Hydrotalcite-Confined Ni Nanoparticles Catalyzed Efficient Hydrogen Storage of N-Methylindole

doi:10.6023/A25060229

Acta Chimica Sinica ›› 2025, Vol. 83 ›› Issue (11): 1340-1348.DOI: 10.6023/A25060229 Previous Articles Next Articles

Article

水滑石限域Ni纳米颗粒催化氮甲基吲哚高效储氢

全洪林^a, 唐鋆磊^a, 张承志^a, 张恒溢^a, 李佳奇^b^,^*(), 周太刚^a^,^c^,^*()

^a 西南石油大学化学化工学院成都 610500
^b 中国农业大学理学院北京 100193
^c 天府永兴实验室成都 610217

投稿日期:2025-06-19 发布日期:2025-08-12
通讯作者: 李佳奇, 周太刚
基金资助:
天府永兴实验室有组织科研(2023KJGG10); 西南石油大学自然科学(2021JBGS07)

Hydrotalcite-Confined Ni Nanoparticles Catalyzed Efficient Hydrogen Storage of N-Methylindole

Quan Honglin^a, Tang Junlei^a, Zhang Chengzhi^a, Zhang Hengyi^a, Li Jiaqi^b^,^*(), Zhou Taigang^a^,^c^,^*()

^a College of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500
^b College of Science, China Agricultural University, Beijing 100193
^c Tianfu Yongxing Laboratory, Chengdu, 610217

Received:2025-06-19 Published:2025-08-12
Contact: Li Jiaqi, Zhou Taigang
Supported by:
Tianfu Yongxing Laboratory Organized Research Project Funding(2023KJGG10); Science and Technology Project of Southwest Petroleum University(2021JBGS07)

1. .pdf(464KB)

Abstract

The advancement of non-noble metal catalysts holds immense importance for the broad industrial use of organic liquid hydrogen storage. In this study, Ni_aAl_b-layered double hydroxides (LDHs) were synthesized via co-precipitation method. Typically, a mixed solution of 100 mL Ni(NO₃)₂•6H₂O and Al(NO₃)₃•9H₂O was dropped into 100 mL Na₂CO₃ solution under vigorous stirring. The precipitation was carried out at room temperature, to achieve the desired pH value, a 3 mol/L NaOH solution was added to maintain the solution pH between 10±0.5. The resultant green precipitate underwent centrifugation and washing until nearly neutral, followed by drying for an extended period at 110 ℃. Thereafter, the sample was subjected to reduction at different temperatures for a duration of 2 h, with a meticulously controlled heating rate of 2.5 ℃/min. Finally, the influence of the Ni/Al ratio and reduction temperature on the catalytic activity was examined. The catalyst obtained by reducing NiAl-LDH at 450 ℃ (Ni₂Al_1-re450) exhibited the highest activity among the catalyst samples examined. Structural and compositional analyses of the catalyst were carried out using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma optical emission spectrometry (ICP-OES), and N₂ physisorption analysis (BET). The results indicated that the high hydrogenation activity of Ni₂Al_1-re450 was attributed to its larger specific surface area and smaller nickel particle size. Under the optimized reaction conditions (150 ℃, 6 MPa H₂, 2 h), the catalyst achieved a 100% conversion rate of NMID and a yield of 8H-NMID of 96.06% in a batch reactor, surpassing the commercial 0.5%Ru/Al₂O₃ hydrogenation catalyst. The hydrogenation reaction rate of NMID was positively correlated with temperature, with an apparent activation energy of 61.25 kJ/mol and a turnover frequency (TOF) of 52.62 h^－1. Moreover, Ni₂Al_1-re450 was continuously operated for 100 h in a micro packed-bed reactor under reaction conditions of 180 ℃ and 6 MPa. The results showed that the NMID conversion rate remained stable between 97%~100%, the selectivity for 8H-NMID was 97%~100%, and the hydrogen storage capacity was 5.55% (w)~5.76% (w).

Key words: organic liquid hydrogen storage, nickel catalyst, N-methylindole, nickel aluminum layered double hydroxide

Cite this article

Quan Honglin, Tang Junlei, Zhang Chengzhi, Zhang Hengyi, Li Jiaqi, Zhou Taigang. Hydrotalcite-Confined Ni Nanoparticles Catalyzed Efficient Hydrogen Storage of N-Methylindole[J]. Acta Chimica Sinica, 2025, 83(11): 1340-1348.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 7

Figure 1. XRD patterns of NiaAlb-LDH catalysts

Figure 2. (a) A schematic diagram of NiaAlb-LDH synthesis; (b) TEM images of Ni2Al1-re450

Figure 3. (a) N2 adsorption-desorption isotherm; (b) pore size distribution of all samples; (c) CO-TPD spectra of Ni2Al1-re450; (d) XPS Spectra of Ni1Al2-re450, Ni1Al1-re450, Ni2Al1-re450 and Ni3Al1-re450

