Research progress of synthesis and properties of coal-based zero-dimensional nanocarbon materials and their applications in energy conversion and storage

doi:10.11949/0438-1157.20220868

Abstract

Abstract:

Coal is the most widely distributed and abundant carbon-containing resource in nature. Its molecular structure has natural similarity with nano-carbon materials, and it is a high-quality nano-carbon material precursor. Over the years, various nanocarbon materials prepared from coal have been widely used in the fields of energy, information, environment, and biomedicine, etc. Among them, coal-based zero-dimensional nanocarbon materials, such as nanodiamonds, fullerenes, carbon nano-onions, and carbon dots, show excellent fluorescence, electrochemical, and catalytic performances due to their small nanometer size, large specific surface area, and unique spherical structure, showing great application potential in the fields of energy conversion and storage. This paper reviews the preparation methods and properties of various zero-dimensional nanocarbon materials based on coal and its derivatives as precursors. This review summarizes the application research progresses of zero-dimensional nanocarbon materials in lighting display, electrochemical energy storage, photo/electrocatalysis, etc. Moreover, this review proposes the current problems, challenges, and improvement strategies of coal-based zero-dimensional nanocarbon materials, and further prospects their future development. This work provides the theoretical and practical support for promoting the high value-added conversion and utilization of coal as well as the large-scale preparation of coal-based zero-dimensional nanocarbon materials.

Key words: coal and its derivatives, zero-dimensional nanocarbon materials, synthesis, energy conversion and storage, fluorescence, electrochemistry, catalysis

摘要：

煤是自然界中分布最广、储量最丰富的含碳资源，其分子结构与纳米碳材料具有天然的相似性，是优质的纳米碳材料前体。多年来，以煤为前体制备的各种纳米碳材料已被广泛应用于能源、信息、环境和生物医学等领域。其中，煤基零维纳米碳材料如纳米金刚石、富勒烯、碳纳米洋葱、碳点等，因其具有小的纳米尺寸、大的比表面积、独特的球形结构等，表现出优异的荧光特性、电化学性能以及催化性能等，在能源转化和存储等领域展现出极大的应用潜力。本文综述了基于煤炭及其衍生物为前驱体的各类零维纳米碳材料的制备方法和性能，并对其在照明显示、电化学储能、光/电催化等方面的应用进展进行总结，指出目前存在的问题与挑战及其解决策略，最后对其未来发展进行了展望。这为促进煤炭的高附加值转化和利用以及大规模制备煤基零维纳米碳材料提供理论和实践支持。

关键词: 煤及其衍生物, 零维纳米碳材料, 合成, 能源转换和存储, 荧光, 电化学, 催化

CLC Number:

O 613.71

Wangjun HOU, Lingpeng YAN, Zheyong CAO, Jingxia ZHENG, Yongzhen YANG. Research progress of synthesis and properties of coal-based zero-dimensional nanocarbon materials and their applications in energy conversion and storage[J]. CIESC Journal, 2022, 73(11): 4791-4813.

侯旺君, 闫翎鹏, 曹哲勇, 郑静霞, 杨永珍. 煤基零维纳米碳材料的合成、性能及其在能源转换和存储应用中的研究进展[J]. 化工学报, 2022, 73(11): 4791-4813.

