A catalyst for low-temperature methanol steam reforming to produce hydrogen, and a preparation method and application thereof

Abstract

The application provides a catalyst for low-temperature methanol steam reforming to produce hydrogen as well as a preparation method and application thereof. The catalyst comprises an oxide nanocarrier and an active component supported on the nanocarrier, the active component is Pt and Cu, and the Pt and Cu form a PtCu alloy phase on the surface of the nanocarrier; wherein the mass percentage of the Pt is 0.3wt%-0.7wt% and the mass percentage of the Cu is 5wt%-15wt% based on the total mass of the catalyst. The application optimizes the loading ratio of Pt and Cu, makes them form a stable PtCu alloy phase on the surface of the carrier, and finally not only realizes the unique synergistic effect of 'accelerating the main reaction (hydrogen production) and inhibiting the side reaction (CO production)', but also avoids the use of a large amount of noble metal Pt, realizes the balance of catalytic performance and material cost. In addition, the strong interface interaction between the oxide nanocarrier (such as ZnO) and the metal not only improves the dispersity of the PtCu alloy phase, but also enhances the carbon deposition resistance of the catalyst, which is helpful to maintain the long-term use stability of the catalyst.

Description

Technical Field

[0001] This invention relates to the fields of hydrogen production technology and catalyst preparation technology, and more specifically, to a catalyst for low-temperature methanol steam reforming for hydrogen production, its preparation method, and its application. Background Technology

[0002] Hydrogen energy is considered one of the most promising clean energy sources due to its high energy density and zero carbon emissions from combustion. Low-temperature methanol steam reforming for hydrogen production is one of the most promising methods due to its mild reaction conditions and high-purity hydrogen products. The core of this reaction lies in the catalyst, whose performance directly determines the hydrogen production efficiency, product selectivity, and reaction stability.

[0003] Existing methanol steam reforming catalysts mainly fall into two categories: (1) Noble metal catalysts (such as Pt, Pd, Rh, etc.): These catalysts have the characteristics of high catalytic activity, good low-temperature performance, and strong resistance to carbon deposition. However, precious metal resources are scarce, and their high material costs directly lead to the high price of the catalysts themselves, making it difficult to meet the economic requirements of large-scale industrial applications.

[0004] (2) Non-precious metal catalysts (such as Cu, Ni, Co, etc.): Among them, Cu-based catalysts have attracted widespread attention due to their low cost and high activity in methanol reforming reactions. However, under low-temperature reaction conditions, Cu-based catalysts have insufficient activation ability for reactant molecules, and surface intermediate species such as methoxy groups and formates tend to accumulate on the catalyst surface, covering Cu. 0 / Cu + The number of effective active sites decreases due to the lack of active sites. Furthermore, byproducts and carbon-containing intermediates are difficult to desorb or further transform in a timely manner during low-temperature reactions, potentially causing pore blockage and localized carbon deposition, thus reducing the catalyst's mass transfer performance. Due to technical characteristics such as the easy accumulation of intermediate species at low temperatures and the easy covering of active sites, Cu-based catalysts are prone to activity decay, insufficient stability, and shortened lifespan under low-temperature conditions, severely limiting their continued application in industrial low-temperature catalytic processes.

[0005] Therefore, how to develop a low-temperature methanol steam reforming catalyst with high activity, low CO selectivity and good stability has become a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0006] The purpose of this invention is to overcome the shortcomings of the prior art, such as the high cost of precious metal catalysts and the poor stability and easy deactivation of non-precious metal copper-based catalysts, and to provide a low-temperature methanol steam reforming hydrogen production catalyst and its preparation method that has high activity, low CO selectivity, high stability and relatively low cost.

[0007] Based on the above, the present invention provides a catalyst for hydrogen production by low-temperature methanol steam reforming. The catalyst includes an oxide nanosupport and an active component supported on the nanosupport. The active component is Pt and Cu, and the Pt and Cu form a PtCu alloy phase on the surface of the nanosupport. Wherein, based on the total mass of the catalyst, the mass percentage of Pt is 0.3wt%~0.7wt%, and the mass percentage of Cu is 5wt%~15wt%.

[0008] Optionally, the Pt mass percentage is 0.5 wt%, and the Cu mass percentage is 10 wt%.

[0009] Optionally, the oxide nanocarrier may be made of any one of zinc oxide, aluminum oxide, silicon dioxide, titanium dioxide, or cerium dioxide.

