Nickel-based catalyst based on bimetallic solid solution oxide as carrier, preparation method and application of nickel-based catalyst in hydrogen production
By using bimetallic solid solution oxides as supports in nickel-based catalysts, highly dispersed small-sized nickel nanoparticles were prepared, solving the problems of poor activity and high temperature in the dehydrogenation process of nickel catalysts in LOHCs. This achieved low-temperature and efficient hydrogen generation, which is suitable for distributed hydrogen supply systems.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- JILIN UNIVERSITY
- Filing Date
- 2026-02-10
- Publication Date
- 2026-05-19
AI Technical Summary
Existing nickel catalysts exhibit poor activity and require high temperatures in the dehydrogenation of liquid organic hydrides (LOHCs), and precious metal catalysts are expensive, making large-scale application difficult.
Nickel-based catalysts were prepared using bimetallic solid solution oxides as supports via reducing agent combustion and chemical reduction methods. The strong metal-support interaction between the support and the active metal was utilized to anchor highly dispersed small-sized nickel nanoparticles, thereby enhancing their catalytic activity and stability under low-temperature photothermal coupling conditions.
The catalyst achieves efficient dehydrogenation under low-temperature conditions, exhibits excellent activity and long-term stability, and is suitable for safe hydrogen production from liquid organic hydrides, especially for distributed hydrogen supply scenarios combined with solar thermal systems.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of hydrogen production technology, specifically relating to a nickel-based catalyst based on a bimetallic solid solution oxide as a support, its preparation method, and its application in low-temperature photothermal coupling-driven hydrogen production from liquid organic hydrides. Background Technology
[0002] Hydrogen, as one of the most promising clean energy sources in the 21st century, is considered a crucial option for achieving energy structure transformation and carbon neutrality goals due to its combustion product being only water and its high energy density (142 MJ / kg, three times that of gasoline). However, hydrogen's low density (only 0.0899 g / L under standard conditions) and wide explosion limits (4%–75%) pose significant technical challenges and economic bottlenecks in its storage and transportation. Current mainstream hydrogen storage methods include high-pressure gaseous hydrogen storage, cryogenic liquid hydrogen storage, and solid-material hydrogen storage, but all suffer from low storage density, high energy consumption, and high costs, making it difficult to meet the demands of large-scale commercial applications. Liquid organic hydrides (LOHCs) technology is a novel hydrogen energy storage and transportation method with advantages such as being in a liquid state at room temperature and pressure and having high safety. However, its dehydrogenation process largely relies on high-temperature thermal energy, which limits the energy efficiency and safety of practical applications.
[0003] Currently, the dehydrogenation reaction of LOHCs mainly relies on noble metal catalysts (such as Pt, Pd, Ru, etc.) at high temperatures. However, the high cost of noble metals makes large-scale application difficult. Non-noble metal catalysts, such as nickel-based catalysts, have been widely studied due to their low cost and abundant reserves, but their activity is insufficient under mild conditions and they have poor thermal stability. The design of the support has a significant impact on the dispersion and electronic structure regulation of nickel particles. In particular, bimetallic solid solution oxides with oxygen vacancies and tunable electronic structures are promising candidates as excellent support materials. Furthermore, nickel is an environmentally friendly metal with low toxicity, meeting the requirements of green chemistry and sustainable development.
[0004] Furthermore, traditional thermocatalytic dehydrogenation processes are energy-intensive, and the reaction temperature is difficult to lower. Photothermal coupled catalysis technology utilizes both light and heat energy to drive the catalytic reaction, enabling efficient dehydrogenation at lower temperatures and avoiding the high energy consumption and safety risks associated with high temperature and high pressure. Summary of the Invention
[0005] The purpose of this invention is to overcome the problems of poor activity and high temperature requirements of existing nickel catalysts in the dehydrogenation process of LOHCs, and to propose a nickel-based catalyst based on a bimetallic solid solution oxide as a support, its preparation method, and its application in low-temperature photothermal coupling driven hydrogen production from liquid organic hydrides.
[0006] This invention relates to a nickel-based catalyst obtained by loading nickel active metal onto a bimetallic solid solution oxide support. The invention first prepares the bimetallic solid solution oxide support via a reducing agent combustion method, and then loads the active metal onto the support using a chemical reduction method. The core of this invention lies in utilizing the metal-support interaction between the support and the active metal. The support firmly anchors nickel nanoparticles through this strong metal-support interaction effect, effectively preventing sintering and maintaining a highly dispersed, small-sized active phase, thereby exposing more active sites. Finally, after reduction and calcination treatment, a nickel-based catalyst with high stability and high activity is obtained.
