SBA-15. The preparation method is simple, the reagents are safe and non-toxic, and the risk is low. The prepared nanocatalyst is a black powdery substance, and its metal loading is 4.66 wt% - 12.80 wt%; at 298 K, the hydrogen selectivity of this catalyst reaches 100%, and it has a high turnover frequency, high activity, high stability and high selectivity, etc., and can be widely used in hydrogen production by ammonia borane hydrolysis.

[0009] Preferably, the amination reagent is 3-aminopropyltriethoxysilane, polyethyleneimine, amino acid or p-phenylenediamine.

[0010] Preferably, the ratio of SBA-15, amination reagent and ethanol is 1.0 g : 4 mL : 8 mL.

[0011] Preferably, the molybdenum precursor is phosphomolybdic acid, ammonium molybdate or molybdic acid. More preferably, the molybdenum precursor is phosphomolybdic acid, and the dosage ratio of amine-functionalized SBA-15 and phosphomolybdic acid is 1 g : 2 g. When phosphomolybdic acid is used as the most preferred molybdenum source, mainly because the generated MoO₂ has a unique activation ability for water molecules in water splitting and shows better hydrophilicity than other molybdenum sources. In addition, the generated MoO₂ is more inclined to interact with nearby active metal nanoparticles to form a heterojunction, which will effectively optimize its adsorption ability for reaction intermediates, thereby improving the catalytic performance. When the dosage ratio of amine-functionalized SBA-15 and phosphomolybdic acid is 1 g : 2 g, the hydrogen selectivity can reach 100%, and the hydrogen production time is only 0.42 min, which can shorten the hydrogen production time.

[0012] Preferably, the heat treatment temperature is 700 °C. When the heat treatment temperature is 700 °C, the hydrogen production time is the shortest. The hydrogen production time at 900 °C is nearly four times that at 700 °C, and at 600 °C it is nearly twice that at 700 °C, with a large difference. When continuous industrial production is carried out, the time gap will be further enlarged. Therefore, heat treatment at 700 °C is more suitable for industrial production.

[0013] Specific steps of heat treatment: Under the condition that the heating rate is 1 °C / min - 5 °C / min, raise the temperature to 600 °C

[0014] - 900 °C, and then keep the temperature for 2 h - 4 h. The MoO2-SBA-15 prepared by heat treatment has good affinity for water molecules, which is beneficial to the activation of water molecules (RDS) in the subsequent hydrolysis reaction of ammonia borane catalyzed by the catalyst, and further improves the catalytic activity. When the heating rate, temperature, and heat preservation time exceed the above ranges, other impurity phases will be generated in the phase, and the single-phase nature of the material cannot be guaranteed.

[0015] Preferably, the ratio of the MoO2-SBA-15 support, nickel precursor, and sodium borohydride is (20 mg - 60.0 mg): 0.05 mmol: (20 mg - 40 mg). More preferably, the ratio of the MoO2-SBA-15 support, nickel precursor, and sodium borohydride is 40 mg: 0.05 mmol: 30 mg. When the dosage of the MoO2-SBA-15 support is 40 mg, the nickel precursor can be completely reduced, its metal loading is 6.83 wt%, the hydrogen selectivity can reach 100%, and the hydrogen production time is significantly lower than that of other dosages, which can not only ensure material saving but also shorten the hydrogen production time.

[0016] According to the second aspect of the present invention, there is provided a nano-catalyst for hydrogen production by hydrolysis of ammonia borane, which is prepared by any of the above methods.

[0017] The nano-catalyst prepared by the present invention is a black powdery substance, and its metal loading is 4.66 wt% - 12.80 wt%; at 298 K, the hydrogen selectivity of this catalyst reaches 100%, it has a high turnover frequency, and has the characteristics of high activity, high stability, and high selectivity, and can be widely used in hydrogen production by hydrolysis of ammonia borane.

[0018] According to the third aspect of the present invention, there is provided an application of the above nano-catalyst in hydrogen production by hydrolysis.

