CN107930697A - A kind of 67 composite materials of Pt/ZIF for being used to be catalyzed ammonia borane hydrolysis hydrogen manufacturing - Google Patents

Abstract

Translated fromChinese

本发明公开了一种用于催化氨硼烷水解制氢的Pt/ZIF‑67复合材料，由氯铂酸和金属有机框架ZIF‑67混合后，通过一步还原法制备而成。其结构保留了ZIF‑67框架结构，Pt纳米粒子的平均尺寸为1‑2 nm，且分布均匀，经XRD检测无明显的Pt金属衍射特征峰。其制备方法包括：步骤1）ZIF‑67的制备与活化；步骤2）Pt纳米粒子的负载，将活化后的ZIF‑67加入到水中超声分散，然后加入氯铂酸，再滴加NaBH₄水溶液，然后将产物过滤、洗涤后、干燥即可。作为催化氨硼烷水解制氢的应用，反应速率的转化频率值（Turn over frequency，TOF）达到70‑100 mol H₂min^‑1 Pt mol^‑1，活化能为30‑40 kJ mol^‑1。ZIF‑67和Pt纳米粒子的协同作用，带来更好的催化性能，因此，本发明在氢气制备领域具有广阔的应用前景。

The invention discloses a Pt/ZIF-67 composite material for catalyzing the hydrolysis of ammonia borane to produce hydrogen, which is prepared by a one-step reduction method after mixing chloroplatinic acid and metal organic framework ZIF-67. Its structure retains the ZIF-67 framework structure, the average size of Pt nanoparticles is 1-2 nm, and the distribution is uniform, and there is no obvious Pt metal diffraction characteristic peak detected by XRD. The preparation method includes: step 1) preparation and activation of ZIF-67; step 2) loading of Pt nanoparticles, adding activated ZIF-67 to water for ultrasonic dispersion, then adding chloroplatinic acid, and then adding dropwise NaBH₄ aqueous solution , and then the product is filtered, washed and dried. As an application to catalyze the hydrolysis of ammonia borane to produce hydrogen, the reaction rate has a turn over frequency (Turn over frequency, TOF) value of 70‑100 mol H₂ min^‑1 Pt mol^‑1 , and an activation energy of 30‑40 kJ mol^‑1 . The synergistic effect of ZIF-67 and Pt nanoparticles brings better catalytic performance, therefore, the invention has broad application prospects in the field of hydrogen preparation.

Description

Translated fromChinese

一种用于催化氨硼烷水解制氢的Pt/ZIF-67复合材料A Pt/ZIF-67 Composite Catalytic Hydrogen Production from Ammoniaborane

技术领域technical field

本发明属于能源技术领域，具体是一种用于催化氨硼烷水解制氢的Pt/ZIF-67复合材料。The invention belongs to the field of energy technology, in particular to a Pt/ZIF-67 composite material used to catalyze the hydrolysis of ammonia borane to produce hydrogen.

