A lanthanum-cerium dioxide nanorod modified nickel-based catalyst, a preparation method and application thereof
By modifying nickel-based catalysts with La-CeO2 nanorods, the low yield problem of nickel-based catalysts in the synthesis of high-carbon alcohols from small molecules in aqueous phase was solved, achieving efficient synthesis of high-carbon alcohols and improving catalyst stability.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- GUANGDONG UNIV OF TECH
- Filing Date
- 2026-04-15
- Publication Date
- 2026-07-10
AI Technical Summary
When existing nickel-based catalysts are used for the synthesis of higher alcohols from small molecules in the aqueous phase, the yield of C4+ higher alcohols is low and the cost is high.
The nickel-based catalyst was modified with La-CeO2 nanorods. By introducing La-CeO2 nanorods, the high-temperature sintering of Ni particles was prevented, the dispersion was improved, and the diffusion of reactants was promoted through oxygen vacancies and one-dimensional structure. The surface alkalinity was regulated, carbon-carbon coupling was promoted, and carbon-carbon cracking was inhibited.
It significantly improved the selectivity and yield of higher alcohols, extended catalyst life, reduced carbon deposition, and enhanced reaction efficiency and catalyst stability.
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Figure CN122352272A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of catalyst technology, and particularly relates to a lanthanum-cerium dioxide nanorod modified nickel-based catalyst, its preparation method, and its application. Background Technology
[0002] Higher alcohols generally refer to alcohol compounds containing four or more carbon atoms. These alcohols include n-butanol, isoamyl alcohol, and octanol, and possess high calorific value, excellent fuel performance, and low volatility. Compared to lower alcohols (such as methanol and ethanol), higher alcohols are an excellent liquid blending fuel, significantly improving fuel quality and reducing exhaust pollution. Furthermore, they are compatible with existing petrochemical energy infrastructure, making them a highly promising high-quality biomass-based fuel. Moreover, higher alcohols are widely used in plastic additives, lubricant additives, coatings, and pharmaceuticals, and are also crucial raw materials in modern industrial chains.
[0003] The synthesis of higher alcohols is currently a key research focus. Among these methods, the Guerbet reaction offers advantages such as readily available raw materials, simple process, and environmental friendliness, demonstrating good economic efficiency and practicality in the selective synthesis of higher alcohols. The Guerbet reaction is a method that achieves alcohol chain growth through the formation of C-C bonds between alcohol molecules. It typically requires a catalyst and involves several key steps: dehydrogenation, aldehyde condensation, and hydrogenation. Lower-carbon alcohols (such as ethanol) undergo dehydrogenation on the catalyst surface to generate the corresponding aldehyde intermediate (such as acetaldehyde). Subsequently, aldehyde molecules undergo aldol condensation to form intermediate compounds with longer carbon chains, accompanied by the reconstruction of C-C bonds. These intermediates are then hydrogenated by a catalyst to finally generate stable higher alcohol products.
[0004] Catalysts for the Guerbet reaction are also a key research focus. Currently, most catalytic systems utilize organometallic compounds and transition noble metals such as Ru, Rh, Pd, Os, Ir, and Pt, but the high cost of noble metal catalysis remains a concern. Nickel, a relatively abundant transition metal element in the Earth's crust, is one of the best alternatives to noble metals. Ni-based catalysts possess advantages such as strong dehydrogenation capabilities and adaptability to aqueous systems. Furthermore, Ni-based catalysts are less expensive than noble metal catalysts and exhibit better thermal stability and resistance to poisoning. Metal catalysts are typically combined with supports to enhance their stability and dispersibility. Simultaneously, the type, structure, and surface properties of the support also affect the degree of metal dispersion and catalyst activity. Therefore, it is necessary to provide a novel nickel-based catalyst to address the problems existing in current nickel-based catalysts. Summary of the Invention
[0005] To address the problem of low yield (<25.0%) of C4+ higher alcohols when using existing nickel-based catalysts for the synthesis of higher alcohols from small molecules in aqueous phase, this invention proposes a lanthanum-cerium dioxide (La-CeO2) nanorod modified nickel-based catalyst, its preparation method, and its application.