[0007] The present invention discloses a nickel-based catalyst based on a bimetallic solid solution oxide support. The catalyst consists of a bimetallic solid solution oxide support and an active metal supported thereon. The bimetallic solid solution oxide support is composed of metal A and metal B. Metal A is selected from cerium, lanthanum, praseodymium, neodymium, samarium, and yttrium, and metal B is selected from zirconium, zinc, aluminum, titanium, and hafnium. The active metal is nickel, which is supported on the surface of the bimetallic solid solution oxide support in the form of nanoparticles. The nickel loading is 5 to 100 wt% of the bimetallic solid solution oxide support.
[0008] Furthermore, metal A is cerium (Ce), and metal B is zirconium (Zr).
[0009] The present invention discloses a method for preparing a nickel-based catalyst based on a bimetallic solid solution oxide as a support, comprising the following steps:
[0010] (1) Preparation of cerium-zirconium solid solution by reducing agent combustion method: Weigh cerium salt, zirconium salt and reducing agent, disperse them in deionized water, and stir continuously at room temperature until completely dissolved; transfer the resulting solution to an evaporating dish, heat to evaporate the solvent, and then raise the temperature to initiate a spontaneous combustion reaction to generate cerium-zirconium solid solution precursor through exothermic redox reaction; finally, calcine the cerium-zirconium solid solution precursor at high temperature to obtain cerium-zirconium solid solution, denoted as CZ;
[0011] (2) Preparation of nickel-based catalyst with cerium-zirconium solid solution as support by chemical reduction method: Weigh the cerium-zirconium solid solution in step (1), ultrasonically disperse it in deionized water, add an aqueous solution of nickel salt, react under magnetic stirring, then weigh the reducing agent and slowly pour it into the above solution and stir overnight to chemically deposit metallic nickel on the cerium-zirconium solid solution; then filter the precipitate by vacuum filtration, wash the precipitate several times with deionized water, vacuum dry, grind and calcine at room temperature to obtain nickel-based catalyst with cerium-zirconium solid solution as support.
[0012] Furthermore, the cerium salt mentioned in step (1) is one of cerium nitrate hexahydrate, cerium chloride heptahydrate, cerium carbonate pentahydrate, and cerium acetate trihydrate; the zirconium salt is one of zirconium oxynitrate dihydrate, zirconium oxychloride octahydrate, zirconium nitrate pentahydrate, and zirconium acetate tetrahydrate; and the reducing agent is one of glycine, tartaric acid, and citric acid.
[0013] In step (1), the molar ratio of cerium salt to zirconium salt is 0.1~9:1, which involves dispersing 0.01~100 mmol of cerium salt and zirconium salt in 5~500 mL of deionized water; the ratio of the total molar amount of cerium salt and zirconium salt to the molar amount of reducing agent is 0.1~10:1; the stirring is performed by magnetic stirring at 500~1000 r / min for 0.25~12 h; the temperature for heating to evaporate the solvent is 90~120℃; the temperature for initiating the auto-ignition reaction is 150~250℃; the temperature for high-temperature calcination is 600~1000℃; and the calcination time is 2~4 h.
[0014] Furthermore, the nickel salt in step (2) is one of nickel nitrate hexahydrate, nickel chloride hexahydrate, nickel sulfate hexahydrate, and nickel acetate tetrahydrate, and the reducing agent is one or a mixture of several of sodium borohydride, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, lithium bicarbonate, and ammonia water.
[0015] In step (2), 50-500 mg of cerium-zirconium solid solution is dispersed in 50-500 mL of deionized water, the mass concentration of nickel salt aqueous solution is 1-20 mg / mL, the volume of nickel salt aqueous solution added is 0.01-10 mL, and the nickel loading is 5-100 wt% of the cerium-zirconium solid solution carrier; magnetic stirring is carried out at 500-1000 r / min for 0.5-12 h, the amount of reducing agent added is 1-200 mg; the calcination atmosphere is hydrogen, air, nitrogen, argon or ammonia, the calcination temperature is 200-600℃, and the calcination time is 2-4 h.
[0016] The nickel-based catalyst based on cerium-zirconium solid solution as a support described in this invention is prepared by the above method.
[0017] The nickel-based catalyst based on cerium-zirconium solid solution as a support described in this invention can be applied in low-temperature photothermal coupling-driven hydrogen production from liquid organic hydrides.
[0018] Furthermore, the liquid organic hydride is one or a mixture of several of the following: cyclohexane, methylcyclohexane, dimethylcyclohexane, decahydronaphthalene, butane, pentane, hexane, ethyldodecylcarbazole, indoline, decahydroquinoline, and octahydrophenazine.
