Process for producing hydrogen by catalyzing methanol

Abstract

The invention belongs to the technical field of catalytic hydrogen production. The invention provides a process for catalyzing methanol to produce hydrogen, which comprises the following steps: by taking a mixed solution of methanol and sodium hydroxide as a raw material, adding a bimetallic core-shell catalyst, introducing N2, sealing, heating in a water bath to 70 + / -0.5 DEG C, and magnetically stirring; the bimetallic core-shell catalyst is prepared by loading Pt and Au core-shell structure nanoparticles on a mesoporous silica-etched molybdenum disulfide composite carrier, the loading amount of Pt is 7.5 wt%, and the mass ratio of Pt to Au is 7.5: (2.25-2.35). The methanol hydrogen production catalytic performance of the prepared bimetallic core-shell catalyst is improved while the Au doping amount is further increased.

Description

Technical Field

[0001] This invention belongs to the field of hydrogen production technology, and in particular relates to a catalytic methanol-to-hydrogen process. Background Technology

[0002] Hydrogen (H2) is widely used in many fields such as steel, metallurgy, chemical industry, pharmaceutical industry, light industry, building materials, and electronics due to its environmental friendliness and high energy density. Methanol reforming to produce hydrogen has the advantages of low investment, no pollution, and convenient operation, and has been widely used in various unit operations that require pure hydrogen.

[0003] In existing technologies, to achieve catalytic methanol reforming for hydrogen production at low temperatures and atmospheric pressure, platinum (Pt) metal nanoparticles are loaded onto a suitable support. Simultaneously, a bimetallic core-shell catalyst with controllable gold (Au) shells is prepared using an impregnation method. Electrons are transferred from Au to Pt, forming a unique electronic structure of Ptδ- and Au+ on the catalyst surface. This electron-rich Ptδ- and electron-deficient Au+ coating structure enables electronic interactions between the Au shell, the Pt core, and the support, thereby promoting an overall improvement in catalytic performance. With increasing Au doping content, the synergistic effect between Au and the core Pt species, as well as the protective effect on the Pt nanoparticles, are enhanced, resulting in improved methanol-to-hydrogen catalytic performance of the prepared bimetallic core-shell catalyst.

[0004] However, when the Au doping level is increased to an excessively high level, the Pt active sites will be covered, resulting in a decrease in catalytic performance. Summary of the Invention

[0005] To address the aforementioned problems, this invention proposes a catalytic methanol-to-hydrogen process that further increases the Au doping content while improving the methanol-to-hydrogen catalytic performance of the prepared bimetallic core-shell catalyst.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A catalytic methanol-to-hydrogen process is disclosed, using a mixture of methanol and sodium hydroxide as raw material, adding a bimetallic core-shell catalyst, purging with N2 and sealing, heating in a water bath to 70±0.5℃ and magnetically stirring; the bimetallic core-shell catalyst is prepared by loading Pt@Au core-shell nanoparticles onto a mesoporous silica-etched molybdenum disulfide composite support, wherein the loading of Pt is 7.5wt% and the mass ratio of Pt to Au is 7.5:(2.25-2.35).

[0007] Furthermore, the preparation method of the mesoporous silica-etched molybdenum disulfide composite carrier is as follows: A1. Add 4-5g of mesoporous silica and 10-11g of etched molybdenum disulfide to 500mL of deionized water and disperse by ultrasonication to obtain silica dispersion and molybdenum disulfide dispersion. A2. Mix the silica dispersion and molybdenum disulfide dispersion obtained in A1, add 18-20 mL of precipitant, stir at room temperature, then heat to 80±2℃ and continue stirring to form a precipitate. Centrifuge, wash, and dry to obtain the mesoporous silica-etched molybdenum disulfide composite carrier.

[0008] Furthermore, the etched molybdenum disulfide is prepared by H2 / Ar plasma etching of molybdenum disulfide ball milling material.

[0009] Furthermore, during the plasma etching process, the volume ratio of H2 to Ar is 1:(4-8).

[0010] Furthermore, the molybdenum disulfide ball milling material is prepared by ball milling molybdenum disulfide at a speed of 4800-5000 r / min for 6-6.5 h.

[0011] Furthermore, in A2, the precipitant is ammonia.

