NiO-CuO-Mo catalyst and preparation method and application thereof
By designing the NiO-CuO-Mo catalyst, the problem of low catalytic efficiency of existing non-precious metal catalysts is solved, and a highly efficient and stable catalytic effect is achieved in the catalytic ammonia boranol hydrogen production reaction.
Patent Information
- Application Number
- CN202411744664.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-01
- Publication Date
- 2025-03-07
AI Technical Summary
Existing non-precious metal catalysts have low catalytic efficiency in catalyzing hydrogen production reactions of ammonia borane.
A NiO-CuO-Mo catalyst is designed which hydrothermal reactions of nickel salts, copper salts and molybdenum salts in deionized water, and then calcination is obtained with the molar ratio of NiO, CuO and Mo in the catalyst of 10:10:1-4.
This catalyst exhibits excellent catalytic activity and stability in the catalytic hydrogen production reaction of ammonia boranol, with a long cycle life and a significant improvement in catalytic efficiency.
Smart Images
Figure CN119565625A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of hydrogen production by alcoholysis of ammonia borane, and in particular to a NiO-CuO-Mo catalyst and a preparation method thereof, and application thereof in catalyzing hydrogen production by alcoholysis of ammonia borane. Background Art
[0002] In recent years, the comprehensive development of society and economy has led to an unprecedented growth in the demand for energy in industry, agriculture, service industry and daily life, and the global consumption of energy such as coal, oil and natural gas has risen rapidly. The burning of fossil fuels has caused significant damage to the ecological environment. Therefore, the demand for clean energy for environmental protection and ecological improvement is also increasing. In order to solve the energy crisis and environmental deterioration problems in contemporary society, creating sustainable development is an imminent clean energy. Hydrogen is considered to be the most promising energy carrier due to its huge energy density, renewable resource production capacity and environmental friendliness.
[0003] Chemical hydrogen storage materials catalyzed hydrogen production has attracted widespread attention as a reliable, effective and simple way to solve the problem of safe and controllable hydrogen management in the future hydrogen economy. Ammonia borane (AB, NH 3 BH 3 ) is one of the most promising chemical hydrogen storage materials, which has the advantages of high hydrogen storage capacity (19.6wt%), non-toxicity, strong stability and good solubility. In existing studies, the research on AB alcoholysis catalysts mainly includes two categories: precious metal and non-precious metal catalysts. Among them, precious metal catalysts are mainly divided into two categories: palladium-based and ruthenium-based. However, the price of using precious metals to produce hydrogen is relatively high and is not suitable for further industrial development; the catalytic activity of a single non-precious metal is generally low. For this reason, the research on a combination of multiple non-precious metal catalysts has attracted a lot of attention from researchers. The present invention designs a catalyst of a combination of three non-precious metals suitable for catalyzing the alcoholysis of ammonia borane to produce hydrogen. Summary of the invention
[0004] The purpose of the present invention is to provide a NiO-CuO-Mo catalyst and a preparation method and application thereof, so as to solve the problem of low catalytic efficiency of existing non-precious metal ammonia borane hydrogen production catalysts.
[0005] In order to achieve the above object, the present invention relates to a method for preparing a NiO-CuO-Mo catalyst, which specifically comprises the following steps:
[0006] (1) adding nickel salt, copper salt and molybdenum salt into deionized water and mixing them evenly, and performing a hydrothermal reaction at 100-300° C.;
[0007] (2) The precipitate obtained in step (1) is centrifuged, washed, dried overnight, and calcined at 300-600° C. to obtain a NiO-CuO-Mo catalyst, wherein the molar ratio of NiO, CuO and Mo in the catalyst is 10:10:1-4.
[0008] Preferably, in step (1), the nickel salt, copper salt and molybdenum salt are added to deionized water and then magnetically stirred for 20-40 minutes to mix evenly.
[0009] Preferably, in step (1), the nickel salt is one or more of nickel hydroxide, nickel nitrate, nickel acetate and nickel chloride, the copper salt is one or more of copper nitrate, copper hydroxide, copper sulfate, copper chloride and copper acetate, and the molybdenum salt is one or more of ammonium molybdate and sodium molybdate.