背景技术Background technique

在各种化学储氢材料中，氨硼烷（ammonia borane, NH₃BH₃, AB）具有高达19.6wt％的储氢量，在固态和溶液中具有高稳定性，无毒，溶解性好。因此，它被认为是各种应用中有希望的化学储氢材料之一。储存在氨硼烷中的氢可以利用合适的催化剂通过水解释放出来。迄今为止，已经有各种各样用于催化氨硼烷水解的催化剂，其中贵金属催化剂在水解制氢时表现出快的放氢速率和低的活化能，拥有优异的催化性能。然而，较高的价格限制了其在实际中的生产和应用。为了降低成本，许多研究人员趋向于将贵金属纳米粒子负载在不同的基底（如碳材料，聚合物，金属有机框架）上，不仅可以利用贵金属的高催化活性，而且可以抑制纳米粒子的团聚，进一步提高催化性能。金属有机骨架（Metal organicframeworks, MOFs）也因其独特的高比表面积和孔洞特性以及良好的化学稳定性而备受关注。与其他基底相比，MOFs可以在其框架内控制贵金属纳米粒子的成核和生长，从而防止其团聚。此外，高比表面积和可调孔尺寸的孔洞可以较好地分散贵金属纳米粒子。研究人员发现，将贵金属纳米粒子分散在MOF表面或嵌入MOFs孔中均能提高AB水解的放氢性能。Cai等合成了Ru/MIL-96 催化剂并用于氨硼烷的催化水解，其活化能E_a较高为47.7 kJ mol^-1[Int. J. Hydrogen Energy, 2014, 39, 17129-17135]。Luo等将超细的Pd 纳米粒子固定在MIL-101框架中，并测试了其催化氨硼烷水解的性能，但TOF较低，为45 mol H₂min^-1 Pdmol^-1 [Int. J. Hydrogen Energy, 2014, 39, 4947-4953]。Wang等将AgPd 合金粒子（5-9nm）负载在UIO-66-NH₂上，作为氨硼烷水解制氢的催化剂表现出良好的性能，但主要存在金属纳米粒子团聚的问题[Int. J. Hydrogen Energy, 2016, 41, 944-950]。Among various chemical hydrogen storage materials, ammonia borane (NH₃ BH₃ , AB) has a hydrogen storage capacity as high as 19.6wt%, has high stability in solid state and solution, is non-toxic, and has good solubility. Therefore, it is considered as one of the promising chemical hydrogen storage materials in various applications. The hydrogen stored in ammonia borane can be released by hydrolysis using a suitable catalyst. So far, there have been a variety of catalysts used to catalyze the hydrolysis of ammonia borane, among which noble metal catalysts exhibit fast hydrogen desorption rate and low activation energy during hydrolysis to hydrogen production, and have excellent catalytic performance. However, the high price limits its production and application in practice. In order to reduce the cost, many researchers tend to support noble metal nanoparticles on different substrates (such as carbon materials, polymers, metal organic frameworks), which can not only take advantage of the high catalytic activity of noble metals, but also inhibit the agglomeration of nanoparticles, further Improve catalytic performance. Metal organic frameworks (MOFs) have also attracted much attention due to their unique high specific surface area and porosity properties as well as good chemical stability. Compared with other substrates, MOFs can control the nucleation and growth of noble metal nanoparticles within their framework, thereby preventing their agglomeration. In addition, the pores with high specific surface area and tunable pore size can better disperse noble metal nanoparticles. The researchers found that dispersing noble metal nanoparticles on the surface of MOFs or embedding them in the pores of MOFs can enhance the hydrogen release performance of AB hydrolysis. Cai et al. synthesized Ru/MIL-96 catalyst and used it for the catalytic hydrolysis of ammonia borane, and its activation energy E_a was as high as 47.7 kJ mol^-1 [Int. J. Hydrogen Energy, 2014, 39, 17129-17135]. Luo et al. immobilized ultrafine Pd nanoparticles in the MIL-101 framework and tested its catalytic performance for the hydrolysis of ammonia borane, but the TOF was low at 45 mol H₂ min^-1 Pdmol^-1 [Int. J. Hydrogen Energy, 2014, 39, 4947-4953]. Wang et al. supported AgPd alloy particles (5-9nm) on UIO-66-NH₂ , which showed good performance as a catalyst for hydrogen production from ammonia borane hydrolysis, but there was mainly the problem of metal nanoparticles agglomeration [Int. J. Hydrogen Energy, 2016, 41, 944-950].

金属纳米粒子的催化性质与其周围的化学环境密切相关，鉴于MOF结构的高度可调控特性，具有不同官能团的配体与金属纳米粒子具有不同的相互作用，因此金属粒子的催化活性也不同。因此，选择适当的配体及MOF材料，才能实现MOF材料与金属纳米粒子之间的协同作用，带来更好的催化性能，是解决上述技术问题的有效途径。The catalytic properties of metal nanoparticles are closely related to their surrounding chemical environment. Given the highly tunable nature of the MOF structure, ligands with different functional groups have different interactions with metal nanoparticles, so the catalytic activity of metal nanoparticles is also different. Therefore, selecting appropriate ligands and MOF materials can realize the synergistic effect between MOF materials and metal nanoparticles and bring about better catalytic performance, which is an effective way to solve the above technical problems.

发明内容Contents of the invention

本发明的目的是提供一种用于催化氨硼烷水解制氢的Pt/ZIF-67复合材料，解决现有技术金属纳米粒子团聚以及TOF值较低，活化能较高的问题。通过使用ZIF-67与Pt进行复合，可以提供更高的比表面积和吸附能力，使金属纳米粒子更加均匀地分散在MOF材料表面；同时，利用ZIF-67实现与Pt纳米粒子之间的协同作用，提高催化性能。The purpose of the present invention is to provide a Pt/ZIF-67 composite material for catalyzing the hydrolysis of ammonia borane to produce hydrogen, which solves the problems of metal nanoparticle agglomeration, low TOF value and high activation energy in the prior art. By using ZIF-67 to combine with Pt, it can provide higher specific surface area and adsorption capacity, so that metal nanoparticles can be more uniformly dispersed on the surface of MOF materials; at the same time, ZIF-67 can be used to achieve synergy with Pt nanoparticles , improve catalytic performance.