[0012] Furthermore, in A2, the drying temperature is 110±5℃ and the drying time is 12-14h.

[0013] Furthermore, the preparation method of the bimetallic core-shell catalyst is as follows: S1. Disperse the mesoporous silica-etched molybdenum disulfide composite support in an ethanol solution, add chloroplatinic acid, stir for 30-35 min, then add chloroauric acid, stir for 3-3.2 h to obtain a mixture; S2. The mixture is centrifuged and washed three times with water and ethanol respectively. It is then dried in a vacuum oven at 60°C for 4 hours, ground, and calcined in an inert atmosphere to obtain the bimetallic core-shell catalyst.

[0014] Furthermore, in S1, the volume ratio of anhydrous ethanol to water in the ethanol solution is (3.5-4.5):6.

[0015] Furthermore, in S2, calcination is carried out in a N2 atmosphere at 350±5℃ for 3-3.2h.

[0016] Compared with the prior art, the present invention has the following beneficial effects: In the preparation of the bimetallic core-shell catalyst of this invention, further increasing the Au content (2wt%→2.3wt%) can, on the one hand, enhance the electronic coordination effect and anti-sintering ability, thus producing a positive effect; on the other hand, excessive Au will physically shield the Pt active sites, thus producing a negative effect.

[0017] Meanwhile, this invention uses a mesoporous silica-etched molybdenum disulfide composite support. On the one hand, the molybdenum disulfide ball milling material is etched with H2 / Ar plasma to obtain etched molybdenum disulfide, which can enhance the metal-support interaction, provide more anchoring points, and thus increase the active sites, weakening / counteracting the negative impact of further increasing the Au doping (2wt%→2.3wt%) (the positive effects are retained). On the other hand, the etched molybdenum disulfide and mesoporous silica are co-assembled to perform three-dimensional support topology reconstruction, which not only provides a three-dimensional support framework to inhibit nanoparticle aggregation, but also creates multi-level channels to accelerate mass transfer. This synergistically improves the methanol-to-hydrogen catalytic performance of the prepared bimetallic core-shell catalyst. Attached Figure Description

[0018] Figure 1 This is a comparative trend graph showing the methanol-to-hydrogen catalytic performance of the bimetallic core-shell catalysts prepared in Example 1 and Comparative Examples 1-3 of the present invention. Figure 2 This is a comparative trend diagram of the methanol-to-hydrogen catalytic performance of the bimetallic core-shell catalysts prepared in Examples 1, 2, 4 and 5 of the present invention. Detailed Implementation

[0019] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0020] Unless otherwise specified, the raw materials used in the embodiments and comparative examples of this application are all commercially available.

[0021] Example 1 (I) Preparation of mesoporous silica-etched molybdenum disulfide composite support, the preparation method is as follows: A1. Add 4.5g of mesoporous silica and 10.5g of etched molybdenum disulfide to 500mL of deionized water and sonicate them for 30min to obtain silica dispersion and molybdenum disulfide dispersion, respectively.

[0022] A2. Mix the silica dispersion and molybdenum disulfide dispersion obtained in A1, add 19 mL of ammonia water as a precipitant, first stir magnetically at room temperature for 60 min, then heat to 80℃ and continue stirring for 30 min to form a precipitate, centrifuge at 5000 rpm for 10 min, wash three times alternately with deionized water and anhydrous ethanol, and finally dry at 110℃ for 13 h to obtain the mesoporous silica-etched molybdenum disulfide composite carrier.

[0023] Among them, the etched molybdenum disulfide is prepared by H2 / Ar plasma etching of molybdenum disulfide ball milling material.

[0024] Specifically, the molybdenum disulfide ball milling material is placed in the center of the sample stage. The reaction chamber sealing valve is closed, and the mechanical pump is started to roughly pump to <10 Pa. The turbomolecular pump is then started to finely pump to a base pressure ≤1×10-3 Pa. High-purity Ar (99.999%) is introduced through the inlet valve to a transition pressure of ~10 Pa to displace residual moisture in the chamber. Simultaneously, H2 (flow rate 10 sccm) and Ar (flow rate 60 sccm) are turned on, and the RF power is slowly increased to 100 W to excite plasma discharge. The appearance of a blue-violet glow indicates that the plasma has stabilized. The main etching is performed for 5 min. Then, the RF power is turned off, the gas supply is stopped, and the sample is allowed to cool naturally to <50℃ to eliminate lattice distortion caused by thermal stress. High-purity Ar is slowly introduced to atmospheric pressure, the sample is removed, and ultrasonically cleaned in anhydrous ethanol for 2 min. Then, it is purged and dried with a high-purity Ar gas flow to obtain the etched molybdenum disulfide.