[0006] To achieve the above objectives, the present invention provides the following technical solution: This invention provides a method for preparing a La-CeO2 nanorod modified nickel-based catalyst, comprising the following steps: S1. Add soluble lanthanum salt and soluble cerium salt to water and stir to form a homogeneous solution; S2. Add sodium hydroxide solution to the homogeneous solution and stir until homogeneous. Then heat the resulting mixture to achieve precipitation. After filtration, washing and drying, a yellow solid is obtained. S3. Anneal the yellow solid to obtain La-CeO2 nanorods; S4. Dissolve soluble nickel salt and citric acid in water containing the La-CeO2 nanorods, and dry to obtain the precursor; S5. The precursor is calcined to obtain the La-CeO2 nanorod modified nickel-based catalyst.
[0007] This invention introduces La-CeO2 nanorods to prevent high-temperature sintering of Ni particles. The nanorods expose highly active crystal faces, forming a catalyst morphology with smaller particle size and higher dispersion with the Ni particles. The La-CeO2 nanorods introduce a large number of oxygen vacancies, effectively eliminating carbon deposition and improving catalyst activity. The one-dimensional structure of the La-CeO2 nanorods provides long-range mass transfer channels, facilitating the diffusion of reactants and products, significantly enhancing oxygen storage and release capacity and redox cycle rate, thereby promoting the reaction. Simultaneously, the La-CeO2 nanorods regulate surface alkalinity, directionally promoting carbon-carbon coupling and inhibiting carbon-carbon cracking, enhancing low-temperature activity and stability, and driving the Guerbet pathway synergistically through electronic effects, alkalinity regulation, and oxygen vacancies.
[0008] Further, in step S1, the mass percentage of the soluble lanthanum salt relative to the soluble cerium salt, based on lanthanum and cerium, is 1-15%, preferably 1-10%.
[0009] Furthermore, in step S2, the heating temperature is 100°C and the heating time is 12 hours.
[0010] Furthermore, in step S3, the annealing temperature is 400°C and the time is 4 hours.
[0011] Further, in step S4, the molar ratio of citric acid to soluble nickel salt is 2:1; The mass ratio of the La-CeO2 nanorods to the soluble nickel salt is 10:1.
[0012] Furthermore, in step S5, the calcination temperature is 550°C and the time is 2 hours.
[0013] The present invention also provides a La-CeO2 nanorod modified nickel-based catalyst prepared according to the above method.
[0014] The present invention also provides an application of the above-mentioned La-CeO2 nanorod modified nickel-based catalyst in the catalytic aqueous synthesis of higher alcohols from small molecule alcohols.
[0015] The La-CeO2 nanorod modified nickel-based catalyst of this invention can effectively promote further carbon-carbon coupling reactions and improve reaction efficiency when used for the preparation of higher alcohols from aqueous small molecule alcohols via carbon-carbon coupling. It has high organic phase yield and C6+ higher alcohol yield and has broad application prospects.
[0016] For example, small molecule alcohols are ethanol, and higher alcohols are alcohols with 4 to 16 carbon atoms.
[0017] When using the above-mentioned La-CeO2 nanorod modified nickel-based catalyst to catalyze the aqueous phase synthesis of higher alcohols from small molecule alcohols, the reaction temperature is 190~220℃.
[0018] Compared with the prior art, the present invention has the following advantages and technical effects: In the La-CeO2 nanorod modified nickel catalyst of this invention, the La-CeO2 nanorods help stabilize metal particles, prevent high-temperature sintering, and form a catalyst morphology with smaller particle size and higher dispersion. Simultaneously, they effectively eliminate carbon deposits, reducing the amount of carbon deposits and thus extending the catalyst lifetime.
[0019] La-CeO2 nanorod-modified nickel catalysts can regulate surface alkalinity, directionally promote carbon-carbon coupling, and accelerate acetaldehyde adsorption and α-H activation, thereby significantly improving the selectivity of higher alcohols. The high specific surface area of La-CeO2 nanorods increases the density of alkaline sites, resulting in higher condensation efficiency. Simultaneously, the catalyst can lower the energy barrier for ethanol dehydrogenation and weaken carbon-carbon bond adsorption (inhibiting methanation and cracking), thus reducing the generation of byproducts and improving the yield and selectivity of higher alcohols.
