水热法制备质子化钛纳米管的影响因素及其应用研究进展

doi:10.16085/j.issn.1000-6613.2020-1633

摘要/Abstract

摘要：

水热合成法制备质子化钛纳米管（TNTs）是一种操作简单、条件温和、适合规模化生产的方法，受到广泛关注，由此方法得到的钛纳米管具有开放的管道结构、比表面积大、稳定性高、离子交换等特点。本文简述了水热法制备TNTs的机理，分析了前体材料、水热反应条件、后处理方法等因素对水热法制备TNTs的影响规律，介绍了近年来TNTs作为载体、光催化剂、酸催化剂、吸附剂的应用研究现状。分析表明，通过调控水热条件及后处理方法可获得结构、性能各异的TNTs材料，并且利用离子交换、掺杂、有机表面修饰等多样化方法获得改性TNTs材料，进一步提升了TNTs材料在光催化、酸催化、吸附等方面的性能。最后指出，未来主要研究热点是提高水热法合成效率、优化化学改性策略，获得性能各异的TNTs材料。

关键词: 钛纳米管, 水热法, 载体, 催化剂, 酸催化, 吸附剂

Abstract:

The preparation of titanate nanotubes by hydrothermal method is regarded as a simple, convenient and mild technique, and is suitable for large-scale production, which had received a lot of attention. Titanate nanotubes prepared by this method have unique features, including open-ended structure, large specific surface area, good stability and ion-exchangeable ability. In this paper, the formation mechanism of TNTs was introduced briefly. The influence of various preparation conditions such as precursor materials, hydrothermal conditions, post-treatment on the structure of the TNTs were reviewed in detail. Recent advances in the applications of TNTs as supports, photocatalysts, acid catalysts, and adsorbents were also reviewed. TNTs materials with different structures and properties can be obtained by adjusting both hydrothermal conditions and post-treatment process. In order to improve the performance of TNTs, the modified TNTs materials can be obtained by doping, ion exchange method, surface modification and other methods. Improving the efficiency of hydrothermal synthesis, optimizing chemical modification strategies and obtaining TNTs with different properties were the main development trends in the future.

Key words: titanate nanotubes, hydrothermal method, support, catalyst, acid catalysis, adsorbents

中图分类号:

O612.4

周硕林, 赖金花, 游高林, 刘贤响, 尹笃林. 水热法制备质子化钛纳米管的影响因素及其应用研究进展[J]. 化工进展, 2021, 40(7): 3791-3802.

ZHOU Shuolin, LAI Jinhua, YOU Gaolin, LIU Xianxiang, YIN Dulin. Progress in influence factors and applications of protonated titanate nanotubes prepared via hydrothermal method[J]. Chemical Industry and Engineering Progress, 2021, 40(7): 3791-3802.

图/表 12

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前体	水热温度，时间/℃，h	氢氧化钠浓度/mol·L^-1	比表面积/m²·g^-1	孔体积/cm³·g^-1	纳米管外径，内径/ nm	参考文献
金红石型TiO₂	180，8	10	20	—	9.6，4.8	［15］
锐钛矿型TiO₂	150~155，24	10	286	0.947	12，6	［17］
锐钛矿型TiO₂	160，24	—	234	0.62	—	［18］
锐钛矿型TiO₂	160，48	—	314	0.81	—	［18］
锐钛矿型TiO₂	160，72	—	182	0.74	—	［18］
锐钛矿型TiO₂	130，6	8	210.32	—	8	［19］
P25	150，24	10	325.4	—	—	［21］
P25	180，10	10	156.42	0.316	27.48，16.90	［22］
P25	180，24	10	197.70	0.325	25.21，15.91	［22］
P25	180，48	10	20.88	0.060	37.78，9.44	［22］
P25	120，48	10	408	2.43	8，3.5	［23］
无定形的TiO₂	室温，48	10	735	1.63	3，0.7	［23］