[0019] The beneficial effects of the present invention are as follows: The preparation method of the present invention is simple, the reagents are safe and non-toxic, and the risk is low. Moreover, the prepared Ni / MoO2-SBA-15 nano-catalyst is composed of Ni / MoO2 heterojunction nanoparticles uniformly distributed on the SBA-15 support, with small particles and high dispersion of metal particles; it can efficiently catalyze the hydrolysis of ammonia borane to produce hydrogen at room temperature, the hydrogen selectivity reaches 100%, the turnover frequency is high, and it has high hydrophilicity, catalytic activity and stability, and is a catalyst with great development prospects. Description of the Drawings

[0020] Figure 1The SEM image of the Ni / MoO₂-SBA-15 heteronanocatalyst obtained in Example 1 is shown;

[0021] Figure 2 The TEM and particle size distribution diagrams of the Ni / MoO₂-SBA-15 heteronanocatalyst obtained in Example 1 are shown; among them, (a) is the TEM image at 50 nm, (b) is the TEM image at 20 nm, (c) is the TEM image at 2 nm, and (d) is the particle size distribution diagram;

[0022] Figure 3 The Ni 2p XPS spectrum of the Ni / MoO₂-SBA-15 heteronanocatalyst obtained in Example 1 is shown;

[0023] Figure 4 The Mo 3d XPS spectrum of the Ni / MoO₂-SBA-15 heteronanocatalyst obtained in Example 1 is shown;

[0024] Figure 5 The contact angle test diagrams of MoO₂-SBA-15 and SBA-15 obtained in Example 1 are shown; among them, (a) is SBA-15 and (b) is MoO₂-SBA-15;

[0025] Figure 6 The performance diagram of the Ni / MoO₂-SBA-15 heteronanocatalyst obtained in Example 1 for catalyzing the hydrolysis of ammonia borane to produce hydrogen under the condition of 298 K is shown;

[0026] Figure 7 The cyclic use performance diagram of the Ni / MoO₂-SBA-15 heteronanocatalyst obtained in Example 1 for catalyzing the hydrolysis of ammonia borane to produce hydrogen under the condition of 298 K is shown. Detailed implementation manners

[0027] The concept and technical effects of the present invention will be clearly and completely described below in combination with the examples and the drawings to fully understand the purpose, scheme and effects of the present invention. It should be noted that, without conflict, the examples and the features in the examples in this application can be combined with each other.

[0028] Example 1:

[0029] A Ni / MoO₂-SBA-15 nanocatalyst, and its preparation method includes the following steps:

[0030] (1) Disperse 1.0 g of SBA-15 and 4 mL of 3-aminopropyltriethoxysilane (APTES) in 8 mL of ethanol, ultrasonically mix evenly, and centrifuge and dry to obtain amino-functionalized SBA-15;

[0031] (2) Take 1.0 g of the amino-functionalized SBA-15 obtained in step (1), disperse it in a mixed solution of water and ethanol, add 2.0 g of phosphomolybdic acid, stir in a water bath at 30 °C for 5 h, and obtain a solid by centrifugation, washing, and drying.

[0032] (3) Place the solid obtained in step (2) in a tubular furnace. Under a flowing argon atmosphere, with a heating rate of 3 °C / min, heat up to 700 °C and perform heat treatment for 3 h to obtain a support.

[0033] (4) Take 40.0 mg of the support obtained in step (3), disperse it in 5 mL of water, add 0.05 mmol of nickel chloride, ultrasonically mix evenly, and then add 30.0 mg of the reducing agent sodium borohydride. Stir vigorously until the reaction is complete to obtain a Ni / MoO2-SBA-15 heterogeneous nanocatalyst with a metal loading of 6.83 wt%.

[0034] The inventors also carried out relevant detections on the Ni / MoO2-SBA-15 nanocatalyst prepared in this example, and the detection results are as follows.

[0035] As Figure 1 shown is the SEM image of the nanocatalyst. It can be seen that the catalyst has the same typical joint-like structure as the substrate SBA-15, proving the excellent stability of the SBA-15 substrate.

[0036] As Figure 2 shown are the TEM and particle size distribution diagrams of the Ni / MoO2-SBA-15 heterogeneous nanocatalyst obtained in Example 1. The TEM image (Figure (a)) shows an obvious ordered mesoporous structure of the catalyst; from Figure (b), it can be seen that the nanoparticles are evenly distributed on SBA-15, and the average particle size is only 1.5 nm. Ni and MoO2 are in close contact to form a heterogeneous interface.

[0037] As Figure 3 shown is the Ni 2p XPS spectrum of the Ni / MoO2-SBA-15 heterogeneous nanocatalyst obtained in Example 1. Through analysis, it can be obtained that the characteristic peak of the Ni 2p orbital in the catalyst shifts negatively to a lower binding energy, indicating that Ni gains electrons and shows a surface electron-rich state.

[0038] As Figure 4 shown is the Mo 3d XPS spectrum of the Ni / MoO2-SBA-15 heterogeneous nanocatalyst obtained in Example 1. When the characteristic peak of the Mo 3d orbital in the catalyst shifts positively to a higher binding energy, it can indicate that there is an electron transfer from MoO2 to Ni at the heterogeneous interface in the catalyst.