Entry	Catalyst	S_BET^a/(m²•g^－1)	V_pore^b/(cm³•g^－1)	D_pore^c/nm	w_Ni^d/%	D_s^e
1	Ni₁Al_2-re450	135	0.14	3.8	—	—
2	Ni₁Al_1-re450	64	0.07	3.8	—	—
3	Ni₂Al_1-re450	142	0.28	5.3	53.28	0.5568
4	Ni₃Al_1-re450	68	0.21	9.6	—	—
5	Ni₂Al_1-re350	189	0.32	4.3	—	—
6	Ni₂Al_1-re550	130	0.27	6.5	—	—
7	Ni₂Al_1-re650	101	0.28	7.8	—	—

Table 1. Specifications of the prepared catalyst samples

Figure 4. (a) NMID hydrogenation products; (b) effect of different Ni/Al molar ratios; (c) effect of different reduction temperatures; (d) effect of different reaction temperatures; (e) effect of reaction time on Ni2Al1-re450 hydrogenation NMID; (f) comparison with noble metal catalysts; (g) cycle experiment; (reaction conditions: 0.2 g NMID, 20 mg catalyst)

Figure 5. (a) Relationship between ln(1－x) and reaction time; (b) relationship between ln k and 1/T; (c) thermal filtration experiment; (d), (e), (f) product distribution over Ni2Al1-re450 catalyst at various temperatures (100 ℃, 110 ℃, 130 ℃, 6 MPa H2). Reaction conditions: 0.2 g NMID, 20 mg catalyst

Figure 6. (a) Schematic diagram of hydrogenation NMID in Micro-packed bed reactor; (b) effect of reaction temperature on NMID continuous hydrogenation (reaction conditions: catalyst loading: 6 g Ni2Al1-re450; system pressure: 6 MPa; gas flow rate: 100 mL/min; liquid flow rate: 0.4 mL/min); (c) effect of liquid flow rate on NMID (reaction conditions: catalyst loading: 6 g Ni2Al1-re450; system pressure: 6 MPa; gas flow rate: 100 mL/min; reaction temperature: 180 ℃); (d), (e) long-term stability test for NMID hydrogenation over Ni2Al1-re450 (reaction conditions: reaction temperature: 180 ℃; gas flow rate: 100 mL/min; system pressure: 6 MPa; liquid flow rate: 0.05 mL/min; catalyst loading: 6 g Ni2Al1-re450)