[0010] Another aspect of the present invention provides a method for preparing a catalyst for low-temperature methanol steam reforming to produce hydrogen, comprising the following steps: S1 provides oxide nanocarriers; S2, using an equal-volume impregnation method, Pt precursor and Cu precursor are co-loaded on the nano-support, and after aging, drying and calcination, a catalyst precursor is obtained; S3. The catalyst precursor is reduced in a reducing atmosphere to obtain the catalyst; Wherein, based on the total mass of the catalyst, the mass percentage of Pt is 0.3wt%~0.7wt%, and the mass percentage of Cu is 5wt%~15wt%.

[0011] Optionally, the oxide nanocarrier is a zinc oxide nanocarrier, and the specific operation of step S1 includes: S1.1 Weigh Zn(NO3)2·6H2O and add it to deionized water. Heat and stir in an oil bath at 70℃-90℃ until completely dissolved. S1.2, Slowly add sodium carbonate aqueous solution to the above solution to adjust the pH to 8-10, stir in an oil bath, let the precipitate stand for several hours, and then wash the precipitate with deionized water until neutral; S1.3, the precipitate obtained is dried and then ground into powder; S1.4, the powder is subjected to calcination treatment: the temperature is increased to 350℃-450℃ at a heating rate of 2℃-5℃ / min, and calcined for 4 h-6 h to obtain ZnO nanocarrier.

[0012] Optionally, the specific operations of step S2 include: S2.1 Weigh out Cu(NO3)2·3H2O and H2PtCl6·6H2O and dissolve them in deionized water to form a mixed solution; S2.2, the mixed solution is added dropwise to the oxide nanocarrier provided in step S1, and the mixture is aged at room temperature for 6 h-10 h and then dried; S2.3, The product obtained in step S2.2 is ground and then calcined: the temperature is increased to 300℃-400℃ at a heating rate of 2℃-5℃ / min for 4 h-6 h to obtain the catalyst precursor.

[0013] Optionally, the volume of the mixed solution is equal to or comparable to the pore volume of the oxide nanocarrier provided in step S1.

[0014] Optionally, in step S3, the reducing gas is an H2 / Ar mixture, and the reduction treatment conditions are: reduction at 200℃-300℃ for 4-6 hours.

[0015] In another aspect, the present invention provides the application of the aforementioned catalyst, or the catalyst prepared by the aforementioned method, in the low-temperature methanol steam reforming for hydrogen production.

[0016] Optionally, the reaction temperature for the low-temperature methanol steam reforming to produce hydrogen is 180℃-220℃.

[0017] Compared with the prior art, the beneficial effects of the present invention include at least the following: (1) The present invention uses a PtCu dual-active component to support a ZnO support. By optimizing the loading ratio of Pt and Cu, a stable PtCu alloy phase is formed on the support surface. By utilizing the high catalytic activity of Pt and the low cost and good selectivity of Cu, the unique synergistic effect of "accelerating the main reaction (hydrogen production) and inhibiting the side reaction (CO production)" is achieved under low temperature conditions. Furthermore, the use of a large amount of precious metal Pt is avoided, thus achieving a balance between catalytic performance and material cost.

[0018] (2) By controlling the impregnation liquid volume to match the pore volume of the support, Pt / Cu simultaneous impregnation, calcination heating rate of 2℃-5℃ / min, calcination at 300℃-400℃, and reduction at 200℃-300℃, the present invention ensures the uniform dispersion of Pt and Cu on the ZnO support surface, effectively inhibits the sintering and aggregation of active components, and significantly improves the long-term stability of the catalyst.

[0019] (3) The present invention uses oxide nanocarriers (such as ZnO), which can not only disperse Pt / Cu precursors and inhibit the agglomeration of metal particles during reduction and reaction, thus helping to maintain the long-term stability of the catalyst, but also the oxygen species / hydroxyl groups on the surface of the carrier and the metal-carrier interface are conducive to the adsorption and activation of methanol and water molecules, promote the further conversion of oxygen-containing intermediates, reduce the tendency of deep decomposition to generate CO and carbon deposits, and enhance the catalyst's resistance to carbon deposits and structural stability.

[0020] (4) The preparation process of this invention is simple, easy to operate, cost controllable, and has good repeatability, making it suitable for large-scale industrial production. The catalyst obtained exhibits excellent catalytic activity, hydrogen selectivity, and long-term stability in the low-temperature methanol steam reforming hydrogen production reaction, and can be widely used in fuel cells, chemical raw material hydrogen production and other fields. Attached Figure Description

[0021] Figure 1 The X-ray diffraction (XRD) spectra of the catalysts prepared in the embodiments and comparative examples of this invention are shown.