[0020] The La-CeO2 nanorod modified nickel catalyst of the present invention is a heterogeneous catalyst, which is easy to separate, recover and reuse in the preparation of higher alcohols. Attached Figure Description
[0021] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings: Figure 1 The images show the XRD patterns of the La-CeO2 nanorod modified nickel-based catalyst prepared in Example 1 and the nickel-based catalyst prepared in Comparative Example 1, where Ni@C-LaCeO2 is from Example 1 and Ni@C is from Comparative Example 1.
[0022] Figure 2 The image shows an electron microscope image of the nickel-based catalyst prepared in Comparative Example 1.
[0023] Figure 3 This is an electron microscope image of the La-CeO2 nanorod modified nickel-based catalyst prepared in Example 1. Detailed Implementation
[0024] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.
[0025] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.
[0026] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.
[0027] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be obvious to those skilled in the art. This specification and embodiments are merely exemplary.
[0028] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.
[0029] An embodiment of the present invention provides a method for preparing a La-CeO2 nanorod modified nickel-based catalyst, comprising the following steps: S1. Add soluble lanthanum salt and soluble cerium salt to water and stir to form a homogeneous solution; S2. Add sodium hydroxide solution to the homogeneous solution and stir until homogeneous. Then heat the resulting mixture to achieve precipitation. After filtration, washing and drying, a yellow solid is obtained. S3. Anneal the yellow solid to obtain La-CeO2 nanorods; S4. Dissolve soluble nickel salt and citric acid in water containing La-CeO2 nanorods, and dry to obtain the precursor; S5. The precursor was calcined to obtain a La-CeO2 nanorod modified nickel-based catalyst.
[0030] In a preferred embodiment of the present invention, in step S1, the mass percentage of soluble lanthanum salt relative to soluble cerium salt, based on lanthanum and cerium, is 1-15%, preferably 1-10%, and more preferably 1%.
[0031] For example, the soluble lanthanum salt is lanthanum nitrate; the soluble cerium salt is cerium nitrate.
[0032] In a preferred embodiment of the present invention, in step S2, the heating temperature is 100°C and the heating time is 12 hours.
[0033] In a preferred embodiment of the present invention, in step S3, the annealing temperature is 400°C and the time is 4 hours.
[0034] In a preferred embodiment of the present invention, in step S4, the molar ratio of citric acid to soluble nickel salt is 2:1; The mass ratio of La-CeO2 nanorods to soluble nickel salt is 10:1.
[0035] For example, a soluble nickel salt is nickel nitrate.
[0036] In a preferred embodiment of the present invention, in step S5, the calcination temperature is 550°C and the time is 2 hours.
[0037] Embodiments of the present invention also provide a La-CeO2 nanorod modified nickel-based catalyst prepared according to the above method.
[0038] The embodiments of the present invention also provide an application of the above-mentioned La-CeO2 nanorod modified nickel-based catalyst in the catalytic aqueous synthesis of higher alcohols from small molecule alcohols.
[0039] For example, small molecule alcohols are ethanol, and higher alcohols are alcohols with 4 to 16 carbon atoms.
[0040] When using the above-mentioned La-CeO2 nanorod modified nickel-based catalyst to catalyze the aqueous phase synthesis of higher alcohols from small molecule alcohols, the reaction temperature is 190~220℃, preferably 200~220℃.
[0041] In a preferred embodiment of the present invention, the steps for catalyzing the aqueous synthesis of higher alcohols from small molecule alcohols using the above-mentioned La-CeO2 nanorod-modified nickel-based catalyst are as follows: The La-CeO2 nanorod-modified nickel catalyst, sodium hydroxide (NaOH), ethanol, and water are mixed in a mass ratio of 1:1:20:20. After leak detection, the air inside the reactor is replaced with high-purity hydrogen. The reaction is carried out continuously for 8-14 hours at a reaction temperature of 190-220°C, an initial pressure of 0.1 MPa, and a stirring speed of 1200-1500 rpm. After the reaction, the substrate spontaneously separates into oil and water phases. After centrifugation, the oil and water phases are analyzed separately by gas chromatography.
