CN116726970A - Sulfur-nitrogen doped MXene hydrogen storage material catalyst, hydrogen storage material containing catalyst and preparation method - Google Patents
Sulfur-nitrogen doped MXene hydrogen storage material catalyst, hydrogen storage material containing catalyst and preparation method Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 148
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 148
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 239000011232 storage material Substances 0.000 title claims abstract description 66
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 40
- 238000003860 storage Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 56
- 229910052717 sulfur Inorganic materials 0.000 claims description 34
- 239000011593 sulfur Substances 0.000 claims description 32
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 30
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 12
- 238000005530 etching Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000012300 argon atmosphere Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 230000002441 reversible effect Effects 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
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- 230000001681 protective effect Effects 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 19
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 17
- 229910012375 magnesium hydride Inorganic materials 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000003795 desorption Methods 0.000 abstract description 7
- 239000011777 magnesium Substances 0.000 abstract description 7
- 238000012360 testing method Methods 0.000 abstract description 6
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- 229910052758 niobium Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
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- 229910019080 Mg-H Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 150000004681 metal hydrides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 239000010963 304 stainless steel Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000003775 Density Functional Theory Methods 0.000 description 1
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 1
- -1 SC Chemical class 0.000 description 1
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- 229910052804 chromium Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
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- 229910052735 hafnium Inorganic materials 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
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- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/20—Sulfiding
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
Description
技术领域Technical field
本发明属于储氢技术领域,涉及硫氮掺杂MXene储氢材料催化剂、含该催化剂的储氢材料及制备方法。The invention belongs to the field of hydrogen storage technology and relates to a sulfur and nitrogen doped MXene hydrogen storage material catalyst, a hydrogen storage material containing the catalyst and a preparation method.
背景技术Background technique
由于氢气是一种可大规模存储、可持续和可再生的能源,因此被认为是一种极具吸引力的能源载体。然而,氢能的实际应用还需要低成本制氢、高效氢转化为电能的燃料电池、安全紧凑的储氢等技术的突破。常温常压下的氢气密度仅为0.089kg·m-3,因此,安全、紧密地储存氢气对于氢能的应用至关重要。Since hydrogen is a large-scale storable, sustainable and renewable energy source, it is considered an attractive energy carrier. However, the practical application of hydrogen energy still requires technological breakthroughs such as low-cost hydrogen production, efficient hydrogen-to-electricity fuel cells, and safe and compact hydrogen storage. The density of hydrogen at normal temperature and pressure is only 0.089kg·m -3 . Therefore, safe and compact storage of hydrogen is crucial for the application of hydrogen energy.
固态储氢是一种被广泛研究和开发的方法,因为它比其他方法(如储存在高压气体钢瓶或绝热罐)更安全、紧密。目前,固态储氢已有金属氢化物、配位金属氢化物、氨基化合物、新型碳基吸附剂等多个分支。镁基储氢材料作为其中很有前景的金属基储氢材料,其理论储氢量可达到7.6wt.%,高于美国能源部(DOE)提出的轻型车载氢源指标(5.5wt.%),且其放氢平台较缓,可逆性好,同时质量轻,资源丰富,价格低廉。但是,由于其吸放氢动力学性能差,放氢温度高等缺点,实际应用受到了很大的限制。因此,研究者们采用添加催化剂、表面处理改性、纳米化和制备复合储氢材料等方法在一定程度上改善了镁基储氢材料的性能,但其放氢温度高于实际应用温度,吸放氢动力学较差的问题依然存在。Solid-state hydrogen storage is a widely researched and developed method because it is safer and more compact than other methods (such as storage in high-pressure gas cylinders or insulated tanks). At present, solid-state hydrogen storage has multiple branches such as metal hydrides, coordination metal hydrides, amino compounds, and new carbon-based adsorbents. Magnesium-based hydrogen storage materials are among the most promising metal-based hydrogen storage materials. Their theoretical hydrogen storage capacity can reach 7.6wt.%, which is higher than the light-duty vehicle hydrogen source indicator (5.5wt.%) proposed by the U.S. Department of Energy (DOE). , and its hydrogen release platform is slow, reversible, light in weight, rich in resources, and low in price. However, due to its poor hydrogen absorption and release kinetic properties and high hydrogen release temperature, its practical application has been greatly limited. Therefore, researchers have improved the performance of magnesium-based hydrogen storage materials to a certain extent by adding catalysts, surface treatment modifications, nanometerization, and preparing composite hydrogen storage materials. However, their hydrogen release temperature is higher than the actual application temperature, and the absorption temperature is higher than the actual application temperature. The problem of poor hydrogen evolution kinetics still exists.