[0022] Figure 2 for Figure 1 A magnified view of a portion of the image.

[0023] Figure 3 The images show the activity test results of the catalysts prepared in the embodiments and comparative examples of this invention.

[0024] Figure 4 This is a scanning electron microscope (SEM) image of the catalyst in Example 2 of the present invention. Detailed Implementation

[0025] The technical solution of the present invention will be further described below with reference to the accompanying drawings and embodiments.

[0026] As described in the background section, developing a low-temperature methanol steam reforming catalyst with high activity, low CO selectivity, good stability, and low cost has become a pressing technical challenge in this field.

[0027] To address the aforementioned technical problems, this invention provides a catalyst for low-temperature methanol steam reforming to produce hydrogen. The catalyst comprises an oxide nanosupport and an active component supported on the nanosupport. The active component is Pt and Cu, and the Pt and Cu form a PtCu alloy phase on the surface of the nanosupport. The Pt content is 0.3wt% to 0.7wt% by mass, and the Cu content is 5wt% to 15wt% by mass, based on the total mass of the catalyst.

[0028] It is important to emphasize that the Pt and Cu on the surface of the oxide nanocarrier are not simply physically mixed, but rather form a PtCu alloy phase. Specifically, this PtCu alloy phase does not refer to Pt and Cu particles being independently dispersed, but rather to Pt and Cu undergoing atomic-scale contact / solution or alloying within the same nanoparticle or adjacent metal phase after reduction, forming Pt-Cu alloy / alloyed nanoparticles supported on the ZnO surface. This PtCu alloy phase not only retains the high catalytic activity of Pt, but also utilizes Cu to regulate catalytic kinetics, lowering the water dissociation barrier and providing more active hydroxyl groups for the oxidation of CH2O* (formaldehyde intermediate). Simultaneously, the CO desorption barrier on the PtCu alloy is raised, thus hindering the decomposition of CH2O*. This dual function simultaneously achieves high methanol conversion efficiency and low selectivity for the byproduct CO. More importantly, this PtCu alloy phase avoids the problems of poor high-temperature stability, easy sintering, and easy carbon deposition inherent in individual Cu particles, thereby ensuring the stability of the catalyst's performance during long-term operation.

[0029] In some embodiments, the oxide nanocarrier is made of any one of ZnO, Al2O3, SiO2, TiO2, and CeO2.

[0030] Taking zinc oxide nanocarriers as an example, this invention provides a method for preparing a catalyst for low-temperature methanol steam reforming to produce hydrogen, comprising the following steps: S1 provides an oxide nanocarrier, and the specific operation is as follows: S1.1 Weigh Zn(NO3)2·6H2O and add it to deionized water. Heat and stir in an oil bath at 70℃-90℃ until completely dissolved. S1.2, Slowly add sodium carbonate aqueous solution to the above solution to adjust the pH to 8-10, stir in an oil bath, let the precipitate stand for several hours, and then wash the precipitate with deionized water until neutral; S1.3, the precipitate obtained is dried and then ground into powder; S1.4, The powder is calcined: the temperature is increased to 350℃-450℃ at a heating rate of 2℃-5℃ / min, and calcined for 4 h-6 h to obtain ZnO nanocarriers. It should be noted that in this step, if the temperature rises too quickly, it can easily cause pore structure collapse and particle agglomeration; if the temperature rises too slowly, prolonged heating may also lead to ZnO grain growth or sintering of metal oxide particles, resulting in a decrease in specific surface area and a reduction in active sites. Experimental investigations have shown that 2℃-5℃ / min is a relatively mild and controllable heating rate range, allowing nitrates, carbonates, etc., in the powder to gradually decompose and crystal phases to gradually form, while minimizing the risk of violent agglomeration or sintering of the ZnO carrier.

[0031] S2, using an equal-volume impregnation method, Pt precursor and Cu precursor are co-loaded onto the nanosupport, followed by aging, drying, and calcination to obtain the catalyst precursor. The specific operation is as follows: S2.1 Weigh out Cu(NO3)2·3H2O and H2PtCl6·6H2O and dissolve them in deionized water to form a mixed solution; S2.2, the mixed solution is added dropwise to the oxide nanocarrier provided in step S1, and the mixture is aged at room temperature for 6 h-10 h and then dried; S2.3, The product obtained in step S2.2 is ground and then calcined: the temperature is increased to 300℃-400℃ at a heating rate of 2℃-5℃ / min for 4 h-6 h to obtain the catalyst precursor.

