杂多酸H3PW12O40高效催化MgH2储氢

doi:10.3866/PKU.WHXB202308032

Abstract

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

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

Figures/Tables 9

Table 1

Fig 1

Fig 2

Fig 3

Table 2

Fig 4

Fig 5

Fig 6

Fig 7

References 44

1	Dan L. ; Wang H. ; Yang X. B. ; Liu J. W. ; Ouyang L. Z. ; Zhu M. ACS Appl. Mater. Interfaces 2023, 15, 30372. doi: 10.1021/acsami.3c06033
2	Zhang X. L. ; Liu Y. F. ; Zhang X. ; Hu J. J. ; Gao M. X. ; Pan H. G. Mater. Today Nano 2020, 9, 100064. doi: 10.1016/j.mtnano.2019.100064
3	Wang J. S. ; Han S. M. ; Li Y. ; Shen N. ; Zhang W. Acta Phys.-Chim. Sin. 2014, 30, 2323.
	王家盛; 韩树民; 李媛; 沈娜; 张伟. 物理化学学报, 2014, 30, 2323. doi: 10.3866/PKU.WHXB201410081
4	Jing Z. J. ; Tan K. C. ; He T. ; Yu Y. ; Pei Q. J. ; Wang J. T. ; Wu H. ; Chen P. Acta Phys.-Chim. Sin. 2021, 37, 2009039.
	荆子君; TanKhai Chen; 何腾; 于洋; 裴启俊; 王金涛; HuiWu; 陈萍. 物理化学学报, 2021, 37, 2009039. doi: 10.3866/PKU.WHXB202009039
5	Shao Y. T. ; Gao H. G. ; Tang Q. K. ; Liu Y. N. ; Liu J. C. ; Zhu Y. F. ; Zhang J. G. ; Li L. Q. ; Hu X. H. ; Ba Z. X. Appl. Surf. Sci. 2022, 585, 152561. doi: 10.1016/j.apsusc.2022.152561
6	Wang P. ; Tian Z. H. ; Wang Z. X. ; Xia C. Q. ; Yang T. ; Ou X. L. Int. J. Hydrog. Energy 2021, 46, 27107. doi: 10.1016/j.ijhydene.2021.05.172
7	Zhang X. ; Liu Y. F. ; Ren Z. H. ; Zhang X. L. ; Hu J. J. ; Huang Z. G. ; Lu Y. H. ; Gao M. X. ; Pan H. G. Energy Environ. Sci. 2021, 14, 2302. doi: 10.1039/d0ee03160g
8	Xu N. ; Wang K. W. ; Zhu Y. F. ; Zhang Y. Adv. Mater. 2023, 35, 2303173. doi: 10.1002/adma.202303173
9	Liu H. Z. ; Lu C. L. ; Wang X. C. ; Xu L. ; Huang X. T. ; Wang X. H. ; Ning H. ; Lan Z. Q. ; Guo J. ACS Appl. Mater. Interfaces 2021, 13, 13235. doi: 10.1021/acsami.0c23150
10	Zhu W. ; Ren L. ; Lu C. ; Xu H. ; Sun F. Z. ; Ma Z. W. ; Zou J. X. ACS Nano 2021, 15, 18494. doi: 10.1021/acsnano.1c08343
11	Ren L. ; Zhu W. ; Zhang Q. Y. ; Lu C. ; Sun F. Z. ; Lin X. ; Zou J. X. Chem. Eng. J. 2022, 434, 134701. doi: 10.1016/j.cej.2022.134701
12	Ma Z. W. ; Zou J. X. ; Khan D. ; Zhu W. ; Hu C. Z. ; Zeng X. Q. ; Ding W. J. J. Mater. Sci. Technol. 2019, 35, 2132. doi: 10.1016/j.jmst.2019.05.049
13	Yuan Z. R. ; Li S. H. ; Wang K. W. ; Xu N. ; Sun W. W. ; Sun L. T. ; Cao H. J. ; Lin H. J. ; Zhu Y. F. ; Zhang Y. Chem. Eng. J. 2022, 435, 135050. doi: 10.1016/j.cej.2022.135050