References 37

[1]	Peraldo Bicelli L. Int. J. Hydrog. Energ. 1986, 11, 555.
[2]	Schlapbach L.; Züttel A. Natur. 2001, 414, 353.
[3]	Zou Y.-Q.; von Wolff N.; Anaby A.; Xie Y.; Milstein D. Nat. Catal. 2019, 2, 415.
[4]	Kim T. W.; Kim M.; Kim S. K.; Choi Y. N.; Jung M.; Oh H.; Suh Y.-W. Appl. Catal. B-Environ. Energ. 2021, 286, 119889.
[5]	Gianotti E.; Taillades-Jacquin M.; Rozière J.; Jones D. J. ACS Catal. 2018, 8, 4660.
[6]	Fan Y.; Wang P.; Zhang J.; Huang M.; Liu W.; Xu Y.; Duan X.; Li Y.; Zhang J. Chem. Eng. J. 2024, 484, 149404.
[7]	Zhang X.-Q.; Qi Y.-Q.; Liu H.; Wang J.-Y.; Xie L.-Y.; Shi J.-L.; Wang F.; Liu Y.-L.; Wang Z.-X.; Guo A.-J. Chem. Eng. J. 2024, 498, 155203.
[8]	Jeong H.; Kim T. W.; Kim M.; Han G. B.; Jeong B.; Suh Y.-W. ACS Sustain. Chem. Eng. 2022, 10, 15550.
[9]	Zhao Y.; Li C.; Zhu Y.; Liu L.; Zhu T.; Dong Y.; Cheng H.; Yang M. Appl. Catal. B-Environ. Energy. 2023, 334, 122792.
[10]	Rao P. C.; Kim Y.; Kim H.; Son Y.; Choi Y.; Na K.; Yoon M. ACS Sustain. Chem. Eng. 2023, 11, 12656.
[11]	Lee Y.-G.; Shin D. Y.; Yoon C. W.; Lim D.-H. Appl. Surf. Sci. 2023, 641, 158471.
[12]	Le T.-H.; Tran N.; Lee H.-J. Int. J. Mol. Sci. 2024, 25, 1359.
[13]	Sotoodeh F.; Huber B. J. M.; Smith K. J. Appl. Catal. A-Gen. 2012, 419-420, 67.
[14]	Dong Y.; Yang M.; Mei P.; Li C.; Li L. Int. J. Hydrog. Energ. 2016, 41, 8498.
[15]	Li C.; Luo R.; Zhu T.; Zhao Y.; Xu K.; Wu M.; Wang S.; Dong Y.; Yang M. Appl. Catal. B-Environ. Energ. 2025, 371, 125197.
[16]	Li L.; Yang M.; Dong Y.; Mei P.; Cheng H. Int. J. Hydrog. Energ. 2016, 41, 16129.
[17]	Lee J.; Park B. G.; Sung K.; Lee H.; Kim J.; Nam E.; Han J. W.; An K. ACS Catal. 2023, 13, 13691.
[18]	Zhang X.; Wang H.; Wang X.; Wang N.; Wu X. Int. J. Hydrog. Energ. 2025, 109, 1437.
[19]	Dong Y.; Yang M.; Li L.; Zhu T.; Chen X.; Cheng H. Int. J. Hydrog. Energ. 2019, 44, 4919.
[20]	Dong Y.; Zhao H.; Zhao Y.; Yang M.; Zhang H.; Cheng H. RSC Adv. 2021, 11, 15729.
[21]	Chen Z.; Yang M.; Zhu T.; Zhang Z.; Chen X.; Liu Z.; Dong Y.; Cheng G.; Cheng H. Int. J. Hydrog. Energ. 2018, 43, 12688.
[22]	Dong Y.; Yang M.; Yang Z.; Ke H.; Cheng H. Int. J. Hydrog. Energ. 2015, 40, 10918.
[23]	Liu L.; Zhu T.; Li C.; Zhao Y.; Yang M.; Ke H.; Dong Y. ACS Sustain. Chem. Eng. 2023, 11, 14497.
[24]	Oh J.; Jeong K.; Kim T. W.; Kwon H.; Han J. W.; Park J. H.; Suh Y.-W. Chemsusche. 2018, 11, 661.
[25]	Yang M.; Cheng G.; Xie D.; Zhu T.; Dong Y.; Ke H.; Cheng H. Int. J. Hydrog. Energy. 2018, 43, 8868.
[26]	Guo X.; Hong P.; Yao L.; Liu X.; Jiang Z.; Shi B. Fue. 2023, 353, 129231.
[27]	Zhao M.; Wang X.; Liu Y.; He Y.; Li D. Acta Chim. Sinic. 2021, 79, 1518 (in Chinese).
	(赵敏, 王雪, 刘雅楠, 贺宇飞, 李殿卿, 化学学报, 2021, 79, 1518.)
[28]	Jiao H.; Xu G.; Sang Y.; Chen H.; Li Y. Catal. Toda. 2024, 430, 114542.
[29]	Shi Z.; Wan C.; Huang M.; Pan J.; Luo R.; Li D.; Jiang L. Int. J. Hydrog. Energ. 2020, 45, 17299.
[30]	Koskin A. P.; Zhang J.; Belskaya O. B.; Bulavchenko O. A.; Konovalova D. A.; Stepanenko S. A.; Ishchenko A. V.; Danilova I. G.; Yurpalov V. L.; Larichev Y. V.; Kukushkin R. G.; Yeletsky P. M. J. Magnes. Alloy. 2024, 12, 3245.
[31]	Ding H.; Qi X.; Yun X.; Ge J.; Tian Y.; Lei X.; Zhang F. ACS Sustain. Chem. Eng. 2022, 10, 9687.
[32]	Jia H.; Yang Z.; Yun X.; Lei X.; Kong X.; Zhang F. Ind. Eng. Chem. Res. 2019, 58, 22702.
[33]	Li L.; Tang J.; Wang L.; Li J.; Quan H.; Lin B.; Wang H.; Li J.; Zhou T. Acta Chim. Sinic. 2024, 82, 748 (in Chinese).
	(李雷, 唐鋆磊, 王丽涛, 李江涛, 全洪林, 林冰, 王宏, 李佳奇, 周太刚, 化学学报, 2024, 82, 748.)
[34]	Wang B.; Li P.-Y.; Dong Q.; Chen L.-Q.; Wang H.-Q.; Han P.-L.; Fang T. ACS Appl. Energ. Mater. 2023, 6, 1741.
[35]	Xu Z.; Zhao N.; Hillmansen S.; Roberts C.; Yan Y. Energie. 2022, 15, 6467.
[36]	Sotoodeh F.; Smith K. J. J. Catal. 2011, 279, 36.
[37]	Sotoodeh F.; Huber B. J. M.; Smith K. J. Int. J. Hydrog. Energ. 2012, 37, 2715.

水滑石限域Ni纳米颗粒催化氮甲基吲哚高效储氢

Hydrotalcite-Confined Ni Nanoparticles Catalyzed Efficient Hydrogen Storage of N-Methylindole

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 7

References 37

Related Articles 1

Recommended Articles

Metrics

Comments