Ni-Ir/Al2O3 负载型催化剂的制备及其用于水合肼分解制氢性能

doi:10.11900/0412.1961.2021.00337

金属学报

2023, Vol. 59

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

研究论文

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Ni-Ir/Al₂O₃ 负载型催化剂的制备及其用于水合肼分解制氢性能

杜宗罡(

), 徐涛, 李宁, 李文生, 邢钢, 巨璐, 赵利华, 吴华, 田育成

西安航天动力试验技术研究所西安 710100

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

引用本文:

杜宗罡, 徐涛, 李宁, 李文生, 邢钢, 巨璐, 赵利华, 吴华, 田育成. Ni-Ir/Al₂O₃ 负载型催化剂的制备及其用于水合肼分解制氢性能[J]. 金属学报, 2023, 59(10): 1335-1345.
Zonggang DU, Tao XU, Ning LI, Wensheng LI, Gang XING, Lu JU, Lihua ZHAO, Hua WU, Yucheng TIAN. Preparation of Ni-Ir/Al₂O₃ Catalyst and Its Application for Hydrogen Generation from Hydrous Hydrazine[J]. Acta Metall Sin, 2023, 59(10): 1335-1345.

全文: PDF(3029 KB) HTML

摘要:

采用一种简单的浸渍-还原工艺制备出镍-铱/氧化铝(Ni-Ir/Al₂O₃)负载型催化剂用于水合肼(N₂H₄·H₂O)催化分解制氢。该催化剂是将活性组分Ni-Ir负载于颗粒状Al₂O₃载体上制备而成，采用TEM、XRD、XPS、BET和H₂-TPD等对其结构进行表征，并结合N₂H₄·H₂O催化分解制氢实验开展了催化剂配方优化、催化反应动力学及循环耐久性研究。结果表明，粒径2~4 nm的Ni-Ir合金活性金属均匀负载于Al₂O₃载体表面，Ni₆₀Ir₄₀/Al₂O₃催化剂在293~353 K温度范围内均表现出优异的肼催化分解活性(> 200 h^-1)，在该宽温域范围内的制氢选择性高达99%以上，且该催化剂具有优异的耐久性，在303 K条件下循环5 cyc后仍保持99%以上的氢选择性，而反应速率仅由249.2 h^-1略减至225.0 h^-1，活性衰减约9.7%。此外，对N₂H₄·H₂O分解制氢反应动力学及各相关参数的影响进行了研究，包括温度、N₂H₄·H₂O浓度、NaOH助剂浓度和催化剂用量，得到其反应动力学方程为r = -k[N₂H₄·H₂O]^0.346/0.054[NaOH]^0.307[Catalyst]^1.004，并初步探究了催化剂在制氢反应过程的活性衰减原因。

关键词 ：催化剂, 水合肼, 制氢, 反应动力学

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

收稿日期: 2021-08-15

ZTFLH:

O643

基金资助:陕西省特种能源化学与材料重点实验室开放基金项目(SPCF-SKL-2020-0006)

通讯作者: 杜宗罡，165s8yf@163.com，主要从事新型液体推进剂及相关技术的研究

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

作者简介: 杜宗罡，男，1971年生，研究员，硕士

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https://www.ams.org.cn/CN/10.11900/0412.1961.2021.00337 或 https://www.ams.org.cn/CN/Y2023/V59/I10/1335

图1 Ni100 - x Ir x /Al2O3系列催化剂的TEM像

图2 Ni100 - x Ir x /Al2O3催化剂XRD谱

图3 Ni100 - x Ir x /Al2O3催化剂样品XPS测试结果

图4 Al2O3载体和Ni60Ir40/Al2O3催化剂样品的N2吸/脱附等温线曲线

表1 Al2O3载体和Ni60Ir40/Al2O3催化剂样品BET测试结果

图5 Ni100 - x Ir x /Al2O3催化N2H4·H2O分解制氢性能及Ir含量对催化活性及制氢选择性的影响

表2 Ni100 - x Ir x /Al2O3系列催化剂催化N2H4·H2O分解性能数据对比

图6 反应温度对Ni60Ir40/Al2O3和NiIr0.1/Al2O3催化N2H4·H2O分解制氢性能的影响，以及利用Arrhenius方程求解其活化能时的反应速率

图7 不同浓度N2H4·H2O催化分解生成的气体体积(VH2+N2)与时间线性关系曲线，N2H4·H2O浓度对Ni60Ir40/Al2O3在303 K条件下催化分解反应制氢速率的影响，以及高、低浓度条件下lnr与ln[N2H4·H2O]的拟合关系

图8 NaOH浓度对Ni60Ir40/Al2O3催化N2H4·H2O分解反应制氢的影响，及lnr对ln[NaOH]的拟合关系

图9 Ni60Ir40/Al2O3催化剂浓度对N2H4·H2O催化分解反应速率的影响，及lnrN2H4对ln[catalyst]拟合关系

图10 Ni60Ir40/Al2O3催化N2H4·H2O分解制氢循环耐久性测试曲线和反应前后催化剂的H2-TPD曲线

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