[0039] As Figure 5The following is the contact angle test diagram of MoO₂-SBA-15 and SBA-15 obtained in Example 1, indicating that MoO₂-SBA-15 has good hydrophilicity and can be wetted instantly when contacting with water. The contact angle of SBA-15 with water is 90.05°, and it is a hydrophobic material.

[0040] As Figure 6 The following is the performance diagram of the Ni / MoO₂-SBA-15 heterogeneous nanocatalyst obtained in Example 1 for catalytic hydrolysis of ammonia borane to produce hydrogen at 298K. It can be seen that the catalyst can completely catalyze the hydrolysis of ammonia borane to produce hydrogen within only 0.42 min, and the turnover frequency is as high as 143.9 min -1 。

[0041] As Figure 7 The following is the recycling performance diagram of the Ni / MoO₂-SBA-15 heterogeneous nanocatalyst obtained in Example 1 for catalytic hydrolysis of ammonia borane to produce hydrogen at 298K, indicating that the catalyst can still efficiently catalyze the hydrolysis of ammonia borane to produce hydrogen after ten cycles and has excellent recycling stability.

[0042] Example 2:

[0043] A Ni / MoO₂-SBA-15 nanocatalyst, whose preparation method only changes APTES in step (1) of Example 1 to polyethyleneimine, and other steps are the same as those in Example 1, to obtain the Ni / MoO₂-SBA-15 heterogeneous nanocatalyst.

[0044] Example 3:

[0045] A Ni / MoO₂-SBA-15 nanocatalyst, whose preparation method only changes APTES in step (1) of Example 1 to amino acid, and other steps are the same as those in Example 1, to obtain the Ni / MoO₂-SBA-15 heterogeneous nanocatalyst.

[0046] Example 4:

[0047] A Ni / MoO₂-SBA-15 nanocatalyst, whose preparation method only changes APTES in step (1) of Example 1 to p-phenylenediamine, and other steps are the same as those in Example 1, to obtain the Ni / MoO₂-SBA-15 heterogeneous nanocatalyst.

[0048] Example 5:

[0049] A Ni / MoO₂-SBA-15 nanocatalyst, whose preparation method only changes phosphomolybdic acid in step (2) of Example 1 to ammonium molybdate, and other steps are the same as those in Example 1, to obtain the Ni / MoO₂-SBA-15 heterogeneous nanocatalyst..

[0050] Example 6:

[0051] A Ni / MoO2-SBA-15 nanocatalyst, the preparation method of which only changes phosphomolybdic acid to molybdic acid in step (2) of Example 1, and other steps are the same as those in Example 1, to obtain a Ni / MoO2-SBA-15 heterogeneous nanocatalyst.

[0052] Example 7:

[0053] A Ni / MoO2-SBA-15 nanocatalyst, the preparation method of which only changes the dosage of molybdenum precursor in step (2) of Example 1 to 1.0 g, and other steps are the same as those in Example 1, to obtain a Ni / MoO2-SBA-15 heterogeneous nanocatalyst.

[0054] Example 8:

[0055] A Ni / MoO2-SBA-15 nanocatalyst, the preparation method of which only changes the dosage of molybdenum precursor in step (2) of Example 1 to 1.5 g, and other steps are the same as those in Example 1, to obtain a Ni / MoO2-SBA-15 heterogeneous nanocatalyst.

[0056] Example 9:

[0057] A Ni / MoO2-SBA-15 nanocatalyst, the preparation method of which only changes the dosage of molybdenum precursor in step (2) of Example 1 to 2.5 g, and other steps are the same as those in Example 1, to obtain a Ni / MoO2-SBA-15 heterogeneous nanocatalyst.

[0058] Example 10:

[0059] A Ni / MoO2-SBA-15 nanocatalyst, the preparation method of which only changes the water bath temperature in step (2) of Example 1 to 25 °C, and other steps are the same as those in Example 1, to obtain a Ni / MoO2-SBA-15 heterogeneous nanocatalyst.

[0060] Example 11:

[0061] A Ni / MoO2-SBA-15 nanocatalyst, the preparation method of which only changes the water bath temperature in step (2) of Example 1 to 35 °C, and other steps are the same as those in Example 1, to obtain a Ni / MoO2-SBA-15 heterogeneous nanocatalyst.

[0062] Example 12:

[0063] A Ni / MoO2-SBA-15 nanocatalyst, the preparation method of which only changes the stirring time in step (2) of Example 1 to 4 h, and other steps are the same as those in Example 1, to obtain a Ni / MoO2-SBA-15 heterogeneous nanocatalyst.

