钴-镁协同纳米洋葱碳催化剂的制备及低温催化氨分解制氢性能

doi:10.15541/jim20250211

无机材料学报 ›› 2026, Vol. 41 ›› Issue (4): 500-508.DOI: 10.15541/jim20250211 CSTR: 32189.14.10.15541/jim20250211

钴-镁协同纳米洋葱碳催化剂的制备及低温催化氨分解制氢性能

薛新燕¹^,²(), 张晓卫¹^,², 鲁恒¹^,², 李世杰¹^,², 张卫珂¹^,²(), 曾少华²^,³

¹ 太原理工大学材料科学与工程学院, 太原 030024
² 中新国际联合研究院, 广州 510555
³ 南洋理工大学机械与航空航天工程学院, 新加坡 639798

收稿日期:2025-05-15 修回日期:2025-09-23 出版日期:2026-04-20 网络出版日期:2025-10-17
通讯作者: 张卫珂, 副教授. E-mail: zhangweike@tyut.edu.cn
作者简介:薛新燕(2000-), 女, 硕士研究生. E-mail: 17336334425@163.com
基金资助:
山西省自然科学基金(202103021224071);海事转型计划创新孵化基金(SMI-2023-MTP-02)

Co-Mg Synergistic Carbon Nano Onions Catalyst: Preparation and Low-temperature Catalytic Hydrogen Production from Ammonia Decomposition

XUE Xinyan¹^,²(), ZHANG Xiaowei¹^,², LU Heng¹^,², LI Shijie¹^,², ZHANG Weike¹^,²(), CHAN Siewhwa²^,³

¹ School of Material Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, China
² Sino-Singapore International Joint Research Institute (SSIJRI), Guangzhou 510555, China
³ School of Mechanical and Aerospace Engineering, Nanyang Technological University, Singapore 639798, Singapore

Received:2025-05-15 Revised:2025-09-23 Published:2026-04-20 Online:2025-10-17
Contact: ZHANG Weike, associate professor. E-mail: zhangweike@tyut.edu.cn
About author:XUE Xinyan (2000-), female, Master candidate. E-mail: 17336334425@163.com
Supported by:
Natural Science Foundation of Shanxi Province(202103021224071);Maritime Transformation Programme White Space(SMI-2023-MTP-02)

摘要/Abstract

摘要：

氨分解制氢作为一种极具前景的氢气制备方法, 其关键在于开发具有高活性、高选择性和低成本的中低温催化剂。本研究以甲烷850 ℃裂解制氢副产物纳米洋葱碳(CNOs)为载体, 采用均匀沉积沉淀法负载活性金属钴(Co), 并引入碱金属氧化镁(MgO)作助剂, 成功制备了高性能氨分解催化剂。通过系统研究酸洗及钾(K)活化处理对CNOs载体形貌的调控作用, 深入探究了其对催化剂性能的影响机制。多种表征与化学吸附实验证实, 催化剂碱性强度与其氨分解性能呈正相关。引入CNOs显著提升了催化剂的电子导电性, 并促进了Co₂MgO₄纳米颗粒在载体上的均匀分散。这种均匀分散增加了碱性活性位点的暴露度, 从而增强了催化剂表面对氨分子的吸附能力。酸洗处理在CNOs表面引入了更多含氧官能团, 这些官能团可作为锚定位点, 与Co²⁺或Mg²⁺形成强化学键(配位键或离子键), 进而稳定Co₂MgO₄颗粒。这种强相互作用提高了金属氧化物的还原难度, 导致其还原温度升高。催化性能测试表明, CNOs、MgO、K和Co的协同作用显著优化了催化剂的结构特性、金属粒径及催化性能。在一系列合成催化剂中, Co₂Mg/K-CNO’展现出最优异的氨分解催化活性, 在12000 mL·g_cat^-1·h^-1、550 ℃条件下氨转化率为99.6%。

关键词: 氨分解, 催化剂, 纳米洋葱碳, 酸洗, 碱度, 金属-载体相互作用

Abstract:

Decomposition of ammonia for hydrogen production is a promising method, but still needs developing low-cost, highly active and selective catalysts which can operate at moderate temperatures. In this study, carbon nano-onions (CNOs), a byproduct of methane pyrolysis at 850 ℃, were used as a support for loading active metal cobalt (Co) via a uniform deposition-precipitation method. Additionally, magnesium oxide (MgO) was introduced as a promoter to prepare a high-performance ammonia decomposition catalyst. An investigation was conducted on the effects of acid washing and potassium (K) activation treatments on morphology of the CNOs support and catalyst performance with in-depth exploration of their influence mechanisms. Various characterization and chemical adsorption experiments confirmed a positive correlation between basicity strength of the catalyst and its ammonia decomposition performance. It was revealed that incorporation of CNOs significantly enhanced electronic conductivity of the catalyst and facilitated uniform dispersion of Co₂MgO₄ nanoparticles on the support. This uniform dispersion increased the exposure of basic active sites, thereby enhancing the catalyst's ability to adsorb ammonia molecules. The acid washing treatment introduced more oxygen-containing functional groups on the CNOs surface which acted as anchoring sites to form strong chemical bonds (coordination or ionic bonds) with Co²⁺ or Mg²⁺, thus stabilizing Co₂MgO₄ particles. These strong chemical bonds increased the reduction difficulty of the metal oxides, leading to an elevated reduction temperature. Catalytic performance tests demonstrated that the synergistic effect of CNOs, MgO, K, and Co significantly optimized structural characteristics, metal particle size and catalytic performance of the catalyst. Among a series of synthesized catalysts, Co₂Mg/K-CNO’ exhibited the best catalytic activity for ammonia decomposition, achieving a conversion rate of 99.6% at 550 ℃ and a space-time yield of 12000 mL·g_cat^-1·h^-1.