[0019] Compared with the prior art, the present invention has the following beneficial effects:
[0020] This invention employs a chemical reduction method to successfully prepare a nickel-based catalyst with a cerium-zirconium solid solution as the support and nickel as the active center. This catalyst, through strong metal-support interactions, firmly anchors highly dispersed, small-sized nickel nanoparticles, effectively inhibiting sintering and agglomeration during the reaction process, thereby maintaining abundant active sites. The cerium-zirconium support possesses unique redox properties and abundant oxygen vacancies, which can further modulate the electronic structure of nickel, enhancing its adsorption and activation capabilities for reactants. Simultaneously, its moderate surface acidity and alkalinity promote rapid product desorption and suppress side reactions. Through the synergistic regulation of structural design and electronic effects, this catalyst exhibits excellent dehydrogenation activity and long-term stability under low-temperature photothermal coupling conditions, making it suitable for efficient and safe hydrogen production from liquid organic hydrides, particularly for distributed hydrogen supply scenarios combined with solar thermal systems, providing a reliable technical solution for green hydrogen energy conversion and supply. Attached Figure Description
[0021] Figure 1 The image shown is a high-resolution TEM image of the product of Example 4 of the present invention; it shows that the nickel nanoparticles of the nickel-based catalyst based on cerium-zirconium solid solution as a support have a diameter of about 4-6 nm, a crystal interplanar spacing of 0.200 nm, and are uniformly dispersed.
[0022] Figure 2 The graph shows a comparison of the hydrogen production rates of the products from Examples 4, 8-13 of this invention under light irradiation. It indicates that, under the same nickel loading of 10 wt%, the nickel-based catalyst Ni / CZ with CZ support exhibits a hydrogen production rate far exceeding that of all other single oxide supported catalysts, demonstrating the best catalytic performance.
[0023] Figure 3 The graph shows a comparison of the hydrogen production rates of the products from Examples 4-7 of this invention under light irradiation. It indicates that in the studied nickel-based catalyst system, the nickel loading has a significant impact on the hydrogen production rate, and there is an optimal loading of 50 wt%, at which the catalytic activity reaches its peak. However, subsequent XRD patterns show that carbon deposition occurred after the reaction of the Ni / CZ catalyst with the optimal loading of 50 wt%.
[0024] Figure 4 The graph shows the relationship between the hydrogen generation rate and the incident light intensity of the product of Example 4 of the present invention; it indicates that the hydrogen generation rate and the incident light intensity have an approximately linear proportional relationship.
[0025] Figure 5 The graph shows the relationship between the hydrogen generation rate of the product in Example 4 of this invention and the wavelength of incident light, indicating that the catalyst has the best overall performance when using a full-spectrum light source.
[0026] Figure 6The XRD patterns of the products from Examples 4-7 of this invention before the hydrogen production reaction are shown. No obvious impurity peaks or diffraction peak shifts can be observed. The sample has high purity and good crystallinity, indicating that a catalyst with metallic nickel as the active center and cerium-zirconium solid solution as the support has been successfully synthesized.
[0027] Figure 7 The XRD patterns of the hydrogen production products from Examples 4-7 of this invention are shown below. It can be observed that the low-loading samples (5wt%, 10wt%) only show characteristic diffraction peaks of the cerium-zirconium support and metallic nickel, indicating that their structure remains stable after the reaction. However, the high-loading samples (50wt%, 100wt%) show obvious graphitic carbon crystal plane diffraction peaks at approximately 26°, and nickel oxide impurity peaks near approximately 37° and 43°. The appearance of these additional diffraction peaks confirms that under high loading, nickel particles undergo significant sintering and growth, leading to a decrease in their sintering resistance and catalytic selectivity (partial Ni...). 0 (It is oxidized to NiO), which triggers a severe carbon deposition side reaction, indicating that excessive nickel loading will be detrimental to the structural stability and anti-carbon deposition ability of the catalyst.
[0028] Figure 8 The images show the XRD patterns of the products from Examples 1, 2, 4, and 12 before the hydrogen production reaction and the XRD patterns of the products from Examples 4 and 12 after the hydrogen production reaction. It can be seen that compared with the Ni peak of Ni / C before the reaction, the peak intensity of Ni / C after the reaction is significantly weakened and the peak shape is more broadened, indicating that its stability is poor. Compared with the Ni peak of Ni / CZ before the reaction, the peak position, peak intensity, and peak shape of Ni / CZ after the reaction are almost completely overlapped, indicating that it is resistant to sintering and has excellent stability.