近些年来,二维层状MXenes由于其层状结构、相对较大的表面积、显著的化学耐久性和高的电导率,在催化、传感器、转换、储能、气体吸附和电子器件等许多领域都显示出了巨大的潜力。MXenes的一般通式为Mn+1XnTx,其中M为过渡金属,如SC、Ti、Zr、Hf、V、Nb、Ta、Cr、Mo等,X为碳、氮或碳氮,n=1、2、3,T代表表面基团,如O2-,OH-,或F-等。现已经有研究人员将其作为催化剂运用到储氢材料的性能改性当中,通过对MXenes材料本身的改性,进一步提升其催化性能,但基于MXenes的材料(如Ti2C)尽管具有卓越的容量(根据密度泛函理论高达8.5wt.%),其缓慢的吸放氢动力学性能仍大大制约了其储氢应用,因此仍需进一步挖掘它们在储氢应用方面的潜力。In recent years, two-dimensional layered MXenes have been used in many fields such as catalysis, sensors, conversion, energy storage, gas adsorption, and electronic devices due to their layered structure, relatively large surface area, remarkable chemical durability, and high electrical conductivity. All show great potential. The general formula of MXenes is M n+1 X n T x , where M is a transition metal, such as SC , Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, etc., and , n=1, 2, 3, T represents surface group, such as O 2- , OH - , or F - , etc. Researchers have already used it as a catalyst to modify the performance of hydrogen storage materials. By modifying the MXenes material itself, its catalytic performance can be further improved. However, although MXenes-based materials (such as Ti 2 C) have excellent capacity (up to 8.5 wt.% according to density functional theory), and their slow hydrogen absorption and desorption kinetics still greatly restrict their hydrogen storage applications, so their potential in hydrogen storage applications still needs to be further explored.
发明内容Contents of the invention
有鉴于此,本发明的目的之一在于提供硫氮掺杂Nb2CTx储氢材料催化剂;目的之二在于提供硫氮掺杂Nb2CTx储氢材料催化剂的制备方法;目的之三在于提供含该催化剂的储氢材料;目的之四在于提供含该催化剂的储氢材料的制备方法。In view of this, one of the purposes of the present invention is to provide a sulfur and nitrogen doped Nb 2 CT x hydrogen storage material catalyst; the second purpose is to provide a preparation method of a sulfur and nitrogen doped Nb 2 CT x hydrogen storage material catalyst; and the third purpose is to Provide a hydrogen storage material containing the catalyst; the fourth object is to provide a preparation method of the hydrogen storage material containing the catalyst.
为达到上述目的,本发明提供如下技术方案:In order to achieve the above objects, the present invention provides the following technical solutions:
1、一种硫氮掺杂MXene储氢材料催化剂,所述储氢材料催化剂为硫氮掺杂Nb2CTx。1. A sulfur and nitrogen doped MXene hydrogen storage material catalyst, the hydrogen storage material catalyst is sulfur and nitrogen doped Nb 2 CT x .
优选地,氮掺杂量占所述储氢催化剂总质量的5~7wt.%,硫掺杂量占所述储氢催化剂总质量的0.5~1.2wt.%。Preferably, the nitrogen doping amount accounts for 5 to 7 wt.% of the total mass of the hydrogen storage catalyst, and the sulfur doping amount accounts for 0.5 to 1.2 wt.% of the total mass of the hydrogen storage catalyst.
2、一种硫氮掺杂MXene储氢材料催化剂的制备方法,所述制备方法如下:2. A method for preparing a sulfur and nitrogen doped MXene hydrogen storage material catalyst. The preparation method is as follows:
(1)将LiF溶于浓盐酸,得刻蚀液,然后将Nb2AlC置于所述刻蚀液中,水热反应后离心洗涤,最后真空干燥,制得Nb2CTx;(1) Dissolve LiF in concentrated hydrochloric acid to obtain an etching solution, then place Nb 2 AlC in the etching solution, undergo hydrothermal reaction, centrifuge and wash, and finally vacuum dry to obtain Nb 2 CT x ;
(2)将硫脲溶于乙醇中,然后加入步骤(1)中制得的Nb2CTx,混匀后真空干燥得Nb2CTx与硫脲的混合物,将所述混合物置于管式炉中保护气氛下煅烧,即可。(2) Dissolve thiourea in ethanol, then add Nb 2 CT x prepared in step (1), mix and dry under vacuum to obtain a mixture of Nb 2 CT x and thiourea, and place the mixture in a tube Just calcine in the furnace under protective atmosphere.
优选地,步骤(1)中,所述LiF、Nb2AlC和浓盐酸的质量体积比为:1~1.4:0.8~1.2:10~30,g:g:mL;所述水热反应具体为:于反应釜内100~150℃下反应12~36h;所述离心洗涤具体为:以去离子水按3000~8000rpm的转速离心洗涤至混合体系呈中性;所述真空干燥具体为:在60~100℃下真空干燥8~16h。Preferably, in step (1), the mass volume ratio of LiF, Nb 2 AlC and concentrated hydrochloric acid is: 1~1.4:0.8~1.2:10~30, g:g:mL; the hydrothermal reaction is specifically: : react in the reaction kettle at 100-150°C for 12-36 hours; the centrifugal washing is specifically: centrifugal washing with deionized water at a rotation speed of 3000-8000 rpm until the mixed system becomes neutral; the vacuum drying is specifically: at 60 Vacuum dry at ~100℃ for 8~16h.
优选地,步骤(2)中,所述Nb2CTx、硫脲和乙醇的质量体积比为:10:10~40:1~2,mg:mg:mL;所述真空干燥具体为:在60~100℃下真空干燥8~16h;所述煅烧具体为:于管式炉中氩气氛围、200~600℃下煅烧1~4h。Preferably, in step (2), the mass volume ratio of Nb 2 CT x , thiourea and ethanol is: 10:10~40:1~2, mg:mg:mL; the vacuum drying is specifically: Vacuum drying at 60 to 100°C for 8 to 16 hours; the calcination specifically includes: calcining in a tube furnace in an argon atmosphere at 200 to 600°C for 1 to 4 hours.
