Method for controlling the hydrolytic hydrogen generation of ammonia borane in a solid phase system

Abstract

The present application relates to the field of new energy technology, in particular to a method for controlling ammonia borane hydrolysis hydrogen release in solid phase system, the solid phase system is AB@metal M / aerogel porous material; the amount of water added to the solid phase system is controlled to control the amount of AB hydrolysis hydrogen release. The AB@metal M / aerogel porous material is: AB is encapsulated in the aerogel porous material loaded with metal catalyst M. The catalyst is loaded on the aerogel porous material, and AB can be encapsulated in these aerogel porous materials due to the certain solid morphology of the aerogel porous material. The amount of water added to the AB@metal M / aerogel porous material is controlled to control the AB hydrolysis hydrogen release process. The method for controlling hydrogen release in the solid phase system can solve the problem that the liquid phase hydrogen release process is difficult to control, and can be applied to vehicle-mounted energy devices, and has the characteristics of convenient vehicle-mounted, simple operation and easy process control.

Description

Technical Field

[0001] This invention relates to the field of new energy technology, and in particular to a method for controlling the hydrolysis of hydrogen by ammonia borane in a solid-phase system. Background Technology

[0002] Currently, with the development of human society, fossil fuels are nearing depletion, and the energy problem urgently needs to be solved. Human society needs green and sustainable new energy sources to overcome the energy problems caused by oil depletion and the environmental challenges, including global warming, resulting from long-term industrial activities. Against this backdrop, hydrogen energy has emerged in the public eye due to its renewable, clean, and environmentally friendly advantages. Hydrogen is the most abundant element in the universe, accounting for approximately 75% of the mass of known matter, and is also one of the most abundant elements on the Earth's surface. Using hydrogen energy as a power source is a potential way to reduce greenhouse gas and toxic gas emissions, and can simultaneously solve both energy and environmental problems. Ammonia borane (NH3BH3, abbreviated as AB) is a simple hydrogen storage compound with a density of 0.76 g / cm³ at room temperature. -3 It is a white crystalline solid. Ammonia borane has a high bulk density, simple decomposition conditions, and remains stable at room temperature and pressure. It is soluble in water and organic solvents such as tetrahydrofuran. Furthermore, AB has a high hydrogen storage capacity of 19.6 wt%, requiring minimal storage conditions and no high-pressure transportation. Currently, compared to its thermal decomposition, the hydrolysis of AB has advantages such as a lower hydrogen release temperature (at room temperature), no volatile byproducts, and no system expansion, making it one of the most widely used hydrogen production methods.

[0003] However, the hydrolysis process of AB is difficult to control, limiting its practical application in vehicles. Currently, research on controlling the hydrogen release from AB hydrolysis is limited and mainly focuses on liquid-phase systems. For example, Chen et al. used zinc ions to cover the active sites of nanocatalysts in AB aqueous solutions to stop the hydrogen release process, and then used ethylenediaminetetraacetic acid to chelate the zinc ions, reactivating the nanocatalyst and achieving controlled hydrogen release (ACS Applied Materials & Interfaces 2021, 13, 50017-50026). Wang et al. used hydrochloric acid and sodium hydroxide to control hydrogen release in AB aqueous solutions (Journal of the American Chemical Society, 2017, 139, 11610-11615). Tu et al. controlled hydrogen release by controlling the amount of catalyst in the AB solution (ACS Applied Materials & Interfaces, 2022, 14, 8417-8426). However, controlling the hydrogen decomposition process of AB water in a liquid system is complex, requires the addition of other chemical reagents, and is bulky when used in vehicle-mounted equipment, requiring special equipment and is not convenient for vehicle use.

[0004] Therefore, a method for controlling the hydrogen release of ammonia borane hydrolysis using a solid-phase system is urgently needed to solve the above-mentioned technical problems. Summary of the Invention

[0005] The purpose of this invention is to overcome the existing technical problems by encapsulating AB in a porous aerogel material supported by a metal catalyst, thereby achieving controllable release of hydrogen from the hydrolysis of AB in a solid-phase system, making it convenient for vehicle transport. To achieve this objective, the technical solution adopted is as follows:

[0006] To achieve the above objectives, the present invention is implemented according to the following technical solution:

[0007] A method for controlling the hydrogen decomposition of ammonia borane hydrolysis using a solid-phase system, wherein the solid-phase system is AB@metal M / aerogel porous material;

[0008] The amount of hydrogen released by AB through hydrolysis is controlled by adjusting the amount of water added to the solid-phase system.

[0009] Preferably, the AB@metal M / aerogel porous material is: AB is encapsulated within an aerogel porous material loaded with metal catalyst M.

[0010] Preferably, the preparation process of the AB@metal M / aerogel porous material includes the following steps:

[0011] S1, hydrolyzed tetraethyl orthosilicate:

[0012] Tetraethyl orthosilicate, ethanol, and water are mixed, and oxalic acid is added. The mixture is stirred until the solution becomes clear and transparent to obtain silica sol.

[0013] S2, Preparation of aerogel porous materials:

[0014] After mixing porous materials, silica sol, and silica fibers, sodium alginate is added and mixed to obtain a slurry. The slurry is then poured into a mold and freeze-dried to obtain an aerogel porous material.

[0015] S3, loading metal M onto the aerogel porous material:

[0016] The aerogel porous material was immersed in an aqueous solution of metal M salt, and then sodium borohydride solution was added for liquid-phase reduction. After the liquid-phase reduction was completed, the material was washed and dried to obtain the metal M-loaded aerogel porous material, denoted as metal M / aerogel porous material.

[0017] S4, loading AB onto the metal M / aerogel porous material:

[0018] AB was dissolved in tetrahydrofuran to obtain a mixed solution; the mixed solution was dropped into a metal M / aerogel porous material and allowed to stand; the above process was repeated several times and then dried to obtain a metal M / aerogel porous material loaded with AB, denoted as AB@metal M / aerogel porous material.

[0019] Preferably, in step S1, the volume ratio of tetraethyl orthosilicate, ethanol, and water is 5:3:92.

[0020] Specifically, step S1 is as follows: Tetraethyl orthosilicate, ethanol and water are mixed in a volume ratio of 5:3:92, and 10-30 mg of oxalic acid is added to every 50 mL of solution. The mixture is then stirred for 6-8 hours until the solution becomes clear and transparent to obtain silica sol.

[0021] Preferably, in step S2, the mass ratio of porous material, silica fiber, and sodium alginate is 2:1:1; the mass-to-volume ratio of porous material to silica sol is 20:1, and the unit of the mass-to-volume ratio is mg:mL.

[0022] Preferably, in step S2, the porous material is one of halloysite nanotubes (HNT), kaolin, montmorillonite (MMT), zinc 2-methylimidazolium MOF (ZIF-8), reduced graphene oxide (RGO), microcrystalline cellulose (MCC), carbon nanotubes (CNT), molecular sieves (Zeolite), and biomass carbon.