[0010] Specifically, the reaction time of the hydrothermal reaction in step (2) is 4-10 hours.
[0011] Specifically, the ambient temperature for drying overnight in step (3) is 60-110°C.
[0012] Specifically, the calcination time in step (3) is 2-8 hours.
[0013] The calcination temperature in step (2) is 300-600°C. The hydrogen production rate of the catalyst obtained at 300-400°C is relatively low, and preferably 500-600°C.
[0014] The NiO-CuO-Mo catalyst prepared by the method is used in catalyzing the alcoholysis of ammonia borane to produce hydrogen.
[0015] Compared with the prior art, the present invention has the following beneficial effects: (1) The catalyst exhibits excellent catalytic activity and stability in the catalytic ammonia borane alcoholysis hydrogen production reaction, and the catalyst has a long cycle life, and the activity only slightly decreases after 10 cycles, which greatly improves the catalytic efficiency of the catalyst. (2) The catalyst preparation process is simple, has low equipment requirements, low cost, and is easy to mass produce, which is convenient for large-scale industrialization and industrialization application in the future. BRIEF DESCRIPTION OF THE DRAWINGS
[0016] Figure 1 NiO prepared in Example 1 5 -CuO 5 -SEM image of Mo catalyst.
[0017] Figure 2 NiO prepared in Example 1 5 -CuO 5 -XRD pattern of Mo catalyst.
[0018] Figure 3 This is the performance diagram of the catalyst prepared in Example 1-6 catalyzing the alcoholysis of ammonia borane to produce hydrogen.
[0019] Figure 4 NiO involved in Example 1 5 -CuO 5 -Mo-catalyzed ammonia borane alcoholysis to produce hydrogen catalytic reaction life test diagram. DETAILED DESCRIPTION
[0020] The present invention will be further described below through specific embodiments and drawings.
[0021] Embodiment 1:
[0022] (1) 4.0 mmol nickel hydroxide, 4.0 mmol copper nitrate, and 0.8 mmol ammonium molybdate were dissolved in 50 ml deionized water, and then subjected to a hydrothermal reaction at 120° C. for 8 h.
[0023] (2) After the hydrothermal reaction, the precipitate was washed and dried to obtain a powder, and then the powder was added to a muffle furnace, the heating rate was controlled to be 10°C / min, and the calcination was performed at 600°C for 8h to obtain a catalyst NiO with a molar ratio of NiO:CuO:Mo of 5:5:1 5 -CuO 5 -Mo.
[0024] Embodiment 2:
[0025] This example is the same as Example 1 except step (1) to prepare a NiO catalyst.
[0026] (1) 4.0 mmol nickel hydroxide was dissolved in 50 ml deionized water, and then a hydrothermal reaction was carried out at 120° C. for 8 h.
[0027] Embodiment 3:
[0028] This example is the same as Example 1 except step (1) to prepare a CuO catalyst.
[0029] (1) 4.0 mmol of copper nitrate trihydrate was dissolved in 50 mL of deionized water, and then a hydrothermal reaction was carried out at 120° C. for 8 h.
[0030] Embodiment 4:
[0031] Except for step (1), the other steps of this embodiment are the same as those of embodiment 1 to prepare a NiO-CuO catalyst.
[0032] (1) 4.0 mmol nickel hydroxide and 4.0 mmol copper nitrate were dissolved in 50 mL deionized water, and then subjected to a hydrothermal reaction at 120° C. for 8 h.
[0033] Embodiment 5:
[0034] This example is the same as Example 1 except step (1), and a catalyst NiO with a molar ratio of NiO:CuO:Mo of 5:5:2 is prepared. 5 -CuO 5 -Mo 2 .
[0035] (1) 4.0 mmol nickel hydroxide, 4.0 mmol copper nitrate, and 1.6 mmol ammonium molybdate were dissolved in 50 ml deionized water, and then subjected to a hydrothermal reaction at 120° C. for 8 h.