3、一种MgH2-硫氮掺杂Nb2CTx复合储氢材料,按质量百分比计,所述复合储氢材料包括:硫氮掺杂Nb2CTx 1wt.%~15wt.%,MgH2 85wt.%~99wt.%。3. A MgH 2 -sulfur and nitrogen doped Nb 2 CT x composite hydrogen storage material. In terms of mass percentage, the composite hydrogen storage material includes: sulfur and nitrogen doped Nb 2 CT x 1wt.%~15wt.%, MgH 2 85wt.%~99wt.%.
优选地,按质量百分比计,所述复合储氢材料包括:硫氮掺杂Nb2CTx 3wt.%~10wt.%,MgH2 90wt.%~97wt.%。Preferably, in terms of mass percentage, the composite hydrogen storage material includes: sulfur and nitrogen doped Nb 2 CT x 3wt.%~10wt.%, MgH 2 90wt.%~97wt.%.
优选地,按质量百分比计,所述复合储氢材料包括:硫氮掺杂Nb2CTx 4wt.%~6wt.%,MgH2 94wt.%~96wt.%。Preferably, in terms of mass percentage, the composite hydrogen storage material includes: sulfur and nitrogen doped Nb 2 CT x 4wt.%~6wt.%, MgH 2 94wt.%~96wt.%.
4、一种MgH2-硫氮掺杂Nb2CTx复合储氢材料的制备方法,所述制备方法如下:将MgH2和硫氮掺杂Nb2CTx在氩气气氛下,按球料比10~60:1,以200~800rpm的转速正反转间歇球磨8~24h。4. A method for preparing MgH 2 -sulfur and nitrogen-doped Nb 2 CT x composite hydrogen storage materials. The preparation method is as follows: press MgH 2 and sulfur and nitrogen-doped Nb 2 CT x into pellets under an argon atmosphere. Ratio 10~60:1, forward and reverse intermittent ball milling at 200~800rpm for 8~24h.
优选地,所述正反转间歇球磨具体为:每球磨5~20min后暂停5~30min。Preferably, the forward and reverse intermittent ball milling is specifically: every 5 to 20 minutes of ball milling followed by a pause of 5 to 30 minutes.
本发明的有益效果在于:本发明提供硫氮掺杂Nb2CTx储氢材料催化剂、含该催化剂的储氢材料及制备方法,该催化剂为二维层状结构颗粒,颗粒长度在5-30μm之间,氮掺杂量为5~7wt.%,硫掺杂量为0.5~1.2wt.%,该催化剂对氢化镁的吸放氢过程具有优异的催化效果,是因为具有M2X结构的Nb2CTx MXene的结构层数较少,因而具有高的比表面积,提供更多的催化活性位点,从而有利于吸放氢反应的顺利进行。另外,原位生成的Nb和NbO2物质能够拉长Mg-H键,促进氢气快速释放。S元素的掺杂主要起到扩大Nb2CTx层间距的作用,过多的掺杂会破坏层状结构不利于电子的传输和转移,当掺杂量为0.5~1.2wt.%时Nb2CTx仍能保持层状结构;N元素的掺杂则主要起到提升Nb2CTx导电性的作用,由于硫脲同时作为S源和N源,N元素的掺杂量由S元素决定。N、S元素的掺杂进一步增强了Nb2CTx表面存在的多价态形式Nb元素(NbO2、Nb-C、Nb)促进Mg2+与H-间电子转移的能力,从而有效地加速氢分子的解离与镁氢键的断裂,对氢化镁具有较好的催化效果。以该催化剂与氢化镁制备的复合储氢材料,颗粒尺寸在1~15μm之间,且硫氮掺杂Nb2CTx均匀地分布在MgH2颗粒的表面,为后续MgH2颗粒的吸放氢过程提供均匀分布的活性催化位点,使得MgH2能够通过这些位点快速、高效的释放和吸收氢气,因此在放氢动力学测试时MgH2可实现275℃、5分钟内放氢5.32wt.%,在吸氢动力学测试时可实现150℃、2分钟内吸氢5.08wt.%。此外,该复合储氢材料的起始放氢温度相比于纯氢化镁下降了105.48℃,可见硫氮掺杂Nb2CTx对氢化镁的吸放氢过程具有优异的催化效果。该催化剂制备方法简单,且原料易得,适合扩大化生产。The beneficial effects of the present invention are: the present invention provides a sulfur and nitrogen doped Nb 2 CT x hydrogen storage material catalyst, a hydrogen storage material containing the catalyst and a preparation method. The catalyst is a two-dimensional layered structure particle with a particle length of 5-30 μm. The nitrogen doping amount is 5~7wt.%, and the sulfur doping amount is 0.5~1.2wt.%. This catalyst has excellent catalytic effect on the hydrogen absorption and release process of magnesium hydride because it has an M 2 Nb 2 CT x MXene has fewer structural layers, so it has a high specific surface area and provides more catalytically active sites, which is conducive to the smooth progress of the hydrogen absorption and release reaction. In addition, the Nb and NbO 2 substances generated in situ can elongate the Mg-H bond and promote the rapid release of hydrogen. The doping of S element mainly plays the role of expanding the distance between Nb 2 CT CT x can still maintain a layered structure; the doping of N element mainly plays a role in improving the conductivity of Nb 2 CT x . Since thiourea serves as both S source and N source, the doping amount of N element is determined by S element. The doping of N and S elements further enhances the ability of the multivalent Nb elements (NbO 2 , Nb-C, Nb) existing on the surface of Nb 2 CT x to promote electron transfer between Mg 2+ and H-, thereby effectively accelerating The dissociation of hydrogen molecules and the breaking of magnesium hydrogen bonds have a good catalytic effect on magnesium hydride. The composite hydrogen storage material prepared with this catalyst and magnesium hydride has a particle size between 1 and 15 μm, and the sulfur and nitrogen - doped Nb 2 CT The process provides evenly distributed active catalytic sites, allowing MgH 2 to quickly and efficiently release and absorb hydrogen through these sites. Therefore, in the hydrogen release kinetic test, MgH 2 can achieve 5.32wt hydrogen release in 5 minutes at 275°C. %, during the hydrogen absorption kinetics test, it can achieve 5.08wt.% hydrogen absorption within 2 minutes at 150°C. In addition, the initial hydrogen release temperature of the composite hydrogen storage material is 105.48°C lower than that of pure magnesium hydride. It can be seen that sulfur and nitrogen doped Nb 2 CT x has an excellent catalytic effect on the hydrogen absorption and release process of magnesium hydride. The preparation method of the catalyst is simple, the raw materials are easily available, and it is suitable for expanded production.