Key words: ammonia decomposition, catalyst, carbon nano-onion, acid washing, alkalinity, metal-support interaction

中图分类号:

O643

薛新燕, 张晓卫, 鲁恒, 李世杰, 张卫珂, 曾少华. 钴-镁协同纳米洋葱碳催化剂的制备及低温催化氨分解制氢性能[J]. 无机材料学报, 2026, 41(4): 500-508.

XUE Xinyan, ZHANG Xiaowei, LU Heng, LI Shijie, ZHANG Weike, CHAN Siewhwa. Co-Mg Synergistic Carbon Nano Onions Catalyst: Preparation and Low-temperature Catalytic Hydrogen Production from Ammonia Decomposition[J]. Journal of Inorganic Materials, 2026, 41(4): 500-508.

图/表 11

图1 不同催化剂的N2吸附-解吸等温线(a)和孔径分布(b)

Fig. 1 N2 adsorption-desorption isotherms (a) and pore size distributions (b) of different catalysts

表1 不同催化剂的比表面积和孔结构参数

Table 1 Specific surface area and pore structure parameters of different catalysts

Catalyst	BET specific surface area/ (m²·g^-1)	Micropore volume/ (cm³·g^-1)	Micropore area/ (m²·g^-1)	Average pore size/nm	Co content/% (in mass)
Co₂Mg	12.7434	0.002212	6.0318	14.6403	50
Co₂Mg/CNO	23.4634	0.002876	6.0278	19.4730	29
Co₂Mg/CNO’	23.4880	0.003788	8.6815	20.0063	29
Co₂Mg/K-CNO	28.5727	0.002307	4.8487	18.2552	29
Co₂Mg/K-CNO’	34.8266	0.002539	8.6815	17.6383	29

图2 催化剂在500 ℃还原前(a)、后(b)的XRD图谱

Fig. 2 XRD patterns of catalysts before (a) and after (b) reduction at 500 ℃

图3 Co2Mg/CNO、Co2Mg/K-CNO和Co2Mg/K-CNO’的XPS谱图

Fig. 3 XPS spectra of Co2Mg/CNO, Co2Mg/K-CNO and Co2Mg/K-CNO’ (a) Co2p; (b) Mg1s; (c) C1s

图4 催化剂的SEM照片

Fig. 4 SEM images of catalysts (a) CNOs; (b) Co2MgO4; (c) Co2Mg/CNO; (d) Co2Mg/CNO’; (e) Co2Mg/K-CNO; (f) Co2Mg/K-CNO’

图5 Co2Mg/K-CNO’的TEM照片(a)和高分辨率TEM(HRTEM)照片(b)

Fig. 5 TEM (a) and HRTEM (b) images of Co2Mg/K-CNO’

图6 催化剂的H2-TPR (a)和CO2-TPD (b)曲线

Fig. 6 H2-TPR (a) and CO2-TPD (b) profiles of catalysts

图7 催化剂氨分解活性对比

Fig. 7 Comparison of catalytic activity for ammonia decomposition (a) Co-Mg synergy; (b) K-activated carriers; (c) Different ratios of Co-Mg

图8 催化剂的氨转化率(a)、氢生成速率(b)、活化能(c)

Fig. 8 Ammonia conversion (a), hydrogen generation rate (b) and activation energy (c) of catalysts

表2 Co基催化剂氨分解性能

Table 2 Catalytic performance of Co-based catalysts for ammonia decomposition

Catalyst	Temperature/℃	GHSV/(mL·g_cat^-1·h^-1)	NH₃ conversion/%	Ref.
Co₂Mg/K-CNO’	550	12000	99.6	This work
20CoNaTi-NT	550	6000	41	[22]
35%Co/SiC-700	550	30000	78.3	[23]
CoO_x@C-700A	500	15000	55	[24]
90CoAl	500	30000	37.8	[25]
Co/CNTs	500	6000	61	[26]
Co-Mo/SiO₂-Cap	500	6000	20	[27]
Co/CeO₂	500	6000	62	[28]
26Co-CAT(A)	500	6000	58	[29]
Fe/CNTs	500	6000	15	[26]
Co/MWCNTs	500	6000	74.6	[30]

图9 Co2Mg/K-CNO’的氨转化率(a)、长期稳定性(b)

Fig. 9 Ammonia conversion (a) and long-term stability (b) of Co2Mg/K-CNO’

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钴-镁协同纳米洋葱碳催化剂的制备及低温催化氨分解制氢性能

Co-Mg Synergistic Carbon Nano Onions Catalyst: Preparation and Low-temperature Catalytic Hydrogen Production from Ammonia Decomposition

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