杂多酸H3PW12O40高效催化MgH2储氢

doi:10.3866/PKU.WHXB202308032

摘要/Abstract

摘要：

本文研究了杂多酸对储氢材料的催化效应，通过机械球磨法制备MgH₂-xH₃PW₁₂O₄₀ (x = 7%、10%、13%，质量分数)复合物样品，与纯的球磨MgH₂对比，展示了杂多酸H₃PW₁₂O₄₀对MgH₂储氢动力学的提升作用。其中，MgH₂-10H₃PW₁₂O₄₀的放氢活化能比纯MgH₂降低了46.23 kJ∙mol⁻¹，可在250 ℃、1 min内吸收6.25%的氢，在300 ℃、15 min内释放6.54%的氢气，而同等温度下MgH₂在30 min内仅释放1.2%氢。即使是在较低的温度100 ℃，MgH₂-10H₃PW₁₂O₄₀也可在1 h内吸收5%的氢，而MgH₂只能吸收0.9%的氢。结构表征结果表明H₃PW₁₂O₄₀分子在球磨和储氢过程中被转变为WO₃和W簇，其作用一方面是催化Mg―H键、H―H键的断裂，另一方面是促进MgH₂颗粒在球磨过程中细化并抑制其团聚长大。该研究开创了多酸分子在储氢领域的催化应用。

关键词: 储氢材料, 氢化镁, 磷钨酸, 催化, 动力学性能

Abstract:

Developing hydrogen energy to replace carbon-rich fossil fuels is the future direction of energy technology, but there is still a lack of safe and efficient hydrogen storage technology. Hydrogen storage in solid medium is a relatively safe way to store hydrogen, among which magnesium hydride (MgH₂) is one of the most promising solid hydrogen storage materials. MgH₂ has the advantages of high hydrogen storage density, low cost and good reversibility of hydrogen absorption and release. However, improving its poor thermodynamic and slow kinetic characteristics are still challenging. Catalysts derived from polyoxometalates have been successfully used for catalyzing hydrogen evolution reaction, oxidation of organic compounds, desulfurization reaction, and so on. However, these catalysts have not been applied to the hydrogen storage materials yet. In this paper, H₃PW₁₂O₄₀ is selected as a representative of polyoxometalates and its catalytic effect on hydrogen storage is studied. MgH₂-xH₃PW₁₂O₄₀ (x = 7%, 10%, 13%, mass percentage) and pure MgH₂ samples are prepared by mechanical ball milling method. Among them, MgH₂-10H₃PW₁₂O₄₀ exhibits the optimal performance in both kinetic characteristic and hydrogen storage capacity. It can rapidly absorb 6.25% hydrogen within 1 min at 250 ℃ and release 6.54% hydrogen within 15 min at 300 ℃, while ball-milled MgH₂ only releases 1.2% hydrogen within 30 min at 300 ℃. At the same time, the activation energy of the composite decreases to 106.08 kJ∙mol⁻¹, which is 46.23 kJ∙mol⁻¹ lower than MgH₂. The catalytic effect of H₃PW₁₂O₄₀ on the hydrogen storage properties of MgH₂ mainly comes from three aspects. Firstly, the addition of H₃PW₁₂O₄₀ helps to avoid the agglomeration of MgH₂ during the ball milling process, which makes the MgH₂ particles become smaller after ball milling, thus increasing the specific surface area of the interaction with hydrogen. Secondly, the addition of H₃PW₁₂O₄₀ makes MgH₂ produce a large number of defects and lattice distortion during ball milling, which provides more channels for hydrogen diffusion. Thirdly, the catalytic components of WO₃ and W are in situ formed during the ball milling process. They can be used as active components to accelerate the electron migration process, which promotes the cleavage of the Mg―H bond and the adsorption and dissociation of hydrogen.

Key words: Hydrogen storage material, MgH₂, Phosphotungstic acid, Catalysis, Kinetics property

于冉, 胡晨, 郭锐利, 刘若男, 夏力行, 杨岑玉, 水江澜. 杂多酸H₃PW₁₂O₄₀高效催化MgH₂储氢[J]. 物理化学学报, 2025, 41(1), 100001. doi: 10.3866/PKU.WHXB202308032

Ran Yu, Chen Hu, Ruili Guo, Ruonan Liu, Lixing Xia, Cenyu Yang, Jianglan Shui. Catalytic Effect of H₃PW₁₂O₄₀ on Hydrogen Storage of MgH₂[J]. Acta Phys. -Chim. Sin. 2025, 41(1), 100001. doi: 10.3866/PKU.WHXB202308032

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202308032

https://www.whxb.pku.edu.cn/CN/Y2025/V41/I1/100001

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Sample name	MgH₂-7H₃PW₁₂O₄₀	MgH₂-10H₃PW₁₂O₄₀	MgH₂-13H₃PW₁₂O₄₀
MgH₂	1.86 g	1.80 g	1.74 g
H₃PW₁₂O₄₀	0.14 g	0.20 g	0.26 g

Catalysts	Catalysts addition amount (%, mass percentage)	Hydrogen absorption capacity (%, mass percentage)	Hydrogen desorption capacity (%, mass percentage)	Ref.
H₃PW₁₂O₄₀	10	4.5 at 150 ℃ in 20 min	6 at 300 ℃ in 10 min	This work
H_0.23WO₃	50	2.6 at 300 ℃ in 100 s	2.2 at 300 ℃ in 200 s	28
WS₂	50	2.8 at 150 ℃ in 22 min	4.4 at 350 ℃ in 21 min	41
Na₂WO₄	20	2.3 at 150 ℃ in 20 min	3.5 at 350 ℃ in 20 min	29
Fe₂O₃/Na₂WO₄	20	2.5 at 150 ℃ in 20 min	1.2 at 300 ℃ in 20 min	42
Ni@C	10	4.8 at 300 ℃ in 80 s	6 at 300 ℃ in 46 min	17
VS₂	2.5	3 at 300 ℃ in 60 s	2.6 at 300 ℃ in 10 min	18
CoMoO₄	10	4.9 at 250 ℃ in 10 min	3.3 at 300 ℃ in 60 min	20
MoO₃	2	4.5 at 300 ℃ in 5 min	5 at 300 ℃ in 15 min	21
K₂NbF₇	10	3 at 150 ℃ in 20 min	5.6 at 320 ℃ in 60 min	22
MoSA-N-CNTs	6		5 at 300 ℃ in 100 min	23
Ti₃AlCN	10	4 at 150 ℃ in 20 min	4.5 at at 300 ℃ in 20 min	24

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杂多酸H₃PW₁₂O₄₀高效催化MgH₂储氢

Catalytic Effect of H₃PW₁₂O₄₀ on Hydrogen Storage of MgH₂

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