酚醛树脂基炭微球结构调控与功能化制备研究进展

doi:10.11949/0438-1157.20220472

摘要/Abstract

摘要：

炭微球具有化学稳定性好、电导率优良、比表面积大、孔结构丰富等优点，在吸附、催化等领域具有广阔的应用前景，引起了研究人员的广泛关注。酚醛基炭微球以酚醛树脂为前体，经高温炭化制备而成，这种制备方法工艺简单、对设备要求低、产率高，而且通过调整反应物和反应条件可实现对炭微球结构和功能性的精细调控，从而更好地满足实际应用的需求。概述了酚醛基炭微球的最新研究进展，分为小粒径炭微球制备、多孔炭微球制备和功能化炭微球制备三个方面，并介绍了酚醛基炭微球在储能、吸附和电催化领域的应用，最后对其未来发展方向进行了展望。

关键词: 纳米材料, 聚合物, 微球, 热解, 吸附, 催化, 燃料电池

Abstract:

With the advantages of favorable chemical stability and electrical conductivity, large specific surface area, and rich pore structure, carbon microspheres have broad application prospects in adsorption, catalysis, and other fields, which have attracted extensive attentions from researchers. As one of the preparation methods of carbon microspheres, phenolic-based carbon microspheres are obtained by high-temperature carbonization process with phenolic resin as the precursor. This preparation method has the advantages of simple process, low requirements on equipment, and high yield of the carbon microspheres. In addition, the structure and functionality of the obtained carbon microspheres can be regulated by adjusting the reactants and reaction conditions, which can be better conform to the requirements of practical applications. In this paper, recent studies of phenolic-based carbon microspheres are reviewed, which are mainly divided into three aspects: small-particle carbon microspheres preparation, porous carbon microspheres preparation, and functionalized carbon microspheres preparation, it also introduces the applications of phenolic-based carbon microspheres in the fields of energy storage, adsorption and electro-catalysis, and the future directions of their development are prospected in the end.

Key words: nanomaterials, polymers, microspheres, pyrolysis, adsorption, catalysis, fuel cells

中图分类号:

TB 321

邵健, 冯军宗, 柳凤琦, 姜勇刚, 李良军, 冯坚. 酚醛树脂基炭微球结构调控与功能化制备研究进展[J]. 化工学报, 2022, 73(9): 3787-3801.

Jian SHAO, Junzong FENG, Fengqi LIU, Yonggang JIANG, Liangjun LI, Jian FENG. Research progress on structural modulation and functionalized preparation of phenolic resin-based carbon microspheres[J]. CIESC Journal, 2022, 73(9): 3787-3801.

图/表 16

图1 酚醛微球形成过程示意图[14]

Fig.1 Schematic diagram of the formation process of phenolic microspheres[14]

表1 小粒径炭微球制备相关参数

Table 1 Parameters related to the preparation of small particle size carbon microspheres

炭前体	溶剂	催化剂	添加剂	炭球粒径/nm	比表面积/(m²/g)	文献
间苯三酚、对苯二甲醛、间苯二酚、甲醛	水	氨水	—	30~90	—	[19]
苯酚、甲醛	水	—	F127	约110	219	[20]
间苯三酚、对苯二胺、甲醛	水、乙醇	对苯二胺	—	79.2~137.0	—	[15]
间苯三酚、甲醛	水	盐酸	F108，F127，F86，P123^②	80~90	—	[17]
间苯二酚、甲醛	水、乙醇	乙二胺	PVP^③	60~875	516~1083	[21]
间苯二酚、甲醛	水	乙二胺、氨水	F127	约180	711	[22]
苯酚、甲醛	水	Bis-tris^①	CTAB ^④	86~205	441~1462	[23]
苯酚、甲醛	水	氢氧化钠	F127	约100	1602	[24]
间苯二酚、甲醛	水、甲醇	氨水	—	160~1800	—	[14]
间苯二酚、甲醛	水、乙醇	氨水	F127	52	304~3259	[25]
二羟基沙林、甲醛	水、甲醇	氨水	F127	106~188	499~528	[26]
三聚氰胺、甲醛	水	氢氧化钠	F127	40~160	795~883	[27]

图2 “种子”合成策略制备聚合物纳米球的示意图(a)；胶体种子(b)和聚合物微球(c)的TEM图像[19]

Fig.2 Schematic diagram of the “seed” synthesis strategy for the preparation of polymer nanospheres (a); TEM images of colloidal seeds (b) and polymer microspheres (c) [19]

图3 小粒径酚醛树脂基球体合成示意图[23]

Fig.3 Schematic diagram of the synthesis of small particle size phenolic resin-based spheres[23]

表2 多孔炭微球制备相关参数

Table 2 Parameters related to the preparation of porous carbon microspheres

添加剂	粒径/nm	孔型	比表面积/（m²/g）	孔体积/（cm³/g）	文献
正硅酸乙酯、硅溶胶	300~500	微孔、介孔	430~560	0.23~0.60	[32]
F127、CTAB	40~750	大孔	67~1295	0.05~0.84	[34]
F127	约110	介孔	219	0.27	[20]
聚乙二醇	—	微孔	556~625	0.25~0.26	[10]
—	约850	超微孔	1113~1235	0.60~0.88	[35]
F127	约300	微孔	409	0.25	[30]
正硅酸乙酯	100~500	大孔	—	—	[36]
PVP	约260	大孔	—	—	[37]
F108、F127、F86、P123	80~90	介孔	—	—	[17]
PVP	60~875	微孔	516~1083	0.28~0.82	[21]
F127	约180	介孔	711	—	[22]
CTAB	86~205	微孔、介孔	441~1462	0.56~1.00	[23]
F127	约100	介孔	1602	2.09	[24]
—	约600	微孔	836	0.40	[38]
F127	50~700	微孔	304~3259	0.34~2.44	[25]
F127	40~160	介孔	795~883	—	[27]
CTAB、正硅酸乙酯	320~400	微孔、介孔	550~1261	0.53~1.05	[39]
聚乙二醇	300~1000	微孔、介孔	1101~1835	0.28~0.48	[31]