为了实现上述发明目的，本发明采用的技术方案包括：In order to realize the foregoing invention object, the technical scheme that the present invention adopts comprises:

Pt/ZIF-67复合材料由氯铂酸和金属有机框架ZIF-67混合后，通过一步还原法制备而成，其结构保留了ZIF-67框架结构。Pt纳米粒子的平均尺寸为1-2 nm，且分布均匀，经XRD检测无明显的Pt金属衍射特征峰。The Pt/ZIF-67 composite was prepared by a one-step reduction method after mixing chloroplatinic acid and metal-organic framework ZIF-67, and its structure retained the ZIF-67 framework structure. The average size of Pt nanoparticles is 1-2 nm, and the distribution is uniform, and there is no obvious Pt metal diffraction characteristic peak through XRD detection.

Pt/ZIF-67复合材料的制备方法，包括以下步骤：The preparation method of Pt/ZIF-67 composite material, comprises the following steps:

步骤1）ZIF-67的制备与活化，将乙酸钴四水合物和2-甲基咪唑加入到水中，超声混合均匀后，随后装入高压反应釜，放入烘箱，恒温加热引发反应，待反应体系缓慢冷却至室温后，将产物取出、洗涤、干燥后得到ZIF-67，并将所得的ZIF-67进行活化，得到活化后的ZIF-67；Step 1) Preparation and activation of ZIF-67, adding cobalt acetate tetrahydrate and 2-methylimidazole into water, ultrasonically mixing evenly, then putting them into a high-pressure reactor, putting them in an oven, heating at a constant temperature to initiate the reaction, and waiting for the reaction After the system is slowly cooled to room temperature, the product is taken out, washed and dried to obtain ZIF-67, and the obtained ZIF-67 is activated to obtain activated ZIF-67;

步骤2）Pt纳米粒子的负载，将活化后的ZIF-67加入到水中，超声分散30-60 min，得到ZIF-67水溶液，然后以活化后的ZIF-67和氯铂酸的质量比满足（5-15）:100，将氯铂酸加入ZIF-67水溶液中，室温下搅拌6-24 h，然后在冰水浴下，再将浓度为0.01-0.05 mol/L的NaBH₄水溶液边搅拌边滴加到溶液中，继续搅拌1-6 h后，静置，然后将产物过滤，用无水乙醇和去离子水反复多次洗涤后，在60-100^oC下真空干燥10-20 h，得到Pt/ZIF-67复合材料。Step 2) Loading of Pt nanoparticles, adding activated ZIF-67 into water, ultrasonically dispersing for 30-60 min to obtain ZIF-67 aqueous solution, and then satisfying the mass ratio of activated ZIF-67 and chloroplatinic acid ( 5-15): 100, add chloroplatinic acid into the ZIF-67 aqueous solution, stir at room temperature for 6-24 h, and then drop the NaBH₄ aqueous solution with a concentration of 0.01-0.05 mol/L in an ice-water bath while stirring Add it into the solution, continue to stir for 1-6 h, let it stand, then filter the product, wash it repeatedly with absolute ethanol and deionized water, and dry it in vacuum at 60-100^o C for 10-20 h to obtain Pt/ZIF-67 composite.

本发明所述的Pt/ZIF-67复合材料用于催化氨硼烷水解放氢，明显提升了放氢性能，较高的TOF值，为70-100 mol H₂min^-1 Pt mol^-1，以及较低的活化能，为30-40 kJ mol^-1。The Pt/ZIF-67 composite material of the present invention is used to catalyze the hydrolysis of ammonia borane to decompose hydrogen, which significantly improves the dehydrogenation performance, and has a higher TOF value of 70-100 mol H₂ min^-1 Pt mol^-1 , and a lower activation energy of 30-40 kJ mol^-1 .

