Ni-Mg-Al类水滑石衍生镍基催化剂的制备及其氨分解性能

doi:10.15541/jim20240140

无机材料学报 ›› 2025, Vol. 40 ›› Issue (1): 53-60.DOI: 10.15541/jim20240140 CSTR: 32189.14.10.15541/jim20240140

Ni-Mg-Al类水滑石衍生镍基催化剂的制备及其氨分解性能

连敏丽(), 苏佳欣, 黄鸿杨, 嵇玉寅, 邓海帆, 张彤, 陈崇启, 李达林()

福州大学化工学院, 化肥催化剂国家工程研究中心, 福州 350002

收稿日期:2024-03-22 修回日期:2024-07-19 出版日期:2025-01-20 网络出版日期:2024-07-26
通讯作者: 李达林, 研究员. E-mail: dalinli@fzu.edu.cn
作者简介:连敏丽(1999-), 女, 硕士研究生. E-mail: 975216049@qq.com
基金资助:
国家重点研发计划(2022YFB4002401);国家自然科学基金(22378070)

Supported Ni Catalysts from Ni-Mg-Al Hydrotalcite-like Compounds：Preparation and Catalytic Performance for Ammonia Decomposition

LIAN Minli(), SU Jiaxin, HUANG Hongyang, JI Yuyin, DENG Haifan, ZHANG Tong, CHEN Chongqi, LI Dalin()

National Engineering Research Center of Chemical Fertilizer Catalyst, College of Chemical Engineering, Fuzhou University, Fuzhou 350002, China

Received:2024-03-22 Revised:2024-07-19 Published:2025-01-20 Online:2024-07-26
Contact: LI Dalin, professor. E-mail: dalinli@fzu.edu.cn
About author:LIAN Minli (1999-), female, Master candidate. E-mail: 975216049@qq.com
Supported by:
National Key R&D Program of China(2022YFB4002401);National Natural Science Foundation of China(22378070)

摘要/Abstract

摘要：

氨分解作为一种很有前景的现场制氢技术, 关键在于开发出廉价、高性能的催化剂。本研究通过共沉淀法合成系列Ni_xMg_75-_xAl₂₅类水滑石化合物(HTlc)作为前驱体, 经过焙烧和还原处理制备负载型高分散Ni/Mg(Al)O催化剂并用于氨分解制氢, 采用不同研究手段对样品进行了表征, 考察了Ni含量和氨还原对催化性能的影响。结果显示, HTlc前驱体经过焙烧分解形成Mg(Ni, Al)O固溶体, Ni物种与载体之间存在较强的相互作用, 经750 ℃氨还原得到高分散Ni金属纳米颗粒, 其平均晶粒尺寸为5.9~7.7 nm。质谱分析表明, 氨还原过程中无氮氧化物(NO_x)生成, 同时750 ℃氨还原与氢还原催化剂的活性相当, 说明氨是一种合适的还原气。催化剂活性随着Ni含量和还原温度升高而增加。其中, 750 ℃氨还原Ni₂₀Mg₅₅Al₂₅催化剂在30000 mL·g_cat^-1·h^-1、600 ℃下的氨转化率为98%, 且在100 h反应过程中转化率保持不变, Ni金属无明显烧结现象, 催化剂表现出良好的活性、稳定性和抗烧结性能。

关键词: 制氢, 氨分解, 镍催化剂, 类水滑石化合物

Abstract:

Ammonia decomposition is a promising approach for on-site hydrogen generation for fuel cells, and the development of a cost-effective and efficient catalyst is highly desired. In this study, a series of Ni_xMg_75-_xAl₂₅ hydrotalcite-like compounds (HTlc) with different Ni contents were synthesized by co-precipitation, followed by calcination and reduction treatments. Influences of Ni content and ammonia reduction on the catalytic performance for ammonia decomposition were investigated. The characterization results of the as-prepared samples showed that HTlc was decomposed into Mg(Ni, Al)O solid solution by calcination, which displayed a strong interaction between Ni species and support, while upon reduction with ammonia at 750 ℃, well-dispersed Ni metal nanoparticles with an average crystallite size range of 5.9-7.7 nm were formed. No nitrogen oxides (NO_x) were produced during the NH₃ reduction process as indicated by mass spectrometry analysis, and the catalyst reduced with ammonia showed comparable activity with that reduced with hydrogen, suggesting that ammonia can be used as a reductant gas. The catalyst activity increased with the increase of Ni content and reduction temperature. Among the catalysts, the Ni₂₀Mg₅₅Al₂₅ catalyst reduced with ammonia at 750 ℃ showed the best activity, which afforded 98% ammonia conversion at 600 ℃ at a space velocity of 30000 mL·g_cat^-1·h^-1, and no evident deactivation was observed during a 100 h test, demonstrating good activity, stability, and sintering resistance.

Key words: hydrogen production, ammonia decomposition, nickel catalyst, hydrotalcite-like compound

中图分类号:

O643

连敏丽, 苏佳欣, 黄鸿杨, 嵇玉寅, 邓海帆, 张彤, 陈崇启, 李达林. Ni-Mg-Al类水滑石衍生镍基催化剂的制备及其氨分解性能[J]. 无机材料学报, 2025, 40(1): 53-60.

LIAN Minli, SU Jiaxin, HUANG Hongyang, JI Yuyin, DENG Haifan, ZHANG Tong, CHEN Chongqi, LI Dalin. Supported Ni Catalysts from Ni-Mg-Al Hydrotalcite-like Compounds：Preparation and Catalytic Performance for Ammonia Decomposition[J]. Journal of Inorganic Materials, 2025, 40(1): 53-60.