[0023] Specifically, step S2 is as follows: 100 mg of porous material is added to 5 mL of hydrolyzed silica sol, and then 50 mg of chopped silica fiber is added to the slurry. The mixture is stirred for at least 1 hour until the slurry is evenly dispersed. After even dispersion, 50 mg of sodium alginate is added to the slurry, and the mixture is stirred again until the sodium alginate is completely dissolved. The slurry is then poured into a mold, and unidirectionally frozen using liquid nitrogen. The frozen sample is then placed in a freeze dryer and dried for 2-3 days to obtain the aerogel porous material. Among them, the porous materials are halloysite nanotubes (HNT), kaolin, montmorillonite (MMT), zinc 2-methylimidazolium MOF (ZIF-8), reduced graphene oxide (RGO), microcrystalline cellulose (MCC), carbon nanotubes (CNT), molecular sieves, biomass carbon, etc.; the corresponding aerogel porous materials obtained are respectively denoted as HNTA, KA, MMTA, ZIFA, RGOA, MCCA, CNTA, ZA, and BCA.

[0024] Preferably, in step S3, the metal M is at least one of Co, Ni, Cu, Ag, Pt, Pd, Ru, and Rh.

[0025] Preferably, in step S3, the aqueous solution of metal M salt is obtained by dissolving metal M salt and / or metal M salt hydrate in water;

[0026] The mass ratio of the porous aerogel material to the metal M salt and / or the hydrate of the metal M salt is 100:30-50, based on the mass of the porous material; the mass-volume ratio of the metal M salt and / or the hydrate of the metal M salt to water in the aqueous solution of the metal M salt is 30-50:20, and the unit of the mass-volume ratio is mg:mL.

[0027] Preferably, the mass ratio of the aerogel porous material to sodium borohydride is 5:6, based on the mass of the porous material.

[0028] Specifically, step S3 is as follows: 40 mg of metal M salt and / or the hydrate of metal M salt is dissolved in 20 mL of water. The aerogel porous material obtained in step S2 is then immersed in the solution for 12 h. 120 mg of sodium borohydride is then dissolved in 4 mL of water. The sodium borohydride solution is added dropwise to the solution impregnated with the aerogel porous material for liquid-phase reduction. After the liquid-phase reduction process is completed, the impregnated aerogel porous material is washed three times with deionized water and then dried in a vacuum drying oven at 60 °C for 10 h to obtain the M-loaded aerogel porous material, denoted as M / aerogel porous material.

[0029] When the aerogel porous materials are HNTA, KA, MMTA, ZIFA, RGOA, MCCA, CNTA, ZA, and BCA, M is loaded according to step S3 above, and the resulting products are M / HNTA, M / KA, M / MMTA, M / ZIFA, M / RGOA, M / MCCA, M / CNTA, M / ZA, and M / BCA, respectively.

[0030] Preferably, in step S4, the mass-to-volume ratio of AB to tetrahydrofuran is 25:2, and the unit of the mass-to-volume ratio is mg:mL.

[0031] Preferably, in step S4, the loading ratio of AB to the mass ratio of the porous material used in the AB@metal M / aerogel porous material is 0.5-1.5:1.

[0032] Specifically, step S4 is as follows: 25 mg of AB is dissolved in 2 mL of tetrahydrofuran, and then uniformly added dropwise to the M / aerogel porous material. The mixture is then allowed to stand at room temperature for 4 hours. This process is repeated until the AB loading in the M / aerogel porous material reaches 50-150 mg. The resulting sample is dried in a vacuum drying oven at 25°C to obtain the finished AB@M / aerogel porous material.

[0033] When the M / aerogel porous material is M / HNTA, M / KA, M / MMTA, M / ZIFA, M / RGOA, M / MCCA, M / CNTA, M / ZA, or M / BCA, AB is loaded according to step S4 above, and the resulting products are AB@M / HNTA, AB@M / KA, AB@M / MMTA, AB@M / ZIFA, AB@M / RGOA, AB@M / MCCA, AB@M / CNTA, AB@M / ZA, and AB@M / BCA.

[0034] Preferably, after the AB in the AB@metal M / aerogel porous material is completely hydrolyzed, it is dried and then reloaded with AB to obtain a secondary AB-loaded AB@metal M / aerogel porous material; this process can be repeated multiple times to obtain multiple AB-loaded AB@metal M / aerogel porous materials.

[0035] Specifically, in the AB@metal M / aerogel porous material with secondary AB loading, AB is completely hydrolyzed, dried, and then reloaded with AB to obtain the AB@metal M / aerogel porous material with tertiary AB loading; in the AB@metal M / aerogel porous material with tertiary AB loading, AB is completely hydrolyzed, dried, and then reloaded with AB to obtain the AB@metal M / aerogel porous material with quaternary AB loading; ...; in the AB@metal M / aerogel porous material with nth AB loading, AB is completely hydrolyzed, dried, and then reloaded with AB to obtain the AB@metal M / aerogel porous material with n+1th AB loading.

[0036] The specific performance testing process for the AB@metal M / aerogel porous material obtained in this invention in controlling the hydrolysis of hydrogen from ammonia borane is as follows:

[0037] AB@M / HNTA, AB@M / KA, AB@M / MMTA, AB@M / ZIFA, AB@M / RGOA, AB@M / MCCA, AB@M / CNTA, AB@M / ZA, and AB@M / BCA were placed in three-necked flasks, and the generated hydrogen gas was measured using the water displacement method. 10, 15, and 20 μL of water were added to the sample each time, and the hydrogen gas generated was measured each time, until the AB loaded on the sample was completely hydrolyzed.

[0038] The AB@metal M / aerogel porous material obtained by the present invention can be reloaded with AB after its AB is completely hydrolyzed, so that it can be repeatedly recycled. Moreover, the hydrogen release process of the recycled AB@metal M / aerogel porous material can also be controlled by controlling the amount of water added.

[0039] The specific performance tests for the controlled hydrogen release through recycling are as follows:

[0040] 1) The sample processing method was as follows: After the AB was completely hydrolyzed, AB@M / HNTA, AB@M / KA, AB@M / MMTA, AB@M / ZIFA, AB@M / RGOA, AB@M / MCCA, AB@M / CNTA, AB@M / ZA, and AB@M / BCA were dried in a vacuum drying oven at 60℃. Then, 100mg of AB was dissolved in tetrahydrofuran and added dropwise to the sample to obtain AB@M / HNTA, AB@M / KA, AB@M / MMTA, AB@M / ZIFA, AB@M / RGOA, AB@M / MCCA, AB@M / CNTA, AB@M / ZA, and AB@M / BCA.

[0041] 2) Place AB@M / HNTA, AB@M / KA, AB@M / MMTA, AB@M / ZIFA, AB@M / RGOA, AB@M / MCCA, AB@M / CNTA, AB@M / ZA, and AB@M / BCA into a three-necked flask and measure the generated hydrogen gas using the water displacement method. Add 15 μL of water to the sample each time, and then measure the hydrogen gas generated each time until the AB loaded on the sample is completely hydrolyzed.

[0042] 3) By repeating the above process, AB@metal M / aerogel porous materials loaded with AB can be obtained multiple times, which can be used to control the controlled hydrogen release of AB.

[0043] like Figure 10 The diagram shown is a schematic representation of the application of the AB@metal M / aerogel porous material of the present invention.