[0025] Among them, molybdenum disulfide ball milling material is prepared by ball milling molybdenum disulfide at a speed of 5000 r / min for 6 hours.

[0026] (II) Preparation of a bimetallic core-shell catalyst, which is prepared by supporting Pt@Au core-shell nanoparticles on a mesoporous silica-etched molybdenum disulfide composite support. The Pt loading is 7.5 wt%, meaning the mass of Pt is 7.5% of the mass of the mesoporous silica-etched molybdenum disulfide composite support; the mass ratio of Pt to Au is 7.5:2.3. The specific preparation method is as follows: S1. Disperse the mesoporous silica-etched molybdenum disulfide composite carrier in an ethanol solution (the volume ratio of anhydrous ethanol to water is 2:3), add chloroplatinic acid, stir for 30 min, then add chloroauric acid, stir for 3 h to obtain a mixture.

[0027] S2. The mixture obtained in S1 is centrifuged and washed three times with water and ethanol respectively. It is then dried in a vacuum oven at 60°C for 4 hours, ground, and calcined in a N2 atmosphere at 350°C for 3 hours to obtain the bimetallic core-shell catalyst.

[0028] (iii) A catalytic methanol-to-hydrogen process, using a mixture of methanol and sodium hydroxide as raw material, adding a bimetallic core-shell catalyst, passing N2 through and sealing, heating in a water bath to 70±0.5℃ and performing magnetic stirring.

[0029] Example 2 The difference between this embodiment and Example 1 is that a bimetallic core-shell catalyst was prepared, which was made by supporting Pt@Au core-shell nanoparticles on a mesoporous silica-etched molybdenum disulfide composite support. The loading of Pt was 7.5 wt%; the mass ratio of Pt to Au was 7.5:2.25.

[0030] Example 3 The difference between this embodiment and Example 1 is that a bimetallic core-shell catalyst was prepared, which was made by supporting Pt@Au core-shell nanoparticles on a mesoporous silica-etched molybdenum disulfide composite support. The loading of Pt was 7.5 wt%; the mass ratio of Pt to Au was 7.5:2.35.

[0031] Comparative Example 1 The difference between this comparative example and Example 1 is that in the preparation of the bimetallic core-shell catalyst, the mesoporous silica-etched molybdenum disulfide composite support is replaced with molybdenum disulfide ball milling material; and the mass ratio of Pt to Au is 7.5:2.

[0032] Specifically, a bimetallic core-shell catalyst was prepared by supporting Pt@Au core-shell nanoparticles on molybdenum disulfide ball milling aggregate. The Pt loading was 7.5 wt%, meaning the mass of Pt was 7.5% of the mass of the molybdenum disulfide ball milling aggregate; the mass ratio of Pt to Au was 7.5:2. The specific preparation method is as follows: S1. Disperse molybdenum disulfide ball milling material in an ethanol solution (the volume ratio of anhydrous ethanol to water is 2:3), add chloroplatinic acid, stir for 30 min, then add chloroauric acid, stir for 3 h to obtain a mixture.

[0033] S2. The mixture obtained in S1 is centrifuged and washed three times with water and ethanol respectively. It is then dried in a vacuum oven at 60°C for 4 hours, ground, and calcined in a N2 atmosphere at 350°C for 3 hours to obtain the bimetallic core-shell catalyst.

[0034] Comparative Example 2 The difference between this comparative example and Example 1 is that in the preparation of the bimetallic core-shell catalyst, the mesoporous silica-etched molybdenum disulfide composite support is replaced with molybdenum disulfide ball milling material.

[0035] Specifically, a bimetallic core-shell catalyst was prepared by supporting Pt@Au core-shell nanoparticles on molybdenum disulfide ball milling aggregate. The Pt loading was 7.5 wt%, meaning the mass of Pt was 7.5% of the mass of the molybdenum disulfide ball milling aggregate; the mass ratio of Pt to Au was 7.5:2.3. The specific preparation method is as follows: S1. Disperse molybdenum disulfide ball milling material in an ethanol solution (the volume ratio of anhydrous ethanol to water is 2:3), add chloroplatinic acid, stir for 30 min, then add chloroauric acid, stir for 3 h to obtain a mixture.

