Research progress on synthesis and regulation of lignocellulose-based carbon quantum dots

doi:10.16085/j.issn.1000-6613.2023-0737

Abstract

Abstract:

In recent years, various lignocellulosic biomasses have been used as green carbon sources to prepare carbon quantum dots, which are widely used in anti-counterfeiting, imaging, catalysis and other fields. Preparing carbon quantum dots from lignocellulosic biomasses can achieve low-cost, large-scale, and rapid preparation. However, the structure of lignocellulosic biomass is complex. The synthesis process of carbon quantum dots is affected by the type of raw materials and preparation process, and its fluorescence properties are closely related to the core structure and surface morphology. These factors make the preparation and regulation process of lignocellulose-based carbon quantum dots difficult to carry out precisely, and it is important to investigate the formation mechanism of lignocellulosic-based carbon quantum dots and the regulating mechanism for the quality improvement. In view of this, this paper reviews the formation methods and process of lignocellulose-based quantum dots, analyzes the advantages and disadvantages of various preparation and modification methods, discusses in-depth their synthesis mechanisms and regulation methods, and presents an outlook on their problems and challenges.

Key words: carbon quantum dots, lignocellulose, synthesis mechanism, optical modification

摘要：

近年各种木质纤维素类生物质被作为绿色碳源制备碳量子点，并广泛应用于防伪、成像、催化等领域。使用木质纤维素类生物质制备碳量子点可以实现其低成本、大规模、快速制备。然而木质纤维素类生物质结构复杂，木质纤维素基碳量子的合成过程受原料种类、制备过程影响，且其荧光特性与其碳的内核结构与表面形态紧密关联。这些因素使木质纤维素基碳量子点的制备与调控过程难以精准进行，因此探究木质纤维素基碳量子点的形成过程机理和调控提质机制十分重要。鉴于此，本文对木质纤维素基量子点的形成方法、过程影响等进行了综述，分析评价了各种制备与改性方法的优缺点，深入讨论了木质纤维素基碳量子点的合成机理与调控方法，并对其存在的问题以及挑战提出了展望。

关键词: 碳量子点, 木质纤维素, 合成机理, 光学调控

CLC Number:

CHEN Zhiqiang, XIA Mingwei, YANG Haiping, CHEN Yingquan, WANG Xianhua, CHEN Hanping. Research progress on synthesis and regulation of lignocellulose-based carbon quantum dots[J]. Chemical Industry and Engineering Progress, 2024, 43(6): 3100-3113.

陈志强, 夏明巍, 杨海平, 陈应泉, 王贤华, 陈汉平. 木质纤维素基碳量子点合成与调控研究进展[J]. 化工进展, 2024, 43(6): 3100-3113.

Figures/Tables 15

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序号	合成方法	碳源	前体	结构尺寸/nm	质量产率/%	量子产率/%	参考文献
1	热解碳化-氧化剥离	枯叶	热解焦炭	5~6	—	1	[24]
2	热解碳化-氧化剥离	椰子壳	热解焦炭	约1	—	—	[25]
3	水热碳化-氧化剥离	稻壳	热解焦炭	约8	10	—	[26]
4	水热碳化-氧化剥离	纤维素木质素半纤维素	水热炭	1.6~4.1	42.5	16.6	[27]
5	热解法	西瓜皮	—	约2	—	7.1	[28]
6	热解法	树叶	—	约3.7	—	16.4	[29]
7	热解法	花生壳	—	0.4~2.4	—	9.91	[30]
8	热解法	荔枝皮	—	0.4~2.4	—	—	[31]
9	热解法	胺化木质素	—	4~10	—	8.1	[32]
10	热解法	芒果叶	—	2~10	—	18.2	[33]
11	热解法	螺旋藻	—	约10	—	23.5	[34]
12	微波热解	松果	—	约15.2	—	17	[35]
13	水热合成	烟叶	—	约2.14	—	27.9	[36]
14	水热合成	淀粉	葡萄糖	2.25~3.5	—	21.7	[37]
15	水热合成	榴莲肉	小分子糖类	2~6	6.8	79	[38]
16	水热合成	氧化纤维素	—	1~3.4	16.1	30.3	[39]
17	水热合成	玉米芯	半纤维素为主的组分	约2.54	55	1.05	[40]
18	微波水热	稻草	—	2~3	—	—	[41]
19	微波水热	壳聚糖丙烯酰胺	—	—	45.9	12.7	[42]
20	酸预处理水热合成	碱木质素	碱木质素酸解产物	约4.76	45.8	30.6	[43]