[0032] The volume of the mixed solution is equal to or comparable to the pore volume of the oxide nanocarrier provided in step S1. When the volume of the impregnation solution (i.e., the mixed solution) matches the pore volume of the carrier, the metal precursor can enter the carrier pores and surface more uniformly with the liquid, reducing metal salt migration, local enrichment, and large particle formation during drying. This is beneficial for uniform Pt / Cu dispersion and subsequent reduction to form the PtCu active phase. The solution volume can be slightly adjusted, but should not significantly exceed the pore volume of the carrier. If there is too much solution, it will become excessive impregnation / wet impregnation, requiring filtration or evaporation, which can easily cause the precursor to precipitate on the outer surface and be unevenly distributed, affecting reproducibility.

[0033] In addition, the heating rate of 2℃-5℃ / min and the calcination temperature of 300℃-400℃ are to avoid prolonged heating and sintering or high-temperature sintering, which would lead to a decrease in specific surface area and a reduction in active sites.

[0034] S3. The catalyst precursor is reduced in a reducing atmosphere (H2 / Ar mixed gas) (reduction at 200℃-300℃ for 4 h-6 h) to obtain the catalyst; wherein, based on the total mass of the catalyst, the mass percentage of Pt is 0.3wt%~0.7wt% and the mass percentage of Cu is 5wt%~15wt%.

[0035] The reduction temperature in step S3 is 200℃-300℃, which not only avoids high-temperature sintering but also promotes the activation of Pt / Cu.

[0036] It should be noted that the oxide nanocarrier used in this invention has the following advantages: (1) Structural level: it disperses Pt / Cu precursors and inhibits the agglomeration of metal particles during reduction and reaction, which helps to maintain the long-term stability of the catalyst; (2) Performance level: the oxygen species / hydroxyl groups on the surface of the carrier and the metal-carrier interface are conducive to the adsorption and activation of methanol and water molecules, promote the further conversion of oxygen-containing intermediates, thereby reducing the tendency of deep decomposition to generate CO and carbon deposits.

[0037] In another aspect, the present invention provides the application of the aforementioned catalyst, or the catalyst prepared by the aforementioned method, in low-temperature methanol steam reforming for hydrogen production. Specifically, the catalyst is packed into a fixed-bed reactor, the reaction feedstock is a mixture of methanol and deionized water, and the reaction conditions are: reaction temperature 180-220°C, water-to-methanol molar ratio 1.2-1.5:1, and reaction pressure at atmospheric pressure.

[0038] Example 1 This embodiment provides a method for preparing a low-temperature methanol steam reforming hydrogen production catalyst, a PtCu / ZnO catalyst, with a target loading of 0.5 wt% Pt and 5 wt% Cu. The method includes the following steps: (1) Preparation of ZnO support by precipitation method Weigh 10.97 g of Zn(NO3)2·6H2O and dissolve it in 80 mL of deionized water. Heat and stir in an oil bath at 80 °C until completely dissolved. Slowly add sodium carbonate aqueous solution to adjust the pH to 9, continue stirring, and let stand for several hours (e.g., 6 hours). Wash the precipitate with deionized water until neutral, and dry it in an oven at 90 °C for 12 hours. Grind the dried solid into powder and calcine it in a muffle furnace from room temperature to 400 °C at a rate of 2 °C / min for 4 hours to obtain the ZnO support.

[0039] (2) Loading active components by equal volume impregnation method Weigh 0.571 g Cu(NO3)2·3H2O and 0.039 g H2PtCl6·6H2O, dissolve them in 3 mL of deionized water to form an impregnation solution. Add the impregnation solution dropwise to the ZnO powder prepared in step (1), let it stand at room temperature for 8 hours, and then dry it in an oven at 110℃ for 12 hours. Grind the dried solid and calcine it in a muffle furnace from room temperature to 350℃ at a rate of 2℃ / min for 4 hours to obtain the catalyst precursor.

[0040] (3) Reduction treatment The catalyst precursor was placed in an H2 / Ar mixed atmosphere and reduced at 250°C for 4 hours. After natural cooling, a powdered catalyst was obtained, denoted as Pt0.5Cu5 / ZnO.