本发明相对于现有技术，具有以下优点：Compared with the prior art, the present invention has the following advantages:

1. 平均尺寸为1-2 nm 的Pt纳米粒子均匀分布在金属有机框架ZIF-67的表面，有效地抑制了纳米粒子的团聚现象；1. The Pt nanoparticles with an average size of 1-2 nm are uniformly distributed on the surface of metal organic framework ZIF-67, which effectively inhibits the agglomeration of nanoparticles;

2. Pt/ZIF-67复合材料用于催化氨硼烷水解放氢，表现出较好的催化性能，具体表现为较高的TOF值，为70-100 mol H₂min^-1 Pt mol^-1，以及较低的活化能，为30-40 kJ mol^-1。2. The Pt/ZIF-67 composite material is used to catalyze the hydrolysis of ammonia borane to decompose hydrogen, showing good catalytic performance, specifically showing a high TOF value of 70-100 mol H₂ min^-1 Pt mol^-1 , and a lower activation energy of 30-40 kJ mol^-1 .

3. 相对于UIO-66-NH₂来说，ZIF-67可以提供更高的比表面积以及较好的吸附能力，可以使金属纳米粒子更好地分散在MOF的表面，更为重要的是，发挥了ZIF-67和Pt纳米粒子的协同作用，带来更好的催化性能；3. Compared with UIO-66-NH₂ , ZIF-67 can provide higher specific surface area and better adsorption capacity, which can better disperse metal nanoparticles on the surface of MOF. More importantly, Played the synergistic effect of ZIF-67 and Pt nanoparticles, resulting in better catalytic performance;

4. 本发明的制氢材料成本低廉，环境友好，工艺简单，适合大批量的制备。4. The hydrogen production material of the present invention is low in cost, environmentally friendly, simple in process, and suitable for mass production.

因此，本发明在氢气制备领域具有广阔的应用前景。Therefore, the present invention has broad application prospects in the field of hydrogen production.

附图说明：Description of drawings:

图1为具体实施例的X射线衍射图；Fig. 1 is the X-ray diffraction figure of specific embodiment;

图2为具体实施例的透射电镜图Fig. 2 is the transmission electron microscope figure of specific embodiment

图3为具体实施例的Pt纳米粒子的粒径分布图；Fig. 3 is the particle size distribution figure of the Pt nanoparticle of specific embodiment;

图4为具体实施例在不同温度下催化氨硼烷水解的放氢速率图；Fig. 4 is the hydrogen release rate figure of specific embodiment catalyzing the hydrolysis of ammonia borane at different temperatures;

图5为具体实施例的阿伦尼乌斯曲线。Fig. 5 is an Arrhenius curve of a specific embodiment.

具体实施方式Detailed ways

本发明通过实施例，结合说明书附图对本发明内容作进一步详细说明，但不是对本发明的限制。The present invention will be described in further detail through the embodiments in conjunction with the accompanying drawings, but it is not intended to limit the present invention.

实施例Example

用于催化氨硼烷水解制氢的Pt/ZIF-67复合材料的具体操作步骤如下：The specific operation steps of the Pt/ZIF-67 composite material used to catalyze the hydrolysis of ammonia borane to produce hydrogen are as follows:

步骤1）ZIF-67的制备与活化，将1 mmol乙酸钴四水合物和20 mmol 2-甲基咪唑加入到20 mL水中，超声混合均匀后，随后装入高压反应釜，放入烘箱，恒温加热到120^oC引发反应，反应时间为18 h，待反应体系缓慢冷却至室温后，将产物取出，用无水乙醇和去离子水反复多次洗涤，在80^oC下干燥后得到ZIF-67，并将所得的ZIF-67在真空条件下，在150^oC下，保温12 h进行活化，得到活化后的ZIF-67；Step 1) Preparation and activation of ZIF-67, add 1 mmol of cobalt acetate tetrahydrate and 20 mmol of 2-methylimidazole into 20 mL of water, mix well by ultrasonic, then put into autoclave, put into oven, keep constant temperature The reaction was initiated by heating to 120^o C, and the reaction time was 18 h. After the reaction system was slowly cooled to room temperature, the product was taken out, washed repeatedly with absolute ethanol and deionized water, and dried at 80^o C to obtain ZIF- 67, and the obtained ZIF-67 was activated under vacuum conditions at 150^o C for 12 h to obtain activated ZIF-67;

步骤2）Pt纳米粒子的负载，将100 mg活化后的ZIF-67加入到15 mL水中，超声分散40min，然后将5 mg氯铂酸加入溶液中，室温下搅拌18 h，然后在冰水浴下，将10mL 0.02 mol/L的NaBH₄边搅拌边滴加到溶液中，继续搅拌4 h后，静置，然后将产物过滤，用无水乙醇和去离子水反复多次洗涤后，在80^oC下真空干燥12 h，得到Pt/ZIF-67复合材料。Step 2) Loading of Pt nanoparticles, 100 mg of activated ZIF-67 was added to 15 mL of water, ultrasonically dispersed for 40 min, then 5 mg of chloroplatinic acid was added to the solution, stirred at room temperature for 18 h, and then placed in an ice-water bath , add 10mL of 0.02 mol/L NaBH₄ dropwise into the solution while stirring, continue to stir for 4 h, then let it stand, then filter the product, wash it repeatedly with absolute ethanol and deionized water, and put it at 80^o C under vacuum for 12 h to obtain the Pt/ZIF-67 composite.

