不同浓度甲烷对熔融盐催化裂解碳产物的形貌调控研究

doi:10.15541/jim20250236

无机材料学报 ›› 2026, Vol. 41 ›› Issue (3): 385-392.DOI: 10.15541/jim20250236 CSTR: 32189.14.10.15541/jim20250236

不同浓度甲烷对熔融盐催化裂解碳产物的形貌调控研究

唐依帆¹(), 黄泽皑¹^,²(), 张瑞阳¹^,², 詹俊杰¹, 陈国星³, 杨茗凯¹, 刘彤¹, 陈红吉¹, 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:2025-06-04 修回日期:2025-08-26 出版日期:2025-09-11 网络出版日期:2025-09-11
通讯作者: 黄泽皑, 副教授. E-mail: zeai.huang@swpu.edu.cn;
周莹, 教授. E-mail: yzhou@swpu.edu.cn
作者简介:唐依帆(2001-), 女, 硕士研究生. E-mail:15309939516@139.com
基金资助:
国家杰出青年科学基金(52325401);四川省科技计划“揭榜挂帅”项目(2023YFG0375)

Morphology Control of Carbon Products from Catalytic Pyrolysis of Methane with Different Concentrations in Molten Salt

TANG Yifan¹(), HUANG Zeai¹^,²(), ZHANG Ruiyang¹^,², ZHAN Junjie¹, CHEN Guoxing³, YANG Mingkai¹, LIU Tong¹, CHEN Hongji¹, 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:2025-06-04 Revised:2025-08-26 Published:2025-09-11 Online:2025-09-11
Contact: HUANG Zeai, associate professor. E-mail: zeai.huang@swpu.edu.cn;
ZHOU Ying, professor. E-mail: yzhou@swpu.edu.cn
About author:TANG Yifan (2001-), female, Master candidate. E-mail: 15309939516@139.com
Supported by:
National Science Fund for Distinguished Young Scholars(52325401);“Jiebang Guashuai” (Open Challenge and Leadership) Project of Sichuan Science and Technology Program(2023YFG0375)

摘要/Abstract

摘要：

甲烷(CH₄)作为温室气体和重要的能源资源, 其高效低碳催化转化对实现“双碳”目标具有重要意义。不同来源的CH₄具有显著的浓度差异, 这对其转化技术的选择产生了重要影响。然而, 关于CH₄浓度变化对催化性能的影响研究较少, 尤其是在CH₄催化裂解制备碳材料领域。本研究以熔融盐催化裂解技术为核心, 系统研究了不同浓度(20%~100%) CH₄在CuCl₂-NaCl熔融盐体系中的催化裂解行为及碳产物形貌调控机制。结果发现, 石墨烯薄膜的生成归因于高浓度CH₄下气泡表面碳原子二维拼接及后续薄膜生长。在CuCl₂-NaCl体系下, 高浓度CH₄有利于生成规整的石墨烯结构, 低浓度CH₄则以形成碎片化碳为主。不同种类的熔融盐体系可形成石墨片、短棒状碳管、薄膜状碳等不同形貌的碳产物, 多种表征手段揭示, 不同浓度条件决定了碳核的生长方式。本研究为明确熔融盐体系中CH₄浓度梯度驱动下碳产物形貌调控机制提供了理论依据, 对高附加值碳材料绿色制备和低碳技术开发具有重要的参考意义。

关键词: CH₄裂解, 熔融介质, 浓度梯度, CuCl₂-NaCl, 形貌调控

Abstract:

Methane (CH₄), as both a greenhouse gas and a crucial energy source, plays an important role in achieving China’s carbon peaking and carbon neutrality goals. The significant concentration differences of CH₄ from various sources influence the selection of relevant conversion technologies. However, little research has addressed the impact of CH₄ concentration variation on catalytic performance, and studies focusing on the catalytic pyrolysis of methane for carbon material production are especially scarce. In this work, molten salt catalytic pyrolysis was employed as the core strategy to systematically investigate the catalytic decomposition behavior of CH₄ with varying concentrations (20%-100%) and the morphology control mechanisms of carbon products in a CuCl₂-NaCl molten salt system. The results revealed that the formation of graphene films was attributed to the two-dimensional assembly of carbon atoms on bubble surfaces at high CH₄ concentrations, followed by subsequent film growth. High CH₄ concentration in the CuCl₂-NaCl system favored the formation of well-ordered graphene structures, while low concentrations primarily produced fragmented carbon. Furthermore, various molten salt systems yielded different carbon morphologies, including graphite sheets, short rod-like carbon nanotubes, and film-like carbon. Comprehensive characterizations demonstrated that the CH₄ concentration determined growth mode of the carbon products. This study elucidates morphology control mechanisms of the carbon products driven by the CH₄ concentration gradient in molten salt systems, providing a theoretical basis for the environmentally friendly synthesis of high-value-added carbon materials and development of low-carbon technologies.

