水热-软模板法制备介孔炭球及其应用

doi:10.16085/j.issn.1000-6613.2020-0612

摘要/Abstract

摘要：

介孔炭球兼具炭材料以及球状胶体的优点，即优异的流动性、分散性、导电性以及可调控的孔径大小和粒径尺寸，使其在生物、催化、吸附分离和电化学等领域展示出良好应用前景。近年来，水热-软模板法作为一种有效的制备介孔炭球的方法被广泛报道，它通过水热实现球形结构的控制并借助软模板实现对介孔的调控。本文综述了水热-软模板法制备介孔炭球的最新进展，包括其结构与形貌的调控、改性和其应用。对如何选取碳源、软模板和溶剂等问题进行了总结并展望了其在各应用中的发展方向。

关键词: 介孔炭球, 软模板, 水热, 制备, 应用

Abstract:

Mesoporous carbon spheres integrate the advantages of carbon materials with spherical colloids, including excellent fluidity, dispersity, conductivity and the controllability of their particle sizes and pore sizes, making them able to be applied in biology, catalysis, adsorption and electrochemistry. Recently, hydrothermal/soft-templating method, as a promising way to prepare mesoporous carbon spheres, is widely reported. The spherical morphology and mesoporous structure can be controlled through hydrothermal carbonization and soft template, respectively. This review presented the preparation of mesoporous carbon spheres and the control of its pore size and particle size by using hydrothermal carbonization and soft template together. Moreover, the modification and application of mesoporous carbon spheres were covered. The selection of carbon precursor, soft template and solvent were also summarized, and the perspectives of its research directions on various applications were proposed.

Key words: mesoporous carbon spheres, soft-template, hydrothermal, preparation, application

中图分类号:

O648

吴振威, 李伟, 鄂雷, 孙佳明, 刘禹衫, 刘守新. 水热-软模板法制备介孔炭球及其应用[J]. 化工进展, 2021, 40(2): 932-948.

Zhenwei WU, Wei LI, Lei E, Jiaming SUN, Yushan LIU, Shouxin LIU. Preparation and applications of mesoporous carbon spheres via combination of hydrothermal and soft-templating[J]. Chemical Industry and Engineering Progress, 2021, 40(2): 932-948.

图/表 16

表1 不同原料及制备条件制得的介孔炭球的性质与应用

碳源	模板	催化剂	水热温度 /℃	水热时间 /h	形貌	改性	应用	参考文献
间苯二酚和甲醛	F127	HCl	150	10	实心	Se	锂电池	[20]
间苯二酚和甲醛	F127、FC4	HCl	100	24	实心	N	氧还原反应	[21]
间苯二酚和甲醛	F127	HCl	120	12	实心	Fe、N	氧还原反应	[22]
间苯二酚和甲醛	F127	NaOH	180	4	实心	—	超级电容器	[23]
间苯二酚和甲醛	CTAB	NH₄OH	100	24	壳核	N	直接甲醇燃料电池	[24]
间苯二酚和甲醛	CTAB	NH₄OH	100	24	壳核	—	超级电容器	[25]
间苯二酚和甲醛	CTAB	NH₄OH	80	24	中空	—	超级电容器	[26]
酚醛树脂	F127	NaOH	130	10	实心	Fe₃O₄	锂电池	[27]
酚醛树脂	F127	NaOH	130	24	实心	—	细胞透性	[28]
三聚氰胺、间苯二酚和甲醛	F127	NaOH	180	7	实心	N、石墨烯	超级电容器	[29]
三聚氰胺、间苯二酚和甲醛	CTAC	NH₄OH	100	24	壳核	N	超级电容器	[30]
2,4-二羟基苯甲酸和甲醛	油酸	NH₄OH	100~160	4	中空	Fe、Ag	催化	[31]
2,4-二羟基苯甲酸和甲醛	油酸钠	NH₄OH	140	4	壳核	Cu	催化	[32]
2,4-二羟基苯甲酸和环六亚甲基四氨	P123和油酸钠	NH⁴⁺	160	2	中空	Pt、Co	催化	[33]
2,4-二羟基苯甲酸和环六亚甲基四氨	P123和油酸钠	NH⁴⁺	160	5	壳核	Pd	催化	[34]
2,4-二羟基苯甲酸和环六亚甲基四氨	P123和油酸钠	NH⁴⁺	160	8	中空	Fe、N	氧还原反应	[35]
2,4-二羟基苯甲酸和环六亚甲基四氨	P123和油酸钠	NH⁴⁺	160	8	中空	N、石墨烯	氧还原反应	[36]
葡萄糖	SDS	—	250	5	中空	Ni	析氢反应	[37]
D-果糖	F127	—	130	24	实心	—	超级电容器	[38]
α-环糊精	F127	—	200	6	壳核	—	锂电池	[39]

图1 以甲阶酚醛树脂为碳源通过低浓度水热法制备有序介孔炭纳米球[28]

图2 以D-果糖为碳源制备有序介孔花状炭球的形成机理[54]

图3 用于软模板法制备介孔炭球的嵌段共聚物F127、P123和F108的结构式[63]

图4 在乳液系统中通过水热形成碗状介孔颗粒[73]

图5 有着不同形貌的介孔炭球

图6 氮掺杂卵壳型炭球制备，经NaOH刻蚀后形成多孔结构[24]

图7 不同TMB添加量下合成具有不同孔径大小的介孔聚合物纳米球（MPNs-n）

图8 不同氮掺杂介孔炭球的XPS谱图[89]

图9 制备Cu@炭卵壳纳米球的过程[32]

图10 IONP@mC-600的合成示意图[27](a)IONPs和F127胶束；(b)酚醛树脂-Fe3O4和酚醛树脂-F127单胶束；(c)IONP@PC；(d)IONP@mC；(e)IONP@mC的横截面；(f)IONP@mC的孔道放大图

图11 锐钛矿型TiO2/炭复合纳米球（meso-ATCCNs）的性能[99]

图12 不同电极的CV曲线、GCD曲线及不同电流密度下各电极的比电容[101]

图13 (a)N-OMCS的合成过程以及它对H2S的选择性捕获和氧化；(b)0°C时不同吸附剂对H2S的吸附等温线（1bar=105Pa）；(c)反应温度对H2S转换率的影响[79]

图14 (a)FeNCS-1000的SEM图（插图为中空球体的壳厚分布以及中空石墨球的示意图）；(b)FeNCS-1000的TEM图；(c)单个无Fe掺杂的NHCS颗粒的TEM图；(d)FeNCSs和其他对照样品在O2饱和的0.1mol·L-1 KOH溶液；(e)O2饱和的0.5mol·L-1 H2SO4溶液中的RDE伏安图（转速1600r·min-1；扫速10mV·s-1）[35]

图15 OMCN/P0-Cy3适体传感器的感应机理以及其在个体上的感应性能（体内荧光成像）[106]

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