Figures/Tables 14

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产物	前体	合成方法	粒径	产率/荧光量子产率（QY）	性能	应用领域	文献
NDs	煤	超声法	4~15 nm	—	紫外光下激发为明亮蓝色荧光	生物成像，光伏工程	[7]
	无烟煤	激光烧蚀法	3~5 nm	产率6.2%	在420 nm激发下在乙醇溶液中为绿色荧光，在水溶液中为蓝色荧光	生物成像，光伏，光电子学	[31]
	焦炭	激光烧蚀法	3.2 nm	产率6%	在420 nm激发下在乙醇溶液中为绿色荧光，在水溶液中为蓝色荧光	生物成像，光伏，光电子学	[31]
	煤	化学氧化法	2.1~6.6 nm	产率4%~6%	—	生物传感，药物运输	[32]
C₆₀	褐煤	电弧放电法	—	产率4.5%	—	—	[33]
	烟煤	电弧放电法	—	产率0.67%~2.38%	—	—	[34]
	无烟煤	电弧放电法	—	产率5.96%	—	电化学储能	[34]
CNOs	煤	化学氧化法	5~20 nm	产率76.25%	自然光下，作为催化剂对2-硝基苯酚降解效率很高	光催化降解	[35]
	煤层气	CVD法	5~200 nm	产率70%	内嵌催化剂CNOs具有铁磁性；比容量达到142.31 F/g；电化学性能良好	超级电容器，气敏传感器	[29]
	煤	射频等离子法	10~35 nm	—	CNOs具有空心多面体或准球形形态，化学性能稳定	—	[15]
CDs	煤	激光烧蚀法	9.75~30.25 nm	—	紫外光下激发为绿色荧光；优异的光稳定性、低毒性和生物相容性	生物成像	[36]
	焦煤	激光烧蚀法	约35 nm	QY 34%	蓝色荧光，激发依赖性；随着粒径减小，最强发射峰蓝移	—	[37]
	焦炭	超声法	5.0~6.0 nm	QY 9.2%	蓝色荧光，最佳发射波长为410 nm	照明显示，LED	[38]
	无烟煤	溶剂热法	3.0~6.5 nm	产率25.6%，QY 47%	在紫外激发下显示蓝色荧光	光动力治疗，生物成像	[39]
	煤焦油	溶剂热法	1.5~4.5 nm	QY 29.7%	激发依赖；495~575 nm激发波长下发出橙色荧光，发射波长红移为598~612 nm	生物成像	[40]
	煤焦油沥青	溶剂热法	1.9~5.8 nm	产率18%~23%	结晶度高，分散性好；粒径可控，光吸附能力强	光催化制氢	[41]
	煤焦油中喹啉不溶物	化学氧化法	1.0~14.0 nm	QY 8.5%	紫外光激发下发出绿色荧光，最佳发射波长为578 nm	光学照明，生物成像	[42]
	褐煤	化学氧化/超声法	35 nm	QY 7%	激发依赖，分别在435和403 nm处观察到最佳发射峰；室温磷光	传感	[43]

产物	前体	合成方法	粒径	产率/荧光量子产率（QY）	性能	应用领域	文献
NDs	煤	超声法	4~15 nm	—	紫外光下激发为明亮蓝色荧光	生物成像，光伏工程	[7]
	无烟煤	激光烧蚀法	3~5 nm	产率6.2%	在420 nm激发下在乙醇溶液中为绿色荧光，在水溶液中为蓝色荧光	生物成像，光伏，光电子学	[31]
	焦炭	激光烧蚀法	3.2 nm	产率6%	在420 nm激发下在乙醇溶液中为绿色荧光，在水溶液中为蓝色荧光	生物成像，光伏，光电子学	[31]
	煤	化学氧化法	2.1~6.6 nm	产率4%~6%	—	生物传感，药物运输	[32]
C₆₀	褐煤	电弧放电法	—	产率4.5%	—	—	[33]
	烟煤	电弧放电法	—	产率0.67%~2.38%	—	—	[34]
	无烟煤	电弧放电法	—	产率5.96%	—	电化学储能	[34]
CNOs	煤	化学氧化法	5~20 nm	产率76.25%	自然光下，作为催化剂对2-硝基苯酚降解效率很高	光催化降解	[35]
	煤层气	CVD法	5~200 nm	产率70%	内嵌催化剂CNOs具有铁磁性；比容量达到142.31 F/g；电化学性能良好	超级电容器，气敏传感器	[29]
	煤	射频等离子法	10~35 nm	—	CNOs具有空心多面体或准球形形态，化学性能稳定	—	[15]
CDs	煤	激光烧蚀法	9.75~30.25 nm	—	紫外光下激发为绿色荧光；优异的光稳定性、低毒性和生物相容性	生物成像	[36]
	焦煤	激光烧蚀法	约35 nm	QY 34%	蓝色荧光，激发依赖性；随着粒径减小，最强发射峰蓝移	—	[37]
	焦炭	超声法	5.0~6.0 nm	QY 9.2%	蓝色荧光，最佳发射波长为410 nm	照明显示，LED	[38]
	无烟煤	溶剂热法	3.0~6.5 nm	产率25.6%，QY 47%	在紫外激发下显示蓝色荧光	光动力治疗，生物成像	[39]
	煤焦油	溶剂热法	1.5~4.5 nm	QY 29.7%	激发依赖；495~575 nm激发波长下发出橙色荧光，发射波长红移为598~612 nm	生物成像	[40]
	煤焦油沥青	溶剂热法	1.9~5.8 nm	产率18%~23%	结晶度高，分散性好；粒径可控，光吸附能力强	光催化制氢	[41]
	煤焦油中喹啉不溶物	化学氧化法	1.0~14.0 nm	QY 8.5%	紫外光激发下发出绿色荧光，最佳发射波长为578 nm	光学照明，生物成像	[42]
	褐煤	化学氧化/超声法	35 nm	QY 7%	激发依赖，分别在435和403 nm处观察到最佳发射峰；室温磷光	传感	[43]