[0029] Figure 9 The images show the ultraviolet-visible diffuse reflectance spectra of the products from Examples 2 and 12 of this invention. It can be seen that the Ni / C obtained after light treatment (red curve) has a significantly improved light absorption intensity in the entire visible to near-infrared band of 400~1000nm, indicating that it has the ability to efficiently utilize full-spectrum solar energy.
[0030] Figure 10 The images show the UV-Vis diffuse reflectance spectra of the products from Examples 1 and 4 of this invention. Ni loading enables the CZ support to achieve broad-spectrum absorption from UV to near-infrared (blue curve), and subsequent illumination treatment (red curve) further and significantly enhances its absorption intensity across the entire spectral range, especially in the central visible region (approximately 500-800 nm). Furthermore, the absorption curves of Ni / C (…) Figure 9 The blue and red curves show a clear downward trend between 500 and 800 nm, while the absorption curve of Ni / CZ ( Figure 10The blue and red curves show a strong and stable performance in the visible light region, with no downward trend. This indicates that Ni / CZ has a higher and more stable efficiency in capturing and converting the most important energy portion of sunlight. Detailed Implementation
[0031] The present invention will be further described in detail below through specific embodiments. Unless otherwise specified, the experimental reagents, materials, and methods used in the embodiments are all from conventional sources in the art or prepared using conventional methods. It should be understood that the embodiments described herein are only for illustrating the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. All equivalent modifications or changes made based on the substantive content of the present invention are included within the scope of protection of the present invention.
[0032] Example 1: Preparation of CZ
[0033] Weigh 4.34 g of Ce(NO3)3·6H2O (10 mmol), 2.31 g of ZrO(NO3)2·2H2O (10 mmol), and 1.5 g of glycine (20 mmol). Disperse them in 5 mL of deionized water and stir magnetically at 800 r / min for 15 min at room temperature until completely dissolved. Then, transfer the solution to a 300 mL evaporating dish and heat to 90 °C to evaporate the solvent. Then, raise the temperature to 200 °C. At 200 °C, the sample undergoes an exothermic auto-ignition reaction via redox reaction to generate a cerium-zirconium solid solution precursor. Finally, transfer the cerium-zirconium solid solution precursor to a muffle furnace and raise the temperature to 650 °C at 5 °C / min. Calcine at this temperature for 4 h to obtain 2.60 g of cerium-zirconium solid solution, denoted as CZ. X-ray diffraction (XRD) was performed on the product of this example. The results are shown in [Figure number missing]. Figure 8 .
[0034] Example 2: Preparation of C
[0035] Weigh 4.34 g of Ce(NO3)3·6H2O (10 mmol) and 0.75 g (20 mmol) of glycine, disperse them in 5 mL of deionized water, and magnetically stir at 800 r / min for 15 min at room temperature until completely dissolved. Then transfer the solution to a 300 mL evaporating dish, heat to 90 °C to evaporate the solvent, and then raise the temperature to 200 °C. At 200 °C, the sample undergoes an exothermic auto-ignition reaction via redox reaction to generate a cerium dioxide precursor. Finally, transfer the cerium dioxide precursor to a muffle furnace and calcine at 650 °C at 5 °C / min for 4 h under the same conditions to obtain 1.71 g of cerium dioxide, denoted as C. X-ray diffraction (XRD) was performed on the product of this example, and the results are shown in [Figure number missing]. Figure 8 .
[0036] Example 3: Preparation of Z
[0037] Weigh 2.31 g of ZrO(NO3)2·2H2O (10 mmol) and 0.75 g (20 mmol) of glycine, disperse them in 5 mL of deionized water, and stir magnetically at 800 r / min for 15 min at room temperature until completely dissolved. Then transfer the solution to a 300 mL evaporating dish, heat to 90 °C to evaporate the solvent, and then raise the temperature to 200 °C. The sample initiates a reaction at 200 °C through an exothermic redox reaction to generate a zirconium dioxide precursor. Finally, transfer the zirconium dioxide precursor to a muffle furnace and raise the temperature to 650 °C at 5 °C / min. Calcine at high temperature for 4 h under the same conditions to obtain 1.22 g of zirconium dioxide, denoted as Z.
