Preparation of Ni-Ir/Al2O3 Catalyst and Its Application for Hydrogen Generation from Hydrous Hydrazine

doi:10.11900/0412.1961.2021.00337

Acta Metall Sin

2023, Vol. 59

Issue (10): 1335-1345 DOI: 10.11900/0412.1961.2021.00337

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Preparation of Ni-Ir/Al₂O₃ Catalyst and Its Application for Hydrogen Generation from Hydrous Hydrazine

DU Zonggang(

), XU Tao, LI Ning, LI Wensheng, XING Gang, JU Lu, ZHAO Lihua, WU Hua, TIAN Yucheng

Xi'an Aerospace Propulsion Test Technique Institute, Xi'an 710100, China

Cite this article:

DU Zonggang, XU Tao, LI Ning, LI Wensheng, XING Gang, JU Lu, ZHAO Lihua, WU Hua, TIAN Yucheng. Preparation of Ni-Ir/Al₂O₃ Catalyst and Its Application for Hydrogen Generation from Hydrous Hydrazine. Acta Metall Sin, 2023, 59(10): 1335-1345.

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Abstract

Hydrogen is clean energy that can replace traditional fossil fuels in the future because of its high energy density, easy recharging, and availability of current liquid fuel infrastructure. However, the polymer-electrolyte membrane fuel cell requires controlled storage and efficient hydrogen release. Recently, liquid-phase chemical hydrogen storage materials with high gravimetric hydrogen density have emerged as promising candidates to overcome such challenges. Among these materials of interest, hydrous hydrazine (N₂H₄·H₂O) is the best candidate; however, it has not been fully explored as an alternative for chemical hydrogen storage applications. A catalyst is essential to hydrogen production at a sufficient reaction rate for N₂H₄·H₂O-based hydrogen generation systems. In this study, a series of supported Ni_{100 -}_x Ir _x /Al₂O₃catalysts were prepared using simple impregnation, roasting, and reduction method. The effect of reaction conditions on the activity and selectivity was evaluated in decomposing N₂H₄·H₂O to hydrogen. The phase/structure of the catalysts was characterized using XRD, TEM, XPS, BET, and H₂-TPD to gain insight into the catalytic performance of the Ni_{100 -}_x Ir _x /Al₂O₃catalysts. It indicated that the Ni₆₀Ir₄₀/Al₂O₃ catalyst, comprising Ni-Ir alloy nanoparticles with an average size of 2-4 nm and crystalline γ-Al₂O₃, exhibited excellent catalytic activity (> 200 h^-1) and selectivity (> 99%) toward hydrogen generation from N₂H₄·H₂O at different temperatures, from 293 K to 353 K. The Ni₆₀Ir₄₀/Al₂O₃ catalyst is durable and stable; however, the catalytic activity decreased from 249.2 to 225.0 h^-1 (~9.7%) after five runs with 99% H₂ selectivity at 323 K toward the dehydrogenation of N₂H₄·H₂O. In addition, parameters, such as temperature, N₂H₄·H₂O and NaOH concentration, and catalyst mass on N₂H₄·H₂O decomposition were investigated over the Ni₆₀Ir₄₀/Al₂O₃catalyst. The kinetic rate equation for catalytic decomposition of N₂H₄·H₂O could be represented using the following expression: r = -k[N₂H₄·H₂O]^0.346/0.054[NaOH]^0.307[Catalyst]^1.004, where k = 4.62 × 10⁹exp(-5088.49 / T). The results could provide a theoretical foundation for applying N₂H₄·H₂O as a promising hydrogen storage material.

Key words: catalyst hydrous hydrazine hydrogen generation reaction kinetics

Received: 15 August 2021

ZTFLH:

O643

Fund: Special Fund of Shaanxi Key Laboratory of Special Fuel Chemistry and Material(SPCF-SKL-2020-0006)

Corresponding Authors: DU Zonggang, professor, Tel: (029)85602796, E-mail: 165s8yf@163.com

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	Articles by authors
	DU Zonggang
	XU Tao
	LI Ning
	LI Wensheng
	XING Gang
	JU Lu
	ZHAO Lihua
	WU Hua
	TIAN Yucheng

URL:

https://www.ams.org.cn/EN/10.11900/0412.1961.2021.00337 OR https://www.ams.org.cn/EN/Y2023/V59/I10/1335

Fig.1 TEM images of Ni_{100 -}_x Ir _x /Al₂O₃ catalysts samples (d—diameter of particle)
(a) Ni/Al₂O₃ (b) Ni₈₀lr₂₀/Al₂O₃ (c) Ni₆₀lr₄₀/Al₂O₃ (d) Ni₄₀lr₆₀/Al₂O₃ (e) Ni₂₀lr₈₀/Al₂O₃ (f) lr/Al₂O₃

Fig.2 XRD spectra of Ni_{100 -}_x Ir _x /Al₂O₃ catalysts samples

Fig.3 XPS results of Ni_{100 -}_x Ir _x /Al₂O₃ catalysts
(a) Ni2p (b) Ir4f (c) O1s

Fig.4 N₂ adsorption/desorption isotherm curves of Al₂O₃ carrier and Ni₆₀Ir₄₀/Al₂O₃catalyst (STP—standard temperature and pressure, P is the partial pressure of nitrogen, and P₀ is the saturated vapor pressure of nitrogen at liquid nitrogen temperature)

Table 1 Comparisons of BET resutts between Al₂O₃carrier and Ni₆₀Ir₄₀/Al₂O₃catalyst

Fig.5 Time course profiles for the N₂H₄·H₂O decomposition over the Ni_{100 -}_x Ir _x /Al₂O₃catalysts (a) and effect of Ir content (molar ratio) in the catalyst on the reaction rate (r) and H₂ selectivity (b) ( $n H 2 + N 2$ / $n N 2 H 4$ —molar fraction of (H₂ + N₂) to N₂H₄)

Table 2 Comparisons of catalytic performance of the Ni_{100 -}_x Ir _x /Al₂O₃ catalysts

Fig.6 Effects of reaction temperature on N₂H₄·H₂O decomposition in the presence of Ni₆₀Ir₄₀/Al₂O₃(a) and NiIr_0.1/Al₂O₃(c), and the responding reaction rates for the activation energy determination according Arrhenius equation (R²—goodness of fit) (b, d)

Fig.7 Time profiles for the total gas volume ( $V H 2 + N 2$ ) from the catalytic decomposition of N₂H₄·H₂O solutions with varied concentrations (a), effects of N₂H₄·H₂O concentration on its initial reaction rate in the presence of Ni₆₀Ir₄₀/Al₂O₃at 303 K (b), and plots of lnrvs ln[N₂H₄·H₂O] with low (c) and high (d) N₂H₄·H₂O concentrations

Fig.8 Effects of NaOH concentration on N₂H₄·H₂O decomposition in the presence of Ni₆₀Ir₄₀/Al₂O₃(a) and a plot of lnr vs ln[NaOH] (b)

Fig.9 Effects of catalyst concentration on N₂H₄·H₂O decomposition in the presence of Ni₆₀Ir₄₀/Al₂O₃(a) and a plot of $l n r N 2 H 4$ vs ln[catalyst] (b)

Fig.10 Durability test for H₂ generation from N₂H₄·H₂O over Ni₆₀Ir₄₀/Al₂O₃catalyst (a) and the H₂-TPD profiles of fresh and post-used catalysts (b) (TPD—temperature programmed desorption)

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