[0044] The solid-phase system obtained by this invention can be applied to vehicle-mounted energy devices, and has the characteristics of being easy to install in vehicles, simple to operate, and easy to control the process.

[0045] Mechanism of action:

[0046] Aerogel porous materials possess abundant pore structures and a large specific surface area, providing ample encapsulation space for AB molecules, which can be encapsulated within the aerogel porous material through hydrogen bonding. Simultaneously, metal nanoparticle catalysts can be deposited on the surface of the aerogel porous material. The hydrogen desorption process of AB in the solid-phase system can be controlled by adjusting the amount of water added to the AB@metal / aerogel porous material.

[0047] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0048] This invention features a simple process and convenient operation. The catalyst is loaded onto an aerogel porous material (such as halloysite nanotubes, kaolin, montmorillonite, ZIF-8, reduced graphene oxide, microcrystalline cellulose, carbon nanotubes, molecular sieves, and biomass carbon). Due to the aerogel porous material's specific solid morphology, high porosity, and pore volume, AB can be encapsulated within it through hydrogen bonding. The hydrogen release process of AB is controlled by adjusting the amount of water added to AB@metal M / aerogel porous material. This solid-phase system-controlled hydrogen release method solves the problem of difficult-to-control liquid-phase hydrogen release processes and can be applied to vehicle-mounted energy devices, featuring easy vehicle mounting, simple operation, and easy process control. Attached Figure Description

[0049] Figure 1 The images show the morphology and SEM characterization of the relevant products obtained in Example 1 of this invention.

[0050] Figure 2This is a TEM image of AB@Co / HNTA from Embodiment 1 of the present invention;

[0051] Figure 3 The FTIR and XRD patterns of the relevant products obtained in Example 1 of this invention are shown.

[0052] Figure 4 The different hydrogen production performances of AB@Co / HNTA in Example 1 of this invention;

[0053] Figure 5 The images show the morphology and SEM characterization of the products obtained in Examples 2-3 and 5-6 of this invention.

[0054] Figure 6 The XRD patterns are of the relevant products obtained in Examples 2-3 and 5-6 of this invention.

[0055] Figure 7 The FTIR spectra of the relevant products obtained in Examples 2-3 and 5-6 of this invention are shown below.

[0056] Figure 8 The controllable hydrogen production performance of AB@Co / MMTA in Example 3, AB@Co / RGOA in Example 5, AB@Co / MCCA in Example 6, and AB@Co / KA in Example 2 of this invention (20 μL of water added each time);

[0057] Figure 9 The controllable hydrogen production performance of AB@Co / ZIFA in Example 4, AB@Cu / KA in Example 10, AB@NiCo / HNTA in Example 11, and AB@Pt / RGOA in Example 12 of this invention (20 μL of water added each time);

[0058] Figure 10 This is a schematic diagram illustrating the application of the AB@metal M / aerogel porous material of the present invention. Detailed Implementation

[0059] The present invention will be further described below with reference to specific embodiments. The illustrative embodiments and descriptions herein are used to explain the present invention, but are not intended to limit the present invention.

[0060] All raw materials used in this invention are not particularly restricted in their source and can be purchased from the market or prepared using conventional methods known to those skilled in the art.

[0061] The devices involved in this invention are not particularly limited to those commonly used in the field, and their operation and usage are well known to those skilled in the art.

[0062] The present invention will be further described below with reference to specific embodiments. The illustrative embodiments and descriptions herein are used to explain the present invention, but are not intended to limit the present invention.

[0063] The silica sol used in the following examples is obtained by hydrolyzing tetraethyl orthosilicate. The specific steps are as follows: Tetraethyl orthosilicate, ethanol and water are mixed in a volume ratio of 5:3:92. 10 mg of oxalic acid is added to every 50 mL of solution. The mixture is then stirred for 6-8 hours until the solution becomes clear and transparent to obtain silica sol.

[0064] Example 1

[0065] A method for controlling the hydrogen desorption of ammonia borane by hydrolysis in a solid-phase system, wherein the amount of hydrogen desorption by AB is controlled by controlling the amount of water added to the solid-phase system.

[0066] The preparation method of the solid-phase system includes the following steps:

[0067] 1) Sample processing method is as follows:

[0068] S10. Add 100 mg HNT to 5 mL of hydrolyzed silica sol, then add 50 mg of chopped silica fiber to the slurry and stir for at least 1 hour until the slurry is evenly dispersed. After even dispersion, add 50 mg of sodium alginate to the slurry and stir again until the sodium alginate is completely dissolved. Then pour the slurry into a mold and freeze it unidirectionally using liquid nitrogen. After freezing, place the sample in a freeze dryer and dry for 2-3 days to obtain HNT aerogel, denoted as HNTA.

[0069] S20. Dissolve 40 mg of cobalt chloride hexahydrate in 20 mL of water, then immerse the sample from step two in the solution for 12 h. Next, dissolve 120 mg of sodium borohydride in 4 mL of water and add the sodium borohydride solution dropwise to the solution used to immerse the sample from step two. After the reduction process is complete, wash the aerogel three times with deionized water and then dry it in a vacuum drying oven at 60 °C for 10 h to obtain HNT aerogel loaded with metallic cobalt, denoted as Co / HNTA.

[0070] S30. Dissolve 25 mg of AB in 2 mL of tetrahydrofuran, and add it dropwise evenly to the sample obtained in step three. Then let it stand at room temperature for 4 hours. Repeat this process three times until the AB loading in the aerogel is 100 mg. Dry the obtained sample in a vacuum drying oven at 25 °C to obtain the finished product, denoted as AB@Co / HNTA.

[0071] 2) Performance Testing:

[0072] AB@Co / HNTA was placed in a three-necked flask, and the generated hydrogen gas was measured using the water displacement method. 10, 15, and 20 μL of water were added to the sample at different times, and the hydrogen gas generated each time was measured until the AB loaded on the sample was completely hydrolyzed. This test evaluated the controllable hydrolysis hydrogen production performance of the AB@Co / HNTA solid-phase system.

[0073] 3) Reuse performance test:

[0074] After complete hydrolysis of AB, AB@Co / HNTA was dried in a vacuum drying oven at 60℃. Then, 100 mg of AB was dissolved in tetrahydrofuran and added dropwise to the sample to obtain AB@Co / HNTA with secondary AB loading. The AB@Co / HNTA was placed in a three-necked flask, and the generated hydrogen gas was measured using the water displacement method. 15 μL of water was added to the sample each time, and the hydrogen gas generated was measured each time until the AB loaded on the sample was completely hydrolyzed. By repeating the above process, AB@Co / HNTA with multiple AB loadings can be obtained and used for controlled hydrogen release.

[0075] like Figure 1 As shown, Figure 1 a is a physical image of AB@Co / HNTA from Example 1; Figure 1 b is a SEM image of the cross-section of Co / HNTA in Example 1; Figure 1 c is a SEM image of the longitudinal section of Co / HNTA in Example 1; Figure 1 d is a SEM image of the cross-section of AB@Co / HNTA in Example 1; Figure 1 e is a SEM image of the longitudinal section of AB@Co / HNTA in Example 1; Figure 1 f is a high-magnification SEM image of AB@Co / HNTA from Example 1.