[0042] Unless otherwise specified, the room temperature in this invention is 25±2℃.
[0043] All raw materials used in the embodiments of the present invention were obtained through commercial purchase.
[0044] It should be noted that any aspects not described in detail in this invention are conventional practices in the field and are not the focus of this invention.
[0045] The technical solution of the present invention will be further illustrated by the following embodiments.
[0046] Example 1 A method for preparing a La-CeO2 nanorod modified nickel-based catalyst, comprising the following steps: S1. Add 0.02g of lanthanum nitrate and 1.74g of cerium nitrate to 30mL of deionized water and stir to form a homogeneous solution. In this example, the mass percentage of lanthanum nitrate relative to cerium nitrate is 1%. S2. Add 40 mL of 0.45 g / mL sodium hydroxide solution dropwise to the homogeneous solution obtained in S1 and stir until homogeneous. Then transfer the resulting mixture to a stainless steel autoclave lined with polytetrafluoroethylene and heat at 100 °C for 12 h to achieve precipitation. Collect the solid with a Buchner funnel, wash five times each with deionized water and ethanol, and dry overnight to obtain a yellow solid. S3. The yellow solid obtained above was placed in a muffle furnace and annealed in air at 400°C for 4 h to obtain La-CeO2 nanorods; S4. Dissolve nickel nitrate and citric acid in distilled water containing La-CeO2 nanorods, and dry to obtain the precursor. In this embodiment, the molar ratio of nickel nitrate to citric acid is 1:2, and the mass ratio of La-CeO2 nanorods to nickel nitrate is 10:1. S5. The above precursor was placed in a muffle furnace and calcined in nitrogen at 550°C for 2 h to obtain the final product, La-CeO2 nanorod modified nickel-based catalyst, denoted as Ni@C-LaCeO2.
[0047] Example 2 A method for preparing a La-CeO2 nanorod modified nickel-based catalyst is the same as in Example 1, except that the mass percentage of lanthanum nitrate relative to cerium nitrate in step S1 is 3%.
[0048] Example 3 A method for preparing a La-CeO2 nanorod modified nickel-based catalyst is the same as in Example 1, except that the mass percentage of lanthanum nitrate relative to cerium nitrate in step S1 is 5%.
[0049] Example 4 A method for preparing a La-CeO2 nanorod modified nickel-based catalyst is the same as in Example 1, except that the mass percentage of lanthanum nitrate relative to cerium nitrate in step S1 is 10%.
[0050] Comparative Example 1 A method for preparing a nickel-based catalyst, comprising the following steps: S1. Dissolve 0.55g of nickel nitrate and 0.72g of citric acid in 1:2 in 40mL of deionized water and stir until homogeneous to form a homogeneous solution. S2. Stir the homogeneous solution obtained in S1 at 80℃ for 12 hours and dry it to obtain the precursor; S3. The above precursor was calcined at 550°C for 2 hours under a nitrogen atmosphere to obtain a nickel-based catalyst, denoted as Ni@C.
[0051] Figure 1 The XRD patterns of the La-CeO2 nanorod-modified nickel-based catalyst prepared in Example 1 and the nickel-based catalyst prepared in Comparative Example 1 are shown below. Ni@C-LaCeO2 represents Example 1, and Ni@C represents Comparative Example 1. It can be seen that the La-CeO2 nanorod-modified nickel catalyst prepared in Example 1 has several more diffraction peaks with sharper peak shapes, indicating the formation of a stable La-CeO2 nanorod crystal structure. Simultaneously, the Ni peak intensity is weakened and broadened, indicating that the Ni particles on the La-CeO2 nanorod-modified nickel catalyst prepared in Example 1 are more dispersed and have higher activity. It is possible that some Ni interacts with the La-CeO2 nanorods, forming an interfacial phase or solid solution.