[0038] Example 4: Preparation of 10wt% Ni / CZ
[0039] (1) Preparation of CZ: Same as in Example 1;
[0040] (2) Preparation of 10wt% Ni / CZ: Weigh 50mg of CZ into a beaker, add 50mL of deionized water, and sonicate for 30min. Use a pipette to transfer 250μL of 20mg / mL nickel nitrate solution into the above solution. React for 2h under magnetic stirring at 800r / min. Then weigh 50mg of NaBH4 and slowly pour it into the above solution and stir overnight to chemically deposit metallic nickel on the cerium-zirconium solid solution. Subsequently, filter the precipitate by vacuum filtration and wash it three times with deionized water. Dry it overnight in a vacuum drying oven at room temperature. After grinding, calcine it at 400℃ in a hydrogen atmosphere for 2h to obtain 51mg of 10wt% Ni / CZ catalyst (10wt% means that the mass percentage of active metal Ni relative to the CZ support is 10wt%). The test results of the relevant tests on the product of this example are shown in [link to relevant test results]. Figures 1-10 .
[0041] Example 5: Preparation of 5wt% Ni / CZ
[0042] (1) Preparation of CZ: Same as in Example 1;
[0043] (2) Preparation of 5wt% Ni / CZ: Weigh 50mg of CZ into a beaker, add 50mL of deionized water, and sonicate for 30min. Use a pipette to transfer 125μL of 20mg / mL nickel nitrate solution into the above solution. React for 2h under magnetic stirring at 800r / min. Then weigh 50mg of NaBH4 and slowly pour it into the above solution and stir overnight to chemically deposit metallic nickel on the cerium-zirconium solid solution. Subsequently, filter the precipitate by vacuum filtration and wash it three times with deionized water. Dry it overnight in a vacuum drying oven at room temperature. After grinding, calcine it at 400℃ in a hydrogen atmosphere for 2h to obtain 47mg of 5wt% Ni / CZ catalyst (5wt% means that the mass percentage of active metal Ni relative to the CZ support is 5wt%). The catalytic evaluation results of the product in this example are shown in [reference to relevant documentation]. Figure 3 The X-ray diffraction (XRD) test results are shown in [link to X-ray diffraction test results]. Figure 6 .
[0044] Example 6: Preparation of 50wt% Ni / CZ
[0045] (1) Preparation of CZ: Same as in Example 1;
[0046] (2) Preparation of 50wt% Ni / CZ: Weigh 50mg of CZ into a beaker, add 50mL of deionized water, and sonicate for 30min. Use a pipette to transfer 1250μL of 20mg / mL nickel nitrate solution into the above solution. React for 2h under magnetic stirring at 800r / min. Then weigh 50mg of NaBH4 and slowly pour it into the above solution and stir overnight to chemically deposit metallic nickel on the cerium-zirconium solid solution. Subsequently, filter the precipitate by vacuum filtration and wash it three times with deionized water. Dry it in a vacuum drying oven at room temperature, grind it, and then calcine it at 400℃ in a hydrogen atmosphere for 2h to obtain 70mg of 50wt% Ni / CZ catalyst (50wt% means that the mass percentage of active metal Ni relative to the CZ support is 50wt%). The catalytic evaluation results of the product in this example are shown in [reference to relevant documentation]. Figure 3 The X-ray diffraction (XRD) test results are shown in [link to XRD test results]. Figure 6 .
[0047] Example 7: Preparation of 100wt% Ni / CZ
[0048] (1) Preparation of CZ: Same as in Example 1;
[0049] (2) Preparation of 100wt% Ni / CZ: Weigh 50mg of CZ into a beaker, add 50mL of deionized water, and sonicate for 30min. Use a pipette to transfer 2500μL of 20mg / mL nickel nitrate solution into the above solution. React for 2h under magnetic stirring at 800r / min. Then weigh 50mg of NaBH4 and slowly pour it into the above solution and stir overnight to chemically deposit metallic nickel on the cerium-zirconium solid solution. Subsequently, filter the precipitate by vacuum filtration and wash it three times with deionized water. Dry it overnight in a vacuum drying oven at room temperature. After grinding, calcine it at 400℃ in a hydrogen atmosphere for 2h to obtain 94mg of 100wt% Ni / CZ catalyst (100wt% means that the mass percentage of active metal Ni relative to the CZ support is 100wt%). The catalytic evaluation results of the product in this example are shown in [reference to relevant documentation]. Figure 3 The X-ray diffraction (XRD) test results are shown in [link to XRD test results]. Figure 6 .
[0050] Example 8: Preparation of 10wt% Ni / MgO
[0051] Weigh 50 mg of nano-magnesium oxide into a beaker, add 50 mL of deionized water, and sonicate for 30 min. Then, pipette 250 μL of a 20 mg / mL nickel nitrate solution and add it to the above solution. React for 2 h under magnetic stirring at 800 r / min. Next, weigh 50 mg of NaBH4 and slowly pour it into the above solution, stirring overnight to chemically deposit metallic nickel onto the magnesium oxide. The precipitate is then filtered through vacuum filtration and washed three times with deionized water. It is dried overnight in a vacuum drying oven at room temperature, ground, and then calcined at 400 °C under a hydrogen atmosphere for 2 h to obtain 50 mg of a 10 wt% Ni / MgO catalyst (10 wt% represents the mass percentage of active metal Ni relative to the MgO support). The catalytic evaluation results of the product in this example are shown in [reference needed]. Figure 2 .