14	Wang K. ; Zhang X. ; Liu Y. F. ; Ren Z. H. ; Zhang X. L. ; Hu J. J. ; Gao M. X. ; Pan H. G. Chem. Eng. J. 2021, 406, 126831. doi: 10.1016/j.cej.2020.126831
15	Ma Z. W. ; Panda S. ; Zhang Q. Y. ; Sun F. Z. ; Khan D. ; Ding W. J. ; Zou J. X. Chem. Eng. J. 2021, 406, 126790. doi: 10.1016/j.cej.2020.126790
16	Ding Z. ; Li Y. T. ; Yang H. ; Lu Y. F. ; Tan J. ; Li J. B. ; Li Q. ; Chen Y. A. ; Shaw L. L. ; Pan F. S. J. Magnes. Alloy. 2022, 10, 2946. doi: 10.1016/j.jma.2022.09.028
17	Meng Q. F. ; Huang Y. Q. ; Ye J. K. ; Xia G. L. ; Wang G. F. ; Dong L. X. ; Yang Z. X. ; Yu X. B. J. Alloy. Compd. 2021, 851, 156874. doi: 10.1016/j.jallcom.2020.156874
18	Verma S. K. ; Abu Shaz M. ; Yadav T. P. Int. J. Hydrog. Energy 2023, 48, 21383. doi: 10.1016/j.ijhydene.2021.12.269
19	Zhang H. H. ; Kong Q. Q. ; Hu S. ; Zhang D. F. ; Chen H. P. ; Xu C. C. ; Li B. J. ; Fan Y. P. ; Liu B. Z. ACS Sustain. Chem. Eng. 2022, 10, 363. doi: 10.1021/acssuschemeng.1c06444
20	Huang T. ; Huang X. ; Hu C. ; Wang J. ; Liu H. ; Ma Z. ; Zou J. ; Ding W. Mater. Today Energy 2021, 19, 100613. doi: 10.1016/j.mtener.2020.100613
21	Dan L. ; Hu L. ; Wang H. ; Zhu M. Int. J. Hydrog. Energy 2019, 44, 29249. doi: 10.1016/j.ijhydene.2019.01.285
22	Yahya M. S. ; Ismail M. J. Phys. Chem. C 2018, 122, 11222. doi: 10.1021/acs.jpcc.8b02162
23	L Duan C. W. ; Tian Y. T. ; Wang X. Y. ; Wu J. H. ; Liu B. G. ; Fu D. ; Zhang Y. L. ; Lv W. ; Hu L. X. ; Wang F. ; et al Nano Energy 2023, 113, 108536. doi: 10.1016/j.nanoen.2023.108536
24	Duan X. Q. ; Li G. X. ; Zhang W. H. ; Luo H. ; Tang H. M. ; Xu L. ; Sheng P. ; Wang X. H. ; Huang X. T. ; Huang C. K. ; et al Rare Metals 2023, 42, 1923. doi: 10.1007/s12598-022-02231-7
25	Liang G. ; Huot J. ; Boily S. ; Van Neste. A. ; Schulz R. J. Alloy. Compd. 1999, 292, 247. doi: 10.1016/S0925-8388(99)00442-9
26	Barkhordarian G. ; Klassen T. ; Bormann R. J. Phys. Chem. B 2006, 110, 11020. doi: 10.1021/jp0541563
27	Malka I. E. ; Pisarek M. ; Czujko T. ; Bystrzycki J. Int. J. Hydrog. Energy 2011, 36, 12909. doi: 10.1016/j.ijhydene.2011.07.020
28	Tonus F. ; Fuster V. ; Urretavizcaya G. ; Castro F. J. ; Bobet J. L. Int. J. Hydrog. Energy 2009, 34, 3404. doi: 10.1016/j.ijhydene.2009.02.030
