基于Cu与金属氧化物-KCl熔融介质的甲烷热解制备少层石墨烯与氢气联产研究

doi:10.15541/jim20240445

无机材料学报 ›› 2025, Vol. 40 ›› Issue (5): 473-480.DOI: 10.15541/jim20240445

基于Cu与金属氧化物-KCl熔融介质的甲烷热解制备少层石墨烯与氢气联产研究

杨茗凯¹(), 黄泽皑¹^,², 周芸霄¹, 刘彤¹, 张魁魁¹, 谭浩¹, 刘梦颖¹, 詹俊杰¹, 陈国星³, 周莹¹^,²()

1.西南石油大学新能源与材料学院, 成都 610500
2.西南石油大学油气藏地质及开发工程全国重点实验室, 成都 610500
3.达姆施塔特工业大学材料与地球科学系, 达姆施塔特 64287

收稿日期:2024-10-25 修回日期:2025-01-10 出版日期:2025-05-20 网络出版日期:2025-01-24
通讯作者: 周莹, 教授. E-mail: yzhou@swpu.edu.cn
作者简介:杨茗凯(1997-), 男, 硕士研究生. E-mail: yangmk97@163.com
基金资助:
国家自然科学基金杰出青年基金(52325401);四川省重点研发项目(2023YFG0106)

Co-production of Few-layer Graphene and Hydrogen from Methane Pyrolysis Based on Cu and Metal Oxide-KCl Molten Medium

YANG Mingkai¹(), HUANG Zeai¹^,², ZHOU Yunxiao¹, LIU Tong¹, ZHANG Kuikui¹, TAN Hao¹, LIU Mengying¹, ZHAN Junjie¹, CHEN Guoxing³, ZHOU Ying¹^,²()

1. School of New Energy and Materials, Southwest Petroleum University, Chengdu 610500, China
2. State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu 610500, China
3. Department of Materials and Earth Sciences, Technical University Darmstadt, Darmstadt 64287, Germany

Received:2024-10-25 Revised:2025-01-10 Published:2025-05-20 Online:2025-01-24
Contact: ZHOU Ying, professor. E-mail: yzhou@swpu.edu.cn
About author:YANG Mingkai (1997-), male, Master candidate. E-mail: yangmk97@163.com
Supported by:
National Natural Science Fund for Distinguished Young Scholars of China(52325401);Key Research and Development Project of Sichuan Province(2023YFG0106)

摘要/Abstract

摘要：

甲烷热解是一种利用化石能源制备高附加值碳材料和氢气的技术。然而, 传统的化学气相沉积(CVD)法和熔融金属催化法在制备石墨烯时存在固体催化剂失活、石墨烯与催化剂分离困难以及反应温度高(≥1100 ℃)等问题, 限制了其工业化应用。本研究提出了通过金属Cu与金属氧化物-KCl熔融介质催化甲烷热解制备石墨烯的创新方案。通过添加金属氧化物(Al₂O₃、TiO₂、ZrO₂、MgO、SiO₂)作为分散剂, 增强了Cu球活性位点的分散性, 特别是Cu球体积分数为50%的Cu/ZrO₂和Cu球体积分数为75%的Cu/MgO催化剂, 可有效制备少层石墨烯。前者表现出最佳活性, 其甲烷转化率为22%, 氢气产率为21.5 mmol/h, 而且能产生大面积、平整的少层石墨烯。本研究为甲烷热解联产石墨烯与氢气的工业化发展提供了新的技术路线, 未来有望实现石墨烯的规模化制备。

关键词: 甲烷热解, 熔融介质, 少层石墨烯, 氢气, 铜/金属氧化物

Abstract:

Methane pyrolysis is a technology that utilizes fossil energy to produce high added value carbon materials and hydrogen. However, traditional methods, such as chemical vapor deposition (CVD) and molten metal catalysis, face challenges in the production of graphene, including catalyst deactivation, difficulty in separating graphene from the catalyst, and high reaction temperatures (≥1100 ℃), which limit their industrial applications. This study proposes an innovative approach to produce graphene by catalyzing methane pyrolysis using Cu and metal oxides-KCl molten medium. By adding metal oxides (Al₂O₃, TiO₂, ZrO₂, MgO, SiO₂) as dispersants, the dispersion of active Cu sites is enhanced. Notably, Cu/ZrO₂ with a Cu content of 50% (in volume) and Cu/MgO with a Cu content of 75% (in volume) catalysts enable the efficient production of few-layer graphene. Cu/ZrO₂ catalyst with a Cu content of 50% (in volume) exhibits the highest activity, achieving a methane conversion rate of 22%, a hydrogen production yield of 21.5 mmol/h, and formation of large-area and smooth few-layer graphene. This study provides a new technical route for co-production of graphene and hydrogen via methane pyrolysis, offering potential for large-scale graphene production in the future.

Key words: methane pyrolysis, molten medium, few-layer graphene, hydrogen, copper/metal oxide

中图分类号:

O643

杨茗凯, 黄泽皑, 周芸霄, 刘彤, 张魁魁, 谭浩, 刘梦颖, 詹俊杰, 陈国星, 周莹. 基于Cu与金属氧化物-KCl熔融介质的甲烷热解制备少层石墨烯与氢气联产研究[J]. 无机材料学报, 2025, 40(5): 473-480.