测试结果如下：The test results are as follows:

如图1为本发明所制备的ZIF-67以及Pt/ZIF-67复合材料的XRD谱图。在2θ=7.4˚，12.7˚，16.5˚处的特征峰对应的是ZIF-67晶面(011)，(112)，(013)，表明在催化剂制备过程中较好地保留了ZIF-67框架结构。此外，从Pt/ZIF-67的PXRD图谱中没有发现明显的Pt金属衍射特征峰，可能是由于金属纳米颗粒良好的分散性和较低的金属负载量。Figure 1 shows the XRD spectra of ZIF-67 and Pt/ZIF-67 composite materials prepared in the present invention. The characteristic peaks at 2θ=7.4˚, 12.7˚, and 16.5˚ correspond to the ZIF-67 crystal planes (011), (112), (013), indicating that the ZIF-67 framework is well preserved during the catalyst preparation process structure. In addition, no obvious Pt metal diffraction characteristic peaks were found from the PXRD pattern of Pt/ZIF-67, which may be due to the good dispersion of metal nanoparticles and low metal loading.

如图2为本发明所制备的Pt/ZIF-67复合材料的透射电镜图。从图2可以看出，大多数Pt纳米粒子（黑点）分布在ZIF-67的外表面上，从图3可知，Pt纳米粒子的平均尺寸为1-2nm。Figure 2 is a transmission electron microscope image of the Pt/ZIF-67 composite material prepared in the present invention. It can be seen from Figure 2 that most of the Pt nanoparticles (black dots) are distributed on the outer surface of ZIF-67, and from Figure 3 that the average size of the Pt nanoparticles is 1-2 nm.

如图4为本发明所制备的Pt/ZIF-67复合材料在不同温度下催化氨硼烷水解的放氢速率图及阿伦尼乌斯曲线。测试结果如图所示，Pt/ZIF-67复合材料的TOF为72.29 molH₂min^-1 Pt mol^-1，活化能通过结算可得，为39.42 kJ mol^-1，如图5所示。Figure 4 shows the hydrogen desorption rate diagram and Arrhenius curve of the Pt/ZIF-67 composite material prepared in the present invention to catalyze the hydrolysis of ammonia borane at different temperatures. The test results are shown in the figure. The TOF of the Pt/ZIF-67 composite is 72.29 molH₂ min^-1 Pt mol^-1 , and the activation energy is 39.42 kJ mol^-1 , as shown in Figure 5.

Claims (9)