[0052] Figure 2 The image shows an electron microscope image of the nickel-based catalyst prepared in Comparative Example 1. Figure 3The image shows an electron microscopy (EM) image of the La-CeO2 nanorod-modified nickel-based catalyst prepared in Example 1. It can be seen that in Comparative Example 1, the Ni nanoparticles in the Ni@C catalyst aggregate into clusters, with a relatively dense particle distribution and an overall irregular aggregated state; no obvious one-dimensional or regular morphology was observed. In contrast, the La-CeO2 nanorod-modified nickel-based catalyst clearly shows La-CeO2 nanorods with a significant aspect ratio acting as a framework support, with Ni particles dispersed on the surface and in the gaps between the nanorods. Compared to pure Ni@C, the Ni particle distribution in the La-CeO2 nanorod-modified nickel-based catalyst is more uniform, and the agglomeration phenomenon is significantly alleviated. The porous structure constructed by the nanorods provides abundant dispersion sites. This indicates that the addition of La-CeO2 nanorods can maintain the high dispersion state of Ni nanoparticles, expose more active sites, and the high specific surface area and porous structure of the nanorods broaden the mass transfer channels of the catalyst, improving the contact efficiency of the reactants.
[0053] Application Example 1 The catalyst prepared in this invention is used in conjunction with a homogeneous base to catalyze the carbon-carbon coupling reaction of ethanol to produce higher alcohols. The specific steps are as follows: 0.5 g of the La-CeO2 nanorod modified nickel-based catalyst prepared in Examples 1-4 or the nickel-based catalyst prepared in Comparative Example 1, 0.5 g of NaOH, 10 g of ethanol, and 10 g of water are added to a 70 mL high-pressure reactor. After leak detection, the air in the reactor is replaced with high-purity hydrogen. The reaction is carried out continuously for 9 hours at a reaction temperature of 190 °C, an initial pressure of 0.1 MPa, and a stirring speed of 1500 rpm. After the reaction, the reaction system is cooled to room temperature, and the gas phase is collected using a gas bag. The liquid phase product is then removed from the reactor. The liquid and solid phase catalysts are separated by centrifugation and filtration. After standing, the liquid phase naturally separates into an oil phase and an aqueous phase. The gas phase product, aqueous phase, and oil phase are all qualitatively and quantitatively analyzed by gas chromatography. The results are shown in Table 1.
[0054] Table 1 Table 1 shows that the main product in the oil phase was C4+ higher alcohols. Because Comparative Example 1 used a catalyst with a carbon layer as the support and metallic nickel as the active component, it suffered from severe carbon deposition, leading to a higher ethanol conversion rate. However, the yield of C4+ higher alcohols in Comparative Example 1 is very low. Application Example 2 0.5 g of the La-CeO2 nanorod-modified nickel-based catalyst prepared in Examples 1-4 or the nickel-based catalyst prepared in Comparative Example 1, 0.5 g of NaOH, 10 g of ethanol, and 10 g of water were added to a 70 mL high-pressure reactor. After leak testing, the air in the reactor was replaced with high-purity hydrogen, and the reaction was carried out continuously for 9 hours at a reaction temperature of 200 °C, an initial pressure of 0.1 MPa, and a stirring speed of 1500 rpm. The post-reaction treatment was the same as in Application Example 1, and the results are shown in Table 2.
[0055] Table 2 Application Example 3 0.5 g of the La-CeO2 nanorod modified nickel-based catalyst prepared in Examples 1-4 or the nickel-based catalyst prepared in Comparative Example 1, 0.5 g of NaOH, 10 g of ethanol, and 10 g of water were added to a 70 mL high-pressure reactor. After leak testing, the air in the reactor was replaced with high-purity hydrogen, and the reaction was carried out continuously for 9 hours at a reaction temperature of 210 °C, an initial pressure of 0.1 MPa, and a stirring speed of 1500 rpm. The post-reaction treatment was the same as in Application Example 1, and the results are shown in Table 3.
[0056] Table 3 Application Example 4 0.5 g of the La-CeO2 nanorod modified nickel-based catalyst prepared in Examples 1-4 or the nickel-based catalyst prepared in Comparative Example 1, 0.5 g of NaOH, 10 g of ethanol, and 10 g of water were added to a 70 mL high-pressure reactor. After leak testing, the air in the reactor was replaced with high-purity hydrogen, and the reaction was carried out continuously for 9 hours at a reaction temperature of 220 °C, an initial pressure of 0.1 MPa, and a stirring speed of 1500 rpm. The post-reaction treatment was the same as in Application Example 1, and the results are shown in Table 4.