[0036] S2. The mixture obtained in S1 is centrifuged and washed three times with water and ethanol respectively. It is then dried in a vacuum oven at 60°C for 4 hours, ground, and calcined in a N2 atmosphere at 350°C for 3 hours to obtain the bimetallic core-shell catalyst.

[0037] Comparative Example 3 The difference between this comparative example and Example 1 is that the mass ratio of Pt to Au in the preparation of the bimetallic core-shell catalyst is 7.5:2.

[0038] Specifically, a bimetallic core-shell catalyst was prepared by loading Pt@Au core-shell nanoparticles onto a mesoporous silica-etched molybdenum disulfide composite support. The Pt loading was 7.5 wt%, meaning the mass of Pt was 7.5% of the mass of the mesoporous silica-etched molybdenum disulfide composite support; the mass ratio of Pt to Au was 7.5:2. The specific preparation method is as follows: S1. Disperse the mesoporous silica-etched molybdenum disulfide composite carrier in an ethanol solution (the volume ratio of anhydrous ethanol to water is 2:3), add chloroplatinic acid, stir for 30 min, then add chloroauric acid, stir for 3 h to obtain a mixture.

[0039] S2. The mixture obtained in S1 is centrifuged and washed three times with water and ethanol respectively. It is then dried in a vacuum oven at 60°C for 4 hours, ground, and calcined in a N2 atmosphere at 350°C for 3 hours to obtain the bimetallic core-shell catalyst.

[0040] Comparative Example 4 The difference between this comparative example and Example 1 is that in the preparation of the bimetallic core-shell catalyst, the mesoporous silica-etched molybdenum disulfide composite support is replaced with etched molybdenum disulfide.

[0041] Specifically, a bimetallic core-shell catalyst was prepared by etching molybdenum disulfide-supported Pt@Au core-shell nanoparticles. The Pt loading was 7.5 wt%, meaning the mass of Pt was 7.5% of the mass of the etched molybdenum disulfide; the mass ratio of Pt to Au was 7.5:2.3. The specific preparation method is as follows: S1. Etching molybdenum disulfide is dispersed in an ethanol solution (the volume ratio of anhydrous ethanol to water is 2:3), chloroplatinic acid is added, and the mixture is stirred for 30 min. Then chloroauric acid is added, and the mixture is stirred for 3 h to obtain a mixed solution.

[0042] S2. The mixture obtained in S1 is centrifuged and washed three times with water and ethanol respectively. It is then dried in a vacuum oven at 60°C for 4 hours, ground, and calcined in a N2 atmosphere at 350°C for 3 hours to obtain the bimetallic core-shell catalyst.

[0043] Comparative Example 5 The difference between this comparative example and Example 1 is that in the preparation of the bimetallic core-shell catalyst, the mesoporous silica-etched molybdenum disulfide composite support is replaced with a mesoporous silica-molybdenum disulfide ball milling composite support.

[0044] Specifically, (I) a mesoporous silica-molybdenum disulfide ball milling composite carrier is prepared, and the preparation method is as follows: A1. Add 4.5g of mesoporous silica and 10.5g of molybdenum disulfide ball milling material to 500mL of deionized water and ultrasonically disperse them for 30min to obtain silica dispersion and molybdenum disulfide dispersion, respectively.

[0045] A2. Mix the silica dispersion and molybdenum disulfide dispersion obtained in A1, add 19 mL of ammonia water as a precipitant, first stir magnetically at room temperature for 60 min, then heat to 80℃ and continue stirring for 30 min to form a precipitate, centrifuge at 5000 rpm for 10 min, wash three times alternately with deionized water and anhydrous ethanol, and finally dry at 110℃ for 13 h to obtain the mesoporous silica-molybdenum disulfide ball milling composite carrier.

