Research progress on structural modulation and functionalized preparation of phenolic resin-based carbon microspheres

doi:10.11949/0438-1157.20220472

Abstract

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

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

CLC Number:

TB 321

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.

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.

Figures/Tables 16

References 75

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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]

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]

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]

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]

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]