[0076] Figure 1 Photo a shows AB@Co / HNTA placed on the stamen of a flower. It can be seen that the sample is extremely light; its density was calculated to be 0.132 g / cm³. -3 . Figure 1 b shows the regular interlayer structure of Co / HNTA in cross-section, with an interlayer spacing of 60 μm. Figure 1 c shows the densely distributed pore structure in the longitudinal section of Co / HNTA. Figure 1 Figures d and e show the cross-sectional and longitudinal structures of AB@Co / HNTA, revealing that AB fills the pores of Co / HNTA. Figure 1 f shows HNTs on AB@Co / HNTA. As can be seen from the figure, the nanotube structure of HNTs is well preserved, with tube lengths of 0.2-1 μm, outer diameters of 40-60 nm, and inner diameters of 15-20 nm. Furthermore, the surface of HNTs is coated with a layer of AB.

[0077] TEM testing was performed on the Co / HNTA from Example 1, and the results are as follows: Figure 2 As shown, uniformly distributed metal particles can be seen on HNT. The inset shows that the lattice fringe spacing of the metal particles is 0.216 nm, which corresponds to the (100) crystal plane of cobalt, confirming that cobalt was successfully loaded onto the aerogel.

[0078] FTIR and XRD analyses were performed on HNTA, Co / HNTA, and AB@Co / HNTA obtained in Example 1, as well as AB. The results are as follows: Figure 3 As shown. Figure 3 As can be seen from graph a, the infrared spectra of Co / HNTA, AB@Co / HNTA, and AB are located at 910 cm⁻¹. -1 The absorption peak at 532 cm⁻¹ is attributed to the stretching and bending vibrations of Al-OH. -1 and 753cm -1 The absorption peak at the point is attributed to the bending vibration of Si-O and the vertical stretching of Si-O-Al. The HNT characteristic peaks of the three samples remained unchanged, indicating that the HNT structure was well preserved. At the same time, the NH, BH and BN bonds on the FTIR lines of AB@Co / HNTA correspond to those on AB, indicating that AB was successfully loaded onto the HNT aerogel.

[0079] Figure 3 In b, the peaks corresponding to HNT in the standard card PDF#29-1487 are: 11.79°, 20.07°, and 24.5°. (From...) Figure 3 As shown in b, the XRD patterns of HNTA, Co / HNTA, and AB@Co / HNTA correspond well to these standard cards. Furthermore, the characteristic peaks of AB correspond to those of AB@Co / HNTA, further demonstrating that AB was successfully loaded onto the HNT aerogel.

[0080] Analysis of the controlled hydrolysis hydrogen production performance of AB@Co / HNTA in Example 1 is as follows: Figure 4 As shown, Figure 4 Add 10 μL of water each time. Figure 4 b. Add 15 μL of water each time. Figure 4 c. Add 20 μL of water each time. Figure 4 Schematic diagram of hydrogen production cycle after multiple loadings (15 μL of water added each time).

[0081] like Figure 4 As shown in a, the hydrolysis of AB@Co / HNTA can be controlled stepwise by adding 10 μL of water in stages, while maintaining a consistent amount of hydrogen produced in each hydrolysis. Figure 4 b and Figure 4 c demonstrates the controlled hydrolysis performance of AB by stepwise addition of 15 μL and 20 μL of water. Figure 4Figure d demonstrates the controlled hydrogen release performance of the solid-phase system in AB@Co / HNTA after complete hydrolysis of AB and repeated encapsulation of AB. From Figure 4 As can be seen from d, after AB undergoes complete hydrolysis of hydrogen in the solid-phase system, the aerogel can still repeatedly encapsulate AB, and the amount of hydrogen production can be controlled again by adjusting the amount of water added. Meanwhile, from... Figure 4 As can be seen from d, the AB loading and controllable hydrogen production performance of the sample can be maintained.

[0082] Example 2

[0083] A method for controlling the hydrogen desorption of ammonia borane by hydrolysis in a solid-phase system, wherein the amount of hydrogen desorption by AB is controlled by controlling the amount of water added to the solid-phase system.

[0084] The preparation method of the solid-phase system includes the following steps:

[0085] The basic content (process and conditions) of this embodiment is the same as S10, S20, and S30 in Example 1, except that: in the aerogel preparation process S10, kaolin is used in place of HNT as the aerogel filler at the same mass. Other synthesis steps are the same as S10, S20, and S30 in Example 1. The specific steps are as follows: 100 mg of kaolin is added to 5 mL of hydrolyzed silica sol, and then 50 mg of shredded silica fiber is added to the above slurry. The mixture is stirred for more than 1 hour until the slurry is evenly dispersed. After even dispersion, 50 mg of sodium alginate is added to the slurry, and the mixture is stirred again until the sodium alginate is completely dissolved. The slurry is then poured into a mold, and the slurry is unidirectionally frozen using liquid nitrogen. The frozen sample is then placed in a freeze dryer and dried for 2-3 days to obtain kaolin aerogel, denoted as KA. 40 mg of cobalt chloride hexahydrate was dissolved in 20 mL of water, and KA was immersed in the solution for 12 h. Then, 120 mg of sodium borohydride was dissolved in 4 mL of water, and the sodium borohydride solution was added dropwise to the solution impregnated with KA. After the reduction process, the aerogel was washed three times with deionized water and dried in a vacuum drying oven at 60 °C for 10 h to obtain a kaolin aerogel loaded with metallic cobalt, denoted as Co / KA. 25 mg of AB was dissolved in 2 mL of tetrahydrofuran and added dropwise evenly to Co / KA, and then allowed to stand at room temperature for 4 h. This process was repeated three times until the AB loading in the aerogel reached 100 mg. The obtained sample was dried in a vacuum drying oven at 25 °C to obtain the finished product, denoted as AB@Co / KA.

[0086] The solid-phase system obtained in this embodiment was tested using the same performance tests and reuse performance tests as in Example 1.

[0087] Example 3

[0088] A method for controlling the hydrogen desorption of ammonia borane by hydrolysis in a solid-phase system, wherein the amount of hydrogen desorption by AB is controlled by controlling the amount of water added to the solid-phase system.

[0089] The preparation method of the solid-phase system includes the following steps:

[0090] The basic content (process and conditions) of this embodiment are the same as S10, S20, and S30 in Example 1, except that montmorillonite (MMT) is used in S10 of the aerogel preparation process instead of HNT as the aerogel filler. Other synthesis steps are the same as S10, S20, and S30 in Example 1. Specifically, 100 mg of MMT is added to 5 mL of hydrolyzed silica sol, and then 50 mg of chopped silica fiber is added to the slurry. The mixture is stirred for at least 1 hour until the slurry is evenly dispersed. After even dispersion, 50 mg of sodium alginate is added to the slurry, and the mixture is stirred again until the sodium alginate is completely dissolved. The slurry is then poured into a mold, and unidirectionally frozen using liquid nitrogen. The frozen sample is then placed in a freeze dryer and dried for 2-3 days to obtain MMT aerogel, denoted as MMTA. 40 mg of cobalt chloride hexahydrate was dissolved in 20 mL of water, and MMTA was immersed in the solution for 12 h. Then, 120 mg of sodium borohydride was dissolved in 4 mL of water, and the sodium borohydride solution was added dropwise to the MMTA-impregnated solution. After the reduction process, the aerogel was washed three times with deionized water and dried in a vacuum drying oven at 60 °C for 10 h to obtain cobalt-loaded MMT aerogel, denoted as Co / MMTA. 25 mg of AB was dissolved in 2 mL of tetrahydrofuran and uniformly added dropwise to Co / MMTA, and then allowed to stand at room temperature for 4 h. This process was repeated three times until the AB loading in the aerogel was 100 mg. The obtained sample was dried in a vacuum drying oven at 25 °C to obtain the final product, denoted as AB@Co / MMTA.