29	Zhang W. ; Shen N. ; Han S. M. ; Chen Y. ; Xu G. ; Ke D. D. Mater. Res. Bull. 2015, 72, 197. doi: 10.1016/j.materresbull.2015.07.042
30	Yang H. K. Acta Phys.-Chim. Sin. 2017, 33, 582.
	杨海宽. 物理化学学报, 2017, 33, 582. doi: 10.3866/PKU.WHXB201611292
31	Horn M. R. ; Singh A. ; Alomari S. ; Goberna-Ferrón S. ; Benages-Vilau R. ; Chodankar N. ; Motta N. ; Ostrikov K. ; MacLeod J. ; Sonar P. ; et al Energy Environ. Sci. 2021, 14, 1652. doi: 10.1039/d0ee03407j
32	Bijelic A. ; Aureliano M. ; Rompel A. Angew. Chem. Int. Ed. 2019, 58, 2980. doi: 10.1002/anie.201803868
33	Du D. Y. ; Qin J. S. ; Li S. L. ; Su Z. M. ; Lan Y. Q. Chem. Soc. Rev. 2014, 43, 4615. doi: 10.1039/c3cs60404g
34	Chen X. F. ; Yang A. B. ; Wang G. X. ; Wei M. F. ; Liu N. ; Li B. ; Wu L. X. Chem. Eng. J. 2022, 446, 137134. doi: 10.1016/j.cej.2022.137134
35	Gautam J. ; Liu Y. ; Gu J. ; Ma Z. Y. ; Zha J. J. ; Dahal B. ; Zhang L. N. ; Chishti A. N. ; Ni L. B. ; Diao G. W. ; et al Adv. Funct. Mater. 2021, 31, 2106147. doi: 10.1002/adfm.202106147
36	Yan H. J. ; Xie Y. ; Jiao Y. Q. ; Wu A. P. ; Tian C. G. ; Zhang X. M. ; Wang L. ; Fu H. G. Adv. Mater. 2018, 30, 1704156. doi: 10.1002/adma.201704156
37	Yan G. ; Wu C. X. ; Tan H. Q. ; Feng X. J. ; Yan L. K. ; Zang H. Y. ; Li Y. G. J. Mater. Chem. A 2017, 5, 765. doi: 10.1039/c6ta09052d
38	Peng Y. W. ; Shan C. S. ; Wang H. J. ; Hong L. Y. ; Yao S. ; Wu R. J. ; Zhang Z. M. ; Lu T. B. Adv. Energy Mater. 2019, 9, 1900597. doi: 10.1002/aenm.201900597
39	Guo X. ; Wan X. ; Liu Q.T. ; Li Y.C. ; Li W.W. ; Shui J. L. eScience 2022, 2, 304. doi: 10.1016/j.esci.2022.04.002
40	Wang S. S. ; Yang G. Y. Chem. Rev. 2015, 115, 4893. doi: 10.1021/cr500390v
41	Wang B. ; Chen C. X. ; Jiang Y. Y. ; Ni P. J. ; Zhang C. H. ; Yang Y. ; Lu Y. Z. ; Liu P. Chem. Eng. J. 2021, 412, 128690. doi: 10.1016/j.cej.2021.128690
42	Huang T. Y. ; Ji P. Y. ; Huang J. J. ; Yu B. ; Wu X. M. Surf. Coat. Technol. 2021, 410, 126941. doi: 10.1016/j.surfcoat.2021.126941
43	Wei X. ; Dai H. B. ; Li Y. N. ; Wang T. Y. ; Li S. Int. J. Hydrog. Energy 2023, 48, 23866. doi: 10.1016/j.ijhydene.2023.03.225
44	Chen M. ; Pu Y. H. ; Li Z. Y. ; Huang G. ; Liu X. F. ; Lu Y. ; Tang W. K. ; Xu L. ; Liu S. Y. ; Yu R. H. ; et al Nano Res. 2020, 13, 2063. doi: 10.1007/s12274-020-2808-7