图/表 10

图1 NixMg75-xAl25 HTlc前驱体的(A)XRD谱图和(B)SEM照片

Fig. 1 (A) XRD patterns and (B) SEM images of the as-synthesized NixMg75-xAl25 HTlc precursors (a) Ni5Mg70Al25-HTlc; (b) Ni10Mg65Al25-HTlc; (c) Ni15Mg60Al25-HTlc; (d) Ni20Mg55Al25-HTlc; (e) Ni25Mg50Al25-HTlc

表1 NixMg75-xAl25 HTlc前驱体的金属含量和晶格参数

Table 1 Metal contents and lattice parameters of the NixMg75-xAl25 HTlc precursors

Sample	Metal content/(%, in atom)			Lattice parameter/nm
Sample	Ni	Mg	Al	a	c
Ni₅Mg₇₀Al₂₅-HTlc	5.5	68.1	26.4	0.306	2.344
Ni₁₀Mg₆₅Al₂₅-HTlc	10.4	63.1	26.5	0.305	2.344
Ni₁₅Mg₆₀Al₂₅-HTlc	15.9	58.4	25.7	0.306	2.344
Ni₂₀Mg₅₅Al₂₅-HTlc	20.5	53.5	26.0	0.305	2.344
Ni₂₅Mg₅₀Al₂₅-HTlc	25.6	48.9	25.5	0.305	2.347

图2 NixMg75-xAl25焙烧样品的(A)XRD谱图和(B)H2-TPR曲线

Fig. 2 (A) XRD patterns and (B) H2-TPR profiles of calcined NixMg75-xAl25 (a) Ni5Mg70Al25; (b) Ni10Mg65Al25; (c) Ni15Mg60Al25; (d) Ni20Mg55Al25; (e) Ni25Mg50Al25

表2 焙烧样品的织构性质和还原催化剂中Ni金属晶粒尺寸

Table 2 Textural properties of the calcined samples and crystallite size of Ni metal in the reduced catalysts

Sample	Surface area/ (m²·g_cat^-1)	Pore volume/ (cm³·g_cat^-1)		Ni crystal size/ nm
Ni₅Mg₇₀Al₂₅	197.3	0.45	7.5	7.7
Ni₁₀Mg₆₅Al₂₅	173.0	0.31	5.6	7.6
Ni₁₅Mg₆₀Al₂₅	217.4	0.36	5.6	5.9
Ni₂₀Mg₅₅Al₂₅	218.6	0.38	5.5	5.9
Ni₂₅Mg₅₀Al₂₅	204.4	0.43	7.0	6.7

图3 Ni20Mg55Al25样品的NH3-TPR质谱分析

Fig. 3 Analysis of NH3-TPR mass spectrum for Ni20Mg55Al25 Colorful figure is available on website

图4 750 ℃氨还原NixMg75-xAl25催化剂的XRD谱图

Fig. 4 XRD patterns of NixMg75-xAl25 catalysts reduced at 750 ℃ with NH3 (a) Ni5Mg70Al25; (b) Ni10Mg65Al25; (c) Ni15Mg60Al25; (d) Ni20Mg55Al25; (e) Ni25Mg50Al25

图5 750 ℃氨还原Ni20Mg55Al25催化剂的(a)HAADF-STEM照片、(b~f)EDX元素分布图、(g, h)TEM和HRTEM照片、(i)Ni金属粒径分布图

Fig. 5 (a) HAADF-STEM image, (b-f) EDX elemental mappings, (g) TEM image, (h) HRTEM image, and (i) Ni particle size distribution for the Ni20Mg55Al25 catalyst reduced at 750 ℃ with NH3

图6 NixMg75-xAl25催化剂的氨分解活性

Fig. 6 Catalytic ammonia decomposition over the NixMg75-xAl25 catalysts Influence of (A) Ni contents, (B) reduction temperature, and (C) reduction atmosphere

图7 Ni20Mg55Al25催化剂(A)在不同空速下的活性、(B)长期稳定性和(C)反应后XRD谱图

Fig. 7 (A) Catalytic activities at different space velocities and (B) long-term stability of Ni20Mg55Al25 (pre-reduced with NH3 at 750 ℃), and (C) XRD patterns of the fresh and used Ni20Mg55Al25

表3 Ni催化剂的氨分解性能

Table 3 Catalytic performance of Ni catalysts for ammonia decomposition

Catalyst	Feed gas	Space velocity/ (mL·g_cat^-1·h^-1)	Temperature/ ℃	NH₃ conversion/ %	NH₃ reaction rate/ (mmol· g_cat^-1·min^-1)	Ref.
Ni₂₀Mg₅₅Al₂₅	Pure NH₃	30000	550	68.5	15.3	This work
NiCe_0.85Zr_0.15O	Pure NH₃	30000	550	63	14.1	[33]
Ni/cCeO₂(IMP)	Pure NH₃	30000	550	51	11.4	[34]
Ni_MgAl(6:1)	Pure NH₃	30000	550	48	10.7	[26]
Ni/MCM-41(TIE)	Pure NH₃	30000	550	47.6	10.6	[31]
Ni/BaZrO₃	Pure NH₃	20000	550	62	9.2	[29]
Ni_1.2Ce_0.1Al	Pure NH₃	45000	550	26	8.7	[32]
Ni/La₂O₃	Pure NH₃	6000	550	78.9	3.5	[30]

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Ni-Mg-Al类水滑石衍生镍基催化剂的制备及其氨分解性能

Supported Ni Catalysts from Ni-Mg-Al Hydrotalcite-like Compounds：Preparation and Catalytic Performance for Ammonia Decomposition

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