[0091] The solid-phase system obtained in this embodiment was tested using the same performance tests and reuse performance tests as in Example 1.

[0092] Example 4

[0093] A method for controlling the hydrogen desorption of ammonia borane by hydrolysis in a solid-phase system, wherein the amount of hydrogen desorption by AB is controlled by controlling the amount of water added to the solid-phase system.

[0094] The preparation method of the solid-phase system includes the following steps:

[0095] The basic content (process and conditions) of this embodiment are the same as S10, S20, and S30 in Example 1, except that ZIF-8 is used instead of HNT as the aerogel filler in the aerogel preparation process S10. Other synthesis steps are the same as S10, S20, and S30 in Example 1. Specifically, 20 mg of ZIF-8 is added to 5 mL of hydrolyzed silica sol, and then 50 mg of chopped silica fiber is added to the slurry. The mixture is stirred for at least 1 hour until the slurry is evenly dispersed. After even dispersion, 50 mg of sodium alginate is added to the slurry, and the mixture is stirred again until the sodium alginate is completely dissolved. The slurry is then poured into a mold, and unidirectionally frozen using liquid nitrogen. The frozen sample is then dried in a freeze dryer for 2-3 days to obtain ZIF-8 aerogel, denoted as ZIFA. 40 mg of cobalt chloride hexahydrate was dissolved in 20 mL of water, and ZIFA was immersed in the solution for 12 h. Then, 120 mg of sodium borohydride was dissolved in 4 mL of water, and the sodium borohydride solution was added dropwise to the ZIFA impregnation solution. After the reduction process, the aerogel was washed three times with deionized water and dried in a vacuum drying oven at 60 °C for 10 h to obtain cobalt-loaded ZIF-8 aerogel, denoted as Co / ZIFA. 25 mg of AB was dissolved in 2 mL of tetrahydrofuran and uniformly added dropwise to Co / ZIFA, and then allowed to stand at room temperature for 4 h. This process was repeated three times until the AB loading in the aerogel reached 100 mg. The obtained sample was dried in a vacuum drying oven at 25 °C to obtain the finished product, denoted as AB@Co / ZIFA.

[0096] The solid-phase system obtained in this embodiment was tested using the same performance tests and reuse performance tests as in Example 1.

[0097] like Figure 9 As shown in Figure a, the hydrolysis of AB@Co / ZIFA can be controlled by adding 20 μL of water dropwise in stages, while maintaining a consistent amount of hydrogen produced in each hydrolysis.

[0098] Example 5

[0099] A method for controlling the hydrogen desorption of ammonia borane by hydrolysis in a solid-phase system, wherein the amount of hydrogen desorption by AB is controlled by controlling the amount of water added to the solid-phase system.

[0100] The preparation method of the solid-phase system includes the following steps:

[0101] The basic content (process and conditions) of this embodiment are the same as S10, S20, and S30 in Example 1, except that reduced graphene oxide (RGO) is used instead of HNT as the aerogel filler in the aerogel preparation process S10. Other synthesis steps are the same as S10, S20, and S30 in Example 1. Specifically, 20 mg of RGO is added to 5 mL of hydrolyzed silica sol, and then 50 mg of shredded silica fiber is added to the slurry. The mixture is stirred for at least 1 hour until the slurry is evenly dispersed. After even dispersion, 50 mg of sodium alginate is added to the slurry, and the mixture is stirred again until the sodium alginate is completely dissolved. The slurry is then poured into a mold, and unidirectionally frozen using liquid nitrogen. The frozen sample is then dried in a freeze dryer for 2-3 days to obtain RGO aerogel, denoted as RGOA. 40 mg of cobalt chloride hexahydrate was dissolved in 20 mL of water, and RGOA was immersed in the solution for 12 h. Then, 120 mg of sodium borohydride was dissolved in 4 mL of water, and the sodium borohydride solution was added dropwise to the RGOA-impregnated solution. After the reduction process, the aerogel was washed three times with deionized water and dried in a vacuum drying oven at 60 °C for 10 h to obtain cobalt-loaded RGO aerogel, denoted as Co / RGOA. 25 mg of AB was dissolved in 2 mL of tetrahydrofuran and uniformly added dropwise to Co / RGOA, and then allowed to stand at room temperature for 4 h. This process was repeated three times until the AB loading in the aerogel reached 100 mg. The obtained sample was dried in a vacuum drying oven at 25 °C to obtain the finished product, denoted as AB@Co / RGOA.

[0102] The solid-phase system obtained in this embodiment was tested using the same performance tests and reuse performance tests as in Example 1.

[0103] Example 6

[0104] A method for controlling the hydrogen desorption of ammonia borane by hydrolysis in a solid-phase system, wherein the amount of hydrogen desorption by AB is controlled by controlling the amount of water added to the solid-phase system.

[0105] The preparation method of the solid-phase system includes the following steps:

[0106] The basic content (process and conditions) of this embodiment are the same as S10, S20, and S30 in Example 1, except that microcrystalline cellulose (MCC) is used instead of HNT as the aerogel filler in the aerogel preparation process S10. Other synthesis steps are the same as S10, S20, and S30 in Example 1. Specifically, 100 mg of MCC is added to 5 mL of hydrolyzed silica sol, and then 50 mg of chopped silica fiber is added to the slurry. The mixture is stirred for at least 1 hour until the slurry is evenly dispersed. After even dispersion, 50 mg of sodium alginate is added to the slurry, and the mixture is stirred again until the sodium alginate is completely dissolved. The slurry is then poured into a mold, and unidirectionally frozen using liquid nitrogen. The frozen sample is then dried in a freeze dryer for 2-3 days to obtain MCC aerogel, denoted as MCCA. 40 mg of cobalt chloride hexahydrate was dissolved in 20 mL of water, and MCCA was immersed in the solution for 12 h. Then, 120 mg of sodium borohydride was dissolved in 4 mL of water, and the sodium borohydride solution was added dropwise to the solution used to impregnate MCCA. After the reduction process, the aerogel was washed three times with deionized water and then dried in a vacuum drying oven at 60 °C for 10 h to obtain a cobalt-loaded MCC aerogel, denoted as Co / MCCA. 25 mg of AB was dissolved in 2 mL of tetrahydrofuran and uniformly added dropwise to Co / MCCA, and then allowed to stand at room temperature for 4 h. This process was repeated three times until the AB loading in the aerogel reached 100 mg. The obtained sample was dried in a vacuum drying oven at 25 °C to obtain the final product, denoted as AB@Co / MCCA.