[0064] Example 13:

[0065] A Ni / MoO2-SBA-15 nanocatalyst, the preparation method of which only changes the stirring time in step (2) of Example 1 to 6 h, and other steps are the same as those in Example 1, to obtain the Ni / MoO2-SBA-15 heterogeneous nanocatalyst.

[0066] Example 14:

[0067] A Ni / MoO2-SBA-15 nanocatalyst, the preparation method of which only changes the heating rate in step (3) of Example 1 to 1 °C / min, and other steps are the same as those in Example 1, to obtain the Ni / MoO2-SBA-15 heterogeneous nanocatalyst.

[0068] Example 15:

[0069] A Ni / MoO2-SBA-15 nanocatalyst, the preparation method of which only changes the heating rate in step (3) of Example 1 to 5 °C / min, and other steps are the same as those in Example 1, to obtain the Ni / MoO2-SBA-15 heterogeneous nanocatalyst.

[0070] Example 16:

[0071] A Ni / MoO2-SBA-15 nanocatalyst, the preparation method of which only changes the heat treatment temperature in step (3) of Example 1 to 600 °C, and other steps are the same as those in Example 1, to obtain the Ni / MoO2-SBA-15 heterogeneous nanocatalyst.

[0072] Example 17:

[0073] A Ni / MoO2-SBA-15 nanocatalyst, the preparation method of which only changes the heat treatment temperature in step (3) of Example 1 to 800 °C, and other steps are the same as those in Example 1, to obtain the Ni / MoO2-SBA-15 heterogeneous nanocatalyst.

[0074] Example 18:

[0075] A Ni / MoO2-SBA-15 nanocatalyst, the preparation method of which only changes the heat treatment temperature in step (3) of Example 1 to 900 °C, and other steps are the same as those in Example 1, to obtain the Ni / MoO2-SBA-15 heterogeneous nanocatalyst.

[0076] Example 19:

[0077] A Ni / MoO2-SBA-15 nanocatalyst, the preparation method of which only changes the heat treatment time in step (3) of Example 1 to 2 h, and other steps are the same as those in Example 1, to obtain the Ni / MoO2-SBA-15 heterogeneous nanocatalyst.

[0078] Example 20:

[0079] A Ni / MoO₂-SBA-15 nanocatalyst, the preparation method of which only changes the heat treatment time in step (3) of Example 1 to 4 h, and other steps are the same as those in Example 1, to obtain a Ni / MoO₂-SBA-15 heteronanocatalyst.

[0080] Example 21:

[0081] A Ni / MoO₂-SBA-15 nanocatalyst, the preparation method of which only changes the dosage of the carrier in step (4) of Example 1 to 20.0 mg, and other steps are the same as those in Example 1, to obtain a Ni / MoO₂-SBA-15 heteronanocatalyst with a metal loading of 12.80 wt%.

[0082] Example 22:

[0083] A Ni / MoO₂-SBA-15 nanocatalyst, the preparation method of which only changes the dosage of the carrier in step (4) of Example 1 to 60.0 mg, and other steps are the same as those in Example 1, to obtain a Ni / MoO₂-SBA-15 heteronanocatalyst with a metal loading of 4.66 wt%.

[0084] Example 23:

[0085] A Ni / MoO₂-SBA-15 nanocatalyst, the preparation method of which only changes nickel chloride in step (4) of Example 1 to nickel nitrate, and other steps are the same as those in Example 1, to obtain a Ni / MoO₂-SBA-15 heteronanocatalyst.

[0086] Example 24:

[0087] A Ni / MoO₂-SBA-15 nanocatalyst, the preparation method of which only changes nickel chloride in step (4) of Example 1 to nickel sulfate, and other steps are the same as those in Example 1, to obtain a Ni / MoO₂-SBA-15 heteronanocatalyst.

[0088] Example 25:

[0089] A Ni / MoO₂-SBA-15 nanocatalyst, the preparation method of which only changes nickel chloride in step (4) of Example 1 to nickel acetate, and other steps are the same as those in Example 1, to obtain a Ni / MoO₂-SBA-15 heteronanocatalyst.

[0090] Example 26:

[0091] A Ni / MoO2-SBA-15 nanocatalyst, the preparation method of which only changes the amount of sodium borohydride in step (4) of Example 1 to 20.0 mg, and the other steps are the same as those in Example 1, to obtain a Ni / MoO2-SBA-15 heterogeneous nanocatalyst.