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

[1]	Yu Liu, Pengfei Li, Yize Liu, Zaicheng Sun. Recent advances in carbon dots as a single photocatalyst [J]. Acta Phys. -Chim. Sin., 2026, 42(2): 100167-.
[2]	Yuhang Zhang, Yi Li, Yuehan Cao, Yingjie Shuai, Yu Zhou, Ying Zhou. Regulating the formation type by Ir of intermediates to suppress product overoxidation in photocatalytic methane conversion [J]. Acta Phys. -Chim. Sin., 2026, 42(2): 100173-.
[3]	Chengxiao Zhao, Zhaolin Li, Dongfang Wu, Xiaofei Yang. SBA-15 templated covalent triazine frameworks for boosted photocatalytic hydrogen production [J]. Acta Phys. -Chim. Sin., 2026, 42(1): 100149-.
[4]	Shiyi Chen, Jialong Fu, Jianping Qiu, Guoju Chang, Shiyou Hao. Waste medical mask-derived carbon quantum dots enhance the photocatalytic degradation of polyethylene terephthalate (PET) over BiOBr/g-C₃N₄ S-scheme heterojunction [J]. Acta Phys. -Chim. Sin., 2026, 42(1): 100135-.
[5]	Fengying Zhang, Yanglin Mei, Yuman Jiang, Shenshen Zheng, Kaibo Zheng, Ying Zhou. Research progress of transient absorption spectroscopy in solar energy conversion and utilization [J]. Acta Phys. -Chim. Sin., 2025, 41(9): 100118-.
[6]	Jianan Hong, Chenyu Xu, Yan Liu, Changqi Li, Menglin Wang, Yanwei Zhang. Decoding the interfacial competition between hydrogen evolution and CO₂ reduction via edge-active-site modulation in photothermal catalysis [J]. Acta Phys. -Chim. Sin., 2025, 41(9): 100099-.
[7]	Menglan Wei, Xiaoxia Ou, Yimeng Wang, Mengyuan Zhang, Fei Teng, Kaixuan Wang. S-scheme heterojunction g-C₃N₄/Bi₂WO₆ highly efficient degradation of levofloxacin: performance, mechanism and degradation pathway [J]. Acta Phys. -Chim. Sin., 2025, 41(9): 100105-.
[8]	Jingping Li, Suding Yan, Jiaxi Wu, Qiang Cheng, Kai Wang. Improving hydrogen peroxide photosynthesis over inorganic/organic S-scheme photocatalyst with LiFePO₄ [J]. Acta Phys. -Chim. Sin., 2025, 41(9): 100104-.
[9]	Ruizhi Duan, Xiaomei Wang, Panwang Zhou, Yang Liu, Can Li. The role of hydroxyl species in the alkaline hydrogen evolution reaction over transition metal surfaces [J]. Acta Phys. -Chim. Sin., 2025, 41(9): 100111-.
[10]	Jiajie Cai, Chang Cheng, Bowen Liu, Jianjun Zhang, Chuanjia Jiang, Bei Cheng. CdS/DBTSO-BDTO S-scheme photocatalyst for H₂ production and its charge transfer dynamics [J]. Acta Phys. -Chim. Sin., 2025, 41(8): 100084-.
[11]	Lewang Yuan, Yaoyao Peng, Zong-Jie Guan, Yu Fang. Insights into the development of 2D covalent organic frameworks as photocatalysts in organic synthesis [J]. Acta Phys. -Chim. Sin., 2025, 41(8): 100086-.
[12]	Yu Wang, Haiyang Shi, Zihan Chen, Feng Chen, Ping Wang, Xuefei Wang. Hollow AgPt@Pt core-shell cocatalyst with electron-rich Pt^δ− shell for boosting selectivity of photocatalytic H₂O₂ production for faceted BiVO₄ [J]. Acta Phys. -Chim. Sin., 2025, 41(7): 100081-.
[13]	Honghong Zhang, Zhen Wei, Derek Hao, Lin Jing, Yuxi Liu, Hongxing Dai, Weiqin Wei, Jiguang Deng. Recent advances in synergistic catalytic valorization of CO₂ and hydrocarbons by heterogeneous catalysis [J]. Acta Phys. -Chim. Sin., 2025, 41(7): 100073-.
[14]	Yadan Luo, Hao Zheng, Xin Li, Fengmin Li, Hua Tang, Xilin She. Modulating reactive oxygen species in O, S co-doped C₃N₄ to enhance photocatalytic degradation of microplastics [J]. Acta Phys. -Chim. Sin., 2025, 41(6): 100052-.
[15]	Liuyun Chen, Wenju Wang, Tairong Lu, Xuan Luo, Xinling Xie, Kelin Huang, Shanli Qin, Tongming Su, Zuzeng Qin, Hongbing Ji. Soft template-induced deep pore structure of Cu/Al₂O₃ for promoting plasma-catalyzed CO₂ hydrogenation to DME [J]. Acta Phys. -Chim. Sin., 2025, 41(6): 100054-.

Catalytic Effect of H₃PW₁₂O₄₀ on Hydrogen Storage of MgH₂

RichHTML

Full text @ ScienceDirect

Like

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 9

References 44

Related Articles 15

Metrics

Recommended 0

Catalytic Effect of H3PW12O40 on Hydrogen Storage of MgH2

RichHTML

Full text @ ScienceDirect

Like

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 9

References 44

Related Articles 15

Metrics

Recommended 0

Catalytic Effect of H₃PW₁₂O₄₀ on Hydrogen Storage of MgH₂