[0107] The solid-phase system obtained in this embodiment was tested using the same performance tests and reuse performance tests as in Example 1.

[0108] like Figure 5 As shown, Figure 5 a is a physical image of MMTA from Example 3, RGOA from Example 5, MCCA from Example 6, and KA from Example 2; Figure 5 b is the SEM image of MMTA in Example 3; Figure 5 c is the SEM image of RGOA in Example 5; Figure 5 d is the SEM image of KA in Example 2. Figure 5 From top to bottom, the aerogels are MMTA, RGOA, MCCA and KA aerogels. It can be seen that the aerogels have complete morphology and no collapse or shrinkage occurs. Figure 5 b- Figure 5 d shows the interlayer structure of MMTA, RGOA, and KA respectively, and it can be seen that Figure 5 The interlayer spacing of MMTA in b is approximately 60-80 μm. Figure 5 The interlayer spacing of RGOA in c is approximately 10-50 μm. Figure 5In addition to the macropores of the aerogel itself, KA also contains a dense network of micropores on the aerogel framework. This multi-scale porosity can greatly increase the loading capacity of AB and make it uniformly dispersed.

[0109] like Figure 6 As shown, Figure 6 a is the XRD pattern of MMTA, AB@Co / MMTA, and AB in Example 3. Figure 6 b is the XRD pattern of RGOA, AB@Co / RGOA, and AB in Example 5. Figure 6 c shows the XRD patterns of MCCA, AB@Co / MCCA, and AB in Example 6. Figure 6 d represents the XRD patterns of KA, AB@Co / KA, and AB in Example 2. Figure 6 a to Figure 6 The aerogel filling materials for d are MMTA, RGOA, MCCA and KA. Figure 6 The characteristic peaks of AB in a correspond to the characteristic peaks of AB@metal M / aerogel porous material. At the same time, no characteristic peaks of AB were found in the XRD pattern of the original aerogel, indicating that AB was successfully loaded onto HNT aerogel.

[0110] like Figure 7 As shown, Figure 7 a is the FTIR plot of MMTA, AB@Co / MMTA, and AB in Example 3. Figure 7 b is the FTIR plot of RGOA, AB@Co / RGOA, and AB in Example 5. Figure 7 c is the FTIR plot of MCCA, AB@Co / MCCA, and AB in Example 6. Figure 7 d is the FTIR plot of KA, AB@Co / KA, and AB in Example 2. Figure 7 a to Figure 7 The aerogel filling materials for d are MMTA, RGOA, MCCA, and KA, respectively. Figure 7 As can be seen from the data, the NH, BH and BN bonds on the FTIR lines of the AB@metal M / aerogel porous material correspond to those on the AB. At the same time, no characteristic peaks of AB were found in the XRD pattern of the original aerogel porous material, indicating that AB was successfully loaded onto the HNT aerogel.

[0111] like Figure 8 As shown, Figure 8 As shown in Figure a, the hydrolysis of AB@Co / MMTA can be controlled stepwise by adding 20 μL of water in stages, while maintaining a consistent amount of hydrogen produced in each hydrolysis. Figure 8 As shown in b, the hydrolysis of AB@Co / RGOA can be controlled stepwise by adding 20 μL of water in stages, while maintaining a consistent amount of hydrogen produced in each hydrolysis. Figure 8As shown in Figure c, the hydrolysis of AB@Co / MCCA can be controlled stepwise by adding 20 μL of water in stages, while maintaining a consistent amount of hydrogen produced in each hydrolysis. Figure 8 As shown in d, the hydrolysis of AB@Co / KA can be controlled to proceed in steps by adding 20 μL of water in stages, while maintaining a consistent amount of hydrogen produced in each hydrolysis.

[0112] The solid-phase system obtained in this embodiment was tested using the same performance tests and reuse performance tests as in Example 1.

[0113] Example 7

[0114] A method for controlling the hydrogen desorption of ammonia borane by hydrolysis in a solid-phase system, wherein the amount of hydrogen desorption by AB is controlled by controlling the amount of water added to the solid-phase system.

[0115] The preparation method of the solid-phase system includes the following steps:

[0116] The basic content (process and conditions) of this embodiment are the same as S10, S20, and S30 in Example 1, except that carbon nanotubes (CNTs) are used instead of HNTs as aerogel filler in the aerogel preparation process S10. Other synthesis steps are the same as S10, S20, and S30 in Example 1. Specifically, 100 mg of CNTs are added to 5 mL of hydrolyzed silica sol, and then 50 mg of shredded silica fibers are added to the slurry. The mixture is stirred for at least 1 hour until the slurry is evenly dispersed. After even dispersion, 50 mg of sodium alginate is added to the slurry, and the mixture is stirred again until the sodium alginate is completely dissolved. The slurry is then poured into a mold, and unidirectionally frozen using liquid nitrogen. The frozen sample is then dried in a freeze dryer for 2-3 days to obtain CNT aerogel, denoted as CNTA. 40 mg of cobalt chloride hexahydrate was dissolved in 20 mL of water, and CNTA was immersed in the solution for 12 h. Then, 120 mg of sodium borohydride was dissolved in 4 mL of water, and the sodium borohydride solution was added dropwise to the CNTA-impregnated solution. After the reduction process, the aerogel was washed three times with deionized water and dried in a vacuum drying oven at 60 °C for 10 h to obtain a cobalt-loaded CNT aerogel, denoted as Co / CNTA. 25 mg of AB was dissolved in 2 mL of tetrahydrofuran and uniformly added dropwise to Co / CNTA, and then allowed to stand at room temperature for 4 h. This process was repeated three times until the AB loading in the aerogel reached 100 mg. The obtained sample was dried in a vacuum drying oven at 25 °C to obtain the finished product, denoted as AB@Co / CNTA.

[0117] The solid-phase system obtained in this embodiment was tested using the same performance tests and reuse performance tests as in Example 1.

[0118] Example 8

[0119] A method for controlling the hydrogen desorption of ammonia borane by hydrolysis in a solid-phase system, wherein the amount of hydrogen desorption by AB is controlled by controlling the amount of water added to the solid-phase system.