[0041] Example 2 The difference between this embodiment and Example 1 lies in step (2): 1.141g Cu(NO3)2·3H2O and 0.039g H2PtCl6·6H2O are weighed to prepare a catalyst with a Pt loading of 0.5wt% and a Cu loading of 10wt%, denoted as Pt0.5Cu10 / ZnO. The remaining steps are the same as in Example 1.

[0042] Example 3 The difference between this embodiment and Example 1 lies in step (2): 1.712g Cu(NO3)2·3H2O and 0.024g H2PtCl6·6H2O are weighed to prepare a catalyst with a Pt loading of 0.5wt% and a Cu loading of 15wt%, denoted as Pt0.5Cu15 / ZnO. The remaining steps are the same as in Example 1.

[0043] Comparative Example 1 This comparative example provides a method for preparing a single Pt component catalyst, which differs from Example 1 in step (2): only 0.039 g of H2PtCl6·6H2O is weighed, without adding Cu(NO3)2·3H2O, to prepare a catalyst with a Pt loading of 0.5 wt%, denoted as Pt0.5 / ZnO. The remaining steps are the same as in Example 1.

[0044] Comparative Example 2 This comparative example provides a method for preparing a single Cu component catalyst, which differs from Example 1 in step (2): only 1.141 g of Cu(NO3)2·3H2O is weighed, without adding H2PtCl6·6H2O, to prepare a catalyst with a Cu loading of 10 wt%, denoted as Cu10 / ZnO. The remaining steps are the same as in Example 1.

[0045] The catalysts obtained in Examples 1-3 and Comparative Examples 1-2 were characterized and tested as follows: (1) XRD characterization See Figure 1 and Figure 2The XRD patterns showed that the main diffraction peaks of the catalysts in all examples and comparative examples corresponded completely to the characteristic peaks of the ZnO standard card (JCPDS#99-0111), indicating that the ZnO support maintained a stable crystal structure and did not undergo crystal destruction during the loading of Pt and Cu active components and subsequent preparation. The single active component samples (Pt0.5 / ZnO, Cu10 / ZnO) exhibited characteristic diffraction peaks of elemental Pt and elemental Cu, respectively. However, with increasing Cu content in the support, detailed scanning of the catalysts in Examples 1-3 within the 37°-40° range revealed the formation of a distinct alloy with subtle broad peaks, proving that Pt and Cu formed a PtCu alloy phase on the ZnO support surface. Furthermore, the intensity of the alloy phase diffraction peaks varied among catalysts with different Pt and Cu loadings, demonstrating the tunability of the Pt-Cu mass ratio in relation to the PtCu alloy crystal structure. Furthermore, no other miscellaneous diffraction peaks were detected in the spectrum, further indicating that the change in the PtCu doping value in the support did not introduce other phases, providing a structural basis for the synergistic effect of the two active components in the catalyst, and supporting the technical effect of improving its catalytic activity and stability.

[0046] (2) Catalyst activity test The catalyst was packed into tubes and fixed in the reactor. A 10 vol% H₂ / Ar mixture was introduced at a flow rate of 20-40 mL / min for reduction at 200℃-300℃ for 4-6 hours. The reaction temperature was controlled at 200℃ using a three-stage temperature control system. A mixture of water and methanol was then injected into the reactor using a micropump at a liquid phase rate of 0.1-0.15 mL / min. The molar ratio of methanol to water vapor was 1:1.2-1.5. Simultaneously, N₂ was introduced at a rate of 20-40 mL / min, and the reaction pressure was atmospheric pressure. Gas and liquid samples were collected at the hydrogen outlet and tail liquid outlet of the reactor, respectively. Gas chromatography was used for qualitative and quantitative analysis of the product composition.

[0047] The results are as follows Figure 3 As shown, the catalyst Pt0.5Cu10 / ZnO in Example 2 exhibited the best performance, with a methanol conversion rate close to 98% and a CO selectivity of less than 1%. Although the performance of Examples 1 and 3 was slightly inferior to that of Example 2, their methanol conversion rates were significantly higher than those of Comparative Example 1 (pure Pt) and Comparative Example 2 (pure Cu), and their CO selectivity was much lower than that of Comparative Example 2.