[0052] Example 9: Preparation of 10wt% Ni / ZnO
[0053] 50 mg of nano-zinc oxide was weighed into a beaker, and 50 mL of deionized water was added. The mixture was ultrasonically stirred for 30 min. 250 μL of a 20 mg / mL nickel nitrate solution was then added to the solution using a pipette. The mixture was reacted for 2 h under magnetic stirring at 800 r / min. 50 mg of NaBH4 was then slowly poured into the solution and stirred overnight to chemically deposit metallic nickel onto the zinc oxide. The precipitate was then filtered through vacuum filtration and washed three times with deionized water. The precipitate was dried overnight in a vacuum drying oven at room temperature, ground, and then calcined at 400 °C under a hydrogen atmosphere for 2 h to obtain 52 mg of a 10 wt% Ni / ZnO catalyst (10 wt% represents the mass percentage of active metal Ni relative to the ZnO support). The catalytic evaluation results of the product in this example are shown in [reference needed]. Figure 2 .
[0054] Example 10: Preparation of 10wt% Ni / Al2O3
[0055] 50 mg of nano-alumina was weighed into a beaker, and 50 mL of deionized water was added. The mixture was ultrasonically stirred for 30 min. 250 μL of a 20 mg / mL nickel nitrate solution was added to the above solution using a pipette. The mixture was reacted for 2 h under magnetic stirring at 800 r / min. Then, 50 mg of NaBH4 was slowly poured into the above solution and stirred overnight to chemically deposit metallic nickel onto the alumina. The precipitate was then filtered through vacuum filtration and washed three times with deionized water. The precipitate was dried overnight in a vacuum drying oven at room temperature, ground, and then calcined at 400 °C under a hydrogen atmosphere for 2 h to obtain 49 mg of a 10 wt% Ni / Al2O3 catalyst (10 wt% represents the mass percentage of active metal Ni relative to the Al2O3 support). The catalytic evaluation results of the product in this example are shown in [reference needed]. Figure 2 .
[0056] Example 11: Preparation of 10wt% Ni / TiO2
[0057] 50 mg of nano-titanium dioxide was weighed into a beaker, and 50 mL of deionized water was added. The mixture was ultrasonically stirred for 30 min. 250 μL of a 20 mg / mL nickel nitrate solution was then added to the above solution using a pipette. The mixture was reacted for 2 h under magnetic stirring at 800 r / min. Then, 50 mg of NaBH4 was slowly poured into the above solution and stirred overnight to chemically deposit metallic nickel onto the titanium dioxide. The precipitate was then filtered through vacuum filtration and washed three times with deionized water. The precipitate was dried overnight in a vacuum drying oven at room temperature, ground, and then calcined at 400 °C under a hydrogen atmosphere for 2 h to obtain 51 mg of a 10 wt% Ni / TiO2 catalyst (10 wt% represents the mass percentage of active metal Ni relative to the TiO2 support). The catalytic evaluation results of the product in this example are shown in [reference needed]. Figure 2 .
[0058] Example 12: Preparation of 10wt% Ni / C
[0059] (1) Preparation of C: Same as in Example 2;
[0060] (2) Preparation of 10wt% Ni / C: Weigh 50mg of C into a beaker, add 50mL of deionized water, and sonicate for 30min. Use a pipette to transfer 250μL of 20mg / mL nickel nitrate solution into the above solution. React for 2h under magnetic stirring at 800r / min. Then weigh 50mg of NaBH4 and slowly pour it into the above solution and stir overnight to chemically deposit metallic nickel on cerium dioxide. Subsequently, filter the precipitate by vacuum filtration and wash it three times with deionized water. Dry it overnight in a vacuum drying oven at room temperature. After grinding, calcine it at 400℃ in a hydrogen atmosphere for 2h to obtain 48mg of 10wt% Ni / C catalyst (10wt% means that the mass percentage of active metal Ni relative to the C support is 10wt%). The catalytic evaluation results of the product in this example are shown in [reference needed]. Figure 2 The X-ray diffraction (XRD) test results are shown in [link to XRD test results]. Figure 8 .