本发明的其他优点、目标和特征在某种程度上将在随后的说明书中进行阐述,并且在某种程度上,基于对下文的考察研究对本领域技术人员而言将是显而易见的,或者可以从本发明的实践中得到教导。本发明的目标和其他优点可以通过下面的说明书来实现和获得。Other advantages, objects, and features of the present invention will, to the extent that they are set forth in the description that follows, and to the extent that they will become apparent to those skilled in the art upon examination of the following, or may be derived from This invention is taught by practicing it. The objects and other advantages of the invention may be realized and obtained by the following description.
附图说明Description of drawings
为了使本发明的目的、技术方案和优点更加清楚,下面将结合附图对本发明作优选的详细描述,其中:In order to make the purpose, technical solutions and advantages of the present invention clearer, the present invention will be described in detail below in conjunction with the accompanying drawings, in which:
图1为实施例1中制备的Nb2CTx的SEM图;Figure 1 is an SEM image of Nb 2 CT x prepared in Example 1;
图2为实施例1中制备的硫氮掺杂Nb2CTx的SEM图;Figure 2 is an SEM image of the sulfur and nitrogen doped Nb 2 CT x prepared in Example 1;
图3为实施例5中制备的MgH2+5wt.%Nb2CTx/SN复合储氢材料的SEM图;Figure 3 is an SEM image of the MgH 2 +5wt.%Nb 2 CT x /SN composite hydrogen storage material prepared in Example 5;
图4为实施例4-6中制备的MgH2+y wt.%Nb2CTx/SN(y=3,5,10)复合储氢材料及对比实施例中制备的球磨MgH2的TPD曲线;Figure 4 is the TPD curve of the MgH 2 +y wt.% Nb 2 CT x /SN (y = 3, 5, 10) composite hydrogen storage material prepared in Examples 4-6 and the ball-milled MgH 2 prepared in the Comparative Example. ;
图5为实施例5中制备的MgH2+5wt.%Nb2CTx/SN复合储氢材料和对比实施例制备球磨MgH2的275℃放氢曲线;Figure 5 is a 275°C hydrogen release curve of the MgH 2 +5wt.% Nb 2 CT x /SN composite hydrogen storage material prepared in Example 5 and the ball-milled MgH 2 prepared in the Comparative Example;
图6为实施例5中制备的MgH2+5wt.%Nb2CTx/SN复合储氢材料和对比实施例制备球磨MgH2的150℃吸氢曲线;Figure 6 is the 150°C hydrogen absorption curve of the MgH 2 +5wt.% Nb 2 CT x /SN composite hydrogen storage material prepared in Example 5 and the ball-milled MgH 2 prepared in the Comparative Example;
图7为实施例6中制备的MgH2+5wt.%Nb2CTx/SN复合储氢材料在不同状态时的Nb3d XPS图。Figure 7 is the Nb3d XPS pattern of the MgH 2 +5wt.%Nb 2 CT x /SN composite hydrogen storage material prepared in Example 6 in different states.
具体实施方式Detailed ways
以下通过特定的具体实例说明本发明的实施方式,本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用,本说明书中的各项细节也可以基于不同观点与应用,在没有背离本发明的精神下进行各种修饰或改变。The following describes the embodiments of the present invention through specific examples. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments. Various details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present invention.