[0036] Embodiment 6:
[0037] This example is the same as Example 1 except step (1), and a catalyst NiO with a molar ratio of NiO:CuO:Mo of 10:10:1 is prepared. 10 -CuO 10 -Mo.
[0038] (1) 4.0 mmol nickel hydroxide, 4.0 mmol copper nitrate, and 0.4 mmol ammonium molybdate were dissolved in 50 ml deionized water, and then subjected to a hydrothermal reaction at 120° C. for 8 h.
[0039] The catalysts prepared in Examples 1-6 were tested for their catalytic performance in the catalytic hydrogen production by alcoholysis of ammonia borane. Figure 1 .
[0040] The NiO prepared in Example 1 5 -CuO 5 -Mo catalyst was used to test the catalytic reaction life of hydrogen production by alcoholysis of ammonia borane. For specific results, see Figure 2 The results show that after eight cycles, it still exhibits high catalytic activity, and the catalytic performance decreases to a certain extent after 10 reuses. Compared with the catalyst life reported so far, the service life has been significantly improved.
[0041] The catalytic ammonia borane alcoholysis hydrogen production performance test comprises the following steps:
[0042] Step 1: 10 mg of the catalyst was placed in 0.8 g of methanol and dispersed by ultrasonication.
[0043] Step 2: 0.8 g of sodium hydroxide and 3 mmol of ammonia borane were added to 10 mL of methanol and quickly injected into the reactor. The reaction temperature was controlled at 298 K in a constant temperature water bath.
[0044] Step 3: When the first bubble appears, the reaction timer starts running. By tracking the displacement of water in the gas burette, the volume of generated gas can be measured, and the change of hydrogen production of different catalysts over time can be recorded to obtain Figure 3 .
[0045] Step 4: After the alcoholysis of ammonia borane is completed, collect, wash and dry the catalyst, and then repeat steps 1-4 to record the catalyst NiO 5 -CuO 5 -Mo usage time and hydrogen production each time, get Figure 4 .
Claims
1. A method for preparing a NiO-CuO-Mo catalyst, characterized in that: The following steps are involved: (1) adding nickel salt, copper salt and molybdenum salt into deionized water and mixing them evenly, and performing a hydrothermal reaction at 100-300° C.; (2) The precipitate obtained in step (1) is centrifuged, washed, dried overnight, and calcined at 300-600° C. to obtain a NiO-CuO-Mo catalyst, wherein the molar ratio of NiO, CuO and Mo in the catalyst is 10:10:1-4.
2. The method for preparing the NiO-CuO-Mo catalyst according to claim 1, characterized in that: In step (1), nickel salt, copper salt and molybdenum salt are added to deionized water and then magnetically stirred for 20-40 minutes to mix evenly.
3. The method for preparing the NiO-CuO-Mo catalyst according to claim 1, characterized in that: In step (1), the nickel salt is one or more of nickel hydroxide, nickel nitrate, nickel acetate and nickel chloride, the copper salt is one or more of copper nitrate, copper hydroxide, copper sulfate, copper chloride and copper acetate, and the molybdenum salt is one or more of ammonium molybdate and sodium molybdate.
4. The method for preparing the NiO-CuO-Mo catalyst according to claim 1, characterized in that: The reaction time of the hydrothermal reaction in step (2) is 4-10 hours.
5. The method for preparing the NiO-CuO-Mo catalyst according to claim 1, characterized in that: The ambient temperature for drying overnight in step (3) is 60-110°C.
6. The method for preparing the NiO-CuO-Mo catalyst according to claim 1, characterized in that: The calcination time in step (3) is 2-8 hours.
7. The method for preparing the NiO-CuO-Mo catalyst according to claim 1, characterized in that: The calcination temperature in step (2) is 500-600°C.
8. A NiO-CuO-Mo catalyst prepared according to the method according to any one of claims 1 to 7.
9. Use of the NiO-CuO-Mo catalyst according to claim 8 in catalyzing the alcoholysis of ammonia borane to produce hydrogen.