[0061] Example 13: Preparation of 10wt% Ni / Z
[0062] (1) Preparation of Z: Same as in Example 3;
[0063] (2) Preparation of 10wt% Ni / Z: Weigh 50mg of Z into a beaker, add 50mL of deionized water, and sonicate for 30min. Use a pipette to transfer 250μL of 20mg / mL nickel nitrate solution into the above solution. React for 2h under magnetic stirring at 800r / min. Then weigh 50mg of NaBH4 and slowly pour it into the above solution and stir overnight to chemically deposit metallic nickel onto zirconium dioxide. Subsequently, filter the precipitate by vacuum filtration and wash it three times with deionized water. Dry it overnight in a vacuum drying oven at room temperature. After grinding, calcine it at 400℃ in a hydrogen atmosphere for 2h to obtain 44mg of 10wt% Ni / Z catalyst (10wt% means that the mass percentage of active metal Ni relative to the Z support is 10wt%). The catalytic evaluation results of the product in this example are shown in [reference needed]. Figure 2 .
[0064] Example 14: Hydrogen Production Reaction
[0065] (1) The catalysts obtained in Examples 4-13 were tested for hydrogen production reaction. 10 mg of the catalyst obtained in Example 4 was weighed into a 10 mL beaker, 5 mL of deionized water was added and ultrasonically dispersed evenly. Then, a glass fiber membrane was placed on the filter paper of a vacuum filtration device, and the catalyst was evenly coated on the glass fiber membrane under vacuum filtration. The catalyst-coated glass fiber membrane was then placed in an intermittent quartz reactor, and the reactor was placed in an electric furnace. The vacuum was evacuated to a pressure of less than 1 Pa, and then the temperature was raised to 200 °C for 30 min to remove impurities adsorbed on the catalyst surface. After cooling to room temperature, 60 μL of cyclohexane was injected into the quartz reactor, and a 300 W xenon lamp was used to irradiate it for 1 min (full-spectrum light source with an intensity of 2.42 W / cm²). 2 Simultaneously, the reactor temperature was maintained at 25°C using a water cooling system. After the reaction was complete, 1 mL of the post-reaction gas was extracted using a gas-tight needle, and the catalytic products were collected online using gas chromatography for quantitative analysis and calculation of the hydrogen production rate. The measured hydrogen production rate was 1324.21 mmol / g / h. The hydrogen production reaction tests using the catalysts obtained in Examples 5-13 followed the same steps, and the measured hydrogen production rates were 496.41 mmol / g / h, 2752.32 mmol / g / h, 1776.40 mmol / g / h, 319.36 mmol / g / h, 105.88 mmol / g / h, 727.85 mmol / g / h, 472.70 mmol / g / h, 284.68 mmol / g / h, and 222.07 mmol / g / h, respectively. These results are shown in […]. Figures 2-3 .
[0066] (2) The catalyst obtained in Example 4 was tested for hydrogen production reaction under different incident light intensities. The steps were the same as in (1), except that the light intensity was different. The incident light intensity was 1.3 W / cm².2 1.87W / cm 2 2.42W / cm 2 2.98W / cm 2 3.5W / cm 2 At these times, the corresponding hydrogen production rates were 326.92 mmol / g / h, 777.42 mmol / g / h, 1324.21 mmol / g / h, 1900.96 mmol / g / h, and 2496.14 mmol / g / h, respectively. These results are shown in [reference needed]. Figure 4 .
[0067] (3) The catalyst obtained in Example 4 was tested for hydrogen production reaction under different incident light wavelengths. The steps were the same as in (1), except that the wavelength of the light was different. When irradiated with full spectrum and monochromatic light of specific wavelengths of 300nm, 400nm, 600nm and 800nm, the corresponding hydrogen production rates were 1324.21mmol / g / h, 813.17mmol / g / h, 557.25mmol / g / h, 418.19mmol / g / h and 52.56mmol / g / h, respectively. The above results are shown in […]. Figure 5 .
Claims
1. A nickel-based catalyst based on a bimetallic solid solution oxide as a support, characterized in that: The catalyst consists of a bimetallic solid solution oxide support and an active metal supported thereon. The bimetallic solid solution oxide support is composed of metal A and metal B. Metal A is selected from cerium, lanthanum, praseodymium, neodymium, samarium, and yttrium, and metal B is selected from zirconium, zinc, aluminum, titanium, and hafnium. The active metal is nickel, which is supported on the surface of the bimetallic solid solution oxide support in the form of nanoparticles. The nickel loading is 5 to 100 wt% of the bimetallic solid solution oxide support.
2. The nickel-based catalyst based on a bimetallic solid solution oxide as a support as described in claim 1, characterized in that: Metal A is cerium (Ce), and metal B is zirconium (Zr).