[0048] (3) Morphology and stability analysis See Figure 4SEM images of the catalyst in Example 2 show an aggregated structure of nanoscale particles. The particles are mainly irregular spherical, with individual particle sizes concentrated around 20-50 nm. There are no obvious large agglomerates between the particles, indicating good overall dispersion. Simultaneously, certain porosity exists between the particles. This morphology represents the microstructure of the Pt-Cu dual-active component supported on a ZnO support: the nanoscale particle size provides a larger specific surface area, exposing more Pt-Cu active sites and improving the contact efficiency of the catalytic reaction; good dispersion prevents agglomeration of the active component / support particles, helping to maintain the long-term stability of the catalyst; the porosity between particles facilitates the mass transfer process of reactants / products in the methanol steam reforming reaction, further optimizing catalytic efficiency and providing morphological support for the high activity and high stability of the catalyst.

[0049] In summary, this invention successfully solves the problem of balancing performance and cost in existing single-component catalysts by constructing a catalyst with a PtCu alloy phase supported on a ZnO support, achieving unexpected technical results and showing good prospects for industrial application.

[0050] Although the present invention has been described in detail through the preferred embodiments above, it should be understood that the above description should not be considered as a limitation of the present invention. Various modifications and substitutions to the present invention will be apparent to those skilled in the art after reading the above description. Therefore, the scope of protection of the present invention should be defined by the appended claims.

Claims

1. A catalyst for low temperature methanol steam reforming for hydrogen production, characterized in that, The catalyst includes an oxide nanosupport and an active component supported on the nanosupport, wherein the active component is Pt and Cu, and the Pt and Cu form a PtCu alloy phase on the surface of the nanosupport; Wherein, based on the total mass of the catalyst, the mass percentage of Pt is 0.3wt%~0.7wt%, and the mass percentage of Cu is 5wt%~15wt%.

2. The catalyst according to claim 1, characterized in that, The Pt content is 0.5 wt% and the Cu content is 10 wt%.

3. The catalyst of claim 1, wherein The oxide nanocarrier is made of any one of zinc oxide, aluminum oxide, silicon dioxide, titanium dioxide, or cerium dioxide.

4. A method for the preparation of a catalyst for the low temperature methanol steam reforming for hydrogen production, characterized by, Includes the following steps: S1 provides oxide nanocarriers; S2, using an equal-volume impregnation method, Pt precursor and Cu precursor are co-loaded on the nano-support, and after aging, drying and calcination, a catalyst precursor is obtained; S3. The catalyst precursor is reduced in a reducing atmosphere to obtain the catalyst; Wherein, based on the total mass of the catalyst, the mass percentage of Pt is 0.3wt%~0.7wt%, and the mass percentage of Cu is 5wt%~15wt%.

5. The method of claim 4, wherein the catalyst is prepared by the steps of: The oxide nanocarrier is a zinc oxide nanocarrier, and the specific operations of step S1 include: S1.1 Weigh Zn(NO3)2·6H2O and add it to deionized water. Heat and stir in an oil bath at 70℃-90℃ until completely dissolved. S1.2, Slowly add sodium carbonate aqueous solution to the above solution to adjust the pH to 8-10, stir in an oil bath, let the precipitate stand for several hours, and then wash the precipitate with deionized water until neutral; S1.3, the precipitate obtained is dried and then ground into powder; S1.4, the powder is subjected to calcination treatment: the temperature is increased to 350℃-450℃ at a heating rate of 2℃-5℃ / min, and calcined for 4 h-6 h to obtain ZnO nanocarrier.

6. The method of claim 4, wherein the catalyst is prepared by the steps of: The specific operations of step S2 include: S2.1 Weigh out Cu(NO3)2·3H2O and H2PtCl6·6H2O and dissolve them in deionized water to form a mixed solution; S2.2, the mixed solution is added dropwise to the oxide nanocarrier provided in step S1, and the mixture is aged at room temperature for 6-10 hours and then dried. S2.3, The product obtained in step S2.2 is ground and then calcined: the temperature is increased to 300℃-400℃ at a heating rate of 2℃-5℃ / min for 4 h-6 h to obtain the catalyst precursor.

7. The method of claim 6, wherein the catalyst is prepared by the steps of: The volume of the mixed solution is equal to or comparable to the pore volume of the oxide nanocarrier provided in step S1.

8. The method for preparing the catalyst according to claim 4, characterized in that, In step S3, the reducing gas is a mixture of H2 and Ar, and the reduction treatment conditions are: reduction at 200℃-300℃ for 4-6 hours.

9. The application of the catalyst according to any one of claims 1-3, or the catalyst prepared by any one of claims 4-8, in the low-temperature methanol steam reforming for hydrogen production.

10. The application as described in claim 9, characterized in that, The reaction temperature for hydrogen production via low-temperature methanol steam reforming is 180℃-220℃.

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