[0092] Example 27:

[0093] A Ni / MoO2-SBA-15 nanocatalyst, the preparation method of which only changes the amount of sodium borohydride in step (4) of Example 1 to 40.0 mg, and the other steps are the same as those in Example 1, to obtain a Ni / MoO2-SBA-15 heterogeneous nanocatalyst.

[0094] Example 28:

[0095] The Ni / MoO2-SBA-15 heterogeneous nanocatalysts obtained in Examples 1, 7, 8, and 9 were used to detect the catalytic hydrolysis of ammonia borane to produce hydrogen at 25 °C, and the results are shown in Table 1.

[0096] Table 1

[0097]

[0098] The results show that when the amount of phosphomolybdic acid is different and the metal loading is 6.83 wt%, the hydrogen selectivity reaches 100%, while the hydrogen production times are slightly different, being 0.42 min, 0.58 min, 0.50 min, and 0.67 min respectively.

[0099] Example 29:

[0100] The Ni / MoO2-SBA-15 heterogeneous nanocatalysts obtained in Examples 1, 16, 17, and 18 were used to detect the catalytic hydrolysis of ammonia borane to produce hydrogen at 25 °C, and the results are shown in Table 2.

[0101] Table 2

[0102]

[0103] The results show that when the heat treatment temperature is different and the metal loading is 6.83 wt%, the hydrogen selectivity reaches 100%, while the hydrogen production time at 900 °C is nearly four times that at 700 °C, with a slightly larger difference, being 0.42 min, 0.78 min, 0.53 min, and 1.43 min respectively.

[0104] Example 30:

[0105] The Ni / MoO2-SBA-15 heterogeneous nanocatalysts obtained in Examples 1, 21, and 22 were used to detect the catalytic hydrolysis of ammonia borane to produce hydrogen at 25 °C, and the results are shown in Table 3.

[0106] Table 3

[0107]

[0108] The results show that when the dosage of the carrier is different and the metal loadings are 6.83 wt%, 4.66 wt%, and 12.80 wt% respectively, the hydrogen selectivity reaches 100%, and the hydrogen production times are slightly different, being 0.42 min, 0.63 min, and 0.70 min respectively.

[0109] Although the description of the present invention has been quite detailed and has particularly described several of the described embodiments, it is not intended to be limited to any of these details or embodiments or any particular embodiment, but rather should be regarded as providing a broad interpretation of these claims in light of the prior art by reference to the appended claims, so as to effectively cover the intended scope of the present invention. In addition, the present invention has been described above in terms of embodiments foreseeable by the inventors for the purpose of providing a useful description, and those non-substantive modifications to the present invention that are not currently foreseeable may still represent equivalent modifications of the present invention.

Claims

1. A preparation method of a nanocatalyst for hydrogen production by ammonia borane hydrolysis, comprising the following steps: First, mix SBA-15, an amination reagent, and ethanol evenly, centrifuge and wash, and obtain amino-functionalized SBA-15 after drying; then add it and a molybdenum precursor to an ethanol aqueous solution, stir and mix evenly, centrifuge and wash, and dry to obtain an intermediate product; Subsequently, under the condition of 600 °C - 900 °C, heat-treat the intermediate product to obtain a MoO2-SBA-15 support; finally, mix the MoO2-SBA-15 support, a nickel precursor, and sodium borohydride evenly, and stir until the reaction is complete to obtain a Ni / MoO2-SBA-15 catalyst; The amination reagent is 3-aminopropyltriethoxysilane, polyethyleneimine, amino acid, or p-phenylenediamine; The ratio of SBA-15, the amination reagent, and ethanol is 1.0 g : 4 mL : 8 mL; The molybdenum precursor is phosphomolybdic acid, and the dosage ratio of amino-functionalized SBA-15 and phosphomolybdic acid is 1 g : 2 g; The ratio of the MoO2-SBA-15 support, the nickel precursor, and sodium borohydride is (20 mg - 60 mg) : 0.05 mmol : (20 mg - 40 mg).

2. The preparation method according to claim 1, characterized in that The heat treatment temperature is 700 °C.

3. The preparation method according to claim 1, wherein, The ratio of the MoO2-SBA-15 support, the nickel precursor, and sodium borohydride is 40 mg : 0.05 mmol : 30 mg.

4. A nano-catalyst for hydrogen production by hydrolysis of ammonia borane, characterized in that, Prepared by the method according to any one of claims 1 - 3.

5. Use of the nanocatalyst according to claim 4 in hydrogen production by ammonia borane hydrolysis.

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