前体	水热温度，时间/℃，h	氢氧化钠浓度/mol·L^-1	比表面积/m²·g^-1	孔体积/cm³·g^-1	纳米管外径，内径/ nm	参考文献
金红石型TiO₂	180，8	10	20	—	9.6，4.8	［15］
锐钛矿型TiO₂	150~155，24	10	286	0.947	12，6	［17］
锐钛矿型TiO₂	160，24	—	234	0.62	—	［18］
锐钛矿型TiO₂	160，48	—	314	0.81	—	［18］
锐钛矿型TiO₂	160，72	—	182	0.74	—	［18］
锐钛矿型TiO₂	130，6	8	210.32	—	8	［19］
P25	150，24	10	325.4	—	—	［21］
P25	180，10	10	156.42	0.316	27.48，16.90	［22］
P25	180，24	10	197.70	0.325	25.21，15.91	［22］
P25	180，48	10	20.88	0.060	37.78，9.44	［22］
P25	120，48	10	408	2.43	8，3.5	［23］
无定形的TiO₂	室温，48	10	735	1.63	3，0.7	［23］

酸	酸浓度/mol·L^-1	水热温度，时间/℃，h	比表面积/m²·g^-1	孔体积/cm³·g^-1	参考文献
HCl	0.025	140，20	206	0.52	［16］
HCl	0.05	140，20	239	0.53	［16］
HCl	0.075	140，20	227	0.55	［16］
HCl	0.1	140，20	218	0.53	［16］
HCl	0.1	130，24	307	0.85	［34］
HCl	0.5	130，24	392	1.13	［34］
HCl	1.0	130，24	333	0.56	［34］
HCl	—	140，24	375	1.33	［35］
H₂SO₄	—	140，24	369	1.49	［35］
HNO₃	—	140，24	422	1.37	［35］
HAc	0.1	135，72	324	1.13	［36］

酸	酸浓度/mol·L^-1	水热温度，时间/℃，h	比表面积/m²·g^-1	孔体积/cm³·g^-1	参考文献
HCl	0.025	140，20	206	0.52	［16］
HCl	0.05	140，20	239	0.53	［16］
HCl	0.075	140，20	227	0.55	［16］
HCl	0.1	140，20	218	0.53	［16］
HCl	0.1	130，24	307	0.85	［34］
HCl	0.5	130，24	392	1.13	［34］
HCl	1.0	130，24	333	0.56	［34］
HCl	—	140，24	375	1.33	［35］
H₂SO₄	—	140，24	369	1.49	［35］
HNO₃	—	140，24	422	1.37	［35］
HAc	0.1	135，72	324	1.13	［36］

催化剂	应用	能带/eV	文献
TNTs	光催化降解亚甲基蓝	3.00	［42］
TNTs	光催化降解亚甲基蓝	3.15	［16］
Fe/TNTs	光催化降解活性红X-3B	3.02~2.75	［43］
Fe-TNTs	光催化降解罗丹明B	2.83~2.60	［44］
La³⁺-TNTs	光催化降解气态乙苯	—	［45］
Co-TNTs	光催化降解亚甲基蓝	—	［46］
Mo-TNTs	光催化还原NO₂和CO₂	＜2.6	［47］
SnO₂/TNTs	光催化降解亚甲基蓝	—	［48］
SnO₂/TNTs	光催化降解亚甲基蓝	—	［49］
（Cu/TNTs_O）_R	光催化灭活大肠杆菌	—	［50］
MnO₂/TNTs	光催化降解17β-雌二醇	2.7	［51］
Ag@TNTs-0.5	光催化降解阿替洛尔	2.76	［52］
Ag@TNTs-1.0	光催化降解阿替洛尔	2.87	［52］
Ag@TNTs-2.5	光催化降解阿替洛尔	2.73	［52］
Al-Fe-TNTs	光催化降解腐殖酸	3.06	［53］
Pt-V₂O₅/TNTs	光催化降解罗丹明B	2.7	［54］
Pt-WO₃/TNTs	光催化降解罗丹明B	2.9	［54］
C-TNTs	光催化氧化、吸附汞	3.17	［55］
N-TNTs	光催化降解罗丹明B	—	［56］
C/S@TNTs	光催化分解水制氢	2.33	［57］
C，N，F/TNTs	光催化降解甲基橙	3.04	［58］
Cu，N-TNTs	光催化降解双酚A	—	［59］
rGO/TNTs	光催化降解亚甲基蓝	—	［60］
TNTs@GO	光催化降解亚甲基蓝	—	［61］
SWCNTs/TNTs	光催化乙醛	—	［62］
CQDs/TNTs	光催化降解亚甲基蓝	—	［63］
维生素B12-TNTs	光催化降解苯酚、罗丹明B	3.11	［64］
FeTCPP/TNTs	光催化降解亚甲基蓝	—	［65］