实施例1Example 1
制备硫氮掺杂Nb2CTx Preparation of sulfur and nitrogen doped Nb 2 CT x
(1)将1g LiF溶于20mL浓度为12mol/L的浓盐酸中,得刻蚀液,然后将1g Nb2AlC置于该刻蚀液中,于100mL高压反应釜内125℃下反应24h后以去离子水按5000rpm的转速离心洗涤至混合体系呈中性,最后在60℃下真空干燥12h,制得Nb2CTx;(1) Dissolve 1g LiF in 20mL of concentrated hydrochloric acid with a concentration of 12mol/L to obtain an etching solution. Then place 1g of Nb 2 AlC in the etching solution and react in a 100mL high-pressure reactor at 125°C for 24 hours. Centrifuge and wash with deionized water at 5000 rpm until the mixed system becomes neutral, and finally vacuum dry at 60°C for 12 hours to obtain Nb 2 CT x ;
(2)将1200mg硫脲溶于50mL乙醇中,在60℃水浴锅内搅拌至硫脲溶解,然后加入300mg步骤(1)中制得的Nb2CTx,搅拌1h混匀后在80℃下真空干燥12h得Nb2CTx与硫脲的混合物,将该混合物置于管式炉中氩气氛围、400℃下煅烧3h,制得硫氮掺杂Nb2CTx,其中,S掺杂量为0.69wt.%,N掺杂量为6.39wt.%。(2) Dissolve 1200 mg of thiourea in 50 mL of ethanol, stir in a 60°C water bath until thiourea is dissolved, then add 300 mg of Nb 2 CT x prepared in step (1), stir for 1 hour, mix well, and then place at 80°C Vacuum-dry for 12 hours to obtain a mixture of Nb 2 CT x and thiourea. The mixture is placed in an argon atmosphere in a tube furnace and calcined at 400°C for 3 hours to obtain sulfur-nitrogen-doped Nb 2 CT x . The amount of S doped is is 0.69wt.%, and the N doping amount is 6.39wt.%.
以扫描电镜分别对制得的Nb2CTx和硫氮掺杂Nb2CTx进行表征,图1为Nb2CTx的SEM图,可知Nb2CTx为典型的二维层状结构颗粒,颗粒长度在5-30μm之间。图2为硫氮掺杂Nb2CTx的SEM图,可知经硫氮掺杂后,Nb2CTx仍保持着二维层状结构,具有高的比表面积,从而提供更多的催化活性位点。表1展示了扫描电镜统计下该硫氮掺杂Nb2CTx中各元素的质量比。The prepared Nb 2 CT x and the sulfur and nitrogen doped Nb 2 CT x were characterized by scanning electron microscopy respectively. Figure 1 is the SEM image of Nb 2 CT x . It can be seen that Nb 2 CT x is a typical two-dimensional layered structure particle. Particle length is between 5-30μm. Figure 2 is an SEM image of sulfur and nitrogen doped Nb 2 CT x . It can be seen that after sulfur and nitrogen doping, Nb 2 CT x still maintains a two-dimensional layered structure and has a high specific surface area, thereby providing more catalytic active sites. point. Table 1 shows the mass ratio of each element in the sulfur-nitrogen-doped Nb 2 CT x under scanning electron microscopy statistics.
表1实施例1中硫氮掺杂Nb2CTx中各元素的质量比Table 1 The mass ratio of each element in the sulfur and nitrogen doped Nb 2 CT x in Example 1
实施例2Example 2
制备硫氮掺杂Nb2CTx Preparation of sulfur and nitrogen doped Nb 2 CT x
(1)将1g LiF溶于30mL浓度为12mol/L的浓盐酸中,得刻蚀液,然后将1.2g Nb2AlC置于该刻蚀液中,于100mL高压反应釜内100℃下反应36h后以去离子水按3000rpm的转速离心洗涤至混合体系呈中性,最后在80℃下真空干燥16h,制得Nb2CTx;(1) Dissolve 1g LiF in 30mL of concentrated hydrochloric acid with a concentration of 12mol/L to obtain an etching solution. Then place 1.2g Nb 2 AlC in the etching solution and react in a 100mL high-pressure reactor at 100°C for 36 hours. Then, centrifuge and wash with deionized water at 3000 rpm until the mixed system becomes neutral, and finally vacuum dry at 80°C for 16 hours to obtain Nb 2 CT x ;
(2)将300mg硫脲溶于30mL乙醇中,在60℃水浴锅内搅拌至硫脲溶解,然后加入300mg步骤(1)中制得的Nb2CTx,搅拌1h混匀后在60℃下真空干燥16h得Nb2CTx与硫脲的混合物,将该混合物置于管式炉中氩气氛围、600℃下煅烧1h,制得硫氮掺杂Nb2CTx,其中,S掺杂量为0.58wt.%,N掺杂量为5.64wt.%。(2) Dissolve 300 mg of thiourea in 30 mL of ethanol, stir in a 60°C water bath until thiourea is dissolved, then add 300 mg of Nb 2 CT x prepared in step (1), stir for 1 hour, mix well, and then place at 60°C Vacuum-dry for 16 hours to obtain a mixture of Nb 2 CT x and thiourea. The mixture is placed in an argon atmosphere in a tube furnace and calcined at 600°C for 1 hour to obtain sulfur-nitrogen-doped Nb 2 CT x . The amount of S doped is is 0.58wt.%, and the N doping amount is 5.64wt.%.