[0046] (II) Preparation of a bimetallic core-shell catalyst, which is prepared by loading Pt@Au core-shell nanoparticles onto a mesoporous silica-molybdenum disulfide ball milling composite support. The loading amount of Pt is 7.5 wt%, meaning the mass of Pt is 7.5% of the mass of the mesoporous silica-molybdenum disulfide ball milling composite support; the mass ratio of Pt to Au is 7.5:2.3. The specific preparation method is as follows: S1. Disperse the mesoporous silica-molybdenum disulfide ball milling composite carrier in an ethanol solution (the volume ratio of anhydrous ethanol to water is 2:3), add chloroplatinic acid, stir for 30 min, then add chloroauric acid, stir for 3 h to obtain a mixture.

[0047] S2. The mixture obtained in S1 is centrifuged and washed three times with water and ethanol respectively. It is then dried in a vacuum oven at 60°C for 4 hours, ground, and calcined in a N2 atmosphere at 350°C for 3 hours to obtain the bimetallic core-shell catalyst.

[0048] Test case Test subjects: Bimetallic core-shell catalysts prepared in Examples 1-3 and Comparative Examples 1-5.

[0049] Experimental Method: 5 mL of a mixture of 1 M methanol and 5 M sodium hydroxide was transferred into a 55 mL quartz tube using a pipette. 40 mg of a bimetallic core-shell catalyst was added, N2 was bubbled into the tube, and the tube was sealed with a silicone stopper. The tube was placed in a water bath on a magnetic stirrer, and the reaction temperature was maintained at 70 ± 0.5 °C. Vigorous magnetic stirring was used to eliminate the effect of stirring rate on the reaction rate. Every 0.5 h, 400 μL of gas was extracted from the tube using a syringe and injected into a GC-TCD sampler to detect the gas (H2) content.

[0050] Experimental results: see Table 1 and Figures 1-2 .

[0051] Table 1. Test Data for Experimental Examples Results Analysis: Based on the data in Table 1, the analysis of Examples 1-3 shows that the bimetallic core-shell catalysts prepared by the present invention (Examples 1-3) exhibit excellent catalytic performance for methanol-to-hydrogen conversion.

[0052] The following section combines the data from Table 1 and... Figure 1 Example 1 and Comparative Examples 1-3 were analyzed.

[0053] Specifically, comparing Comparative Example 1 and Comparative Example 2, it can be seen that compared to Pt:Au=7.5:2 in Comparative Example 1, increasing the Au content to Pt:Au=7.5:2.3 in Comparative Example 2 resulted in a decrease in the methanol-to-hydrogen catalytic performance of the bimetallic core-shell catalyst. This indicates that simply increasing the Au content to an excess (Pt:Au=7.5:2 → Pt:Au=7.5:2.3) leads to a decrease in the methanol-to-hydrogen catalytic performance of the bimetallic core-shell catalyst.

[0054] This is mainly because, when the Au content is further increased to an excess (2wt%→2.3wt%), on the one hand, it can enhance the electronic coordination effect and anti-sintering ability, thus producing a positive effect; on the other hand, excess Au will physically shield the Pt active sites, thus producing a negative effect; the negative effect is greater than the positive effect, ultimately leading to a decrease in the methanol-to-hydrogen catalytic performance of the prepared bimetallic core-shell catalyst.

[0055] Specifically, comparing Comparative Examples 1 and 3, it can be seen that, compared to Comparative Example 1, Comparative Example 3, by replacing the molybdenum disulfide ball milling material with the mesoporous silica-etched molybdenum disulfide composite support of this invention, resulted in improved methanol-to-hydrogen catalytic performance of the prepared bimetallic core-shell catalyst. This indicates that replacing the molybdenum disulfide ball milling material with the mesoporous silica-etched molybdenum disulfide composite support of this invention can improve the methanol-to-hydrogen catalytic performance of the prepared bimetallic core-shell catalyst.

[0056] Comparing with Example 1, it can be seen that increasing the Au doping amount (Pt:Au=7.5:2 → Pt:Au=7.5:2.3) and replacing the molybdenum disulfide ball milling material with the mesoporous silica-etched molybdenum disulfide composite support of the present invention, with the increase of Au doping amount, can better exert a synergistic effect with the mesoporous silica-etched molybdenum disulfide composite support of the present invention, and synergistically improve the methanol-to-hydrogen catalytic performance of the prepared bimetallic core-shell catalyst.

[0057] The following section combines the data from Table 1 and... Figure 2 Examples 1, 2, 4 and 5 were analyzed.