序号	合成方法	碳源	前体	结构尺寸/nm	质量产率/%	量子产率/%	参考文献
1	热解碳化-氧化剥离	枯叶	热解焦炭	5~6	—	1	[24]
2	热解碳化-氧化剥离	椰子壳	热解焦炭	约1	—	—	[25]
3	水热碳化-氧化剥离	稻壳	热解焦炭	约8	10	—	[26]
4	水热碳化-氧化剥离	纤维素木质素半纤维素	水热炭	1.6~4.1	42.5	16.6	[27]
5	热解法	西瓜皮	—	约2	—	7.1	[28]
6	热解法	树叶	—	约3.7	—	16.4	[29]
7	热解法	花生壳	—	0.4~2.4	—	9.91	[30]
8	热解法	荔枝皮	—	0.4~2.4	—	—	[31]
9	热解法	胺化木质素	—	4~10	—	8.1	[32]
10	热解法	芒果叶	—	2~10	—	18.2	[33]
11	热解法	螺旋藻	—	约10	—	23.5	[34]
12	微波热解	松果	—	约15.2	—	17	[35]
13	水热合成	烟叶	—	约2.14	—	27.9	[36]
14	水热合成	淀粉	葡萄糖	2.25~3.5	—	21.7	[37]
15	水热合成	榴莲肉	小分子糖类	2~6	6.8	79	[38]
16	水热合成	氧化纤维素	—	1~3.4	16.1	30.3	[39]
17	水热合成	玉米芯	半纤维素为主的组分	约2.54	55	1.05	[40]
18	微波水热	稻草	—	2~3	—	—	[41]
19	微波水热	壳聚糖丙烯酰胺	—	—	45.9	12.7	[42]
20	酸预处理水热合成	碱木质素	碱木质素酸解产物	约4.76	45.8	30.6	[43]

序号	碳源	制备方法	改性方式	量子产率/%	（激发/发射）/nm	应用	参考文献
1	小白菜	水热合成	钝化/功能化	10.28	413/488/678	细胞成像	[77]
2	木聚糖	水热合成	钝化/功能化	16.18	320/415	细胞成像	[78]
3	大米	热解法	钝化/功能化	54	340/440	细胞成像	[79]
4	青稞	水热合成	钝化/功能化	14.4	400/480	汞离子检测	[80]
5	悬铃木	热解碳化激光烧蚀	钝化/功能化	32.4	377/447 397/476	细胞成像	[81]
6	玫瑰花瓣	微波水热	磷掺杂	—	390/435	四环素检测	[82]
7	毛尖茶叶	水热合成	氮掺杂	12.79	290/385	汞离子检测	[83]
8	柚子皮	水热合成	氮自掺杂	6.9	365/444	汞离子检测	[84]
9	麦秸	水热合成	氮自掺杂	9.2	304/418 364/464	细胞成像	[85]
10	纤维素	水热合成	氮掺杂	10.9	360/438	亚铁离子检测	[86]
11	绿茶叶	热解碳化氧化剥离	氮、硫共掺杂	14.8	320/410	吉非替尼检测	[87]
12	预水解木质素	水热合成	硫掺杂	13.5	320/410	苏丹Ⅰ检测	[88]
13	玉米芯木质素	水热合成	氮、镁共掺杂	46.38	405/510	pH检测	[89]
14	碱木质素	水热合成	氮、硫共掺杂	21	380/488	过氧化氢检测	[90]
15	碱木质素	水热合成	氮、硫共掺杂	30.5	450/520	荧光防伪	[91]
16	碱木质素	水热合成	氮、硼共掺杂	7.4	300/346 330/428 490/514	荧光防伪	[92]
17	木质素	水热合成	磷掺杂	—	310/388	光催化	[93]

序号	碳源	制备方法	改性方式	量子产率/%	（激发/发射）/nm	应用	参考文献
1	小白菜	水热合成	钝化/功能化	10.28	413/488/678	细胞成像	[77]
2	木聚糖	水热合成	钝化/功能化	16.18	320/415	细胞成像	[78]
3	大米	热解法	钝化/功能化	54	340/440	细胞成像	[79]
4	青稞	水热合成	钝化/功能化	14.4	400/480	汞离子检测	[80]
5	悬铃木	热解碳化激光烧蚀	钝化/功能化	32.4	377/447 397/476	细胞成像	[81]
6	玫瑰花瓣	微波水热	磷掺杂	—	390/435	四环素检测	[82]
7	毛尖茶叶	水热合成	氮掺杂	12.79	290/385	汞离子检测	[83]
8	柚子皮	水热合成	氮自掺杂	6.9	365/444	汞离子检测	[84]
9	麦秸	水热合成	氮自掺杂	9.2	304/418 364/464	细胞成像	[85]
10	纤维素	水热合成	氮掺杂	10.9	360/438	亚铁离子检测	[86]
11	绿茶叶	热解碳化氧化剥离	氮、硫共掺杂	14.8	320/410	吉非替尼检测	[87]
12	预水解木质素	水热合成	硫掺杂	13.5	320/410	苏丹Ⅰ检测	[88]
13	玉米芯木质素	水热合成	氮、镁共掺杂	46.38	405/510	pH检测	[89]
14	碱木质素	水热合成	氮、硫共掺杂	21	380/488	过氧化氢检测	[90]
15	碱木质素	水热合成	氮、硫共掺杂	30.5	450/520	荧光防伪	[91]
16	碱木质素	水热合成	氮、硼共掺杂	7.4	300/346 330/428 490/514	荧光防伪	[92]
17	木质素	水热合成	磷掺杂	—	310/388	光催化	[93]

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