Key words: CH₄ pyrolysis, molten medium, concentration gradient, CuCl₂-NaCl, morphology control

中图分类号:

O643

唐依帆, 黄泽皑, 张瑞阳, 詹俊杰, 陈国星, 杨茗凯, 刘彤, 陈红吉, 周莹. 不同浓度甲烷对熔融盐催化裂解碳产物的形貌调控研究[J]. 无机材料学报, 2026, 41(3): 385-392.

TANG Yifan, HUANG Zeai, ZHANG Ruiyang, ZHAN Junjie, CHEN Guoxing, YANG Mingkai, LIU Tong, CHEN Hongji, ZHOU Ying. Morphology Control of Carbon Products from Catalytic Pyrolysis of Methane with Different Concentrations in Molten Salt[J]. Journal of Inorganic Materials, 2026, 41(3): 385-392.

图/表 10

表1 金属盐筛选实验的药品用量计算

Table 1 Calculation of drug dosage for metal salt screening experiment

Medicine	P_XCl/%	M_X/(g·mol^-1)	M_XCl/(g·mol^-1)
MnCl₂·4H₂O	99	54.9	197.9
CaCl₂	96	40.1	111.0
NiCl₂·6H₂O	98	58.7	237.7
CuCl₂	98	63.6	134.5
LiCl	99	6.9	42.4

图1 熔融法热解甲烷在线进样反应系统结构示意图

Fig. 1 Schematic diagram of online sampling reaction system for methane pyrolysis using the molten method

图2 金属氯盐的催化裂解结果

Fig. 2 Results on catalytic pyrolysis of metal chlorides (a) Time variation curves of CH4 conversion rate; (b) H2 production ratio in the product after 3 h of reaction

表2 金属氯盐催化裂解活性测试实验数据

Table 2 Experimental data on catalytic pyrolysis activity of metal chlorides

Molten metal	CH₄ conversion rate/%	Carbon yield/ (mg·min^-1)
CuCl₂-NaCl	4.6	0.5
MnCl₂-NaCl	3.3	0.4
CaCl₂-NaCl	2.8	0.3
NiCl₂-NaCl	14.6	1.6
LiCl-NaCl	0.9	0.1

图3 熔融金属氯盐催化裂解碳产物的SEM照片

Fig. 3 SEM images of carbon products from catalytic pyrolysis of molten metal chlorides (a) CuCl2-NaCl; (b) MnCl2-NaCl; (c) CaCl2-NaCl; (d) NiCl2-NaCl

图4 CH4进气浓度对CH4转化率的影响

Fig. 4 Effect of CH4 inlet concentration on CH4 conversion rate

图5 不同CH4浓度所得碳产物的XRD图谱和局部放大图(2θ=20°~28°)

Fig. 5 XRD patterns and local magnification (2θ=20°-28°) of carbon products obtained from methane concentration control groups

图6 不同CH4浓度下碳产物的(a) Raman图谱和(b~e) SEM照片

Fig. 6 (a) Raman spectra and (b-e) SEM images of carbon products under different methane concentrations (b) 40%; (c) 60%; (d) 80%; (e) 100%

图7 (a, b) 40% CH4和(c, d) 100% CH4浓度下碳产物的高倍(a, c) SEM和(b, d) TEM照片

Fig. 7 High magnification (a, c) SEM and (b, d) TEM images of carbon products under (a, b) 40% CH4 and (c, d) 100% CH4

图8 不同CH4浓度下碳的生长过程

Fig. 8 Growth process of carbon under different methane concentrations

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不同浓度甲烷对熔融盐催化裂解碳产物的形貌调控研究

Morphology Control of Carbon Products from Catalytic Pyrolysis of Methane with Different Concentrations in Molten Salt

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