[0058] Specifically, by comparing Comparative Example 2 and Comparative Example 4, it can be seen that, compared with Comparative Example 2, Comparative Example 4 replaced the molybdenum disulfide ball milling material with etched molybdenum disulfide (the molybdenum disulfide ball milling material was prepared by H2 / Ar plasma etching), and the resulting bimetallic core-shell catalyst showed improved methanol-to-hydrogen catalytic performance.

[0059] Specifically, by comparing Comparative Example 2 and Comparative Example 5, it can be seen that, compared with Comparative Example 2, Comparative Example 5 replaced the molybdenum disulfide ball milling material with a mesoporous silica-molybdenum disulfide ball milling material composite support (the composite of molybdenum disulfide ball milling material and mesoporous silica), and the catalytic performance of the bimetallic core-shell catalyst for methanol-to-hydrogen production was also improved.

[0060] In comparison with Example 1, it can be seen that the molybdenum disulfide ball milling material, after being etched by H2 / Ar plasma and combined with mesoporous silica to form a mesoporous silica-etched molybdenum disulfide composite support, can produce a synergistic effect, thereby synergistically improving the methanol-to-hydrogen catalytic performance of the prepared bimetallic core-shell catalyst.

[0061] Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A catalytic methanol-to-hydrogen process, using a mixture of methanol and sodium hydroxide as raw material, adding a bimetallic core-shell catalyst, purging with N2 and sealing, heating in a water bath to 70±0.5℃ and magnetically stirring; characterized in that, The bimetallic core-shell catalyst was prepared by loading Pt@Au core-shell nanoparticles onto a mesoporous silica-etched molybdenum disulfide composite support, wherein the loading of Pt was 7.5 wt% and the mass ratio of Pt to Au was 7.5:(2.25-2.35).

2. The catalytic methanol-to-hydrogen process according to claim 1, characterized in that, The preparation method of the mesoporous silica-etched molybdenum disulfide composite carrier is as follows: A1. Add 4-5g of mesoporous silica and 10-11g of etched molybdenum disulfide to 500mL of deionized water and disperse by ultrasonication to obtain silica dispersion and molybdenum disulfide dispersion. A2. Mix the silica dispersion and molybdenum disulfide dispersion obtained in A1, add 18-20 mL of precipitant, stir at room temperature, then heat to 80±2℃ and continue stirring to form a precipitate. Centrifuge, wash, and dry to obtain the mesoporous silica-etched molybdenum disulfide composite carrier.

3. The catalytic methanol-to-hydrogen process according to claim 2, characterized in that, The etched molybdenum disulfide is prepared by H2 / Ar plasma etching of molybdenum disulfide ball milling material.

4. The catalytic methanol-to-hydrogen process according to claim 3, characterized in that, During plasma etching, the volume ratio of H2 to Ar is 1:(4-8).

5. The catalytic methanol-to-hydrogen process according to claim 2, characterized in that, The molybdenum disulfide ball milling material is prepared by ball milling molybdenum disulfide at a speed of 4800-5000 r / min for 6-6.5 h.

6. The catalytic methanol-to-hydrogen process according to claim 2, characterized in that, In A2, the precipitant is ammonia.

7. The catalytic methanol-to-hydrogen process according to claim 2, characterized in that, In A2, the drying temperature is 110±5℃ and the drying time is 12-14h.

8. The catalytic methanol-to-hydrogen process according to any one of claims 1-7, characterized in that, The preparation method of the bimetallic core-shell catalyst is as follows: S1. Disperse the mesoporous silica-etched molybdenum disulfide composite support in an ethanol solution, add chloroplatinic acid, stir for 30-35 min, then add chloroauric acid, stir for 3-3.2 h to obtain a mixture; S2. The mixture is centrifuged, washed, dried, ground, and then calcined in an inert atmosphere to obtain the bimetallic core-shell catalyst.

9. The catalytic methanol-to-hydrogen process according to claim 8, characterized in that, In S1, the volume ratio of anhydrous ethanol to water in the ethanol solution is (3.5-4.5):

6.

10. The catalytic methanol-to-hydrogen process according to claim 8, characterized in that, In S2, calcined in a N2 atmosphere at 350±5℃ for 3-3.2h.

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