YANG Mingkai, HUANG Zeai, ZHOU Yunxiao, LIU Tong, ZHANG Kuikui, TAN Hao, LIU Mengying, ZHAN Junjie, CHEN Guoxing, ZHOU Ying. Co-production of Few-layer Graphene and Hydrogen from Methane Pyrolysis Based on Cu and Metal Oxide-KCl Molten Medium[J]. Journal of Inorganic Materials, 2025, 40(5): 473-480.

图/表 16

图1 金属氧化物和Cu含量对甲烷转化率(a)和氢气产率(b)的影响

Fig. 1 Effects of metal oxides and Cu contents on CH4 conversion rate (a) and hydrogen production yield (b)

图2 反应时间对甲烷转化率(a)和氢气产率(b)的影响

Fig. 2 Effects of reaction time on CH4 conversion rate (a) and hydrogen production yield (b)

图3 xCu/ZrO2(a)和xCu/MgO(b)催化剂制备碳材料的Raman光谱图

Fig. 3 Raman spectra of carbon materials produced using xCu/ZrO2 (a) and xCu/MgO (b) catalysts

图4 xCu/ZrO2催化剂制备碳材料的SEM照片

Fig. 4 SEM images of carbon materials produced using xCu/ZrO2 catalysts (a) x=0; (b, c) x=25%; (d) x=50%; (e) x=75%; (f) x=100%

图5 xCu/MgO催化剂制备碳材料的SEM照片

Fig. 5 SEM images of carbon materials produced using xCu/MgO catalysts (a) x=0; (b) x=25%; (c) x=50%; (d, e) x=75%; (f) x=100%

图6 (a~c) 50%Cu/ZrO2催化剂制备的碳材料的TEM照片; (d) 75%Cu/MgO催化剂制备的碳材料的HRTEM照片

Fig. 6 (a-c) TEM images of carbon materials produced using 50%Cu/ZrO2 catalysts; (d) HRTEM image of carbon materials produced using 75%Cu/MgO catalysts

图7 50%Cu/MO催化剂制备的碳材料的XRD图谱

Fig. 7 XRD patterns of carbon materials produced using 50%Cu/MO catalysts

图8 50%Cu/MO催化剂制备的碳材料的TG曲线

Fig. 8 TG curves of carbon materials produced using 50%Cu/MO catalysts

图9 50%Cu/MO催化剂制备的碳材料的氮气吸脱附曲线(a)和孔径分布图(b)

Fig. 9 Nitrogen adsorption-desorption isotherms (a) and pore size distributions (b) of carbon materials produced using 50%Cu/MO catalysts

图10 反应机理示意图

Fig. 10 Schematic diagram of the reaction mechanism 1. Methane pyrolysis to few-layer graphene growth; 2. Few-layer graphene growth to separation; 3. Few-layer graphene separation to floating

表S1 50%Cu/MO催化剂制备的碳材料及杂质的含量

Table 1 S1 Contents of carbon materials and impurity produced using 50%Cu/MO catalysts

Sample	Carbon/% (in mass)	Impurity/% (in mass)
50%Cu/SiO₂	43.4	56.6
50%Cu/MgO	67.5	32.5
50%Cu/ZrO₂	52.2	47.8
50%Cu/TiO₂	62.2	37.8
50%Cu/Al₂O₃	80.2	19.8

表S2 50%Cu/MO催化剂制备碳材料的BET数据

Table 2 S2 BET data for carbon materials produced using 50%Cu/MO catalysts

Sample	Specific surface area/(m²·g^-1)	Pore volume/ (cm³·g^-1)	Average pore diameter/nm
50%Cu/SiO₂	9.03	0.04	19.75
50%Cu/MgO	11.76	0.06	19.26
50%Cu/ZrO₂	10.33	0.05	19.76
50%Cu/TiO₂	13.45	0.07	21.86
50%Cu/Al₂O₃	12.52	0.07	20.78

图S1 xCu/Al2O3(a)、xCu/TiO2(b)和xCu/SiO2(c)催化剂制备碳材料的Raman光谱图

Fig. 11 S1 Raman spectra of carbon materials produced using xCu/Al2O3 (a), xCu/TiO2 (b) and xCu/SiO2 (c) catalysts

图S2 xCu/Al2O3催化剂制备碳材料的SEM照片

Fig. 12 S2 SEM images of carbon materials produced using xCu/Al2O3 catalysts (a) x=0; (b) x=25%; (c, d) x=50%; (e) x=75%; (f) x=100%

图S3 xCu/TiO2催化剂制备碳材料的SEM照片

Fig. 13 S3 SEM images of carbon materials produced using xCu/TiO2 catalysts (a) x=0; (b) x=25%; (c) x=50%; (d, e) x=75%; (f) x=100%

图S4 xCu/SiO2催化剂制备碳材料的SEM照片

Fig. 14 S4 SEM images of carbon materials produced using xCu/SiO2 catalysts (a) x=0; (b) x=25%; (c) x=50%; (d) x=75%; (e, f) x=100%

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基于Cu与金属氧化物-KCl熔融介质的甲烷热解制备少层石墨烯与氢气联产研究

Co-production of Few-layer Graphene and Hydrogen from Methane Pyrolysis Based on Cu and Metal Oxide-KCl Molten Medium

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