实施例3Example 3
制备硫氮掺杂Nb2CTx Preparation of sulfur and nitrogen doped Nb 2 CT x
(1)将1.4g LiF溶于10mL浓度为12mol/L的浓盐酸中,得刻蚀液,然后将0.8gNb2AlC置于该刻蚀液中,于100mL高压反应釜内150℃下反应12h后以去离子水按8000rpm的转速离心洗涤至混合体系呈中性,最后在100℃下真空干燥8h,制得Nb2CTx;(1) Dissolve 1.4g LiF in 10mL of concentrated hydrochloric acid with a concentration of 12mol/L to obtain an etching solution. Then place 0.8gNb 2 AlC in the etching solution and react in a 100mL high-pressure reactor at 150°C for 12h. Then, it is centrifuged and washed with deionized water at 8000 rpm until the mixed system becomes neutral, and finally vacuum dried at 100°C for 8 hours to obtain Nb 2 CT x ;
(2)将750mg硫脲溶于60mL乙醇中,在60℃水浴锅内搅拌至硫脲溶解,然后加入300mg步骤(1)中制得的Nb2CTx,搅拌1h混匀后在100℃下真空干燥8h得Nb2CTx与硫脲的混合物,将该混合物置于管式炉中氩气氛围、200℃下煅烧4h,制得硫氮掺杂Nb2CTx,其中,S掺杂量为0.76wt.%,N掺杂量为6.67wt.%。(2) Dissolve 750 mg of thiourea in 60 mL of ethanol, stir in a 60°C water bath until thiourea is dissolved, then add 300 mg of Nb 2 CT x prepared in step (1), stir for 1 hour, mix well, and then place at 100°C Vacuum-dry for 8 hours to obtain a mixture of Nb 2 CT x and thiourea. The mixture is placed in an argon atmosphere in a tube furnace and calcined at 200°C for 4 hours to obtain sulfur-nitrogen-doped Nb 2 CT x . The amount of S doped is is 0.76wt.%, and the N doping amount is 6.67wt.%.
实施例4Example 4
制备MgH2-3wt.%硫氮掺杂Nb2CTx复合储氢材料(MgH2+3wt.%Nb2CTx/SN复合储氢材料)Preparation of MgH 2 -3wt.% sulfur and nitrogen doped Nb 2 CT x composite hydrogen storage material (MgH 2 +3wt.% Nb 2 CT x /SN composite hydrogen storage material)
在真空手套箱中将MgH2和实施例1中制备的硫氮掺杂Nb2CTx按质量比97:3称量混合,总质量为1g,然后将混合物倒入球磨罐内,混合物与304不锈钢球的球料比20:1,向球磨罐中充入0.2Mpa氩气并安装到高能球磨机上,以400rpm的转速正转运行10min间歇10min,再反转运行10min间歇10min,有效球磨时间10h,即可。In a vacuum glove box, weigh and mix MgH2 and the sulfur-nitrogen - doped Nb2CT The ball-to-material ratio of stainless steel balls is 20:1. Fill the ball milling tank with 0.2Mpa argon gas and install it on the high-energy ball mill. Run forward at a speed of 400rpm for 10 minutes with 10 minutes of intermission, and then run in reverse for 10 minutes with 10 minutes of intermission. The effective ball milling time is 10 hours. , that’s it.
实施例5Example 5
制备MgH2-5wt.%硫氮掺杂Nb2CTx复合储氢材料(MgH2+5wt.%Nb2CTx/SN复合储氢材料)Preparation of MgH 2 -5wt.% sulfur and nitrogen doped Nb 2 CT x composite hydrogen storage material (MgH 2 +5wt.%Nb 2 CT x /SN composite hydrogen storage material)
与实施例4的区别在于:将MgH2和实施例1中制备的硫氮掺杂Nb2CTx按质量比95:5称量混合,总质量为1g,制得MgH2+5wt.%Nb2CTx/SN复合储氢材料。The difference from Example 4 is that MgH 2 and the sulfur-nitrogen-doped Nb 2 CT x prepared in Example 1 are weighed and mixed at a mass ratio of 95:5, with a total mass of 1 g, to obtain MgH 2 +5wt.%Nb 2 CT x /SN composite hydrogen storage material.
以扫描电镜对实施例5中制备的MgH2+5wt.%Nb2CTx/SN复合储氢材料进行表征,图3为MgH2+5wt.%Nb2CTx/SN复合储氢材料的SEM图,由图可知,其颗粒平均尺寸为1~15μm,相比于原始氢化镁(30~50μm)有较大的降低。颗粒尺寸的降低有利于提升氢化镁的吸放氢动力学性能,原因在于当氢化镁颗粒尺寸大幅降低时,其比表面积也随之增加,而比表面积的增加会提升颗粒的反应活性,从而使氢气的释放和吸放更容易;此外,颗粒尺寸的降低还缩短了氢原子从颗粒内部到表面或从表面到内部的扩散路径,从而加快氢气的释放和吸放。The MgH 2 +5wt.%Nb 2 CT x /SN composite hydrogen storage material prepared in Example 5 was characterized using a scanning electron microscope. Figure 3 is an SEM of the MgH 2 +5wt.%Nb 2 CT x /SN composite hydrogen storage material. As can be seen from the figure, the average particle size is 1 to 15 μm, which is significantly lower than that of the original magnesium hydride (30 to 50 μm). The reduction in particle size is conducive to improving the hydrogen absorption and release kinetic properties of magnesium hydride. The reason is that when the size of magnesium hydride particles is greatly reduced, its specific surface area also increases, and the increase in specific surface area will increase the reactivity of the particles, thereby making The release and absorption of hydrogen is easier; in addition, the reduction in particle size also shortens the diffusion path of hydrogen atoms from the inside of the particle to the surface or from the surface to the inside, thereby accelerating the release and absorption of hydrogen.