图4 F127辅助合成介孔炭微球示意图[30]

Fig.4 Schematic diagram of F127-assisted synthesis of mesoporous carbon microspheres[30]

图5 PVP辅助合成空心炭球示意图[37]

Fig.5 Schematic diagram of PVP-assisted synthesis of hollow carbon spheres[37]

图6 受限热解制备介孔炭球示意图(a)；SiO2包裹酚醛微球的TEM图像[(b)，(c)]；介孔炭球的TEM图像[(d)，(e)]；受限热解和直接热解得到炭球的氮气吸附-脱附等温线和孔径分布曲线[(f),(g)][24]

Fig.6 Schematic diagram of mesoporous carbon spheres prepared by restricted pyrolysis(a); TEM images of MPS@SiO2[(b), (c)]; TEM images of mesoporous carbon spheres[(d), (e)]; Nitrogen adsorption-desorption isotherms and pore size distribution curves of carbon spheres obtained by restricted pyrolysis and direct pyrolysis[(f), (g)][24]

表3 功能化炭微球制备相关参数

Table 3 Relevant parameters for the preparation of functionalized carbon microspheres

炭前体	添加剂	催化剂	粒径/nm	功能化措施	氮掺杂量	文献
间苯二酚、甲醛	F127	氨水	—	负载Ag	—	[32]
间苯二酚、甲醛	F127	氨水	150~900	负载Pt	—	[29]
氨基苯酚、甲醛	—	氨水	80~2500	负载Pt	—	[28]
苯酚、甲醛	F127	氢氧化钠	约110	负载Fe	—	[20]
单宁酸、甲醛	—	氨水	60~2100	负载Fe	—	[45]
间苯三酚、对苯二胺、甲醛	—	对苯二胺	79.2~137	掺N	9.77%(质量分数)	[15]
氨基苯酚、六氯甲烷	F127	氨水	约300	掺N	5.31%(质量分数)	[30]
间苯二酚、甲醛	PVP	氨水	约260	掺N	1.5%(原子分数)	[37]
单宁酸、甲醛	F127	氨水	约300	负载Co、Fe、Ni 等	—	[46]
间苯二酚、甲醛	PVP	乙二胺	60~875	掺N	5%(质量分数)	[21]
苯酚、甲醛	CTAB	Bis-tris	86~205	掺N	2.32%(原子分数)	[23]
苯酚、甲醛	F127	氢氧化钠	约100	掺N	—	[24]
间苯二酚、HMTA	—	HMTA	约800	掺N	2.05%(原子分数)	[47]
二羟基沙林、甲醛	F127	氨水	106~188	掺N	35%(质量分数)	[26]
三聚氰胺、甲醛	F127	氢氧化钠	40~160	掺N	15.6%(质量分数)	[27]
间苯二酚、甲醛	PEG	氨水、乙二胺或己二胺	300~1000	掺N	—	[31]

图7 TA的化学结构(a)；金属-酚醛键的形成(b)

Fig.7 Chemical structure of TA (a); Formation of metal-phenolic bonds (b)

表4 各种炭材料电化学性能的比较

Table 4 Comparison of electrochemical performance of various carbon materials

电极材料	比表面积/(m²/g)	比电容/（F/g）	电解液	文献
酚醛基炭微球	409	288 (0.1 A/g)	6 mol/L KOH	[30]
		173 (0.5 A/g)	6 mol/L KOH	[37]
	1602	326 (1.0 A/g)	6 mol/L KOH	[24]
		201 (0.5 A/g)	6 mol/L KOH	[47]
	836	282 (0.5 A/g)	6 mol/L KOH	[38]
	3259	225 (0.5 A/g)	6 mol/L KOH	[25]
	1835	234 (1.0 A/g)	6 mol/L KOH	[31]
泡沫炭	1286	227 (1.0 A/g)	6 mol/L KOH	[55]
石墨烯	2582	186 (1.0 A/g)	6 mol/L KOH	[56]

图8 不同文献中超级电容器循环稳定性(a)和不同电流密度下的面积比电容(b)的比较

Fig.8 Comparison of cycling stability (a) and area specific capacitance at different current densities (b) of supercapacitors in different literature

图9 DHCSs/RGO制备示意图(a)；DHCSs/RGO活化前循环性能(b)；DHCSs/RGO活化后循环性能(c)[57]Cycling performance after DHCSs/RGO activation (c)[57]

Fig.9 Schematic diagram of DHCSs/RGO preparation (a); Cycling performance before DHCSs/RGO activation (b);

图10 NNSC制备示意图(a)；循环9000次时，NNSC的容量保留率和容量(b)[60]

Fig.10 Schematic diagram of NNSC preparation (a); Capacity retention and capacity of NNSC at 9000 cycles (b)[60]

图11 不同文献中吸附材料CO2吸附性能的对比(1 bar=100 kPa)

Fig.11 Comparison of CO2 adsorption performance of different adsorbent materials in the literatures (1 bar=100 kPa)

图12 TAF-C@Fe制备示意图(a);不同电极的CV曲线(b);添加0.5 mol/L甲醇后TAF-C@Fe和Pt/C的CV曲线(c)[45]

Fig.12 Schematic diagram of TAF-C@Fe preparation (a); CV curves of different electrodes (b); CV curves of TAF-C@Fe and Pt/C after adding 0.5 mol/L methanol (c) [45]

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