3. A method for preparing a nickel-based catalyst based on a bimetallic solid solution oxide support, comprising the following steps: (1) Preparation of cerium-zirconium solid solution by reducing agent combustion method: Weigh cerium salt, zirconium salt and reducing agent, disperse them in deionized water, and stir continuously at room temperature until completely dissolved; transfer the resulting solution to an evaporating dish, heat to evaporate the solvent, and then raise the temperature to initiate a spontaneous combustion reaction to generate cerium-zirconium solid solution precursor through exothermic redox reaction; finally, calcine the cerium-zirconium solid solution precursor at high temperature to obtain cerium-zirconium solid solution, denoted as CZ; (2) Preparation of nickel-based catalyst with cerium-zirconium solid solution as support by chemical reduction method: Weigh the cerium-zirconium solid solution in step (1), ultrasonically disperse it in deionized water, add an aqueous solution of nickel salt, react under magnetic stirring, then weigh the reducing agent and slowly pour it into the above solution and stir overnight to chemically deposit metallic nickel on the cerium-zirconium solid solution; then filter the precipitate by vacuum filtration, wash the precipitate several times with deionized water, vacuum dry, grind and calcine at room temperature to obtain nickel-based catalyst with cerium-zirconium solid solution as support.
4. The method for preparing a nickel-based catalyst based on a bimetallic solid solution oxide support as described in claim 3, characterized in that: The cerium salt mentioned in step (1) is one of cerium nitrate hexahydrate, cerium chloride heptahydrate, cerium carbonate pentahydrate, and cerium acetate trihydrate; the zirconium salt is one of zirconium oxynitrate dihydrate, zirconium oxychloride octahydrate, zirconium nitrate pentahydrate, and zirconium acetate tetrahydrate; and the reducing agent is one of glycine, tartaric acid, and citric acid.
5. The method for preparing a nickel-based catalyst based on a bimetallic solid solution oxide support as described in claim 3, characterized in that: In step (1), the molar ratio of cerium salt to zirconium salt is 0.1~9:1, which involves dispersing 0.01~100 mmol of cerium salt and zirconium salt in 5~500 mL of deionized water; the ratio of the total molar amount of cerium salt and zirconium salt to the molar amount of reducing agent is 0.1~10:1; the stirring is performed by magnetic stirring at 500~1000 r / min for 0.25~12 h; the temperature for heating to evaporate the solvent is 90~120℃; the temperature for initiating the auto-ignition reaction is 150~250℃; the temperature for high-temperature calcination is 600~1000℃; and the calcination time is 2~4 h.
6. The method for preparing a nickel-based catalyst based on a bimetallic solid solution oxide support as described in claim 3, characterized in that: The nickel salt in step (2) is one of nickel nitrate hexahydrate, nickel chloride hexahydrate, nickel sulfate hexahydrate, and nickel acetate tetrahydrate, and the reducing agent is one or a mixture of several of sodium borohydride, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, lithium bicarbonate, and ammonia water.
7. The method for preparing a nickel-based catalyst based on a bimetallic solid solution oxide support as described in claim 3, characterized in that: In step (2), 50-500 mg of cerium-zirconium solid solution is dispersed in 50-500 mL of deionized water, the mass concentration of nickel salt aqueous solution is 1-20 mg / mL, the volume of nickel salt aqueous solution added is 0.01-10 mL, and the nickel loading is 5-100 wt% of the cerium-zirconium solid solution carrier; magnetic stirring is carried out at 500-1000 r / min for 0.5-12 h, the amount of reducing agent added is 1-200 mg; the calcination atmosphere is hydrogen, air, nitrogen, argon or ammonia, the calcination temperature is 200-600℃, and the calcination time is 2-4 h.
8. A nickel-based catalyst based on a bimetallic solid solution oxide as a support, characterized in that: It is prepared by the preparation method described in any one of claims 3 to 7.
9. The application of the nickel-based catalyst based on a bimetallic solid solution oxide as a support as described in claim 8 in low-temperature photothermal coupling-driven hydrogen production from liquid organic hydrides.
10. The application of a nickel-based catalyst based on a bimetallic solid solution oxide as a support, as described in claim 9, in low-temperature photothermal coupling-driven hydrogen production from liquid organic hydrides, characterized in that: The liquid organic hydride is one or a mixture of several of the following: cyclohexane, methylcyclohexane, dimethylcyclohexane, decahydronaphthalene, butane, pentane, hexane, ethyldodecylcarbazole, indoline, decahydroquinoline, and octahydrophenazine.