实施例6Example 6
制备MgH2-10wt.%硫氮掺杂Nb2CTx复合储氢材料(MgH2+10wt.%Nb2CTx/SN复合储氢材料)Preparation of MgH 2 -10wt.% sulfur and nitrogen doped Nb 2 CT x composite hydrogen storage material (MgH 2 +10wt.% Nb 2 CT x /SN composite hydrogen storage material)
与实施例4的区别在于:将MgH2和实施例1中制备的硫氮掺杂Nb2CTx按质量比90:10称量混合,总质量为1g,制得MgH2+10wt.%Nb2CTx/SN复合储氢材料。The difference from Example 4 is that MgH 2 and the sulfur-nitrogen-doped Nb 2 CT x prepared in Example 1 are weighed and mixed at a mass ratio of 90:10, with a total mass of 1 g, to obtain MgH 2 +10wt.%Nb 2 CT x /SN composite hydrogen storage material.
对比实施例Comparative Example
制备球磨MgH2 Preparation of ball-milled MgH 2
在真空手套箱中将1g MgH2倒入球磨罐内,MgH2与304不锈钢球的球料比20:1,向球磨罐中充入0.2Mpa氩气并安装到高能球磨机上,以400rpm的转速正转运行10min间歇10min,再反转运行10min间歇10min,有效球磨时间10h,即可。Pour 1g MgH 2 into the ball mill tank in the vacuum glove box. The ball-to-material ratio of MgH 2 to 304 stainless steel balls is 20:1. Fill the ball mill tank with 0.2Mpa argon gas and install it on the high-energy ball mill, rotating at 400 rpm. Run forward for 10 minutes with an interval of 10 minutes, then run reversely for 10 minutes with an interval of 10 minutes, and the effective ball milling time is 10 hours.
在手套箱中分别称取200mg实施例4-6中制备的复合储氢材料(MgH2+y wt.%Nb2CTx/SN(y=3,5,10))及对比实施例中制备的球磨MgH2分别置于高压气体吸脱附仪专用样品管中,之后分别装入仪器中进行TPD测试。结果如图4所示,由图可知,随着硫氮掺杂Nb2CTx催化剂添加量的增加,MgH2的起始放氢温度有不同程度的下降。实施例4-6中制备的复合储氢材料(MgH2+y wt.%Nb2CTx/SN(y=3,5,10))的起始放氢温度分别为248.05℃、212.58℃和209.91℃,相比于对比实施例中制备的球磨MgH2分别下降了70.01℃、105.48℃和108.15℃。其中,MgH2+5wt.%Nb2CTx/SN复合储氢材料展现出最优的催化效果:一方面,相比于MgH2+3wt.%Nb2CTx/SN复合储氢材料,其起始放氢温度下降了35.47℃;另一方面,相比于MgH2+10wt.%Nb2CTx/SN复合储氢材料,其起始放氢温度虽然相差不大(2.67℃),但其放氢量较多、放氢速率较快。Weigh 200 mg of the composite hydrogen storage material (MgH 2 +y wt.% Nb 2 CT x /SN (y=3, 5, 10)) prepared in Examples 4-6 and the comparative example in the glove box. The ball-milled MgH 2 were placed in special sample tubes for high-pressure gas adsorption and desorption instruments, and then loaded into the instruments for TPD testing. The results are shown in Figure 4. It can be seen from the figure that as the amount of sulfur-nitrogen-doped Nb 2 CT x catalyst increases, the initial hydrogen release temperature of MgH 2 decreases to varying degrees. The initial hydrogen release temperatures of the composite hydrogen storage material (MgH 2 +y wt.%Nb 2 CT x /SN (y=3, 5, 10)) prepared in Example 4-6 are 248.05°C, 212.58°C and 209.91°C, which decreased by 70.01°C, 105.48°C and 108.15°C respectively compared to the ball-milled MgH 2 prepared in the comparative example. Among them, MgH 2 +5wt.%Nb 2 CT x /SN composite hydrogen storage material shows the best catalytic effect: on the one hand, compared with MgH 2 +3wt.%Nb 2 CT x /SN composite hydrogen storage material, its The initial hydrogen release temperature dropped by 35.47°C; on the other hand, compared to the MgH 2 +10wt.%Nb 2 CT x /SN composite hydrogen storage material, although the initial hydrogen release temperature is not much different (2.67°C), it It releases more hydrogen and its hydrogen release rate is faster.