合成方法	主要前体	主要产物	优点	缺点
CVD法	煤层气（甲烷），乙炔，煤沥青	C₆₀，CDs，CNOs	操作简单，成本低，易于大批量生产	伴随有杂质相（无定形碳、石墨、催化剂），纯化困难
化学氧化法	褐煤，烟煤，无烟煤，焦炭	NDs，GQDs，CDs	设备简单，能耗低，操作简便	含有杂质，纯化困难
溶剂热法	煤焦油，烟煤，无烟煤	GQDs，CDs	操作简单，能耗低，不需要特殊的反应条件和设备	产量低，伴随着有毒气体的释放
超声法	烟煤，无烟煤	NDs，CQDs	反应速率快，操作简便	加热效率低，能耗高
电化学氧化法	焦炭或无烟煤混合煤焦油	C₆₀，CNOs，CDs	成本低，效率高，产量高	含有杂质相（金属杂质、无定形碳），设备复杂，原料需力学性能好
电弧放电法	焦炭，无烟煤，石墨	C₆₀，CNOs，CDs	产物结晶性好，能够大量制备，易于收集	含有大量含碳杂质（无定形碳、碳纳米管及金属杂质等），设备复杂
等离子体法	烟煤，无烟煤	CNOs，CDs	成本低，能大量制备	含有金属杂质及无定形碳
热解法	炭黑，纳米金刚石	C₆₀，CNOs	可大量制备，操作简便	产物纯净度低，纯化困难
微波法	褐煤，烟煤，无烟煤	NDs，CDs	反应速率快，高效	产量不高，纯化过程复杂
热处理法	烟煤，无烟煤，石墨	CNOs，CDs	可大量制备，操作简单	能耗高，产物纯净度低，纯化困难

合成方法	主要前体	主要产物	优点	缺点
CVD法	煤层气（甲烷），乙炔，煤沥青	C₆₀，CDs，CNOs	操作简单，成本低，易于大批量生产	伴随有杂质相（无定形碳、石墨、催化剂），纯化困难
化学氧化法	褐煤，烟煤，无烟煤，焦炭	NDs，GQDs，CDs	设备简单，能耗低，操作简便	含有杂质，纯化困难
溶剂热法	煤焦油，烟煤，无烟煤	GQDs，CDs	操作简单，能耗低，不需要特殊的反应条件和设备	产量低，伴随着有毒气体的释放
超声法	烟煤，无烟煤	NDs，CQDs	反应速率快，操作简便	加热效率低，能耗高
电化学氧化法	焦炭或无烟煤混合煤焦油	C₆₀，CNOs，CDs	成本低，效率高，产量高	含有杂质相（金属杂质、无定形碳），设备复杂，原料需力学性能好
电弧放电法	焦炭，无烟煤，石墨	C₆₀，CNOs，CDs	产物结晶性好，能够大量制备，易于收集	含有大量含碳杂质（无定形碳、碳纳米管及金属杂质等），设备复杂
等离子体法	烟煤，无烟煤	CNOs，CDs	成本低，能大量制备	含有金属杂质及无定形碳
热解法	炭黑，纳米金刚石	C₆₀，CNOs	可大量制备，操作简便	产物纯净度低，纯化困难
微波法	褐煤，烟煤，无烟煤	NDs，CDs	反应速率快，高效	产量不高，纯化过程复杂
热处理法	烟煤，无烟煤，石墨	CNOs，CDs	可大量制备，操作简单	能耗高，产物纯净度低，纯化困难

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