[0120] The preparation method of the solid-phase system includes the following steps:

[0121] The basic content (process and conditions) of this embodiment are the same as S10, S20, and S30 in Example 1, except that zeolite is used instead of HNT as the aerogel filler in the aerogel preparation process S10. Other synthesis steps are the same as S10, S20, and S30 in Example 1. Specifically, 100 mg of zeolite is added to 5 mL of hydrolyzed silica sol, and then 50 mg of chopped silica fiber is added to the slurry. The mixture is stirred for at least 1 hour until the slurry is evenly dispersed. After even dispersion, 50 mg of sodium alginate is added to the slurry, and the mixture is stirred again until the sodium alginate is completely dissolved. The slurry is then poured into a mold, and unidirectionally frozen using liquid nitrogen. The frozen sample is then dried in a freeze dryer for 2-3 days to obtain zeolite aerogel, denoted as ZA. 40 mg of cobalt chloride hexahydrate was dissolved in 20 mL of water, and ZA was immersed in the solution for 12 h. Then, 120 mg of sodium borohydride was dissolved in 4 mL of water, and the sodium borohydride solution was added dropwise to the ZA-impregnated solution. After the reduction process, the aerogel was washed three times with deionized water and dried in a vacuum drying oven at 60 °C for 10 h to obtain a cobalt-loaded zeolite aerogel, denoted as Co / ZA. 25 mg of AB was dissolved in 2 mL of tetrahydrofuran and uniformly added dropwise to Co / ZA, and then allowed to stand at room temperature for 4 h. This process was repeated three times until the AB loading in the aerogel reached 100 mg. The obtained sample was dried in a vacuum drying oven at 25 °C to obtain the finished product, denoted as AB@Co / ZA.

[0122] The solid-phase system obtained in this embodiment was tested using the same performance tests and reuse performance tests as in Example 1.

[0123] Example 9

[0124] A method for controlling the hydrogen desorption of ammonia borane by hydrolysis in a solid-phase system, wherein the amount of hydrogen desorption by AB is controlled by controlling the amount of water added to the solid-phase system.

[0125] The preparation method of the solid-phase system includes the following steps:

[0126] The basic content (process and conditions) of this embodiment are the same as S10, S20, and S30 in Example 1, except that: in the aerogel preparation process S10, biomass carbon is used in place of HNT as the aerogel filler at the same mass. Other synthesis steps are the same as S10, S20, and S30 in Example 1. The specific steps are as follows: 100 mg of biomass carbon is added to 5 mL of hydrolyzed silica sol, and then 50 mg of chopped silica fiber is added to the above slurry. The mixture is stirred for more than 1 hour until the slurry is evenly dispersed. After even dispersion, 50 mg of sodium alginate is added to the slurry, and the mixture is stirred again until the sodium alginate is completely dissolved. The slurry is then poured into a mold, and the slurry is unidirectionally frozen using liquid nitrogen. The frozen sample is then placed in a freeze dryer and dried for 2-3 days to obtain biomass carbon aerogel, denoted as BCA. 40 mg of cobalt chloride hexahydrate was dissolved in 20 mL of water, and BCA was immersed in the solution for 12 h. Then, 120 mg of sodium borohydride was dissolved in 4 mL of water, and the sodium borohydride solution was added dropwise to the solution used to impregnate BCA. After the reduction process, the aerogel was washed three times with deionized water and then dried in a vacuum drying oven at 60 °C for 10 h to obtain a cobalt-loaded biomass carbon aerogel, denoted as Co / BCA. 25 mg of AB was dissolved in 2 mL of tetrahydrofuran and uniformly added dropwise to Co / BCA, and then allowed to stand at room temperature for 4 h. This process was repeated three times until the AB loading in the aerogel reached 100 mg. The obtained sample was dried in a vacuum drying oven at 25 °C to obtain the finished product, denoted as AB@Co / BCA.

[0127] The solid-phase system obtained in this embodiment was tested using the same performance tests and reuse performance tests as in Example 1.

[0128] Example 10

[0129] A method for controlling the hydrogen desorption of ammonia borane by hydrolysis in a solid-phase system, wherein the amount of hydrogen desorption by AB is controlled by controlling the amount of water added to the solid-phase system.

[0130] The preparation method of the solid-phase system includes the following steps:

[0131] The basic content (process and conditions) of this embodiment are the same as S10, S20, and S30 in Example 1, except that: in the aerogel preparation process S10, an equal mass of kaolin is used instead of HNT as the aerogel filler; in the metal loading process S20, copper sulfate pentahydrate is used instead of cobalt chloride hexahydrate; other synthesis steps are the same as S10, S20, and S30 in Example 1. The specific steps are as follows: 100 mg of kaolin is added to 5 mL of hydrolyzed silica sol, and then 50 mg of shredded silica fiber is added to the above slurry. The mixture is stirred for more than 1 hour until the slurry is evenly dispersed. After even dispersion, 50 mg of sodium alginate is added to the slurry, and the mixture is stirred again until the sodium alginate is completely dissolved. The slurry is then poured into a mold, and the slurry is unidirectionally frozen using liquid nitrogen. The frozen sample is then placed in a freeze dryer and dried for 2-3 days to obtain kaolin aerogel, denoted as KA. 40 mg of copper sulfate pentahydrate was dissolved in 20 mL of water, and KA was immersed in the solution for 12 h. Then, 120 mg of sodium borohydride was dissolved in 4 mL of water, and the sodium borohydride solution was added dropwise to the solution impregnated with KA. After the reduction process, the aerogel was washed three times with deionized water and dried in a vacuum drying oven at 60 °C for 10 h to obtain a kaolin aerogel loaded with metallic Cu, denoted as Cu / KA. 25 mg of AB was dissolved in 2 mL of tetrahydrofuran and uniformly added dropwise to Cu / KA, and then allowed to stand at room temperature for 4 h. This process was repeated three times until the AB loading in the aerogel reached 100 mg. The obtained sample was dried in a vacuum drying oven at 25 °C to obtain the finished product, denoted as AB@Cu / KA.

[0132] The solid-phase system obtained in this embodiment was tested using the same performance tests and reuse performance tests as in Example 1.

[0133] like Figure 9 As shown in b, the hydrolysis of AB@Cu / KA can be controlled to proceed in steps by adding 20 μL of water in stages, while maintaining a consistent amount of hydrogen produced in each hydrolysis.

[0134] Example 11

[0135] A method for controlling the hydrogen desorption of ammonia borane by hydrolysis in a solid-phase system, wherein the amount of hydrogen desorption by AB is controlled by controlling the amount of water added to the solid-phase system.

[0136] The preparation method of the solid-phase system includes the following steps:

[0137] The basic content (process and conditions) of this embodiment are the same as S10, S20, and S30 in Example 1, except that nickel nitrate hexahydrate and cobalt chloride hexahydrate are used instead of cobalt chloride hexahydrate alone in the metal loading process S20. Other synthesis steps are the same as S10, S20, and S30 in Example 1. Specifically, 100 mg of HNT is added to 5 mL of hydrolyzed silica sol, and then 50 mg of shredded silica fiber is added to the slurry. The mixture is stirred for at least 1 hour until the slurry is evenly dispersed. After even dispersion, 50 mg of sodium alginate is added to the slurry, and the mixture is stirred again until the sodium alginate is completely dissolved. The slurry is then poured into a mold, and unidirectionally frozen using liquid nitrogen. The frozen sample is then dried in a freeze dryer for 2-3 days to obtain HNT aerogel, denoted as HNTA. 20 mg of nickel nitrate hexahydrate and 20 mg of cobalt chloride hexahydrate were dissolved in 20 mL of water. HNTA was then immersed in the solution for 12 h. Next, 120 mg of sodium borohydride was dissolved in 4 mL of water, and the sodium borohydride solution was added dropwise to the HNTA-impregnated solution. After the reduction process, the aerogel was washed three times with deionized water and dried in a vacuum drying oven at 60 °C for 10 h to obtain NiCo alloy-loaded HNTA, denoted as NiCo / HNTA. 25 mg of AB was dissolved in 2 mL of tetrahydrofuran and uniformly added dropwise to NiCo / HNTA, then allowed to stand at room temperature for 4 h. This process was repeated three times until the AB loading in the aerogel reached 100 mg. The obtained sample was dried in a vacuum drying oven at 25 °C to obtain the final product, denoted as AB@NiCo / HNTA.