Translated fromChinese

1.一种用于催化氨硼烷水解制氢的Pt/ZIF-67复合材料，其特征在于：Pt/ZIF-67复合材料由氯铂酸和金属有机框架ZIF-67混合后，通过一步还原法制备而成。1. A Pt/ZIF-67 composite material used to catalyze the hydrolysis of ammonia borane to produce hydrogen, characterized in that: after the Pt/ZIF-67 composite material is mixed with chloroplatinic acid and metal organic framework ZIF-67, it is reduced by one step prepared by method.2.根据权利要求1所述的Pt/ZIF-67复合材料，其特征在于：其结构保留了ZIF-67框架结构。2. The Pt/ZIF-67 composite material according to claim 1, characterized in that: its structure retains the ZIF-67 frame structure.3. 根据权利要求1所述的Pt/ZIF-67复合材料，其特征在于：Pt纳米粒子的平均尺寸为1-2 nm，且分布均匀，经XRD检测无明显的Pt金属衍射特征峰。3. The Pt/ZIF-67 composite material according to claim 1, characterized in that: the average size of the Pt nanoparticles is 1-2 nm, and the distribution is uniform, and there is no obvious Pt metal diffraction characteristic peak through XRD detection.4.根据权利要求1所述的一种用于催化氨硼烷水解制氢的Pt/ZIF-67复合材料的制备方法，包括步骤1）ZIF-67的制备与活化，将乙酸钴四水合物和2-甲基咪唑加入到水中，超声混合均匀后，随后装入高压反应釜，放入烘箱，恒温加热引发反应，待反应体系缓慢冷却至室温后，将产物取出、洗涤、干燥后得到ZIF-67，并将所得的ZIF-67进行活化，得到活化后的ZIF-67；其特征在于还包括：步骤2）Pt纳米粒子的负载，将活化后的ZIF-67加入到水中，超声分散得到ZIF-67水溶液，然后以活化后的ZIF-67和氯铂酸满足一定质量比，将氯铂酸加入ZIF-67水溶液中，室温下搅拌，然后在冰水浴下，再将一定浓度的NaBH₄水溶液边搅拌边滴加到溶液中，继续搅拌后，静置，然后将产物过滤，用无水乙醇和去离子水反复多次洗涤后，在真空干燥，得到Pt/ZIF-67复合材料。4. A method for preparing a Pt/ZIF-67 composite material for catalyzing the hydrolysis of ammonia borane to produce hydrogen according to claim 1, comprising step 1) preparation and activation of ZIF-67, and cobalt acetate tetrahydrate Add 2-methylimidazole and 2-methylimidazole into water, mix evenly by ultrasonic, then put it into a high-pressure reactor, put it in an oven, and heat it at a constant temperature to initiate the reaction. After the reaction system is slowly cooled to room temperature, the product is taken out, washed, and dried to obtain ZIF -67, and the obtained ZIF-67 is activated to obtain activated ZIF-67; it is characterized in that it also includes: step 2) loading of Pt nanoparticles, adding activated ZIF-67 into water, and ultrasonically dispersing to obtain ZIF-67 aqueous solution, then meet a certain mass ratio of activated ZIF-67 and chloroplatinic acid, add chloroplatinic acid into the ZIF-67 aqueous solution, stir at room temperature, and then add a certain concentration of NaBH₄ The aqueous solution is added dropwise into the solution while stirring, after continuing to stir, stand still, then filter the product, wash repeatedly with absolute ethanol and deionized water, and dry in vacuum to obtain the Pt/ZIF-67 composite material.5.根据权利要求4所述的制备方法，其特征在于：所述步骤2）活化后的ZIF-67和氯铂酸的质量比满足（5-15）:100关系。5. The preparation method according to claim 4, characterized in that: the mass ratio of activated ZIF-67 and chloroplatinic acid in the step 2) satisfies the relationship of (5-15):100.6. 根据权利要求4所述的制备方法，其特征在于：所述步骤2）NaBH₄水溶液的浓度为0.01-0.05 mol/L。6. The preparation method according to claim 4, characterized in that: the concentration of the NaBH₄ aqueous solution in the step 2) is 0.01-0.05 mol/L.7. 根据权利要求4所述的制备方法，其特征在于：所述步骤2）超声分散的时间为30-60min，室温下搅拌的时间为6-24 h，冰水浴的搅拌时间为1-6 h，真空干燥的条件是干燥温度为60-100 ℃，干燥时间为10-20 h。7. The preparation method according to claim 4, characterized in that: said step 2) the ultrasonic dispersion time is 30-60 min, the stirring time at room temperature is 6-24 h, and the stirring time in ice-water bath is 1-6 h, the condition of vacuum drying is that the drying temperature is 60-100°C and the drying time is 10-20 h.8. 根据权利要求1所述Pt/ZIF-67复合材料作为催化氨硼烷水解制氢的应用，其特征在于：催化氨硼烷水解放氢，明显提升了放氢性能，代表其反应速率的转化频率值（Turnover frequency，TOF）达到70-100 mol H₂min^-1 Pt mol^-1。8. According to the application of the Pt/ZIF-67 composite material described in claim 1 as the hydrogen production by catalyzing the hydrolysis of ammonia borane, it is characterized in that: catalyzing the hydrolysis of ammonia borane to decompose hydrogen, obviously improving the dehydrogenation performance, representing its reaction rate The turnover frequency value (Turnover frequency, TOF) reaches 70-100 mol H₂ min^-1 Pt mol^-1 .9. 根据权利要求1所述Pt/ZIF-67复合材料作为催化氨硼烷水解制氢的应用，其特征在于：催化氨硼烷水解放氢的活化能为30-40 kJ mol^-1。9. The application of the Pt/ZIF-67 composite material according to claim 1 as catalyzing the hydrolysis of ammonia borane to produce hydrogen, characterized in that: the activation energy of catalyzing the hydrolysis of ammonia borane to decompose hydrogen is 30-40 kJ mol^-1 .