分别对实施例5中制备的MgH2+5wt.%Nb2CTx/SN复合储氢材料和对比实施例制备球磨MgH2在275℃时进行放氢性能测试,在150℃时进行吸氢性能测试,结果如图5和图6及表2所示。其中,图5为两种储氢材料在275℃的放氢曲线图,图6为两种储氢材料在150℃时的放氢曲线图,由图5可知,球磨MgH2在5分钟内仅可放出约0.03wt.%的氢气,MgH2+5wt.%Nb2CTx/SN复合储氢材料5分钟内可放出5.31wt.%的氢气,是球磨MgH2放氢量的近177倍,这表明硫氮掺杂Nb2CTx储氢催化剂的添加可以大幅度提升氢化镁的放氢速率。由图6可知,放氢后的MgH2+5wt.%Nb2CTx/SN复合储氢材料可在150℃下、120s内吸收约5.08wt.%的氢气,而球磨MgH2在相同的条件下只能吸收3.51wt.%的氢气,且20分钟的时间也只能够吸收4.15wt.%的氢气。上述结果表明硫氮掺杂Nb2CTx催化剂的添加能够促进氢气分子的解离和重组,使MgH2具有快速的吸放氢速率。The MgH 2 +5wt.% Nb 2 CT x /SN composite hydrogen storage material prepared in Example 5 and the ball-milled MgH 2 prepared in the Comparative Example were tested for hydrogen release performance at 275°C and hydrogen absorption performance at 150°C. Test, the results are shown in Figure 5 and Figure 6 and Table 2. Among them, Figure 5 is the hydrogen release curve of the two hydrogen storage materials at 275°C, and Figure 6 is the hydrogen release curve of the two hydrogen storage materials at 150°C. It can be seen from Figure 5 that ball milling MgH 2 only takes 5 minutes. It can release about 0.03wt.% hydrogen. MgH 2 +5wt.%Nb 2 CT x /SN composite hydrogen storage material can release 5.31wt.% hydrogen within 5 minutes, which is nearly 177 times the amount of hydrogen released by ball milling MgH 2 . This shows that the addition of sulfur and nitrogen-doped Nb 2 CT x hydrogen storage catalyst can greatly increase the hydrogen release rate of magnesium hydride. It can be seen from Figure 6 that the MgH 2 +5wt.%Nb 2 CT x /SN composite hydrogen storage material after hydrogen release can absorb about 5.08wt.% hydrogen within 120s at 150°C, while the ball-milled MgH 2 can absorb about 5.08wt.% of hydrogen under the same conditions. It can only absorb 3.51wt.% of hydrogen, and it can only absorb 4.15wt.% of hydrogen in 20 minutes. The above results show that the addition of sulfur and nitrogen-doped Nb 2 CT x catalyst can promote the dissociation and recombination of hydrogen molecules, allowing MgH 2 to have a rapid hydrogen absorption and release rate.
表2MgH2+5wt.%Nb2CTx/SN复合储氢材料及球磨MgH2吸放氢性能测试数据Table 2 MgH 2 +5wt.%Nb 2 CT x /SN composite hydrogen storage material and ball milling MgH 2 hydrogen absorption and release performance test data
对实施例5中制备的MgH2+5wt.%Nb2CTx/SN复合储氢材料在不同状态时的Nb 3d进行能谱分析,结果如图7所示,由图7可知,球磨态、放氢态、吸氢态以及循环放氢态的物相组成为Nb、Nb-C和Nb的氧化物,其中球磨态为Nb2O5,而其他三种状态为NbO2,表明经过放氢后,高价态的Nb2O5被还原为低价态的NbO2并且此后的吸放氢循环保持不变。总的来说,吸放氢循环过程中的物相组成为Nb、Nb-C和NbO2,其中,Nb-C的存在表明硫氮掺杂Nb2CTx催化剂在MgH2的吸放氢过程中仍保持着稳定的二维层状结构,为MgH2提供大量的活性催化位点,有利于吸放氢反应的进行;同时原位生成的Nb和NbO2物质能够拉长Mg-H键,促进氢气快速释放;此外,N、S元素的掺杂可进一步增强Nb2CTx表面存在的多价态形式Nb元素(NbO2、Nb-C、Nb)促进Mg2+与H-间电子转移的能力,从而有效地加速氢分子的解离与镁氢键的断裂。The energy spectrum analysis of Nb 3d in different states of the MgH 2 +5wt.%Nb 2 CT x /SN composite hydrogen storage material prepared in Example 5 is shown in Figure 7. From Figure 7, it can be seen that the ball-milled state, The phase compositions of the hydrogen-releasing state, the hydrogen-absorbing state and the cyclic hydrogen-releasing state are Nb, Nb-C and Nb oxides, among which the ball-milled state is Nb 2 O 5 and the other three states are NbO 2 , indicating that after hydrogen release Finally, the high-valence Nb 2 O 5 is reduced to the low-valence NbO 2 and the subsequent hydrogen absorption and release cycle remains unchanged. In general, the phase composition during the hydrogen absorption and release cycle is Nb, Nb-C and NbO 2 . Among them, the presence of Nb-C indicates that the sulfur and nitrogen doped Nb 2 CT x catalyst absorbs and releases hydrogen in MgH 2 It still maintains a stable two-dimensional layered structure, providing a large number of active catalytic sites for MgH 2 , which is conducive to the hydrogen absorption and release reaction; at the same time, the Nb and NbO 2 substances generated in situ can elongate the Mg-H bond, Promote the rapid release of hydrogen; in addition, the doping of N and S elements can further enhance the multivalent form of Nb elements (NbO 2 , Nb-C, Nb) existing on the surface of Nb 2 CT x to promote electron transfer between Mg 2+ and H - The ability to effectively accelerate the dissociation of hydrogen molecules and the breaking of magnesium hydrogen bonds.
最后说明的是,以上实施例仅用以说明本发明的技术方案而非限制,尽管参照较佳实施例对本发明进行了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本技术方案的宗旨和范围,其均应涵盖在本发明的权利要求范围当中。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not limiting. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified. Modifications or equivalent substitutions without departing from the purpose and scope of the technical solution shall be included in the scope of the claims of the present invention.
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