[0138] like Figure 9 As shown in c, the hydrolysis of AB@NiCo / HNTA can be controlled by adding 20 μL of water dropwise in stages, while maintaining a consistent amount of hydrogen produced in each hydrolysis.

[0139] Example 12

[0140] A method for controlling the hydrogen desorption of ammonia borane by hydrolysis in a solid-phase system, wherein the amount of hydrogen desorption by AB is controlled by controlling the amount of water added to the solid-phase system.

[0141] The preparation method of the solid-phase system includes the following steps:

[0142] The basic content (process and conditions) of this embodiment are the same as S10, S20, and S30 in Example 1, except that: in the aerogel preparation process S10, reduced graphene oxide (RGO) is used instead of HNT as the aerogel filler; in the metal loading process S20, tetraammineplatinum(II) chloride is used instead of cobalt chloride hexahydrate. Other synthesis steps are the same as S10, S20, and S30 in Example 1. Specifically, 20 mg of HNT is added to 5 mL of hydrolyzed silica sol, and then 50 mg of shredded silica fiber is added to the slurry. The mixture is stirred for more than 1 hour until the slurry is evenly dispersed. After even dispersion, 50 mg of sodium alginate is added to the slurry, and the mixture is stirred again until the sodium alginate is completely dissolved. The slurry is then poured into a mold, and unidirectionally frozen using liquid nitrogen. The frozen sample is then placed in a freeze dryer and dried for 2-3 days to obtain RGO aerogel, denoted as RGOA. 40 mg of tetraammineplatinum(II) chloride was dissolved in 20 mL of water, and HNTA was immersed in the solution for 12 h. Then, 120 mg of sodium borohydride was dissolved in 4 mL of water, and the sodium borohydride solution was added dropwise to the solution impregnated with RGOA. After the reduction process, the aerogel was washed three times with deionized water and dried in a vacuum drying oven at 60 °C for 10 h to obtain Pt-loaded RGOA, denoted as Pt / RGOA. 25 mg of AB was dissolved in 2 mL of tetrahydrofuran and uniformly added dropwise to Pt / RGOA, and then allowed to stand at room temperature for 4 h. This process was repeated three times until the AB loading in the aerogel reached 100 mg. The obtained sample was dried in a vacuum drying oven at 25 °C to obtain the finished product, denoted as AB@Pt / RGOA.

[0143] The solid-phase system obtained in this embodiment was tested using the same performance tests and reuse performance tests as in Example 1.

[0144] like Figure 9 As shown in d, the hydrolysis of AB@Pt / RGOA can be controlled to proceed in steps by adding 20 μL of water in stages, while maintaining a consistent amount of hydrogen produced in each hydrolysis.

[0145] The technical solutions of the present invention are not limited to the specific embodiments described above. Any technical modifications made in accordance with the technical solutions of the present invention fall within the protection scope of the present invention.

Claims

1. A method for controlling the hydrolysis of hydrogen from ammonia borane in a solid-phase system, characterized in that: The solid-phase system is AB@metal M / aerogel porous material; The amount of hydrogen derivation by AB is controlled by controlling the amount of water added to the solid system. The AB@metal M / aerogel porous material is: AB is encapsulated in an aerogel porous material loaded with metal catalyst M; Preparation process of the AB@metal M / aerogel porous material Includes the following steps: S1, hydrolyzed tetraethyl orthosilicate: Tetraethyl orthosilicate, ethanol, and water are mixed, and oxalic acid is added. The mixture is stirred until the solution becomes clear and transparent to obtain silica sol. S2, Preparation of aerogel porous materials: After mixing porous materials, silica sol, and silica fibers, sodium alginate is added and mixed to obtain a slurry. The slurry is then poured into a mold and freeze-dried to obtain an aerogel porous material. S3, loading metal M onto the aerogel porous material: The aerogel porous material was impregnated in an aqueous solution of metal M salt, and then sodium borohydride solution was added for liquid-phase reduction. After liquid-phase reduction, the material is washed and dried to obtain aerogel porous material loaded with metal M, denoted as metal M / aerogel porous material. S4, loading AB onto the metal M / aerogel porous material: AB was dissolved in tetrahydrofuran to obtain a mixed solution; the mixed solution was dropped into a metal M / aerogel porous material and allowed to stand; the above process was repeated several times and then dried to obtain a metal M / aerogel porous material loaded with AB, denoted as AB@metal M / aerogel porous material.

2. The method for controlling the hydrolysis of hydrogen from ammonia borane in a solid-phase system according to claim 1, characterized in that: In step S2, the porous material is one of halloysite nanotubes, kaolin, montmorillonite, 2-methylimidazolium zinc MOF, reduced graphene oxide, microcrystalline cellulose, carbon nanotubes, molecular sieves, and biomass carbon.

3. The method for controlling the hydrolysis of hydrogen from ammonia borane in a solid-phase system according to claim 1, characterized in that: In step S3, the metal M is at least one of Co, Ni, Cu, Ag, Pt, Pd, Ru, and Rh.

4. The method for controlling the hydrolysis of hydrogen from ammonia borane in a solid-phase system according to claim 1, characterized in that: In step S3, the aqueous solution of metal M salt is obtained by dissolving metal M salt and / or metal M salt hydrate in water; The mass ratio of the aerogel porous material to the metal M salt and / or the hydrate of the metal M salt is 100:30-50, based on the mass of the porous material; the mass-volume ratio of the metal M salt and / or the hydrate of the metal M salt to water in the aqueous solution of the metal M salt is 30-50:20, and the unit of the mass-volume ratio is mg:mL.

5. The method for controlling the hydrolysis of hydrogen from ammonia borane in a solid-phase system according to claim 1, characterized in that: The mass ratio of the aerogel porous material to sodium borohydride is 5:6, based on the mass of the porous material.

6. The method for controlling the hydrolysis of hydrogen from ammonia borane in a solid-phase system according to claim 1, characterized in that: In step S4, the mass-to-volume ratio of AB to tetrahydrofuran is 25:2, and the unit of the mass-to-volume ratio is mg:mL.

7. The method for controlling the hydrolysis of hydrogen from ammonia borane in a solid-phase system according to claim 1, characterized in that: In step S4, the loading ratio of AB to the mass ratio of the porous material used in the AB@metal M / aerogel porous material is 0.5-1.5:

1.

8. The method for controlling the hydrolysis of hydrogen from ammonia borane in a solid-phase system according to claim 1, characterized in that: After complete hydrolysis of AB in the AB@metal M / aerogel porous material, it is dried and then reloaded with AB to obtain a secondary AB-loaded AB@metal M / aerogel porous material; this process is repeated multiple times to obtain a multi-loaded AB@metal M / aerogel porous material.

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