[0057] Table 4 As shown in Tables 1-4, the La-CeO2 nanorod-modified nickel catalysts prepared in Examples 1-4 by changing the ratio of soluble lanthanum salt to soluble cerium salt exhibited the best catalyst performance and optimal reaction conditions when the reaction temperature for the carbon-carbon coupling of ethanol to prepare higher alcohols was 210℃. The ethanol conversion rate, organic phase product yield, selectivity of C4+ higher alcohols in the liquid phase product, and yield of C4+ higher alcohols all reached relatively high levels. In contrast, Comparative Example 1, due to the absence of La-CeO2 nanorods, resulted in excessive agglomeration of the carbon shell support in its catalyst, which hindered the dispersion of the active component nickel. Furthermore, severe carbon deposition led to a higher conversion rate, but its yield of C4+ higher alcohols and organic phase yield were both lower. Experiments also revealed that the conversion rate and yield of C4+ higher alcohols of the La-CeO2 nanorod modified nickel catalyst prepared in this invention were significantly improved compared with the comparative example, indicating that most of the ethanol participated in the reaction. Furthermore, the catalyst greatly promoted carbon-carbon coupling and inhibited carbon-carbon bond breaking, thereby significantly improving the selectivity of higher alcohols and the conversion rate of ethanol.
[0058] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.
Claims
1. A method for preparing a lanthanum-cerium dioxide nanorod modified nickel-based catalyst, characterized in that, Includes the following steps: S1. Add soluble lanthanum salt and soluble cerium salt to water and stir to form a homogeneous solution; S2. Add sodium hydroxide solution to the homogeneous solution and stir until homogeneous. Then heat the resulting mixture to achieve precipitation. After filtration, washing and drying, a yellow solid is obtained. S3. Anneal the yellow solid to obtain lanthanum-cerium dioxide nanorods; S4. Dissolve soluble nickel salt and citric acid in water containing the lanthanum-cerium dioxide nanorods, and dry to obtain the precursor; S5. The precursor is calcined to obtain the lanthanum-cerium dioxide nanorod modified nickel-based catalyst.
2. The method for preparing the lanthanum-cerium dioxide nanorod modified nickel-based catalyst according to claim 1, characterized in that, In step S1, the mass percentage of the soluble lanthanum salt relative to the soluble cerium salt is 1-15%, based on lanthanum and cerium.
3. The preparation method of the lanthanum-cerium dioxide nanorod modified nickel-based catalyst according to claim 2, characterized in that, In step S1, the mass percentage of the soluble lanthanum salt relative to the soluble cerium salt is 1 to 10%, based on lanthanum and cerium.
4. The preparation method of the lanthanum-cerium dioxide nanorod modified nickel-based catalyst according to claim 1, characterized in that, In step S2, the heating temperature is 100℃ and the heating time is 12h.
5. The method for preparing the lanthanum-cerium dioxide nanorod modified nickel-based catalyst according to claim 1, characterized in that, In step S3, the annealing temperature is 400℃ and the time is 4 hours.
6. The method for preparing the lanthanum-cerium dioxide nanorod modified nickel-based catalyst according to claim 1, characterized in that, In step S4, the molar ratio of citric acid to soluble nickel salt is 2:1; The mass ratio of the lanthanum-cerium dioxide nanorods to the soluble nickel salt is 10:
1.
7. The method for preparing the lanthanum-cerium dioxide nanorod modified nickel-based catalyst according to claim 1, characterized in that, In step S5, the calcination temperature is 550°C and the time is 2 hours.
8. A lanthanum-cerium dioxide nanorod modified nickel-based catalyst, characterized in that, It is prepared according to any one of claims 1-7.
9. The application of the lanthanum-cerium dioxide nanorod modified nickel-based catalyst as described in claim 8 in the catalytic aqueous-phase synthesis of higher alcohols from small molecule alcohols.
10. The application according to claim 9, characterized in that, The reaction temperature is 190~220℃.